US3608232A

US3608232A - Gasoline composition containing vanadium salts of phosphorus compounds

Info

Publication number: US3608232A
Application number: US723580A
Authority: US
Inventors: Frederick L Voelz; Walter F Schoen
Original assignee: Atlantic Richfield Co
Current assignee: Atlantic Richfield Co
Priority date: 1968-04-23
Filing date: 1968-04-23
Publication date: 1971-09-28
Anticipated expiration: 1988-09-28

Abstract

A GASOLINE COMPOSITION CONSISTING ESSENTIALLY OF A HYDROCARBON GASOLINE, AN ANTI-KNOCK QUANTITY OF A TETRALOWER-ALKYL LEAD COMPOUND, AND A GASOLINE-SOLUBLE VANADIUM OR CHROMIUM SALT OF A PHOSPHORUS COMPOUND HAVING THE FORMULA

R-O-P(=O)(-O-R'')-OH OR R''-O-P(=S)(-O-R)-SH

WHEREIN R IS A HYDROCARBON RADICAL OF UP TO 30 CARBON ATOMS, R'' IS SELECTED FROM THE GROUP CONSISTILNG OF HYDROGEN AND R, S IS SULFUR AND O IS OXYGEN. THE AMOUNT OF METAL SALT ADDED IS SUFFICIENT TO PROVIDE ABOUT 0.002 TO 0.8 MILLIGRAM ATOMS, PREFERABLY ABOUT 0.025 TO 0.3 MILLIGRAM ATOMS, OF THE SELECTED METAL PER GALLON OF GASOLINE. A GASOLINE SOLUBLE NON-METALLIC AUXILIARY PHOSPHORUS COMPOUND CAN BE ADDED TO THE COMPOSITION TO PROVIDE ADDITIONAL BENEFICIAL EFFECTS.

Description

United States Paten 3,608,232 GASOLINE COMPOSITION CONTAINING VANA- DIUM SALTS F PHOSPHORUS COMPOUNDS Frederick L. Voelz, Orland Park, and Walter F. Schoen, South Holland, Ill., assignors to Atlantic Richfield Company, New York, N.Y.

N0 Drawing. Continuation-impart of applications Ser. No. 427,078, Jan. 21, 1965, and Ser. Nos. 470,598 and 470,628, both July 8, 1965, said application Ser. No. 427,078 being a continuation-in-part of application Ser. No. 306,273, Sept. 3, 1963. This application Apr. 23, 1968, Ser. No. 723,580 Int. Cl. C011 1/26 US. C]. 44-69 22 Claims ABSTRACT OF THE DISCLOSURE A gasoline composition consisting essentially of a hydrocarbon gasoline, an anti-knock quantity of a tetralower-alkyl lead compound, and a gasoline-soluble vanadium or chromium salt of a phosphorus compound having the formula RO OH RO\ /SH RO/ \O RO \S wherein R is a hydrocarbon radical of up to 30 carbon atoms, R is selected from the group consisting of hydrogen and R, S is sulfur and O is oxygen. The amount of metal salt added is sufiicient to provide about 0.002 to 0.8 milligram atoms, preferably about 0.025 to 0.3 milligram atoms, of the selected metal per gallon of gasoline. A gasoline soluble non-metallic auxiliary phosphorus compound can be added to the composition to provide additional beneficial effects.

This application is a continuation-in-part of applications Ser. No. 427,078, filed Jan. 21, 1965, now abandoned, Ser. No. 470,598, filed July 8, 1665 now abandoned, and Ser. No. 470,628, filed July 8, 1965 now abandoned. Application Ser. No. 427,078 is a continuation-in-part of application Ser. No. 306,273, filed Sept. 3, 1963, now abandoned.

The present invention relates to distillate hydrocarbon fuel compositions which when employed in spark ignition engines lead to improvements especially with respect to rumble. The compositions also exhibit other desirable characteristics such as increased anti-corrosive, anti-preignition and anti-stalling properties. Some compositions of the invention improve octane requirement increase when used in spark ignition engines.

