SE433752B - FUEL ENGINES CONTAINING DIAMIDS OF FAT ACID AND POLYAMINES AND ESTATES OF FAT ACIDS AND ETHYLENOXIDE AND / OR PROPYLENOXIDE - Google Patents

Description

7711283-7 10 15 20 25 30 35 It has now been found that the effect of petrol additives can be further improved and in particular the risk of corrosion eliminated, if component b is replaced by condensation products of saturated or unsaturated carboxylic acids having 8 to 20 carbon atoms and a 2- to 20-molar amount of ethylene oxide and / or propylene oxide.

Carboxylic acids suitable for condensation products are primarily 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 may be not only straight-chain but also branched, or they may contain in the molecule a five- or six-membered ring.

The carboxylic acids, preferably fatty acids, are condensed with a 2- to 20-molar amount of ethylene oxide and / or propylene oxide, for example with 1 to 10 moles of ethylene oxide and 1 to 10 moles of propylene oxide in any order, or with a mixture of these oxides. Preferably, those compounds are selected which simultaneously contain 2 to H molecules of ethylene oxide and 2 to 5 molecules of propylene oxide.

As the fatty acid amides of polyamines, diolic acid diethylenetriamide, distearic acid dipropylenetriamide, dipalmitic acid diethylenediamide, dilauric acid methyldipropylenetriamide or diundecanoic acid triethylenetetramide are used. As sterically hindered phenols, 2, H-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,4-dimethyl-β-tert-butylphenol and other dialkylated phenols, cresols and xylenols are separately operated. The substances a + b or a + b + c are generally added in amounts of between 0.002 and 0.2%, preferably between 0.005 and 0.5%.

Furthermore, it has been found that in general residual oils from oxosynthesis, especially those starting from olefins having 3 to 16 carbon atoms, preferably 3 to 12 carbon atoms, are not only very suitable as solvents, but also give the substance mixtures to be added to the gasoline very much. good low-temperature properties. This is especially true for residual oils from oxosynthesis for the production of butyraldehyde and butanol. Such residual oils can be characterized, for example, in the following manner. 10 15 20 25 30 35 7711283-7 3 Residual oil from butanol synthesis Density <20 ° c> 0.051 g / cm3 solidification point (DIN 51 seen) -s0 ° c Neutralization number 0.05 - 0.4 mg KOH per gram Flash point (Abel-Pensky )> s0 ° c Plampunkt (Marcusson) 75 - 85 ° C viekeeitet <20 ° c> s - 10 est viscosity (50 ° c) 2 - 0 est Booking process 5 volume percent 175 in 10 ° C 50 "190 1 10 ° c 00 "210 h 10 ° c Ash content <1% leek oil from nonanol decanol synthesis Boiling process beginning> 2s0 ° c 50 volume percent approx. 330 ° C 00" ce a50 ° c Density (20 ° c) 0.85 - 0.80 g / cm3 solidification point (DIN 51 saa) <-20 ° c Flash point (Pensky-Martens)> 100 ° C Ash content <1% p Another surprising advantage of residual oils from oxosynthesis, especially residual oils from butanol synthesis, has been discovered by combining these carburetor purifiers components with the long-known mineral oil-based top oils known as valve cleaners.

If only top lubricating oils on a mineral oil basis are used in the petrol additives, top oil dosages of, for example, 0.08 to more than 2% by volume thereof are required for a sufficiently good valve cleaning effect.

If the additives recommended according to the invention are combined with top oil on mineral oil base using a residual oil from oxo synthesis, in particular a residual oil from butanol synthesis, the amount of top oil on mineral oil base required to achieve a sufficiently good valve cleaning effect can be considerably reduced. . 7711283-7 10 15 20 25 30 35 The combination of oxo oil, top lubricating oil on mineral oil base and the other additives recommended according to the invention thus make a significant contribution to environmental protection, since it is necessary to use a significantly smaller amount of lubricating oil and because the oxygen-containing oxo oil residues of its composition (higher alcohols, esters, ethers, acetals and aldehydes) burns far more efficiently in the engine than mineral oil-based lubricating oils.

