NO152058B - LOCK WITH ELECTROMAGNETIC SWITCHING OF THE FALL PIPE - Google Patents

Description

Lubricating oil mixture.

The present invention relates to lubricating mixtures and a combination of additives for this.

It is known that a number of substances can be dispersed in lubricating oils to give them the desired improvements. Calcium acetate is one such substance. It is particularly advantageous with regard to load capacity and anti-wear properties. Because of its acid-neutralizing ability, calcium acetate is a particularly desirable additive for lubricating oils, used in engines fueled with high-sulfur fuel, such as marine diesel engines.

However, simple dispersions of calcium acetate in lubricating oil are unstable, as the calcium acetate is washed out during transport and/or storage of the oil mixture. In order to overcome this problem and, as far as possible, obtain the advantages provided by calcium acetate, particularly in liquid lubricants such as marine diesel oil, it has been the practice to use emulsion type oils, i.e. those formed by emulsifying a water solution of calcium acetate with lubricating oil. However, these emulsion oils have not been completely satisfactory. Because of their water content, they tend to increase the corrosion problem, and they are unstable under the various conditions encountered during storage and use. For example high temperatures, which occur during storage in engine rooms in ships, tend to break down the emulsion. On the other hand, under the low temperatures that often occur in cold climates, the aqueous phase can be frozen, so that the emulsion is destroyed.

Today, large marine diesel engines are operated under great stress, and thus great demands are placed on the lubricating oils used. In particular, clogging of the cylinder outlet port is a serious problem. As more of the ports become clogged, the lubrication effect is reduced and eventually this results in one or more of the engine parts, such as piston rings, failing. Not only the degree of clogging of the ports is of importance, but also the nature of the deposits formed by the splitting or degradation of the oil used to lubricate the cylinders, and of one or more of the additives generally present in the oil. Sticky, varnish-like deposits are difficult to remove from the engine, and cause wear on moving engine parts, such as pistons, while soft consistency grease-like deposits are not a disadvantage.

It will therefore be understood that stable dispersions of calcium acetate in lubricating oils would be of considerable value, as such a "single phase" oil does not have the previously mentioned disadvantages of emulsion oils. Of further value would be such stable dispersions which are reinforced so that exhaust deposits and wear on engine parts as described above are reduced to a minimum. The invention relates to such stable dispersions of calcium acetate and lubricating mixtures containing this.

It is therefore an aim of the present invention to provide lubricating mixtures which are suitable for effective lubrication of machine parts, which are operated under strict conditions. A particular purpose of the invention is to provide lubricating mixtures which are effective in large marine diesel engines, without the formation of any significant cylinder-exhaust deposits and minimum wear on engine parts. Another purpose is to obtain such mixtures which are also characterized by load capacity (ability to withstand extreme pressures) and capacity to neutralize sulphurous acids, which are formed during the combustion of fuel with a high sulfur content in diesel engines. A further purpose of the invention is to provide mineral oil concentrates, which contain particularly effective combinations of additives for use in lubricating mixtures. A further purpose of the invention is to provide new mixtures, comprising combinations of additives which can be incorporated into lubricating oils, in order to increase their lubricating value. Other purposes will be apparent from the following description.

In a study to develop a single-phase lubricating oil, which can be used in large marine diesel engines, with only little exhaust deposit formation while also providing excellent load characteristics, and the desired neutralization of sulfur-containing acids formed during the combustion of high-sulfur fuel , it has surprisingly been found that extremely low wear of machine parts is achieved in addition to achieving the purpose of the study, when special combinations of additives are used which include calcium acetate in lubricating oils. The new oil mixtures thus found, and which form the basis of the present invention, comprise: (a) a main quantity of a mineral lubricating oil, (b) from 1 to 20 wt. of the mixture of

calcium acetate,

(c) from 0.01 to 3 wt. of the mixture of N-acyl-substituted sarcosine compounds of formula

wherein R means an aliphatic hydrocarbon radical having from 8 to 24 carbon atoms, (d) from 0.1 to 10 wt. of the mixture

of an oil-soluble metal sulfonate, and (e) from 0.1 to 5 wt. of the mixture of an oil-soluble phosphorus and sulphurous

reaction product obtained by reaction at a temperature between 100 and 160°C, of essentially 1 mole of a phosphorus sulphide and 4 moles of a material selected from the group consisting of a dicyclic terpene and an essential oil, consisting mainly of a dicyclic terpene.

