United States Patent (19) 11 Patent Number: 4,487,658 Ciuti 45 Date of Patent: Dec. 11, 1984

3,234,131 2/1966 Morway ...... 252/40.5

(54) AQUEOUS NEUTRALIZING AND LUBRICATING COMPOSITION FOR 3,374, 171 3/1968 Davis et al. ... 252A49.3 X DESEL ENGINES 3,791,971 2/1974 Lowe ...... 252A33.4 3,983,044 9/1976 Felton, Jr...... 252A49.3 X (75) Inventor: Brunello Ciuti, S.Donato Milanese, 4,149,983 4/1979 Grier et al...... 252A9.3 X Italy 4, 152,915 5/1979 Bussi et al...... 252/49.3 X 73) Assignee: Agip Petroli S.p.A, Rome, Italy 4,243,537 1/1981 Knepp et al...... , 252/49.3 OTHER PUBLICATIONS 21 Appl. No.: 528,526 Kirk-Othmer, "Ency. of Chem. Tech.'', vol. 10, pp. 22 Filed: Sep. 1, 1983 641-643, 649-651, 654, 655 and 657-659, 1966. Serov, V. A. et al., "Prop. of Certain Polyalkylene Related U.S. Application Data Glycols for Use in Syn. LCF's' Chem. & Tech. of Fuels 63) Continuation of Ser. No. 327,687, Dec. 4, 1981, aban and Oils (Russian), vol. 12, Nos. 1-2, 1/76. doned. Primary Examiner-Andrew Metz (30) Foreign Application Priority Data Attorney, Agent, or Firm-Hedman, Gibson, Costigan & Dec. 23, 1980 IT Italy ...... 26903 AA8O Hoare

51) Int. Cl. ... ------C1OM 3/34 57 ABSTRACT 52) U.S. C...... 252/33.2; 252/33.4; Aqueous-base compositions are disclosed for the lubri 252/34.7; 252/49.3 cation of the piston and the cylinder liner of Diesel 58 Field of Search ...... 252/33.2, 33.4, 34.7, engines, particularly large engines, said compositions 252/38, 40.5, 49.3, 52 A essentially comprising one or more water soluble anti (56) References Cited acid neutralizers, a water soluble organic fluid having a U.S. PATENT DOCUMENTS high boiling point temperature and one or more water 800,895 9/1956 Socony ...... 252/33.4 soluble detergents. 1,093,959 6/1966 Peabody ...... 252/34.7 Tests on large engines have shown that it is possible to 2,944,02 7/1960 Ulzheimer et al...... 252A33.4 lubricate the piston and the cylinder liner with an aque 2,944,022 7/1960 Ulzheimer et al...... 252/33.4 ous base fluid without using any crude petroleum deriv 2,944,023 7/1960 Kolarik ...... 252A33.4 ative. 3,121,689 2/964 Davis ...... X 252A.O.5 3,125,521 3/1964 Detweiler et al...... 252/33.2 X 3,230,169 1/1966 Morway et al...... 252/40.5 X 16 Claims, No Drawings 4,487,658 1. 2 composed of an aqueous solution which is substantially AQUEOUS NEUTRALIZING AND LUBRICATING stable in the temperature range from -10° C. to -- 70 COMPOSITION FOR DESEL ENGINES C. and which permits that the acidic products deriving from the combustion may rapidly be neutralized, said This is a continuation of application Ser. No. 327,687 5 composition having quite surprisingly proven to have a filed Dec. 4, 1981 and now abandoned. lubricating efficiency which is not certainly lower than This invention relates to a neutralizing and lubricat that of the corresponding oil-based compositions. An ing composition and its use in Diesel engines. More object of the present invention is to provide an aqueous particularly, the present invention relates to a neutraliz composition to be obtained by dissolving in water from ing and lubricating composition which is not based on O 2% to 20% of one or more anti-acid neutralizing sub the use of the conventional lubricating fluids, and in stances and from 2% to 20% of one or more substances which an aqueous component predominates. composed of a water soluble organic fluid having a high It is known that in the large 2-stroke Diesel engines, boiling point temperature, and/or from 0.5% to 5% of the lubrication system is twofold: in these engines, actu one or more substances having a detergent action. ally, there is a normal closed loop system which is com 15 Examples of anti-acid neutralizing substances are the posed by a sump and a set of tubings through which the salts of alkali metals and/or alkaline earth metals, of lubricant is dispensed to all the points to be lubricated, ammonium, and of monoethanolamine, diethanolamine whereas, for other spots, such as for the inner top por and triethanolamine, such salts being preferably se tion of the piston, the fluid is conveyed also to display a lected from among the corresponding salts of the acetic, typically cooling action. 