US2400611A - Turbine oils - Google Patents

Description

I attach TURBINE one Herschel G. Smith, Wallingfofll, and Troy L Cantrell, Lansdowne, Pa, and John'G. Peters, Audubon, N. 3., asslgnors to Gulil H Corporation, Pittsburgh, Pa,

vania a corporation of Pennsyl- No Drawing. Application March '19, 1945,

: Serial No. 583,057

12 Claims. (Cl. sass-32.5)

This invention relates to turbine oils, and it comprises improved anti-rust turbine oils having outstanding rust preventive qualities, in addition to a plurality of other advantageous properties, said improved turbine oils containing small amounts of a composite improvement agent dissolved therein; and it further comprises a homogeneous, oil-soluble, composite improvement agent which is readily soluble in turbine oils and is capable of imparting marked rust preventive qualities thereto, in addition to a plurality of other advantageous properties; all as more fully hereinafter described and claimed.

In the lubrication of turbines; it is essential that the lubricating oil protect the metal parts, particularly from rust and corrosion, as well as satisfactorily lubricate the moving parts thereof. Further, under service conditions, turbine oils are subjected to various conditions, some of which are rather drastic.

Accordingly, commercial turbine oils are sub- I jected to various drastic tests, such as accelerated corrosion tests, emulsion tests, oxidation tests, and Falex wear test, as well as various other tests as to lubricating qualities. To be acceptable commercially, turbine oils must satisfactorily pass all of such tests.

Therefore, commercial turbine oils generally are highly refined, high grade mineral lubricating oils having the desired physical properties. Usually, commercial turbine oils are of viscosities ranging from 150 to 600 seconds, SUV at 100 F.,

and. are substantially free of non-hydrocarbon compounds. also, they usually are quite resistant to oxidation.

However, such highly refined mineral lubricatlng oils or turbine oils do not give satisfactory protection to metals against rust and corrosion, especially in the presence or water and steam, gulch as encountered in the lubrication of turines.

between 0.01 and 1.0 per cent by weight on the oil of our new composite improvement agent dissolved therein have given markedly superior results in turbines, the metal parts of the turbine and of the 011 system being maintained bright and free of rust for long periods. Further, such improved turbine oils also gave improved lubrication under service conditions for long periods.

Our new oil-soluble, composite ,improvement agents comprise a blended mixture of polyvalent metal salts of N-substituted phthalamidic acids and amine salts of3-methyl-butyl, 2-ethyl-hexyl phosphoric acid with cyclohexyl amines and primary fatty amines, respectively; these salts being blended together into a homogeneous oil-soluble composite improvement agent. Usually, the two amine salts and the said polyvalent metal salt are blended together in equal proportions. However, the respective proportions thereof may be Accordingly, various addition agents have been proposed for incorporation in turbine oils as improvement agents, to modify or improve various properties of the oil. In general, the improvement agents or additive compounds previously usedor proposed have not been commercially sat isiactory in all respects.

We have now discovered a new, oil-soluble composite improvement agent which is readily soluble in turbine oils. and which is capable of imparting marked rust preventive qualities and a plurality of other advantageous properties to turbine oils when dissolved therein in small amounts. For instance, turbine oils containing varied in our composite improvement agents. For instance, they may vary, depending upon the particular amine salts and particular polyvalent metal salts used in preparing the same. Further, inblending the said salts into a homogeneous composite agent, varying amounts of mineral oil may be employed as a blending agent.

The following example illustrates one useful composite improvement agent and an advantageous method of preparing same within the scope of this invention; this example being a typical embodiment thereoi.

Example I.In preparing this composite improvement agent,'the procedure was as follows:

Into a suitable kettle, equipped with means for heating, cooling, and agitating the charge, there were charged 2,000 pounds of the dodecyl amine salt of 3 -methyl-butyl,Z-ethyl-hexyl phosphoric acid. Next, 2,000 pounds of the di-cyclohexyl amine salt of 3-methyl-butyl, z-ethyl-hexyl phosphoric acid were gradually added with stirring. Then, while continuing the stirring, this .mixture of liquid amine salts was heated to F. to form a uniform blend thereof. Then, 6,000 pounds of a hot solution of the substantially neutral'calcium salt of N-dodecyl phthalamidic solution of said calcium salt contained the said salt and oil in a ratio of 1:3 by weight. Finally, this mixture, containing said calcium saltand amine salts admixed with a minor amount of oil,

was further heated and stirred until a uniform, homogeneous blend 'was obtained. After a homogeneous blend had been obtained, the composite improvement agent was cooled to Ingredient g gfgg Dodecyl amine salt Di-cyclohexyl amine salt Calcium sal Oil Total 100 The above composite agent may be incorporated in any suitable mineral turbine oil in producing improved,superior turbine oils in accordance with this invention.