The invention also relates to oil concentrates which contain the additives identified by (b) to (e) above and new substance mixtures comprising combinations of the aforementioned additives (b) to (e).

The ratio of the additives is important to achieve the unexpected and unusual combinations of the desired results. In this connection, calcium acetate (b) must be present in the oil mixture in concentrations of at least 1% by weight, as the mixtures would otherwise have insufficient load capacity (extreme pressure characteristics). In addition, the maximum concentration of calcium acetate in the oil mixtures must not exceed 20% by weight. to avoid excessively high viscosity of the mixtures and the formation of consistency fat or gel. Preferred concentrations for acetate are from 2 to 8 wt. With regard to the sarcosinphor compound (c), the concentration can vary between 0.1 to 3 wt.%, with a preferred approximate range of 0.1 to 1. In general, larger amounts of the sarcosinphor compound are used with larger amounts of calcium acetate, and less with less quantities of the latter. The metal sulphonate (d) concentration is in the range from 0.1 to 10% by weight. and preferably from 1 to 5. Here again the concentration of the sulphonate depends on the concentration of the acetate, e.g. larger amounts of sulfonate accompanied with larger amounts of acetate. The use of insufficient concentrations or an excess of sulphonate must be avoided, as inferior mixtures will otherwise be formed. That is, the dispersions can be unstable and show deposits or the viscosity control can be destroyed. The concentration of the reaction product(s) is regulated between 0.1 and 5% by weight. of the oil mixtures, and the preferred range is 1 to 3. Here again, insufficient reaction product leads to higher wear, and too high a concentration results in poor water resistance.

The total quantity of additives (b) to (e) in the oil mixture according to the present invention will therefore lie in the range from 1 to 35 wt. In marine diesel engine oils, particularly those operated with high sulfur fuels (1 to 5 percent sulfur), the total amount is generally at the higher end of the range, namely 15 to 25 percent. While oil blending for marine diesel engines is highlighted here, it should be understood that the new oil mixtures can be used to lubricate other equipment. For example oils intended for the lubrication of small two-stroke diesel engines, which run on fuel with a low sulfur content (up to 1 per cent), will contain a total amount of 1 to 6 per cent of additives (b) to (e).

As pointed out above, the invention also relates to oil concentrates. Thus, far less oil can be used with the combination of additives than in oil mixtures for use in an engine, than to form a concentrate, and the concentrate can then be diluted with additional oil to form the desired oil mixture. Concentrates are particularly desirable, as they can be produced in a refinery or related facility, and can then be shipped to other locations where such facilities are lacking, but where mixing equipment is available. Significant savings can thereby be achieved in terms of transport and equipment. Furthermore, mixtures of additives can be prepared, which are free of oil, and these mixtures can be transported to places where they can be incorporated into oil to form the desired oil mixtures. In the mixtures, the parts by weight of the individual additives are as follows:

It is to be understood that the amount of each additive, as stated above, is expressed on an oil-free basis unless otherwise stated.

