US3639110A

US3639110A - Detergent gasoline composition

Info

Publication number: US3639110A
Application number: US780573A
Authority: US
Inventors: Arthur Lee Larsen
Original assignee: Marathon Oil Co
Current assignee: Marathon Oil Co
Priority date: 1968-12-02
Filing date: 1968-12-02
Publication date: 1972-02-01
Anticipated expiration: 1989-02-01
Also published as: FR2024985A1; GB1224710A; DE1948264A1; SE344336B

Abstract

Improved detergent gasoline composition is obtained by incorporating within the gasoline stock from about 0.0001 to about 1.5 weight percent of the reaction product obtained by reacting an N-secondary-alkyl trimethylene diamine (e.g. can contain 10-20 carbon atoms in the alkyl group) and a phosphate ester obtained, e.g., by reacting equal molar amounts of polyphosphoric acid and a condensation product of an alcohol (can contain three to six carbon atoms) and 1-10 moles of ethylene oxide.

Description

States Patent Larsen [451 Feb. 11, 11972 211 App1.No.: 780,573

[52] US. Cl ..44/72 [51] llnt.Cl.

[58] Field of Search ..44/56 D, 69 P, 72

[56] References Cited UNITED STATES PATENTS 3,504,055 3/1970 Andress et a1. ..44/72 X 3,007,782 11/1961 Brown et a1 ....44/72 X 3,035,905 5/1962 Keller ....44/72 X 3,169,923 2/1965 Guarnaccio et al ...252/32.5 3,228,758 1/1966 Bauer ..44/72 3,389,980 6/1968 Kautsky ..44/72 X 3,425,815 2/1969 Rosenwald et al...... 3,436,195 4/1969 Rosenwald et al ..44/72 Primary ExaminerDanie1 E. Wyman Assistant ExaminerW. .l. Shine Attorney-Joseph C. Herring, Jack L. Hummel and Richard C. Willson, Jr.

[5 7] ABSTRACT Improved detergent gasoline composition is obtained by incorporating within the gasoline stock from about 010001 to about 1.5 weight percent of the reaction product obtained by reacting an N-secondary-alkyl trimethylene diamine (e.g. can contain 10-20 carbon atoms in the alkyl group) and a phosphate ester obtained, e.g., by reacting equal molar amounts of polyphosphoric acid and a condensation product of an alcohol (can contain three to six carbon atoms) and l-lO moles of ethylene oxide.

8 Claims, N0 Drawings DETERGENT GASOLINE COMPOSITION BACKGROUND OF THE INVENTION This invention relates to gasolines and more specifically to detergent additives for gasolines. These detergent additives reduce substantially undesirable deposits in a carburetor, etc.

Engines run at idle speeds, and especially those that are run on fuel containing high-boiling components, have a tendency to accumulate deposits on the inner walls of the carburetor. Also, circulating gas from the crankcase into the carburetor, in addition to contaminants from exhaust and crankcase fumes drawn into the carburetor intake tend to accumulate deposits on the inner walls. Such accumulation tends to interfere with the airflow and alters the air/fuel ratio resulting in poor performance, stalling, rough idling and increased fuel consumption of the engine. Also, such adverse conditions are accelerated during stop-and-go driving in metropolitan areas. In order to cure such an adverse condition, continuous carburetor adjustments are made and in some cases the carburetor has to be torn down, cleaned of these deposits and put back into operation. Even after a cleaning is effected on the carburetor, future maintenance is still necessary to compensate for the deposit buildup, i.e., adjustments need to be continuously made to maintain correct air/fuel ratios.

These conditions are accelerated in the case of multithroat carburetors of the type employed in present day automobiles. Rough idling and engine stalling have been found principally due to the accumulation of deposits in the throttle body section of the carburetor. As these deposits continue to build up, the amount of air desired for a given amount of fuel is impeded and thus the air/fuel mixture is overly rich for satisfactory engine operation.

To reduce carburetor deposits, additives such as amides, alkylammonium dialkyl phosphates and similar compositions having surface-active properties have been incorporated within the gasoline. However, such additives have suffered certain disadvantages and research has continued for more suitable additives.

Applicant has discovered an improved detergent additive for gasoline. From about 0.000] to about 1.5 percent by weight of the reaction product of an N-secondary-alkyl trimethylene diamine (e.g., can contain 10-20 carbon atoms in the alkyl group) and a phosphate ester obtained, e.g., by reacting equal molar amounts of polyphosphoric acid and a condensation product of an alcohol (can contain 3-6 carbon atoms) and l-l moles of ethylene oxide.

DESCRIPTION OF THE INVENTION Examples of useful phosphate esters include those found in U.S. Pat. No. 3,331,896 to Eiseman, Jr. et al. Particularly useful phosphate esters are obtained by reacting about equal molar amounts of polyphosphoric acid and a condensation product of an alcohol containing from about 3 to about 6 carbon atoms and from about 1 to about moles of an alkylene oxide, e.g., ethylene oxide.

