EP0786018B1 - Compositions inhibant la corrosion - Google Patents

Compositions inhibant la corrosion Download PDF

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EP0786018B1
EP0786018B1 EP95933529A EP95933529A EP0786018B1 EP 0786018 B1 EP0786018 B1 EP 0786018B1 EP 95933529 A EP95933529 A EP 95933529A EP 95933529 A EP95933529 A EP 95933529A EP 0786018 B1 EP0786018 B1 EP 0786018B1
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group
formula
acid
composition according
phosphono
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EP0786018A1 (fr
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Suresh Patel
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Lanxess Switzerland GmbH
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Great Lakes Chemical Europe GmbH
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Priority claimed from GB9420478A external-priority patent/GB9420478D0/en
Priority claimed from GBGB9512032.5A external-priority patent/GB9512032D0/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors

Definitions

  • This invention relates to compositions useful as additives for aqueous systems in order to inhibit the corrosion of metal surfaces which are in contact with these systems, to methods of inhibiting corrosion which comprise adding these novel compositions to aqueous systems and to aqueous systems which contain certain novel combinations of known corrosion inhibitors.
  • USP 4689200 discloses the use of 2-hydroxy phosphono acetic acid or a water soluble salt thereof as an additive for aqueous systems in order to inhibit the corrosion of metal in contact with that aqueous system.
  • This disclosure also suggests that the 2-hydroxy phosphono acetic acid may be used in conjunction with other known corrosion inhibitors.
  • the many known corrosion inhibitors which are mentioned in this disclosure are phosphonic acids and their salts.
  • USP 4689200 also proposes that the 2-hydroxy phosphono acetic acid may be used in conjunction with other additives and in particular scale inhibiting additives.
  • scale inhibitors which are mentioned are the phosphino polycarboxylic acids which are described in British Patent 1458235.
  • EPA 277412 describe a process for the reduction of corrosion of iron based metals in contact with aqueous systems which comprises adding combination of hydroxy phosphono acetic acid and water soluble 1-acrylamido-2-methyl propane sulphonic acid copolymer with acrylic or methacrylic acid to that aqueous system.
  • EPA 516346 discloses a process for the production of phosphono (co)telomers which are useful as scale inhibitors and corrosion inhibitors in aqueous systems.
  • the telomeric portion of these compounds may be derived from a wide variety of olefinic compounds including 2-acrylamido-2-methyl propane sulphonic acid (AMPS) or from mixtures of such olefins including in particular mixtures of AMPS and acrylic acid.
  • AMPS 2-acrylamido-2-methyl propane sulphonic acid
  • AMPS 2-acrylamido-2-methyl propane sulphonic acid
  • acrylic acid acrylic acid
  • the use of these phosphonic (co)telomers in conjunction with other compounds known to be useful in the treatment of aqueous systems is also proposed.
  • 2-hydroxy phosphono acetic acid is 2-hydroxy phosphono acetic acid.
  • EPA360746 discloses novel phosphono cotelomers which are useful inter alia as corrosion inhibitors. The use of these cotelo
  • the phosphono cotelomer which has been discovered to be useful in the compositions of this invention is that derived from a combination of acrylic acid and 2-acrylamido 2-methyl propane sulphonic acid (AMPS).
  • AMPS 2-acrylamido 2-methyl propane sulphonic acid
  • EPA 516346 The production of such a cotelomer is described in EPA 516346.
  • this invention provides a composition useful as an additive to aqueous systems in order to inhibit the corrosion of metal surfaces in contact with that aqueous system which comprises:
  • R 2 represents a hydrogen atom or a methyl group; and
  • R 4 represents a hydroxyl group.
  • the phosphono telomer may be any compound of Formula II which is sufficiently water soluble to be effective. It may comprise repeat units of Formula III and repeat units of Formula IV in a wide range of proportions.
  • the ratio of the number of units of formula III to the number of units of formula IV may vary from 99:1 to 1:99 but is more usually in the range 25:1 to 1:25.
