JPH0556799B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] This invention relates to transition metal salts of organic acids, hydrocarbon-
A distillate fuel composition containing a soluble ashless dispersant and a phenolic antioxidant. Typically, the invention provides a method in which the organic acid is a carboxylic acid, a sulfonic acid, or a phosphorus-containing acid, the ashless dispersant is an ester dispersant with or without nitrogen, and the antioxidant is a steric The present invention relates to compositions that are harmful phenols. This invention is
It also relates to hydrocarbon systems containing said compositions, such as lubricants based on oils of lubricating viscosity and hydrocarbon fuels.

[Prior art]

Hydrocarbon systems, such as lubricants based on lubricating oils of lubricating viscosity (e.g., greases, lubricating oils, etc.) and hydrocarbon fuels, both solid and usually liquid, can be combined with transition metals and transition metal compounds ( Organic and inorganic) treatments are known in the art. Such treatment increases the system's resistance to oxidative degradation, promotes conversion to adhesive films when used in paints and lacquers, and improves combustion, such as in fuels.

Organic transition metal compounds used for this purpose include salts of carboxylic and sulfonic acids and mixtures of these salts. For example, Alkaitis et al., U.S. Pat. No. 4,162,986 describes transition metal salts of mixed organic carboxylic acids and sulfonic acids or second carboxylic acids and their uses such as catalysts, anti-knock agents, combustion improvers, smoke suppressants, curing agents, etc. agent,
Uses are described as a desiccant, micronutrient source, lubricant additive, etc.

Collins U.S. Pat. No. 3,762,890 discloses hydrolyzable manganese fibers stabilized by the inclusion of propionic acid and moisture absorbing agents for pigments, varnishes and inks of such materials;
Use has been described as a stabilizer and additive for greases and lubricating oils for various plastics, and as a smoke suppressant and anti-corrosion additive for fuels and fuel oils.

US Pat. No. 3,723,152 to Alkaitis et al. describes basic cobalt salts of carboxylic acids and desiccant compositions for oil vehicles.

Other patents, such as US Pat. No. 4,202,671 to Diehl et al., describe the use of organomagnesium compounds as fuel conditioners to reduce fuel usage and combustion emissions.

With increasing concerns about pollution and rising costs of hydrocarbon-based fuels and lubricants, interest in the use of transition metal compounds in such systems continues to grow. However, it has been found that such use has both deleterious and beneficial effects. A detrimental effect is an increase in sedimentation and sludge, especially in lubricants and fuel oils. Such deposits promote corrosion, create a barrier to pumps, instrumentation, and related equipment, and impede oil storage and transportation.

[Purpose of the invention]

It is therefore an object of the present invention to provide distillate fuel compositions containing organic transition metal salts in combination with ashless dispersants and phenolic antioxidants, which optimally balance beneficial and detrimental effects. Our goal is to provide the following.

Other objects of the invention will become apparent to those skilled in the art from the following disclosure.

[Structure of the invention]

Useful compounds containing (A) one or more transition metal salts of at least one organic acid; (B) at least one hydrocarbon-soluble ashless dispersant; and (C) at least one phenolic antioxidant. A distillate fuel composition has been discovered. Hydrocarbon systems such as lubricant and fuel compositions (such as distillate fuel compositions containing a predominant amount of hydrocarbon fuel and a minor amount of the salt/dispersant/antioxidant compositions described above); Additive concentrate compositions are also within the scope of this invention.

(A) Transition Metal Salts The transition metal in the organic salts of this invention is selected from the group consisting of copper, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, and mixtures of two or more thereof. Manganese salts and mixtures of manganese-containing salts with other metals are most often used. Salts containing only manganese are often used. Lead salts can also be used.

