US3707361A - Gasoline compositions - Google Patents

Abstract

A GASOLINE COMPOSITION CONTAINING A TETRAALKYL LEAD COMPOUND, AN ALKYL ARYL PHOSPHATE ESTER AND ABOUT 0.0004 TO 0.02% OF THE N-OLEYL-1,3-PROPYLENEDIAMINE SALT OF TALL OIL FATTY ACIDS.

Description

United States Patent 3,707,361 GASOLINE COMPOSITIONS Weldon G. Annable, Crystal Lake, Ill., assignor to Union Oil Company of California, Los Angeles, Calif. No Drawing. Continuation of application Ser. No. 430,464, Feb. 4, 1965. This application June 23, 1969, Ser. No. 838,036

. Int. Cl. C10] 1/26 US. C]. 44-58 4 Claims ABSTRACT OF THE DISCLOSURE A gasoline composition containing a tetraalkyl lead compound, an alkyl aryl phosphate ester and about 0.0004 to 0.02% of the N-oleyl-l,3-propylenediamine salt of tall oil fatty acids.

This application is a continuation of Ser. No. 430,464 filed Feb. 4, 1965, now abandoned.

This invention relates to an improved gasoline composition containing hydrocarbons boiling in the gasoline boiling range, a detergent, de-icer, deposit modifier, corrosion inhibitor, and anti-wear agent, wherein one or more of the ingredients exhibit known qualities in the composition and at least two ingredients combine to give a heretofore unknown quality to the gasoline composition. More particularly this invention is based on the discovery that quite unexpectedly the Noleyl-1,3-propylenediamine salt of tall oil fatty acids exhibits improved carburetor cleanliness (detergency), anti-icing, corrosion-inhibition and anti-Wear in gasolines containing less than about 0.001 wt. percent mercaptan sulfur and that when the salt is used in conjunction with aliphatic, aryl or mixed aliphatic-aryl phosphates the antiwear properties are greatly enhanced.

US. Pat. 2,736,658 discloses the use of the N-oleyl-l,3- propylenediamine salt of tall oil fatty acid as a corrosion inhibitor for gasoline, lubricating oils and fluids generally when used in amounts ranging from 0.01% by wt. to 0.3% and as much as 5% by Wt., the latter concentration being suggested for greases. The superior surface activity, strong cation activity, solubility in various hydrocarbons and the corrosion inhibiting properties of this particular salt and other salts of tall oil fatty acids and other fatty acids is also known. The N-oleyl-1,3-propylenediamine salt of tall oil fatty acids as defined and illustrated in said patent is the same as used in the instant compositions.

New materials and combinations of old materials are continually being evaluated to define their performance levels in gasoline compositions for use in the internal combustion engines of today. Dimensional changes of critical parts of the engine, such as bearings, cam lobes, cylinders, pistons, and piston rings to attain high performance limit the useful life of the engine unless gasoline and lubricating oil performance is sufficient to meet the demands of these parts. Engine life has been extended by improved metallurgy, new metal alloys, improved lubricating oil compositions, thermo-static temperature control, crankcase ventilation and more recently fuel additives. With the advent of todays high-composition, high-rpm, high-torque engine, the dimensional clearance of moving parts of the engine were further greatly re duced, and the influence of these dimensional changes on engine performance and engine life have been amplified by stop-and-go driving, high-speed driving, acceleration, deceleration, the use of'automatic transmissions and the like. Todays engine is more susceptible to abrasive wear due to the'actien of extremely fine dust particles taken "Ice into the carburetor systems, to corrosion, to engine deposits, to icing in the carburetor system, to carburetor deposits and other adverse influences all of which impair performance and engine life.