Examples of N-secondary-alkyl trimethylene diamines are found in U.S. Pat. No. 3,398,196 to Fuller, Jr. et al. The diamines can be represented by the formula:

wherein x and y are positive integers having a sum of from about 6 to about 30 and n is a positive integer within the range of from about 2 to about 4 and preferably is 3. The polyamines are preferably oleophilic and contain substantially saturated alkyl chains. Additional examples of diamines useful with this invention can be found in Product Data Bulletin," Bulletin No. 68-3, under the title Beta Amines and Derivatives," Armour Industrial Chemicals, Box 1805, Chicago, Illinois.

A particularly useful N-secondary-alkyl trimethylene diamine is one wherein the alkyl group contains an average of from about 10 to about 21 aliphatic carbon atoms.

The diamine and the phosphate ester are reacted in sufficient amounts to give a resulting pH within the range of from about 5 to about 9 and more preferably from about 6 to about 8. A composition having a pH greater than about 7 has the ad vantage of imparting improved deicing characteristics to the fuel. A solvent for the reactants can be utilized during the neutralization to facilitate mixing of the diamine and the phosphate ester, e.g., isopropyl alcohol. Temperatures within the range of from about 60 F. to about 100 F. are useful in the neutralization and more preferably the temperature can be within the range of from about F. to about F.

Reaction product of the diamine and the phosphate ester can be incorporated in the fuel in amounts ranging from about 0.0001 to about 1.5 weight percent or more. Generally, concentrations within the range of from about 5 to about 15 lb. per 1,000 barrels of gasoline stock are useful to obtain improved detergency characteristics. 1n addition, other additives, including detergents, can be used with the compositions of this invention to impart improved detergency characteristics, etc., to the fuel.

The following examples are presented to illustrate specific working embodiments of this invention. These examples are not intended to limit the invention in any way. Rather, all equivalents obvious to those skilled in the art are meant to be incorporated within the teachings of this invention as defined within the specification and appended claims.

The products of this invention are tested in a Marine Onan Electric Plant, Model No. lMAJ-lR-IM, a lKW electric generator generating volts, 60-cycle plant. The engine is a vertical single cylinder, 4-cycle, internal combustion engine having a compression ratio of 6.25:l, maximum brake horsepower of 2.75 at 1,800 r.p.m. and 3.6 at 2,400 r.p.m., displacement 14.9 cubic inch, bore 2% inches and stroke 2% inches. The test engine contains an aluminum alloy 3-ring piston with full floating pin. The carburetor is a Marvel Schebler Carburetor, Model VD34, downdraft carburetor. The carburetor is modified slightly in that the original inside diameter of 7/8 inch is bored out to 15/16 inch 1D. for a distance of 1% inches from the mounting flange face. This permits the insertion of an 0" ring (O.D.=6l/64 inch, l.D.=23/3 2 inch and H32 inch thick) at the top of the carburetor throat, the inside of the ring is beveled and the beveled edge faces down into the carburetor. Two inserts, 'l/32 inch thick, are inserted and fit snugly around the inside of the carburetor throat. These inserts hold the O-ring in place and also provide a means of evaluating the detergency characteristics of the fuel. The O-ring permits better distribution of the gas over the center portion of the throttle plate. The engine is water cooled with inlet water at about 110 F. and outlet water at about 160 F. The three rings on the cylinder are adjusted by increasing the gap of the top two rings by fourfold and increasing the gap of the bottom ring by twofold. The crankcase oil used is a nondetergent, lubricating oil identified as Pennzoil 30 (a trade name of Pennsylvania Oil Company, 30 SAE weight) and has been subjected to 20,000 miles of wear, i.e., the crankcase oil is old and used.

The carburetor is subjected to a dirty up cycle which lasts for 1.5 hours. During this cycle, the engine is run under repeated cycles of 3 minutes at no load at 1,800 r.p.m. and 0.5 minutes at 30 percent load at 1,800 r.p.m. The fuel is untreated regular gasoline, i.e., it does not have a detergent additive. The air intake into the carburetor is at F. and is composed of about 78 percent fresh air, 2 percent blow-by from the crankcase and 20 percent as exhaust from an emissions engine.

The emissions engine is a vertical single-cylinder, four cycle internal combustion engine rated at 2.75 horsepower at 1,800 r.p.m. and is run under 30 percent load on a fuel composed of 67 percent regular gasoline (contains no detergent additive), 33 percent toluene and 1 gram per liter of lndoline (a trade name of Aldrich Chemical Co., 2,371 North 30th, Milwaukee, Wisconsin, 53210, and defines an additive to give a very black, dirty emission). The vapor going into the test engine is at 125 F.