In order to improve the efficiency and increase the horsepower ratings of gasoline engines, engine manufacturers have significantly increased compression ratios during the past decade. In 1952, for example, no major US. automobile manufacturer made a stock engine having a compression ratio as high as 8.0/1. Today engines having compression ratios greater than 10.0/ 1 are common. These high compression ratio engines have revealed a relatively new type of abnormal combustion called rumble. In fact, rumble is one of the major factors restricting compression ratios at the current levels. The rumble phenomenon is the result of deposit induced ignition which creates abnormal pressure rises in the combustion chambers, thereby causing flexing of the crankshaft. The flexing crankshaft manifests itself by loud unnatural or shuddering engine noises.

Another disadvantage attending the use of known additives to lessen abnormal combustion of gasoline in, for instance, automobile engines, is that they adversely affect the nature and increase the amount of deposits within the combustion space. These effects take on greater importance in the case of the higher compression ratio engines. A fuel having an octane number appropriate to the designed engine compression ratio is therefore unable to give the same anti-knock performance after the formation of such extensive deposits. To obtain the intended autiknock performance requires a fuel of higher octane number; and this effect has become known as the octane requirement increase" or Ori of the engine.

Various commonly employed gasoline additives as, for example, phosphate compounds such as tricresyl phosphate, cresyl diphenyl phosphate, etc., although known to improve engine operation with respect to preignition, rumble, wild ping, autoignition and spark plug fouling, have no decreasing effect on octane number requirement increase and many even have an adverse effect. Also to combat rumble effectively, relatively large amounts of the additives may be needed.

It has now been found that leaded gasolines having added thereto a small amount of a gasoline-soluble chromium or vanadium salt of certain phosphorus and thiophosphorus compounds provides a composition which improves rumble. Further improvements in terms of octane requirement increase and in some cases rumble are afforded by also including in the gasoline composition a nickel or cobalt salt of the phosphorus compounds of the invention. Thus in a preferred form the gasoline includes a partial ester salt of a metal having an atomic number from 23 to 24 and a partial ester salt of a metal having an atomic number from 27 to 28, especially a combination of such chromium and nickel salts. The compositions of the invention also exhibit anti-rusting vanti-preignition and anti-stalling or carburetor deicing properties. The nickel and chromium salts are further advantageous in that they are especially resistant towards deposit formation when gasoline containing them is stored over water.

While the present invention is directed to the use of the phosphorus compounds in gasolines compositions which contain a lead anti-knock compound to reduce rumble and/or other adverse effects created by the addition of the lead compound the additives can also be advantageously employed in metal octane-improving additivefree, e.g. non-leaded gasolines to, for example aid in rust preventing, reducing preignition and anti-stalling or carburetor deicing.

The phosphorus compounds, from which metal salts of the invention are made, have the following formulae:

wherein R is a hydrocarbon radical of up to about 30 or more carbon atoms on the average, often at least about 5 and preferably about 8 to 18 carbon atoms, S is sulfur, R is hydrogen or R, and O is oxygen. R can be an aliphatic, aromatic or mixed aliphatic-aromatic radical and is preferably non-olefinic and non-acetylenic, i.e. having adjacent carbon atoms no closer than 1.40 angstroms. The total number of carbon atoms in a molecule of the phosphorus compound is preferably up to about 30 or even up to about 40 and the chromium or vanadium salt of the phosphorus compound is soluble in gasoline at least to the extent employed in this invention.

The phosphorus compounds from which the metal salts of the invention are made can be obtained by methods known to the art as, for instance, by reacting aliphatic alcohols, including cycloaliphatic alcohols, or aromatic hydroxy compounds With P 0 to form the phosphoric acid esters (I) and with P 8 to form the dithiophosphoric acid esters (II). The preferred alcohols are alkanols which can be straight or branch chained and alkyl-substituted phenols Whose alkyl substituents contain a total of up to 18 carbon atoms, and preferably are lower alkyl, especially methyl. The aromatic hydroxy compounds and aliphatic alcohols may be substituted with non-deleterious groups. Illustrative of suitable alcohols are pentanol, butanol, octanol, isooctanol, Z-ethyl-heptanol, dodecanol, oleyl alcohol, octadecyl alcohol, tetradecyl alcohol, alcohols prepared by the x0 process, phenol and alkylated phenols such as cresol, xylenol, propyl phenol, butyl phenol, dibutyl phenol, monoamylphenol, diamyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol and octadecyl phenol.