The organic acids used in making the transition metal salts used in this invention have carbon atoms, carboxylic acids especially those containing from 1 to 30 carbon atoms, and sulfonic acids especially those containing an alkyl group containing from 4 to about 22 carbon atoms. Examples include those having one or more substituted aromatic ring structures (for example, a benzene ring), and phosphorus acids having one or more organic groups having from 1 to about 30 carbon atoms in their structure.

Such carboxylic, sulfonic and phosphorous acids are known in the art. The carboxylic acids may be monocarboxylic acids or polycarboxylic acids (in the latter case, typical ones are di- or tricarboxylic acids). Monocarboxylic acids include C _1-7 lower acids (acetic acid, propionic acid, etc.), C ₈ or higher acids (e.g. octanoic acid, decanoic acid, etc.), and known fatty acids having about 12-30 carbon atoms. included. The fatty acids are often in mixtures or for example from 5 to about 30
% straight chain acids and from about 70% to about 95% (moles) branched chain acids. Other commercially available fatty acid mixtures with higher proportions of straight chain acids are also useful. Mixtures obtained by dimerization of unsaturated fatty acids can also be used.

Higher carboxylic acids include known dicarboxylic acids obtained by alkylation of maleic anhydride or its derivatives. The products of such reactions are hydrocarbon-substituted succinic acids, anhydrides, and the like. Low molecular weight dicarboxylic acids such as polymethylene bridged acids (glutaric acid, adipic acid, etc.) also yield the salts of this invention and low molecular weight substituted succinic acids such as tetrapropenylsuccinic acid and its substituted acid congeners up to about _C30 . can be used for.

High molecular weight substituted succinic anhydrides, succinic acids and analogs useful in preparing the salts of this invention are described in a number of patents, particularly those dealing with acylated compounds useful as dispersants. Typical high molecular weight acids have 30 or more carbon atoms.
It is obtained by reacting a poly(isobutene) fraction of 400 (usually 50 to 250) with maleic anhydride. Such materials are described in US Pat. Nos. 3,172,892, 3,219,666 and
No. 3272746, which is hereby incorporated by reference for the disclosure of high molecular weight carboxylic acids. Other monocarboxylic acids with similar molecular weights can be obtained by alkylating acrylic acid and its homologs. Mixtures of such acids can be used.

Useful salts can also be prepared from acidic hydroxy compounds such as carbocyclic carboxylic acids and alkylated phenols. Such materials are described in U.S. Pat. No. 4,100,082, in particular 15-
17 column, the description thereof is incorporated herein by reference for its disclosure.

The aforementioned US Pat. No. 4,100,082 also describes a number of sulfonic acids useful in preparing the salts of the present invention. The 12-14 column of that patent is incorporated herein by reference for its disclosure regarding sulfonic acids.

Transition metals prepared from phosphorus-containing acids are also useful in the present invention. Such phosphorus-containing acids are disclosed in numerous US patents and other publications. A representative example of the former is U.S. Patent No. 4191658.
and the following formula (In the formula, M is the above-mentioned transition metal; R ¹ and R ² are each a hydrocarbon group; X ¹ , X ² , X ³
and X ⁴ are each oxygen or sulfur; a and b are each 0 or 1. ) are disclosed.

The organic acids used to prepare the salts of the invention are typically carboxylic acids, sulfonic acids or mixtures thereof. A particularly useful group of such salts are those disclosed in Alkalitis et al., U.S. Pat. No. 4,162,986;
It is incorporated herein by reference for its disclosure of metallic organic compositions and particularly transition metal salts of organic acids useful in the compositions of the present invention.

The transition metal salts used in this invention are often overbased salts;
Note that it contains more than enough metal to neutralize the acid present. In other words, the salts contain one or more equivalents of metal per equivalent of acid-derived moiety. Such salts are known in the art. See, e.g., the '4162986 patent cited above and the following U.S. patents: No. 3827979 (Piotrowski et al.);
No. 3312618 (Lesuer et al.), No. 3616904 and 3616905 (Asseff et al.), No. 2595790 (Norman et al.) and No. 3725441 (Murphy
etc). These patents are incorporated herein by reference for their disclosure of basic salts of organic acids.

