DE1289354B - Motor fuels containing detergents - Google Patents

Description

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The invention relates to motor fuels, which efficiency as well as arise as a detergent, which the deposition of combustion costs as particularly favorable,
residues in the carburettor of Otto Explosionsmoto- To make handling easier, the in

prevent or reduce, 0.0001 to 1.5 G the motor fuels according to the invention contain weight percent a branched chain primary alene deposit preventing additives in the form kylamins with 9 to 24 carbon atoms are used in the Al of concentrates. These additives are contain kyl group. unusually stable and have good solubility

During the operation of explosion engines arise on, so that the production of the concentrates no often difficulties in idling and by difficulty. To make these condrosses, so that the carburettor is often overhauled and newly io centrates one solves the additive in a suitably set must become. The trouble was caused by hydrocarbon or alcohol with one strengthen themselves under the boiling range of around 66 to 204 ° C in modern city traffic, and that prevailing For conditions that require constant start-up, it is preferable to use an aromatic carbon and make stopping necessary, in particular hydrogen, such as benzene, toluene, xylene or higher specifics in the case of multi-way carburetors, the currently 15 boiling aromatic or aromatic diluent Art built into many motor vehicles. Aliphatic alcohols with about 3 to 8 carbohydrates and difficulties in idling are primarily lenstoffatomen, e.g. B. isopropanol, isobutylcarbmol, Line on the accumulation of deposits in n-butanol, as well as mutually compatible Ge suction part of the carburetor. In the mix of the mentioned alcohols with hydrocarbon proportions, as the deposits accumulate, substances are also used in the manufacture of the rinsing agent Inflow of medium concentrates suitable for a certain amount of fuel. The amount of what is needed Obstructed the amount of air and the amount of air storage preventing additive in the Concentrate itself greatly reduced so that the air-fuel step is usually at least 10 weight per mixture for a satisfactory operation of the zent and can possibly up to about 70 GeMotors is too fat. As a result, the carburetor must make up 25 percent by weight.

initially taking into account the deposits together with the in the inventive Mo-

are constantly reset; Finally, there will be other additives that may contain petrol necessary to replace it or at least find full use of fuel additives. The decrease to overtake. the formation of deposits can be found in the

There are already various additives for motor fuels according to the invention, even then It has been suggested that the training chen when these still anti-knock drugs, such as Tetravon To prevent deposits in the carburetor. methyl lead or tetraethyl lead. Such None of the previously known additives is ever- Anti-knock agents are generally used in quantities but completely satisfactory. from about 0.13 to 1.05 ml / 1 used as this

It has now been found that the amount of deposits is sufficient, based on experience, to increase the octane number of gasoline explosion engines considerably to the desired value,
can, if you use a fuel, the non-volatile light mineral lubricating oils, eg

mainly from a hydrocarbon, pre-petroleum spray oil, also make suitable additives a hydrocarbon from the gasoline agent for the gasoline concentrate. consists, and of an addition of about 40, that these oils act as a carrier for the disper-0.0001 Up to 1.5 percent by weight of a branched-chain deposit is used. They will be in abundance term primary alkylamine with about 9 to 24 carbon from about 0.05 to 0.5 percent by volume, based on the Contains substance atoms in the alkyl part of the compound. finished gasoline mixture, used.

Alkylated aromatic amines are already available as to- The branched-chain primary alkylamines, which are used in

rates for motor fuels in the German patent 45 contain the motor fuels according to the invention Scripture 912 277 has been proposed, however, as are easily obtained. For example, you can Means to increase the octane value. They are not the straight-chain olefinic hydrocarbons of the ge gasifier detergents such as the desired chain length proposed here in a known manner in shark branched chains aliphatic amines. genalkane with halogen atoms in the 2-, 3- or

Convert the 4-position in the motor fuels according to the invention. The halogen thus obtained branched-chain primary amines allow alkanes to react with ammonia, whatever by the formula at one the corresponding branched chain alkyl

amine receives. The olefins can also initially with

Rj v concentrated (90 to 95%) sulfuric acid to

CHNH 55 set and then treated with hydrocyanic acid

P / ² will be. The reaction obtained by this treatment

- tion product is hydrolyzed with water and

finally supply with excess aqueous alkali in which R _{1 is} a straight-chain alkyl group, the amine being obtained. Olefins can also have 1 to 4 carbon atoms and R _{2 is} a straight 60 with nitrogen oxides, z. B. nitrogen tetroxide (N ₂ O ₄ ), chain alkyl group with 5 to 22 carbon atoms are treated in ethereal solution, where one means. a mixture of nitronitrites, dinitroalkanes and

In general, a branched-chain nitronitrate content is obtained in the presence of a base primary alkylamine in the fuel in amounts of being converted into nitroalkenes when heated, about 0.0001 to about 1.5 percent by weight are sufficient. These latter can be assigned to the corresponding ones ching. However, amounts of aminoalkanes are preferably used to hydrogenate. Suitable aminoalkanes from about 0.003 to about 0.03 weight percent; these are also made up of unsaturated aliphatic carbon quantities are both with regard to the achievable oil hydrogen according to the so-called "Ritter"

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Settlement can be obtained (cf. US patent specification inlet port of the carburetor, as one recognized

2,573,673). has that these vapors are particularly suitable for the

A particularly large part of the deposits are responsible for the purposes of the invention, Appropriate class of branched chain primary alkyl. Start the engine and use a lead amine or from such amine mixtures can be 5 th motor fuel with the usual content of by converting cracked wax olefins, initially tetraethyl lead (0.4 ml / l), but without surface the corresponding haloalkanes and then in active additives of any kind win the corresponding aminoalkanes. Crack engine run 4 hours with the crankshaft wax olefins contain about 9 to 24 carbon vapors constantly directed to the air inlet port atoms, preferably about 12 to 18 carbon atoms. Then the motor is stopped, the glass atoms. Mixtures of cracked wax olefins, which are removed from the body, and both sides of the latter are thermally treated Cracking paraffin waxes obtained the photographed. Then the dirty are particularly suitable. Such mixtures of vitreous bodies are used again in the engine; the and their production are for example in the engine is now, however, with a detergent-containing, U.S. Patent 2,172,228. The primed motor fuel (which except for the dishwasher Amines, which are produced from these olefins, additive that is used in the first part of the experiment, contain the amino group in 2, 3 or reversed corresponds) operated. In this part of the 4-position to the branched-chain alkyl group, the gases from the crankshaft bond, so that a mixture of branched housings is not directed into the carburetor. After quitting Alkyl groups, d. H. secondary alkyl group of the test period is the glass throttle body pen, results. photographed again; the effect of the detergent

The production of the gasoline contained in the invention (the percentage of removal of the

Branched-chain deposits containing motor fuels) is visually estimated

primary amines takes place, for example, as follows: In these experiments, branched-chain pri-

A mixture of alkyl chlorides is first prepared from alkylamine mixtures consisting of C ₁₅ -C ₂₀ cracking

by hydrochlorination of a mixture of therwax olefins in the manner described above

mix cracked wax olefins, which had been obtained from about 15 to

Contain 20 carbon atoms per molecule. concentration of 0.003 weight percent checked. It

A mixture of secondary alkyl is thus obtained, which has been shown to clean the carburetor by up to

Chlorides, d. H. 2-, 3- and 4-chloroalkanes, in which 30 give 76%, whereas common straight-chain amines,

mainly (about 95 percent by weight) 2-chloro namely oleylamine, only a purification of about

alkanes are present, while the remainder 3 and higher make 57%.

is substituted. 1 mol of these alkyl chlorides is converted into an autoclave in further experiments, the oxidation of about 10 to 20 mol of ammonia at about 160 ° C resistance of the branched-chain primary alkyl under autogenous pressure in an autoclave, which sets in the motor fuel according to the invention. The reaction time is about 10 hours. The resulting reaction product is initially compared to similar straight-chain aminoalkanes. washed with lye and then with water. In each of these experiments, 0.5 g of 1-amino yield of primary amines is 80% and the (C, _{-C 20} ) alkanes obtained from cracked wax olefins yield of secondary amines is 4%; 5% had not been converted, heated in an open aluminum-converted olefins and 11% unconverted crucible for 24 hours at 130 ° C. This resulted in alkyl chlorides being recovered. The olefins an evaporation loss of 0.4 g. The remaining residue was 0.1 g of the converted and unconverted alkyl chlorides. This residue is removed and reused if necessary. was in an aqueous-organic solvent

