EP0096619A1 - Corrosion-inhibiting means and compositions containing them - Google Patents

Corrosion-inhibiting means and compositions containing them Download PDF

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Publication number
EP0096619A1
EP0096619A1 EP83401050A EP83401050A EP0096619A1 EP 0096619 A1 EP0096619 A1 EP 0096619A1 EP 83401050 A EP83401050 A EP 83401050A EP 83401050 A EP83401050 A EP 83401050A EP 0096619 A1 EP0096619 A1 EP 0096619A1
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EP
European Patent Office
Prior art keywords
formula
inhibiting
aqueous
fluorophosphate
corrosion
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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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EP83401050A
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German (de)
French (fr)
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EP0096619B1 (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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Priority to AT83401050T priority Critical patent/ATE25113T1/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
    • 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

  • the present invention relates to a new means for inhibiting aqueous corrosion belonging to the family of fluorophosphates, for protecting metallic surfaces, in particular those of installations and devices using water as energetic or thermal fluid.
  • the invention also relates to a composition containing this means in combination, where appropriate, with one or more other substances useful in the field of protection against aqueous corrosion.
  • 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
  • FR-A-2 192 192 and FR-A-2 231 777 which use an inhibiting composition comprising in combination (i) an orthophosphate, ie a non-fluorinated phosphate, and (ii) a derivative of water-soluble organophosphonic acid or a polymer such as polyacryl- amides, polyacrylic acids and polyacrylates.
  • fluorophosphates also designated by the expression “oxyfluorinated phosphorus derivatives 5" are known substances, in particular from FR-A-2 352 895, as means for treating metal surfaces before painting.
  • a new technical solution is recommended, to solve the problem of protecting metal surfaces from aqueous corrosion, which uses new inhibitory means structurally different from the means previously known in the field of inhibiting corrosion.
  • 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).
  • 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.
  • thermal fluid cooling or heating circuits
  • 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 not very water-soluble, the solubility threshold in water being of the order of 10 g / 1.
  • an aqueous corrosion inhibiting composition which is characterized in that it contains in aqueous solution or suspension a corrosion inhibiting means chosen from all of the fluorophosphates of the points ( i) to (viii) above.
  • This composition is used in such a way that, after introduction into the corrosive aqueous fluid, the content of the inhibitor means is from 3 to 500 ppm by weight (preferably 5 to 200 ppm by weight, in particular for ZnP0 3 F) relative to the weight of the fluid.
  • 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 be made in particular of the products known under the brand names DUOMEEN, DINORAM, TRINORAM, POLYRAM, LILAMIN and CEMULCAT which contain at least one polyamine I.
  • DINORAM 0 which 'contains approximately 75% by dry weight of oleylamino-propylene amine, 9% by dry weight of stearylaminopropyleneamine and 6% by dry weight of hexadecylaminopropyleneamine
  • DINORAM S which contains approximately 43% by dry weight of stearylinopropyleneamine , 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 about 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 in which M 1 , M 2 , M 3 or M 4 , which may be identical or different, each represent the hydrogen atom, a C 1 -C 4 alkyl group, nitrile, aldehyde, alcohol, amine, amide, imine, imide, ammonium, CO 2 H or SO 3 M (wherein M is H, lkyle a C 1 -C 4, NH 4 + or a metal cation, in particular Na + or K +).
  • a method for protecting metallic surfaces in contact with water from aqueous corrosion and in particular those of installations using water as an energetic or thermal fluid.
  • This process comprises the introduction into the corrosive aqueous fluid of an amount of corrosion inhibiting fluorophosphate such that, after introduction into said fluid, the fluorophosphate content is between 3 and 500 ppm by weight relative to the weight of said fluid.
  • the corrosion inhibiting fluorophosphate is ZnP0 3 F
  • the content of ZnP0 3 F, after introduction into said corrosive fluid will be between 5 and 200 ppm by weight relative to the weight of the corrosive aqueous fluid.
  • 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 / 1 of ZnP0 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 two other means, said mixture having been obtained according to the methods described in the European patent and the above-mentioned European patent application.
  • the products of Examples 8-10 are prepared by introducing into water ZnPO 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 a steel oil well operating by 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 ⁇ / year is considerably reduced with the products of Examples 1, 3 and 6 compared with the control (injection of aqueous mud only).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

