GB2094776A - Prevention of corrosion in aqueous systems - Google Patents
Prevention of corrosion in aqueous systems Download PDFInfo
- Publication number
- GB2094776A GB2094776A GB8107611A GB8107611A GB2094776A GB 2094776 A GB2094776 A GB 2094776A GB 8107611 A GB8107611 A GB 8107611A GB 8107611 A GB8107611 A GB 8107611A GB 2094776 A GB2094776 A GB 2094776A
- Authority
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- United Kingdom
- Prior art keywords
- phosphonate
- triazole
- polymer
- acid
- zinc salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 16
- 230000007797 corrosion Effects 0.000 title claims abstract description 16
- 230000002265 prevention Effects 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- MVRGLMCHDCMPKD-UHFFFAOYSA-N 3-amino-1h-1,2,4-triazole-5-carboxylic acid Chemical compound NC1=NNC(C(O)=O)=N1 MVRGLMCHDCMPKD-UHFFFAOYSA-N 0.000 claims abstract description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 21
- 150000003751 zinc Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 150000003852 triazoles Chemical class 0.000 claims description 11
- -1 nitrilo tris methylene phosphonic acid Chemical compound 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical group OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 6
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- RZMGZEJEAAVXRG-UHFFFAOYSA-N 1,2-dihydrotriazole-3-carboxylic acid Chemical compound N1NN(C=C1)C(=O)O RZMGZEJEAAVXRG-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- JPKFMSXLYUZRBA-UHFFFAOYSA-N 4-amino-1,2,4-triazole-3,5-dicarboxylic acid Chemical compound NN1C(C(O)=O)=NN=C1C(O)=O JPKFMSXLYUZRBA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XVUPGBZRZLSDDE-UHFFFAOYSA-L N1N=NC=C1.P([O-])([O-])=O.[Zn+2] Chemical compound N1N=NC=C1.P([O-])([O-])=O.[Zn+2] XVUPGBZRZLSDDE-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NGFNIPDMIZZXLP-UHFFFAOYSA-L [Zn+2].[O-]P([O-])=O Chemical compound [Zn+2].[O-]P([O-])=O NGFNIPDMIZZXLP-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- YVPJCJLMRRTDMQ-UHFFFAOYSA-N ethyl diazoacetate Chemical compound CCOC(=O)C=[N+]=[N-] YVPJCJLMRRTDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
A method of preventing corrosion in an aqueous system is provided which comprises adding to the system 5-amino-1,2,4-triazole- 3-carboxylic acid or a salt thereof.
Description
SPECIFICATION
Prevention of corrosion in aqueous systems
This invention relates to the prevention of corrosion in aqueous systems.
The use of certain arylene triazoles to prevent corrosion in aqueous systems, in particular systems in contact with ferrous metal, has been known for some time. Likewise, certain organic phosphonates, low molecular weight polymers and zinc salts show some corrosion inhibiting properties but are not of sufficient effectiveness to be used alone. The present invention resides in the discovery that a particular type of triazole is effective for protecting ferrous metals from corrosion. This triazole is 5-amino-l ,2,4-triazole-3-carboxylic acid which has the formula:
Accordingly the present invention provides a method of preventing corrosion in an aqueous system which comprises adding to the aqueous system 5-amino-1,2,4-triazole-3-carboxylic acid.
In general the concentration of the triazole is 0.5 to 20, especially 1 to 10, mg/litre.
Not only does this particular triazole provide superior corrosion inhibition to, say, benzotriazole but it has also been found that by combining this triazole with zinc salts, organic phosphates and phosphonates, and low molecular weight polymers, typically either a zinc salt and an organic phosphonate, or an organic phosphonate and a low molecular weight polymer, synergistic effects can be obtained. In other words, results can be obtained which are better than one would expect from the summation of the results of the individual ingredients.
Accordingly, the present invention also provides a composition suitable for addition to aqueous media which comprises 5-amino-l ,2,4-triazole-3-carboxylic acid and at least one of a zinc salt, an organic phosphonate, and a low molecular weight polymer. Of course, it is possible to incorporate the ingredients individually in the system.
