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(11) | EP 0 037 221 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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Method and composition for inhibiting corrosion of metal surfaces in aqueous solutions Verfahren und Zusammensetzung zur Verhinderung der Korrosion von Metalloberflächen in wässrigen Lösungen Procédé et composition pour l'inhibition de la corrosion de surfaces métalliques en contact avec un milieu aqueux |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
[0001] The present invention relates to a method and a composition for reducing corrosion of metal surfaces in contact with aqueous systems.
[0002] Chromates are widely referred to in the literature, and their effectiveness in reducing the rate of corrosion of metallic surfaces exposed to corroding aqueous mediums is well known. However, if used in low concentrations these inhibitors can cause considerable pitting and tuberculation. Indeed, if added in insufficient quantities to stop metal surface attach altogether, corrosion can become so severely localized and the intensity of attack so intense that perforations may occur more extensively than if no inhibitor treatment had been added.
[0003] In Corrosion Inhibitors, 3rd edition; National Association of Corrosion Engineers; Houston, Texas (1977); p. 134, it is stated that the critical concentration for passivation by chromate in distilled water is 81 to 162 ppm and that the critical level for chromate increases as chloride and sulfate levels increase. Present practice in industrial water systems is to employ chromates alone in concentrations no lower than 200 ppm.
[0004] Economic and environmental considerations make it desirable to minimize chromate levels in water. This goal has been attained by combining the chromate with other compounds such as phosphate and zinc. For example, U.S. 2,711,391 to Kahler discloses the use of water-soluble chromate in combination with water-soluble phosphate. According to this reference, the combined treatment permits the use of lower levels of chromate than had theretofore been used. However, the lowest dosage rate for chromate achievable, according to Kahler, is 5 ppm. In fact, the reference specifically sets the preferred lower limit for chromate at 11 ppm. U.S. 2,900,222 to Kahler et al teaches the use of chromate compound at levels as low as 1 ppm, but only in combination with both water-soluble orthophosphate and water-soluble zinc compound. A problem related to supplemented chromate treatments such as those disclosed in the Kahler references is that the discharge of industrial waters containing heavy metals and/or phosphorous compounds is under strict environmental control. The quality of water discharged to natural waters is presently being regulated and is expected to be under greater scrutiny in the future.
[0005] U.S. Patent 4, 209, 398 (corresponding to DE-A-2 643 422) discloses a water treatment composition comprising a polymer containing a structural unit that is derived from a monomer having an ethylenically unsaturated bond and one or more carboxyl radicals, at least a portion of which radicals have been modified. Compounds such as inorganic phosphates, phosphonic acids, organic phosphoric acid esters and polyvalent metal salts are combined with the polymer for treating the particular system. The polymer may be used in combination with conventional corrosion inhibitors for iron, steel, copper, copper alloys or other metals, conventional scale and contamination inhibitors, metal ion sequestering agents and other conventional water treating agents. As such corrosion inhibitors there are can be enumerated chromates, bichromates, tungstate, molybdates, nitrites, borates, silicates, oxycarboxylic acids, amino acids, catechols, aliphatic amino surface active agents, benzotriazole, and mercaptobenzotriazole.
[0006] U.S. Patent 3,658,710 discloses a method of removing tubercles of corrosion from a substrate and inhibiting scale formation using organic polymers and silica and/or chromium compounds. A second polymer, such as an organic phosphonate may also be used.
[0007] According to the present invention, a chromate-based corrosion inhibitor for metal surfaces exposed to a corroding aqueous medium consists essentially of (i) water-soluble chromate and (ii) a particular type of water-soluble polymer comprised of units derived from acrylic acid or derivatives thereof (AA) and 2-hydroxy-propyl acrylate units (HPA). It was unexpectedly discovered that when combined with the polymer, very low levels of chromate could successfully be used for corrosion inhibition in aqueous mediums without the use of additional treatment compounds such as zinc and phosphate. In those systems treated with this two-component treatment, zinc, a heavy metal, and phosphate, a compound which causes eutrophication, are eliminated. Accordingly, not only would such a treatment be a less toxic, but it would also be less expensive than, for example, a four-component treatment which also includes zinc and phosphate.
