US-12624303-B2 - Gasoline additive composition for improved engine performance

US12624303B2US 12624303 B2US12624303 B2US 12624303B2US-12624303-B2

Abstract

The present disclosure provides fuel additives including Mannich detergent additive(s) and succinimide detergent additive(s) effective to improve engine performance in both port fuel injected and gasoline direct injection engines.

Inventors

Janice Jianzhao Wang
Julienne Galante-Fox

Assignees

AFTON CHEMICAL CORPORATION

Dates

Publication Date: 20260512
Application Date: 20230728

Claims (15)

1 . A gasoline fuel composition comprising a fuel additive for a spark-ignition engine, the fuel additive consisting of: a Mannich detergent prepared from polyisobutylene cresol, dibutylamine, and formaldehyde; a succinimide detergent prepared by reacting a hydrocarbyl-substituted succinic acylating agent with tetraethylene pentamine (TEPA) C16 to C18 propoxylated alcohol; and optionally a corrosion inhibitor, a solvent, a demulsifier, a lubricity additive, a friction modifier, a PIB amine detergent, a quaternary ammonium detergent, a bis-aminotriazole detergent, an aminoguanidine detergent, a dispersant, a carrier fluid, or combinations thereof; wherein a weight ratio of the Mannich detergent to the succinimide detergent is from 22:1 to about 30:1; wherein the succinimide detergent is a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or a combination thereof; and wherein the hydrocarbyl-substituted succinic acylating agent is a hydrocarbyl-substituted succinic anhydride, wherein the hydrocarbyl group has a molecular weight of about 700 to about 1500, and wherein a molar ratio of the hydrocarbyl-substituted succinic anhydride to the tetraethylene pentamine (TEPA) is from about 0.5:1 to about 2:1; and wherein the gasoline fuel composition includes about 55 to about 190 ppmw of the Mannich detergent, about 0.5 to about 20 ppmw of the succinimide detergent; and about 15 to about 60 ppmw of the C16 to C18 propoxylated alcohol.
2 . The gasoline fuel composition of claim 1 , wherein the hydrocarboyl-substituted succinic anhydride is polyisobutylene substituted succinic anhydride, and wherein the polyisobutylene has a number average molecular weight of about 700 to about 1200 as measured by GPC using polystyrene as reference.
3 . The gasoline fuel composition of claim 1 , wherein a weight ratio of the C16 to C18 propoxylated alcohol to the Mannich detergent is about 1.0 or less.
4 . The gasoline fuel composition of claim 3 , wherein the C16 to C18 propoxylated alcohol is a polyether having the structure of Formula III: wherein R 6 of Formula III is an aryl group or a linear, branched, or cyclic aliphatic group having 16 to 18 carbons, R 7 of Formula III is a C1 alkyl group, and n is an integer from 5 to 100.
5 . The gasoline fuel composition of claim 1 , wherein the fuel additive includes about 20 to about 60 weight percent of the Mannich detergent, about 0.5 to about 10 weight percent of the succinimide detergent, and about 5 to about 30 weight percent of the C16 to C18 propoxylated alcohol.
6 . A method of reducing deposits in a gasoline engine, the method consists of: operating a gasoline engine on a fuel composition containing a major amount of a gasoline fuel and a minor amount of a fuel additive by injecting the gasoline fuel through one or more injectors; wherein the fuel additive consists of (i) a Mannich detergent prepared from polyisobutylene cresol, dibutylamine, and formaldehyde; (ii) a succinimide detergent prepared by reacting a hydrocarbyl-substituted succinic acylating agent with tetraethylene pentamine (TEPA) (iii) C16 to C18 propoxylated alcohol; (iv) optionally a corrosion inhibitor, a solvent, a demulsifier, a lubricity additive, a friction modifier, a PIB amine detergent, a quaternary ammonium detergent, a bis-aminotriazole detergent, an aminoguanidine detergent, a dispersant, a carrier fluid, or combinations thereof; and (v) wherein the fuel additive has a weight ratio of the Mannich detergent to the succinimide detergent of from 22:1 to about 30:1; wherein the fuel additive reduces deposits in the gasoline engine; and wherein the succinimide detergent is a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or a combination thereof; and wherein the hydrocarbyl-substituted succinic acylating agent is a hydrocarbyl-substituted succinic anhydride, wherein the hydrocarbyl group has a molecular weight of about 700 to about 1500, and wherein a molar ratio of the hydrocarbyl-substituted succinic anhydride to the tetraethylene pentamine (TEPA) is from about 0.5:1 to about 2:1; and wherein the gasoline fuel composition includes about 55 to about 190 ppmw of the Mannich detergent, about 0.5 to about 20 ppmw of the succinimide detergent; and about 15 to about 60 ppmw of the C16 to C18 propoxylated alcohol.
7 . The method of claim 6 , wherein the fuel additive reduces deposits in a port fuel injection (PFI) engine, a gasoline direct injection (GDI) engine, or both.
8 . The method of claim 6 , wherein the reduced deposits are reduced injector deposits measured by one of injector pulse width, injection duration, injector flow, or combinations thereof.
9 . The method of claim 6 , wherein the fuel additive reduces deposits when sprayed from an injector configured to spray droplets of about 10 to about 30 microns, about 120 to about 200 microns, or both.
10 . The method of claim 6 , wherein the hydrocarboyl-substituted succinic anhydride is polyisobutylene substituted succinic anhydride, and wherein the polyisobutylene has a number average molecular weight of about 700 to about 1200 as measured by GPC using polystyrene as reference.
11 . The method of claim 6 , wherein a weight ratio of the C16 to C18 propoxylated alcohol to the Mannich detergent is about 1.0 or less.
12 . The method of claim 11 , wherein the C16 to C18 propoxylated alcohol is a polyether having the structure of Formula III: wherein R 6 of Formula III is an aryl group or a linear, branched, or cyclic aliphatic group having 16 to 18 carbons, R 7 of Formula III is a C1 alkyl group, and n is an integer from 5 to 100.
13 . The method of claim 6 , wherein the fuel additive includes about 20 to about 60 weight percent of the Mannich detergent, about 0.5 to about 10 weight percent of the succinimide detergent, and about 5 to about 30 weight percent of the C16 to C18 propoxylated alcohol.
14 . The gasoline fuel composition of claim 1 , wherein the gasoline fuel composition includes about 55 to about 125 ppmw of the Mannich detergent.
15 . The method of claim 6 , wherein the gasoline fuel composition includes about 55 to about 125 ppmw of the Mannich detergent.

Description

TECHNICAL FIELD This disclosure is directed to fuel additives for spark-ignition engines providing enhanced engine, intake valve, and/or injector performance, to fuel compositions including such additives, and to methods for using such fuel additives in a fuel composition for improved performance. BACKGROUND Fuel compositions for vehicles are continually being improved to enhance various properties of the fuels in order to accommodate their use in newer, more advanced engines including both gasoline port fuel injected engines as well as gasoline direct injected engines. Often, improvements in fuel compositions center around improved fuel additives and other components used in the fuel. For example, friction modifiers may be added to fuel to reduce friction and wear in the fuel delivery systems of an engine. Other additives may be included to reduce the corrosion potential of the fuel or to improve the conductivity properties. Still other additives may be blended with the fuel to improve fuel economy. Engine and fuel delivery system deposits represent another concern with modern combustion engines, and therefore other fuel additives often include various deposit control additives to control and/or mitigate engine deposit problems. Thus, fuel compositions typically include a complex mixture of additives. However, there remain challenges when attempting to balance such a complex assortment of additives. For example, some of the conventional fuel additives may be beneficial for one characteristic or one type of engine, but at the same time be detrimental to another characteristic of the fuel. In some instances, fuel additives effective in gasoline port fuel injection engines (PFI) do not necessarily provide comparable performance in gasoline direct injection engines (GDI) and vice versa. In yet other circumstances, fuel additives often require an unreasonably high treat rate to achieve desired effects, which tends to place undesirable limits on the available amounts of other additives in the fuel composition. Yet other fuel additives tend to be expensive and/or difficult to manufacture or incorporate in fuels. SUMMARY In one embodiment or approach, a fuel additive or fuel additive package for a spark-ignition engine is described herein to provide improved engine performance and includes a Mannich detergent including the reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more amines; a succinimide detergent prepared by reacting a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine, or alkyl amine having one or more primary, secondary, or tertiary amino groups; and wherein a weight ratio of the Mannich detergent to the succinimide detergent is from about 15:1 to about 30:1. As discussed more herein, such weight ratios provide a synergistic effect with improved engine and/or injector performance in both port fuel injection (PFI) engines as well as gasoline direct injection (GDI) engines. In other embodiments or approaches, the fuel additive of the previous paragraph may include one or more optional features or embodiments in any combination. The optional features or embodiments may include one or more of the following: wherein the weight ratio of the Mannich detergent to the succinimide detergent is from about 20:1 to about 30:1; and/or wherein the Mannich detergent has the structure of Formula I: wherein R1 of Formula I is hydrogen or a C1 to C4 alkyl group, R2 of Formula I is a hydrocarbyl group having a molecular weight of about 500 to about 3000, R3 of Formula I is a C1 to C4 alkylene or alkenyl group (preferably a C1 group), and R4 and R5 of Formula I are, independently, hydrogen, a linear or branched C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl amino C1-C12 alkyl group; and/or wherein R2 of Formula I is polyisobutenyl having a number average molecular weight of about 500 to about 1500; and/or wherein the succinimide detergent is a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or a combination thereof; and/or wherein the hydrocarbyl-substituted succinic acylating agent is a hydrocarbyl-substituted succinic anhydride, wherein the hydrocarbyl group has a molecular weight of about 450 to about 3000, and wherein a molar ratio of the hydrocarbyl-substituted succinic anhydride to the amine, polyamine, or alkyl amine is from about 0.5:1 to about 2:1; and/or wherein the hydrocarbyl-substituted succinic anhydride is polyisobutylene substituted succinic anhydride, and wherein the polyisobutylene has a number average molecular weight of about 500 to about 1200 as measured by GPC using polystyrene as reference; and/or wherein the amine, polyamine, or alkyl amine is tetraethylene pentamine (TEPA), triethylene tetraamine (TETA), or a polyamine or alkyl amine having the formula H2N—((CHR20—(CH2)q—NH)r—H, wherein R20 thereof is hydrogen or an alkyl group having from 1 to 4 carbon atoms, q i