20 formic and carbonic acids, or morpholine combined For the latter type of circuit it has been usual to adopt with the formic, acetic, propionic, lactic, chloroacetic, oily fluids which contained specific oil-soluble additives thioacetic, butyric, glycerophosphoric and oxalic acids. such as, for example, the rust-preventing additives, the Examples of water soluble organic substances having wear-reducing additives, antioxidant and, seldom a high boiling point temperature are ethylene glycol, enough, also neutralizing agents, the more so that in this 25 propylene glycol, polyethylene glycol, polypropylene kind of lubricants the presence of the latter additive is glycol and a few esters, be they water soluble or not. not of primary importance: as a matter of fact, in the Lastly, examples of substances having a detergent closed-loop system, the fluid is active only on those action are the oxyethylated fatty acids, oxyethylated movable component parts of the engine which are com sorbitol oleate, polyoxylated glycols, ammonium diode prised between the piston area and the sump area, 30 cylbenzene sulphonate, alkyldimethylammonium chlo which are not exposed to the corrosion of the acidic ride, trimethylamine lauryl sulphate, diethanolamine products originated by the combustion. It is known, in lauryl sulphate and monoethanolamine lauryl sulphate. fact, that, to reduce their running costs, these engines The instant composition may be supplemented, more are fed with heavy fuels containing a high percentage of over, by the additives having an action like that of the sulphur (up to 4% and over) and it is apparent that, 35. additives used in the lubrication of internal combustion under these conditions, the acidic combustion products, engine, namely: mainly sulphuric acid, must be neutralized so as not to (1) from 0.5% to 5% of substances having a wear allow enough time to corrode the metal of the cylinder reducing and jam-preventing action such as dibenzylbi liners with which they come into contacts. sulphide, dibenzylpolysulphide, thiourea and ammo In addition to the closed loop, there is, in the large nium molybdate, 2-stroke Diesel engines, another open loop lubrication (2) from 0.5% to 5% of substances having a rust-pre circuit which is intended for the lubrication of the liner venting action such as ammonium nitrite, sodium nitrite, and-piston area: the lubricant to be employed for said boramide and alkali metal bichromates, circuit is directly dispensed onto the liner via an array (3) from 0.5% to 5% of anticorrosive and passivating of bores ("channels') and special dispensing channels 45 substances for nonferrous metals, such as benzotriazole. ("spider marks') and has, in addition to the lubrication The procedure for obtaining the solutions according function, the task of neutralizing the condensed acidic to the present invention do not require any special expe residue produced by the combustion. dient, with the exception of causing the dissolution of A lubricant intended for said circuit, therefore, must the products enumerated above to take place within a have quite particular properties and composition and its 50 temperature range of from -40°C. to +60 C., prefera anti-acid neutralizing action plays a leading role. bly, but not compulsorily, the solutions are produced by At present, the neutralizing function displayed by the first dissolving the antiacid neutralizing substance in conventional lubricants which contain the usual anti about one half of the water, whereafter, once the disso acid additives is characterized by the defect that it is lution has been obtained, the substance having a deter always comparatively toned down because the neutral 55 gent action is added and, subsequently, all the other ization reaction takes place in a prevailingly oily envi components which had previously been dissolved in the ronment, or, at least, in an environment in which the second half of the water volume. only water which is present is that produced in the The solutions are clear and have a colour which tends combustion. Consequently, in the case of the lubrication to brown-yellow and, as outlined above, they are stable of the liner-piston couple in the large Diesel engines, the 60 within the temperature range of from -10° C. to -70 result is that, during the very short time of stay of the C.: this is a property which enables such solutions to be portions of anti-acid lubricant which are progressively stored for long periods of time. Examples of such solu dispensed on the liner, very often the ideal conditions tions, to be used for the lubrication of the liner-piston for neutralizing the entire acidity which is present are couple of 2-stroke Diesel engines may be as follows: not satisfied. 