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Publication numberUS2235466 A
Publication typeGrant
Publication dateMar 18, 1941
Filing dateJun 6, 1938
Priority dateJun 15, 1937
Publication numberUS 2235466 A, US 2235466A, US-A-2235466, US2235466 A, US2235466A
InventorsLucas Stedehouder Pieter, Melsen Johannes Andreas Van, Nieolaas Max, Peski Adrianus Johannes Van
Original AssigneeShell Dev
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Antiknock motor fuel
US 2235466 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented Mar. 18, 1941 UNITED TATE PATENT OFFICE ANTIKNOCK MOTOR FUEL No Drawing. Application June c, 1938, Serial No.

212,128. In the Netherlands June 15, 1937 a 1 Claim.

This invention relates to gasoline type motor fuels, 1. e., motor fuels suitable for use in gasoline engines, and more particularly deals with gasoline type motor fuels of high antiknock properties containing metal organic knock suppressors.

As is well known, certain mlneral oil-soluble metal organic compounds, such as tetraethyl lead, nickel and iron carbonyls, ethyl selenide, etc., have the property of suppressing detonation or knock in spark-ignition engines. These compounds are generally known as antiknock compounds. While some of them are highly effective, they are all subject to at least one or sev-' eral serious disadvantages, such as extremely insufliclent solubility in hydrocarbons, high toxicity, poor storage stability, corrosiveness to the engine, etc.

It is a purpose of this invention to provide a class of efllcient knock suppressors comprising metal organic compounds which are substantially free from the above disadvantages or at least possess them to a very much smaller extent, It is another purpose to provide non-toxic antiknock compounds readily soluble in gasoline having efllciencis comparable to those of tetraethyl lead; and it is a further purpose to produce antiknock gasolines containing metal organic antiknock compounds which upon storage for several months do not substantially decompose and depreciate in antiknock value.

We have discovered that metal organic compounds belonging to a class of compounds similar to those described in U. S. Patent No. 2,023,372

0 but differing from the latter by greater solubility in gasoline and greater antiknock value, may have knock-suppressing properties equal to or even better than the most potent known antiknock compounds. Our knock-suppressors are non-toxic, reasonably stable in storage, and gasolines containing small amounts thereof, i. e., equal in antiknock value to about 3 cm; tetraethyl lead per gallon of gasoline, do not corrode valves and valve seats, nor do they cause undue wear of moving engine parts.

Our knock-suppressors are compounds of a metal having an atomic number of 26 to 29 inclusive, i. e., a metal selected from the class consisting of iron, nickel, cobalt and copper, and an organic substance containing both nitrogen and oxygen based on the following structural formula or its equivalent:

HOC=CC=NR| R1 and R1 are hydrogen or organic radicals and R3 is an organic radical selected from the group consisting of alkyl, aryl and aralkyl, which may or may not contain one substituent. The radicals R1, R2 and R3 should preferably not contain more than 6 carbon atoms in total. Moreover, R2 jointly with R1 may form a ring structure, if the joined radicals contain a suificient number of carbon atoms to form at least a 4-carbon ring. Suitable substituents in hydrocarbon radicals R1 to R3 are all those which are capable of forming substantially stable compounds with hydrocarbons, such as halogen, CN, OH, OH,, COR, NHz, NHR, NR2, --SH, SR, COOR, etc., neutral and basic substituents being preferred to those which are strongly acidic, such as COOH, SOsH, etc.

As is well known, in compounds of the above formula the double bonds are capable of shifting their exact location within the molecule depending upon the surrounding conditions, thereby forming the enol or keto forms and amino or imino forms, respectively. Therefore the following structures are considered full equivalents of the above:

i. at

The metal compounds of our invention may be conceived as salts or complex compounds or both. It is believed that the metal is usually attached to the oxygen as follows:

where Me is a metal having an atomic number of 26 to 29, and n is the valence of the metal. It is, however, likely that in addition there are links of secondary valences between the metal and the nitrogen, giving the compounds the character of complex compounds.

