DE2840930A1 - FUEL OR LUBRICATING OIL COMPOSITION - Google Patents

Description

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands

"Fuel or lubricating oil composition"

It is well known per se that internal combustion engine ^ for example, engines operating with spark plugs, show the phenomenon of increasing the octane rating. This Effect can be described as the tendency of a new or cleaned engine to develop one over the course of its service life Needing higher and higher octane fuel, whereby this increase in octane number is the same as that Formation of deposits in the area of the combustion chamber

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of the motor. Accordingly, there will be a gradual increase during the initial phase of operation of a new or cleaned engine in the octane number requirement (OR), i.e. the octane number of the fuel required for knock-free operation, and at the same time an increase in the precipitates separating out in the combustion chamber was observed, until finally one stable or equilibrium state is reached with regard to the octane number requirement, which in turn corresponds to a point in time seems to be where the amount of precipitate deposited in the combustion chamber and on the valve surfaces no longer increases, but remains relatively constant. This so-called "equilibrium value" is usually after a Travel distance between approximately 3000 and 20,000 miles or the corresponding operating hours. The actual equilibrium value with this increase in the octane number requirement can vary depending on the engine design and even with individual engines of the same design. In almost in all cases, however, the observed increase is

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significant, with the relevant ORI values number requirement), which is usually used in modern engines observed, are in the range of about 2 to 10, expressed, as research octane numbers (RON).

It is also known that additives can serve to prevent the formation of precipitates in the combustion chamber and on the adjacent surfaces of the engine to prevent or to reduce or to remove or modify such precipitates and thereby overall also the octane number

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to reduce the need. Such additives are commonly used referred to as means for decreasing the octane count requirement (hereinafter abbreviated to ORR).

Surprisingly, there has now been a new class of compounds found which are excellent as such ORR agents suitable.

The fuel according to the invention or. Lubricating oil composition, which contains a larger proportion of a fuel or lubricating oil is accordingly characterized in that the composition a minor amount of a compound of general formula I below. .

TT TT

£> NR ₁ -NCNR ₁ -N <£ (I)

contains as an additive in which each R is the same or a different C, g-alkyl group, each R _{1 is} the same or a different C ₂ _g -alkylene group and X is oxygen or sulfur.

According to a preferred embodiment, the composition according to the invention contains a compound of the above formula I in which R denotes a C 1, alkyl group, in particular the methyl group. Furthermore, within the scope of the invention, compositions are preferred which contain a compound of the above general formula I in which R _{1 is} a

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C ₃ ~ alkylene group. Furthermore, compositions according to the invention are preferred which contain additives of the formula I in which X is oxygen.

In particular, compounds of the general above are suitable Formula I as additives in which all groups R are identical alkyl groups and all groups R are identical alkylene groups mean. The preferred additive is characterized by the following general formula II:

t Γ T CH

3> N-CH ₂ -CH ₂ -CH ₂ -NCN-CH ₂ -CH ₂ -CH ₂ -N ^ p (II)

3 ft ■ ³

Such additives have the advantage that, although they are highly polar, they are nevertheless soluble in hydrocarbons.

The compounds suitable as additives according to the invention of general formula I can be obtained by adding at least about 2 moles of an amine of formula III below

(III)

in which R and R are as defined above with one mole Urea or thiourea converts. Suitably this reaction is carried out at elevated temperatures in the range of about 70 to 150 ° C until no more ammonia is found-.Gke.lt *: ·! - Excess;: Amin ^ kanfLtfestillafeiy. abgetsennfc ····. · ■ * -. · ...-. will.

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The ORR additives according to the invention can be used in a wide variety of ways Manner to be fed to the combustion zone of the engine, so as to prevent the build-up of deposits or the To reduce the amount of precipitation or to modify its type. For example, the ORR additives in question injected directly into the engine's intake duct, periodically or practically continuously. A preferred one The method, however, is to incorporate the additive in question into the fuel itself. For example, you can use the Additive separately or in combination with other additives Mix with the base fuel.

Another method of introducing the ORR additives according to of the invention in the combustion zone consists in adding the additive to add the lubricating oil of the crankcase, which in the course of the engine operation finally on the walls of the Combustion chamber reaches, for example by means of the lubricating oil film on the ring in the area of sliding contact with the cylinder.

A gasoline, which is leaded or unleaded, is preferably suitable as the fuel to which the additive can be incorporated can be. It is well known per se that gasoline is generally used as a mixture of hydrocarbons with different boiling points can be defined and a boiling range, determined according to the ASTM method · D-86 ^ of about 20 to 230 ° C. A suitable gasoline includes, typically about 0 to 30 percent by volume of olefins, about 5 to 55 and preferably about 10 to 45 percent by volume of aromatics,

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while the remainder consists of saturated hydrocarbons. In the context of the invention, suitable base fuels can Be gasoline that also contains a smaller proportion of an anti-knock agent in the form of an organic lead compound, such as Tetraalkyl lead. The base fuel can also contain other organometallic additives, for example Manganese derivatives suitable for the same purpose. In such cases, the fuel can also contain small amounts a halogen detergent such as ethylene dibromide and ethylene dichloride. Fuel compositions according to the invention on the basis of leaded or unleaded Gasoline may also contain other common additives, such as dyes, anti-spark plug agents, Oxidation inhibitors, detergents with a dispersing effect, additives and metal deactivators to prevent icing.