After the dirty up cycle, the engine is subjected to a cleaning cycle lasting for 3 hours, only fresh air and blow-by from the crankcase is fed to the carburetor. The sequence of operation for the 3-hour period is a repetitive cycle of 3 minutes under load at 1,800 r.p.m. and 0.5 minute under 30 percent load at 1,800 r.p.m. The fuel is regular gasoline (i.e., has an octane rating of about 97) and contains about lb. per 1,000 barrels of fuel of the additive. After the 3-hour cycle, the inserts are removed from the carburetor throat, the amount of deposits left on the inserts indicates the detergency characteristics of the additive incorporated in the fuel. A rating of N indicates 0 percent clean surface, S indicates 25 percent of clean surface, F indicates 50 percent clean surface, G indicates 75 percent clean surface, and E indicates 100 percent clean surface. Thus, an N indicates failure whereas an E indicates an excellent result.

EXAMPLE 1 A monophosphate ester is obtained by reacting equal molar amounts of polyphosphoric acid and a condensation product of one mole of iso-amyl alcohol with 4.0 moles of ethylene oxide.

To equal volumes of isopropanol and Duomeen L-l5 (a trade name of Armour Industrial Chemicals, Chicago, lll., identified as an N-secondary-alkyl trimethylene diamine wherein the alkyl group contains from about -20 carbon atoms), there is added enough of the above phosphate ester to neutralize the polyamine to a pH of 7. The reaction is effecte at 90 F.

EXAMPLE 11 A monophosphate ester is obtained by reacting equal molar amounts of phosphoric acid and the condensation product obtained by reacting one mole of n-butyl alcohol and 10 moles of ethylene oxide.

To two parts of Duomeen L-ll (a trade name of Armour Industrial Chemicals, Chicago, lll., identifying an N-secondary-alkyl trimethylene diamine wherein the alkyl group contains from about I 1-14 carbon atoms) and two parts of isopropyl alcohol, there is added 1.5 parts of the above phosphate ester. The mixture is maintained at 80 F. for about 2 hours. There is added 1.5 additional parts of isopropyl alcohol to the mixture. The resulting mixture has a pH of about 6.0.

EXAMPLE [II To one part of the Duomeen L] 1 and one part of isopropyl alcohol, there is added enough of the monophosphate ester identified within example I to give a resulting pH of about 7.0, the mixture is reacted at F. for about 2 hours.

Examples 1, ll, and Ill indicate excellent results in the carburetor detergency tests.

What is claimed is:

1. An improved detergent gasoline composition comprising a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling range and from about 0.000l to about l.5 percent by weight of the product obtained by neutralizing to a pH of from about 5 to about 9 a l diamine of the formula by reacting about equal molar amounts of polyphosphoric acid and a condensation product of an alcoho containing from about three to about five carbon atoms and from 1 to about 10 moles of an alkylene oxide.

2. The detergent gasoline composition of claim I wherein the product is neutralized to a pH of from about 6 to about 8.

3. The detergent gasoline composition of claim 1 wherein the diamine is an N-secondary-alkyl trimethylene diamine.

4. The detergent gasoline composition of claim 3 wherein the alkyl group contains an average of from about 10 to about 20 carbon atoms.

5. The detergent gasoline composition of claim 1 wherein the condensation product is obtained by reacting about one mole of the alcohol with about 1 to about 4 moles of ethylene oxide.

6. The detergent gasoline composition of claim 1 wherein the diamine and phosphate ester are reacted at a temperature up to about F.

7. An improved detergent gasoline composition comprising a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling range and from about 0.0001 to about 1.5 percent by weight of the product obtained by neutralizing to a pH of from about 6 to about 8 and at a temperature up to about 100 F. a (l) N-secondary-alkyl trimethylene diamine wherein the alkyl group contains an average of from about l0 to about 20 carbon atoms with (2) a phosphate ester obtained by reacting about equal molar amounts of polyphosphoric acid and the condensation product of one mole of an alcohol containing from about three to about five carbon atoms and from about 1 to about 4 moles of ethylene oxide.

8. The detergent gasoline composition of claim 7 wherein the alcohol is iso-amyl.

Claims

2. The detergent gasoline composition of claim 1 wherein the product is neutralized to a pH of from about 6 to about 8.
3. The detergent gasoline composition of claim 1 wherein the diamine is an N-secondary-alkyl trimethylene diamine.
4. The detergent gasoline composition of claim 3 wherein the alkyl group contains an average of from about 10 to about 20 carbon atoms.
5. The detergent gasoline composition of claim 1 wherein the condensation product is obtained by reacting about one mole of the alcohol with about 1 to about 4 moles of ethylene oxide.
6. The detergent gasoline composition of claim 1 wherein the diamine and phosphate ester are reacted at a temperature up to about 100* F.
7. An improved detergent gasoline composition comprising a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling range and from about 0.0001 to about 1.5 percent by weight of the product obtained by neutralizing to a pH of from about 6 to about 8 and at a temperature up to about 100* F. a (1) N-secondary-alkyl trimethylene diamine wherein the alkyl group contains an average of from about 10 to about 20 carbon atoms with (2) a phosphate ester obtained by reacting about equal molar amounts of polyphosphoric acid and the condensation product of one mole of an alcohol containing from about three to about five carbon atoms and from about 1 to about 4 moles of ethylene oxide.
8. The detergent gasoline composition of claim 7 wherein the alcohol is iso-amyl.