Coolant having rapid metal passivation properties

Abstract

It has been found that the chemical reactivity of the metal surface of heat exchangers with coolants in presence of nitrites can be reduced by the addition of additives such as phosphonates or phosphinates. Aluminum, other Group III metals, as well as other metals commonly used in cooling systems, such as those of automobile engines, may thus be effectively protected.

Claims

1. A heat transfer solution which provides passivation when placed in contact with metal surfaces, said solution comprising: (a) water, an alcohol, or a mixture of both; (b) from 0.01 to 1 wt % of a nitrite; (c) from 0.0001 to 1 wt % of a phosphonate or a phosphinate, the phosphonate having the formula R[CR.sub.2].sub.mPO.sub.3M.sub.2 wherein each R-group is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyl, phosphono group, carbonyl group, amino, alkylamino and an aryl group, wherein m is 1 or an integer greater than 1, and each M is hydrogen or an alkali metal ion; the phosphinate having the formula R[CR.sub.2].sub.mP(O.sub.2M)H wherein each R-group is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyl, phosphino group, carbonyl group, amino, alkylamino and an aryl group, wherein m is 1 or an integer greater than 1, and M is hydrogen or an alkali metal ion; (d) an alkaline earth metal compound; and (e) a corrosion inhibitor selected from the group consisting of 2-ethylhexanoic acid, sebacic acid, and mixtures thereof, wherein the heat transfer solution is free of inorganic phosphates.

2. The solution of claim 1, wherein the alcohol is water soluble.

3. The solution of claim 2, wherein the water soluble alcohol is selected from the group consisting of methanol, ethanol, propanol, ispropanol, butanol, glycols, glycol monoethers, glycerins and mixtures thereof.

4. The solution of claim 3, wherein the glycol is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, butylene glycol and mixtures thereof.

5. The solution of claim 4, wherein the glycol is ethylene glycol.

6. The solution of claim 1, wherein the solution further comprises a corrosion inhibitor salt which is selected from the group consisting of silicates, molybdates, nitrates, azoles and combinations thereof.

7. The solution of claim 1, which comprises from 50 to 99.8 wt % of the liquid of (a).

8. The solution of claim 1, wherein the nitrite is sodium nitrite.

9. The solution of claim 1 which further comprises additives selected from the group consisting of pH buffers, hard water stabilizers, antifoam agents, and colorants.

10. The solution of claim 1, wherein the alkaline earth metal compound is a strontium or magnesium compound.

11. The solution of claim 1, wherein the alkaline earth metal compound comprises strontium nitrate and (c) is a phosphonate which comprises 1-hydroxyethylidene-1,1-diphosphonic acid or phenylphosphonic acid.

12. The solution of claim 1, wherein (c) is a phosphonate and comprises 1-hydroxyethylidene-1,1-diphosphonic acid or phenylphosphonic acid.

13. A process for passivation of metal surfaces, wherein the surfaces are treated with a solution comprising: (a) a liquid selected from the group consisting of water, an alcohol, and mixtures thereof; (b) from 0.01 to 1 wt % of a nitrite; (c) from 0.0001 to 1 wt % of: a phosphonate having the formula R[CR.sub.2].sub.mPO.sub.3M.sub.2 wherein each R-group is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyl, phosphono group, carbonyl group, amino, alkylamino and an aryl group, wherein m is 1 or an integer greater than 1, and each M is hydrogen or an alkali metal ion; or a phosphinate having the formula R[CR.sub.2].sub.mP(O.sub.2M)H wherein each R-group is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyl, phosphino group, carbonyl compound, amino, alkylamino and an aryl group, wherein m is 1 or an integer greater than 1, and M is hydrogen or an alkali metal ion; (d) an alkaline earth metal compound; and (e) and a corrosion inhibitor selected from the group consisting of 2-ethylhexanoic acid, sebacic acid, and mixtures thereof, wherein the solution is free of inorganic phosphates.

14. The process of claim 13, wherein the solution further comprises a corrosion inhibitor salt selected from the group consisting of silicates, molybdates, nitrates, azoles and combinations thereof.

15. The process of claim 13, wherein the alkaline earth metal compound comprises strontium nitrate and (c) is a phosphonate and comprises 1-hydroxyethylidene-1,1-diphosphonic acid or phenylphosphonic acid.

16. The process of claim 13, wherein (c) is a phosphonate and comprises 1-hydroxyethylidene-1,1-diphosphonic acid or phenylphosphonic acid.