(B) Ashless Dispersants Ashless dispersants useful in the present invention are well known in the art and commonly used in lubricants based on oils of lubricating viscosity and hydrocarbon fuels, such as hydrocarbon fuels that are normally liquid. It is a dispersant that is widely used. Ashless dispersant is used during combustion (metallic)
It leaves little or no residue or ash. Generally, this means that in addition to carbon, oxygen, hydrogen and often nitrogen, phosphorus,
Although it contains elements like sulfur, boron etc.
Means substantially free of metals.

Typically, the ashless dispersants of the present invention contain only C, H, O and N. Ester type dispersants (see below) often contain only CH and O. More complex ashless dispersants that are metal-free also contain other elements such as sulfur, boron, phosphorus, etc. However, typical examples of ashless dispersants used in the present invention are of the ester type, with or without nitrogen.

Many types of ashless dispersants are known; e.g.
−ments” and earlier “Lubricant”
Additives” (both by MWRanney, Noyes
Data Inc., Park Ridge, New Jersey, 1978 and 1973).
These references and US Pat. No. 4,136,043 are incorporated herein by reference for their disclosure of ashless dispersants.

Usually readily available and therefore useful hydrocarbons -
Soluble ashless dispersants include: (1) Acylated nitrogen-containing dispersants such as those described in U.S. Pat. No. 4,100,082. This patent (particularly columns 18-20) is incorporated herein by reference.

These dispersants are acylating agents (e.g.
carboxylic acids or anhydrides) and amino compounds (amines, polyamines or other -NH-
(containing compounds). Representative acylating agents include the substituted succinic acids mentioned above and also described in the '082 patent. Other useful acylating agents are described in detail in a number of patents, such as U.S. Pat. No. 4,234,435, and include acylating agents that can be used to prepare ashless dispersants and Both contained compounds are described in detail. This patent is also incorporated herein by reference for its disclosure in that regard.

Acylated ashless dispersants useful in this invention can be either high molecular weight or low molecular weight. In addition to moieties from amino compounds, the dispersant may contain moieties from mono- and polyalcohols, including the group of aminohydroxy compounds such as the known amino alcohols. Typical ashless dispersants contain 2 to 7 amino groups and 1 to 6 alkylene groups.
(each having from 2 to 4 carbon atoms). Commercially available ethylene polyamines are also useful reagents in this connection.

Low molecular weight acylated nitrogen-containing compounds are also useful as dispersants in the compositions of this invention. Such compounds are prepared from the aforementioned amino compounds and mono- and dicarboxylic acids containing from about 12 to about 20 carbon atoms. Such dispersants often contain imidazoline groups and are those known in the art; e.g.
No. 3405064 and No. 3240575, which are incorporated herein by reference for their disclosure in this regard.

Both amino and alcohol compounds (or amino-alcohols) are acylated,
High molecular weight acylated nitrogen-containing ashless dispersants are also known and useful in the compositions of the present invention; they are described in U.S. Pat. ).

(2) High molecular weight nitrogen-free esters.

As mentioned above, these esters are prepared by reacting the above-described acylating agents (e.g., poly(isobutene)succinic anhydride) with polyols and monoalcohols and are known; See, eg, US Pat. No. 3,522,179, incorporated herein by reference for its disclosure of such esters.

(3) Hydrocarbyl-substituted amines.

Hydrocarbyl-substituted amines useful as ashless dispersants are known in the art; for example, U.S. Pat.
See 3454555 and 3565804.
A discussion of such materials is provided above.
This can also be seen in the 082 patent. All of these patents are incorporated herein by reference to disclose suitable hydrocarbylamines for use as ashless dispersants in the present invention.

(4) Nitrogen-containing condensates of phenols, aldehydes and amino compounds.