[0008] In the context of permitting the deletion of zinc from a corrosion inhibitor treatment, methods according to the present invention would comprise the use of zinc-free corrosion inhibitor treatments comprising components (i) and (ii) as defined above. In the context of permitting the deletion of both zinc and phosphate, methods according to the present invention would comprise the use of zinc-free and phosphate free corrosion inhibitors comprising the noted components (i) and (ii).
[0009] From an environmental acceptability point of view, chromate levels of less than 5 ppm of active chromate are most desirable. However, at such low levels pitting is extremely severe. It was unexpectedly discovered that a corrosion inhibitor treatment comprising less than 5 ppm water-soluble chromate in combination with AA/HPA significantly reduced such pitting. Accordingly, the present invention relates to a corrosion inhibitor treatment comprising water-soluble chromate AA/HPA wherein the chromate is added in an amount of less than 5 parts of active chromate per million parts of aqueous medium.
[0010] Although the present invention is considered to have applicability to any aqueous system. It is particularly useful in cooling water systems. Accordingly, the present invention will hereinafter be described as it relates to cooling water systems.
[0011] The polymers according to the present invention are those effective for the purpose which contain essentially units derived from an acrylic acid compound (AA), i.e.,
wherein R is a hydrogen or a lower alkyl of from 1 to 3 carbon atoms and R, = OH, NH2 or OM, where M is a water-soluble cation, e.g. NH4, alkali metal (K, Na); and units of 2-hydroxypropyl acrylate (HPA) as represented by the formula:
[0012] In terms of mole ratios, the polymers are considered, more broadly, to have a mole ratio of AA:HPA of from about 1:4 to 36:1. This mole ratio is preferably 1:1 to 11:1, and most preferably 1:1 to 5:1. The only criteria that is considered to be of importance with respect to mole ratios is that the copolymer should be water-soluble. As the proportion of hydroxylated alkyl acrylate moieties increases, the solubility of the copolymer decreases. It is noted that, from an efficacy point of view, the polymers having a mole ratio of AA:HPA of 1:1 to 5:1 are considered the best.
[0013] The polymers preferably have a molecular weight of from 1,000 to 50,000 with from 2,000 to 6,000 being most preferred.
[0014] The polymers utilized in accordance with the invention can be prepared by vinyl addition polymerization or by treatment of an acrylic acid or salt polymer. More specifically, acrylic acid or derivatives thereof or their water soluble salts, e.g., sodium, potassium, ammonium, etc. can be copolymerized with the hydroxy alkyl acrylate under standard copolymerization conditions utilizing free radical initiators such as benzoyl peroxide, azobisisobutyronitrile or redox initiators such as ferrous sulfate and ammonium persulfate. The molecular weight of the resulting copolymer can be controlled utilizing standard chain control agents such as secondary alcohols (isopropanol), mercaptans, halocarbons, etc. Copolymers falling within the scope of the invention are commercially available from, for example, National Starch Company.
[0016] The polymers of the invention may also be prepared by reacting a polyacrylic acid or derivative thereof with an appropriate amount of propylene oxide. The reaction takes place at the COOH or COM group of the units to provide the hydroxylated propyl acrylate unit.
[0017] The polymer prepared either by copolymerization of AA with hydroxypropyl acrylate (HPA) or reaction of AA with propylene oxide would be composed primarily of units having the structural formulas:
wherein M is as earlier defined. It is noted that in aqueous solution with hydroxypropyl acrylate unit is in equilibrium with a minor amount of 1-methyl-2-hydroxyethyl acrylate.
[0018] Illustrative examples of chromate compounds which could be used in practicing methods according to the present invention are described in U.S. 2,900,222 to Kahler et al. These compounds would include alkali metals or any water-soluble compound that contains hexavalent chromate and provides chromate radical in water solutions. Illustrative water-soluble chromate compounds are sodium chromate dihydrate, sodium chromate anhydrous, sodium chromate tetrahydrate, sodium chromate hexahydrate, sodium chromate decahydrate, potassium dichromate, potassium chromate, ammonium dichromate and chromic acid.
[0019] The amount of each constituent added to the cooling water would, of course, be, an effective amount for the purpose and would depend on such factors as the nature and severity of the corrosion problem being treated and the temperature and pH of the cooling water.
