CN118019833A

CN118019833A - Polyamide fuel additives

Info

Publication number: CN118019833A
Application number: CN202280064836.0A
Authority: CN
Inventors: F·辛普森-格林
Original assignee: Chevron USA Inc
Current assignee: Chevron USA Inc
Priority date: 2021-10-14
Filing date: 2022-10-03
Publication date: 2024-05-10
Also published as: CO2024005982A2; AU2022366282A1; WO2023062477A1; CA3234489A1

Abstract

Methods for preventing or reducing corrosion or wear in a gasoline engine are provided. The steps of the method include supplying a fuel composition comprising the reaction product of a fatty acid and a polyamine.

Description

Polyamide fuel additives

Technical Field

The present disclosure relates to fuel additive compositions and fuel compositions. More particularly, the present disclosure relates to long chain aliphatic polyamide compounds that can prevent corrosion/rust while providing protection against abrasion/friction.

Background

Considerable effort has been made in recent years to improve the fuel economy of motor vehicles. In general, the efficiency of an automotive engine is greatly improved by the presence of effective lubrication, particularly at the interfaces of moving parts where high friction and excessive wear tend to occur. Accordingly, one approach for improving fuel economy is to develop lubricants and lubricating oil additives that reduce engine friction and thus reduce energy requirements.

Some of these efforts have focused on friction modifiers, which are known lubricating oil additives that can reduce boundary friction by adsorbing or reacting on metal surfaces to form thin low shear strength films.

Friction modifiers have been used in limited slip gear oils, automatic transmission fluids, slideway lubricants, and utility tractor fluids. In particular, with the desire for increased fuel economy, friction modifiers have been added to automotive crankcase lubricants. These friction modifiers generally function under boundary layer conditions at temperatures at which antiwear and extreme pressure additives are not yet reactive by forming a thin monolayer of the physically adsorbed polar oil soluble product or a reactive layer that exhibits significantly lower friction than typical antiwear or extreme pressure agents. However, under more severe conditions and under mixed lubrication conditions, these friction modifiers are added with antiwear or extreme pressure agents.

The most common type of antiwear or extreme pressure agent is zinc dialkyldithiophosphate (ZnDTP or ZDDP). ZDDP limits wear by forming a thick protective tribofilm (tribofilm) on the friction surface. Although ZDDP has been widely used in motor vehicles for decades, recent studies have shown that phosphorus-based anti-wear films can cause significant increases in friction in thin film, high pressure, lubricated contacts. This in turn may have a negative impact on fuel efficiency.

While it is important to reduce friction with lubricant additives, it is possible to further increase fuel efficiency with fuel additives. Since the conditions of the internal combustion chamber are significantly different from those in the crankcase, there is no evidence that a particular additive or class of additives that provide performance benefits in lubricating oils will provide similar benefits in fuels. Accordingly, there is a need to develop fuel additives that can reduce friction and/or improve fuel economy.

Drawings

Fig. 1 is described in the examples section.

Disclosure of Invention

In one aspect, a method of preventing or reducing corrosion or wear in a gasoline engine by supplying a fuel composition comprising a reaction product of a fatty acid and a polyamine is provided.

In another aspect, a method is provided for preventing or reducing corrosion or wear in a gasoline engine while providing antiwear or friction protection by supplying a fuel composition comprising a fuel additive comprising the reaction product of a fatty acid and a polyamine.

Detailed Description

Introduction to the invention

In this specification, the following words and expressions have the meanings given below if and when used.

"Gasoline" or "gasoline boiling range component" refers to a composition containing at least predominantly C ₄-C₁₂ hydrocarbons. In one embodiment, gasoline or gasoline boiling range components are also defined as compositions that contain at least predominantly C ₄-C₁₂ hydrocarbons and also have a boiling range of about 37.8 ℃ (100°f) to about 204 ℃ (400°f). In an alternative embodiment, a gasoline or gasoline boiling range component is defined as a composition containing at least predominantly C ₄-C₁₂ hydrocarbons, having a boiling range of about 37.8 ℃ (100°f) to about 204 ℃ (400°f), and is also defined as conforming to ASTM D4814.

The term "diesel" refers to middle distillate fuels containing at least predominantly C ₁₀-C₂₅ hydrocarbons. In one embodiment, diesel is also defined as a composition containing at least predominantly C ₁₀-C₂₅ hydrocarbons and also having a boiling range of about 165.6 ℃ (330°f) to about 371.1 ℃ (700°f). In an alternative embodiment, diesel is defined as above, meaning a composition containing at least predominantly C ₁₀-C₂₅ hydrocarbons, having a boiling range of about 165.6 ℃ (330°f) to about 371.1 ℃ (700°f), and also defined as conforming to ASTM D975.