The new additives for gasoline, though designed to perform a particular function such as anti-icing, detergency, anti-wear, reduction of induction system deposits, octane rating increases, etc., often conflict with one another and offset any specific advantages for which they were intended. A given additive may provide the desired antiicing or detergency and at the same time induce wear to a prohibitive extent. This same additive in the presence of a deposit modifier may lose its detergency qualities and cause some other impairment of function. The present invention is based on the discovery that phosphate ester deposit modifiers have the undesirable property of inducing wear of the engine parts (particularly the cylinders and rings), and that this undesirable property can be offset by adding certain concentrations of the N-oleyl-1,3- propylenediamine salt of tall oil fatty acid. It can be established that (1) the addition of tetraethyl lead to a base fuel actually increases the wear rate of the rings and cylinders of the engine as determined by radioactive tests, (2) the addition of certain anti-wear agents to a fuel containing TEL does not overcome this induced wear while the use of other anti-wear agents has the affect of mitigating such induced wear and (3) the use of certain combinations of additives in a fuel containing TEL, including the best known anti-wear agents, produces a fuel having'little or no wear-reducing properties.

More particularly, this invention is based on the discovery that alkyl phosphates, aryl phosphates or mixed alkylaryl phosphates, a necessary ingredient in leaded gasolines to modify the deposits on spark plugs and combustion chamber walls so that they do not accumulate during or interfere with the operation of the engine, have the undesirable property of inducing wear of the rings and cylinders, along with the lead alkyl, and that this detrimental property can be offset or mitigated by the use of the N-oleyl-1,3-propylenediamine salt of tall oil fatty acids, essentially free of rosin acids, in combination with said phosphates. It will also be demonstrated that the detrimental effect on wear exhibited by mixed triphenyl phosphates is offset by the use of said salt in conjunction therewith, and that this property is not shared with other known anti-icers or detergents. Although the best results are obtained with the combination of the N0leyl-1,3- propylenediamine salt of tall oil fatty acids and mixed triphenyl phosphates, other combinations with trialkyl phosphates produce leaded gasolines which, though not exhibiting Wear reduction, do not induce wear of the rings and cylinders of the engine.

Accordingly, it becomes a primary object of this invention to provide a leaded gasoline composition comprising hydrocarbons boiling in the gasoline boiling range and the N-oleyl-l,3-propylenediamine salt of tall oil acids, which' exhibits the desired level of performance in detergency, anti-icing, carburetor cleanliness and, in addition, reduces the wear rate of the engine parts.

Another object of this invention is to provide a leaded gasoline composition comprising hydrocarbons boiling in the gasoline boiling range, a phosphate ester deposit modifier and the N-oleyl-l,3-propylenediamine salt of tall oil fatty acids which exhibits the desired level of detergency, anti-icing, carburetor cleanliness, deposit modification and which reduces the wear rate of the engine parts.

Still another object of this invention is to provide a leaded gasoline composition comprising hydrocarbons boiling in the gasoline boiling range, a triphenyl phosphate deposit modifier and the N-oleyl1,3-propylenediamine salt of tall oil fatty acids which exhibits the desired level of detergency, anti-icing, carburetor cleanliness, deposit modification and which reduces the wear rate of the engine parts.

This fuel qualified as a premium fuel exhibiting RON of 99.5 and MON of 90.8 and exhibited the following properties.