Lubricating oils (a) as specified here can vary greatly in origin and characteristics. Representatives of these oils are night base, paraffin base, "Coastal" base and mixed mineral oils. Other hydrocarbon lubricants include lubricating oils derived from coal products and alkylene polymers, such as polymers of propylene, butylene, etc., and mixtures thereof. Synthetic oils other than those composed of hydrogen and carbon include: alkylene oxide polymers, dicarboxylic acid esters, liquid esters of phosphorus, polypropylene glycol, di-(2-ethylhexyl) sebasate, di-(2-ethylhexyl) adipate, trimethylolpropane tricaprylate and related esters of pentaeryltriol, neopentylglycol and the like. In general, hydrocarbon oils and synthetic carriers that can be used herein are characterized by a viscosity (U.S.) greater than 70 seconds at 38°C, preferably from 100 to 2000 seconds at 38°C. Particularly good for use in oil mixtures which are particularly suitable for large marine diesel engines are solvent-refined "Coastal" oils and mixtures thereof, with viscosities of 150-170 seconds at 38°C.

The amounts of lubricating oil or oil (a) in the oil mixtures are in the order of magnitude of: 65 to 99% by weight, and preferably 75 to 85. It follows that the concentrates of the oil according to the present invention will contain lower amounts of the oil or oils (a) , than the oil mixtures. In general, the oil concentrate rates will contain 30 to 60 wt. of oil.

The calcium acetate (b) above, which is used here, can be anhydrous or hydrated. The calcium acetate can either be dissolved or can be formed in situ in a suitable oil.

N-acyl-substituted sarcosines, (c) above, as used herein, are represented by the formula:

in which R means an aliphatic hydrocarbon radical having from 8 to 24 carbon atoms, and which can be either saturated or unsaturated. Typical examples are the following sarcosines:

N-pelargonyl

N-undecyloyl

N-lauroyl

N-myristoyl

N-palmitoyl

N-stearoyl

N-oleyl

N-linoleoyl

N-arachidoyl

N-behenoyl

N-hyenoyl.

Several N-acyl-substituted sarcosines are available commercially under the trade marks "Sarkosyl", e.g. "Sarkosyl-1" (lauroyl sarcosine), "Sarkosyl-0" (oleyl-sarcosine) and "Sarkosyl-S" (stearoyl-sarcosine).

Preferred for the mixtures according to the present invention is oleyl-sarcosine.

Everyone . oil-soluble metal sulfonates. (d) above, is covered by the present invention. The sulfonic acids used in the formation of the sulfonates include oil-soluble petroleum sulfonic acids and synthetic alkaryl sulfonic acids, especially those with higher molecular weights, i.e. from 300 to 800. These sulfonic acids can be produced by sulfonation of petroleum or synthetic alkyl aromatic compounds , such as alkyl-substituted benzenes or naphthalenes, in which the alkyl groups attached to the aromatic ring contain at least approx. 8 to approx. 24 or more carbon atoms. Specific synthetic sulphonic acids are e.g. octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, dioctylbenzenesulfonic acid, octadecylbenzenesulfonic acid, waxbenzenesulfonic acid and waxnaphthalenesulfonic acid.

All metals mentioned here are constituents of sulfonates. Most suitable are calcium, barium and magnesium. When the metal constituents are polyvalent, basic as well as neutral metal sulphonates can be formed, all serving the purpose of the present invention. Weakly basic calcium petroleum sulphonates are preferred.

The oil-soluble phosphorus- and sulfur-containing reaction products (e) in the foregoing are those obtained by reacting a dicyclic terpene with a phosphorus sulfide at a temperature above approx. 100°C. Any of several phosphorus sulfides can be used, such as P.,S(i (or PS3), P,^

(or P2S;!), P4S:t, P2S- (or P4SH)), P4S7, etc, when producing the aforementioned reaction products, and particularly preferred are such reaction products obtained from P2S5.

"Dicyclic terpenes" are defined here as such terpenes which are characterized by the presence of a double bond in the molecule, and which are comprised of two ring systems. Typical of such terpenes are pinene, camphene and fenchen. Within this particular framework are such substances which are mainly composed of one or more dicyclic terpenes, and representatives of such substances are essences or volatile oils which are mainly comprised of such as a terpene or terpenes, and an example is turpentine oil, whose main constituent is pinene . Preferred of the dicyclic terpene reaction participants are pinene and turpentine oil.