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 moyen inhibiteur de corrosion aqueuse 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 ce moyen en association, le cas échéant, 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 means for inhibiting aqueous corrosion belonging to the family of fluorophosphates, for protecting metallic surfaces, in particular those of installations and devices using water as energetic or thermal fluid. The invention also relates to a composition containing this means in combination, where appropriate, 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'ùn 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, those recommended in EP-B-10 485 and in EP-A-65 609 are known, 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 connatt celles préconisées par FR-A-2 192 192 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 fluoré, et (ii) un dérivé d'acide organo- phosphonique hydrosoluble ou un polymère tel que les polyacryl- amides, acides polyacryliques et polyacrylates.Among the older and less effective technical solutions, we know those recommended by FR-A-2 192 192 and FR-A-2 231 777 which use an inhibiting composition comprising in combination (i) an orthophosphate, ie a non-fluorinated phosphate, and (ii) a derivative of water-soluble organophosphonic acid or a polymer such as polyacryl- amides, 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 traitement de surfaces métalliques avant peinture.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 for treating metal surfaces before painting.

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 de nouveaux moyens inhibiteurs structurellement différents des moyens 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 from aqueous corrosion, which uses new inhibitory means structurally different from the means previously known in the field of inhibiting corrosion.

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 moyen inhibiteur de corrosion selon l'invention qui appartient à la famille des fluorophosphates est caractérisé en ce qu'il est choisi parmi l'ensemble constitué par

  • (i) les composés de formule MI 2 PO3F, xH20
  • (ii) les composés de formule LiMIPO3F, xH20
  • (iii) les composés de formule NaMIPO3F, xH20
  • (iv) les composés de formule MIIPO3F, xH20
  • (v) les composés de formule M2 MII(PO3F)2, xH2O
  • (vi) les composés de formule MIPO2F2, xH20 , et
  • (vii) les composés de formule MII(PO2F2)2' xH20,
    (dans lesquelles MI est Na, K, Rb, Cs ou NH4 ; MII 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,
  • (viii) leurs mélanges.
The new corrosion inhibitor means according to the invention which belongs to the family of fluorophosphates is characterized in that it is chosen from the group consisting of
  • (i) the compounds of formula M I 2 PO 3 F, xH 2 0
  • (ii) the compounds of formula LiM I PO 3 F, xH 2 0
  • (iii) the compounds of formula NaM I PO 3 F, xH 2 0
  • (iv) the compounds of formula M II PO 3 F, xH20
  • (v) the compounds of formula M2 M II (PO 3 F) 2 , xH 2 O
  • (vi) the compounds of formula M I PO 2 F 2 , xH 2 0, and
  • (vii) the compounds of formula M II (PO 2 F 2 ) 2 ' xH 2 0,
    (in which M I is Na, K, Rb, Cs or NH 4 ; M II is M g, Ca, Ba, Sr, Zn, Cd, Mn, Ni or Co; and, x is an integer or fractional number between 0 and 6), and,
  • (viii) their mixtures.

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/1.The fluorophosphates according to the invention are substances generally not very water-soluble, the solubility threshold in water being of the order of 10 g / 1.

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 ZnP03F. A . ce sujet, il est signalé que par rapport aux eaux brute A et synthétique B décrites ci-aprës, la dose de ZnPO3F..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 especially for ZnP0 3 F. A. On this subject, it is reported that compared to raw water A and synthetic water described below, the dose of ZnPO 3 F.. giving maximum inhibition is 20 to 25 ppm (see Table III below).

Selon un mode de mise en oeuvre de l'invention, on préconise une composition inhibitrice de corrosion aqueuse, qui est caractérisée en ce qu'elle renferme en solution ou suspension aqueuse un moyen inhibiteur de corrosion choisi parmi l'ensemble des fluorophosphates des points (i) à (viii) sus-visés. Cette composition est utilisée de telle façon que, après introduction dans le fluide aqueux corrosif, la teneur du moyen inhibiteur soit de 3 à 500 ppm en poids (de préférence 5 à 200 ppm en poids notamment pour ZnP03F) par rapport au poids du fluide .According to an embodiment of the invention, an aqueous corrosion inhibiting composition is recommended, which is characterized in that it contains in aqueous solution or suspension a corrosion inhibiting means chosen from all of the fluorophosphates of the points ( i) to (viii) above. This composition is used in such a way that, after introduction into the corrosive aqueous fluid, the content of the inhibitor means is from 3 to 500 ppm by weight (preferably 5 to 200 ppm by weight, in particular for ZnP0 3 F) relative to the weight of the fluid.