Another object of this invention is to provide a leaded TABLE III gasoline composition comprising hydrocarbons boiling in Property: Value the gasoline boiling range, a deposit modifier comprising Gravity API F 61.5 a mixture of about 45% by wt. of ,dimethyl phenyl phos- Reid vapor pressure p.s.ii. 11.5 phate, about 40% triphenyl phosphate and about 15% of IBP F 11.5 methyl diphenyl phosphate and the N-oleyl-1,3-propylene- E.P F-.. 408 diamine salt of tall oil fatty acids which exhibits the de- Y t sired level of detergency anti-icing, carburetor cleanliness, The anti-iclng propertles are given 111 terms of equivalent deposit modification and which reduces the wear rate of percent alcohol (90% 1sopropanol-10% methanol). The the engine parts. detergency properties are presented on a deposit rating These and other objects of this invention will be descale of 1 to 10, wherein 10 represents clean. Anti-wear scribed orbecome apparent as the specification proceeds. Properties are Presented as Pfi reduction in Wear rate; In order to demonstrate the invention series of laborathe ring wear is presented under R and cylinder wear tory engine anti-icing, detergency and abrasive-wear tests under C for runs 14 to 18. Anti-wear properties as rewere conducted using a number of different additive comported for runs 1 to 14 are based on ring wear only. binations. The laboratory engine abrasive-wear tests were As seen from these results the N-oleyl-1,3-propylenediconducted on a single-cylinder COT engine employing a amine salt of tall oil acids when used in low concentraradioactive piston ring. tions ranging from 1lb./1000 bbls. (0.0004% by wt.) .to The wear rate is determined by measuring the relative 50 lbs./ 1000 bbls. (0.02% by wt.) in combination with a radioactivity of the iron particles worn from the ring lead alkyl produces a surprising and substantial reduction which are carried away in the oil lubricating the engine. in the wear rate of the engine which is not shared by other This oil is continuously withdrawn into a counting cham- 5 similar salts. In addition, the combination of N-oleyl-l,3- her and the radioactivity is determined in counts per propylenediamine salt of tall oil acids at these low conminute by means of a rate meter and a scintillation countcentrations in combination with the mixed phenylphoser. Wear rate is proportional to the change in counts per phates at concentrations of about 0.005 to 0.06 wt. percent minute/hour, and wear reduction is determined by comor 0.1 to 0.5 theories gives good wear reduction, even pairing the wear rate when using the base fuel with the though the mixed phenyl phosphates alone or in COIllbl! wear rate when using the fuel with additives present. nation with other salts are ineifective to prevent wear of TABLE I Anti-Icing, Detergency and Anti-Wear Tests Composition No 1 2 3 4 5 6 7 8 9 10 Ingredients:

Base gasoline 100%-- lgaL. 1,000 bbL--- 1,000bb1.- 1,000 bbl 1,000 11111.... 1,000 bbL- 1,000 bb1. 1,000bb1 1,000 bbl. TEL (ml. pergal.) 3m 3111 31111 3x111 Sml 3m! 3 :3m1---.. 3ml. Noleyl-1,3-propylene 1b diaanine salt of iso-octanoic 8C1 N-oleyl-1,3-propylene 2111b.

diaanine salt of iso-deeanoic 80!. N-oleyl-1,3-propylene 20 lb 10 lb 20 lb 20111.

dianine salt of tall oil fatty 8, S. Mix ed phenylphosphates 201b'. Tnmethyl phosphate 401b wolgs ffi lb 40lb 40 lb. Olelc nr'id i 4011) Methanol. 30 lb 30 lb- 20 lb Isopropanol 1b. Test results:

Anti-icing- Detergeney Anti-wear (percent wear 25 21 Negative 0 23 18 reduction). negative.

Composition No 11 12 13 14 15 16 17 18 Ingredients: 7

Base gasoline 1,000 bbL- 1,000 bbL- 1,000 bbL. 1, 000 bbL- 1,000 bbl 1,000 bbl 1,000 1901-- 1,000 bbl. TEL (ml. per gal.) 31111 3m! 3ml 3ml 3ml 3ml 3ml 3m]. N-oleyl-1,3-propylene diamine salt of iso-octanoic B0 N-oleyl-1,3-propylene diamlne salt of iso-deeanoic a N-ol elyl-Lii-propylene diamine salt of tall oil fatty 20 lb 25 lb 10 5 15 20 15 20.

801 5. Mixed p y t n .3 101.... 3 TH. Trimethyl phosphate Oleic acid Methanol- Isoprnpannl Test results:

Anti-icing- 5-. 75 Detergency.- 10-. 8. 5-10 R25 R 45 3 45 Anti-wear- 56-33 18 M6.

1 Duplicate results.

In each of the compositions reported in Table I the gasoline was a composition containing 80% by vol. of FCC stock and 20% by vol. of alkylate showing the following analysis.

