DE1094037B - Fuels for gasoline engines - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN MrWG ^. PATENT OFFICE

kl. 46 a ⁶ 7

INTERNAT. KL. ClOl

EDITORIAL NOTICE 1094037

B 50016 IVc / 46 a ⁶

REGISTRATION DATE: AUGUST 19, 1958

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EXIT CHRIFT:

!. DECEMBER 1960

It is already known pyrrolidone and its derivatives, in which the hydrogen atom is connected to nitrogen by a Alkyl, cyclohexyl, aryl, aralkyl or oxyalkyl radical is replaced, as additives to fuels for gasoline engines to be used (German patent specification 1020 209). The additives mentioned, in any proportion with water and fuel are miscible, if larger amounts are added, e.g. B. 0.5 weight percent, a good one Lowering the freezing point of the water and thus preventing the carburetor from icing up (see for example H. K. Livingstone, Ind. Eng. Chem., Vol. 43 [19Sl], p. 665).

It is also known to add phosphoric ester amides to fuels. These compounds have a special affinity to the metal surface in the carburetor. They cover this surface with a very thin one A layer that is sufficient to prevent ice crystals from sticking to the surface of the carburetor. These However, substances have the disadvantage that, when used in larger quantities, they reduce the octane number of the one used Lower gasoline.

It has now been found that you can completely prevent icing and at the same time reduce it the octane number of fuels for gasoline engines avoids, if one avoids additives of 0.05 to 0.5, preferably 0.12 to 0.25 parts by weight, based on the fuel, of a mixture of each individually as a fuel additive known pyrrolidones or their derivatives, in which the hydrogen atom on the nitrogen by a Alkyl, cyclohexyl, aryl, aralkyl or oxyalkyl radical is replaced, and hydrocarbon-soluble phosphoric ester amides used, in which the phosphoric acid ester amide to the pyrrolidone in a weight ratio of 1: 5 to 1: 24 is available.

Through the simultaneous use of pyrrolidone or the derivatives mentioned together with phosphoric ester amides an effect is achieved that is greater

Fuels for gasoline engines

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Günther Nottes, Dr. Dieter Blum

and Dr. Heinrich Pasedach, Ludwigshafen / Rhine,

have been named as inventors

is than the sum of the effects of the individual components.

This is z. B. from the following table, where A is methylpyrrolidone

CH ₂ CH ₂

CH ₂

and B the connection

C ₄ H ₉

₂ CO

/
N-CH ₃

-O.

C ₁₄ H ₂₇ -O ^ P = O

-17 ^ 3.3

is. The values given in the table were measured at an air humidity of 90 to 95 ° / ₀ ; the temperature in the climatic room was +3 ⁰ C, in the carburetor -7 ⁰ C.

Addition of each component to gasoline

Weight percent A Weight percent B mm Hg Time for ice to form Remarks in gasoline in gasoline below 1 at occurs in the carburetor almost no ice formation 0.3 70 to 80 15 minutes very weak ice formation 0.2 - 110 to 130 15 minutes weak ice formation 0.1 - 170 to 180 10 mins clear ice formation 0.05 - 200 to 220 5 minutes almost no ice formation 0.02 80 to 90 15 minutes very weak ice formation 0.01 110 to 120 12 minutes Blank value without very strong ice formation additive 200 to 220 .3 minutes

009 650/233

j
- ■ f t Common addition of A plus B to gasoline still
very Remarks Weight percent A
+ Weight percent in gasoline
B in gasoline Time for ice to form
occurs in the carburetor no ice formation
weak ice formation 0.1 +
0.05 + O ₁ Ot
0.01 more than 30 minutes
20 minutes mm Hg
below 1 at 80 to 90
110 to 120

Another significant advantage of the additives according to the invention is that the addition of Mixtures of the substances known individually as fuel additives not only reduce the anti-ice effect of the individual Components can be raised beyond the sum of the effects of the individual components, but also a drop in the octane number of the gasoline is prevented. While with the addition of the compounds A too large quantities are necessary to achieve a perfect defrosting effect the sole addition of the compounds B already in amounts that are necessary for de-icing and in their effect a corresponding amount of the compound A are equivalent, the octane number is noticeably reduced. In contrast can be obtained by using the mixtures according to the invention of the compounds A and B in a quantity ratio of 24: 1 to 5: 1 with additives of 0.05 to 0.5 percent by weight, based on the fuel base, achieve a perfect de-icing effect without noticeably reducing the octane number of the gasoline used to humiliate.

