CS277200B6

CS277200B6 - Car gasoline additive

Info

Publication number: CS277200B6
Application number: CS505889A
Authority: CS
Inventors: Daniel Ing Csc Bratsky; Juraj Ing Oravkin; Zdenek Ing Zatloukal; Pavol Ing Feher; Oldrich Ing Csc Mikula
Original assignee: Slovnaft
Priority date: 1989-08-31
Filing date: 1989-08-31
Publication date: 1992-12-16
Also published as: CS8905058A1

Abstract

Přísada do nízkoolovnatých a bezolovnatých automobilových benzínov zabraňujúca vytváraniu úsad v sacom systéme motora a chrániacej sedlá výfukových ventilov před zahlbením obsahujúca od 50 % do 98 % hmot. zložky A so struktúrnym vzorcom I, od 1 % do 20 % hmot. zložky B so struktúrnym vzorcom II a od 1 % do 30 % hmot. zložky C so struktúrnym vzorcom III.An additive to low-lead and unleaded automobile gasolines that prevents the formation of deposits in the engine intake system and protects the exhaust valve seats from pitting, containing from 50% to 98% by mass. component A with structural formula I, from 1% to 20% by mass. component B with structural formula II and from 1% to 30% by mass. component C with structural formula III.

Description

Λ 1 CS 277200 B6

BACKGROUND OF THE INVENTION The present invention relates to an additive for low-lead or unleaded automotive gasoline, which reduces or reduces deposition in the suction system and in the combustion engine of a spark-ignition engine and prevents damage to the exhaust valve seats. In order to reduce the emissions of harmful substances, lead, carbon monoxide, nitrogen oxides and unburnt hydrogen oxides, the content of lead anti-knockers (tetraethylol, tetramethylol) in automotive gasoline has been gradually reduced to a minimum concentration of 0.15 g Pb / 1, which is necessary for reliable and long-term operation of engines requiring leaded fuel. At the same time, however, the consumption of lead-free automotive gasoline is increasing, the use of which is a prerequisite for the lifetime of catalytic exhaust gas converters. For unleaded gasoline, a maximum concentration of 0.013 g Pb / l has been determined in virtually worldwide applications, which does not negatively affect the service life of catalytic converters.

However, the expansion of the use of unleaded petrol is limited by the design and the type of material used in the production of exhaust valve seats in addition to the technological possibilities of their production. It has been found that if the seats of the exhaust valves of the cylinder head are not made of particularly hard materials, the combustion of unleaded petrol in such engines causes damage to these seats, resulting in the cylinder head seats being heated up and ultimately destroying the cylinder head and the exhaust valves. . One way of solving this problem is to replace the cylinder head of such engines with another, which exhaust valve seats are made of particularly hard materials and thus resistant to unleaded auto gasoline burning conditions. However, such a solution, given the large number of such cars, is associated with high costs and is therefore unrealistic in the practice. Another possibility is the use of leaded car petrol until such cars are represented in the car park, which makes it impossible to produce and use ibabolines with consequent negative impact on the environment.

The most advantageous solution to this situation is the use of only lead-free automotive gasoline containing an additive according to the invention, the addition of which guarantees that the combustion of full-lead or low-lead gasoline does not cause damage to the exhaust valve seats made of non-cured materials of the same type, e.g. The additive of the invention also has a carburettor detergent effect on the intake tract of the engine, which has a beneficial effect on the cleanliness of the fuel, especially in the case of unleaded gasoline, which usually contains a proportion of aromatic hydrocarbons and oxygen compounds, e.g. MTBE. The additive according to the invention contains from 50% to 98% by weight of the additive. % of component A, from 1% to 20% by weight; % of component B and from 1% to 30 wt. component C.

Component A has the structural chemical formula I: CS 277200 B6 2 has a number of atoms

C

(I) wherein a is zero or 1 b is zero or 1 R 1 is a single-carbon hydrocarbon functional carbon of from 1 to 42 or hydrogen R 2 is a single-carbon hydrocarbon functional group having a carbon number of from 1 to 4;

cationNa +,

To the metal selected. +

Be2 + / 2, Mg2 + / 2, from the group ca2 + / 2, cations ba2 + / 2c R, which is hydrogen and / or comprising Lia Mn2 + / 2 integer from 1 to 3 hydrocarbon group with carbon numbers from 1 to 38 X oxygen or nitrogen

R 1 is a bivalent hydrocarbon group having a carbon number of 1 to 38 Y a single-function functional group - O "M + or a group r 7 wherein L is nitrogen or oxygen, and R 7 is a hydrocarbon functional group having 1 to 42 carbon atoms or hydrogen, and