The term "oil soluble" means that for a given additive, the amount required to provide the desired level of activity or performance can be incorporated by dissolving, being dispersed or being suspended in an oil of lubricating viscosity. Typically, this means that at least 0.001 wt.% of the additive may be incorporated into the lubricating oil composition. The term "fuel-soluble" is a similar expression for additives that are dissolved, dispersed or suspended in the fuel.

"Minor amount" means less than 50% by weight of the composition, expressed for the additive and for the total weight of the composition, considered as the active ingredient of the additive.

An "engine" or "internal combustion engine" is a heat engine in which combustion of fuel occurs in a combustion chamber. An "internal combustion engine" is a heat engine in which combustion of fuel occurs in a confined space ("combustion chamber"). A "spark ignition engine" is a heat engine in which combustion is ignited by a spark, typically from a spark plug. This is in contrast to "compression ignition engines" (typically diesel engines) in which the heat generated by compression, together with the injection of fuel, is sufficient to initiate combustion without external sparks.

The present invention provides fuel additive compositions and fuel compositions having one or more performance benefits. In some embodiments, the composition is effective to prevent or reduce corrosion or rust. In some embodiments, the composition is effective to prevent or reduce wear or friction. In particular, a reduction in friction may lead to an increase in fuel efficiency. In some embodiments, the composition is multifunctional, providing two or more benefits (e.g., reduced corrosion/rust and wear/friction).

In general, the fuel additive composition is the reaction product between a fatty acid and a polyamine, which produces a long chain polyamide. Although conventional rust and/or abrasion inhibitors rely on organic acid type compositions, the polyamides of the present invention are non-acidic, which can minimize interactions with potential refinery process contaminants that may lead to deposit formation or increase filter plugging. Other advantages will be apparent from the disclosure herein.

Fatty acid

According to the invention, the fuel additive is the product of an amidation reaction between a fatty acid and a polyamine. Any fatty acid compatible with the present invention may be used. Typical fatty acids may have the following structure:

wherein R is an organic moiety having from about 5 to 40 carbon atoms, such as from 8 to 35 carbon atoms, from 10 to 30 carbon atoms, or from 15 to 25 carbon atoms. In some embodiments, R comprises one or more heteroatoms. Suitable fatty acids include saturated and unsaturated fatty acids. The fatty acid may also be a monocarboxylic acid or may have more than one acid moiety (e.g., a dicarboxylic acid).

In some embodiments, the fatty acid is an aliphatic fatty acid. Examples of saturated fatty acids include aliphatic fatty acids. The aliphatic groups may be straight or branched.

Suitable aliphatic acids include, but are not limited to, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, 2-ethylbutyric acid, 3-dimethylbutyric acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-dimethylpentanoic acid, 2-propylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, isooctanoic acid, 3, 5-trimethylhexanoic acid, 4-methyloctanoic acid, 4-methylnonanoic acid, isodecanoic acid, 2-butyloctanoic acid, isotridecanoic acid, 2-hexyldecanoic acid, isopalmitic acid, isostearic acid, 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid, and cyclohexanecentanoic acid.

Suitable unsaturated fatty acids include fatty acids containing carbon-carbon double or triple bonds. Representative unsaturated fatty acids include palmitoleic acid, myristoleic acid, hexadecenoic acid, oleic acid, elaidic acid, isooleic acid, linoleic acid, elaidic acid, a-elaidic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

Polyamines as a base material

Preferably, the polyamine has at least three amine nitrogen atoms per molecule, and more preferably from 4 to 12 amine nitrogen atoms per molecule. Most preferred are polyamines having about 6 to 10 nitrogen atoms per molecule.

Preferred polyolefin polyamines also contain about 4 to 20 carbon atoms, preferably 2 to 3 carbon atoms per alkylene unit. The polyamine preferably has a carbon to nitrogen ratio of 1:1 to 10:1.

Suitable polyamines include polyalkylene polyamines. Such polyamines will typically contain from about 2 to about 12 nitrogen atoms and from about 2 to about 24 carbon atoms. Specific examples include Diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and Heavier Polyalkylene Amines (HPA).

Other specific examples of polyamines include N, N' -Bis- (2-aminoethyl) piperazine) (Bis AEP), N- [ (2-aminoethyl) 2-aminoethyl ] Piperazine) (PEEDA), 1- (2-aminoethyl) -4- [ (2-aminoethyl) amino ] ethyl ] piperazine) (AEPEEDA), and 1- [2- [ [2- [ (2-aminoethyl) amino ] ethyl ] Piperazine) (PEDETA).