The diagram (Fig. 1) shows the decrease in octane number (OZ) by determination according to the research method with a commercial gasoline of OZ 94, which contains 0.5 percent by weight of N-methylpyrrolidone increasing additions of a hydrocarbon-soluble phosphoric acid ester amide (B).

Suitable derivatives of pyrrolidone are, for. B. N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, Ny-oxypropylpyrrolidone, N-cyclohexylpyrrolidone, N-phenylpyrrolidone, N-benzylpyrrolidone i.a. You can also use mixtures of the substances mentioned, for. B. pyrrolidone with N-methylpyrrolidone, Use N-methylpyrrolidone with N-ethylpyrrolidone, etc., with good success.

Compounds of the following constitution are suitable as hydrocarbon-soluble phosphoric ester amides :

RO

R "N '
H

where R and R 'are an alkyl, cycloalkyl, aryl or aralkyl radical having 1 to 20 carbon atoms and R " represent an alkyl, cycloalkyl, aryl or aralkyl radical having 4 to 20 carbon atoms.

Suitable compounds are in particular those in which R is a methyl, ethyl or propyl radical, and R 'is a Amyl, octyl, cetyl, cresyl, bornyl or dipentenyl radical and R "represents a butyl, oleyl or stearyl radical.

For the use of pyrrolidone or its derivatives and the phosphoric ester amides it has in In many cases it has been found to be expedient to first place these substances in alcohols such as methanol or isopropanol or butanol, or in mixtures of these alcohols, and the respective phosphoric ester amide in this solution to be entered. In general, from 0.05 to at most 0.5 percent by weight are sufficient, preferably 0.12 to 0.25 percent by weight of such mixtures, based on the fuel, in order to achieve a sufficient

ίο Protection of automobile carburettors against icing too achieve.

The test is carried out in one of the commercially available carburettors for an automobile engine of the 600 cc vehicle class (Fig. 2). The carburetor 1 is installed in a housing made of transparent plastic 2, which serves as a climatic chamber. The intake air flow for the carburetor pulls through a glass column 3 filled with wet glass beads, which saturates the air with moisture into the air-conditioning housing. In addition, water vapor can be fed into the air-conditioning housing through a parallel line 4. The humidity is read in a hygrometer 5 attached next to the carburetor. A thermometer 6 measures the corresponding temperature in the chamber. A second thermometer 7 is attached directly to the carburetor in order to determine its temperature. The carburetor receives its moist intake air from the air conditioning housing via a bent pipe 8 which opens into a glass funnel 9. By setting blocks of ice in the housing can easily be regulated to room temperature in the enclosure and the humidity vary by small addition of steam up to 100% optionally with the aid of solid CO ₂ -Trockeneisstücken temperatures of 0 ⁰ C. The side of the carburetor normally facing the automobile engine (suction side) is connected to a laboratory vacuum system, water jet pump or the like via a suction pipe 10 and a separator 11 for possibly non-gasified gasoline after passing through an oil absorption system 12. A vacuum gauge 13 on the suction side of the carburetor shows if ice forms in the carburetor, the throttling of the air passage, which is caused by more or less stronger ice formation. The gasoline to be tested is introduced into the carburetor from a calibrated measuring vessel 14 and, due to gravity, flow to the carburetor as soon as the intake air is allowed to flow through, which in practice corresponds to starting an automobile engine. Control cocks in all lines allow the setting of constant and at any time reproducible test and test conditions, a flow meter 15 allowing the determination of the air flowing through the carburetor plus the amount of gasoline vapor. The occurrence of ice formations in the gasifier or - when using the mixtures according to the invention - the prevention or absence of these can be clearly observed through the glass funnel attached to the top of the gasifier. With this arrangement, fuel additives can be tested for their anti-icing effect quickly and easily without installing an expensive engine.

example 1
A mixture A ₁ , consisting of

60 parts of methylpyrrolidone,
10 parts of ethanol,
10 parts propanol,
10 parts isopropanol,
10 parts of butanol,

is stirred well, with a clear solution immediately

forms. It is soluble in all proportions in normal commercial automobile gasoline.