Lubricating oil compositions according to the invention can contain conventional synthetic or mineral oil lubricating oils as base lubricating oils. Preferably the base lubricating oil is a mineral oil. Suitable compositions based on mineral oil contain any conventional or commercially available fully alloyed motor oil, for example paraffin-based, naphthenic-based or mixed paraffin-naphthenic-based distillate lubricating oils or residual lubricating oils. It can lubricating base oils having an SUS viscosity at 37.8 ⁰ C in the range of about 50 to 1000 come to the application. Such mineral lubricating oils typically contain a variety of common "additives, such as detergents, improvers for the

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Viscosity Index and "Antioxidants".

The fuel or lubricating oil composition according to the invention usually contains only small proportions of the additives according to the invention. Suitable amounts of additives are in the range from O _r O01 to 0.3 percent by weight and in particular in the range from 0.005 to 0.1 percent by weight.

The invention is illustrated in more detail by the following examples.

Example 1 Preparation of the ORR additive

2.1 moles of the compound N, N-dimethyldiaminopropane are used in 125 ° C reacted with 1 mol of urea until ammonia no longer develops, excess amine is distilled severed. The reaction product has the general formula below

^CH 3 HH ^CH 3

CHO-N-CH ₀ -CH ₀ -CH ₀ -NCN-CH ₀ -CH ₀ -Ch ₀ -N-CH, ο ί 2. JL ν, 1 δ 2 3

Elemental analysis: N% 0%

found: 23.5 7.7

calculated: 24.6 '7.0

Example 2 in which engines were tested, once in a

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According to the degree of compression working version of the Opel 1.7 liter OHC engine and on the other hand in the Ford 1.6 liter OHV engine (cross-flow, bowl-in-piston). Both engines are under cycle conditions operated. The Opel cycle consists of sections with 3 different engine speeds, and about 2 minutes at 2000 rpm, about 4 minutes at 2500 rpm, 2 minutes at 3500 rpm and then 3 minutes idle. Of the Ford cycle consists of about 2.5 minutes of idling and three accelerations by accelerating for a total of about 2.5 Minutes; All engine speeds with the exception of idling are driven under road load conditions. A commercially available oil of the type IOW / 50 is used as the lubricating oil in both test engines. The one in both engines The test fuel used was a gasoline containing 9 mg Pb / liter with a research octane number of 95.8 and a Engine octane number of 84.7.

During the operation of the test engines with the test fuel, the octane number requirement of the engines became periodic using the primary reference fuel (PRF) at constant engine speed (Opel engine: 2500 revolutions; Ford engine: 3200 rpm) under full throttle conditions in top gear. The PRF octane number requirement was "'That octane number of the test fuel' at which a barely audible knocking occurred. If it was ensured that Had set equilibrium conditions, the primary reference fuel was replaced by a fuel mixture. .. measured the invention, which from the test fuel in question

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and an addition of 0.03 percent by weight of the ORR additive prepared according to Example 1. The octane number requirement the engines were then determined in the manner indicated above for a certain period of operation, and then the fuel composition according to the invention was again replaced by the reference fuel. The one on the Opel engine The results obtained are shown in Fig. 1 and the results obtained with the Ford engine are shown graphically in Fig. 2. The curve sections A-B and C-D correspond to the operational run of the engines with the reference fuel and the curve parts B-C correspond to the operating time of the engines with the fuel mixture according to the invention, i.e. a mixture of the reference fuel with the addition of 0.03 percent by weight of the ORR additive according to the invention.

Claims

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Claims (6)

Claims 1. / fuel or lubricating oil composition containing "a larger proportion of a fuel or lubricating oil, characterized in that the composition a minor amount of a compound of general formula I below CSR ₁ -N, -; * (I) contains as an additive, in each of which R is the same or a different C, g-alkyl group, each R. the means the same or a different C ~ _, - ~ alkylene group and X is oxygen or sulfur. 2. Composition according to claim 1, characterized in that it contains a compound of formula I in which each R is a methyl group. 3. Composition according to claim 1 and 2, characterized in that it contains a compound of formula I in 4er of each R- is a C ^ -alkylene group. 4. Composition according to claim 1 to 3, characterized in that it contains a compound of formula I in the X is oxygen. COPY 5. Composition according to claim 1 to 4, characterized in that it contains a gasoline as fuel. 6. Composition according to claim 1 to 5, characterized in that it contains the compound of general formula I. contains in an amount of 0.001 to 0.3 percent by weight. OSO01 570 0 39 COPY