DE1670404A1 - Petrol for engines - Google Patents

Description

ATLANTIC RICHFIELD COMPANY, Philadelphia, Pa./USA

Petrol for engines.

The invention relates to a gasoline fuel for engines with the usual boiling range

Tetrafithyl lead has long been added to motor fuels in order to improve the anti-knock properties which are necessary to meet the requirements of modern automobile engines. The use of tetraethyl lead is associated with the development of various problems. One problem is to be seen in the cost of this component, so that fuel manufacturers have long been looking for cheaper compounds or other ways of "guaranteeing" the required octane rating of the fuel and doing so To reduce the proportion of tetraethyl lead in the gasoline.

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Another problem is that the addition of tetraethyl lead to gasoline in internal combustion engines harmful buildup causes what the addition of various types of detergents and converting agents for precipitation to cancel out the effects of precipitation. In addition, is already For several years, the permissible proportion of tetraethyl lead in fuel has been limited due to the toxicity of this compound. In recent years, however, have been For this reason, the health authorities reduce or completely remove the lead content demanded in fuel.

Other problems exist with the operation of modern automobile engines. One of these problems is in freezing of the carburetor, which leads to the engine stalling in cold, damp weather conditions, especially when the engine is still cold.

It has already been established that tertiary butyl alcohol (2-methyl-2-propanol), when added to motor fuel, not only improves its anti-knock properties improves, but also remedies the icing of the evaporator to a large extent, or in some cases this phenomenon completely prevented. Through the

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Adding tertiary butyl alcohol thus becomes double Improvement of the fuel received, i.e. it will be both the anti-knock properties and the anti-icing properties of the fuel are improved.

Such an addition of tertiary butyl alcohol, however, is not completely free from additives. Of the Alcohol causes the gasoline to absorb water, for example from the bottoms of the refinery tank or from the distribution system for the product. This dissolving effect of the tertiary butyl alcohol leads to the fact that the fuel has a considerably higher water content than is normally found in gasoline. With However, the most serious problem in the presence of water is the corrosion of parts of the fuel system, in particular those made of steel, zinc or magnesium.

It has now been found that the corrosion properties of a tertiary butyl alcohol Engine constituents can be reduced to a minimum can, if you use a certain specific corrosion inhibitor together with the tertiary butyl alcohol. The corrosion inhibitor that is used together with the tertiary butyl alcohol in gasoline as a

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has been found to be particularly suitable, is one of the so-called "dine" acids, in particular one of the dimer acids which are produced by the polymerization of unsaturated CLg fatty acids. The preparation of these acids is described in the article by "Charles G. Goebel in" The Journal of the American Oil Chemists ¹ Society "pp. 65-69, March 1947." In particular, the polymerized C ^ ₈ fatty acids are used, the represent corrosion inhibitor according to the invention. These represent dilinoic acid, with the formula

CH ₃ (CH ₂ J ₅ - CH - CH - CH = CH (CH ₂ ) _- COOH

CH ₃ (CH ₂ ) ₅ - CH CH- (CH ₂ J ₇ COOH 1 ·
CH »CH

According to the invention, therefore, a gasoline fuel for engines is made available which, based on the total fuel, contains 1-20% by volume of tertiary butyl alcohol and, as a corrosion inhibitor, 20-100 ppm of a dimer of an unsaturated C ^ ₈ fatty acid.

In this way a basic motor fuel becomes

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167040A

which boils in the gasoline range, and which may contain tetraethyl lead, provided the additional Has anti-knock properties and superior anti-icing properties for the carburetor, what happens that based on the total volume of the fuel 1-20 vol% tertiary butyl alcohol, preferably 3-15% by volume are added · To reduce the corrosive aggressiveness of the fuel on the metal parts of the fuel system of the internal combustion engine To reduce to a minimum, the fuel, based on the total weight of the fuel 20-100 Parts per million (ppm) of a corrosion inhibitor, such as a dimerized, unsaturated CLg fatty acid represents, added. The preferred inhibitor is dilinoleic acid with the formula already given.

Either gasoline can be used as the basic fuel component can be used with regular or premium grades.

The gasoline component can be up to per gallon of fuel

3 3 cm tetraethyl lead or equivalent amounts of others contain lead-based additives such as tetramethyl lead However, the basic fuel does not need to contain tetraethyl lead if the AnÜ knocking properties already exist is achieved through certain high-octane hydrocarbon components.In addition, the base fuel can contain all additives of phosphoric acid esters such as tri-cresyl phosphate and the like.

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In a particularly preferred embodiment of the Invention, tertiary butyl alcohol is used to at least part of the high anti-knock properties of fuel, increasing the amount of octane required to obtain the desired octane level Tetraethyl lead can be reduced.

