DE2645713A1 - FUELS FOR GASOLINE ENGINES - Google Patents

Description

BAS ¹ ? Corporation

Our reference: 0.Z ₀ 32 227 Hp / Kl 6700 Ludwigshafen, October 6th, 1976

Fuels for gasoline engines

Addition to patent "...". "(Application P 21 44 199.6)

The invention relates to fuels for gasoline engines with a content of (a) diamides of fatty acids and polyamines and (b) Esters of fatty acids with ethylene oxide and / or propylene oxide adducts.

As detailed in German Offenlegungsschrift 2 144 199 described, it is desirable to use fuels for gasoline engines Mix in additives that clean or keep the carburettors clean.

According to the main patent. (Registration P 21 44 199.6)

Fuels for gasoline engines claimed, containing in small amounts as surface- or washing-active petrol-soluble components

a) Diamides from C ₁₂ - bis (^ -fatty acids and polyamines with 2 to 6 carbon atoms and 2 to 4 nitrogen atoms and

b) Esters of C ₁₂ - to C _2Q fatty acids and ethanol or propanol amines, and optionally

c) phenols known per se as antioxidants sterically hindered by space-filling alkyl substituents and optionally further

d) as a solubilizer for components a to c and

Residual oils from the nonanol and decanol oxo synthesis as a top-lubricating oil component.

It has now been found that the effect of the gasoline additives can be improved and, in particular, possible Can prevent corrosion if component (b) is

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sets by condensation products from saturated or unsaturated Carboxylic acids with 8 to 20 carbon atoms with the 2 to 20 molar amount of ethylene oxide and / or propylene oxide.

Suitable carboxylic acids for the condensation products are especially fatty acids. »For example, decanoic acid, undecanoic acid, dodecanoic acid, lauric acid, oleic acid, stearic acid, Palmitic acid, naphthenic acids or castor oil acids are suitable. These acids can not only be straight-chain but also branched or contain a five- or six-membered ring in the molecule » The carboxylic acids, preferably fatty acids, with the 2 to 20 molar amount of ethylene oxide and / or propylene oxide z. B. with 1 to 10 moles of ethylene oxide and 1 to 10 moles of propylene oxide in condensed in any order or with a mixture of oxides. Preferably those compounds are selected which have two to four molecules of ethylene oxide and 2 to 5 moles of propylene oxide included at the same time.

The fuels for gasoline engines are characterized by properties that are known per se. The range of their volatility extends from 6 lbs / sq.in at 100 ° F (37.8 ° C). (0.41 bar) to 16 lbs / sq.in. (1.03 bar) and over a range of "50% points" in the ASTM D-86 test of 170 ⁰ F (77 ° C) to 27O ° F (132 ° C). The ASTM end point of gasoline is between 35O ° F (176 ° C) and 45O ⁰ F (232 ⁰ C). Full specifications for motor gasolines are defined in detail in United States Federal Specification WM-56I a-2 Oct. 30, 195 ^ as Fuel M, Regular and Premium grades of classes A, B and C.

The compounds to be used according to the invention are used appropriately to the gasoline to be improved in such a way that first - e.g. also with the help of a solubilizer, like toluene or a gasoline fraction with a larger proportion of aromatics, a concentrate is prepared that is used in the motor fuel, can preferably be added continuously in the refinery. This concentrate can contain other carburetor cleaning components, in particular contain the polycarboxylic acid esters known from Belgian patent specification 807 489.

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Such overall combinations are particularly advantageous by cleaning and keeping the intake part, the carburettor and the inlet valves of gasoline engines clean »

The propellants according to the invention can also have other per se known petrol additives such as lead alkyls, anti-icing additives, corrosion protection agents, Contain rubber inhibitors and dyes.

This washing action of the propellants according to the invention can be achieved illustrate very clearly if you look at the so-called "Residue on Evaporation Tests, Motor Fuel" described in "Standard Methods for Testing Petroleum (Febr" 1956) The Inst, of Petroleum, London ", Ste 394. According to this Method are gasoline samples of 100 cm each with the individual products proposed as carburetor washing components added and blown off with hot air like in a car carburetor, then the remaining residues in previously weighed glasses weighed back. If these residues are treated with 10 ml of n-heptane, this dissolves the residues more or more less off. After another blow-dry with air and further carrying back shows the percentage of the dissolved away Residue the washing action (Table 1).

dissolved away from the residue

Blank value: cracked gasoline ^x 22 %

1000 ppm di-oleic acid diethylenetriamine diaraide I 66 %

1000 ppm mono-oleic acid ester II 48 %

obtained by reaction with 2 moles of ethylene oxide and 3 moles of propylene oxide

1000 ppm 2,4-di-tert-butyl-phenol III 73 %

1000 ppm of a mixture of:

500 ppm di-oleic acid diethylenetriamine diamide I +

500 ppm mono-oleic acid ester obtained by reaction with 2 moles of ethylene oxide II 3 moles of propylene oxide 95 %

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333 ppm I + 333 ppm II +

333 ppm III 99 «

The effect is further intensified if, as a solubilizer for the mixtures to be added according to the invention, the residues of the oxo synthesis of monanol and decanol are used as further component (d) instead of the known "top lubricating oils" (pure hydrocarbon mixtures). A complete residue resolution of 100 % is then achieved. Component (d) is generally used in a quantitative ratio of 9: 1 to 1: 9 to the sum of (a) + (b) or »(a) + (b) + (c). Particularly good results are achieved with proportions of 1: 1.