Many polyamines suitable for use in the present invention are commercially available and other polyamines can be prepared by methods well known in the art. For example, the methods for preparing amines and their reactions are described in detail in "The Organic Chemistry of Nitrogen" of SIDGEWICK, clarendon Press, oxford,1966; noller, "CHEMISTRY OF ORGANIC COMPOUNDS", saunders, philadelphia, 2 nd edition, 1957; and Kirk-Othmer, "Encyclopedia of Chemical Technology", version 2, especially volume 2, page 99, 116.

The polyamine reactant may be a single compound, but will typically be a mixture of compounds reflecting commercial polyamines. Typically, commercial polyamines will be mixtures in which one or several compounds predominate, with the average composition shown. For example, tetraethylenepentamine produced by polymerization of aziridine or reaction of ethylene dichloride with ammonia will have both lower and higher amine members, such as triethylenetetramine, substituted piperazine and pentaethylenehexamine, but the composition will be predominantly tetraethylenepentamine and the empirical formula of the total amine composition will be close to that of tetraethylenepentamine.

Other examples of suitable polyamines include blends of amines of various molecular weights. Comprising a mixture of diethylenetriamine and a heavy polyamine. The preferred polyamine blend is a mixture containing 20% by weight diethylenetriamine and 80% by weight of a heavy polyamine.

Reaction

The fuel additive of the present invention is the reaction product of a fatty acid and a polyamine. The reaction product is a polyamide or a fatty acid polyamide. The phenolic amine compositions of the present invention may be commercially available or synthesized by any known method.

As an illustrative example, the reaction between a fatty acid and a polyamine is described in U.S. patent No. 3,169,980, incorporated herein by reference. Here, the polyamide is prepared by reacting a fatty acid with a polyamine at a temperature in the range of about 120 ℃ (248°f) to about 260 ℃ (500°f). The amidation reaction takes about 2 to 10 hours. The condensed water is then removed. It may be desirable to reduce the pressure to achieve amidation at lower reaction temperatures. The ratio of fatty acid to polyamine may be such that the moles of fatty acid are equivalent to the molar equivalents of amine groups in the polyamine.

Polyamides derived from mixtures of tetraethylenepentamine with straight and branched chain fatty acids are described below. A mixture of tetraethylenepentamine and a silicone suds suppressor is added to the reaction vessel. The mixture was blanketed with nitrogen and heated to about 120 ℃. Next, a mixture of fatty acids is introduced and the reaction temperature is raised to remove water. The temperature was again raised at atmospheric pressure for about 1 hour and then held under vacuum for about 7 hours.

Fuel composition

The compounds of the present disclosure are useful as additives in hydrocarbon fuels boiling in the gasoline or diesel range.

The concentration of the polyamide compound of the present disclosure in the hydrocarbon fuel may be in the range of 25 to 5000 parts per million (ppm) by weight (e.g., 50 to 1000 ppm).

The compounds of the present disclosure can be formulated into concentrates using inert stable lipophilic (i.e., hydrocarbon fuel soluble) organic solvents that boil in the range of 65 ℃ to 205 ℃. Aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene, or higher boiling aromatic compounds or aromatic diluents may be used. Combinations of aliphatic alcohols containing 2 to 8 carbon atoms (such as ethanol, isopropanol, methyl isobutyl methanol, n-butanol, etc.) with hydrocarbon solvents are also suitable for use with the additives of the present invention. The amount of additive in the concentrate may be in the range of 10 wt% to 70 wt% (e.g., 20 wt% to 40 wt%).

Other well known additives may be used in gasoline fuels, including oxygenates (e.g., ethanol, methyl tertiary butyl ether), other antiknock agents, and detergents/dispersants (e.g., hydrocarbyl amines, hydrocarbyl poly (oxyalkylene) amines, succinimides, mannich reaction products, aromatic esters of polyalkylene phenoxyalkanols, or polyalkylphenoxyaminoalkanes). Additionally, friction modifiers, antioxidants, metal deactivators, and demulsifiers may be present.

In diesel fuel, other well known additives may be used, such as pour point depressants, flow improvers, cetane improvers, and the like.

Fuel-soluble non-volatile carrier fluids (carrier fluids) or oils may also be used with the compounds of the present disclosure. The carrier fluid is a chemically inert hydrocarbon-soluble liquid carrier that significantly increases the non-volatile residue (NVR) or solvent-free liquid fraction of the fuel additive composition while not greatly promoting an increase in octane requirement. The carrier fluid may be a natural or synthetic oil such as mineral oil, refined petroleum, synthetic polyalkanes and olefins, including hydrogenated and unhydrogenated polyalphaolefins, synthetic polyoxyalkylene derived oils, such as U.S. patent nos. 3,756,793, 4,191,537, and 5,004,478; and those described in european patent application publications 356,726 and 382,159.