The reaction of the alcohol and P 0 or P 5 to prepare the partial esters can be conducted by heating the reactants at temperatures of from about 75 C. to about 125 C. for a period of time sufiicient to effect substantially complete reaction, usually about 1 to 15 hours. An inert solvent such as toluene, xylene or the like may be used to facilitate the reaction. Suitable molar ratios of alcohol to P 05 and P S may be about 3:1, and 4:1 respectively.

The ester products of phosphoric acid (I) thus produced, can be, for instance, monoalkyl, dialkyl, mono aryl or diaryl esters or any combination thereof. The mixed esters are often present, for instance, in a mole ratio of at least about 25% of each, say about 60 to 40% monoester: 40 to 60% diester. The metal salts of the esters can be prepared by directly reacting the esters with the metal carbonate or acetate. Either the metal or the acidic component of the salts may be used in excess and either the monoor dipartial ester salts may be employed but they are conveniently prepared and made available as the mixed ester salts. Mixed chromium and vanadium phosphate may also be employed.

The diester products of dithiophosphoric acid (II) thus produced can be, for instance, dialkyl or diary] esters or any combination thereof. The metal salts of the esters can be prepared by directly reacting the esters with the metal carbonate or acetate and either the metal or the acidic component of the salts may be used in excess.

In order to provide leaded gasolines of further enhanced characteristics, for instance, as to preignition, spark plug fouling and even, in at least some cases, rumble, there can be included in the gasoline composition of the invention a gasoline-soluble phosphorus compound having the formula:

RO OR wherein R has the value described above with respect to the phosphorus compounds from which the chromium and vanadium salts of the invention are made; R is hydrogen or R and n is an integer of 0 or 1. R is preferably an aromatic, e.g. phenyl, hydrocarbon radical of 6 to 12 carbon atoms and can be substituted, for instance, With lower alkyl groups say of l to 4 carbon atoms. Thus, the phosphorus compound can be a mono-, di-, or triester, or a mixture of such and is preferably a triester. It is also preferred to employ a phenyl, alkyl phenyl or a mixed phenyl-alkyl phenyl ester of phosphorus. Thus, one or more of the ester groups is preferably an alkyl phenyl radical, often of about 7 to 15 carbon atoms. See U.S. Pat. No. 2,889,212 for a further list of the useful phosphates and phosphites.

These auxiliary phosphate and phosphite additives can be prepared by reacting the appropriate alcohol or aromatic hydroxy compound with phosphoric acid to make the phosphate or with phosphorus trichloride to form the phosphite. Illustrative of suitable alcohols and aromatic hydroxy compounds are those mentioned above in the description of the phosphorous esters used to form the metal salts of the invention. Examples of suitable alkyl phenols are crtho, m a and para a eso g and xylenol; 2,4-dimethyl-6-tertiary butylphenol; octyl and nonyl phenols, etc.

By the term leaded gasoline to which the additives of the present invention are incorporated is meant hydrocarbon fractions boiling primarily in the gasoline range, usually about 100 to 425 F., having added thereto a small amount, generally between about 1 to 6 cc. per gallon, of a tetra-loWer-alkyl lead compound as an antiknock agent. The gasolines are usually composed of a major amount of a blend of hydrocarbon mineral oil fractions boiling primarily in the aforementioned range and will contain varying proportions of parafiins, olefins, naphthenes and aromatics derived by distillation, cracking and other refining and chemical conversion processes practiced upon crude oil fractions. Straight run gasolines, gasolines derived from cracking gas oil, gasolines or reformate from reforming straight run naphtha over a platinum-alumina catalyst in the presence of hydrogen, etc., are components frequently used in making up a gasoline composition. A typical premium gasoline, besides containing a small amount of a te-tra-loWer-alkyl lead compound as an anti-knock agent may also contain small amounts of other non-hydrocarbon constituents used to impart various properties to the gasoline in its use in internal combustion engines, e.g. halohydrocarbon scavengers, oxidation inhibitors, etc. Such gasolines frequently have a Research Method octane number of about 90 to 105, and a Motor Method octane number of about to 98.