Condensates obtained by reacting phenols, aldehydes (such as formaldehyde), and amino compounds (such as those described above) with amino compounds (such as those described above) are useful as ashless dispersants in the compositions of this invention. These substances are generally known as Mannitz condensates. Typically, they are prepared by reacting hydrocarbon-substituted phenols (e.g., alkylated phenols with alkyl groups of about 34-400 carbon atoms), formaldehyde, and amino or polyamino compounds containing at least one -NH- group. It is prepared by Many such materials are known in the art; see, e.g., the aforementioned '082 patent (particularly the 21-22 column) and the references cited therein, including Mannitz condensates and their (Incorporated here for disclosure of manufacturing method.)

(C) Phenolic Antioxidants As will be apparent throughout this specification and claims, the compositions of the present invention are hydrocarbon soluble. In order to ensure this solubility, the antioxidant used in combination with the transition metal salt of the organic acid, component (A) and the ashless dispersant, component (B), has an affinity for the above components and is compatible with the composition. It is necessary that no precipitation occurs, particularly of transition metal salt components. Antioxidants that are compatible with other components described in this specification and claims and do not cause precipitation of transition metal salt components are phenolic antioxidants, preferably sterically hindered phenolic antioxidants. These are the types of antioxidants commonly listed as antioxidants. Here, the term "sterically hindered phenolic antioxidant" refers to a phenolic antioxidant characterized by having at least one substituent at the ortho position of at least one phenolic hydroxyl group. Specifically, the organic transition metal salt of this invention/
Sterically hindered phenols useful in preparing ashless detergent-dispersant/phenolic antioxidant compositions have the formula These are sterically hindered phenols and sterically hindered bisphenols represented by

In the formula, the R group represents hydrogen or an aliphatic hydrocarbon group having 1 to about 8 carbon atoms, and at least one of the R groups is an aliphatic hydrocarbon group in the ortho position to the phenolic hydroxyl group. and X represents an alkylidene group having 1 to about 4 carbon atoms, thio (-S-) and dithio (-S-
S-) group.

In relation to sterically hindered phenols and sterically hindered bisphenols as defined herein,
"Aliphatic hydrocarbon" means saturated alkyl and cycloalkyl hydrocarbons; "alkyldene group" refers to a divalent hydrocarbon derived from an alkyl group in which two hydrogen atoms have been removed from the same carbon; means base.

The sterically hindered phenols and sterically hindered bisphenols useful in preparing the compositions of the present invention are those in which at least one of the R groups in the above formula is
It represents an alkyl group which is ortho-position to a phenolic hydroxyl group, and which is branched particularly at the α-position of the group. Particularly preferred sterically hindered phenols and sterically hindered bisphenols are those in which the two R groups in the above formula are both in the ortho position relative to the phenolic hydroxyl group, and in particular in the α
It represents an alkyl group branched at the - position.