Our knock suppressors may be prepared by reacting for instance oxymethylene acetaldehyde or oxymethylene acetone or homologues thereof, either in the free state or in the form of their alkali metal salts or their compounds with alcohols, such as ethers and acetals, with primary organic amines, such as mono alkyl amines, mono alkanol amines, alkylene diamines, aniline, chlor aniline, etc. When starting from alkali metal salts of the oxymethylene compounds, the amines should be applied in the form of their salts, e. g., the hydrochlorides, whilst when starting from acetals of the oxymethylene compounds it is preferable to carry out the reaction in the presence of water. The resulting reaction products are purified by suitable methods and are then converted to the desired metal compound for instance by treating same with copper acetate whileln solution of a suitable solvent, such as an alcohol having not more than 4 carbon atoms.

The anti-knock value of our compounds depends to some extent on their volatility and solubility in gasoline. In the absence of polar radicais, solubility increases and volatility decreases in general with increasing molecular weight of the organic component. If both R; and R: are hydrogen the solubility in gasoline of the metal compound may be quite low, but suflicient, so that the corresponding compounds of copper and the ferrous metals are useful as antiknoek compounds. If R1 or Rs or both are organic radicals, metal compounds thereof may be miscible with gasoline in substantially all proportions. On the other hand, if the molecular weight of the organic compound exceeds about 300 then the volatility becomes low and under average carbureting conditions a portion of the metal compound may deposit in engine manifolds instead of being drawn into the combustion chambers of the engines.

Compounds which are sufficiently volatile to reach the combustion chamber of gasoline engines under average carburetion conditions without material deposition in the manifold are usually distillable without substantial decomposition under high vacuum 1. e., a vacuum of about 0.1 mm. mercury or lower.

Some of our metallic organic compounds are normally liquid while others are normally solid. Certain of those which possess highest antiknock values, such as the copper compound of methyl amino methylene acetone, are normally solid. However, it appears that the normally solid compounds have certain disadvantages as against those which are normally liquid. For instance, the former have a greater tendency of forming deposits in engine manifolds under average carburetion conditions and also in general are less soluble in gasoline. We have found, that frequently mixtures may be normally liquid, which mixtures consist essentially of our normally solid and normally liquid compounds and may contain the normally solid components in substantial proportions. Such liquid mixtures are highly useful as they may combine all the advantages of the normally liquid compounds with the very high antiknock value of the normally solid compounds.

Solubilities of little soluble compounds may also be improved by the addition of mutual solvents, such as the lower alcohols, ketones, ethers. amines, etc., boiling preferably within gasoline boiling range.

If desired gasoline type motor fuels may be prepared consisting entirely or predominantly of neutral oxyhydrocarbons, such as ethers, ketones, or alcohols, particularly those with branched carbon chains and boiling within gasoline boiling range, containing small amounts of our antlknock compounds.

The amounts of our antiknock compounds nor. mally incorporated into the fuels to effect an improvement in the knock rating may vary from a bare trace to about .5% metal by weight of the fuel, although larger amounts may be used, if degin-on ems-0 si-crn u (or C0) N-CH:

on- B Other suitable compounds are: the cupric or cobalt compound of allyl amino methylene pinacoline having the formula:

the cupric or cobalt compound of ethyl amino methylene acetaldehyde.

u(or Col Further examples of suitable compounds are the copper, iron, nickel or cobalt compounds of the following organic componnets:

CHr-C O-CH=CHNEC1H; (Ethyl aminomethylene acetone) CHr-C OCH=CH-NHC:H (Allyl aminomethylene acetone) CrHs CHr-C O-O=CHNHCH; (Methyl amlnomethylene peutanone-Z) C(CHr):

CHx-C 0- =CB-NHCzHs (Allyl aminomethylene methyl neopentyl ketone) CoHr-C OCH=CH-NHC:H; (Allyl aminomethylene acetopbenonc) CHsC- 0 HELCH=CHNHCH: (Methyl aminomethylone acetaldehyde) 0 on 11 -c=cn-Nrtcin (Methylaminomethyleue propionaldehyde) Also mixed compounds of copper or the ferrous metals with different species of the organic components hereinbefore described, or with other compounds, such as alcohols, phenols, mercaptans may be employed For instance the basic alcoholate of the cuprlc compound of methyl amino methylene pinacoline was found -to be an active antiknock compound. It may be represented by the formula:

Furthermore mixtures of two or more of our anti-knock compounds, as well as mixtures with other anti-knock compounds, such as tetraethyl lead. may often be used to great advantage.