  • the most preferred polymers useful according to this invention are those wherein this ratio is in the range 20:1 to 2:1 ie, those which contain a greater proportion of the repeat unit having the formula III.
  • the cotelomers of formula II will typically have a molecular weight Mw of from 500 to 10,000 and more preferably of from 2,000 to 4,000.
  • These cotelomers may be produced by a variety of processes which are known to the art. Generally these processes comprise the reaction of a monomer of formula III typically acrylic acid or methacrylic acid with the monomer of formula IV which is 2-acrylamido-2-methyl propane sulphonic acid (hereinafter for convenience AMPS) in the presence of a hypophosphite telogen.
  • AMPS 2-acrylamido-2-methyl propane sulphonic acid
  • Such processes have been described in USP 4046707, EPA 150706, EPA 360746 and EPA 516346.
  • the phosphonate telomers are preferably produced by the aqueous process which is described in EPA 516346.
  • Such process typically comprise (a) the reaction of hypophosphorous acid or a hypophosphite with a carbonyl compound which is typically acetone, (b) reacting the product from (a) with the (meth)acrylic acid and the AMPS in the presence of a free radical initiator and converting the product of step (b) to the desired phosphonate (co)telomer by reaction eg, with hypochlorite.
  • the process may vary according to the teachings of EPA 516346.
  • step (a) a variety of carbonyl compounds may be employed in step (a) representative examples being formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, methylethyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, cyclopentanone and cyclohexanone.
  • the products obtained from these processes are aqueous solutions which may be used as such in the compositions or they may be purified prior to use.
  • the phosphonate cotelomers are produced in their acid form and they may be wholly or partially neutralised prior to use. Where the compositions of this inventions are added to alkaline media neutralisation may take place in situ and neutralisation at this production stage may thereby be irrelevant.
  • the second component of the compositions useful in this invention is an organophosphonate corrosion inhibitor having the general formula I.
  • a number of such compounds are known and used in the art.
  • a preferred group of phosphonates of formula I, which are useful according to this invention are those wherein at least one of the groups R 2 and R 4 represents a hydrogen atom.
  • Particularly preferred phosphonates within this group include those wherein the other of the groups R 2 and R 4 also represents a hydrogen atom or a hydroxyl group -OH an amine group - NH 2 or a carboxylic acid group - CO 2 H.
  • a second preferred group of compounds are those of the formula I wherein R 3 represents -CO 2 H or PO(OH 2 ).
  • the most preferred phosphonates for use in the present invention are generally those which are in use or have been proposed to be useful as corrosion inhibitors in aqueous media.
  • these phosphonates include 2-hydroxyphosphono acetic acid, hydroxyethylidene diphosphonic acid (HEDP), hydroxy propylidene diphosphonic acid, hydroxy isobutylidene diphosphonic acid, 2-phosphono butane-1,2,4 tricarboxylic acid, amino tris(methylene phosphonic acid), diethylene triamino penta (methylene phosphonic acid), phosphonoacetic acid, 2-phosphonopropionic acid, 2-phosphonoheptanoic acid, 2-hydroxy-2-methyl phosphonoacetic acid, 2-hydroxy-2-butyl phosphonoacetic acid, 3-phosphono-3-hydroxy butyric acid, 2-phosphonoethane-1,2-dicarboxylic acid, methane diphosphonic acid, 1,2-ethanediphosphonic acid, 1,3-propane- diphosphonic acid, hydroxymethyl diphosphonic acid, 2-amino-phosphonoacetic acid, 2-amino-2-methyl phosphonoacetic
  • Preferred phosphonates are 2-hydroxyphosphono acetic acid, hydroxyethylidene diphosphonic acid and 2-phosphonobutane 1,2,4 tricarboxylic acid.
  • 2-hydroxyphosphono acetic acid has been described in USP 3032500 and EPA 0050792. It can be prepared by known methods eg, by reacting orthophosphorous acid, a salt or a solution thereof, or phosphorus trichloride with glyoxylic acid or a salt or a solution thereof.