Representative (non-limiting) examples of sterically hindered phenols and sterically hindered bisphenols of the formulas above useful in preparing the hydrocarbon-soluble compositions of this invention include: :
2-tert-butylphenol; 2-ethyl-6-
Methylphenol; 2,6-di-tert-butylphenol; 3-methyl-2,6-bis(1-methylethyl)phenol; 4-methyl-2,6-di-tert-butylphenol; 3-methyl- 2,6
-bis(1-methylpropyl)phenol; 2-
Butyl-6-ethylphenol; 4-butyl-
2,6-di-tert-butylphenol; 4-tert
-butyl-2,6-dimethylphenol; 6-
tert-butyl-2,3-dimethylphenol; 2
-tert-butyl-4-methylphenol; 2-cyclohexyl-6-tert-butylphenol; 2
-cyclohexyl-6-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,2'-methylenebis(4,6
-di-tret-butylphenol); 4,4'-methylenebis(2,6-tret-butylphenol); 2,
2'-methylenebis(4,6-bis(1,1-dimethylpropyl)-phenol];4,4'-methylenebis[2,6-bis(2-methylhexyl)phenol];3,3'-methylenebis( 2,6-di-
tret-butyl-4-methylphenol); 4,4'-
Propylidene bis(2-tert-butylphenol); 2,2'-propylidene bis(6-tert-butyl-4-methyl-phenol); 2,2'-ethylidene bis-(4,6-di-tert-butylphenol) ;4,4'-ethylidene bis(2,6-di-tert
-butylphenol); 4,4'-ethylidenebis(2-tert-butyl-6-methylphenol);
2,2'-butylidene bis(4,6-di-tert-butylphenol), 4,4'-butylidene bis(2
-tert-butyl-3-methylphenol); 4,
4'-Butylidene bis(2-tert-butyl-6-methylphenol); 2,4,6-tri-tert-butylphenol; 2,4,6-tris(1,1-
dimethylbutyl)-phenol; 2,2'-thiobis(2,6-di-tert-butylphenol); 4,
4'-thiobis(2,6-di-tert-butylphenol);3,3'-thiobis(2,6-di-tert-butyl-4-methylphenol);4,4'-(2-
tert-butyl-6-methylphenol);4,4'-
Dithiobis(2,6-di-tert-butylphenol);4,4'-dithiobis(2,6-diisopropylphenol);2,2'-dithiobis-(6-
tert-butyl-4-methylphenol);4,4'-
diobis(2-tert-butyl-6-methylphenol) and the like.

The above-mentioned phenolic antioxidant can be used alone,
A mixture of two or more of the above phenolic antioxidants may also be used. Preferred phenolic antioxidants used in preparing the compositions of the invention include 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butylphenol;
2,6-di-tert-butylphenol; 2-tert
-butylphenol; 4,4'-methylenebis(2,6-di-tert-butylphenol) and mixtures thereof.

The hydrocarbon-soluble composition of the present invention is prepared by mixing (A) one or more transition metal salts of organic acids described above with (B) at least one hydrocarbon-soluble ashless dispersant described above, and combining (A) and (B). (C) Prepared by mixing with at least one phenolic antioxidant described above. In the context of the present invention, "hydrocarbon soluble" shall mean that the solubility of the substance in question in the hydrocarbon system used therein at 25° C. is at least 0.001 parts by weight.

Mixing of substances (A) and (B) can be carried out in any convenient manner. It is usually best to avoid mixing the salt and dispersant directly, which avoids precipitation problems. Generally, therefore, the dispersant or salt is mixed with an inert solvent diluent and this material is then mixed with other and/or auxiliary reagents. Solvents used in the compositions of this invention/
The diluent is usually hydrocarbyl, but may contain small amounts of other heteroatoms,
Moreover, in order to improve solubility, it is highly aromatic. Auxiliary reagents used in the compositions of the invention include dyes, metal deactivators, and dispersants/and/or salts that are emulsified in the vehicle used for processing (e.g., fuel oil, lubricant, etc.). There are demulsifiers that suppress the tendency for product formation to accelerate. Many such demulsifiers are known; for example, Encyclopedia of
Chemical Technology-Kivk-Othmer, 8 volumes,
See pp. 151 et seq. and Vol. 19, pp. 507 et seq. (1965). Typical demulsifiers are surfactants that have a hydrophilic portion and a lipophilic portion in their molecules. Such reagents are often prepared by reacting hydroxy compounds (such as phenols and alcohols) with materials such as ethylene oxide and propylene oxide and mixtures thereof in various proportions.

As mentioned above, the compositions of the invention are used to treat lubricating oils of lubricating viscosity and lubricants based on hydrocarbon fuels. Lubricating oils are typically hydrocarbon in nature, but include those with non-hydrocarbyl moieties (e.g. synthetic esters,
ethers and similar oils).