Typical phosphonates which can be used in the present invention include those of the general formula:
where R' is hydrogen or lower (i.e. of 1 to 6, especially 1 to 4, carbon atoms) alkyl and X is hydrogen, lower alkyl or hydroxyl; or of general formula:
where each R2 independently is hydrogen or lower alkyl, and
where x is an integer from 1 to 6, or
where y is an integer from 1 to 3; or of general formula:
where R4 is hydrogen, alkyl or
where R5 is hydrogen, alkyl or carboxyl and R6 is hydrogen or alkyl.
The preferred phosphonates are hydroxy ethylidene diphosphonic acid (HEDPA), i.e. of formula (II) where R1 is methyl and X is hydroxyl; and nitrilo tris methylene phosphonic acid, i.e.
of formula (III) where R2 is hydrogen and R3 is
R -CHPO3H2
The concentration of phosphonate in the system is suitably 1 to 50, especially 2 to 10, mg/litre.
The polymers which can be used in the present invention are vinyl addition products with molecular weight from, say, 500 to 100,000, possessing recurring units of general formula:
where R7 is hydrogen or lower alkyl, and Y is -COOH, and Z is hydrogen or -COOH, or Y and Z together represent -CO-O-CO-. The preferred polymers are polymethacrylic acid, i.e. where R7 is methyl, Y is -COOH and Z is hydrogen, in particular of molecular weight about 5000, and polyacrylic acid i.e. where R7 and Z are both hydrogen and Y is -COOH, in particular of molecular weight about 1 000. The polymer concentration is suitably 1 to 50, preferably 2 to 10, mg/litre.
5-Amino-1 ,2,4-triazole-3-carboxylic acid can be prepared by dehydration of oxalylaminoguanidine
(see, e.g. Ann 1898, 303, 52) or by heating ethyl diazoacetate and potassium hydroxide (see, e.g. Ber 1907, 40, 815, 1194). This latter method also gives some 4-amino-1,2,4-triazole-3,5dicarboxylic acid.
Typical zinc salts which may be used are the chloride, sulphate, nitrate and acetate. Typically the zinc salts can be present in an amount from 0.5 to 20, especially 1 to 10, mg of Zn/litre.
Although the formulae of the phosphonates and polymers have been given in the form of the free acids, it is to be understood that they can also be used in the form of organic or inorganic salts, in particular, an alkaline metal salt, which is preferred, such as sodium or potassium, ammonium or a lower amine salt or other metal salt. The triazole not only forms salts as above but can also form amine salts with inorganic acids; it can be used in these forms.
It will be appreciated that other low-toxic materials conventionally used in water treatment can be included, such as silicate, inorganic phosphate or polyphosphate, and lignin derivatives.
The following Examples further illustrate the present invention.
EXAMPLES 1 TO 4
Effect on Mild Steel
Mild steel test specimens were immersed in aerated water and stood at 1 8 C for five days.
The specimens were cleaned and weighed before and after the test, and the average corrosion rate in mils per year calculated from the weight loss recorded. The water used in these tests was
Widnes mains water, total hardness 140 mg/l, M. alkalinity 100 mg/l, Langelier Index minus 0.5.
Example No Dosage Rate I mg/l Corrosion rate mils/year 1 18.2 2 25 15.8 3 50 14.8 4 100 12.9
EXAMPLES 5 TO 12
Effect in Admixture with Zinc and Phosphonate
Mild steel test specimens were suspended in a stirred reservoir of water maintained at a temperature of 60"C, the stirring being of such a rate as to ensure air entrainment so as to keep the water oxygen-saturated. Water lost by evaporation was replaced from an elevated tank through a syphon constant level control to maintain a constant volume in the reservoir. The water used in these tests was Widnes mains water which concentrated three times during the test due to evaporation.
In each test treatment was applied at three times normal dose for 24 hours in order to passivate the steel; then the water was diluted to the normal dose level for the remainder of the test. Each test was carried out for a minimum of three days.