As already stated, the tertiary butyl alcohol-containing fuel tends to dissolve water, which gives it corrosive effects. The corrosive aggressiveness of the fuel on the fuel system can be reduced by using the above described corrosion inhibitor of the type of a di ^ meren Acidity can be decreased. These inhibitors are marketed by a number of manufacturers, usually as a 50% solution in kerosene.

In addition to the tertiary butyl alcohol and the corrosion inhibitor, a carburetor cleaning agent can be added to the base fuel. Examples of such cleaning agents are the derivatives of N-ßhydoxyethyl-ethylenediamine, such as the condensation product of methyl oleate with N-ß-hydoxyethyl-ethylenediamine suitable.

In the following, the invention will be based on some

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Examples are explained in more detail · Example 1

To determine the effect of tertiary butyl alcohol on the octane number of fuels, a number of Trying carried out. The Testokian number was after ASTM Method D-908 and the motor fuel octane number determined according to ASTM method D -357. In addition, the modified Union Town Road Octane Method was used Street octane number determined, measured on an average of 5 cars.

When examined in commercial fuels, it was found that tertiary butyl alcohol was found in the In addition, a test octane number of 112 and an engine octane number of 103 resulted. When carrying out these provisions, 5 commercially available fuels were used Premium grade (with different lead content) and 6 commercially available Regular grade fuels (with different lead content) are used. With any of these fuels Triple tests were carried out with two different levels of tertiary butyl alcohol. In the Table I lists the for these fuels by the Use of 5% by volume and 10% by volume of tertiary butyl alcohol available savings of tetraethyl lead shown.

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The table shows mean values for regular and premium petrol for each test series «

TABLE I. permissible TEL reduction ml / gal . Butyl alcohol 0.46 Experimental method Motor method
(avq) (aνα.) 0.82 fuel % TBA * 0.53 0.35 Premium 5 0.85 0.69 10 0.45 Regular 5 0.70 10 * TBA «tert

The possible TEL reduction relates to the amount of TEL that is equivalent to TBA · This means for premium users that if 5% TBA is added the amount of TEL can be reduced by 0.53 ml per gallon while maintaining the same octane rating as found in the experimental method, can be retained.

It was found that when 10% by volume of tertiary butyl alcohol was added to unleaded high-voltage Petrol and tertiary butyl alcohol are equivalent to approx. 10% by volume of toluene with regard to the octane number of the mixture is.

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TABEL fuel II Engine octane number unleaded ground
mixture Test octane number 91.5 Basic mixture ♦
10% toluene 100.0 91.7 Basic mix +
10% TBA 101.3 91.9 101.1

Commercially available gasoline was 0 vol%, 5 vol% and 10% by volume of tertiary butyl alcohol, the tetraethyl lead contents of these three fuels being adjusted so that approximately the same laboratory octane numbers were obtained. Then the street octane number became these fuels using the modified ones Union Town Road Octane Method (average of 5 cars) determined.

TABLE III Octane values 99 , 2 engine Street Fuel _test Customary reason 99 , 5 92.1 97.8 mixture + 2.4ml TEL / gal. Basic mix + 5% TBA + 99 , 4 92.1 97.5 2.0 ml. TEL Basic mix + 10% TBA + 92.0 97.7 1.7 ml.TEL / gal.

These results show that the fuels containing tertiary butyl alcohol are on the road

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according to their octane content determined in the laboratory behavior. The results of the octane number behavior of tertiary butyl alcohol in gasoline show that this all or part of the tetraethyl lead can be used in commercial fuels to replace.

Example 2

To demonstrate the superior anti-icing properties of tertiary butyl alcohol in gasoline, a standard icing test was performed on the dynamometer ether chassis. In this test, any car in good mechanical condition on a chassis dynamometer in a space that is maintained at a temperature of 4,44+ O ₁ Il ⁰ C is used. The air introduced into the carburetor also has a temperature of 4.44+, 0.11 ° C. The relative humidity is 95-100%. The following steps are then taken:

1. The car is cooled down until it is in equilibrium with the temperature of the room.

2. Then the car is started and operated for 30 minutes without load at leooupm (approximately 35-4O miles / h),

3. The car is stopped and 15 sea. at idle

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operated.

4. The car is accelerated to 1800 rpm and 30 sea. run.

5. Steps 3 and 4 are repeated. When the car dies while idling, it is restarted and the cycles are continued. It at least 12 complete cycles (levels 3 and 4) are carried out. The test is terminated when three consecutive Cycles have taken place without the engine stalling, or if the engine has stalled 20 times is.