  • Hydroxyethylidene disphosphonic acid and 2- phophono butane, 1, 2,4 tricarboxylic acid are also articles of commerce which are widely used as corrosion inhibitors in aqueous media.
  • the phosphonate corrosion inhibitors may be used as the free acid or as a wholly or partially neutralised salt thereof.
  • suitable salts include the lithium, sodium, potassium, calcium, strontium, magnesium, ammonium, methylamine, ethylamine, n-propylamine, triethylamine, n-butylamine, n-hexylamine, octylamine, ethanolamine, diethanolamine, triethanolamine and morpholine salts.
  • the mixtures of phosphonate corrosion inhibitors and the phosphono cotelomers exhibit synergy over the entire range of proportions.
  • the ratio of the weight of one to the weight of the other may vary from 99:1 to 1:99.
  • they are employed in proportions in which the weight ratio of phosphonate to phosphono cotelomer lies in the range 4:1 to 1:4.
  • the proportions used in a particular application will be chosen so as to balance the benefits of performance against cost.
  • the proportion of 2-hydroxyphosphonoacetic acid will generally be increased to provide a greater degree of corrosion inhibition.
  • a cost effective corrosion inhibitor it may be preferred to utilise a higher proportion of the phosphono cotelomer as this is the less costly component of the mixture.
  • the amount of the mixture which is added to an aqueous medium will generally be the same as is currently known in the art. Typically the mixture will be added so as to result in a concentration of from 0.1 to 50,000 ppm of the mixture of additives in the aqueous system. More usually this concentration will be in the range 0.5 to 100 ppm and most preferably will be in the range 1.0 to 50 ppm.
  • the phosphonate and the phosphono cotelomers are generally compatible and may be mixed together prior to their addition to an aqueous system.
  • the addition of such mixtures to aqueous systems which are in contact with a metal surface in order to inhibit the corrosion of that surface constitutes a further aspect of the invention.
  • the phosphonate and the phosphono cotelomer may be added separately to aqueous systems and processes involving this separate addition constitute a further aspect of the invention.
  • the phosphonate and phosphonate cotelomers may be used in combination to inhibit corrosion in soft waters (typically containing less than 30ppm calcium ions) and hard waters (typically containing say 100ppm, or more) of calcium ions.
  • the mixture of compounds of this invention may be used alone, or in conjunction with other compounds known to be useful in the treatment of aqueous systems.
  • further corrosion inhibitors may be used such as, for example, water soluble zinc salts; phosphates; polyphosphates; nitrates, for example, sodium nitrate; nitrites, eg, sodium nitrite; molybdates, eg, sodium molybdate, tungstates eg, sodium tungstate; silicates, eg, sodium silicate; benzotriazole, bis-benzotriazole or copper deactivating benzotriazole or tolutriazole derivatives eg, their Mannich base derivatives; mercaptobenzotriazole; N-acyl sarcosines especially sodium N-lauryl sarcosinate; N-acylimino diacetic acids; alkanolamines especially the ethanol
  • the inhibitor used according to the invention may be used in conjunction with further dispersing and/or threshold agents, eg,polymaleic acid polymerised acrylic acid (or its salts), eg, copolymers of acrylic acid and hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers, phosphino- polycarboxylic acids (as described in British Patent 1458235), the cotelomeric compounds described in European Patent Application 150706, hydrolysed polyacrylonitrile, polymerised methacrylic acid and its salts, polyacrylamide and copolymers thereof with acrylic and methacrylic acids, lignin sulphonic acid and its salts, tannin, napthalene sulphonic acid/formaldehyde condensation products, starch and its derivatives, cellulose, acrylic acid/lower alkyl hydroxyacrylate copolymers, eg, those described in US Patent Specification No: 4029577,
  • agents which may be incorporated into water treatment compositions or this convention include precipitating agents such as alkali metal orthophosphates, carbonates: oxygen scavengers such as alkali metal sulphites and hydrazines; sequestering agents such as nitrilotriacetic acid and its salts; antifoaming agents such as silicones, eg, polydimethylsiloxanes, distearylsebacamide, distearyl adipamide and related products derived from ethylene oxide and/or propylene oxide condensations, fatty alcohols such as capryl alcohols and their ethylene oxide condensates and biocides, eg, amines, quaternary ammonium compounds, chloro-phenols, sulphur-containing compounds such as sulphones, methylene bis thiocyanates and carbamates, isothiazolones, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine-releasing agents, bromine and bromine
  • the system to be treated by the method of the invention is not completely aqueous, eg, an aqueous machining fluid formulation, it may be eg, a water dilutable cutting or grinding fluid.