The long-known lubricating oils and lubricating oil fractions are suitable as top lubricating oils on a mineral oil base.

A particularly suitable lubricating oil can be characterized, for example, by the following data.

Pärgtal (ASTM) 2 Density (1500) 9862 g / cm3 viscosity (20%) ao mmZ / s Viscosity (SOOC) 30.3 mm2 / s Flash point (Pensky-Martens) 70 ° C srelningpumr (DIN 51 saa) <-2o ° c Neutralization rate 0.01 mg KOH per gram The propellants for carburettor engines are characterized by known properties. The range of their volatility ranges at 37,800 from 0.41 bar to 1.03 bar and within a range of "50 percentage points" when tested according to ASTM D-86 from 77 ° C to 132 ° C. The ASTM endpoint for motor gasoline is between 176 ° C and 23200. Full specifications for motor gasoline can be found in United States Federal Specification VV-M-561 a-2, Oct. 30. 1954, such as "Fuel M", "Regular" and "Premium" of Classes A, B and C.

The substances proposed according to the invention are suitably added to the petrol in such a way that a concentrate is first prepared, for example also with the aid of a solvent mediator, such as toluene or a petrol fraction with a larger proportion of aromatics, which can be added continuously and in dosage to motor propellants. preferably in the refinery. This concentrate may also contain additional carburetor purification components, in particular the polycarboxylic acid esters known from Belgian Patent Specification 807,489. Such total combinations are extremely advantageous because they keep the intake manifolds, carburetor and inlet valves of carburettor engines clean inside.

The propellants of the invention may further contain other known gasoline additives, such as alkyl lead compounds, antifreeze, corrosion inhibitors, resin inhibitors and dyes.

The detergent effect of the ointment according to the invention can be very clearly damaged, if one uses the "Residue on Evaporation Test, Motor Fuel", which is described in "Standard Methods for Testing Petroleum", The Inst. of Petroleum, feb. 1955, 39H. According to this method, petrol samples are placed on each 100 cm3 with the different test products proposed as carburetor detergents and blown off in the same way as in a car carburettor with hot air, after which the residue remains in pre-weighed glass. If these residues are treated separately with 10 ml of n-heptane, this dissolves the residues more or less.

After another dry blow with air and a new Weighing, the content lost indicates the numerical value of the washing effect (see Table I).

Table I Triggered from the residue: Reference value: Cracked petrol 22% 0.1% dioleic acid diethylenetriamine diamide (A) 66% 0.1% monoolic acid ester (B) obtained by reaction with 2 moles of ethylene oxide and 3 moles of propylene oxide H8% 0.1% 2, H- di-tert-butylphenol (C) 73% 0.1% of mixture of 0.05% diolic acid diethylenetriamine diamide A and 0.05% monoolic acid ester, obtained by reaction with 2 moles of ethylene oxide and 3 moles of propylene oxide 95% Mixture of 0.0333% A 0.0333% B 99% o, os3s% c '7711283-7 10 15 20 25 30 35 A further enhancement of the effect is obtained if, as a solution mediator for the additive mixtures proposed according to the invention, instead of the known top lubricating oils ( pure hydrocarbon mixtures) uses residues from oxosynthesis, especially in connection with butanol production as an additional component (d). A complete residual solution is then obtained, ie 100% dissolution of the residue.

Component d is generally used in a ratio of between 9: 1 and 1: 9, calculated on the sum of a and b or a, b and o. Particularly good results are obtained with a ratio of 1: 1. 7 A major and unexpected technical advantage is that these products are not only excellent solvents for resinous residues but also, due to their composition (higher alcohols, ethers, acetals and aldehydes) are burned much better in the engine than those previously used. the top lubricating oils.