The fuels treated with the compositions of this invention are both solid and usually liquid fuels. Solid fuels include coal, shale, peat, wood, organic waste, charcoal, etc. Liquid fuels are light petroleum fractions such as gasoline, kerosene, etc. and other fractions such as middle distillate fuel oils. Representative middle distillate fuel oils that can be treated with the compositions of this invention include ANSI/
No. 1 specified in ASTM standard D-396-97,
2 and 4 of fuel oil and other similar materials. Combinations of such fuel oils with straight run, vacuum run and other specialty treated residue oils are also advantageously treated with the compositions of the present invention.

The concentration of the composition of this invention in a lubricant or oil composition to be treated is such that the lubricant or oil composition to be treated has a transition metal (the concentration of the salt is expressed in terms of metal) of about 1 -500,
Preferably 5-350 ppm (by weight), ashless dispersant about 5-1000, preferably 10-800 ppm (by weight)
and a phenolic antioxidant at a concentration of about 1-50, preferably 1-25 ppm (by weight). In fuel oils, the compositions in practice include transition metal concentrations of about 5-200 ppm (by weight), ashless dispersant concentrations of about 15-450 ppm (by weight), and phenolic antioxidant concentrations of about 1-15 ppm (by weight). weight basis)
It is used as follows.

〔Example〕

Example 1 A poly(isobutene)-substituted succinic anhydride acylating agent (n having a substituent of about 1000) was reacted with a commercially available mixture of ethylene polyamines having an average composition of triethylenetetra-amine. , a known ashless acylated nitrogen-containing dispersion is prepared. The reaction is carried out in an aromatic solvent/diluent in a weight ratio of acid to polyamine of approximately 100:9; water and other low boiling products and impurities are removed by heating to reduce the nitrogen content. Approximately 2% by weight of the desired ashless dispersant is obtained.

Example 2 An intermediate composition is prepared by mixing the following weight proportions: basic manganese carbonate ^* (n40% by weight)
Contains) - 10.82 parts, ashless dispersant of Example 1 - 14.43 parts,
First emulsifier ^** −0.18 parts, second emulsifier (3) −0.14
parts, and aromatic solvent (4) - 74.43 parts.

*Sold as Mooney 910 by Mooney Chemical, **Ethoxylated/propylated/hydroxy compound available as TOLAD from Petrolite's Tretolite Division, St. Louis Missouri, (3) Nalco Chemical, Hyuston, Texas. Ethoxylated proxylated pentaerythritol obtained as NALCO 5RD-648 from (4) Kauri Gum-HI-SOL with butanol value of 95
aromatic solvent.

The above compositions are prepared using aromatic solvents to avoid direct mixing with concentrated carboxylate ashless dispersants. This composition has a specific gravity of 15.6°
0.94, pour point -57°C, manganese content 4.3-4.6% by weight.

Example 3 475.0 parts by weight of the intermediate composition of Example 2 was mixed with 25.0 parts by weight of a phenolic antioxidant, 4,4'-methylenebis(2,6-di-tert-butylphenol), at room temperature with constant stirring, and carbonized. A hydrogen soluble composition is prepared. Stirring is continued until a clear solution is obtained.

Example 4 487.5 parts by weight of the intermediate composition of Example 2 were mixed with 12.5 parts by weight of a phenolic antioxidant, 2,6-di-tert-butyl-4-methylphenol, at room temperature with constant stirring to obtain a hydrocarbon soluble compound. Prepare the composition. Stirring is continued until a clear solution is obtained.

Example 5 Two hydrocarbon soluble compositions are prepared as follows: 2,4,6-tri-tert-butylphenol for 475.0 parts by weight of the composition of Example 2.
8.0% by weight and 2,6-di-tert-butylphenol
25.0 parts by weight of a phenolic antioxidant mixture consisting of 11.0% by weight and Ethy1 735 obtained from Ethy1 Corporation were mixed to give the composition of Example 2 475.0
For other parts by weight, 2,4,6-di-
75.0% by weight of tert-butylphenol, 12.0% by weight of 2,6-di-tert-butylphenol and 2-
tert-butylphenol 7.4% by weight and Ethy1
25.0 parts by weight of a phenolic antioxidant mixture consisting of Ethy1 733, obtained from Corporation. During the preparation of both, mixing is carried out at room temperature with constant stirring, stirring being carried out until a clear solution is obtained.