Additives mg/l
Corrosion rate
Example No Zinc Salt Phosphonate Triazole I mils/year
(as Zn)
5 - - - 105.4
6 10 - - 80.4
7 - 10 - 62.0
8 - - 10 59.2
9 5 4.25 - 32.7 10 10 - 2 22.0 11 - 10 2 35.7 12 5 4.25 2 3.0
In these examples the zinc salt is zinc chloride and the phosphonate is nitrilo tris methylene phosphonic acid. Examples 9 and 1 2 also contain 5 mg/l of a lignin sulphonate.
EXAMPLES 13 TO 20
Effect in Admixture with Phosphonate and Polymer
A laboratory test apparatus was used in which water was circulated by means of a pump from a reservoir maintained at a temperature of 40"C, through a glass tube assembly holding the metal test specimens, and returned to the reservoir entraining air so as to keep the water saturated with oxygen as it would be in an open recirculating cooling system. Water lost by evaporation was replaced from an elevated tank through a float control to maintain a constant volume in the system, the water used being Widnes mains water, which, in this test, concentrated two times due to evaporation.
In each test treatment was applied at three times normal dose for 24 hours in order to passivate the steel, then the water was diluted to the normal dose level for the remainder of the test. Each test was carried out for a minimum of three days.
Additive mg/l
Corrosion rate
Example No Phosphonate Polymer Triazole I mils/year 13 - - - 38.1 14 7 - - 32.7 15 - 3 - 23.3 16 7 3 - 18.3 17 7 - 5 25.5 18 - 3 5 14.6 19 - - 10 12.9 20 7 3 5 2.3
In these Examples the phosphonate was a 1:1 mixture of hydroxy ethylidene diphosphonic acid and nitrilo tris methylene phosphonic acid, and the polymer was polymethacrylic acid of 5000 molecular weight, all present as their potassium salts. Examples 16 and 20 also contained 3 mg/l of potassium orthophosphate.
EXAMPLES 21 AND 22
Comparison with Benzotriazole
These Examples were carried out under the conditions described for Examples 5 to 12, (Example 21) and for Examples 13 to 20, (Example 22).
Additives mg/l Corrosion rate Example No Triazole I Benzotriazole mils/year Zinc Salt Phosphonate Polymer (as Zn) 12 4.25 - 5 2 - 3.0 21 4.25 - 5 - 2 6.1 20 7 3 - 5 - 2.3 22 7 3 - - 5 2.6
In Examples 12 and 21 the phosphonate is nitrilo tris methylene phosphonic acid, the zinc salt is zinc chloride and the compositions also include 5 mg/l of a lignin sulphonate. In
Examples 20 and 22 the phosphonate is a 1:1 mixture of hydroxy ethylidene diphosphonic acid and nitrilo tris methylene phosphonic acid, the polymer is polymethacrylic acid of molecular weight 5000, all present as their potassium salts; and the compositions also include 3 mg/l of potassium orthophosphate.
These Examples show that whilst the triazole I itself has corrosion inhibiting properties these are increased when it is incorporated together with a zinc salt, phosphonate or polymer, and vastly increased when it is incorporated together with zinc salt and phosphonate or phosphonate and polymer, thus demonstrating synergism; it is clearly superior to benzotriazole in performance.
Claims (16)
1. A method of preventing corrosion in an aqueous system which comprises adding to the system 5-amino-1 ,2,4-triazole-3-carboxylic acid or a salt thereof.
2. A method according to claim 1 which comprises adding the said triazole to the system to provide a concentration of 0.5 to 20 mg/litre.
3. A method according to claim 2 in which the concentration of the said triazole is 1 to 10 mg/sitre.
4. A method according to any one of claims 1 to 3 which comprises also adding to the system one or more of a zinc salt, organic phosphate or phosphonate and a polymer.
5. A method according to claim 4 which comprises adding a zinc salt and an organic phosphonate.
6. A method according to Claim 4 which comprises adding an organic phosphonate and a polymer.
7. A method according to any one of claims 4 to 6 in which the phosphonate is hydroxyethylidene diphosphonic acid or nitrilo tris methylene phosphonic acid.