0.1 percent by weight of mixture A _{1 is added} at the same time as 0.01 percent by weight of compound B ₁

Cresyl - O
Cresyl - 0 ^ P = O
stearyi —JN

to a normal car gasoline, no ice formation in the carburettor can be detected in the apparatus described above, even after 20 minutes. The manometer shows only 80 to 90 mm, even at an air humidity of 90 Us 950 /, each of the two products, ie _the mixture A ₁ or the compound B _{1 mentioned} , used on its own, shows after a short time a leak and resistance in the carburetor.

Example 2
Motor behavior

A cold, water-cooled four-stroke automobile engine in an outdoors car of the 1.5-1 car class needs about 5 to 6 minutes after starting up to warm up with normal car gas in damp winter weather with an outside temperature of 0 to about + rC. Dabeiist initially a very strong cooling of the gasifier festzusteUen (about 10 to 15 ⁰ C). Especially in damp weather, the engine stops easily and runs jerkily and restlessly even when the throttle clearjoe is on (ice build-up in the

Carburetor ;. · J τ. rn / - ■ -u * j.

If you add 0.1 percent by weight to the gasoline

", Ti 1-j / α \ -j. j · ir * · λγ

If methylpyrrolidone (A ₂ ) is added, the icing in the carburettor is no longer as strong and the engine performs better than without the additive.

Adding 0.01 percent by weight of compound B _{2 to the same gasoline}

and at the same time 0.01 percent by weight of the above compound B ₂ , no more freezing occurs. The power of the engine is so good after less than 1 minute that you can drive off with the car without further ado.

Example 3

A commercial premium gasoline has a research octane number (OZ) of 95. By adding 0.11 percent by weight a mixture of 10 parts by weight of methylpyrrolidone and 1 part by weight of the compound

changed. The OZ remained at 95. The anti

Run the engine (about 10 minutes). In order to achieve the same ice effect by adding B alone, at least 0.025 to 0.03 percent by weight of B _{1 had to be} added. After adding such a ζ. _π ί ι_ ι,. ·, χ · j t. ι. · Ι · -ua j. ·

Amount of B ₁ , however, with the same anti-ice effect, a clearly visible decrease in OZ _{below 9S} _

Cresyl O-P = O

Oleyl - N
H

this gives the same result.

However, 0.1 percent by weight of a mixture A ₂ , consisting of, is added to the gasoline

60 parts of methylpyrrolidone,

10 parts of methanol,

20 parts isopropanol,

10 parts isobutanol,

Example 4

Em

Gasoline of the trade with a lot of volatile ^ (winter gasoline) is with 0.25 weight percent. ^M ^ schu £ ff ^u f f ^{parts by} weight Methylpyrrohdon } ^G T ^m t ^ f ^ - ^ mdungB ^ offset. After adding the mixture, the ice-cream effect is very good _{(15 minutes of freezing)} . _{The 0} Z of the gasoline ^ _dem ^ _{dep mixed un} .

_änder f ^ _{93 To lekhe An} ti _e iswirkung to achieve especially ₁ with the compound B, is em addition of 0.03 J _{315 0;} 035 percent by weight of compound B _{1 is} necessary. After adding this amount of compound B ₁ , ^ ¹ ; already a clearly demonstrable decrease in the OZ.

Claims (1)

Claim: Fuels for gasoline engines, marked dutch ^^ _yon ^ _{5 to 0> 5} ^s _{preferably 0> 12 to} 0.25 percent by weight, based on the fuel base, a mixture of pyrrolidones or their derivatives, each known individually as a propellant additive, in which the hydrogen atom on nitrogen by an alkyl, cyclohexyl, aryl, aralkyl or Oxyalkyl is replaced, and hydrocarbon-soluble phosphoric acid ester amides, in this Mixture of the phosphoric ester amide to the pyrrolidone is present in a weight ratio of 1: 5 to 1:24. Considered publications:
German Auslegeschriften No. 1 020 209, K 15974 IVc / 46 a ⁶ (published on October 18, 1956). 1 sheet of drawings