[0020] In terms of active polymer, as little as about 0.5 part per million parts of cooling water (ppm) should be effective, while about 2 ppm is the preferred lower limit. Based on economic considerations, the polymer could be fed in amount as high as about 200 ppm, with about 50 ppm being the preferred upper limit.
[0021] In terms of active chromate, that is, active hexavalent chromate ion, as little as about 0.5 ppm should be effective. The upper limit would depend on such factors as cost and toxicity and is less than 5 ppm.
[0022] Methods for feeding corrosion inhibitors to cooling water are well known in the art such that details thereof are not considered necessary. The chromate and the polymer may however be added to the aqueous system separately or together. The treatment is preferably used as an aqueous solution. The constitutes are combined by simply adding them to water. Should long-term stability problems be experienced, a two-barrel treatment may be more desirable. Of course, the constituents could be combined in any relative proportions in dry form.
[0023] Based on experience, compositions according to the present invention could vary widely and preferably comprise, on a weight basis:
(i) 1 to 99% of AA/HPA polymer, and
(ii) 1 to 99% of active chromate (as defined above) of the total amount of polymer and active chromate. The most preferred relative proportions would be 10 to 90% AA/HPA and 10 to 90% active chromate of the total amount of polymer and active chromate.
[0024] It is possible for the cooling water to have a pH of about 5.5 to 9.5. More commonly, the pH is about 6.5 to 8.5, with about 6.5 to 7.5 being most common.
[0025] With respect to the best mode for practicing the present invention, it is believed that methods and compositions in accordance therewith could best be used, with significant economic advantage, in the following systems:
1. in waters with low hardness, where low hardness is defined as less than 100 ppm of calcium carbonate and less than 100 ppm of magnesium as calcium carbonate;
2. in waters with a negative Langelier Saturation Index, as defined in the "BETZ Handbood of Industrial Water Conditioning", Seventh Edition; Betz Laboratories, Inc., Trevose, Pennsylvania (1976); pp 178180;
3. in waters with a corrosion and/or calcium phosphate deposition problem (the phosphate can be a constituent of the make up water); and
4. in waters with a corrosion and/or calcium sulfate, silt or iron oxide fouling problem.
Examples
Example 1
[0026] To demonstrate the corrosion inhibition efficacy of the combination of chromate and AA/HPA polymer, various mixtures were prepared by dissolving varying ratios of the components in water. The combinations were tested using a spinner testing technique.
[0027] The tests were each conducted with two non-pretreated low carbon steel coupons which were immersed and rotated in aerated synthetic cooling water for a 3- or 4-day period. The water was adjusted to the desired pH and readjusted after one day if necessary; no further adjustments were made. Water temperature was 120°F (48.9°C), and rotational speed was maintained to give a water velocity of 1.3 feet per second (0.396 ms-1) past the coupons. The total volume of water was 17 liters. Cooling water was manufactured to give the following conditions:
[0028] Corrosion rate was determined by weight loss measurement. Prior to immersion, coupons were scrubbed with a mixture of trisodium phosphate-pumice, rinsed with water, rinsed with isopropyl alcohol and then air dried. Weight measurement to the nearest milligram was made. At the end of one day, a weighed coupon was removed and cleaned. Cleaning consisted of immersion into a 50% solution of HCI for approximately 20 seconds, rinsing with tap water, scrubbing with a mixture of trisodium phosphate-pumice until clean and then rinsing with tap water and isopropyl alcohol. When dry, a second weight measurement to the nearest milligram was made. At the termination of tests, the remaining coupon was removed, cleaned and weighed.
[0029] Corrosion rates were calculated by differential weight loss according to the following equation:
where N = 3 or 4
[0030] The results of these tests are reported below in TABLE 1 in terms of per cent (%) corrosion inhibition of various treatments as compared to an untreated control test. The polymer tested was an acrylic acid/hydroxypropyl acrylate copolymer (AA/HPA) having a mole ratio of AA to HPA of 3:1 and a nominal molecular weight of 6000. The chromate compound used was sodium dichromate dihydrate. The amounts of chromate reported are active chromate dosages in ppm, and the pH of the test water was 8. The corrosion rates are reported in mils per year (mpy) and millimetres per year (mmpy).