Accordingly, the preferred reaction products are those obtained from P,S5 and pinene and from P2S5 and oil of turpentine.

Further details of the reaction products (e) are given in ILS. Patent No. 2,416,281.

When producing oil mixtures according to the present invention, a stabilized dispersion of the calcium acetate is prepared separately, using sarcosine compound as stabilizer. This is achieved by intimate mixing of the various components, i.e. oil, calcium acetate and sarcosine, preferably in a Manton-Gau-lin homogeniser, operated at a pressure of approx. 70 to approx. 350 kg/cm^. The other ingredients including extra oil are then mixed if desired with stabilized dispersion at temperatures in the range from 20 to 100°C and preferably 90-100°C.

Examples which illustrate and which in no way limit the invention are given below. All parts are parts by weight in the examples unless otherwise stated.

Example 1.

Mineral oil, 57 parts, and calcium acetate, 40 parts, and oleoylsarcosine, 3 parts, were charged

in a fat kettle fitted with a paddle mixer, in the order indicated. The resulting mixture was heated with stirring to 138°C and held at this temperature for 20 minutes and cooled with continuous stirring to room temperature (about 25°C). It is then homogenized by passing once through a Manton-Gaulin homogenizer operated at a pressure of 210 kg/cm 2 . The formed, very stable dispersion of calcium acetate is referred to below as product 1.

The mineral oil used was a solvent-refined naphthenic (Coastal) oil, with a viscosity (U.S.) of 500 seconds at 38°C. Calcium acetate contained 6 percent water, i.e. approximately .2/3 mol of hydrate water.

Example 2.

• A mid-continent distillate with a Saybolt viscosity at 38°C of 95 was treated with oleum, and the sludge formed was settled and removed, and the oil layer was neutralized with a caustic soda solution. The sodium sulphonates thus formed were recovered by adding ethyl alcohol, and the alcohol layer formed was separated and then the alcohol was evaporated. This left a mixture of oil and sodium sulphonate. This mixture was then reacted with

an aqueous solution of barium chlorides. After separation of the oil layer and drying, the formed oil solution of barium petroleum sulphonate (product 2) contained 6.9 per cent barium and 2.5 per cent sulphur.

Example 3.

A mineral oil solution of a weakly basic potash petroleum sulphonate (about 40 per cent active ingredient), indicated above as product 3, was used. This material had the following properties:

Example 4.

800 parts by weight of pine and an equal amount by weight of an engine oil (Saybolt Universal viscosity in 45 seconds at 99° C.) were heated to 105° C. with stirring. 326 parts of P2S5 (a ratio of 4 moles of pinene to 1 mole of P2Sr,) was slowly added as the temperature rose to 115°C due to! of exothermic reaction. The mixture was then heated and the resulting mixture was filtered. The filtrate, consisting of 1842! weight parts were then vacuum treated! at 5 mm pressure to a boiler temperature of; 150°C. The residue, consisting of 1693 parts by weight, was a clear viscous oil — product 4i

— containing 12.5 per cent sulfur and 5.1 per cent! phosphorus. IN

in

Example 5.

IN

A marine diesel engine: oil mixture was formed by using the products<1> of Examples 1, 3 and 4. The oil mixture! was composed of: parts Solvent refined

Coastal oil 55-60 S.U.S.

The oils and the various products were mixed intimately in a mixing tank at approx. 90°C for approx. 2 hours. A clear oil mixture was thus formed — product 5 — with the following properties:

Example 6.

Another diesel engine oil mixture was formed with the products of Examples 1, 3 and 4. The composition is given below:

All components were filled in a mixing tank, heated to approx. 82°C and was stirred thoroughly until a homogeneous mixture was obtained. The properties of the mixture — product 6 — are as follows:

Sample data.