The following illustrative examples further demonstrate our invention:

Example I To two samples of a gasoline, having an octane number or 40, the copper compound of methyl aminomethylene acetone was added in quantities, so that the blended gasoline contained .05% and .1 respectively copper by weight of the gasoline. As a result'the octane numbers were raised [to 59 and 69 respectively.

The same gasoline was blended with tetraethyl lead in quantities to produce two blends containing .05% and .l% lead .by weight or the gasoline.

The resulting octane numbers were 55 and 66 respectively.

' Example II To the gasoline of Example I .05% by weight of copper was added in the form of the copper compound of methyl aminomethylene 2-pentanone. The octane number rose to 58.

Example III .1% copper in the form of the copper compound oi ethyl aminomethylene acetone was added to the gasoline of Example I, thereby raising its octane number to 6'7.

Example IV .l% by weight of copper in the form of the cupric compound.of allyl aminomethylene acetone raiscdthe octane number of a gasoline from Example V To a gasoline. the octane number of which was 40, .04% by weight 01' cobalt was added in the form of the cobaltous compound of ethyl aminomethylene acetone. The octane number rose to 64.

Example VI raised the octane number 01' a gasoline from 40 Example VIII .10% copper in the form of cupric ethyl aminomethylene acetaldehyde (HO-CH=OHNHCQHC) raisedthe octane number 01 a gasoline from 40 to 64.5.

Example IX .03% copper in the form of a normally liquid mixture consisting of 30 parts by weight solid cupric methyl aminomethylene acetone and 70 parts oi. liquid cupric ethyl aminomethylene acetone raised the octane number of a strongly aromatic gasoline from '78 to 86.

Example X .l% copper in the form of cupric ethyl aminomethylene acetone in a mixture of 20% of this compound and 80% aniline raised the antiknock value of a gasoline from 40 to 71.

Example XI .1% cobalt in the form of the cobaltous compound of ethyl aminomethylene acetone raised the octane number oi. a hydrogenation gasoline (prepared from Venezuelan gasoil) from 79 to 9'7.

Example XII .1% nickel in the form of the nickel compound of ethyl aminomethylene pinacoline raised the octane number of a gasoline from 40 to 60.5.

Example XIII .1% cobalt in the form of the cobaltomethylate of ethyl aminomethylene acetone CH:(|J=CH-CII=NC:H

when added to a gasoline with an octane number of 40 raised this number to 61.

Example XIV .1% copper in the form of the cupric compound of beta ethoxyethylamino methylene acetone raised the octane number of a gasoline from 40 to 61.

Example XV .05% cobalt in the form of the cobaltous compound of ethyl aminomethylene acct/aldehyde ratzed the octane number of a gasoline from 40 to 0.

We claim as our invention:

An improved motor fuel, which comprises a gasoline type motor ruel and a small amount or a normally liquid mixture consisting of the normally solid cupric methyl amino methylene acetone and o! the normally liquid cupric ethyl amino methylene acetone.



Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2441172 *Jan 31, 1942May 11, 1948Shappirio SolModified fuels and lubricants
US3006742 *Oct 29, 1958Oct 31, 1961Ethyl CorpFuel compositions
US3246964 *Jun 3, 1963Apr 19, 1966Ethyl CorpFuel and lube compositions
US4189306 *Oct 4, 1978Feb 19, 1980E. I. Du Pont De Nemours And CompanyHexacoordinated transition metal compounds and fuel compositions containing them
US4215997 *Jul 10, 1979Aug 5, 1980E. I. Du Pont De Nemours & Co.Fuel compositions containing tetracoordinated cobalt compounds
U.S. Classification44/367, 564/342, 556/33, 556/32, 556/34
International ClassificationB24B41/00, C10L1/10, C10L1/24
Cooperative ClassificationC10L1/24, B24B41/002
European ClassificationC10L1/24, B24B41/00B