The ester salts of chromium and vanadium are incorporated in the leaded gasoline in minor amounts sulficient to provide a composition exhibiting improved rumble characteristics while the nickel and cobalt salts are used in minor amounts sufiicient to afford a decrease in octane number requirement increase. The actual amount of each additive employed will vary depending upon the particular gasoline employed, its lead contents, etc. In any event the metal salt is employed to supply 0.002 to 0.4 or even 0.8, preferably 0.025 to 0.3 millimole or milligram atoms of the metal chromium and/ or vanadium per gallon of gasoline. The additive will usually provide the gasoline with 0.00004 to 0.008, preferably 0.0005 to 0.006 gram of metal per gram of lead. This often means that about 0.5 to 15 or 20 more of the chromium or vanadium salts to the metal salt ester, preferably about 4 to 10 pounds, per 1000 barrels of gasoline is added. The cobalt or nickel salt when used is also generally present in an amount of about 0.002 to 0.8 millimole of metal per gallon of gasoline. A combination of the chromium or vanadium salts and the cobalt or nickel salt is advantageously in the range of about 0.002 to 0.8 milligram atoms or millimoles per gallon of gasoline.

When used, about 0.05 to 0:6 theory, preferably about 0.15 to 0.5 theory, of the auxiliary phosphate or phosphite additive, based on the lead content of the gasoline, are employed. The term theory as applied to the amount of the second phosphorus additive means the amount required to react stoiehiometrically with the lead so that all of the lead atoms and all of the phosphorus atoms form Pb3(PO4)2.

The following examples are given to illustrate the advantages provided leaded gasolines by the additives of the present invention.

EXAMPLE I One mole of mixed, approximately 50% monoand approximately 5 0% di-, C -0x0 alcohol esters of phosphoric acid was reacted with slightly more than one mole of chromium acetate in a hexane solvent. The reaction was carried out at C. for one hour, and the product was then filtered. The hydrocarbon solubles were Water- Washed several times, refiltered and the resulting chromium salt of mixed monoand di-C oxo esters of phosphoric acid was dried to constant weight, analyzing L827? chromium and 6.86 phosphorus.

The corresponding vanadium salt was made in a similar manner using vanadium pentoxide. Analysis pentox ide. Analysis of the product showed 1.55% vanadium and 6.41 phosphorus.

EXAMPLE H Two moles of mixed, approximately 50% mono and approximately 50% di, C -x0 alcohol esters of phosphoric acid were reacted with slightly more than two moles of cobaltous carbonate in a hexane solvent. The reaction was carried out at 75 C. for one hour, and the product was then filtered. The hydrocarbon solubles were water-washed several times, refiltered and the resulting cobalt salt of mixed monoand di-C oxo esters of phosphoric acid was dried to constant weight, cobalt 4.53% and phosphorus 4.50%.

The corresponding nickel salt was made in a similar manner using nickel carbonate, with the reaction being conducted at 80 to 90 C. Analysis of the product showed 6.52% nickel and 6.35% phosphorus.

EXAMPLE III A sample of a base gasoline was obtained which was composed of 25 volume percent straight run gasoline, 25 volume percent butane-butylene alkylate and 25 volume percent reformed naphtha. The base gasoline analyzed 6% olefins and 20% aromatics and contained 3 cc. per gallon of TEL as Motor Mix (TEL Motor Mix contains 59.2% tetraethyl lead, 13.0% ethylene dibromide, 23.9% ethylene dichloride and 3.9% hydrocarbon diluent, dyes, etc.). The base gasoline containing the tetra-ethyl lead had an API gravity of 61.2, an octane number of 100 by the Research Method and an octane number of 92 by the Motor Method. The ASTM distillation of the gasoline was as follows:

IBP 93 Into the separate portions of the leaded gasoline are added either the chromium salt of Example -I in a concentration that provides 25 lbs. of the ester salt per 1000 barrels of the leaded gasoline or the vanadium salt of Example I in a concentration that provides 25 lbs. of the ester salt per 1000 barrels of the leaded gasoline. The gasoline also contained 0.2 theory of cresyl diphenyl phosphate, about 2.5 pounds of phenylenediamine, an oxidation inhibitor, per 1000 barrels of gasoline and a commercial amine salt of a phosphoric acid ester corrosion inhibitor.