For instance, by incorporating from 0.16 to 16.7 pounds of the above composite agent in 1,000 pounds of turbine oil, superior anti-rust turbine oils can be readily obtained. The improved turbine oils so prepared contain from 0.0033 to 0.3333 per cent of each of the said salts; the total amount of said salts in the turbine oil being 0.01 to 1.0 per cent by weight on the oil; a marked improvement in anti-rust qualities and other properties being greatly in excess of-that obtainable with the corresponding amine of each of these salts involved. That is, the outstanding improvements so obtained are due to the general correlated action of the several salts present in our composite agent. i e

The outstanding improvements obtained by the present invention are illustrated in the following-example, which is typical of our improved turbine oils and our simple method of making the same.

Example H.In this example, a superior, improved turbine oil was prepared from a commercial turbine oil having a viscosity of 150 seconds, SUV at 100 F. and the -other properties set forth post.

In doing so, 66.7 pounds of theqcomposite improved agent obtained in Example I, ante, were mixed with 100,000 pounds of the commercial turbine oil, and the mixture agitated by air blowing until the composite agent had dissolved in the turbine oil and a homogeneous blend was ob-' tained.

, The properties of said commercial turbine oil and the improved turbine oil prepared therefrom as above, were as follows:

Uninhibited Inhibited oil oil Gravity API v mgi' 32.7 32.7 345 344 100 F..- 152. 9 152. 6 130 F..- 87.4: 87 2 210 43.8

o is a as Fire, 60, 455 96 Pour, "F +5 +5 Color, NPA 1. 25 l. 26 Carbon residue, percent Trace Trace Copper stri test, 212 F., 3 hr Passes Passes Neutralizat on N 0-. 0. 01 0. 02 e No., mod; 11811118 7. 1 7. 4

As shown by the above tabulation of properties, the incorporation of this improvement agent in the commercial turbine oil, in the amounts necessary to impart marked rust preventive qualisees ties thereto, did not substantially change any of the above properties thereof.

However, the markedly improved rust-preventive qualities of the improved oil so obtained is clearly shown by the results obtained when our improved turbine oil was subjected to the following standard corrosion test. tained in such'test were as follows:

mercial turbine oils, it successfully passed all of them, even the most drastic ones.

For instance, this improved turbine oil is very resistant to emulsification. Further, when emulsions are formed they readily break. This is clearly shown by the data obtained in standard emulsion tests; the results obtained being as follows:

Uninhibited Inhibited oil oil Emulsion test; F.:

Method 320.l3, Gov't Distilled water 40-40-0 (1) 40-40-0 (l0) 1?, salt solution 40400 (1) 40-40-0 (8) caustic soda solution. 40-400 (1) 40-40-0 (7) Emulsion test, 180 F.:

Method 320.13, Govt- Distilled water 40-40-0 (1) 4040-() (4) 1 salt solution 40-40-41 (1) 40-40-0 (3) caustic soda solution... 40-40-0 1) 40-40-0 (5) Uninhibited Inhibited oil oil Falex wear test:

500 lb. gauge load, 15 min. wear,

No. oi teeth 0 0 Gauge load at seizure, lb 750 l,

Also, in addition to their excellent lubricating qualities, our improved turbine oils are markedly resistant to oxidation and deterioration.

In other words, a plurality of advantageous properties can be imparted to turbine oils by incorporating our new composite improvement asent therein.

The data obasoacu Likewise, similar improvements can be obtained by incorporating our composite improvement agent in other commercial grades of turbine oils. For instance, in Example 11 ante, other commercial turbine oils having viscosities ranging from 150 to 600 seconds, SUV at 100 F., can

be employed and similarly improved,

The following example illustrates the preparationof another such improved turbine oil, prepared with the composite improvement agent disclosed in Example I ante, in accordance with the present invention.