The carrier fluid may be used in an amount of 35ppm to 5000ppm by weight of the hydrocarbon fuel (e.g., 50ppm to 3000ppm of the fuel). When used in a fuel concentrate, the carrier fluid can be present in an amount ranging from 20wt% to 60 wt% (e.g., 30 wt% to 50 wt%).

The following illustrative examples are intended to be non-limiting.

Examples

The polyamide tested is the reaction product of isostearic acid and Tetraethylenepentamine (TEPA). First, 6 samples were prepared and corrosion tested according to ASTM D665B. The samples contained either the base fuel alone (samples 1 and 2) or the base fuel and varying amounts of polyamide (samples 3, 4, 5 and 6).

A summary of the samples tested and the corrosion results (ASTM D665B) is shown in table 1 below. The visual confirmation of the corrosion test is clearly shown in fig. 1.

TABLE 1

Additional tests were performed according to ASTM 6079 to measure the friction properties of polyamides. Sample 7 contained only the base fuel. Samples 8, 9, 10 and 11 contained either baseline formulation 1 or baseline formulation 2 and varying amounts of polyamide.

Table 2 summarizes the samples and results tested (ASTM 6079).

TABLE 2

Baseline formulation 1 (BL 1): base fuel+fuel detergent mixture+5 vol% methyl tert-butyl ether

Baseline formulation 2 (BL 2): base fuel + fuel detergent mixture + E10.

Claims

1. A method of preventing or reducing corrosion or wear in a gasoline engine by supplying a fuel composition comprising the reaction product of a fatty acid and a polyamine.

2. The method of claim 1, wherein the fuel composition comprises a hydrocarbon fuel boiling in the gasoline or diesel range.

3. The method of claim 1, wherein the fatty acid is an aliphatic fatty acid having 2 to 30 carbons.

4. The method of claim 3, wherein the aliphatic fatty acid is caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, 2-ethylbutyric acid, 3-dimethylbutyric acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-dimethylpentanoic acid, 2-propylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, isooctanoic acid, 3, 5-trimethylhexanoic acid, 4-methyloctanoic acid, 4-methylnonanoic acid, isodecanoic acid, 2-butyloctanoic acid, isotridecanoic acid, 2-hexyldecanoic acid, isopalmitic acid, isostearic acid, 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid, or cyclohexane pentanoic acid.

5. The method of claim 1, wherein the polyamine has from about 2 to about 12 nitrogen atoms and from about 2 to about 24 carbon atoms.

6. The method of claim 1, wherein the polyamine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyalkylene amine, N' -bis- (2-aminoethyl) piperazine), N- [ (2-aminoethyl) 2-aminoethyl ] piperazine, 1- (2-aminoethyl) -4- [ (2-aminoethyl) amino ] ethyl ] piperazine), or 1- [2- [ [2- [ (2-aminoethyl) amino ] ethyl ] piperazine.

7. A method of preventing or reducing corrosion or wear in a gasoline engine while providing antiwear or friction protection by supplying a fuel composition comprising a fuel additive comprising the reaction product of a fatty acid and a polyamine.

8. The method of claim 7, wherein the fuel composition comprises a hydrocarbon fuel boiling in the gasoline or diesel range.

9. The method of claim 7, wherein the fatty acid is an aliphatic fatty acid having 2 to 30 carbons.

10. The method of claim 9, wherein the aliphatic fatty acid is caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, 2-ethylbutyric acid, 3-dimethylbutyric acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-dimethylpentanoic acid, 2-propylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, isooctanoic acid, 3, 5-trimethylhexanoic acid, 4-methyloctanoic acid, 4-methylnonanoic acid, isodecanoic acid, 2-butyloctanoic acid, isotridecanoic acid, 2-hexyldecanoic acid, isopalmitic acid, isostearic acid, 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid, or cyclohexane pentanoic acid.

11. The method of claim 7, wherein the polyamine has from about 2 to about 12 nitrogen atoms and from about 2 to about 24 carbon atoms.

12. The method of claim 7, wherein the polyamine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyalkylene amine, N' -bis- (2-aminoethyl) piperazine), N- [ (2-aminoethyl) 2-aminoethyl ] piperazine, 1- (2-aminoethyl) -4- [ (2-aminoethyl) amino ] ethyl ] piperazine), or 1- [2- [ [2- [ (2-aminoethyl) amino ] ethyl ] piperazine.