TABLE II The concentration of N-oleyl-l,3-propylenediamine salt Percent of vol. of tall oil fatty acids to be used in gasolines in accordance Parafi'ins and naphthenes 61 with this invention is about 1 lb. to lbs/1000 bbls. of Olefins 16 gasoline. The broad class of these materials is described Arcma ics Fun us: nunsqa m vsw. 23 75 in LLS. Bat. 2,736,658along with the methodcf p pare;v

the moving parts of the engine. The results also show that the anti-icing, detergency and anti-corrosion properties of the N-oleyl-1,3-propylenediamine salt of tall oil acids are not affected by the use with mixed phenylphosphates.

tion. Commercial tall oil contains 45-50% by Wt. of rosin acids and 45-5 of other fatty acids of which about 48 are linoleic acid, 45% are oleic acid and 7% are palmitic (saturated) acid. The rosin acid portion of tall oil, which is a by-product from woodpulp, is removed by known methods, e.g., acidulation of black liquor soap, centrifugation and distillation. Preferably the concentration of rosin acids, sometimes referred to as resin acids, is not more than about 1% by Wt. which, for purposes of this invention, can be considered to be substantially free of rosin acids. The term tall oil fatty acids" as used in the appended claims is intended to mean the fatty acids of tall oil essentially free of rosin acids.

The alkyl aryl phosphate esters used as deposit modifiers in the'compositions of this invention are preferably dimethyl phenyl phosphate, methyl diphenyl phosphate, triphenylphosphate, and mixtures thereof. Other phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and the like up to those trialkyl phosphates having 6 carbon atoms in each alkyl group may be used. Also, the mixed alkyl aryl phosphates within this group wherein one or two phenyl groups are present may be used such as diethyl phenyl phosphate, ethyl diphenyl phosphate, dibutyl phenyl phosphate, butyl diphenyl phosphate, dihexyl phenyl phosphate, and hexyl diphenyl phosphate. Alkyl-substituted phenyl groups such as methyland ethyl-substituted phenyl groups may b present to include tricresyl phosphate.

Best results are obtained by using a mixture comprising about 45 dimethyl phenyl phosphate, about 15% methyl diphenyl phosphate and about 40% triphenyl phosphate on a weight basis. This product is commercially available diluted with toluene to a phosphorus content of about 11% by wt. as a blendable form of these materials. In a leaded gasoline about 0.2 to about 0.45 theory and preferably about 0.3 theory of the alkyl aryl phosphate ester, or the preferred mixture as herein defined, is used in accordance with this invention. A theory is defined as that amount of a compound containing sufiicient phosphorus to completely react with the lead present to form lead phosphate, e.g., the amount of phosphorus necessary to completely react with the lead present to form lead ortho phosphate which equals a phosphorns-to-lead ratio of 2:3. In general about 0.005 to 0.06 wt. percent of the alkyl aryl phosphate esters are used in the unleaded gasoline compositions of this invention.

The gasoline compositions of this invention contain as the hydrocarbon portion thereof any of the known gasoline hydrocarbons boiling in the range of about 90 to 425 F., and preferably boiling in the range of about 90 to 400 F. The hydrocarbon portion of the gasoline may contain normal, branched-chain, and cyclic hydrocarbons having from 4 to 12 carbon atoms. The hydrocarbon portion of the gasoline also may contain products prepared in the chemical conversion of hydrocarbons to produce gasoline. Such conversion products include the products prepared by isomerization, alkylation, polymerization, cracking, disproportionation, hydrogenation, dehydrogenation, and combinations of such processes. A preferred gasoline composition contains a major proportion of the gasoline hydrocarbons prepared by fluid catalytic cracking and a minor proportion of an alkylate prepared from isobutane and C and/ or C olefins. More specifically, the base fuel may comprise about 80% of gasoline from the fluid catalytic-cracking process, and about 20% of the aforementioned alkylate.

Preferably, the tall oil acid salt and phosphate deposit modifier combination of this invention is used in a leaded fuel since best results are obtained thereby and a premium fuel of this nature is benefited to a greater extent by the additive combination in regard to amti-icing and detergency along with anti-wear. Any lead alkyl compound can be used such as tetramethyl lead, tetraethyl lead, tetrabutyl lead and mixtures thereof. Amounts ranging from about 2 ml. to 4 ml. of lead alkyls per gallon of gasoline can be used, with about 3 m1./gallon preferred. Tetraethyl lead is the preferred lead alkyl and was used to demonstrate the invention.