[0031] It can be seen from TABLE 1 that the chromate-polymer combinations were quite effective in inhibiting corrosion, even at very low levels of active chromate.
Example 2
[0032] As already noted above, the use of insufficient amounts of chromate as a corrosion inhibitor can lead to rather sever pitting of metal surfaces. The ability of chromate-polymer combinations to reduce this pitting is demonstrated in the results of additional tests which were obtained in accordance with ASTM Pit Rating Methods. According to ASTM Pit Rating Methods, the density, size and depth of such localized corrosion is measured as described in "Measurement and Evaluation of Pitting Corrosion", Galvanic and Pitting Corrosion - Field and Laboratory Studies, ASTM Method STP-576, American Society for Testing and Materials, pp. 203-216 (1976). Testing procedures and conditions were substantially the same as those described in Example 1, with the exception that the coupons were additionally microscopically examined for pit rating.
[0033] The results of these tests are reported below in TABLES 2 and 3 in terms of ASTM Pit ratings. In TABLE 3, some corrosion rates and % corrosion inhibition values are also reported. The polymer tested was AA/HPA having a mole ratio of AA to HPA of 3:1 and a nominal molecular weight of 6000. The chromate was sodium dichromate dihydrate. The amounts of chromate reported are active chromate dosages. The ASTM pit ratings are in terms of density, in number of pits/square decimeter (dm2); pit sizes, in square millimeters (mm2), and pit depths, in millimetres (mm)
1. A method for reducing the amount of corrosion of metal surfaces in contact with
an aqueous medium characterised by adding to said aqueous medium an effective amount
for the purpose of a zinc-free and phosphate-free
(i) water-soluble chromate, and
(ii) water-soluble polymer comprising units derived from acrylic acid or water-soluble
salt thereof and units of 2-hydroxypropyl acrylate, wherein the units of said polymer
have the followinq formulas:
where R is a hydrogen or a lower alkyl of from 1 to 3 carbon atoms, R, is OH, NH2 or OM where M is a water-soluble cation, the mole ratio x:y of the former to the
latter units is 1:4 to 36:1, the chromate and the polymer being added either separately
or together and said water-soluble chromate being added in an amount of from 0.5 to
less than 5 parts of active chromate per million parts of said aqueous medium.
2. A method as claimed in claim 1, characterised in that said polymer has a molecular
weight of from 1,000 to 50,000.
3. A method as claimed in claim 1 or 2, characterised in that said mole ratio x:y
is 1:1 to 11:1.
4. A method as claimed in any one of the preceding claims, characterised in that said
water-soluble polymer is added in an amount of from 0.5 to 200 parts of polymer per
million parts of aqueous medium.
5. A method as claimed in any one of the preceding claims, characterised in that said
aqueous medium is cooling water.
6. A method as claimed in any one of the preceding claims, characterised in that the
components (i) and (ii) are added to said aqueous medium together.
7. A composition for reducing the amount of corrosion of metal surfaces in contact
with an aqueous medium characterised in that said composition is zinc-free and phosphate
free and comprises in combination:
(i) water-soluble chromate, and
(ii) water-soluble polymer as defined in any of claims 1 to 3.
8. A composition as claimed in claim 7, characterised in that on a weight basis said
chromate comprises 1 to 99% and said polymer comprises 1 to 99% of the total amount
of water-soluble chromate and water-soluble polymer.
9. A composition as claimed in claim 7 or 8, characterised in that it comprises a
stable aqueous solution of said components (i) and (ii).
1. Verfahren zur Verringerung der Korrosion von Metalloberflächen, die mit einem wäßrigen
Medium in Berührung stehen, gekennzeichnet, durch Zugabe zu diesem wäßrigen Medium
einer für den Zweck wirksamen Menge eines zinkfreien und phosphatfreien
. i) wasserlöslichen Chromats und
ii) wasserlöslichen Polymers, umfassend Einheiten, die abgeleitet sind von Acrylsäure
oder wasserlöslichen Salzen davon und Einheiten von 2-Hydroxypropyl-acrylat, wobei
die Einheiten des Polymers die folgenden Formeln besitzen
wobei R Wasserstoff oder eine niedere Alkylgruppe mit 1 bis 3 Kohlenstoffatomen bedeutet,
R, OH, NH2 oder OM ist, wobei M ein wasserlösliches Kation bedeutet, und das Molverhältnis x:y
der erstgenannten zu den letztgenannten Einheiten 1:4 bis 36:1 beträgt, und das Chromat
und das Polymer entweder getrennt oder zusammen zugesetzt werden und das wasserlösliche
Chromat in einer Menge von 0,5 bis weniger als 5 Teile aktives Chromat pro Millionen
Teile des wäßrigen Mediums zugesetzt wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Polymer Molekulargewicht
von 1 000 bis 50 000 hat.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Molverhältnis
x:y 1:1 bis 11:1 beträgt.
4. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das
wasserlösliche Polymer in einer Menge von 0,5 bis 200 Teilen Polymer pro Millionen
Teile des wäßrigen Mediums zugesetzt wird.
5. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das
wäßrige Medium Kühlwasser ist.
6. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die
Komponenten (i) und (ii) zusammen zu dem wäßrigen Medium zugesetzt werden.
7. Mittel zur Verringerung der Korrosion von Metalloberflächen, die mit einem wäßrigen
Medium in Berührung stehen, dadurch gekennzeichnet, daß das Mittel zinkfrei und phosphatfrei
ist und in Kombination enthält
i) wasserlösliches Chromat und
ii) wasserlösliches Polymer wie in einem der Ansprüche 1 bis 3 definiert.
8. Mittel nach Anspruch 7, dadurch gekennzeichnet, daß, bezogen auf das Gewicht, das
Chromat 1 bis 99% und das Polymer 1 bis 99%, bezogen auf die Gesamtmenge an wasserlöslichem
Chromat und wasserlöslichem Polymer ausmacht.
9. Mittel nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß es eine stabile wäßrige
Lösung der Komponenten (i) und (ii) ist.
1. Procédé de réduction de degré de corrosion de surfaces métalliques en contact avec
un milieu aqueux, caractérisé par l'addition audit milieu aqueux d'une quantité efficace
dans ce but d'une composition exempte de zinc et exempte de phosphate, mais comprenant:
(i) un chromate hydrosoluble, et
(ii) un polymère hydrosoluble comprenant deds motifs dérivant de l'acide acrylique
ou d'un sel hydrosoluble de celui-ci et des motifs d'acrylate de 2-hydroxypropyle,
les motifs dudit polymère ayant les formules suivants:
dans laquelle R est de l'hydrogène ou un groupe alkyle inférieur de 1 à 3 atomes de carbone, Ri est OH, NH2 ou OM où M est un cation hydrosoluble, le rapport molaire x:y des premiers aux derniers motifs étant de 1:4 à 36:1, le chromate et le polymère étant ajoutés séparément soit ensemble, et ledit chromate hydrosoluble étant ajouté en une quantité de 0,5 à moins de 5 parties de chromate actif par million de parties dudit milieu aqueux.
2. Procédé selon la revendication 1, caractérisé en ce que ledit polymère a un poids
moléculaire compris entre 1000 et 50 000.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que ledit rapport molaire
x:y est de 1:1 à 11:1.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce
que ledit polymère hydrosoluble est ajouté en une quantité de 0,5 à 200 parties de
polymère par million de parties de milieu aqueux.
5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce
que ledit milieu aqueux est de l'eau de refroidissement.
6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce
que les composants (i) et (ii) sont ajoutés ensemble audit milieu aqueux.
7. Composition destinée à réduire le degré de corrosion de surfaces métalliques en
contact avec un milieu aqueux, caractérisée en ce qu'elle est exempte de zinc et de
phosphate et comprend, en combinaison:
(i) un chromate hydrosoluble, et
(ii) un polymère hydrosoluble tel que défini dans l'une quelconque des revendications 1 à 3.
8. Composition selon la revendication 7, caractérisée en ce que, sur base pondérale,
ledit chromate constitue 1 à 99% et ledit polymère constitue 1 à 99% de la quantité
totale de chromate hydrosoluble et de polymère hydrosoluble.
9. Composition selon la revendication 7 ou 8, caractérisée en ce qu'elle consiste
en, ou comprend, une solution aqueuse stable desdits composants (i) et (ii).