Selon un autre mode de mise en oeuvre 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 notamment 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 embodiment 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 in particular from the group consisting of polyamines, organic polyelectrolytes resulting from the polymerization or copolymerization of a monomer having a unit C = C, derivatives of alkylene polyphosphonic acid, derivatives of aminoalkylene phosphonic acid 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 0" 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 stèarylaminopropylèneamine, 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 be made in particular 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 0 "which 'contains approximately 75% by dry weight of oleylamino-propylene amine, 9% by dry weight of stearylaminopropyleneamine and 6% by dry weight of hexadecylaminopropyleneamine," DINORAM S "which contains approximately 43% by dry weight of stearylinopropyleneamine , 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 polymeriques 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 about 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 C1-C4, nitrile, aldéhyde, alcool, amine, amide, imine, imide, ammonium, CO2M ou SO3 M (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
 in which M 1 , M 2 , M 3 or M 4 , which may be identical or different, each represent the hydrogen atom, a C 1 -C 4 alkyl group, nitrile, aldehyde, alcohol, amine, amide, imine, imide, ammonium, CO 2 H or SO 3 M (wherein M is H, lkyle a C 1 -C 4, NH 4 + or a metal cation, in particular Na + or K +).

Les définitions données ci-dessus pour la formule II englobert les copolymères obtenus à partir de l'éthylène et de ses analogues éthyléniques (M1, M2, M3 et M4 représentant chacun H ou alkyle), Cependant, pour obtenir notamment des polymères et copolymères du type acrylique, acrylate, acrylamide, acrylaldéhyde, acrylonitrile, maléique, il est clair qu'au moins un des M1, M2, M3 et M4 soit différent de H et du groupe alkyle en C1-C4, dans la formule du monomère II.The definitions given above for formula II include the copolymers obtained from ethylene and its ethylenic analogs (M 1 , 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 M 1 , M 2 , M 3 and M 4 is different from H and the C 1 -C alkyl group 4 , in the formula of monomer II.

Les polyélectrolytes préférés ont été mentionnés ci-après, à savoir :

  • (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 ;
  • (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 ;
  • (iii) les dérivés du type polyacrylamide répondant à la formule générale
    Figure imgb0005
    (où R2 et n1 sont définis comme indiqué ci-dessus) et leurs mélanges ;
  • (iv) les dérivés copolymères du type acrylique- acrylamide présentant schématiquement un motif
    Figure imgb0006
    (où R1, R3 et R 4 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 séquence, représenter 0) et leurs mélanges ;
  • (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 ;
  • (vi) les dérivés copolymères du type acrylique-acryla- amide présentant schématiquement un motif
    Figure imgb0008
    (où R1, R3, R4, n2, n 3 et n 4 sont définis comme indiqué ci-dessus) et leurs mélanges.
The preferred polyelectrolytes have been mentioned below, namely:
  • (i) derivatives of the polyacrylic type corresponding to the general formula
    Figure imgb0003
     (wherein 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 number greater than or equal to 2) and their mixtures;
  • (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) derivatives of the polyacrylamide type corresponding to the general formula
    Figure imgb0005
     (where R 2 and n 1 are defined as indicated above) and their mixtures;
  • (iv) the copolymer derivatives of the acrylic-acrylamide type having schematically 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, only one of n 3 and n 4 which, in the case of a block copolymer, represents 0) and their mixtures;
  • (v) the copolymer derivatives of the styrene-maleic type having schematically a motif
    Figure imgb0007
     (where R 1 , n 2 , n 3 and n4 are defined as indicated above) and their mixtures;
  • (vi) copolymer derivatives of the acrylic-acrylamide type which schematically have a motif
    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 :

  • (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 III.1 étant l'aminotrimethylène- phosphonate de sodium (où n5 est 0) ;
  • (ii) les acides alkylènediphosphoniques, leurs esters et leurs sels, tels que notamment l'acide 1-hydroxyéthylidëne-1,1- diphosphonique de formule
    Figure imgb0010
    et ses sels de sodium, potassium ou d'ammonium ; et
  • (iii) les acides aminoalkylènepolyphosphoniques de formule
    Figure imgb0011
    (où Alk est un groupe alkylène en C1-C6 et n est un nombre entier compris entre 0 et 3), leurs sels métalliques ou d'ammonium.
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) 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 III.1 being sodium aminotrimethylene phosphonate (where n 5 is 0);
  • (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) aminoalkylene polyphosphonic acids of formula
    Figure imgb0011
     (where Alk is a C 1 -C 6 alkylene group and n is an integer between 0 and 3), their metal or ammonium salts.