Example III.In this example, another superior, improved turbine oil was prepared from a commercial turbine oil having a viscosity of 430 seconds, SUV at 100 F. and the other properties set forth post. r

In doing so, 167. pounds of the composite improvement agent obtained in Example I ante were mixed with'100,000 pounds of the commercial turbine oil, and the mixture agitated by air blowing until the composite improvement agent had dissolved in the oil and a homogeneous blend was obtained. .The properties of said commercial turbine oil and the improved turbine oil prepared therefrom, as above, were as follows:

Uninhibited Inhibited oil oil Gravity, API 28. 2 28. 1 Viscosity SUV:

100 1 42s 42s 210 F 58. 57. 3 Color, NPA 2. 75 2. 76 Neutralization No 0. 02 0. 08

As shown by the above tabulation of properties, the incorporation of such a very small amount of our new composite improvement agent in the turbine oil did not substantially change any of these ordinaryw physical properties. However, this small amount of composite agent did markedly. improve the rust-preventative qualities of the turbine oil, as clearly shown by the data obtained in standard corrosion tests, as follows:

Uninhibited Inhibited oil oil Corrosion test, ASTM D Distilled water 10%; 140

steel strip:

Appeal-an Area rusted, per cent Corrosion test, method 412, Gulf:

Distilled water; 122 F., 12 days;

steel strip:

Appearance Area rusted, per cent F., 48 hr.;

cs Bright.

Bright. 0.

In other words, the improved turbine oil ob- I tained in Example 111 also had a plurality of advantageous properties, as did the other improved turbine oils shown in Example II ante.

That-is, Examples 1, II, and 1H ante are typical embodiments of the. present invention. Of course, in the commercial practice thereof, various other embodiments thereof may be employed.

In general, our composite improvement agents, comprising a blended mixture of polyvalent metal salts of N-alkyl phthalamidic acids and amine salts of 3-methyl-butyl,.Z-ethyI-hexyl phosphoric acid with secondary cyclohexyl' amines and priv mary fatty amines, respectively, may be employed in preparing a wide variety of improved mineral oil compositions, as well as improved turbine oils. In preparing such improved mineral oil compositions, various blends ofthe said salts may be employed within the scope of this invention.

In particular, we have found it advantageous to employ composite improvement agents comprising homogeneous, blended mixtures of the said salts in certain proportions, as follows:

Rust inhibitor salt fig i g Primary my amine salt of 3-methyl-butyl, 2-ethyl- 45 to 0 bexyl phosphoric acid. Secondary cyclohexyl amine salt of 3-methyl-butyl, 2- 45 to 10 ethyl-beryl phosphoric acid. Polyvalent metal salt of N-alkyl substituted phthala- 10 to 45 midic acid. Mineraloil.-...; 0to400 In preparing our new composite improvement agents, using said salts in the. proportions given above, we have found it advantageous to employ the particular salts given in Example I ante.

In particular, the di-cyclohexyl amine salt of 3-methyl-butyl, 2-ethyl-hexyl phosphoric acid, itself, is an advantageous rust inhibitor. This amine, salt and methods of making the same are,

. butyl, 2-ethyl-hexyl phosphoric acid is also a good rust inhibitor, as shown in our companion application Serial No. 583,650, filed March 19, 1945, now U. S. Patent No. 2,387,537. In that application, we have described methods of making oilsoluble, amine salts from said acid and primary fatty amines containing 8 to 18carbon atoms.

As a class, the primary fatty amine salts thereof are useful rust inhibitors, as described in that application; Any of the primary fatty amine salts or rust inhibitors there disclosed may be employed in the practice of the present invention. In particular, the fatty amine salts of 3-methylbutyl, 2-ethyl-hexyl phosphoric acid, with primary fatty amines having the formula H2NCH2(CH2) -CI-Ia whereinnrepresents. a number between 8 and 18, are useful and advantageous in preparing our composite improvement agents.

In turn, our said application Serial No. 538,650

is a continuation-inmart of our prior application Serial No. 420,438, filed November 25, 1941, now U. S. Patent No. 2,378,442, wherein we have described and claimed improved mineral oil compositions containing primary fatty amine salts .of 3-methyl-butyl, 2-ethyl-hexyl phosphoric acid as a rust inhibitor.

Further, the neutral calcium salt of N-dodecyl phthalamidic acid, employed in Example I ante,

is itself an excellent improvement agent for min--,

eral oils. For instance, as disclosed in our prior application Serial No.- 516,968, flied January 4,. 1942, now U. 8. Patent No. 2,378,442, improved mineral oil compositions containing said calcium salt alone have improved anti-rust qualities.