The test procedure outlined was used to investigate the anti-icing properties by adding tertiary butyl alcohol in gasoline. In arbitrary Order were 2 trades! ' . she basic fuels without additives and with isopropanol or various amounts of tertiary butyl alcohol. The fuels had different degrees of volatility. The first evaporated at 100 ° C 56% of the fuel, the second at the same temperature 60%. A 1963 Ford KeÜ wagon served as the test car. The results obtained are shown in Table IV.

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TABLE IV
Test fuel 1: at IQO ⁰ C 60% have evaporated

Fuel r total number of stalls

bens / test die

Base fuel 14, 12, 10, 11 11.75

Base fuel + 1 1/2 vol%

Isopropyl alcohol 1, 1, 0, 1 0.75

Base fuel + 2% by volume

tert. Butyl alcohol 2, 6, 3 3.7

Base fuel + 4% VoI

tert. Butyl alcohol 2, 2, 2, 6, 2, 1.1, 2.3

Base fuel + 5 % by volume

tert. Butyl alcohol 1, o, 0, 0, 0.25

Base fuel + 6% by volume

tert. Butyl alcohol 0, 0, 0, 0, 0

Base fuel + 0.01VoI %
commercial de-icer
based on wetting agents 4, 5 4, 5

Test fuel 2: at 100 ^° C., 56% have evaporated

Base fuel
Base fuel + 1 1/2 vol% isopropyl alcohol Base fuel + 2 vol% tert. Butyl alcohol base fuel + 5 vol.% Tert. Butyl alcohol base fuel + 0.01% by volume of commercially available de-icers based on wetting agents

These values show that in the case of a very volatile fuel, the addition of 5% by volume of tertiary butyl alcohol causes icing of the carburetor essentially completely eliminated. The mixture is actually better than the same fuel with 1 1/2 vol% of the technically used isopropyl alcoholIn the case of a fuel with a lower volatility, the addition of 5% by volume is

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6, 12, 8th, 7th 8.3 O, O, O, 0 0 0, 2, 3, 5 2, 5 O, O, O, 0 0 4, 5, 4th 4.3

equivalent to that of 1. 16 % by volume tertiary butyl alcohol and completely eliminates icing of the carburetor.

Example 3

To the effectiveness of the corrosion inhibitor according to the invention, consisting of the dimer acid, in a fuel which contains tertiary butyl alcohol, in the presence of water, various corrosion tests were carried out carried out. In these tests, 750 ml of white spirit and 0.75 ml of distilled water were placed in a flask brought, whereupon the two components were stirred for 1 minute. In the gasoline were sandblasted Freshly cleaned magnesium metal strips (2.54 cm 2.54 cm immersed, whereupon the flask was closed The flask was left at room temperature and except that it was stirred twice for 1 minute every week, left undisturbed. After 30 days the test plaques were removed, dried and weighed. The measured in mg Weight gain reflects the attack of corrosion. Premium grade gasoline with 3 ml Tetraethyl lead used per gallon.

TABLE V

Fuel composition. Inhibitor, ppm weight gain ^{would 1} (mg )

Base fuel none 23.8 22.5 base fuel + 4VoI %

TBA ¹ »29.1 28.8

₅ 25.9 25.8

• Basic fuel + 4 VoI% D.A. 2.5 2.7

^{1 50}

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1. tertiary butyl alcohol, which contains 5.5% by volume of acetone, 0.6 % by volume of methanol, 0.5% by volume of tertiary butyl format,

1.6% by volume water and 50% by volume ppm di-tert-butyl peroxide contains.

2. The dimer of an unsaturated C. _g fatty acid, ie

Dilinoleic acid.

The above values show that the invention '* Inhibitor to prevent the corrosion of a metal, which when used in gasoline blends, the contain tertiary butyl alcohol, easily corroded, is extremely effective.

In addition to these quantitative examinations, a large number of visual examinations were performed using Metals like copper, zinc and steel. Included it was found that the inhibitor according to the invention was effective in all cases, the other commercially available ones Inhibitors, however, showed no effectiveness. It was there. found various additives that one often encounters in fuel mixtures, such as detergents, Carburetor cleaning agents and the like. The do not impair the inhibiting effect of the mixture according to the invention

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Claims (1)

-is- 167Ό404 Claim Gasoline fuel for engines with, based on the total weight of the fuel, 1-20 % by volume of tertiary butyl alcohol characterized by the addition of 20-100 ppm of a dimer of an unsaturated C ^ _ß -fatty acid, preferably oilinoleic acid, as a corrosion inhibitor. 109809/1653