Selon l'invention, on préconise enfin un procédé pour protéger de la corrosion aqueuse les surfaces métalliques en contact avec de l'eau et notamment celles des installations utilisant de l'eau comme fluide énergétique ou thermique. Ce procédé comprend l'introduction dans le fluide aqueux corrosif d'une quantité de fluorophosphate inhibiteur de corrosion telle que, après introduction dans ledit fluide, la teneur en fluorophosphate est comprise entre 3 et 500 ppm en poids par rapport au poids dudit fluide. De façon avantageuse, si le fluorophosphate inhibiteur de corrosion est ZnP03F, la teneur en ZnP03F, après introduction dans ledit fluide corrosif, sera comprise entre 5 et 200 ppm en poids par rapport au poids du fluide aqueux corrosif.According to the invention, finally, a method is recommended for protecting metallic surfaces in contact with water from aqueous corrosion and in particular those of installations using water as an energetic or thermal fluid. This process comprises the introduction into the corrosive aqueous fluid of an amount of corrosion inhibiting fluorophosphate such that, after introduction into said fluid, the fluorophosphate content is between 3 and 500 ppm by weight relative to the weight of said fluid. Advantageously, if the corrosion inhibiting fluorophosphate is ZnP0 3 F, the content of ZnP0 3 F, after introduction into said corrosive fluid, will be between 5 and 200 ppm by weight relative to the weight of the corrosive aqueous fluid.

On a consigné dans le tableau I 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
A number of examples of means for inhibiting aqueous corrosion according to the invention have been recorded in table I below. These nonlimiting examples are given by way of illustration.
Figure imgb0012

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 12 g/1 de ZnP03F 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 ZnPO3F 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 / 1 of ZnP0 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 two other means, said mixture having been obtained according to the methods described in the European patent and the above-mentioned European patent application. The products of Examples 8-10 are prepared by introducing into water ZnPO 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 de moyen A, et
  • - 1 à 100 parties en poids 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 weight of medium A, and
  • - 1 to 100 parts by 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-10 485.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-10 485.

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/1 de chlorure de sodium. Les eaux A et B avaient les caractéristiques suivantes données dans le tableau II.

Figure imgb0013
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 oxygen dissolved) obtained by total demineralization of the raw water "A" by passage through ion exchange resins then addition of 200 mg / 1 of sodium chloride. Waters A and B had the following characteristics given in Table II.
Figure imgb0013

La mesure de la perte de poids a été réalisée 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 µ/an) et en efficacité inhibitrice EX (pourcentage d'inhibition) selon les relations

Figure imgb0014
dans laquelle

  • V - vitesse de corrosion en µ/an,
  • P - perte de poids en mg,
  • J - nombre de jours d'exposition au milieu agressif,
  • S = surface externe de l'éprouvette en µ2,
  • d = masse spécifique du métal de l'éprouvette en mg/µ3 ; et
    Figure imgb0015
    dans laquelle Vo et V représentent respectivement les vitesses de corrosion (exprimées en µ/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 was translated into corrosion rate V (expressed in μ / year ) and in inhibitory efficacy EX (percentage of inhibition) according to the relationships
Figure imgb0014
 in which
  • V - corrosion rate in µ / year,
  • P - weight loss in mg,
  • D - number of days of exposure to the aggressive environment,
  • S = external surface of the test piece in µ 2 ,
  • d = specific mass of the metal of the test piece in mg / µ 3 ; and
    Figure imgb0015
     in which Vo and V represent respectively the corrosion rates (expressed in µ / 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 are 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 aminoalkylënepolyphosphoniques, et/ou des polyélectrolytes organiques inhibent de façon très efficace la corrosion aqueuse de surfaces métalliques.

