DE1645889A1 - Engine fuel mixture - Google Patents

Description

Engine fuel mixture.

The invention relates to an engine fuel mixture for a spark ignited four-stroke internal combustion engine. More particularly, the invention relates to engine fuel mixture containing as an additive polymers and their derivatives in an amount sufficient to be effective harmful deposits on the intake valves or intake valves and around the intake slots and exhaust slots of an internal combustion engine to reduce or eliminate. The invention also relates to a method of prevention the formation of such deposits.

It is known that in the internal combustion engines currently manufactured, substantial and deleterious deposits form on the intake valves and around the intake and exhaust ports of the engines. This is especially true for engines with overhead valves. Due to this precipitation 009823/1516

a «· wall-free functioning of the fuel intake: ^ s severely disabled. When building up such deposits the engine suffers a significant loss of energy, idling is uneven and the valves can even burn out. In the case of larger deposits, parts of them can even break off and be sucked into the combustion chamber, where they can lead to further mechanical damage to the engine.

The cause and nature of these deposits have been carefully investigated. These deposits are made up from the by-products of burned fuel and from lube oil aging products. The investigations did show that the agents contained in the lubricating oil to improve the viscosity index as a binder for the deposits act and that certain types of agents for improving the viscosity index act more detrimental than the other means. "Polymethacrylate-type viscosity index improvers form a class of materials that apparently contributes significantly to the build-up of the deposits.

The aging of the lubricating oil leads to deposits in the intake manifold in the following way. One ignited by sparks Internal combustion engine contains a lubricating oil tank in the crankcase. When the engine is running, the greater part will of the oil in the crankcase is sprayed onto the working engine parts and onto the cylinder walls. Part of the

009823/1516

Oil, however, is pumped to the upper parts of the engine to lubricate the parts working in it. On an overhead valve engine, a small amount of oil flow will be added to the upper part of the engine is pumped and passed constantly over both intake and exhaust valve necks to ensure that they are constantly lubricated in their guides during operation. The Ölbericseiung over the suction valve neck and the other parts of the valve head is apparently under the prevailing there! Temperatures are pyrolyzed and thereby Deposits formed and built up, the viscosity improvers acting as binders.

This particular problem does not arise with the outlet manifold or around the exhaust valves. This is partly due to that there is less oil on the exhaust valves and maybe on the high temperatures that exist in the outlet manifold and prevent the formation of deposits or possibly Burn away any deposits that form.

Surprisingly, it was found that the dissolution of a small amount of certain polyolefin polymers and their corresponding hydrogenated derivatives remove or prevent such deposits from forming such deposits on the intake valves and slots of a spark ignited four-stroke internal combustion engine in can be achieved effectively.

009823/1516

The invention relates to an engine fuel mixture, consisting of a hydrocarbon mixture in the gasoline boiling range, characterized by the content of about 0.01 to 0.20% by volume of a polyolefin polymer or equivalent hydrogenated polymer having a molecular weight in the range of 500 to 3500.

This engine fuel mixture has proven to be special

_ proven beneficial. The molecular weight is determined using a Osmometer measured.

The polyolefin polymers of the invention are made from monoolefins and diolefins, or copolymers of both, which have an average molecular weight in the range of about 500 to 3,500. Mixtures of olefin polymers whose average molecular weight is within the range given above are also effective. To prepare the polyolefin following olefins can be used, for example, W: ethylene, propylene, butylene, isobutylene, Amy1en, hexylene, butadiene and isoprene. In general, the polyolefins are made from olefin monomers composed of unsaturated hydrocarbons having two to six carbon atoms. The polyolefin polymers made from propylene and butylene are preferably used. It is also possible to use polyolefins obtained by cracking polyolefin polymers or copolymers with higher molecular

009823/1516

weight to a polymer in the molecular weight range given above getting produced. Derivatives of the polymers given above, which are obtained by saturating the polymers by hydrogenation can also be obtained advantageously be used. The term "polymers" refers to Polyolefin polymers and their corresponding hydrogenated derivatives.