Examples of carburetor cleaning and cleaning In a single-cylinder test engine with a displacement of 332 m (cylinder diameter 65 mm, stroke 100 mm), test runs were performed every 50 hours at a constant speed of 2,000 rpm and a fuel consumption of 1 The engine was then modified in such a way that 10% of the exhaust gases were returned to the crankcase below the oil level and from there was led into the air filter in the carburettor's ("Solex Type 26VFIS") intake line.

As a lubricating oil, a mixture of 90 parts by weight of unalloyed mineral base oil and 10 parts by weight of high-pressure oil was used for this experiment. The fuel consisted of a high-olefinic unstabilized high-resin cracked petrol (ASTM D 529).

After test runs of 50 hours each, when depositing the fuel without the specified additives, black deposits were determined in the air inlet and in the carburettor valve area as well as on the shaft of the inlet valve. Table II shows that each of the different mixing components individually had a small cleaning effect and that the combination with the same amount of use exaggerates the cleaning effect of the individual components. The evaluation of the degree of soiling in the carburettor (especially in the throttle neck, venturi) was carried out in comparison between the soiled and the clean surface.

The assessment is based on the so-called Demerit valuation, whereby a completely clean carburettor with associated inlet system receives the value 10. If there are dirt deposits, a lower value is set corresponding to their thickness and quantity.

The blind or reference value (ie no additive with a cleaning effect in the propellant), equivalent to a "total soiling", is rated as 0. In this case, "total soiling" means a complete coating of the surfaces which come into contact with the fuel. means in the venturi, in the carburettor valve area and deposits in the test engine inlet valve.

Table II Evaluation number (Demerit evaluation) Ruference or blank value: Motor gasoline containing crack gasoline 0 In 1000 ppm diolic acid diethylenetriamine diamide (A) 5 II 1000 ppm ricinoleic acid ester (B) obtained by reaction with 3 moles of propylene oxide and 3 moles of ethylene oxide 0 III 1000 ppm oil from oxo synthesis of nonanol 0 IV 1000 ppm 2,4-di-tert-butylphenol (C) 3 V 500 ppm diolic acid diethylenetriamine diamide + 500 ppm ricinoleic acid ester from reaction with 3 moles of propylene oxide and 3 moles of ethylene oxide 8 VI 250 ppm diolic acid diethylenetriamine diamine + 250 ppm conversion with 3 moles of propylene oxide and 3 moles of ethylene oxide + 500 ppm residual oil from oxo synthesis of nonanol 9 VII 200 ppm diolic acid diethylenetriamine diamide + 100 ppm castor ester by reaction with 3 moles of propylene oxide and 3 moles of ethylene oxide + 200 ppm 2,4-ditert-butylphenol + 500 ppm residual oil oxosynthesis of nonanol 9.5 VIII 100 ppm A, 50 ppm B, 50 ppm C and 800 ppm D 9.0 IX 100 ppm A, 50 ppm B, 50 ppm C, 400 ppm D and 400 ppm E 9.0 X 200 ppm A, 100 ppm B, 100 ppm C and 500 ppm D 9.5 XI 100 ppm A, 50 ppm B, 50 ppm C and 800 ppm E 8.5 77101283-7 10 15 20 25 30 35 40 8 XII 100 ppm A, 50 ppm B, 50 ppm C, 400 ppm D 9.0 D = residual oil from oxosynthesis for the production of I butyraldehyde and butanol E = top lubricating oil on mineral oil base.

The stated combinations thus show approximately the same washing effect as the additives according to German Offenlegungsschrift 2,144,199, but with the advantage that when using the mixtures according to the invention practically no corrosion can be detected in the carburettor.

The solution-mediating and power-enhancing properties of the oxo oils in combination with the products according to the invention are illustrated by some examples.

Example 1 A mixture of 10 g of diolic acid ethylenetriamine diamide, 5 g of ricinoleic acid ester (from reaction of ricinoleic acid with 3 moles of propylene oxide and 3 moles of ethylene oxide) and 5 g of 2,4-di-tert-butylphenol is dissolved in a glass beaker by heating to 50 ° C. . When cooled to room temperature, the mixture becomes cloudy again.