65 (A) Calcium acetate: 8%; polyethylene glycol: 7%; A lubricating and neutralizing composition has now ammonium dodecylbenzene sulphonate: 2%; dibenzyl been found, which is adapted to the lubrication of the disulphide: 1%; boramide: 2%, water 80%, all on a liner-piston couple of 2-stroke Diesel engines, and is weight basis. 4,487,658 3 (B) Magnesium acetate: 6%; polypropylene glycoli: 7%; diethanolamine lauryl sulphate: 3%; thiourea: 2%; Engine specifications: ammonium molybdate: 1%; water: 81%. No of cylinders (C) Calcium acetate: 5%; magnesium acetate: 3%; Bore 80 mm polyethylene glycol: 9%; oxyethylated sorbitol oleate: Stroke Onn 3%; ammonium molybdate: 3%; boramide: 2%; water: Displacement 553 cm3 Rotation speed 1500 rpm 75%. Compression ratio 20: (D) Acetylmorpholine: 10%; polyethylene glycol: Nominal power 5 HP 8%; monoethanolamine lauryl sulfate: 2%; thiourea: Operation conditions: 2%; ammonium nitrite: 2%; benzotriazole: 1%; water: O Fuel consumption 1.088 kg an hour 75%. Outlet temperature of collant 85 C. Temperature of lubricant in 55° C. (E) Magnesium formate: 7%; ethylene glycol: 9%; Sump alkyldimethylammonium chlorde: 3%; dibenzylpolysul Pressure of lubrication 2.5 kg/cm phide: 3%; potassium bichromate: 2%; benzotriazole: (comp. A) 1%; water: 75%. 15 Lubricant charge 3.4 kg (F) Sodium acetate: 4.5%; sodium carbonate: 3%; ethylene glycol: 10%; diethanolaminelauryl sulphate: On the engine in question a 22-hour test has been 3%; thiourea: 2%; boramide: 2.5%; water: 75%. carried out under standard conditions. A fact which deserves careful consideration is that On completion of the test, the conditions of the sev the indication of 2-stroke Diesel engines having sepa 20 eral component parts of the engine were found to be rate lubrication circuits should be regarded as a mere normal and more particularly, the piston rings appeared example of the invention and does not imply any limita to be free and had no incrustations; also the component tion, the more so that the first practical test for assaying parts which were contacted by the fluid under test were a solution such as suggested above has been performed 25 under normal conditions and no dense residues have by using a small single-cylinder engine, Petter AVl, been found, nor in such an amount as to compromise the which has a single sump lubrication system. With this engine operation. test, very satisfactory results have been obtained, both I claim: from the point of view of the lubrication of the piston 1. A neutralizing and lubricating composition which liner couple, and lubrication of the sump area. This 30 comprises: result confirms, in quite reliable a manner, that also in (a) from 2 to 20% on a weight basis of an antacid certain parts of the engine the lubrication can be made substance selected from the group consisting of without using petroleum-based lubricating fluids and magnesium acetate, calcium acetate, acetylmor non-petroleum based fluids having a high viscosity. pholine, magnesium formate, sodium acetate, so A further confirmation has been received from all a 35 dium carbonate and mixtures thereof; set of tests carried out with the compositions according (b) from 2 to 20% on a weight basis of a water soluble organic substance selected from the group consist to the present invention, which are reported hereafter ing of ethylene glycol, propylene glycol, polyeth by way of example only and without limitations. ylene glycol and polypropylene glycol; EXAMPLE 1. 40 (c) from 0.5% to 5% on a weight basis of a capillary Composition A has been used for the lubrication of active agent selected from the group consisting of the liner-piston couple of the two Diesel engines used oxyethylated sorbitol oleate, ammonium dodecyl for propelling the motor-tanker “Cortemaggiore' hav benzene sulfonate, diethanolamine lauryl sulfate, ing a 18,000 tons carrying capacity (main engine is monoethanolamine lauryl sulfate and alkyldine 45 thylammonium chloride; and FIAT 7510, suction type, 8,050 HP, 125 rpm) and for (d) a major amount of water. the motor tanker AGIP TRIESTE, 50,000 tons d.w. 2. A composition as defined in claim 1 which com (main engine is FIAT 989B, supercharged, 18,900 HP, prises: 125 rpm). as component (a), 8% by weight of calcium acetate; On the engines of the two motor tankers assay tests 50 as component (b), 7% by weight