This invention also relates to the method of operating an internal combustion engine which comprises using therein as the fuel the gasoline compositions described herein. By using the gasoline compositions of this invention in modern internal combustion engines, increases in economy and performance of the engine, along with prolonged spark-plug life, reduced carburetor and induction system deposits, and reductions in piston ring and cylinder wear will be obtained. The compositions of this invention may be in the form of the additive combination without the gasoline components to include an additive composition consisting essentially of about 5 to 30 wt. percent of the N-oleyl-l,3-propylenediamine salt of tall oil fatty acids and about 95 to '70 wt. percent of alkyl aryl phosphate ester, same blended with or without the appropriate amounts of tetra alkyl lead. A specific example of an additive composition comprises TABLE IV Ingredient: Wt. percent Mixture:

Dimethyl phenyl phosphate, 45 Triphenyl phosphate, 40% Methyl diphenyl phosphate, 15% N-oleyl-1,3-propylenediamine salt 20 Besides the combination of the particular salt of tall oil fatty acids and the alkyl aryl phosphates or alkyl phosphates, the gasoline compositions of this invention can, and ordinarily will, contain the usual commercial additives, for example, the anti-detonants already disclosed, scavengers such as ethylene dibromide and ethylene dichloride, dyes, oxidation inhibitors, N,N'-di-secondary butyl phenylene diamine, N-n-butyl-p-aminophenol, 2,6- ditertiarybutyl-4-methylphenol, p-aminophenol, p-phenylenediamine, dialkylphenol type compounds such as mixed tertiary butyl phenols containing about 75% by wt. 2,6-

ditertiarybutylphenol, 1015% by wt. 2,4,6 -'tritertiary butyl phenol and 1015% by Wt. of ortho-tertiarybutylphenol, in the mixture and 2,6-ditertiarybutylparacresol, and metal deactivators such as the copper chelating agents to include N,N' di-salicylidene 1,2-propanediarnine and known rust inhibitors such as polymerized linoleic acids. These additional ingredients, if used, are generally present in amounts ranging from 1 to 20 lbs./ 1000 bbls. of gasoline and more specifically about A to /2 or 1 lb./ 1000 bbls. These additives are produced commercially and'are available either as pure compounds or dissolved in a suitable carrier such as a hydrocarbon solvent or an alcohol as 50% to 80% active ingredients. To illustrate the N,N'- di-salicylidenes-1,2-propanedia-mine is available as a mixture in a concentration of 80% by wt. in 20% xylene or in a 50%-50% mix. Generally about A to /2 1b./ 1000 bbls. is suflicient for the intended purpose in todays gasolines.

Although this invention has been demonstrated by specific examples, there are only illustrative and the only limitations attaching to this invention are defined in the appended claims.

I claim:

1. A methanol free motor gasoline fuel comprising hydrocarbons boiling in the gasoline range, a knock-suppressing proportion of tetra alkyl lead, and about 20 pounds per thousand barrels of an anti-wear additive consisting essentially of the N-oleyl-1,3-propylene diamine salt of tall oil fatty acids, said fuel also being free of trimethyl phosphate.

2. A fuel as defined in claim 1 wherein said tetra alkyl lead is tetraethyl lead.

7 8 3. A fuel as defined in claim 1 containing from about 2,736,658 2/1956 Rfohl et al. 252-34 0.2 to 0.45 theory of -a phenyl phosphate ester combustion 2,765,220 10/ 1956 Yust et al. 4469 P deposit modifier. 3,051,739 8/1962 Gould 4469 P 4. A fuel as defined in claim 1 containing from about 3,084,034 4/ 1963 Kalinowski 4466 0.2 to 0.45 theory of a phenyl phosphate ester combustion 5 3,303,007 2/1967 Mueller 4466 deposit modifier, and wherein said tetra alkyl lead is tetrah l 1 d DANIEL E. WYMAN, Primary Examiner References Cited Y. H. SMITH, Assistant Examiner UNITED STATES PATENTS 10 2,285,853 6/1942 Downing et al 2s2 49.s 2,291,442 7/1942 Bass et al. 4469 P 44DIG. 1, DIG. 4, 66, 70, 76

2,546,422 3/1951 Cross 4469 P