  • aqueous machining fluid formulations of the invention may be eg, metal working formulations.
  • metal working we mean reaming, broaching, drawing, spinning, cutting, grinding, boring, milling, turning, sawing, non-cutting shaping or rolling.
  • water-dilutable cutting or grinding fluids into which the corrosion inhibiting combinations of this invention may be incorporated include
  • the synergistic mixtures according to the invention may be used as such, or in admixture with other additives, eg, known further corrosion inhibitors and/or extreme-pressure additives.
  • Examples of other corrosion inhibitors which may be used in these aqueous systems, in addition to the inhibitor composition used according to the invention, include the following groups:
  • extreme pressure additives which may be present in the systems treated according to the present invention include sulphur and/or phosphorus and/or halogen containing materials, for instance, sulphurised sperm oil, sulphurised fats, tritolyl phosphate, chlorinated paraffins or ethoxylated phosphate esters.
  • the partly-aqueous system treated by the method of the present invention may also be aqueous surface-coating compositions, eg emulsion paints and aqueous coatings for metallic substrates.
  • aqueous surface-coating compositions eg emulsion paints and aqueous coatings for metallic substrates.
  • the aqueous surface-coating composition may be, eg, a paint such as styrene-acrylic copolymer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems, to coat a metal substrate.
  • the inhibitor composition used according to the invention may be employed to prevent flash rusting of the metal substrate during application of the surface coating and to prevent subsequent corrosion during use of the coated metal.
  • the inhibitor composition may be used singly, or in admixture with other additives, eg, known corrosion inhibitors, biocides, emulsifiers and/or pigments.
  • biocides which may be used in these aqueous systems include the following:
  • Phenols, and alkyl and halogenated phenols for example, pentachlorophenol, o-phenylphenol, o-phenyoxyphenol and chlorinated o-phenoxyphenol, and salicylanilides, diamines, triazines and organometallic compounds such as organomercury compounds and organotin compounds.
  • pigments which may be used in these aqueous systems include titanium dioxide, zinc chromate, iron oxide and organic pigments such as the phthalocyanines.