Furthenas described in that application, a wide variety of oil-soluble improvement agents or calcium salts of this type can be readily prepared from lime, phthalic anhydride, and primary alkyl amines by the methods described therein. Indeed, the oil solution of the calcium salt employed in Example I- ante was obtained by the method described m Example 11 of said Patent No 2,378,- 442. Also, other oil soluble polyvalent metal salts of N-alkyl phthalamidic acids can be prepared by such methods, as described in our said prior application. The various oil-soluble, rust-preventive compounds or polyvalent metals described in that application may be employed in the prac- I tice of the present invention,

Indeed, in the generic practice of the present invention, we may broadlyemploy oil-solvent polyvalent metal salts of N-alkyl substituted phthalamidic acids; such metal salts being excellent rust-preventive compounds and readily soluble in mineral oils and compatible with the amine salts employed in making our composite improvement agents. For the present purposes,

we find that the salts of divalent metals having the following formula are particularly advantaseous:

R-N-H wherein M representsa divalent metal and It represents an alkyl group containinga to 18 carbon atoms. However, other polyvalent metal salts of such N-alkyl substituted phthalamidic acids are also useful in certain embodiments of our invention, such as the substantially neutral aluminum salts thereof disclosed in our prior copending application Serial No. 566,402, filed December 2, 1944, now U. S. Patent No. 2,378,443; thatapplidation being a continuation-in-part of our earlier application Serial No. 516,968 mentioned ante.

" In particular, the present invention is directed to ,a new, composite improvement agent for turprising a mineral lubricating oil containing amounts suflicient to retard corrosion o metal of a neutral calcium salt of N-dodecyl ortho phthalamidic acid, of the di-cyclohexyl amine salt of 3-methyl-butyl, 2-ethyl-hexyl phosphoric acid and the primary dodecyl amine salt of 3- 'methyl-butyl, 2-ethyl-hexyl phosphoric aciddissolved therein.

' 5. The improved turbine oil of claim 4 where-- in said mineral oil contains 0.0033 to 0.3333 per cent by weight of the said calcium salt, 0.0033 to 0.3333 per cent by weight of said di-cyclohegyl amine salt and 0.0033 to 0.3333 per cent of dodecyl amine salt dissolved therein.

6. As new compositions of matter, useful as improvement agents for turbine oils and other mineral oil compositions, the oil-soluble, composite improvement agents comprising a homogeneous blended mixture of a polyvalent metal salt of an N-alkyl substituted phthalamidic acid and addition salts of. 3-methyl-butyl, 2- ethyl-hexyl phosphoric acid with secondary cyclohexyl amines and primary fatty amines, re-

spectively, said composite improvement agent being capable of imparting marked anti-rust qualities and resistance to emulsiflcatlon toturbine oils when dissolved therein in small amounts.

'7. The composite improvement agents of claim 6 wherein said polyvalent metal salt is a neutral calcium salt of N-dodecyl ortho phth'alamidic acid.

8. The composite improvement agents of claim mary dodecyl amine salt of 3-methyl-butyl, 2-

ethyl-hexyl phosphoric acid. I

10. The composite improvement agents of claim 6 wherein the blended mixture of said salts comprises 10 to parts by weight of said polyvalent metal salt, 45 to 10 parts by weight of said secondary cyclohexylamine salt, 45 to 10 parts by weight of said primary fatty amine salt and 0 to 400 parts by weight of mineral oil.

11. As an oil-soluble, composite improvemen agent for turbine oils capable of imparting antihomogeneous blended mixture of a polyvalent metal salt of N-alk'yl phthalamidic acid and amine addition salts of 3-methyl-butyl, 2-ethylhexyl phosphoric acid with primary fatty amines 3. The improved turbine oil of claim 1 wherein Y said mineral 011 contains from 0.01 to 1.0 percent by weight of said composite improvement agent dissolved therein, said improved turbine oil hav ing outstanding anti-rust properties. 4. An improved anti-rust turbine oil comrust properties thereto, the composite improvement agent comprising a homogeneous blended mixture containing 20 parts by weight of the diprimary dodecyl amin salt of 3-methyl-butyl, 2-

ethyl-hexyl phosphoric acid, 20 parts by Weight of a neutral calcium salt of N-dodecyl phthalamidic acid and '40 parts by weight of mineral transom a. swan. TROY-1. 0mm 7 some a. 9mm.