The above gasoline with the metal phosphate ester additives is evaluated in a 1962 Chevrolet V-8, 327 cubic inch, 10.2:1 compression ratio engine to obtain the equilibrium rumble requirement (LIB). LIB number is a measure of the rumble tendency of an engine after a given time of use. The number represents the percent isooctane [containing 3 cc./ gal. TEL] required in a blend with benzene [containing 3 cc./gal. TEL] after a given period of engine operation using the fuel under test, to avoid rumble at a given r.p.m., e.g. 2000 rpm. The test procedure comprises stopping the gasoline to the engine at any given period of engine operation and employing as a fuel to the engine containing a certain percent of isooctane in an isooctane-benzene blend (containing 3 cc. T-EL/gal.), manually opening the throttle at a given rate and recording the rpm. at which rumble occurs, if any in fact occurs. The faster you are able to run the engine with the lowest percent of isooctane in the blend the better the rumble resistance of the engine. Thus, the lower the LIB number the better the rumble characteristics of the engine.

The above fuel without the chromium or vanadium salt, gave in this engine an equilibrium rumble requirement of 70 LIB. After the engine was cleaned, the same fuel without the amine phosphate corrosion inhibitor but containing 25 pounds of the chromium salt of Example I per 1000 barrels, when used in the engine gave an LIB number of only 10. In a similar test with the same fuel but containing 25 pounds of the vanadium salt of Example I per 1000 barrels instead of the chromium salt, the LIB rating is also significantly reduced.

EXAMPLE IV The chromium and vanadium salts of Example I were added, in the amount of 2 pounds per 1000 barrels, to a gasoline containing 37 volume percent light straight run gasoline, 23 volume percent light catalytically cracked gasoline, 13 volume percent heavy catalytically reformed gasoline and 27 volume percent heavy catalytically cracked gasoline. In a 4-hour accelerated rust test the base gasoline gave a poor or E rating but after addition of the chromium salt a rust rating of B+ was obtained and after addition of the vanadium salt to the base gasoline a rating of B was obtained. In testing these salts the gasoline also contained 3 cos. TEL/gaL, 0.2 theory of cresyl diphenyl phosphate, 0.15 volume percent methanol and a metal deactivator, 1 lb./1000 barrels. The corrosion test involved placing a steel specimen in contact with agitated gasoline and water at 100 F. for about four hours and the specimen is inspected to ascertain the extent of rust according to ratings A to E, see US. Pat. No. 2,966,458.

EXAMPLE V A composition of superior rumble and octane requirement increase characteristics is the final chromium saltcontaining gasoline of Example III also having in addition 20 lbs. per 1000 barrels of the nickel salt of Example II.

EXAMPLE VI Also included in the gasoline were phenylene diamine oxidation inhibitor and 3.0 cc. of tetraethyl lead admixed with an ethylene dichloride scavenger.

The table below reports data as wild ping counts per hour obtained in preignition tests using the above gasoline containing the chromium salt additive of Example I and from 0 to 0.3 theory of cresyl diphenyl phosphate (CDP).

Chromium salt, N0./1,000 bbls. gasoline GDP, theories 0 These data establish the elficiency of the chromium salt in combating surface ignition in the presence or absence of cresyl diphenyl phosphate.

EXAMPLE VII One mole of dithiodiisodecyl phosphoric acid ester is reacted with slightly more than one mole of chromium acetate in a hexane solvent. The reaction is carried out at C., for one hour, and the product is then filtered. The hydrocarbon solubles are water-washed several times,

refiltered and the resulting chromium salt of the dithiodiisodecylphosphoric acid ester is dried to constant weight. The salt contains a calculated metal content of 6.4% by weight chromium.

The corresponding vanadium salt calculated at 4.0% by weight V, is made in a similar manner using vanadium pentoxide.