Figure imgb0016
Figure imgb0017
Figure imgb0018
 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.
Figure imgb0016
Figure imgb0017
Figure imgb0018

II - Etude de l'inhibition de la corrosion aqueuse au moyen de ZnPO3F en fonction du pH.II - 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 I'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 the aqueous corrosion of steel test pieces was studied by means of ZnPO 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 imgb0019
In these tests ZnPO 3 F was used at a dose of 25 ppm. The results are reported in Table VI.
Figure imgb0019

III - Inhibition de la corrosion d'un puits de forage pétrolierIII - Inhibition of corrosion of an oil wellbore

On injecte dans l'espace annulaire d'un puits pétrolier en acier fonctionnant 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 µ/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 a steel oil well operating by 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 μ / year is considerably reduced with the products of Examples 1, 3 and 6 compared with the control (injection of aqueous mud only).

Claims (10)

1. Nouveau moyen inhibiteur de corrosion aqueuse appartenant à la famille des fluorophosphates pour protéger les surfaces métalliques, notamment celles des installations utilisant de l'eau comme fluide énergétique ou thermique, ledit moyen inhibiteur étant caractérisé en ce qu'il est choisi parmi l'ensemble constitué par (i) les composés de formule MI 2 PO3F, xH20 (ii) les composés de formule LiMIPO3F, xH20 (iii)les composés de formule NaMIPO3F, xH20 (iv) les composés de formule MIIPO3F, xH2O (v) les composés de formule MI 2MII(PO3F)2, xH20 (vi) les composés de formule MIPO2F2, xH20 . (vii)les composés de formule MII(PO2F2)2, xH2O
(dans lesquelles M est Na, K, Rb, Cs ou NH4 ; MII 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, (viii) leurs mélanges. 1. New means for inhibiting aqueous corrosion belonging to the family of fluorophosphates for protecting metal surfaces, in particular those of installations using water as energy or thermal fluid, said means of inhibitor being characterized in that it is chosen from set constituted by (i) the compounds of formula M I 2 PO 3 F, xH 2 0 (ii) the compounds of formula LiM I PO 3 F, xH 2 0 (iii) the compounds of formula NaM I PO 3 F, xH 2 0 (iv) the compounds of formula M II PO 3 F, xH 2 O (v) the compounds of formula M I 2 M II (PO 3 F) 2 , xH 2 0 (vi) the compounds of formula M I PO 2 F 2 , xH 2 0. (vii) the compounds of formula M II (PO 2 F 2 ) 2 , xH 2 O
(in which M is Na, K, Rb, Cs or NH 4 ; M II 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) their mixtures. 2. Nouveau moyen inhibiteur de corrosion aqueuse selon la revendication 1, caractérisé en ce qu'il s'agit du fluorophosphate de zinc ZnP03F.2. New aqueous corrosion inhibitor means according to claim 1, characterized in that it is zinc fluorophosphate ZnP0 3 F. 3. Nouveau moyen inhibiteur de corrosion aqueuse selon la revendication 1, caractérisé en ce qu'il s'agit du fluorophosphate de potassium K2 P0 3 F. 3. New aqueous corrosion inhibitor means according to claim 1, characterized in that it is potassium fluorophosphate K 2 P0 3 F. 4. Composition inhibitrice de corrosion aqueuse, caractérisée en ce qu'elle renferme en solution ou suspension aqueuse un moyen inhibiteur appartenant à la famille des fluorophosphates selon la . revendication 1.4. Composition inhibiting aqueous corrosion, characterized in that it contains in aqueous solution or suspension an inhibiting means belonging to the family of fluorophosphates according to the. claim 1. 