of polyethylene have been carried out, which lasted a few hundreds glycol; hours in order to check the overall behaviour of the as component (c), 2% by weight of ammonium dode fluids in question. cylbenzene: The rate of flow of the dispensed fluid has been the and further comprising 2% by weight of boramide; Same as used for the conventional petroleum-based lu 55 and bricants about 0.8 grams per horsepower and per hour. 1% dibenzoyl disulphide; and On completion of the tests, the readings which have as component (d), 80% by weight of water. been taken have clearly shown that the lubricant com 3. A composition as defined in claim 1 which com positions of the invention fulfil the requirements of prises: those types of engines. 60 a component (a), 6% by weight of magnesium ace What has been noted, above all, is the excellent de tate; gree of cleanliness, the complete freedom of the piston as component (b), 7% by weight of polypropylene rings and the tendency of having wear values for the glycol; rings confined within the standard specifications. as component (c), 3% by weight of diethanolamine 65 lauryl sulfate; EXAMPLE 2 and further comprising 2% by weight of thiourea; Data relating to the test made on the Petter AVJ and engine with the fluid having the composition A, 1% by weight of ammonium moybdate; and 4,487,658 5 6 as component (d), 81% by weight of water. 3% by weight of sodium carbonate; 4. A composition as defined by claim 1 which con as component (b), 10% by weight of ethylene glycol; prises: as component (c), 3% by weight of diethanolamine as component (a), 5% by weight of calcium acetate; lauryl sulphate, and further comprising, and 2% by weight of thiourea and 3% by weight of magnesium acetate; 2.5% by weight of boramide; and as component (b), 9% by weight of polyethylene as component (d), 75% by weight of water. glycol; 8. A composition as defined in claim 1 which further as component (c), 3% by weight of oxyethylated comprises: O (i.) from 0.5 to 5% by weight of a substance having a sorbitol oleate; and further comprising wear-reducing action; 3% by weight of ammonium molybdate; and (ii) from 0.5 to 5% by weight of a substance havin 2% by weight of boramide; and a rust-preventing action; and as component (d), 75% by weight of water. (iii.) from 0.5 to 5% by weight of a corrosion-pre 5. A composition as defined by claim 1 which com 15 venting and passivating substance for nonferrous prises: metals. as component (a), 10% by weight of acetylmorpho 9. A composition as defined in claim 1 which further line; comprises dibenzoylpolysulphide as a substance having as component (b), 8% by weight of polyethylene a wear-reducing action. glycol; 20 10. A composition as defined in claim 1 which further as component (c), 2% by weight of monoethanoloa comprises thiourea as a substance having a wear-reduc mine lauryl sulfate; ing action. and further comprising 2% by weight of thiourea, 11. A composition as defined in claim 1 which further 2% by weight of ammonium nitrite and comprises ammonium molybdate as a substance having 1% by weight of benzotriazole; and 25 a wear-reducing action. as component (d), 75% by weight of water. 12. A composition as defined in claim 8 which further 6. A composition as defined by claim 1 which com comprises ammonium nitrite as a substance having a prises: rust-preventing action. as component (a), 7% by weight of magnesium for 13. A composition as defined in claim 8 which further mate; 30 comprises sodium nitrite as a substance having a rust as component (b), 9% by weight of ethylene glycol; preventing action. as component (c), 3% by weight of alkyldimethylam 14. A composition as defined in claim 8 which further monium chloride; and further comprising comprises boramide as a substance having a rust-pre 3% by weight of dibenzoylpolysulphide, venting action. 2% by weight of potassium bichromate and 35 15. A composition as defined in claim 8 which further 1% by weight of benzotriazole; and comprises an alkali metal bichromate as a substance as component (d), 75% by weight of water. having a rust-preventing action. - 7. A composition as defined by claim 1 which com 16. A composition as defined in claim 8 which further prises: comprises benzotriazole as a corrosion-preventing and passivating substance for nonferrous metals. a component (a), 4.5% by weight of sodium acetate; sk ck s: sk sk and

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