  • a corrosion test was carried out assessing the ability of various blends of 2-hydroxyphosphonoacetic acid, hydroxyethylidene diphosphonic acid and 2-phosphonobutane 1,2,4-tricarboxylic acid (A) with a phosphonated (co)telomer having a molecular weight of 2000 to 3000 derived from acrylic acid and AMPS (B) in the following water: Calcium ions 150 ppm as CaCO 3 Magnesium ions 75 ppm as CaCO 3 Total Alkalinity 350 ppm as CaCO 3 Chloride ions 200 ppm as Cl - ion Sulphate ions 200 ppm as SO 4 ion pH 8
  • the test is carried out by using two cleaned and pre-weighed mild steel coupons which are secured to a stainless steel shaft by means of a threaded PTFE holder. The coupons are then rotated at 150 rpm for 42 hours at 40°C in the above aerated water with the additive present at a total concentration of 20 ppm (actives). The aeration rate used is 1 litre per minute per test.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Claims (22)

  1. Composition utile comme additif à des systèmes aqueux afin d'inhiber la corrosion de surfaces métalliques en contact avec ledit système aqueux qui comprend :
    (i) un inhibiteur de corrosion organophosphoré de formule I
    Figure 00300001
       ou un sel soluble dans l'eau de celui-ci, dans laquelle R3 peut représenter un groupe de formule CO2H, un groupe de formule P(=O)(OH)2, un groupe de formule CH2P(=0) (OH)2, un groupe de formule CH2CH2P(=0) (OH)2 ou un groupe de formule NR5R6 dans lequel R5 et R6 peuvent être identiques ou différents et représentent un atome d'hydrogène, un groupe méthyle, un groupe de formule C[(R7)2]xP(=O)(OH)2 ou un groupe de formule C[(R7)2]xCO2H dans lequel R7 représente un atome d'hydrogène ou un groupe méthyle, et x est un entier ayant une valeur de 1 ou 2 ;
       R2 et R4 qui peuvent être identiques ou différents peuvent représenter un atome d'hydrogène, un groupe hydroxyle, un groupe alkyle comprenant de 1 à 8 atomes de carbone, un groupe de formule -(CH2)nCO2H, où n est égal à zéro ou est un entier ayant une valeur de 1 à 4, ou un groupe amine de formule NH2
    (ii) un cotélomère phosphonique de formule :
    Figure 00310001
       et A représente un résidu copolymérique contenant au moins une unité répétée de formule III
    Figure 00310002
       dans laquelle R1 représente un atome d'hydrogène ou un groupe méthyle
       et au moins une unité répétée de formule IV
    Figure 00310003
       ou un sel soluble dans l'eau de celle-ci.
  2. Composition selon la revendication 1 caractérisée en ce que R3 représente un groupe -CO2H.
  3. Composition selon la revendication 1 ou 2 caractérisée en ce que R3 représente un groupe P(=O)(OH)2.
  4. Composition selon l'une quelconque des revendications précédentes caractérisée en ce que R2 représente un atome d'hydrogène.
  5. Composition selon l'une quelconque des revendications précédentes caractérisée en ce que R4 représente un groupe hydroxyle.
  6. Composition selon la revendication 1 caractérisée en ce que le cotélomère phosphonique a une masse moléculaire Mw située entre 500 et 10.000.
  7. Composition selon la revendication 6 caractérisée en ce que le cotélomère phosphonique a une masse moléculaire située entre 2.000 et 4.000.
  8. Composition selon l'une quelconque des revendications précédentes caractérisée en ce que R1 représente un atome d'hydrogène.
  9. Composition selon l'une quelconque des revendications précédentes caractérisée en ce que le ratio du nombre d'unités répétées de formule III par rapport au nombre d'unités répétées de formule IV est de 25 : 1 à 1 : 25.
  10. Composition selon la revendication 9 caractérisée en ce que le ratio du nombre d'unités répétées de formule III par rapport au nombre d'unités répétées de formule IV est situé dans une fourchette de 20 :1 à 2 :1.
  11. Composition selon l'une quelconque des revendications précédentes caractérisée en ce que l'inhibiteur de corrosion organophosphoré est choisi parmi le groupe constitué de l'acide 2-hydroxyphosphonoacétique, de l'acide hydroxyéthylidène diphosphonique, de l'acide hydroxypropylidène diphosphonique, de l'acide hydroxybutylidène diphosphonique, de l'acide hydroxyisobutylidène diphosphonique, de l'acide 2-phosphonobutane 1,2,4-tricarboxylique, de l'acide amino tris (méthylène phosphonique) et de l'acide diéthylène triamino penta (méthylène phosphonique).
  12. Composition selon la revendication 11 caractérisée en ce que l'inhibiteur de corrosion organophosphoré est choisi parmi le groupe constitué de l'acide 2-hydroxyphosphonoacétique, de l'acide hydroxyéthylidène diphosphonique et de l'acide 2-phosphonobutane 1,2,4-tricarboxylique.
  13. Composition selon l'une quelconque des revendications 11 ou 12 caractérisée en ce que l'inhibiteur de corrosion organophosphoré est l'acide 2-hydroxyphosphonoacétique.