8. A method according to claim 4, 6 or 7 in which the polymer is polyacrylic or polymethacrylic acid.
9. A method'according to any one of claims 4 and 6 to 8 in which the zinc salt is zinc chloride, sulphate, nitrate or acetate.
10. A method according to claim 1 substantially as described in any one of Examples 2 to 4, 8, 10 to 12 and 17 to 20.
11. A composition which comprises 5-amino-I ,2,4-triazole-3-carboxylic acid or a salt thereof and one or more of a zinc salt, organic phosphate or phosphonate and a polymer.
1 2. A composition according to claim 11 which comprises a zinc salt and an organic phosphonate.
1 3. A composition according to claim 11 which comprises an organic phosphonate and a polymer.
14. A composition according to any one of claims 11 to 1 3 in which the phosphonate is hydroxyethylidene diphosphonic acid or nitrilo tris methylene phosphonic acid.
1 5. A composition according to claim 11, 1 3 or 14 in which the polymer is polyacrylic or polymethacrylic acid.
16. A composition according to any one of claims 11, 12, 14 and 15 in which the zinc salt is zinc chloride, sulphate, nitrate or acetate.
1 7. A composition according to claim 11 substantially as described in any one of Examples 10 to 12, 17, 18 and 20.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8107611A GB2094776B (en) | 1981-03-11 | 1981-03-11 | Prevention of corrosion in aqueous systems |
| CA000387564A CA1162726A (en) | 1981-03-11 | 1981-10-08 | Prevention of corrosion in aqueous systems |
| DE19823208119 DE3208119A1 (en) | 1981-03-11 | 1982-03-06 | METHOD FOR PREVENTING CORROSION IN AQUEOUS SYSTEMS |
| ES510242A ES8302795A1 (en) | 1981-03-11 | 1982-03-09 | Prevention of corrosion in aqueous systems |
| IT20056/82A IT1150645B (en) | 1981-03-11 | 1982-03-09 | CORROSION PREVENTION IN AQUEOUS SYSTEMS |
| FR8204049A FR2501709A1 (en) | 1981-03-11 | 1982-03-10 | PROCESS AND COMPOSITION FOR PREVENTING CORROSION IN AQUEOUS SYSTEMS |
| SE8201509A SE8201509L (en) | 1981-03-11 | 1982-03-10 | PREVENTION OF CORROSION IN WATER BASED SYSTEMS |
| JP57036718A JPS57161072A (en) | 1981-03-11 | 1982-03-10 | Water system corrosion prevention |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8107611A GB2094776B (en) | 1981-03-11 | 1981-03-11 | Prevention of corrosion in aqueous systems |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2094776A true GB2094776A (en) | 1982-09-22 |
| GB2094776B GB2094776B (en) | 1984-05-16 |
Family
ID=10520306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8107611A Expired GB2094776B (en) | 1981-03-11 | 1981-03-11 | Prevention of corrosion in aqueous systems |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS57161072A (en) |
| CA (1) | CA1162726A (en) |
| DE (1) | DE3208119A1 (en) |
| ES (1) | ES8302795A1 (en) |
| FR (1) | FR2501709A1 (en) |
| GB (1) | GB2094776B (en) |
| IT (1) | IT1150645B (en) |
| SE (1) | SE8201509L (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1985002207A1 (en) * | 1983-11-14 | 1985-05-23 | Henkel Kommanditgesellschaft Auf Aktien | Corrosion inhibitors for aluminium |
| WO1986007098A1 (en) * | 1985-05-31 | 1986-12-04 | Henkel Kommanditgesellschaft Auf Aktien | UTILIZATION OF 3-AMINO-5-(omega-HYDROXYALKYL)-1,2,4-TRIAZOLES AS CORROSION INHIBITORS FOR NON-FERROUS HEAVY METALS IN AQUEOUS SYSTEMS |