EXAMPLE VIII Two moles fo dithiodiisodecylphosphoric acid ester are reacted with slightly more than two moles of cobaltous carbonate in a hexane solvent. The reaction is carried out at 75 C., for one hour, and the product is then filtered. The hydrocarbon solubles are water-washed several times, refiltered and the resulting cobalt salt of the dithiodiisodecylphosphoric acid ester is dried. The calculated cobalt content of the product is 6.7% by weight.

The corresponding nickel salt, calculated at 6.6% by Weight nickel, is made in a similar manner using nickel carbonate, with the reaction being conducted at 80 to 90 C.

EXAMPLE IX A sample of a base gasoline is obtained which is composed of 25 volume percent straight run gasoline, 25 volume percent light catalytically cracked gasoline, 25 volume percent butane-butylene alkylate and 25 volume percent reformed naphtha. The base gasoline analyzes 6% olefins and 20% aromatics and contains 3 cc., per gallon of TEL as Motor Mix (TEL Motor Mix contains 59.2% tetraethyl lead, 13.0% ethylene dibromide, 23.9% ethylene dichloride and 3.9% hydrocarbon diluent, dyes etc.) The base gasoline containing the tetraethyl lead has an API gravity of 61.2, an octane number of 100 by the Research Method and an octane number of 92 by the Motor Method. The ASTM distillation of the gasoline is as follows:

F. IBP 93 122 50% 201 90% 338 Into separate portions of the leaded gasoline are added either the chromium salt of Example VII in a concentration that provides 25 lbs., of the ester salt per 1000 barrels of the leaded gasoline or the vanadium salt of Example VII in a concentration that provides 25 lbs., of the leaded gasoline. The gasoline also contains 0.2 theory of cresyl diphenyl phosphate, about 2.5 pounds of phenylenediamine, an oxidation inhibitor, per 1000 barrels of gasoline and a commercial amine salt of a phosphoric acid ester corrosion inhibitor.

The above gasoline compositions when evaluated in a 1962. Chevrolet V-8, 327 cubic inch, 10.2:1 compression ratio engine exhibited an improved equilibrium rumble requirement (LIB).

EXAMPLE X The chromium and vanadium salts of Example VII when added, in the amount of 2 pounds per 1000 barrels to a leaded (3 cc. TEL as Motor Mix) gasoline composed of 37 volume percent light straight run gasoline, 23 volume percent light catalytically cracked gasoline, 13 volume percent heavy catalytically reformed gasoline and 27 volume percent heavy catalytically cracked gasoline, provides a composition of enhanced rust resistance.

EXAMPLE XI Compositions of superior rumble and octane requirement increase characteristics are the final chromium saltcontaining gasolines of Example IX also having in addition 20 lbs. per 1000 barrels of the nickel salt of Example VIII.

EXAMPLE XII A leaded (3 cc. TEL as Motor Mix gasoline composed of 14 volume percent straight run gasoline, 32.7 volume O\ /SH RO \S RO wherein R is a hydrocarbon radical of up to 30 carbon atoms, and R is selected from the group consisting of hydrogen and R and the amount of said vanadium salt being 0.002 to 0.8 milligram atoms of metal per gallon of gasoline.

2. The composition of claim 1 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorous compound having the formula and wherein R is a hydrocarbon radical of up to about 30 carbon atoms on the average, R is selected from the group consisting of hydrogen and R, and n is an integer having a value of 0 or 1.

3. The composition of claim 2 wherein at least one R in the structure of claim 2 is an alkyl phenyl radical of 7 to 15 carbon atoms.

4. The composition of claim 3 wherein the amount of phosphorus compound is abuot 0.15 to 0.5 theory.

5. The composition of claim 1 wherein the vanadium salt is a salt of a phosphorus compound having the formula RO\ /OH R'O 0 wherein R is a hydrocarbon radical of from about 8 to 18 carbon atoms, and R is selected from the group consisting of hydrogen and R, the amount of said vanadium salt being 0.025 to 0.3 milligram atoms of vanadium per gallon of gasoline.

6. The composition of claim 5 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorus compound having the formula RO\ /OR RO o wherein R is a lower alkyl phenyl radical of 7 to 15 carbon atoms and R is selected from the group consisting of phenyl and R.

