DE1101853B - fuel - Google Patents

Description

GERMAN

The invention relates to liquid hydrocarbon fuels from the boiling range of gasoline with significantly improved performance parameters and in particular a noticeably reduced engine wear tendency, which in addition to comparatively high, i. H. to wear and tear leading lead concentrations in the form of organic lead anti-knock agents special, high-performance Contains anti-wear agents as additives.

The invention is based on the finding that dicyclopentadienyl iron, so-called ferrocenes, according to the invention Application of a highly effective protective agent against engine wear of the ones described Kind is.

According to the invention, the fuel consists of a liquid hydrocarbon base in the boiling range of gasoline, containing dicyclopentadienyl iron, alkyl lead and halogen detergents, its special The characteristic is that the same per liter contains about 0.560 to 1.675 g of lead in the form of an alkyl lead anti-knock agent, about 0.4 to about 0.6 theoretical units of bromine; and about 0.8 to about 1.2 theoretical units Units of chlorine, calculated on the basis of lead, in the form of halogen detergents, and per liter about 0.0066 to Contains 0.0793 g of iron in the form of dicyclopentadienyl iron.

In and of itself, it is not fundamentally new to using liquid hydrocarbon fuel compositions to provide dicyclopentadienyl iron, alkyl lead and halogen detergent, but one was so far not about the particular anti-wear effectiveness of those used according to the invention Lead and iron concentrations in the clear. In a literature reference are only wide areas for the Iron concentration and wide ranges for the lead concentration given, which have nothing to do with Quantitative ratios of the two materials to one another when they are used in combination can be. This reference not only specifies the proportions of tetraethyl lead according to the invention and dicyclopentadienyl iron not close, but rather steers by preferring iron concentrations, which are above the maximum concentration according to the invention, even from this. About that In addition, there are no indications of any kind regarding the use in the examples of this reference any amount of halogenated detergent.

If, on the other hand, the various components of the fuel according to the invention are specified in the Mixed ratios and this fuel is used for the high-performance operation of carburetor engines there is a considerably lower engine wear, in particular on piston rings and Cylinder bores.

Applicant:

Ethyl Corporation,

New York, N.Y. (V. St. A.)

Representative: Dr. phil. G. Henkel, patent attorney,
Berlin-Schmargendorf, Auguste-Viktoria-Str. 63

Claimed priority:
V. St. v. America July 12, 1957

Jerome Engel Brown, Detroit, Me. (V. St. A.),
has been named as the inventor

The great advantages occurring when using the fuel according to the invention are based on the interaction of the various fuel components mentioned above. So they work special proportions in the bromine and chlorine-containing detergent mixture with the comparative high lead content and the very low dicyclopentadienyl iron content together to achieve these very important and unexpected results. Here the detergent mixture consists preferably of bromine and hydrogen chloride in the specified amount. Particularly good results are achieved with a mixture of ethylene dibromide and ethylene dichloride Quantity ratio achieved. Furthermore, the great reduction in wear is achieved when the Fuel per liter contains about 0.0132 to 0.0264 g of dicyclopentadienyl iron, and therefore these proportions represent represents a particularly preferred embodiment of the invention.

Machine tests were carried out to demonstrate the astonishing behavior of the fuel according to the invention. A paraffin hydrocarbon fuel with 0.79 cm ³ = 0.821 g of tetraethyl lead per liter and 0.5 theoretical units of bromine as ethylene dibromide and 1 theoretical unit of chlorine as ethylene dichloride is used to operate an engine under the heaviest loads. The test engine has a displacement of 573.54 cm ³ and is operated at 2500 rpm and a jacket temperature of 82 ° C. The intake air is filtered to prevent atmospheric dust from entering. The extent of wear is measured according to the method described in the December 1956 issue of the magazine "Nucleonics" on page 70, with

109 529/367

for the engine wear the weight loss at the obe- ^ 9, the ^ machine is made according to this standard verren Piston ring in mg / h during the test period 'Wear test method with two different driving functions. This upper piston ring consists of a substance operated. "The amount of radioactive iron Chrome-plated cast iron body with radioactive isotopes present in the lubricating oil due to wear. If the piston finger surfaces during the 5th particle becomes radioactive after a usual If the engine is subject to wear, the measurement technology is determined.