17. A heat transfer solution which provides passivation when placed in contact with metal surfaces, said solution comprising: (a) water, an alcohol, or a mixture of both; (b) from 0.01 to 1 wt % of a nitrite; (c) from 0.0001 to 1 wt % of a phosphonate having the formula R[CR.sub.2].sub.mPO.sub.3M.sub.2 wherein each R-group is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyl, phosphono group, carbonyl group, amino, alkylamino and an aryl group, wherein m is 1 or an integer greater than 1, and each M is hydrogen or an alkali metal ion; or a phosphinate having the formula R[CR.sub.2].sub.mP(O.sub.2M)H wherein each R-group is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyl, phosphino group, carbonyl group, amino, alkylamino and an aryl group, wherein m is 1 or an integer greater than 1, and M is hydrogen or an alkali metal ion; (d) an alkaline earth metal compound; and (e) a corrosion inhibitor, wherein the heat transfer solution is free of inorganic phosphates.

18. The solution of claim 17, wherein the solution further comprises a corrosion inhibitor salt which is selected from the group consisting of silicates, molybdates, nitrates, azoles and combinations thereof.

19. The solution of claim 17, which comprises from 50 to 99.8 wt % of the liquid of (a).

20. The solution of claim 17, wherein the corrosion inhibitor comprises the combination of an aliphatic monoacid or salt, a hydrocarbyl dibasic acid or salt and a hydrocarbyl triazole.

21. The solution of claim 20, wherein the corrosion inhibitor is selected from the group consisting of 2-ethylhexanoic acid, sebacic acid, tolyltriazole and mixtures thereof.

22. A heat transfer solution which provides passivation when placed in contact with metal surfaces, said solution comprising: (a) water, an alcohol, or a mixture of both; (b) from 0.01 to 1 wt % of a nitrite; (c) from 0.0001 to 1 wt % of a phosphonate having the formula R[CR.sub.2].sub.mPO.sub.3M.sub.2 wherein each R-group is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyl, phosphono group, carbonyl group, amino, alkylamino and an aryl group, wherein m is 1 or an integer greater than 1, and each M is hydrogen or an alkali metal ion; or a phosphinate having the formula R[CR.sub.2].sub.mP(O.sub.2M)H wherein each R-group is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyl, phosphino group, carbonyl group, amino, alkylamino and an aryl group, wherein m is 1 or an integer greater than 1, and M is hydrogen or an alkali metal ion; (d) an alkaline earth metal compound; and (e) a corrosion inhibitor selected from the group consisting of 2-ethylhexanoic acid, sebacic acid, and mixtures thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) This invention is directed to a heat transfer solution which results in rapid passivation when placed in contact with metal surfaces such as aluminum, and the process of passivating such metals with the solution. This solution is composed of a fluid comprising water, alcohol or a mixture of both. This solution further comprises nitrites, at least 1% of an organic corrosion inhibitor organic salt thereof, and at least one component selected out of groups of phosphonates and phosphinates.

(2) The water-soluble liquid alcohols useful in this invention may comprise monohydroxy lower alkyl alcohols and liquid polyhydroxy alcohols such as the alkylene and dialkylene glycols. They may also comprise alkylene glycols, glycol monoethers, glycerins and mixtures thereof. Specific examples of the alcohol contemplated herein are methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol and mixtures thereof. A preferred glycol is ethylene glycol, which as sold commercially often contains a small amount, up to 5% by weight, of diethylene glycol. The term ethylene glycol as used herein is intended to include either the pure or commercial compound. This is also true of the other freezing point depressant alcohols contemplated herein.

(3) The phosphonates have the formula R[CR.sub.2]m-PO.sub.3M.sub.2 (wherein at least one R-group is a hydrogen, alkyl, alkenyl, hydroxyl, phosphono group, CO, amino, alkylamino or R is part of an aryl group, the other R groups may be the same as or different from the first R group is a hydrogen, alkyl, alkenyl, hydroxyl, phophono group, CO, amino, alkylamino, m is 1 or an integer greater than 1, and each M is hydrogen or an alkali metal ion.

(4) The phosphinates have the formula R[CR.sub.2]m-P(O.sub.2M)H (wherein at least one R-group is a hydrogen, alkyl, alkenyl, hydroxyl, phosphino group, CO, amino, alkylamino or R is part of an aryl group, the other R groups may the same as or different from the first R group is a hydrogen, alkyl, alkenyl, hydroxyl, phosphono group, CO, amino, alkylamino, m is 1 or an integer greater than 1, and M is hydrogen or an alkali metal ion combinations of two or more of these phosphonates and/or phosphinates.

(5) The heat transfer fluids described above can further comprise one or more alkaline earth metal (Group II of the periodic table of elements) compounds such as magnesium and/or strontium.

(6) The heat transfer fluid described above can further comprise corrosion inhibitors selected from the group consisting of silicates, molybdates, nitrates, azoles and a combination of the foregoing compounds.

EXAMPLES

(7) The positive effect towards fast passivation and reduced nitrite consumption has been illustrated on controlled atmosphere brazed (CAB) aluminum heat exchanger material immersed in a cooling fluid.