7. The composition of claim 6 wherein the non-metallic phosphorus compound is cresyl diphenyl phosphate.

8. The composition of claim 1 in which there is included about 0.002 to 0.8 milligram atoms per gallon of said gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula R'O\ OH 2: R'O o wherein R is a hydrocarbon radical of up to 30 carbon atoms and R is selected from the group consisting of hydrogen and R said metal having an atomic number of from 27 to 28.

9. The composition of claim 8 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorus compound having the formula wherein R is a hydrocarbon radical of up to about 30 carbon atoms on the average, R' is selected from the group consisting of hydrogen and R, and n is an integer having a value of or 1.

10. The composition of claim 9 wherein at least one R in the structure of claim 9 is an alkyl phenyl radical of 7 to 15 carbon atoms.

11. The composition of claim 10 wherein the amount of prosphorus compound is about 0.15 to 0.5 theory.

12. The composition of claim 8 wherein the metal of atomic number 27 to 28 is nickel.

13. The composition of claim 1 wherein the vanadium salt is a salt of a phosphorus compound having the formula:

wherein R is an alkyl radical of 8 to 18 carbon atoms on the average, the amount of said vanadium salt being sufficient to provide 0.025 to 0.3 milligram atoms of vanadium per gallon of gasoline.

14. The composition of claim 13 in which there is also included about 0.05 to 0.6 theory of a gasolinesoluble phosphorus compound having the formula:

RO\ /OR RO o wherein R is a lower alkyl phenyl radical of 7 to carbon atoms on the average, and R is selected from the group consisting of phenyl and R.

15. The composition of claim 14 wherein the nonmetallic phosphorus compound is cresyl diphenyl phosphate.

16. The composition of claim 1 in which there is included about 0.002 to 0.8 milligram atoms of a gasolinesoluble metal salt of a phosphorus compound having the formula:

wherein R is a hydrocarbon radical of up to 30 carbon atoms on the average, said metal having an atomic number of from 27 to 28.

17. The composition of claim 15 in which there is also included about 16 to 195 pounds per thousand barrels of a gasoline-soluble phosphorus compound having the formula:

R 0 OR RO/ 011 wherein R is a hydrocarbon radical of up to about 30 carbon atoms on the average, R is selected from the group consisting of hydrogen and R, and n is an integer having a value of 0 to 1.

18. The composition of claim 17 wherein at least one R in the structure of claim 23 is an alkyl phenyl radical of 7 to 15 carbon atoms.

19. The composition of claim 18 wherein the amount of phosphorus compound is about 48 to pounds per thousand barrels of gasoline.

20. The composition of claim 16 wherein the metal of atomic number 27 to 28 is nickel.

21. The composition of claim 1 wherein there is included about 0.025 to 0.3 milligram atoms per gallon of gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula:

RO\ /SH I R0 s wherein R is an alkyl group of 8 to 18 carbon atoms on the average, said metal having an atomic number of from 27 to 28.

22. The composition of claim 1 wherein there is included about 0.025 to 0.3 milligram atoms per gallon of gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula:

wherein R is an alkyl group of 8 to 18 carbon atoms on the average and R is selected from the group consisting of hydrogen and R, said metal having an atomic number of from 27 to 28.

References Cited UNITED STATES PATENTS 2,889,212 6/1959 Yust et al. 44--69 3,445,206 5/1969 Revukas 44-69 DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner US. Cl. X.R.

44--68, 78, Dig. 3, Dig. 4

UNITED STATES PATENT eFFroE CERTIFICATE OF CORRECTIGN Patent o, 3, 3 Dated September 28, 1971 Inventor(5) Walter F. SChOen and Frederick L. VO1Z It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line MO: "1665" should be -l965--.

Column 5, lines 2 and 3: Delete "Analysis pentoxide."

Column 7, line 9: "f0" should be --of--.

Column 8, Line 38: "abuot" should be -about-.

Column 10, line 1 "23" should be --17--.

Signed and sealed this 23rd day of May 1972.

(SEAL) Attest:

ROBERT GOTTSCI-ZALK EDWARD MFLETCHR, JR.

Commissioner of Patents Attesting Officer 'ORM PC4050 H0-691 USCOMM-DC bOL-U'G-Pfl r: us, sovznnmam PFHNTING OFFiCE lsus 0-356-334