R 8 is a hydrocarbon functional group having 1 to 42 carbon atoms, hydrogen or a functional group with chemical formula II, and f is zero or 1, and M + is a hydrogen cation, a metal cation selected from the group of Li +, Na +, K +, Mg 2+ / 2, Ca 2+ / 2, Ba 2+ // 2, Mn 2+ / 2, or a cation with structural formula III:

R 5 -NH R 6

(III) in which it means

Rg is a single-bonded hydrocarbon functional group having a carbon number of from 1 to 46 or a hydrogen R 6 bivalent saturated hydrocarbon group having 3 CS 277200 B6 carbon atoms from 1 to 10d an integer from 1 to 6

Component B has the structural chemical formula IV:

in which g is zero or 1 h is zero or 1

Rg is a single-bonded hydrocarbon functional group having a carbon number of from 1 to 42 or a hydrogen atom of R 10 and R 11 is a bonding hydrocarbon functionally functional group of

carbon atoms from 1 to 42, hydrogen or functional groups of structural formula II X nitrogen or oxygen.

Component C has a structural chemical formula I in which, with the exception of R3, all symbols have the same meaning as for component A. For component C in formula I, R 3 is a divalent substituted hydrocarbon group having from 1 to 38 carbon atoms, formula V:

wherein the individual symbols have the same meaning as in structural formula III.

In order to improve the handling, especially the viscosity and hence the pumpability of the packaging, transport and application of the present invention, the auxiliary component D by means of which the organic solvent is preferably used contains an aromatic type. Suitable solvent types are toluene, xylene, 9-13 carbon atom aromatic hydrocarbons, or technical mixtures thereof, such as heavy naphtha reformate, reformate fractions with a boiling point of 75 ° C to 250 ° C, pyrobenzine fractions with a similar distillation range The aromatic hydrocarbon content of these blends is usually above 28% by weight.

In order to provide the above-mentioned effects of the additive according to the invention, the additive comprising components A, B and C is added to the automobile gasoline at a concentration of 0.01 to 1.8% by weight. If the additive of the invention also contains the adjuvant component D, then the resulting additive concentration is selected such that the sum of the concentration of components A, B and C is within the stated range. In order to improve the pumpability and also to maintain the required content in the gasoline, the additive according to CS 277200 B6 4 of the invention can be further diluted with either benzene, one of its components or another hydrocarbon solvent before it is added to the gasoline. The additive of the present invention may be added to the gasoline either at the refining stage of the automotive gasoline (primary addition) or it may already be added to the finished gasoline at the stage of its consumption or distribution, for example at pump stations (secondary addition). The secondary addition of the additive of the invention is particularly advantageous when auto-mobile gasoline is produced without its contents. Next, I document the examples! however, the advantages and practical uses of the automotive gasoline additive according to the invention are without limiting the invention in any way. Example 1

On a four-cylinder Škoda petrol engine with a

A 1174 cm thick cast iron cylinder head was subjected to a stationary engine test under the conditions of Table 1 using complete unleaded gasoline (0.0000 g Pb / l) with octane number 92 using the method and 84 engine method. In the course of the test, every 6 hours was measured and, if necessary, adjusted for the valve so that its minimum value was not less than 0.2 mm. At the end of 48 hours of the engine test, the carburettor, suction pipe and engine cylinder head were removed from which the intake and exhaust valves were removed. After a change in the valve weights, the total hatching of the exhaust valve seats was measured. The results obtained are shown in Table 2, in which the individual values re-present the average congestion of the 4 cylinders, as well as the values for the one most depressed cylinder.

A similar test was also carried out with the mentioned gasoline, which contained 750 ppm of the additive according to the invention. The results of this test showed that no engine cylinder was hollowed out of the exhaust valves, even if the test duration was extended to 96 hours. The carburetor and engine intake tract cleanliness is also evaluated after the test. It turned out there was no formation of deposits and the carburetor was mirror-clean. The additive according to the invention contained 83 wt. % of component A by structural chemical formula 1.1, 8 wt. of component B with formula 1.2 and 9 wt. component C of formula 1.3. The additive of this composition was pre-mixed with the same amount of xylene prior to addition to unleaded gasoline to form the auxiliary component D.

(1.1) R6 = alkyl group C14_ig 5 CS 277200 B6

R1 = alkyl group C14_18 (1.2) 918H37? C16H334H7C-OH.h2n-c6h12 NH. (1.3)

NH C6H12 - NH2 Example 2

On a four-cylinder Škoda G-742.13 petrol engine with a cylinder head, a stationary engine test was carried out as in Example 1, using unleaded petrol with an octane number 96 and 87 engine methods containing a lead lead concentration for unleaded auto-gasoline, ie 0.013 g Pb / 1. The results obtained, which are shown in Table 3, show that such a lead concentration does not provide protection for exhaust valve saddles from heating up and thus that the use of lead-free gasoline with a lead concentration is not possible for this type of engines.

A similar test on this type of engine was also carried out with benzine, which had the same anti-knock properties but contained 0.004 g of Pb / l and 580 ppm of the additive of the invention. The results of this test have shown that no exhaust cylinder was hung in any engine cylinder, although the test lasted 72 hours. The additive according to the invention contained 78 wt. of component A with structural chemical formula 2.1, 15 wt. components B of formula 2.2 and 7 wt. component C of formula 2.3. The additive of this composition was dissolved in the heavy naphtha reformer before being added to the unleaded gasoline so that the resulting additive of the invention contained 42% by weight. mixtures of components A, B and C.

(2.1) CS 277200 B6 6

918H37? C16H33

C - C2H3-- C - OH (2.3) NH - C2H4 - NH - C2H4 - NH - C2H4 - NH2 Example 3

On a ŠKODA petrol engine, a 120 hour engine test with a 742.12X twist hurts in a variable operating mode including idling and 3000, 4000, and 5000 l.min-1a at full retraction. During the tests, the fuel consumption and the carbon monoxide content of the exhaust gas at 3000 and 5000 rpm were measured.

In the first test, unleaded gasoline with OCM 96a OCMM 87 (0.004 g Pb / 1) containing 0.05% by weight was used. additives according to the invention.

In the second test, BA-96 gasoline containing 0.15 g of Pb / l was used, containing 0.05 wt. an externally produced additive which has been declared as a detergent additive to the engine intake system.

After both tests were completed, the test engines were disassembled and the carburetor, intake manifold and engine intake valves were weighed before and after the test. The results of the tests (Table 4) showed that no exhaust valve was hung in both tests, the carburetors were complete with no deposits, and when using the additive of the invention, the exhaust gases contained less carbon monoxide than using the comparative additive. Lower fuel consumption at 5000 turns when using the additive of the invention suggests better combustion than using a comparison additive. The additive according to the invention contained 91 wt. of component A by formula 3.1, 1.5 wt. of component B (formula 3.2) and 7.5% by weight of component C with structural formula 3.3.

ONa (3.1) CH 7 CS 277200 B6 (3.2)

(3.3) CH_ Example 4

A pair of TATRA T-613 cars with 100,000 km of lead lead fuel was tested for the effect of the additive of the invention, which was added at 1600 ppm to lead-free gasoline (0.002 to 0.008 g Pb / 1) with OVMM 97 and extending 15% MTBE.

Both vehicles were driven during the trials mainly with urban and highway traffic in the range of 30,000 km. After every 4000-5000 km, the exhaust valve was inspected, which practically did not change during the entire test. At the end of the test, the carburetors and cylinder heads of the two test vehicles were demounted. It was found that there was no deposit formation in the carburetors and suction system and the exhaust valve seats were not broken. The additive according to the invention contained 52 wt. of component A of structural formula 4.1, 20 wt. % of component B with the formula and 28 wt. component C of formula 4.3. 0 0 Rl II l · (4.1) ~ C6H3— IC - NH -R1 'ok I R1 R1 = alkyl groups C32-42 and .CL Ro .......... .......... X X. 1 Ca and Λ 'J) ~ CH2 - N - CH2 TT; ca (4.2) ^ 0 * R1 = alkyl group C32-42 CS 277200 B6 8 _ NH _ c _ cu _ C - NH - R_, k ; 2 3

NH - (- C 2 H 4 - NH H 3 R 3 = C 28-36 alkyl group)

Said localization of the divalent calcium cations in formula 4.2, as well as the other divalent and optionally monovalent cations mentioned in Examples 1 to 3, which neutralize the hydroxyl groups of the compounds of the invention described herein, which is very important for its desired function. should be understood as one of the statistically possible cations. Intermolecular as well as extra-molecular linkages are also possible, however, the analytical methods currently used cannot be unambiguously determined. Nor is it possible to exclude the existence of a part of these cations in the form of finely dispersed hydroxide molecules, possibly also in the partial form, especially since the additive according to the invention has a relatively high viscosity in the undiluted state.

The acidity of the hydroxyl groups of said compounds is then compensated for by free electron pairs of nitrogen atoms present in these compounds to form quaternary salts.

Table 1

Site engine test conditions

Stage Duration (min.) Test Cycle Composition Engine Speeds (l.min-1) Engine Load 1. 20 3000 Full 2. 10 800 Idle 3. 20 5000 Full 4. 10 800 Idle

Table 2

Influence of the duration of the exhaust seat clogging test on the use of lead-free gasoline (0,000 g Pb / 1) without additive of the invention

Number Exhaust valve seat recess (mm) hours 4 cylinder diameter one cylinder max. 12 0,26 0,35 24 0,45 0,60 36 0,80 1,19 48 1,10 1,60 9 CS 277200 B6

Table 3

Effect of the duration of the exhaust seat clogging test using lead-free gasoline of 0.012 g Pb / 1 according to the invention

Number Exhaust Seat Exhaust (mm) Hours per 4 Cylinders One Cylinder Max 12 0.12 0.23 24 0.32 0.54 36 0.43 0.76 48 0.50 0.93

Table 4

Effect of the additive according to the invention and the additive outside the invention on the composition of the exhaust gases, fuel consumption and intake valve deposits Additive according to the invention

Additives outside the invention

CO content in exhaust gas (% vol.) At 3000 l.min ”1 3.0 3.9 at 5000 l.min” 1 2.1 2.5

Fuel consumption (1 / h) at 3000 l.min ”1 11.1 11.0 at 5000 l.min“ 1 15.4 16.2

Weight of deposits (g) on inlet valves - diameter per 4 cylinders 0.844 0.889

Claims

PATENT CLAIMS of component A, from component C, where, ^R i

Additive for low-lead and unleaded motor gasolines, characterized in that it contains from 50% to 98% by weight.

1% to 20% by weight of component B and from 1% to 30% by weight, component A has the structural chemical formula I:

OO, II ________ / \ ___________ I, r ₂ -J --- x ---- _C ---- L _R J ----- c ------ Y (I) / a \ / b 'v which means.

a zero or 1 ‘b zero or 1

Rj. a monovalent hydrocarbon functional group having 1 to 42 carbon atoms or hydrogen

R _{2 is a} monovalent hydrocarbon functional group having 1 to 42 carbon atoms, hydrogen or a functional group having the chemical structural formula II:

in which it means

Z is hydrogen and / or a metal cation selected from the group of cations comprising Li ⁺ , Na ⁺ , K ⁺ , Be ²⁺ / ² , Mg ^{2 + // 2} , ca ^{2 + y / 2} , Ba ²⁺ / ² and Mn ^{2+ // 2} .

c an integer from 1 to 3

R _{4 is a} hydrocarbon group having 1 to 38 carbon atoms

X is oxygen or nitrogen

R _{3 is a} divalent hydrocarbon group having 1 to 38 carbon atoms

Y is a single bond functional group - O ⁺ M + or a group

^r 7 wherein L is nitrogen or oxygen, and,

Ry is a hydrocarbon functional group having 1 to 42 carbon atoms or hydrogen, and

Rg is a hydrocarbon functional group having 1 to 42 carbon atoms, hydrogen or a functional group having the chemical formula II, and f is zero or 1, and

M ⁺ is a cation of hydrogen, a metal cation selected from the group consisting of cations of Li ^+, Na ^+, K ^+, Mg ^{2 +} / ^{2 +,} Ca ²⁺ / ^2, B a ^{^24/2,} Mn ^{2 + 2 //} or a cation of štruktárnym formula

III:

R ₅ - NH

(III) in which it means

R _{5 is a} monovalent hydrocarbon functional group having 1 to 46 carbon atoms or hydrogen; R 5 is a divalent saturated hydrocarbon group having 1 to 10 d carbon numbers, an integer from 1 to 6, and component B has the structural chemical formula IV:

(IV) wherein g is zero or 1 h is zero or 1

Rg is a monovalent hydrocarbon functional group having 1 to 42 carbon atoms or hydrogen

R 10 and R 10 are monovalent hydrocarbon functional groups having from 1 to 42 carbon atoms, hydrogen or functional groups having the structural formula II

X is nitrogen or oxygen, and component C has the structural chemical formula I, in which, with the exception of R _3, all the symbols have the same meaning as in component A, and thus in chemical formula I for component C it means:

R _{3 is a} divalent substituted hydrocarbon group having from 1 to 38 carbon atoms, the substituent of which has the structural chemical formula V:

^R 5

NH

in which the individual symbols have the same meaning as in structural formula III.