After the mixture has been left at room temperature for 3 days, 2.4 g of sediment are obtained by filtering the mixture. After standing for 3 days at 000, the mixture has almost solidified.

By filtration 7.2 g of sediment are obtained.

If the above components are added with 40 g of residual oil from butanol synthesis and proceed in the same manner as described in the example, the solution of the substances remains clear even after standing for a whole week at 0 ° C. The solidification point of the solution according to DIN 51 583 is below -30 ° C.

Test 'of the' cleaning effect 'on' carburettor and inlet system In the fuel for an Opel-Kadett type engine, 1.2 l (55 hp at 5200 rpm), some of the substances listed in Table II were mixed. The test engine was run under the following conditions. 0.5 min idle at 1000 rpm 1 min at 3000 rpm and 15 hp (equivalent to 80 km / h) 1 min at 1300 rpm and 5.5 hp (equivalent to 35 km / h) 1 min at 1850 rpm and 8.5 hp (equivalent to 50 km / h) Test program 10 15 7111283-7 9 7 Engine operating conditions Temperature of the engine oil in the sump 94 i2 ° C Temperature of the coolant (at outlet from 92 i2 ° C cylinder head) 1oo ° c at the beginning of the experiment, 3.5 in 0.5 volume- Inlet air temperature (at idle) Carbon monoxide content of the exhaust gases percent at idle.

All tests were performed with the constant engine conditions just mentioned, and in all tests with the 0pe1-Kadett engine the same fuel was used.

Table III summarizes the results of the tests with the Opel Kadett engine.

The assessment of the purity of the carburettor and inlet valve took place in accordance with the so-called CRC scale for diesel engines (CRC-Merit Rating; 10.0 = 100% pure). 7711283-7 10 15 20 25 30 35 40 10 Table III Dosage used- Dosage CRC value batch substances (vol-ppm) Carburettor Inlet Deposition on in- valve inlet valve (mg) Reference with f 7.0 7.5 282 cracked petrol - 7.3 7.5 296 haltigt driv- - 7.0 7.0 316 average A 250,, 200 B sou, _, 276 C 500,, 264 A 250 8.5 8.0 212 + B + 125} A 250 + B + 125} 9.5 8.0 203 + C + 125 - A 100 B + so 9.0 9.0 98 C 50 E + 800 A 100 + B + so 9.0 9.5 1 | + s C + 50 + D + 400 A 100 + B + 50 + c + so 9.2 9.5 52 + D + 400 + E + 400 A 200 + B + 100 + c + 100 9.5 9.8 17 + D + 400. + E + 400 A = dioleic acid diethylenetriamine amide 3 moles of propylene oxide and 3 moles of ethylene oxide 2,4-di-tert-butylphenol residual oil from oxanol synthesis of butanol top oil on mineral oil base castor ester, obtained by reacting castoric acid with

Claims (1)

7711283-7 11 PATENT REQUIREMENTS Fuels for carburettor engines, consisting of commercial petrol, any customary additives and 20 - 2000 ppm, preferably 50 - 500 ppm, of a mixture of the composition (a) diamides of C12-C20 fatty acids and polyamines with 2 to 6 carbon atoms and 2 to 4 nitrogen atoms, and (b) esters of carboxylic acids and optionally (c) as antioxidants known with bulky alkyl substituents sterically hindered phenols and optionally also (d) residual oils from nonanol and decanol oxo synthesis as solution - intermediates for components a - c and as top lubricating oil components, the weight ratio a / b being 1: 8 - 8: 1 or a / b / c 1: 1: B - 8: 1: 1 and the weight ratio between the sum a + b or a + b + c and d are 9: 1 - 1: 9, characterized in that the esters consist of condensation products of saturated or unsaturated carboxylic acids having 8 to 20 carbon atoms and a 2- to 20-molar amount of ethylene oxide and / or propylene oxide .