5. Composition inhibitrice de corrosion aqueuse selon la revendication 4, caractérisé en ce qu'elle renferme en association dans de l'eau A) un moyen inhibiteur de corrosion appartenant à la famille des fluorophosphates et tel que défini à la revendication 1, et B) une substance choisie notamment 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 amino-alkylènephosphonique et leurs mélanges. 5. Composition inhibiting aqueous corrosion according to claim 4, characterized in that it contains in association in water A) a corrosion inhibitor means belonging to the family of fluorophosphates and as defined in claim 1, and B) a substance chosen in particular from the group consisting of polyamines, organic polyelectrolytes resulting from the polymerization or copolymerization of a monomer having a C = C unit, derivatives of alkylene polyphosphonic acid, derivatives of amino-alkylene phosphonic acid and their mixtures. 6. Composition inhibitrice de corrosion aqueuse selon la revendication 5, caractérisée en ce qu'elle renferme : - 1 à 15 parties en poids sec de moyen A, et - 1 à 100 parties en poids sec de substance B 6. Composition for inhibiting aqueous corrosion according to claim 5, characterized in that it contains: - 1 to 15 parts by dry weight of medium A, and - 1 to 100 parts by dry weight of substance B 7. Composition inhibitrice de corrosion aqueuse selon l'une quelconque des revendications 4, 5 et 6, caractérisée en ce que, après introduction dans le fluide aqueux corrosif, la teneur en fluorophosphate inhibiteur est comprise entre 3 et 500 ppm.7. A composition for inhibiting aqueous corrosion according to any one of claims 4, 5 and 6, characterized in that, after introduction into the corrosive aqueous fluid, the content of inhibiting fluorophosphate is between 3 and 500 ppm. 8. Composition inhibitrice de corrosion aqueuse selon l'une quelconque des revendications 4, 5 et 6, caractérisée en ce que, après introduction dans le fluide aqueux corrosif, la teneur en fluorophosphate inhibiteur est comprise entre 5 et 200 ppm, le fluorophosphate inhibiteur étant ZnP03F.8. A composition for inhibiting aqueous corrosion according to any one of claims 4, 5 and 6, characterized in that, after introduction into the corrosive aqueous fluid, the content of inhibiting fluorophosphate is between 5 and 200 ppm, the inhibiting fluorophosphate being ZnP0 3 F. 9. Procédé 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 énergétique ou thermique, ledit procédé étant caractérisé en ce que l'on introduit dans un fluide aqueux corrosif une quantité de fluorophosphate selon la revendication 1 telle que, après ladite introduction, la teneur en poids dudit fluorophosphate soit comprise entre 3 et . 500 ppm par rapport au poids dudit fluide aqueux.9. Method for the protection of metallic surfaces against aqueous corrosion, in particular the metallic surfaces of installations using water as energy or thermal fluid, said method being characterized in that one introduces into a fluid corrosive aqueous an amount of fluorophosphate according to claim 1 such that, after said introduction, the content by weight of said fluorophosphate is between 3 and. 500 ppm relative to the weight of said aqueous fluid. 10. Procédé selon la revendication 9, caractérisé en ce que le fluorophosphate inhibiteur est ZnPO3F et en ce que, après introduction dans le fluide aqueux corrosif, la teneur dudit fluorophosphate est comprise entre 5 et 200 ppm en poids par rapport au poids dudit fluide aqueux.10. Method according to claim 9, characterized in that the inhibiting fluorophosphate is ZnPO 3 F and in that, after introduction into the corrosive aqueous fluid, the content of said fluorophosphate is between 5 and 200 ppm by weight relative to the weight of said aqueous fluid.
EP83401050A 1982-05-28 1983-05-26 Corrosion-inhibiting means and compositions containing them Expired EP0096619B1 (en)