(8) Description of the Test

(9) Aluminum radiator cube material is immersed in 275 ml of a 50/50 coolant dilution (50% water and 50% coolant concentrate) in deionized water in a closed flask at 100 C. for 10 days. After the test, the nitrite concentration in the coolant is determined, together with the change in pH.

(10) One can observe that multiple additives can provide a positive effect on pH stability or stability of the nitrite concentration but the solution of this invention gives very good results for both characteristics. Moreover, it can be observed that the selection of the correct phosphonate or phosphinate, respectively is critical to obtain a good performance level. The use of other phosphonates like the ones put forward in the prior art literature (e.g. phosphonocarboxylates as described in patent application US2010116473) does not give the targeted stability of pH, nor does it stop the consumption of nitrite.

(11) In one embodiment, there is provided an antifreeze composition comprising from 50 to 99.8 wt. % of a glycol-based freezing point depressant selected from the group of: alkylene glycols, glycol monoethers, glycerins, and mixtures thereof 0.01 to 1 wt. % of sodium nitrite. From 0.0001 to 1% of a phosphonate with formula R[CR.sub.2].sub.mPO.sub.3M.sub.2 and from 1 to 5% of an organic corrosion inhibitor or a salt thereof.

(12) In a second embodiment, there is provided an antifreeze composition comprising from 50 to 99.8 wt % of a glycol-based freezing point depressant selected from the group of: alkylene glycols, glycol monoethers, glycerins and mixtures thereof; 0.01 to 1 wt % of sodium nitrite. From 0.0001 to 1% of a phosphonate with formula R[CR.sub.2].sub.mPO.sub.3M.sub.2. From 0.0001 to 0.1 wt % of alkaline earth metal (Group II of the periodic table of elements) compounds and from 1 to 5% of an organic corrosion inhibitor or a salt thereof.

(13) In a third embodiment there is provided an antifreeze composition as described in previous embodiments but in which the phosphonates are replaced with 0.0001 to 1% of a phosphinate with formula R[CR.sub.2]m-P(O.sub.2M)H.

(14) Examples of the described embodiments are given in the attached table (Ex. 1-6).

(15) TABLE-US-00001 Comp. Comp. Comp. Component Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 1 Ex. 2 Ex. 3 mono ethylene glycol 94.0855 94.0255 94.1209 94.0609 94.1232 94.0632 94.0009 94.1430 94.1130 94.0930 2-ethylhexanoic acid 3.2400 3.2400 3.2400 3.2400 3.2400 3.2400 3.2400 3.2400 3.2400 3.2400 Sebacic acid 0.2520 0.2520 0.2520 0.2520 0.2520 0.2520 0.2520 0.2520 0.2520 0.2520 Tolyltriazole 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 NaOH.sup.1 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 NaNO.sub.2 0.1650 0.1650 0.1650 0.1650 0.1650 0.1650 0.1650 0.1650 0.1650 0.1650 Sr(NO.sub.3).sub.2 0.0600 0.0600 0.0600 0.0600 0.0300 Dequest 2010.sup.2 0.0575 0.0575 Phenylphosphonic acid 0.0221 0.0221 0.0221 Phenylphosphinic acid 0.0198 0.0198 Dequest 7000.sup.3 0.0500 Sodium molybdate 0.0600 dihydrate pH before test 8.6 8.7 8.6 8.6 8.6 8.6 8.6 8.5 8.5 8.5 pH after test 8.8 8.8 8.9 8.8 9.0 8.8 8.7 9.3 9.1 9.2 pH change 0.2 0.1 0.3 0.2 0.4 0.2 0.1 0.8 0.6 0.7 NO.sub.2 (%).sup.4 6 4 18 14 23 15 11 39 39 39 .sup.1NaOH: 50 wt % aqueous solution of sodium hydroxide .sup.2Dequest 2010: 60 wt % 1-Hydroxyethylidene -1,1,-diphosphonic acid aqueous solution, commercially available at Thermphos .sup.3Dequest 7000: 50 wt % of 2-phosphonobutane-1,2,4-tricarboxylic acid aqueous solution, commercially available at Thermphos .sup.4% percentage of nitrites depleted after test

(16) Comparative examples 1-3 of the Table illustrate the potential negative effect of nitrites in coolants (nitrite depletion and pH increase) without the extra addition of additives described in the claims of this invention. Comparison of Comparative Examples 1-3 with Examples 1-6 demonstrates that with the addition of strontium nitrate, pH change and nitrite depletion is even further reduced.

(17) Additionally to above critical additives also other typical coolant additives can be added comprising but not limited to the group of silicates, molybdates, nitrates, azoles, pH buffers, hard water stabilizers, antifoam agents, colorants.

(18) In one embodiment, the composition is used as a concentrate in a mixture with an aqueous antifreeze solution comprising 10 to 90 wt. % by weight of water.