The base fuel used in the motor fuel mixture according to the invention consists of a mixture of hydrocarbons which boil in the gasoline boiling range. This basic fuel can consist of straight-chain or branched-chain paraffins, cycloparaffins, olefins, aromatic hydrocarbons or mixtures thereof. This base fuel can consist of petroleum (naphtha) obtained by direct distillation from crude oil , polymer gasoline, natural gasoline or catalytically cracked or thermally cracked hydrocarbons or catalytically reformed batches. The composition of the base fuel is not critical. The octane level of the base fuel is also of no importance for the engine fuel mixture according to the invention. Any conventional base fuel can be used for the motor fuel mixture of the invention. The base fuel can include any additive normally used in motor fuels. The base fuel can be an anti-knock agent, for example a tetraalkyl lead compound such as tetraethyl lead, tetramethyl lead, tetrabutyl lead

009823/1516

or mixers thereof and the like. Contain. The Tetraäthyllei-L.Adchung obtained commercially and used for motor vehicles contains an ethylene chloride-ethylene bromide mixture as Rinse aid for removing lead from the combustion chamber in the form of a volatile lead halide. The engine fuel may also contain any of the conventional anti-ice additives, corrosion inhibitors, dyes, top cylinder lubricating oils, and the like.

The engine fuel mixture of the invention is made by mixing an appropriate amount of the above Polymer or a derivative thereof made with the base fuel. The amount of fuel added to the engine Addition is critical. The additive is generally used in a range of from about 0.01 to 0.20 volume percent. Particularly advantageous results are obtained when the additive is added to the fuel mixture in amounts of 0.05 to 0.15 vol. The preferred additional concentration is about 0.06 to 0.12 vol%.

The molecular weight of the polymer or polymer derivative is also critical in producing an effective motor fuel blend according to the invention. Beneficial Motor fuel blends according to the invention require polymers or hydrogenated polymer derivatives with an average Molecular weight in the range from 500 to 3500. This molecular

009823/1516

Weights are determined using the osmometer method. It will advantageous engine fuel mixtures obtained according to the invention when polymers and polymer derivatives with a molecular weight in the range from 650 to 2600 can be used. Particularly polymers with a relatively low molecular weight, for example in the range from 500 to 995, are preferred.

To determine the deposit-preventing effect of the engine fuel mixtures of the invention became two Tests carried out. One experiment is the chassis dynamometer test using a Buiek Wildcat engine. The second The experiment is an induction system deposit test using a 1964 Buick Wildcat car. It works these tests are based on the evaluation of the deposits on the suction valve and the slots »

The chassis dynamometer test is carried out using a Buick 425 CID V-8 motor (built in 1964) equipped with a PCV (Positive Crankcase Ventilation) valve and on a dynamometer test stand with speed and load control equipment and the engine temperatures is built up. This attempt requires approximately 1,325 liters of fuel and 15 liters of lubricant for each run.

Before each run, the cylinder heads are completely overhauled and new intake valves are installed. Special care must be taken, DAQ, the intake valve to valve guide

009823/1516

1 6 A 5 8 8 9

Q _

clearance is kept between 0.0089 and 0.0114 cm. In addition, the valve seat widths must be kept between 1.191 mm and 1.984 mm. The engine block is entirely in accordance with the methods described in Service Manual Buick 1964 obtained when the ^M blow-by ", or the oil consumption to be high.

with
The engine was added / 3.8 l of oil and was on for 15 min

1500 revolutions per minute balanced. After draining the oil a new 3.8 l of oil was added and the experiment started. The engine was running in a 4-speed 6 hour period for a total of 16 runs or 96 hours operated:

step

running time

0-1 1-4 4-5

hours

3 1 1

operation

idle

Road load heavy load rest

operation

Idle level

Speed rpm. 1000 ± load,
Focal-hp air-fuel ratio from 11.5 to 0.5 spark advance ^{0, 0} BTDC Auslaßrückdruck, i η.Hp 0.2

Intake air ^{temperature, 0} C 60 - outside jacket temperature, ⁰ C 93 - l crankcase oil

Road load class e -

2250 -

30 ± 1.5 12.2 -

1.0 - 60 - 1 93 i 1

113 i 1

Heavy load level

2250 ί

75 i 1.5 12.2 ^a 34

3,

60 ί

93 ¹ I.

113

temperature, ⁰ C 93 '

Typical values, not controlled

Approximate values - spark advance position 6 "BTDO at 600

00 9823/1 5 1 B rpm.

After completing an experiment, the cylinder heads were and valves removed and the valves visually inspected for the extent of deposition on the valve cup surface and rated. The deposits on the intake valve are classified according to an advantage rating scale, which has the rating levels 1-10 contains, rated. Evaluation level 10 means a completely clean valve. Evaluation level 1 is used for particularly heavy deposits on the valve. The deposits around the opening slots are marked with T = tracks, L = light, M = medium and H = highly rated.

The induction system fouling test was performed using a 1964 Buick "Wildcat" car. who had a 425 CID V-8 engine. All attempts were under the conditions of a horizontal road at 112 km / h and over a period of 56 hours (6270 km). the Engine overhaul and flushing methods were the same as those described above for the Chassis Dynamometer Test. The suction valves and slots were also rated on the benefit rating scale given above.

Two basic fuels were used in the following examples. A typical premium gasoline containing 3 cnr tetraethyl lead per 3.785 liters was used as the basic fuel A. This gasoline consisted of 27% aromatics, 15.5% olefins and 57.5% aliphatic hydrocarbons (determined according to the FBA analysis). This gasoline had an ASTM initial distillation boiling point of 31 ° C, an end point of i ⁽ .) 8 ° C and an

009823/1516

Research octane number of 101.0.

The base fuel B was similar to the base fuel A, but contained 0.5% by volume of a mixture of a corrosion inhibitor in mineral oil.

In the tests described above, the control fuels, ie the base fuel A and the base fuel B without any additives, resulted in deposits on the valve corresponding to the assessment levels 5.9 to 6.1. An improvement in rating to 6, k is a substantial improvement in the scale of the scale, and an improvement to 7.0 or higher is a particularly significant improvement.

Table I gives the results of the fuel inspections performed after the Induction System Deposit Test.

9 L 9 L / £ c8600 Trials 1-h - 11 - 0 * 03 $. Green fuel 075%. B. 0.1 - 7.6 0% M. Polypropene SCO TABLE Ia Valve slot concentration slot Valve slot Try 5-7 apply- apply- apply apply apply Polypropene 975 tung tung Yentii- tion tion tion Trial 8 Induction system - weight test apply Additive, molar weight Valve Polypropene 1120 ό, 4 Μ do it; T-L 8.3 L. apply Attempt 9 tion Polypropene 897 7, 6 L-M 7.9 9.1 T Attempts 10.11 slot Polypropene 1150 apply T-L Attempt 12 tion 7.9 T-L Polypropene 1370 8.5 L. Trial 13 Polypropene 25t> 0 7 Λ L 8.2 T Attempt 14t Polybutene 300 8.0 L. Attempt 15 Polybutene 730 8.2 M. O
-γ » Attempts 16.18 YY
J Mr Polybutene 1100 7.7 H 5? Attempt 19 I TVf Polybutene 1900 5 Λ Z Attempt 20 hydrogenated polybutene 1100 M. S. Attempt 21 Polybutene-1,800 ΊΛ- Attempt 22 1 to 1 C_-C. Copolymer 1010 Trial 2 $ ^q Cp-C. Ethylene-butylene copolymer L. 7.8 L. 8.2 810

Control no addition 5? 9 attempt

TABLE Ib

Induction system deposit test Base fuel Try 1-k 8.6 810 A. concentration Polypropene 800 0.10% Try 5-7 9.0 Slot valve - Polypropene 975 slot Additive, molar weight Valve- evaluation_ evaluation evaluation Trial 8 valuation Polypropene 1120 Attempt 9 T-L Polypropene 897 Attempt 10.11 T-L Polypropene 1150 Attempt 12 Polypropene 1370 Trial 13 Polypropene 2560 Attempt 14 Polybutene 300 Attempt 15 7.5 Polybutene 730 Attempts £, 18 8.7 Polybutene 1100 Attempt 19 9.3 Polybutene I9OO Attempt 20 8.0 II hydrogenated polybutene 1100 Attempt 21 M-H Polybutene-1,800 Attempt 22 M. 1 to 1 ^C _-C. Copolymer 1010 Attempt 23 M-H Co-C. Ethylene-butylene copolymer

Control experiment no addition 5.9 H

009823/15 16

From the results obtained, the particular effectiveness of fuels containing polyolefins and hydrogenated polyolefins is indicated in the Concentrations and specified molecular weight ranges included, to be seen. One can also see the drawbacks that occur when using motor fuels that are a polypropylene with a low molecular weight.

The results of the investigations are summarized in Table II, those with fuel mixtures according to the invention according to the chassis Dynamometer tests were carried out.

TABLE II

Additive, molar weight

Trial 2k Polypropene 1120 Trials 25.26 Polypropene 1150 Trial 27 Polybutene 1100 Trial 28 Mixture of 0.0375% 800 MW Polypropene and 0.0375% 1370 MW Polypropene 1085

Control attempt no addition

chassis Dynamometer test 0.10% slot
apply
tunjj Base fuel B Valve
apply
tion T-L concentration 7.8 L. 0.075% 7.9 H Valve
apply
tion Slot valve slot
apply- apply-
tung tung tung 7.1 7.8 M.

7.2

6.1

The great advantages of the fuel mixtures according to the invention are clearly recognizable due to the high evaluation levels.

'- ■ • Pi.' 1 / ί ^! ,! ι,

-Your-

It i-s ^J okannt that polymers are added to gasoline in certain amounts unc ¹ ^ voted molecular weight ranges in order ..-; - * to thicken gasoline and to reduce its flow through the carburetor. According to US patent specification 2.0 · '9.0ό2, the kinematic viscosity of a gasoline is ^! i% increased when polymers with molecular weights from 2,000 to 270,000 are added. The kinematic viscosity of the basic fuel is hardly increased when the polymer additives are added to the new fuel odor according to the invention. The amount of polymer that increases the viscosity of a base fuel by less than 1% is essentially ineffective in thickening an engine fuel.

The viscosity tests were carried out on basic fuels and carried out with new fuels according to the invention, which had been made from these basic fuels, the kinematic viscosity was in Stokes at different temperatures certainly. The results obtained are summarized in Table III.

JB 2 1 15 "Ui BAD ORIGINAL TABLE III

Effectiveness of 800 molecular weight polypropylene polymer on gasoline viscosity.

Fuel composition Base fuel A

Base fuel A + 0.05% -jOO MW

Pol ypr * ". J / len Grinid fuel AO, 1% 800 M ₀ W.

V ο 1 y ν ": c ρ yie ii basic fuel A + O.Sfä 800 MW

Pol j propylene base fuel B base fuel E - '% G5 # 800 MW

Flisyl en

viscosity Stokes 25 ^U C
0.589 38 ^U C
0.529 0.591 0.528 0.593 0.530 0.593
0.599 0.529 0.598 - 0.602 - 0.601 - 0 _s 60i

ypiy basic fuel IfO, 075 ^ 800 MW

Polypropylene base fuel B + 0.1 ^ 800 MW

Polypropylene base fuel B + 0.2Each 8OG MW

Polypropylene

From Table III is to. see that the viscosity rises only in a few cases and where it rises it is generally below 1% and mostly below 0.5% «

009823/1516

Claims (1)

PATENT LAWYERS Dipl.-Ing. MARTI N LI CHT 8 MDNCHEN ₂ theres.enstrasse 33 DipL-Wirfsch.-lng. / XEL HANSMANN TEXACO DEVELOPMENT CORPORATION "Ρ" - "**" BASTIAN HERRMANN New York 17, NY _{or similar} »",., ··, Munich, April 24th 42nd Street East 135 V. St. A. Your mark Our mark Patent application; Motor fuel blend PATENT CLAIMS ™ 1. Motor fuel mixture consisting of a hydrocarbon mixture in the gasoline boiling range, characterized by the content of about 0.01 to 0.20 vol .- «* of a polyolefin polymer or a corresponding hydrogenated polymer having a molecular weight in the range from 500 to 3,500. 2. Motor fuel mixture according to claim 1, characterized in that the polyolefin is a polymerization product of a C ₂ -C 6 unsaturated hydrocarbon. 3. engine fuel mixture according to claim 2, characterized in that the unsaturated hydrocarbon of ethylene, Propylene, butylene, amine, hexylene, isoprene or butadiene. k. Motor fuel mixture according to Claims 1 to 3, characterized in that the polymer consists of polybutylene. Patent attorneys Dipl.-Ing. Martin Licnr, Dipr.-winsen.fng. «Xernanemann, Dipl.-Phys. Sebastian Herrmann 8 MÖNCHEN 2, THERESIENSTRASSE 33 · Telephone: 292102 · Telegram address: Lipalli / Munich 5. Motor fuel mixture according to claims 1 to 3 »thereby characterized in that the polyer consists of polypropylene. 6. Motor fuel mixture according to claims 1 to 5 »characterized in that the polyolefin is a copolyesterization product clay C ₂ -Cg unsaturated hydrocarbons, 7. Procedure to prevent rvn. Deposits on the Ameaugreutil and aa Schiita of a four-stroke combustion engine, characterized in that the engine is charged with an engine fuel mixture which consists of a hydrocarbon mixture in the gasoline and fuel sector and about 0.1 bit 0.20 vol.-Jt of a polyolefin polymer or a A corresponding hydrogenated polymer with a molecular weight in the range τ · κ about 500 to 3500 contains. 009823/1 5.16