Product 5 was subjected to various tests to determine its effectiveness as a cylinder lubricant for large marine diesel engines. It was tested on a strictly comparable basis with a widely used high grade commercial marine diesel oil containing carbonated basic calcium sulfonated alkylphenolate. The last oil is identified here as commercial oil A. Results of the different samples are given below.

Accelerated diesel engine test.

This is a powerful CFR diesel engine test. The engine is operated under such conditions as: fuel with a high sulfur content, sooty combustion and very high "blowby" level to accelerate the oil pollution by soot and by acidic "blow.by" gases. The tests were carried out with an SAE 40 grade oil. The engine used was a single-cylinder, four-stroke CFR engine, modified with a "Comet" Diesel head, bore 82.5 mm, displacement 610 ems, compression ratio 17:1, horsepower output -6, and crank- house oil 2500 milliliters plus 1000 ml for the filter.

Operating conditions for the sample include: i

break-in: 3 hours break-in with base oil and No. 2 fuel, filter disconnected during break-in. Oil changed and filter connected before the test.

(1) High "blowby" obtained by applying

four scraper compression rings and a ventilated oil ring.

At the beginning and end of each test, the cylinder was examined to determine if there was wear on the cylinder bore surface.

The results of the test carried out with different oils are set out in Table I below.

It is clear from the results shown in Table I that a significant improvement is achieved with product 5.

Radioactive piston ring wear dampener.

This allows measurement of piston ring wear in a relatively short period of time, as no disassembly of the engine is required for examination and wear measurement. Briefly, the procedure is as follows. The rings used are produced from a simple metal melt. They are activated to a level of approximately 2.5 millicuries per ring. Iron 59 is the prominent radioactive isotope produced.

The engine used is a "Bolnes" Type L Diesel engine. It is a two-cylinder, two-stroke, single-acting diesel engine equipped with a cross-head piston, which acts as a scavenger pump and with a "Brown-Boveri" exhaust gas turbocharger. The engine is equipped to burn light diesel fuel and heavy residual fuels. In the samples listed here, a residual fuel with a sulfur content of 3.75% was used. The cylinder bore was 19 cm and the stroke length 35 cm. Using special tools and equipment to protect against radiation, a radioactive piston ring was installed, as the top compression ring in No. 2 cylinder in the engine, where the highest pressure, temperature and wear occur.

During the operation of the engine, the radioactive iron worn from the piston ring is carried by the oil to the radiation detector which is activated by gamma radiation (from iron 59) from the rings in the circulating oil. The generated pulses are received by a meter and transferred to the number per minute (c.p.m.) which is again recorded as a graphic curve of c.p.m. in relation to time. The wear conditions can be converted to absolute wear in mg/time unit. To do this, a weighed part of a piston ring, which is irradiated at the same time as the test ring, is first converted into an oil-soluble salt such as iron naphthenate. An oil mixture of this salt is then circulated to the detector to determine the c.p.m./mg of iron present. A standard curve is drawn for the destruction of iron 59 based on a half-life of 46.3 days. By comparing c.p.m./mg for the sample oil and c.p.m./mg iron 59 in the iron-naphthenate mixture, a value for wear expressed in mg iron per minute for the sample oil. For comparison purposes, absolute wear values are generally converted to mg (of iron) per hour. The results are set out in Table II below.

As indicated, the rate of wear, which is obtained with product 5, is only approx. half the speed obtained with commercial oil A.

Sea trial.

Product 5 was also tested for an extended period of time in the cylinders of diesel engines on a commercial motor ship on a route between Europe and North America. This is a ship of 16,300 tonnes capacity equipped with a main diesel engine. The engine is a Fiat, 7-cylinder, 757S, 2-stroke, single-acting, supercharged, cross-head marine diesel. Operating conditions observed during regular recording were: Engine output horse power 5900-6900 speed, revolutions per minute 122-128 cylinder-port temperature, °C 285-310

exhaust-collector temperature, °C 310

cylinder feed rate kg/cylinder/hour, about 1

g/HK/hour, about 1

Product 5 was used to lubricate cylinders 3, 4 and 5 in one of the engines and commercial oil A was used in cylinders 6 and 7 in the same engine. The amount and type of exha ustport deposits formed were measured visually at the end of several voyages, totaling over 1450 hours. The test results are set out in Table III, below.