  14. Composition selon l'une quelconque des revendications précédentes caractérisée en ce que le rapport de la masse de l'inhibiteur de corrosion organophosphoré par rapport à la masse du cotélomère phosphonique se situe entre 99:1 et 1:99.
  15. Composition selon la revendication 14 caractérisée en ce que le rapport de la masse de l'inhibiteur de corrosion organophosphoré par rapport à la masse du cotélomère phosphonique se situe entre 4:1 et 1:4.
  16. Procédé pour inhiber la corrosion d'une surface métallique qui est en contact avec un système aqueux caractérisé en ce que une quantité efficace d'un mélange selon l'une quelconque des revendications 1 à 15 est ajoutée au système aqueux.
  17. Procédé selon la revendication 16 caractérisé en ce que le mélange de l'inhibiteur de corrosion organophosphoré et du cotélomère phosphonique est produit par leur addition séparée au système aqueux.
  18. Procédé selon la revendication 16 caractérisé en ce que le système aqueux contient de 0,1 à 50.000 ppm d'un mélange selon l'une quelconque des revendications 1 à 15.
  19. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le système aqueux comprend au moins 100 ppm d'ions calcium.
  20. Procédé selon l'une quelconque des revendications 16 à 19 caractérisé en ce que le système aqueux comprend moins de 300 ppm d'ions calcium.
  21. Système aqueux qui comprend un mélange selon l'une quelconque des revendications 1 à 15.
  22. Système selon la revendication 21 qui comprend entre 0,1 et 50.000 ppm du mélange.
EP95933529A 1994-10-11 1995-10-11 Compositions inhibant la corrosion Expired - Lifetime EP0786018B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9420478 1994-10-11
GB9420478A GB9420478D0 (en) 1994-10-11 1994-10-11 Corrosion inhibiting compositions
GB9512032 1995-06-14
GBGB9512032.5A GB9512032D0 (en) 1995-06-14 1995-06-14 Corrosion inhibiting compositions
PCT/GB1995/002404 WO1996011291A1 (fr) 1994-10-11 1995-10-11 Compositions inhibant la corrosion

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EP0786018A1 EP0786018A1 (fr) 1997-07-30
EP0786018B1 true EP0786018B1 (fr) 2002-01-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11149202B1 (en) 2016-12-13 2021-10-19 Ecolab Usa Inc. Tetracarboxylic acid combinations for corrosion inhibition

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GB9703951D0 (en) * 1997-02-26 1997-04-16 Albright & Wilson Uk Ltd Novel phosphino derivatives
AU2205900A (en) * 1998-12-29 2000-07-31 Calgon Corporation Corrosion inhibitor compositions and methods to control metal corrosion in brinesystems

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DE2963154D1 (en) * 1978-07-19 1982-08-12 Ciba Geigy Ag Corrosion inhibitors; compositions for protecting ferrous metals and the protected metals
EP0122013B1 (fr) * 1983-03-07 1988-12-21 Calgon Corporation Additifs polymères pour l'eau
US4717542A (en) * 1987-01-23 1988-01-05 W. R. Grace & Co. Inhibiting corrosion of iron base metals
GB8822150D0 (en) * 1988-09-21 1988-10-26 Ciba Geigy Ag Compounds
GB9024470D0 (en) * 1990-11-10 1991-01-02 Ciba Geigy Ag Corrision inhibition
GB9111704D0 (en) * 1991-05-31 1991-07-24 Ciba Geigy Telomers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11149202B1 (en) 2016-12-13 2021-10-19 Ecolab Usa Inc. Tetracarboxylic acid combinations for corrosion inhibition

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DE69524967D1 (de) 2002-02-14
WO1996011291A1 (fr) 1996-04-18
CA2202370A1 (fr) 1996-04-18
EP0786018A1 (fr) 1997-07-30
DE69524967T2 (de) 2002-08-29

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