The motor fuel according to the invention with the 45 dissolved and titrated with acid. It turned out that

branched-chain primary alkylamines indicate that the residue did not contain any base. In comparison

excellent flushing effect, compared with Mo-uchen resulted in the corresponding branched chain

petrol containing other alkylamines. primary alkylamine a residue of 0.1 g,

The flushing effect of gasoline becomes 0.2 mmol after all, as was shown by the titration

common usual method, namely the so-called 5 ° of the base contained. In the case of the branched-chain pri-

"Glass throttle body method," which especially the alkylamine were after 24 hours

for observation and evaluation of the deposits at 130 ° C in air, 55.5% of the base is still present.

in carburetors of normal explosion engines, while on the other hand the 1-aminoalkane itself

has been found. had completely decomposed.

With the glass throttle body method, the engine is used. The carburetor of this engine is being investigated further. The additives were blended into the metal throttle body by a removable and replaced white oil at 110 ⁰ C as well as on glass throttle body. This glass throttle body is heated to 149 ° C. A part of a V4 "glass tube with about I ³ A" 60 inhibitor 4,4'-methylene-bis (2,6-di-tert-butylphenol) outside diameter and I ³ A "length was added to the oil as the oxidation is. It was found that after 24 hours the distributor, which consists of an electric motor with the branched-chain primary alkyl constant speed at 110.degree. C. and magnetic coupling amines, which consists of C ₁₅ -C ₂₀ cracked wax olefins, is used in such a way that He had become a period, had lost only about 13% of their original operation of the machine with idling periods 65 borrowed nitrogen content, whereas 7.5 minutes and subsequent five accelerations the analogous 1-aminoalkanes and oleylamine about 2000 rpm The vapors 30% of their nitrogen content under the same conditions from the crankshaft housing are lost in the air. At 149 ° C the decomposition takes place.

settling even faster, so that in 8 hours about 40% of the oleylamine were decomposed, while only about 8% of the branched chain alkyl primary amines present in the motor fuels of the present invention contained, had decomposed with loss of nitrogen.

From the above description of the invention, the effectiveness of amines, which differ from Olefin mixtures, in particular thermal cracking wax olefin fractions, derive clearly. Usual Cjg-CoQ olefins used in the invention Motor fuels are contained, have the following composition in percent by weight:

C ₁₄ 0.6Vo

C ₁₅ 11.2%

C ₁₆ 19.3%

C ₁₇ 18.5%

C ₁₈ 18.4%

C ₁₉ 17.3%

C ₂₀ 14.0%

C ₂₁ 0.7%

cheap. The 2-, 3- and 4-haloalkanes so obtained can easily be converted into amines in a manner known per se (as already stated above) being transformed.

Claims (3)

Patent claims: 1. Motor fuels containing detergent, thereby characterized in that they are used as a detergent from 0.0001 to 1.5 percent by weight of a branched-chain primary alkylamine with 9 to Contains 24 carbon atoms in the alkyl group. 2. Detergent-containing motor fuels according to claim 1, characterized in that they are used as Dish soap an amine formula Such a mixture contains about 92 percent by weight straight-chain α-olefins, 3% α, ω-diolefins, ao 3% internal olefins and 2% branched-chain, naphthenic and other hydrocarbons. B. ferric chloride, is used to control the halogen addition so that the as halogen atom attaches to a non-terminal carbon atom to give the branched chain alkyl structure for the amine end product. The hydrohalogenation is also performed at temperatures of about 30 to 40 ° C, ie at temperatures that are not high enough to a rearrangement of the olefinic double bond to be sawn 1 * CHNHo in which R is a straight-chain alkyl group having 1 to 3 carbon atoms and R _{2 is} a straight-chain alkyl group having 5 to 22 carbon atoms. 3. Detergent-containing motor fuels according to claim 1, characterized in that they are used as Detergents contain an amine, which are also thermally cracked wax olefin mixtures, which are about 15 to have about 20 carbon atoms in the molecule.