Another sea test for product 5, compared with commercial oil A in the same motor ship, is summarized in Table IV below, in which average exhaust port clogging is indicated.

The data set forth in Tables III and IV reveal a substantial superiority of Product 5 over Commercial Oil A. Port plugging is substantially reduced. This constitutes a main commercial advantage, as the "down time" for engine maintenance represents a loss of approx. 10,000 dollars per day, for shipowners and less port clogging naturally requires less lying time for cleaning.

In several other comparison tests in which determinations were made with regard to anti-scratch and load capacity and oxidation resistance at 163°C in

40 hours, product 5 was found to be significantly superior to commercial

oil A, and to other commercially available products.

It should be understood that additional additions

can also be present in the oil mixtures,

oil concentrates and additive combinations described here. For example can it be used

pour point depressants, viscosity index improvers, rust inhibitors, other cleaning agents, such as ashless

cleaning agents, antifoam agents, etc., in normal concentration. As a special illustration, a small amount may be used

(approx. 0.0004 parts by weight) of an anti-foam agent, "Dow Corning Fluid 200", a silicone mixture in product 5 to prevent foam formation.

Claims (8)

1. Lubricating oil mixture, characterized in that it comprises: (a) a main quantity of a mineral lubricating oil, (b) from 1 to 20, preferably 2 to 8 wt. of the mixture of calcium acetate, (c) from 0.01 to 3, preferably 0.1 to 1 wt. of the mixture of an N-acyl-substituted sarcosine compound of the formula wherein R means an aliphatic hydrocarbon radical from 8 to 24 carbon atoms, (d) from 0.1 to 10, preferably 1 to 5 wt. of the mixture of an oil-soluble metal sulfonate, and (e) from 0.1 to 5, preferably 2 to 3 wt. of the mixture of an oil-soluble phosphorus and sulfur-containing reaction product, obtained by reaction at a temperature between 100 and 160°C, of essentially 1 mole of a phosphorus sulfide and 4 moles of a material selected from the group consisting of a dicyclic terpene and an essential oil mainly consisting of a dicyclic terpene. 2. Mixture as stated in claim 1, characterized in that the sarcosinphor bond (c) is oleoyl-sarcosine. 3. Mixture according to claim 1, characterized in that the metal of the sulfonate (d) is calcium. 4. Mixture according to claim 1-3, characterized in that the metal sulphonate (d) is a weakly basic calcium petroleum sulphonate. 5. Mixture according to claims 1-4, characterized in that phosphorus sulphide used in the formation of product (e) is phosphorus pentasulphide. 6. Mixture according to claim 1-5, characterized in that the reaction product (e) is obtained by reaction of essentially one mole of phosphorus pentasulphide and four moles of pinene at approx. 150°C. 7. Lubricating oil mixture according to claims 1-6, characterized in that it comprises: (a) a main quantity of a mineral lubricating oil, (b) approx. 5.6 wt. of the mixture of calcium acetate, (c) approx. 0.42 wt. of the mixture of oleoyl-sarcosine, (d) ca. 0.8% by weight of the mixture of an oil-soluble calcium sulfonate, (e) approx. 1 wt. of the mixture of an oil-soluble phosphorus and sulfur-containing reaction product, obtained by reaction of essentially 1 mol of a phosphorus sulfide and 4 mol of pinene at approx. 150°C. 8. Lubricant concentrate for the preparation of the lubricating oil mixture according to claim 1, characterized in that the relative amounts of the components (a) to (e) are such that when the said concentrate is diluted with mineral lubricating oil, the formed lubricating oil mixture will contain: