SK35192A3 - Derivatives of dicarboxyl acids as additives in to leadless automotive petrols - Google Patents

Abstract

The derivatives have a structural chemical formula I <CHEM> where R1 is a bivalent hydrocarbon functional group or hydrocarbon functional group with nitrogen atoms in amino-position and/or etheric position with total number of carbon atoms from 1 to 38, R2 is a monovalent hydrocarbon functional group with a number of carbon atoms from 1 to 42 or hydrogen, X is a hydrogen and/or alkaline metal and/or alkaline earth metal, Y is oxygen or nitrogen, a and b are cardinal numbers zero or 1, selected such that a + b >/= 1, R3 is hydrogen or a monovalent hydroxy-substituted hydrocarbon functional group with a number of carbon atoms from 1 to 42 or a monovalent hydrocarbon functional group with a number of carbon atoms from 1 to 42 or a monovalent functional group of structural chemical formula II or III or IV, -[-CH2)c-NH-]dR4 (II) <CHEM> <CHEM> where R4 is hydrogen or a monovalent hydrocarbon functional group with a number of carbon atoms from 1 to 42 or a functional group of structural chemical formula III, R5 is hydrogen or a monovalent hydrocarbon functional group having a number of carbon atoms from 1 to 3, R6 is hydrogen or a functional group <CHEM> c is a cardinal number from 1 to 10, d is a cardinal number from zero to 6, e is a cardinal number from 1 to 50, f is a cardinal number from 1 to 50.

Description

Technical field

The invention relates to dicarboxylic acid derivatives as additives to low or unleaded motor gasolines. the effects of which are avoided

wear of exhaust seats valves automobi1ov not designed to fit combustion unleaded motor gasoline. BACKGROUND OF THE INVENTION Trend to use unleaded gasoline

It is noticeable worldwide as a result of efforts towards a healthier environment. The US began production of unleaded gasoline in the early 1970s. In Japan, unleaded gasoline began to be produced in 1974 and in Europe in early 1984. Since then, its share in the production and consumption of gasoline has been rising sharply. The global trend thus clearly leads to the production and use of only unleaded gasoline. For example, since March 1986, only unleaded gasoline has been used exclusively in Japan [1,2]. In the United States, their share of total production in 1990 was over 90¾, and in the early 1990s it is considered to completely exclude the production of leaded petrol. In Europe, the situation is not as clear-cut as overseas due to the time lag and the diversity of the car fleet and the technical possibilities of the refinery. Unleaded petrol is finding its place on the market in different countries differently quickly.

In developed European countries, the share of unleaded gasoline production in the total gasoline production is currently around 50¾. The total production of unleaded petrol is estimated to be at least 75¾ in 1995 [3.4]. compared to 21.3¾ in 1986 and 26¾ in 1987 [5,6]. Unleaded petrol has been produced and sold in Czechoslovakia since 1986. In 1990, the share of its production in total elderberry production did not exceed 3¾.

The production and distribution of unleaded gasoline from the outset encounters a major problem which, together with the technical capabilities of refineries, is a major brake on the immediate transition to the production and use of unleaded fuel only. This problem is the impossibility of burning unleaded gasoline in cars designed for leaded fuel. The combustion of unleaded petrol in such cars results in damage to the cylinder head of the engine to the engine itself and to the decommissioning of the car [7-12]. This is essentially an old-fashioned problem encountered by car manufacturers in the early 1920s, which suddenly resolved when lead-based anti-knockers were added to gasoline. The number of cars at risk of burning unleaded gasoline has been estimated to be as high as 70 million worldwide by 1987 [10], of which around 7 million in the UK [13]. In the CSFR, the number of cars unable to use unleaded fuel is estimated to be around 70¾ of the total number of passenger cars and, due to the statistically found 5¾-year replacement of passenger cars in the CSFR per year, their complete disappearance is expected only around 2010 [7.8].

Almost all cars manufactured by 1971 belong to this group of cars [10]. On the other hand, most car manufacturers have been producing models capable of burning unleaded gasoline since 1986, mostly since 1986 [14,15],

The engine failure in unleaded fuel combustion in these cars is due to the quality of the material from which the exhaust valve seats and / or valve seats are made. the entire cylinder head. If these are made of cast iron or other similarly occurs in the combustion of rapid abrasion and soft material,

As a result, the exhaust valves are getting lead-free wear. they recess more and more into the cylinder head of the engine and the valve clearance is thereby constantly reduced. The final stage of this process is the imperfect closure of the combustion chamber. loss of compression and engine power, tanning of exhaust valves and their seats. Finally, the engine cylinder head [10.12] is destroyed.

The degree and speed of the recess of the exhaust valve seats is dependent on the design and operating parameters of the car. Σ design parameters are in addition to the hardness of the seat material valve rotation, spring tension, seat angle and width, operating temperatures and valve geometry. The most important of the operating parameters are the engine speed, its load and the richness of the fuel-air mixture. Valve rotation, high engine speed and load, and poor seat bore mixtures have a drastic effect on the valves [10.12].

Practically only in gasoline has been shown to be stable in the exhaust twilight of the use of lead compounds that, in addition to increasing detonation gasoline, another very important function of protecting the exhaust valve seats from mechanical wear while operating the engine.

It is assumed that the lead combustion products of lead anti-knockers form a thin protective film on the valve seat surfaces, preventing high-temperature oxidation and abrasion and reducing adhesion and material transfer, thus protecting them from unwanted wear [10].

The solution to the problem that would lead to the use of unleaded fuel in this endangered group of cars is ·.

and / replacing the cylinder heads of these cars with those with specially cured exhaust valve seats; which is practically impossible and financially unacceptable to many types of run-off, b / adding to lead-free petrol such a harmless additive to catalytic converters that would replace the film-forming function of lead compounds and provide the exhaust valve seats with the necessary protection. Only two types of ingredients of this designation are currently offered on the world market. Although functionally satisfactorily satisfying several foreign engines, SKODA engines could not provide effective protection against the bore of their exhaust seats, even at several times the dozing recommended by the manufacturer f8].

Another option is to use leaded petrol until such cars are represented in the fleet. however, this makes it impossible to produce and use only unleaded petrol with the consequent negative impact on the environment.

literature

1. Chem.Econ. and Eng. Rev., 9, 25 (1986).

2. Chem. Ind., 7, 750 (1986).

3. Oil and Gas Journal, 88, 4, 11 (1990).

4. Erdol und Kohle, 3, 119 (1988).

5. Oil and Gas Journal, 85, 14, 15 (1987).

6. Petrole et Techniques 38: 316 (1986).

7. Bratsky, D., Oravkin.J. : Production of gasoline in Czechoslovakia at the turn of the millennium, 33.Konferencia o rop, Bratislava, 1988.

8. Bratsky, D. Fehér.P., Oravkin.J .. Má1ach, V. : Trend in automotive gasoline development and additives. Study. VURUP, Bratislava, 1990,

9. Petrole et Techniques. 60, 326 (1986).

10. Automotive Engineering, 95, 11, 72 (1987).

11. Hydrocarbon Processing, 68, 7, 11 (1989).

12. Grill.R.A .; Landells.R.G.M. : The Reduction of Gasoline Lead and Its Effect on Valve Seat Recession: The Problem and Its Solution., Proceedings of the 33rd International Conference on Oil with Foreign Participation, Bratislava, 1988.

13. Hydrocarbon Processing. 68, 17, 17 (1989).

14. Autozeitung, 20, 67 (1989).

15. Autozeitung, 21, 66 (1989).

SUMMARY OF THE INVENTION

The most preferred solution to this is to use only unleaded gasolines containing the dicarboxylic acid derivatives of the present invention. Their addition ensures that combustion of completely unleaded or low-leaded gasoline does not damage the exhaust valve seats of unhardened materials of various types, e.g.

The dicarboxylic acid derivative additives described in this invention are harmless to health and harmless to catalytic exhaust gas converters.

made of cast iron.

The dicarboxylic acid derivatives according to the invention have the structural chemical formula I:

COOX

R.

CO - Y / ^(R2 > and (I) ^(R3 >

R, a divalent hydrocarbon function or a hydrocarbon function with nitrogen atoms in the amino group and / or oxygen atoms in the hydroxy and / or. an ether moiety having a total carbon number of 1 to 38.

a monovalent hydrocarbon function having from 1 to 42 carbon atoms or hydrogen, hydrogen and / or an alkali metal and / or alkaline earth metal group.

Y a and b

R „is oxygen or nitrogen.

integers zero or 1. where a + b> 1.

hydrogen, or a monovalent hydroxy-substituted hydrocarbon function having a carbon number of 1 to 42. or a monovalent hydrocarbon function having a carbon number of 1 to 42, or a monovalent functional group with structural formulas II or III or IV.

- [- (CH ₂ ) _c -NH-] _d -R ₄ (II) (III) (-CH-CH-O-) -R 2, e 2 (-CH-CH-Q-) ₃ -CH = CH - (- NH- (CH _O) _-) (IV)

1 J,

5 6

R.

hydrogen or a monovalent hydrocarbon functional group having a carbon number of 1 to 42 or a functional group with a structural chemical formula

III.

hydrogen or a monovalent hydrocarbon function having a carbon number of 1 to 3, hydrogen or a - (- CH-CH--0-) - H

L c

d e

F

the whole number from 1 to 10. the whole number from zero to 6, the whole number from 1 to 50th the whole number from 1 to 50th

Such dicarboxylic acid derivatives, applied in unleaded automotive gasoline, are effective inhibitors of exhaust valve seat wear on cars not designed to burn unleaded auyobenzines and thus allow their continuous, trouble-free operation on this fuel.

In order to improve handling, in particular viscosity and hence pumpability at the stage of packaging, transport and application, the dicarboxylic acid derivatives as an additive to the gasoline according to the invention may also contain an auxiliary component which is an organic solvent, preferably of the aromatic type. Suitable solvent types are toluene, xylene, aromatic hydrocarbons having from 9 to 13 carbon atoms in the molecule, or technical mixtures thereof, such as the naphtha reformate, the reformate fraction boiling in the range of 75 ° C to 250 ° C, the fraction from pyrobenzine with a similar distillation range. The aromatic hydrocarbon content of these mixtures is usually above 25% by weight.

In order to ensure the above-mentioned effects of the dicarboxylic acid additives according to the invention, these are added to the gasoline at a concentration of from 0.025 to 1.1% by weight. If the additive according to the invention also contains an auxiliary component which is an organic solvent specified above, then the resulting addition of the additive to the gasoline is chosen so that the concentration of the active ingredient is within the stated range.

In order to improve pumpability and also to maintain the required content in automotive gasoline, the additive according to the invention can be further diluted either directly with gasoline before being added to the gasoline. one of its components or another hydrocarbon solvent.

The additive according to the invention can be added to the gasoline either directly in the refinery gasoline preparation stage (primary additive) or it can already be added to the finished gasoline at its consumption or distribution stage, for example at service stations (secondary additive). The secondary addition of the additive according to the invention is particularly advantageous in cases where automotive gasoline is produced without its content.

DETAILED DESCRIPTION OF THE INVENTION

The following examples illustrate the advantages and practical use of the specified dicarboxylic acids as additives to the gasoline of the invention, but without limiting the scope of the invention in any way.

Example 1

A 4-cylinder petrol engine with a cylinder capacity of 1174 cm with a cast iron cylinder head was subjected to a site engine test under the conditions of Table 1, using completely unleaded petrol (0.0000 g Pb / 1) with an octane rating of 96 by the research method; 87 motor method. as well as unleaded gasoline containing a lead concentration for unleaded gasoline, i. j. 0.013 g Pb / 1 with the same octane level. During the test, the valve clearance was measured every 6 hours and adjusted if necessary so that its minimum value is not less than 0,2 mm. At the end of the 36-hour engine test, the engine cylinder head was removed from the intake and exhaust valves. After detecting the change in valve weight, the overall depression of the exhaust valve seats was measured. The results obtained are shown in Tables 2 and 3, in which the individual values represent both the size of the average recess of the 4 rolls and the values for one, the most recessed roll. The test results showed. that the use of unleaded gasoline is not possible in engines of this type.

A similar test was also carried out with said totally unleaded autobenzine (0.0000 g Pb / l) but containing 850 ppm of the dicarboxylic acid derivative of the invention with chemical structural formula (I), wherein:

R 6 is

X is Ca

2 + / 2

Y is nitrogen. R ₂ is hydrogen.

A-1. b = 1. R 6 is - (- (CH ₂ ) _c -NH-] _d -R ₄ where c = 2.

d = 2 and R1 is a polypropenyl-1 with an average molecular weight of 450 g / mol.

The dicarboxylic acid derivative was prepared by reacting phthalic anhydride with N-polypropenyl 1-diethylenetriamine and subsequent neutralization of the resulting phthalic acid derivative with calcium oxide.

The results of this test showed that none of the engine cylinders had exhausted the exhaust valve seats, even when the test duration was extended to 56 hours (average change in the valve clearance of the exhaust valves was -0.0075 mm, maximum measured value -0.04 mm).

Example 2

On a four-cylinder petrol engine of the type Š 742.13 with a cast-iron cylinder head, a long-term service life test (300 hours) was performed under conditions of ČSN 30 0506 using unleaded petrol with an octane rating of 96 research method and 87 engine method / 1). The fuel used was saturated with 700 ppm of an additive according to the invention with structural chemical formula (I) wherein

R. is -CH-CH-. X is sodium, Y is oxygen, and is zero.

12 ^H 23 b = 1. R ₃ is - (- CH-CH ₂ -O-) _e - ₁ -CH-CH ₂ -NC ₁₄ H. _2g wherein e

3-5 and Rg is taking

H.

The dicarboxylic acid derivative was prepared by reacting tetrapropenyl succinic anhydride with propoxylated tetradecylamine and subsequent neutralization of the resulting intermediate with sodium hydroxide.

The additive of this composition was dissolved in the naphtha reformate prior to addition to unleaded autobenzine so that the resulting solution contained 50% of the active ingredient.

The results of this test showed that none of the engine cylinders had an indentation of the exhaust valve seats (the average change in the valve clearance of the exhaust valves was 0.055 mm). Unleaded gasoline containing the aforementioned additive according to the invention fully protected the exhaust valve seats of the used engine while not deteriorating any of its operating parameters monitored and did not reduce its overall service life.

Example 3

Road motor tests of 50,000 to 80,000 kilometers were carried out on the fleet presented in Table 4. New engines, carburetors, fuel tanks and suction pipes were used in cars. Unleaded autobenzine (0.001-0.005 g Pb / l) with OCVM 95-97 containing an MTBE content of 7-12% by volume was used as a fuel and was added with 750 ppm of a dicarboxylic acid derivative according to the invention with structural chemical formula (I) in which

R 6 is -CH = CH-, X is sodium. Y is nitrogen. R 6 is phenyl! . b - 1. R ₃ is C ₁₂ H ₂₅ The dicarboxylic acid derivative was prepared by reacting the corresponding secondary amine with maleic anhydride followed by neutralization of the resulting intermediate with sodium hydroxide.

For convenience of handling, a composition of this composition was dissolved in an aromatic solvent having a boiling point of from 140 to 190 to give the final solution containing 10¾ of the active ingredient before being added to unleaded autobenzine.

C tak.

All vehicles were driven mostly in urban and highway traffic during the tests. After every 5000 km, the clearance of the exhaust valves was checked, and the vehicle's performance and emission characteristics, as well as their fuel economy and octane demand, were measured every 10,000 km. The efficiency of vehicles with catalytic converters has been determined. After completion of the tests, the engines were dismantled and comprehensively evaluated.

The evaluations have shown that the additive according to the invention provides the exhaust valve seats of all test vehicles with perfect protection against wear during the combustion of unleaded petrol. The additive does not affect the negative engine or its life. Is the exhaust reading systems no spark ignition function harmless to catalytic gases and does not worsen the spark ignition engine emissions,

Table 1

Site engine test conditions

phase

Test cycle composition

Duration Engine speed [min] [l.min]

Engine load

First 20 3000 full Second 10 850 idle Third 20 5000 full 4th 10 850 idle

Table 2

Effect of test duration on exhaust valve seat recesses using lead-free gasoline (0,000 g Pb / 1) and additive-free according to the invention

Count hours Exhaust valve seat recess [mm diameter for 4 cylinders one cylinder max 12 12:26 0.35 24 12:45 0.60 36 0.80 1.19

Table 3

Effect of test duration on exhaust valve seat recesses using 0.013 g Pb / l of lead-free petrol and additive-free according to the invention

Number Exhaust valve recess [mm] hours Average per 4 cylinders One cylinder max.

12 12:12 0.23 24 0.32 0.54 36 0.43 0.76 ========= =================================

Table 4 Car fleet used for road motor tests “- - Vehicle type Count vehicles SKODA 120 3 SKODA 130 8 SKODA FAVORIT 136 L with catalytic converter 4 VOLGA GAZ 2 OLTCIT 11 R 3

Industrial usability

The application of the dicarboxylic acid derivatives according to the invention to unleaded gasoline permits the continuous trouble-free operation of all petrol-engined cars on this more environmentally-friendly fuel and thus allows virtually instantaneous transition from leaded gasoline to the production and use of unleaded fuel only.

Claims (1)

PATENT CLAIMS Dicarboxylic acid derivatives as additive # to low-lead or unleaded automotive gasoline, which prevent wear on the exhaust valve seats of cars not designed to burn unleaded gasoline, characterized by having the structural chemical formula I: _{from (} COOX) / ^(R 2 ⁾ and (I) 'CO-Y wherein R @ 1 is a divalent hydrocarbon function or a hydrocarbon function having nitrogen atoms in the amino group and / or oxygen atoms in the hydroxy and / or ether group having a total number of carbon atoms of from 1 to 38, R 1 is a monovalent hydrocarbon function having from 1 to 42 carbon atoms or hydrogen, X hydrogen and / or an alkali metal and / or alkaline earth metal group, Y oxygen or nitrogen, a and b integers zero or 1, with a + b> 1, Rg is hydrogen, or a monovalent hydrocarbyl function having a carbon number of 1 to 42, or a monovalent hydrocarbon function having a carbon number of 1 to 42, in which or a monovalent functional group having structural chemical formulas II or III or IV, [- (CH ₂ ) _c -NH-] _d -R ₄ (-CH-CH-O-) -R 2. e 2 (-CH-CH-O-) _ω . -CH-CH 2 - [-NH- (CH 2) -], -N-R 2 e -1,2 cd. 2 denotes (II) (III) (IV) rt R @ 1 is hydrogen or a monovalent hydrocarbon functional group having a carbon number of 1 to 42 or a structural chemical formula III. R_ hydrogen or a monovalent hydrocarbon functional b a group having a carbon number of 1 to 3, R, hydrogen or - (- CH - CH - O -) -, - H the whole number from 1 to 10th the whole number from zero to 6, the whole number from 1 to 50th the whole number from 1 to 50. I