Example 6 The compositions of Examples 3, 4 and 5 were prepared as representative commercially available Nos.
2 Used for processing middle distillate fuel oil. In each example, the treatment concentration was 1 part by weight of the composition for 4600 parts by weight of fuel oil.
Parts by weight. This treatment concentration corresponds to 10.7 ppm manganese per part of fuel oil. The resulting fuel is used to operate commercial boilers.

Claims (1)

[Scope of Claims] 1 (A) one or more transition metal salts of at least one organic acid; (B) at least one hydrocarbon-soluble ashless dispersant; and (C) at least one phenol. A distillate fuel composition containing a chemical antioxidant. 2. The distillate fuel composition according to claim 1, wherein the organic acid is a carboxylic acid, a phosphorus-containing acid, a sulfonic acid, or a mixture of two or more thereof. 3. The distillate fuel composition of claim 2, wherein the organic acid has at least about 7 carbon atoms. 4. Claim 3, wherein the metal is selected from the group consisting of copper, scandium, titanium, panadium, chromium, manganese, iron, cobalt, nickel, and mixtures of two or more thereof.
Distillate fuel composition as described in section. 5. The distillate fuel composition according to claim 4, wherein the acid is a carboxylic acid, a sulfonic acid or a mixture thereof. 6. The distillate fuel composition according to claim 5, wherein the metal is manganese. 7 Claim 6 in which the salt (A) is an overbased salt
Distillate fuel composition as described in section. 8. The distillate fuel composition according to claim 7, wherein the dispersant (B) is a nitrogen-containing dispersant, a nitrogen-free ester dispersant, or a mixture thereof. 9 The phenolic antioxidant (C) has the following formula [In the formula, the R groups independently represent hydrogen or an aliphatic hydrocarbon group having 1 to about 8 carbon atoms. However, at least one of the R groups is an aliphatic hydrocarbon group located ortho to the phenolic hydroxyl group. X is a group selected from the group consisting of alkylidene groups having from 1 to about 4 carbon atoms and thio and dithio groups. ] The distillate fuel composition according to any one of claims 1 to 8, which is selected from the group consisting of sterically hindered phenols and sterically hindered bisphenols. 10 At least one type of phenolic antioxidant represented by the formula in which two of the R groups are aliphatic hydrocarbon groups having 1 to about 8 carbon atoms, and phenolic hydroxyl groups are substituted at both ortho positions. The distillate fuel composition according to claim 9, which is a sterically hindered phenol. 11. The distillate fuel composition according to claim 1, wherein a small amount of the composition consisting of (A), (B), and (C) is contained in the majority of the distillate fuel. 12 The transition metal content of the fuel composition is about 1 to
Distillate fuel composition according to claim 1, which has a content of 500 ppm. 13 (A) one or more transition metal salts of at least one organic acid; (B) at least one hydrocarbon-soluble ashless dispersant; (C) at least one phenolic antioxidant; (D) A distillate fuel composition comprising at least one demulsifier; and (E) a substantially inert solvent-diluent. 14 (A) is an overbased manganese salt of a carboxylic acid, a sulfonic acid or a mixture thereof; (B) is an acylated nitrogen-containing dispersant; and (C) is at least one phenolic hydroxyl group; 14. The distillate fuel composition of claim 13, wherein the distillate fuel composition is a phenolic antioxidant substituted in the ortho position with a branched alkyl group having from 1 to about 8 carbon atoms. 15. Claim 13, wherein a small amount of the composition consisting of (A), (B), (C), (D) and (E) is contained in the majority of the distillate fuel. Distillate fuel compositions as described.