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EP0176197A2 (en) * 1984-08-17 1986-04-02 The Dow Chemical Company Improved corrosion inhibition of metals in water systems
EP0288812A1 (en) * 1987-04-30 1988-11-02 Hoechst Aktiengesellschaft Use of an inhibitor of corrosion on ceramic surfaces
EP0322183A2 (en) * 1987-12-17 1989-06-28 Domtar Inc. Method of inhibiting corrosion
US5071579A (en) * 1988-08-29 1991-12-10 Domtar Inc. Corrosion inhibiting systems, products containing residual amounts of such systems, and methods therefor
EP0481669A2 (en) * 1990-10-15 1992-04-22 Calgon Corporation Monofluorophosphate solubility inhibitor for lead in potable water sources
WO1992014796A1 (en) * 1991-02-14 1992-09-03 Domtar Inc. Method to reduce scaling due to freezing and thawing in concrete
EP0506339A1 (en) * 1991-03-28 1992-09-30 Calgon Corporation Monofluorophosphate for calcium carbonate scale control and iron and manganese stabilization

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DE3680112D1 (en) * 1986-09-15 1991-08-08 Desowag Materialschutz Gmbh WOOD PRESERVATIVES.
DE3714051A1 (en) * 1987-04-28 1988-11-17 Desowag Materialschutz Gmbh AGENTS FOR THE PRESERVATION OF WOOD AND WOOD MATERIAL
US5127954A (en) * 1987-12-17 1992-07-07 Domtar Inc. Corrosion inhibiting systems, products containing residual amounts of such systems, and methods therefor
EP0524546A3 (en) * 1991-07-23 1993-03-31 Basf Corporation Antifreeze/coolant additive
US5230819A (en) * 1991-10-30 1993-07-27 Basf Corp. Diphosphonates as corrosion inhibitors for antifreeze coolants and other functional fluids
US5352408A (en) * 1991-10-30 1994-10-04 Basf Corp. Diphosphonates as corrosion inhibitors for antifreeze coolants and other functional fluids
US5419845A (en) * 1994-03-15 1995-05-30 Basf Corporation Perfluorinated gemdiphosphonates as corrosion inhibitors for antifreeze coolants and other functional fluids
US6585933B1 (en) 1999-05-03 2003-07-01 Betzdearborn, Inc. Method and composition for inhibiting corrosion in aqueous systems
CA2390118A1 (en) 2000-01-26 2001-08-02 Domtar Inc. Potassium monofluorophosphate as a common inhibitor
WO2007021961A1 (en) * 2005-08-12 2007-02-22 Honeywell International Inc. Method for stabilizing an engine coolant concentrate and preventing hard water salt formation upon dilution
DE102005052791B4 (en) 2005-11-05 2014-03-06 Bk Giulini Gmbh Use of monofluorophosphate in aqueous solution as a primer, process for the preparation of plastered walls or ceilings made of concrete with improved adhesion between plaster and concrete surface and the use of plaster of mortar containing monofluorophosphate to improve the adhesion of plaster on concrete surfaces
US8613847B2 (en) * 2008-11-19 2013-12-24 King Fahd University Of Petroleum And Minerals Method of applying polyelectrolyte multilayer film for corrosion control
JP6134921B1 (en) * 2015-09-17 2017-05-31 株式会社片山化学工業研究所 Anticorrosion method and anticorrosive for seawater copper alloy piping

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FR2192192A1 (en) * 1972-07-11 1974-02-08 Betz Laboratories
FR2231777A1 (en) * 1973-06-04 1974-12-27 Calgon Corp
FR2352895A1 (en) * 1976-04-21 1977-12-23 Diversey France NEW PROCESS FOR TREATMENT OF METAL SURFACES BY MEANS OF OXYFLUORINE COMPOUNDS OF PHOSPHORUS 5

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0176197A2 (en) * 1984-08-17 1986-04-02 The Dow Chemical Company Improved corrosion inhibition of metals in water systems
EP0176197A3 (en) * 1984-08-17 1987-10-28 The Dow Chemical Company Improved corrosion inhibition of metals in water systems
EP0288812A1 (en) * 1987-04-30 1988-11-02 Hoechst Aktiengesellschaft Use of an inhibitor of corrosion on ceramic surfaces
EP0322183A2 (en) * 1987-12-17 1989-06-28 Domtar Inc. Method of inhibiting corrosion
EP0322183A3 (en) * 1987-12-17 1990-05-09 Domtar Inc. Products and methods of inhibiting corrosion
US5071579A (en) * 1988-08-29 1991-12-10 Domtar Inc. Corrosion inhibiting systems, products containing residual amounts of such systems, and methods therefor
EP0481669A2 (en) * 1990-10-15 1992-04-22 Calgon Corporation Monofluorophosphate solubility inhibitor for lead in potable water sources
EP0481669A3 (en) * 1990-10-15 1993-02-24 Calgon Corporation Monofluorophosphate solubility inhibitor for lead in potable water sources
WO1992014796A1 (en) * 1991-02-14 1992-09-03 Domtar Inc. Method to reduce scaling due to freezing and thawing in concrete
US5314755A (en) * 1991-02-14 1994-05-24 Domtar, Inc. Method to reduce scaling due to freezing and thawing in concrete
EP0506339A1 (en) * 1991-03-28 1992-09-30 Calgon Corporation Monofluorophosphate for calcium carbonate scale control and iron and manganese stabilization

Also Published As

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JPS58213884A (en) 1983-12-12
JPH032234B2 (en) 1991-01-14
ATE25113T1 (en) 1987-02-15
AU1485683A (en) 1983-12-01
EP0096619B1 (en) 1987-01-21
US4613450A (en) 1986-09-23
AU7454687A (en) 1987-10-08
CA1202169A (en) 1986-03-25
FR2527643B1 (en) 1985-09-27
DE3369349D1 (en) 1987-02-26
AU559671B2 (en) 1987-03-19
FR2527643A1 (en) 1983-12-02
ZA833824B (en) 1984-02-29

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