A great, unexpected technical advantage is that these products are not only excellent Solve it for gummy residues, but according to their> The constitution (higher alcohols, ethers, acetals and aldehydes) also burn far better in the engine than those previously used Top lubricating oils.

In a BASF single-cylinder test engine with a displacement of 332 cnr (bore = 65 mm diameter, stroke = 100 mm), 50-hour test runs were carried out at a constant speed of 2000 rpm and an hourly fuel flow of 1.6 liters of propellants according to the invention drove. The plot was modified so that 10 % of the exhaust gases were returned to the crankcase below the oil level and from there into the air filter of the intake line of the carburetor (Solex Type 26VPIS).

A mixture of 90 parts by weight of unalloyed mineral base oil and 10% of an HD oil was used as the lubricating oil for these tests. The fuel consisted of a highly olefinic, non-stabilized cracked gasoline with a high gum content (ASTM D 529). After 50 hours of test runs, black deposits were found on the fuel without the specified additives on the air funnel and in the throttle valve area of the carburetor and on the shaft of the inlet

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valve detected »Table 2 shows the low cleaning effect each of the individual device components alone and that the combination with the same application amount the Cleaning effect of the respective individual components by leaps and bounds exceeds »The evaluation of the degree of soiling in the Carburetor (especially in the Venturi tube) happens in the ratio of the dirty to the clean surface <,

Table 2

The assessment is based on the "Demerit assessment" explained in the main patent.

Rating number (Demerit rating)

Blank value: petrol contains cracked petrol 0

A 1000 ppm di-oleic acid diethylenetriamine diamide 5

B 1000 ppm monooleic acid ester of triethanolamine 0

C 1000 ppm residual oil from the oxo synthesis of

Monanol 0

D 1000 ppm 2,4-di-tert-butyl-phenol 3

E 500 ppm di-oleic acid diethylenetriamine diamide
+ 500 ppm ricinol ester by reacting with 3 mol

Propylene oxide and 3 moles of ethylene oxide 8

F 250 ppm di-oleic acid diethylenetriamine diamide
+ 250 ppm ricinol ester by reacting with 3 mol

Propylene oxide and 3 moles of ethylene oxide
+ 500 ppm residual oil from the oxo synthesis of

Nonanol 9

G 200 ppm di-oleic acid diethylenetriamine diamide
+ 100 ppm ricinol ester by reacting with 3 mol

Propylene oxide and 3 moles of ethylene oxide
+ 200 ppm 2,4-di-tert-butylphenol
+ 500 ppm residual oil from the oxo synthesis of

Nonanol 10

Accordingly, the combinations listed show about the same washing effect as the additives of the main patent, but with the advantage that the reaction products of fatty acid with Alkylene oxides have a more favorable corrosion behavior.

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Claims (6)

O.Z. 32 Containing propellants for gasoline engines as an additive in small quantities a) Diamides from saturated or unsaturated carboxylic acids with 12 to 20 carbon atoms and polyamines with 2 to 6 carbon atoms and 2 to 4 nitrogen atoms and b) Condensation products from saturated or unsaturated Carboxylic acids with 8 to 20 carbon atoms, with the 2 to 20 molar amount of ethylene oxide and / or propylene oxide. 2. Propellants according to claim 1, containing as further component c) sterically hindered by space-filling alkyl substituents known per se as antioxidants Phenols. 3. Teibstoffe according to claims 1 or 2 containing as further component d) as a solubilizer for components a to c and residual oils from the nonanol and decanol oxo synthesis as top lubricating oil components. 4. Fuels according to Claims 1 to 3 containing 20 up to 2000 ppm of components a + bbzw. a + b + c. 5. Fuels according to Claims 1 to 3 containing 50 to 500 ppm of components a + bbzw. a + b + c. 6. Fuels according to claims 1 to 3, in which the weight ratio (a) to (b) 1: 8 to 8: 1 or (a) to (b) to (c) is 1: 1: 8 to 8: 1: 1 and the sum of (a) + (b) or (a) + (b) + (c) to the solubilizer (d) is in a weight ratio of 9: 1 to 1: 9. BASF Aktiengesellschaft 809815/0332