Abrasion in the lubricating oil over where its concentration During the tests, the following fuels

used by measuring the radioactivity of the lubricating oil:

is measured by means of a gamma spectrometer. _Λ τ? -R. "· ·, · _{M n} , ,, _now -r.,.,

τ ,, a "j,. ^r,, ; τ-,,. , ..., ..,. ι. 1 km gasoline with a lead content of 0.837 g /

The extent of the determined radioactivity is in io _T. · -C- τ «, ... ·. ,,,. >. _c °,

j. ,, -r, ■ ■. j, - i_. ι. j -liter in ± <orm of tetra-ethyl lead, 0.5 theore-

direct relationship to the weight loss to the,. · ■ τ, ·,., Τ, · τ? ί ,,,,.

τ; - , ι. · Α- ι. -et -tr ti- · _ο -ι jj table units bromine m .borm of ethylenedi-

Piston rim surfaces as a result of wear during the ΐ. ™stens; j ^ a λ α * .u * u tr t, * r-ί, ι

λ / γ ^ ι r j. j · j i-ι -n j · -MT-X bromide and 1.0 theoretical units of chlorine m

Engine running under these drastic conditions. With ■ &"*■". χα, ι a ui -jj

TT-IJ- j- -Kr οχ ι · ι j j- -Ti _ir 11 -η rorm of atnylene dichloride and

With the help of this _{measuring technique , direct wear and tear 2} ^ kiche ^^ _{Bmzi dem Dicyclopenta-}

measurements Andes chromium and iron surfaces of the above i ₅ i _{e Dieny} isen in a concentration of 0.0528 g

The first piston ring is carried out, with many _{ice cubes being added}

such engine tests basic values for these two s

Types of engine wear can be obtained. - - The white spirit 1 is therefore a typical one in the trade

If these tests are carried out under the same test, leaded gasoline is widely used during the conditions and using the same lead ao test fuel 2 a cohesion according to the invention, but has settlement with 0.0264 g / l dicyclopentadienyl iron.

In comparison, the tests show that the wear occurs

a considerable reduction in wear of the piston ring to 62% of the reference value compared to the basic values.

change on. In a similar way, an obvious set occurs, with the reference value being that of wear and tear

Is a reduction in wear and tear in heavy-duty operation of Ver 25, which occurs in the absence of the iron compound,

gas engines on when you have a liquid coal- In other words, the presence of

hydrogen fuel with the boiling range of gasoline 0.0528 g iron per liter in the form of dicyclopenta-

used, the per liter of about 0.560 g to about 1.675 g of dienyieisen in the leaded gasoline leads to a

Lead in the form of an alkyl lead anti-knock agent, such as reducing wear on the piston ring

0.4 to about 0.6 theoretical units of bromine as 30 of 38%.

Bromine detergent, especially carbon bromide. From this it can be seen that the hydrogen such as ethylene dibromide, about 0.8 Ms about compositions according to the invention bring a really remarkable 1.2 theoretical units of chlorine as a chlorine-containing and unexpected technical advantage.
Rinsing agent, especially chlorinated hydrocarbons such as Furthermore, a gasoline with an octane number of ethylene dichloride, both theoretical units on lead 35 99.0 and a content of 0.793 ecm tetraethyl lead, and 0.0066, 0.0106, 0.0396, 0 in liters , 0528 contains 0.837 g of lead per liter, in Pro or 0.0793 g of iron in the form of dicyclopentadienylben with dicyclopentadienyl iron (ferrocenes) in steieisen. For example, the offset amount is reduced and the increased octane rating is checked for the wear and tear of the chrome surface up to 50% of the basic value. This results in the following and in a similar way the wear of the 40 image:
Iron side up to 60% compared to the missing one
Ferrocenes added back values.

These results are completely unexpected. Until now

it had been found that ferrocene was the disadvantage

of engine wear. This is on the order of 45 0.0132

was attributed to the earlier investigators. 0.0264

with completely different compositions and / or 0.0528

Preservatives than the 0.1321 used according to the invention

Ferrocenes in grams / liter

Octane number

99.5
99.6
99.8
100.1
100.6

worked. 0.2642

The following test results may be 50

the surprising, technical progress of the results of the same kind are also presented with numerous

Use of small iron concentrations in other remaining, commercially available types of gasoline is achieved,

tem propellant according to the invention versus the These series of tests give a characteristic

known use of large iron concentrations Image: The first trace of added iron compound,

clearly resulting in a considerable reduction 55 falling within the scope of the present invention,

of machine wear. - gives the greatest increase in octane number. Were

A single cylinder engine that is as effective as that with a radioactive Elsen all intended as an additive

Iron-containing piston ring was provided, the first 0.0132 g / liter, this would result for every 0.264 g

operated under the following _conditions:; . . Iron addition per liter increases by a full ten

Speed 1800 rpm ^6o octane units. In fact, however, the

Load !*!! ................ Va full load ^gan £ ^{from 0} - ^{1321 to} 0.2642 g iron per liter one

Air supply * * 1 <? '' 6 k / h octane increase of only 0.5 achieved. So would be

-tr i_ "ii · T ^ * 4 '". "ä' t ''''''' ^ all added iron only as effective as the second

Ratio of fuel to air .. 0 080 _{Half of the} total amount of this test series, see above

Intake air temperature 38 ° C _{6g with the addition of 0) 26} 42 g iron per liter only

Water temperature in the coat .. 82? C achieve an octane number increase of 1.0,
oil temperature 66 ° C This statement means that the very small amount of iron in the ignition "40 ° BTC ratio to lead has a synergistic effect.

(in front of the upper gistic effect, which occurs with a high iron-lead dead center) 70 relationship is absent. This phenomenon is completely

1 IUl 8 Ö 3 5 6

surprising and justifies the technical progress, in heavy-duty operation of an engine with this power

by the ferrocenes tetra- substance according to the invention occurs a remarkable reduction in the

Ethyl lead ratio values is achieved. Piston ring wear.

To adjust the fuels according to the invention For the fuels according to the invention, the various additives in the appropriate amount can be used , Methyltriein hydrocarbon from shale oil, coal tar or ethyl lead, dimethyl diethyl lead, trimethyl ethyl lead, synthesis processes can be. A substantial amount of Tetraoctylblei or the like or mixtures thereof. Any reduction in wear occurs when gasoline is blended, so the alkyl group can contain 1 to about 8 hydrocarbons. B. motor or aviation fuel, containing the invention atoms and a straight or branched off appropriate protective additives. Form a chain. Tetraethyl lead is used because of its height. _R. . ren performance characteristics, its occurrence in the ΰ game- ! Trade and its equity are preferred.

A gasoline with 35 percent by volume can be distilled off directly. The components used in the fuel according to the invention, 40 percent by volume of catalytically generated bromine and chlorine-containing detergents are orcracked material, 10 percent by volume of polymeric ganohalide compounds that are used during the incineration mixed material and 15 percent by volume of butane and pen- ning process react in the engine with the lead to form tan (initial boiling point 38.3 ° C, 10% 59.4 ° C, 50% volatile lead halides. This should preferably be 106.6 ° C, 90% 164.6 ° C and end boiling point 198, 3 ° C) 20 bromine-containing detergents do not contain chlorine and the chlorhalwwill contain no bromine per liter with 0.560 g lead in the form of tetraethyl, but mixed halo lead, 0.4 theoretical units of bromine in the form of gene compounds are also suitable, provided that the total bromopropylene dibromide , 0.8 theoretical units of chlorine and chlorine content within the specified limits in the form of 1,2,4-trichlorobenzene and 0.0066 g per liter. Chlorinated hydrocarbon detergents and in particular iron in the form of dicyclopentadienyl iron blended with those with a vapor pressure between 0.1 and th. The gasoline obtained in this way shows an unusually 250 mm Hg at 10 ° C and is below my better storage properties because of its low engine wear when the engine is running preferred to drastic conditions. however, other detergents are also successful. · 1 _TT reversible. Suitable rinsing agents include Example 11 _3o carbon tetrachloride, propylene dibromide, 2-chloro-2,3-Ein gasoline with 85 percent by volume directly distilling off dibromobutane, 1,2,3-tribromopropane, hexachloropropyte components, 10 percent by volume catalytically gel, mixed bromoxylenes , 1,4-dibromobutane, 1,4-dicracked material and 5 volume percent butane and chloropentane, etc.

Pentane (initial boiling point 41.1 ° C, 10% 60 ° C, 50% particularly preferred detergent mixtures ent-97.2 ° C, 90% 127 ° C and boiling point 188 ° C) will hold 35 0.5 theoretical units of bromine as ethylene Liters with 1.675 g of lead in the form of tetraoctyl lead, bromide and 1.0 theoretical units of chlorine as 0.6 theoretical units of bromine in the form of 1,4-ethylene dichloride or 0.6 theoretical units of bromine in dibromobutane, 1.2 theoretical units of chlorine in as Ethylene dibromide and 1.0 theoretical units in the form of hexachlorobutadiene and per liter 0.0793 g of chlorine as ethylene dichloride or 0.45 theoretical iron in the form of dicyclopentadienyl iron combined 40 units of bromine as dibromobutane and 1.0 theoretical. The gasoline thus obtained gives a lower motor units chlorine than ethylene dichloride. This mixed wear factor for very heavy engine operation. genes effectively regulate the amount of exposure during. _{T of} the operation in the engine forming paragraphs and achieve _{this in the most modest} way possible.

A gasoline with 23 percent by volume is directly distilled off.
Cracked material and 15 percent by volume reformed The fuels according to the invention can advantageously-gasoline (initial boiling point 34.4 ° C, 10% 50 ° C, 50 ^fl / o with the following additional additives - 99 ° C, 90% 157.7 ° C and End boiling point 197.2 ° C) 50 are cut: dyes as identification with will be per liter with 0.837 g lead in the form of methyltel; Metal deactivators, e.g. B. N, N'-Ditriäthylblei, 10.4 theoretical units of bromine in salicylidene-1,2-diaminopropane; Icing and rusting form of mixed bromoxylenes, 1,2 theoretical protective agents, surface combustion regulator additives, are called chlorine in the form of / j ^ '- dichlorodiethyl ether such as tricresyl phosphate, tri (/? - chloropropyl) -thionphos- and 0.0528 g per liter Iron in the form of dicyclo- 55 phate, dimethyltolyl phosphate, dimethyl xylyl phosphate, pentadienyl iron blended. The ready-mixed trimethyl phosphate, dixylyl phosphoramidate, trialkyl gasoline reduces engine wear during engine operation, phosphine, etc., antioxidants or the like.
under drastic conditions. The fuel used according to the invention. Basic substances are preferably made such, Example IV _go ^ j ₆ i _nner half the gasoline or all over

A gasoline of 92 percent by volume is catalytically boiling away. This boiling range is in the all cracked Components, 6 percent by volume thermally common between 29.4 and about 216 ° C, although at cracked material and 2 percent by volume of reformed aviation fuel special types a boiling range between gasoline (Initial boiling point 33.9 ° C, 10% 52.2 ° C, see around 27.8 ° C and around 170 ° C is required. 50% 106.1 ° C, 90% 181.1 ° C and boiling end point 65 The basic fuel substances come from the ver-213.3 ° C) per liter with 1.321 g of lead in the form of various refining processes and tetrabutyl lead, 0.6 theoretical units of bromine as sen directly distilled gasoline, catalytic or ether-acetylenetetrabromide, 0.8 theoretical units of mixed cracked raw materials or gasoline-chlorine as 1,4-dichloropentane and 0.0264 g of hydrocarbons per liter from processes such as reforming, Iron added in the form of dicyclopentadienyl iron. 70 Polymerization, isomerization or the like

both individual gasoline hydrocarbons or their blends can be used with success.

Claims (4)

Claims; 1. Hydrocarbon-based power torrent im Gasoline boiling range with a content of dicyclopentadienyl iron, alkyl lead and halogen detergents, characterized in that the same per liter 0.560 to 1.675 g lead in the form of an alkyl lead anti-knock agent, 0.4 to 0.6 theoretical units of bromine and 0.8 to 1.2 theoretical units Chlorine, calculated on lead, in the form of halogen detergents, and in liters from 0.0066 to Contains 0.0793 g of iron in the form of dicyclopentadienyl iron. 2. Fuel according to claim 1, characterized in that the bromine-containing detergent is a Bromocarbon and the detergent containing chlorine is a chlorinated hydrocarbon. 3. Fuel according to claim 1, characterized in that the bromine-containing detergent is ethylene dibromide and the detergent containing chlorine is ethylene dichloride. 4. Fuel according to claim 1, characterized in that the same 0.560 to about 1.675 g of lead per liter in the form of tetraethyl lead, 0.5 "theoretical units of bromine in the form of ethylene dibromide, 1.0 theoretical units of chlorine in the form of ethylene dichloride, each based on lead, and contains from 0.0132 to about 0.0264 grams of iron per liter in the form of dicyclopentadienyl iron. Considered publications:
German Patent No. 935,467;
British Patent No. 737 092;
French patents No. 1 078 519,
080 357, 1 082 934.