| EP0249162A1 (en) * | 1986-06-13 | 1987-12-16 | Henkel Kommanditgesellschaft auf Aktien | Use of acylated 3-amino-1,2,4 triazoles as corrosion inhibitors for non-ferrous heavy metals |
| EP0587434A1 (en) * | 1992-09-11 | 1994-03-16 | The Lubrizol Corporation | Corrosion inhibition composition |
| GB2331999A (en) * | 1997-10-28 | 1999-06-09 | Ibm | Copper preservative treatment using azoles |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1222133A (en) * | 1968-05-25 | 1971-02-10 | Geigy Uk Ltd | Inhibition of corrosion of copper and its alloys using 3-amino-1:2:4-triazole |
| JPS4862634A (en) * | 1971-12-04 | 1973-09-01 | ||
| US3794603A (en) * | 1972-01-17 | 1974-02-26 | Sherwin Williams Co | Zn++-benzotriazole-h2so4 corrosioninhibitor |
| US3985503A (en) * | 1975-03-17 | 1976-10-12 | The Sherwin-Williams Company | Process for inhibiting metal corrosion |
| DE2934461A1 (en) * | 1979-08-25 | 1981-03-26 | Henkel KGaA, 40589 Düsseldorf | CORROSION INHIBITORS FOR COLORED METALS |
-
1981
- 1981-03-11 GB GB8107611A patent/GB2094776B/en not_active Expired
- 1981-10-08 CA CA000387564A patent/CA1162726A/en not_active Expired
-
1982
- 1982-03-06 DE DE19823208119 patent/DE3208119A1/en not_active Withdrawn
- 1982-03-09 ES ES510242A patent/ES8302795A1/en not_active Expired
- 1982-03-09 IT IT20056/82A patent/IT1150645B/en active
- 1982-03-10 FR FR8204049A patent/FR2501709A1/en not_active Withdrawn
- 1982-03-10 JP JP57036718A patent/JPS57161072A/en active Pending
- 1982-03-10 SE SE8201509A patent/SE8201509L/en not_active Application Discontinuation
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1985002207A1 (en) * | 1983-11-14 | 1985-05-23 | Henkel Kommanditgesellschaft Auf Aktien | Corrosion inhibitors for aluminium |
| US4647429A (en) * | 1983-11-14 | 1987-03-03 | Henkel Kommanditgesellschaft Auf Aktien | Corrosion inhibitors for aluminum |
| WO1986007098A1 (en) * | 1985-05-31 | 1986-12-04 | Henkel Kommanditgesellschaft Auf Aktien | UTILIZATION OF 3-AMINO-5-(omega-HYDROXYALKYL)-1,2,4-TRIAZOLES AS CORROSION INHIBITORS FOR NON-FERROUS HEAVY METALS IN AQUEOUS SYSTEMS |
| EP0249162A1 (en) * | 1986-06-13 | 1987-12-16 | Henkel Kommanditgesellschaft auf Aktien | Use of acylated 3-amino-1,2,4 triazoles as corrosion inhibitors for non-ferrous heavy metals |
| US4874579A (en) * | 1986-06-13 | 1989-10-17 | Henkel Kommanditgesellschaft Auf Aktien | Acylated 3-amino-1,2,4-triazoles as corrosion inhibitors for non-ferrous metals |
| EP0587434A1 (en) * | 1992-09-11 | 1994-03-16 | The Lubrizol Corporation | Corrosion inhibition composition |
| US5338347A (en) * | 1992-09-11 | 1994-08-16 | The Lubrizol Corporation | Corrosion inhibition composition |
| US5407471A (en) * | 1992-09-11 | 1995-04-18 | The Lubrizol Corporation | Corrosion inhibition composition |
| GB2331999A (en) * | 1997-10-28 | 1999-06-09 | Ibm | Copper preservative treatment using azoles |
| GB2331999B (en) * | 1997-10-28 | 2003-01-22 | Ibm | Copper preservative treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2501709A1 (en) | 1982-09-17 |
| ES510242A0 (en) | 1983-01-16 |
| SE8201509L (en) | 1982-09-12 |
| ES8302795A1 (en) | 1983-01-16 |
| GB2094776B (en) | 1984-05-16 |
| DE3208119A1 (en) | 1982-11-11 |
| JPS57161072A (en) | 1982-10-04 |
| CA1162726A (en) | 1984-02-28 |
| IT8220056A0 (en) | 1982-03-09 |
| IT1150645B (en) | 1986-12-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |