DE1052742B - Liquid hydrocarbon fuel for internal combustion engines - Google Patents

Description

The invention relates to new fuel compositions and, more particularly, to fuels with improved anti-knock properties, the cyclopentadienyl metal compounds contain.

Together with the construction and development of internal combustion engines for cars and trucks the need for anti-knock properties arose for the petroleum industry of hydrocarbon fuels to keep improving. These improvements were made in general effected by two specific procedures. One of these methods is process improvements in refining, ζ. Β. by thermal and catalytic cracking, as well as in reforming or Alkylation process. The other method is to use fuel additives to control the To improve the knock resistance of hydrocarbon fuels. Improvements in the refining technique but require considerable capital expenditures; the use of fuel additives has as better way, especially from an economic point of view, bigger and more widespread inclusion found. The present invention therefore relates to the improvement of hydrocarbon fuels with regard to their ignition and combustion properties. Apart from the effectiveness the anti-knock agents showed other significant effects with regard to the hydrocarbon solubility, Resistance, toxicity of these agents and the like.

The invention relates to a liquid, hydrocarbon-containing fuel for internal combustion engines, the contains a cyclopentadienyl compound of a metal or a metal-like element as an anti-knock agent, wherein the cyclopentadienyl group, if the metal is iron, with at least one alkyl, alkenyl, Aryl, aralkyl and / or alkaryl group and, if another metal is present, either is substituted or unsubstituted. The cyclopentadienyl group is attached to the metal or metallähnliehe Element bound directly via the methylene group.

In the simplest case, the basic structure of the anti-knock agents according to the invention can be as follows general formula are shown:

in which η is a low integer from 1 to 4 and M is a metallic element. Among the elements that may be contained in these compounds, liquid hydrocarbonaceous
Fuel for internal combustion engines

Applicant:

Ethyl Corporation,

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

Representative: Dr. W. Beil and A. Hoeppener,
Lawyers, Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority:
V. St. v. America 5 July 1952

Hymin Shapiro, Detroit, Mich.,

Earl George DeWitt, Royal Oak, Mich.,

and Jerome Engel Brown, Detroit, Mich. (V. St. A.),

have been named as inventors

include copper, silver and gold, ie the elements of group IB of the periodic table. It is also possible to use: beryllium, magnesium, calcium, strontium, barium and radium, ie the elements of group IIA of the periodic table; Zinc, cadmium and mercury, ie the elements of group IIB of the periodic table; the elements of Group IHA of the Periodic Table, ie boron, aluminum, gallium, indium and thallium; the elements of Group IHB of the Periodic Table, ie scandium, yttrium, lanthanum and actinium, as well as the lanthanides and actinides; the elements of Group IVA of the Periodic Table, ie silicon, germanium, tin and lead; the elements of Group IVB of the Periodic Table, ie titanium, zirconium and hafnium; the elements of group VA of the periodic table, e.g. B. arsenic, antimony and bismuth; the elements of group Y ¹ B of the periodic table, ie vanadium, niobium and tantalum; the elements of group VIA of the periodic table, e.g. B. Selenium, Tellurium and Pelonium; the elements of group VIB of the periodic table, ie chromium, molybdenum and tungsten; the elements of Group VIIB of the Periodic Table, that is, manganese, masurium (technetium) and rhodium; the elements of group VIII of the periodic table, ie iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum.

809 769/285

However, the additives according to the invention are not limited to the above general formula, which represents the basic structure of the group of anti-knock compounds according to the invention, since the Cyclopentadienyl radical can also be motii-, di-, tri-, tetra- or penta-substituted by monovalent groups can; in addition, the said portion can directly have at least one conjugated ring structure be connected. The cyclopentadienyl component can, for. B. be substituted by monovalent radicals, with further anti-knock agents useful in accordance with the present invention result from the following general Formula can be represented:

R ₁ -

-R *

in which R ₁ , R ₂ , R ₃ , R ₄ and R _{5 are} identical or different and can represent hydrogen or organic radicals and in which η and M have the same meanings as above.

Thus, the R ₁ , R ₂ , R ₃ , R ₄ and R ₅ groups of the anti-knock agents according to the invention can be alkyl or alkenyl radicals, both straight-chain and branched, or else aryl, phenyl, aralkyl or alkaryl groups.

If the cyclopentadienyl portion of the anti-knock compounds according to the invention directly with at least is connected to a conjugated ring system, one comes z. B. to cyclopentadienyl groups, in which the organic ring system combined with the cyclopentadienyl component is alicyclic or aromatic can be. If it is alicyclic, there results a group of connections which are represented by the following general Formula can be represented:

(CH ₃ ); j; ) (CH ₂ ) MM

40

45

in which α and b can be identical or different and can mean lower integers, including 0 and exclusively 1, η and M have the same meanings as above and R ₆ , as also described above, can mean hydrogen or organic radicals. If α is 0, there is hydrogen or an organic radical on each of the carbon atoms labeled 2 and 3. These monovalent radicals can be identical or different. The same applies to the carbon atoms labeled 4 and 5 when b is 0.

If that with the cyclopentadienyl portion of the invention Compounds combined organic ring system is aromatic, one obtains a group of compounds, which can be represented by the following formulas:

70

/ R ₂ - R ₉
ι \ / Ri- \ -R ₈ R ₇ \.
R ₆

in which R ₁ , R ₃ , R ₅ , R ₆ , R ₇ , Rg, R _? , R ₁₀ , R ₁₁ , R ₁₂ and R _{13 can be} identical or different and can represent hydrogen or organic radicals and in which η and M have the same meaning as above.

In addition, various organic radicals that do not have any cyclopentadienyl components can sit on the metal atom need to contain, so that one can get alkyl-cyclopentadienyl metal compounds comes.

Certain polyvalent metals such as lead, tin, silicon, germanium and the like are also capable of forming bonds from metal to metal manufacture. In such cases, the anti-knock agents according to the invention consist of compounds which contain a polymetallic cyclopentadienyl component, e.g. B. Hexa- (cyclopentadienyl) -diblei, Hexa- (indenyl) -ditin, di- (fluorenyl) - tetra - ethyl digermanium, diethyl tetra - (cyclopentadienyl) - digermanium, octa- (cyclopentadienyl) trisilicon and the like.

One advantage of the compounds with a metallic cyclopentadienyl component is their effectiveness Compounds in various hydrocarbon fuels, e.g. B. in untreated and treated Hydrocarbons, including thermally or catalytically cracked, after reforming and Hydroforming processes etc. of treated hydrocarbons in the gasoline boiling range. Also are the anti-knock agents can be used as additives to fuels with a wide range of sulfur contents.

About the surprising anti-knock effectiveness of the compounds with a metallic cyclopentadienyl component To show there was 4 parts of di (cyclopentadienyl) iron in 1,300 parts of a typical petroleum hydrocarbon fuel dissolved and stirred so that they were uniformly distributed in it.

The original hydrocarbon fuel had an octane rating of 77.5. The fuel mixture obtained, which contained 2.25 parts of di (cyclopentadienyl) iron per liter, was compared with another mixture of the same petroleum hydrocarbon fuel which contained various concentrations of lead retraethyl. The gasoline containing di (cyclopentadienyl) iron was found to have an octane rating of 91.7. In order to achieve the same octane number, it was necessary ^{to add 1.17 cm 8} tetraethyl lead per liter. Thus, in connection with the cyclopentadienyl component, iron was 1.83 times more effective than lead in the form of tetraethyl lead.

In addition, compounds containing cyclopentadienyl can be used successfully as anti-knock additives for various, Commercially available fuels are used which are hydrocarbon species and the sulfur content. have very different chemical compositions. So you can z. B. Mix Cyclopentadienyl thallium with the following typical gasoline which is 51.4% untreated Hydrocarbon, 22.8% catalytically cracked hydrocarbon, 14.3% thermally cracked hydrocarbon, Contains 8.6% isopentane and 2.9% butane, the sulfur content of which is 0.162%. amounts and that without addition has the octane number 81.2, and after addition

from 0.0079 to 2.12 g of thallium per liter gives a fuel with superior knock resistance.

Fluorenylthallium can also be added to the following typical gasoline which is 61.0% untreated Contains hydrocarbon and 39.0% catalytically cracked hydrocarbon, its sulfur content 0.168% and which has an octane number of 82.1 without the addition of anti-knock agents. With additives From about 0.0079 to 2.12 g of thallium per liter, on the other hand, results in a fuel with superior knock resistance.

You can also use 4,5,6,7-tetrahydroindenylthallium Mix in the following typical gasoline which is 45.1% untreated hydrocarbon, 28.7% catalytic cracked hydrocarbon, 13.5%. thermally reformed hydrocarbon, 8.7% catalytic Polymer and contains 4.0% butane, the sulfur content of which is 0.067% and that without additives of anti-knock agents has an octane rating of 81.2. With additions between about 0.0079 and 2.12 g Thal-Hum per liter you get a fuel with superior knock resistance.

Diindenyl iron can also be used for the following typical gasoline which is 34.8% catalytic cracked hydrocarbons, 29.1% untreated hydrocarbon, 25.2% thermally cracked hydrocarbon and contains 10.9% catalytically cracked aromatic hydrocarbons, its sulfur content 0.083% and that has an octane number of 83.9 without the addition of anti-knock agents. Of the Addition of amounts between about 0.0026 and 2.12 grams of iron per liter results in a superior fuel Anti-knock.

Diindenylosmium gives a typical gasoline additive that is 60.6% catalytically cracked Hydrocarbon, 29.3% untreated hydrocarbon and 10.1% of a catalytically reformed one Contains hydrocarbons with a sulfur content of 0.042% without the addition of anti-knock agents has an octane rating of 85.4. By adding amounts between about 0.0079 to about 2.12 grams Osmium per liter produces a fuel with superior knock resistance.

The following typical gasoline that is 63.0% untreated hydrocarbon and 37.0% thermally cracked Contains hydrocarbons with a sulfur content of 0.120% and without the addition of anti-knock agents has an octane number of 81.6, when diindenylruthenium is added in amounts between about 0.0039 and about 2.12 grams of ruthenium per liter of a fuel of superior knock resistance.

By adding 3-methylfluorenylgallium to the following typical gasoline containing 32.7% untreated hydrocarbon, 22.6% catalytically cracked hydrocarbon, 22.7% catalytically reformed hydrocarbon, 19.8% thermally cracked hydrocarbon and 2.2% butane, the sulfur content of which is 0.096%, without the addition of anti-knock agents has an octane rating of 52.1, amounts between about 0.013 and about 2.12 g are obtained Gallium per liter is a fuel with superior knock resistance.

A gasoline made from 46.1% catalytically cracked hydrocarbons, 27.4% untreated hydrocarbon, 11.2% thermally cracked and thermally reformed hydrocarbon, 9.1% catalytic Polymers and 6.2% butane, the sulfur content of which is 0.050%, without the addition of anti-knock agents Has an octane number of 81.7, results in two quantities when 5-phenylindenylindium is added about 0.011 and 2.12 g indium per liter a fuel with superior knock resistance.

As an additive to a gasoline that contains 50.0% catalytically cracked hydrocarbon, 40.0% untreated Contains hydrocarbon and 10.0% catalytic polymer, the sulfur content of which is 0.036% and which has an octane number of 81.3 without the addition of anti-knock agents, one takes tri- (2,4-diethylcyclopentadienyl) -scandium in amounts between about 0.0053 to about 2.12 grams of scandium per liter. A fuel with superior knock resistance is obtained.

Tetra (cyclopentadienyl) dysprosium as an additive to a gasoline that contains 56.0% catalytically cracked hydrocarbon, 18.0% untreated hydrocarbon, 17.1% thermally reformed hydrocarbon, Contains 6.3% catalytic polymer, 2.4% butane and 0.2% solvent, the sulfur content of which is 0.038% and which has an octane number of 85.0 without the addition of anti-knock agents, results in quantities between about 0.016 and 2.12 g dysprosium per liter a fuel with superior knock resistance.

It has also been found that it is advantageous in some fuel mixtures according to the present invention, which contain certain compounds with cyclopentadienyl moieties, still others, in the art to use known fuel additives. So it is z. B. to recommend with some of the mentioned Compounds at the same time still use such improvers, commonly called dishwashing detergents are known for engines, e.g. B. in U.S. Patents 1,592,954, 1668 022, 2,364,921, 2,398,281, 2,479,900, 2,479,901, 2,479,902, 2,479,903, 2,496,983. With some other fuel additives with cyclopentadienyl components, the simultaneous addition of wear-reducing agents, as described in U.S. Patents 2,546,421 and 2,546,422, for example. aside from that It has been found that the hydrocarbon fuel mixtures according to the invention also contain antioxidants, organic dyes and the like Success can be inflicted.

In general, compounds containing a cyclopentadienyl moiety can be added to the improved fuel blends contain, add in amounts between about 0.0026 and 2.12 g of metal per liter. In detail The amount of additives with cyclopentadienyl content depends on the type of fuel and the type of additives and the desired increase in octane number. In general, however, one usually takes quantities between about 0.026 and 1.2 grams of metal per liter.

Claims (13)

Patent claims: 1. Liquid hydrocarbon fuel for internal combustion engines, characterized in that that he used as an anti-knock agent a cyclopentadienyl compound of a metal or a containing metal-like element, the cyclopentadienyl group, if the metal is iron is substituted with at least one alkyl, alkenyl, aryl, aralkyl and / or alkaryl group and, if another metal is present, either substituted or unsubstituted. 2. Fuel according to claim 1, characterized in that the cyclopentadienyl compound Contains 1 to 4 cyclopentadienyl groups on a metal atom. 3. Fuel according to claim 1, characterized in that the compound is a di- (cyclopentadienyl) iron is. 10 4. Fuel for internal combustion engines according to claim 1 and 2, characterized by the addition of small amounts of organometallic compounds of the general formula MR ₂ , where M is an iron, nickel or ruthenium atom and R is a substituted cyclopentadienyl group. 5. Fuel according to claim 4, characterized in that R is one by an acyl, alkyl or Means carboxyl group substituted cyclopentadienyl group. 6. Fuel according to claim 5, characterized in that the organometallic compound di- (ethylcyclopentadienyl) -iron is. 7. Fuel according to claim 4, characterized in that the organometallic compound is dicyclopentadienyl iron is, 8. Fuel according to claim 1 to 7, characterized in that it contains 0.132 to 2.64 g of the organometallic compound contains in the liter. 9. Fuel according to claim 1 to 6, characterized characterized in that it consists of a gasoline as the main component. 10. Fuel according to claim 1 to 9, characterized in that it is also smaller Contains quantities of oil-soluble organic compounds containing phosphorus or arsenic. 11. Fuel according to claim 10, characterized in that it is used as a phosphorus-containing additive still contains tricresyl orthophosphate. 12. Fuel according to claim 1 to 11, characterized in that it also has a smaller one Contains amount of tetraethyl lead. 13. Fuel according to claim 12, characterized in that it also contains a halogenated hydrocarbon MotOT detergent for the tetraethyl lead. Legacy Patents Considered:
German Patent No. 935 467. © 809 769/285 3.59