CA1189307A - Organo transition metal salt/ashless detergent- dispersant phenolic antioxidant combinations - Google Patents

Abstract

Abstract Compositions comprising the combination of a transition metal salt of an organic acid, a hydrocarbon-soluble ashless dispersant, and a phenolic antioxidant are useful in treating lubricants and fuels. Typical composi-tions comprise manganese carboxylates, acylated nitrogen-containing dispersants and a hindered phenolic antioxidant.

Description

L-2lo8s 3q~7 ORGANO TRANSITION METAL SALT/ASHLESS
DETERGENT-DISPERSANT/PHENOLIC ANTIOXIDANT COMBINATIONS

Backaround of the Invention Field of the Inven~ion ____ This invention relates to hydrocarbon-soluble compositions containing a transition me~al salt of an or ganic acid, a hydrocarbon solubie ashless dispersant, and a phenolic antioxidant. Typically, it relates to such compo-sitions wherein the organic acid is a carboxylic, sulfonic or phosphorus acid, the ashless dispersant is a nitrogen or non-nitrogen containing ester d:ispersan~ and the antioxidant is a hindered phenol. It also relates to hydrocarbon sys-tems containing the aforesaid compositions, such as lub-ricants based on oils of lubricating viscosity and hydro-carbon fuels, Prior ~rt The ~reatment of hydrocarbon systems such aslubricants based on lubricating oils of lubricating Vi5-cosity (e.g., greases, lubricating oils and the like) and hydrocarbon`fuels of both the solid and normally liquid type with transition metals and transition metal-containing com-pounds, both organic and inorganic~ is well known to the art. Such treatments are used to increase the systems' re-sistance to oxidative deterioration, promote their conver-sion to cohe.Rlve films in the case of paints and lacquersand improve their combustion as, for example t fu ls.
Among the organic txansition metal compounds that 3 ~'t~

have been used for such purposes are carboxylate and sul-fona~e salts and mixtures of such sal~s. For example, U.S.
Patent 4,162,986 to Alkaitis, et. al. describes transition metal salts of mixed organic carboxylic and sulfonic acids or a second carboxylic acid and their use as catalysts, an~i knock agents, combustion improvers, smoke suppressants, curing agents, driers, micronutrient sources, lubricant additives, and the like.
U.S. Patent 3,762,890 to Collins describes hydro-lyzable mangane~e soaps~ stabilized by the inclusion ofpropionic acid and the use of such materials as siccatives fox paints, varnishes and inks, stabilizers in various plastics and additives for greases and lubricating oils as well as smoke-suppressing and anti-corrosion additives for 15 ~uel and fuel oils.
U.S. Patent 3,723,152 to Alkaitis, et. al. de-scribes basic cobalt salts of carboxylic acids and their use as drier compositions for oil vehicles.
Other patents such as U.S. Patent 4,202,671 to 20 Diehl, et. alO describe the use of organic magnesium com-pounds as fuel conditioners for the reduction of fuel re-quirements and emiss~ons.
Incxeasing concern with pollution and the xising cost of hydrocarbon-based fuels and lubricants ha~ promoted 25 continued interest in the use of transikion metal compounds in such systems~ It has been found, however, that such u~e~
sometimes causes deleterious as well as beneficial effects.
Among the deleterious effects are promotion of ssdiment and sludge, particularly in lubricants and fuel oils. Such 30 deposits can inter~ere with storage and transport of the oil by promoting corrosion and interfering with pumps, meters and associated equipment.
Therefore, it is an ob~ect of the present inven-tion to provide hydrocarbon-soluble composi~ions containing 35 organic transition metal salts in combination with ashless dispexsants, and phenolic antioxidants which provide an optimum balance between beneficial and deleterious effects.
Other o~jects will be apparent to those of skill in the art upon reading this disclusure.
Summary of the Inven~ _ It has now been found that useful hydrocarbon-soluble compositions comprise (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.
~ydrocarbon systems such as lubricant and fuel compositions (such as distillate fuel composi~ions compris-ing a ma~or amount of hydrocaxbon fuel and a minor amount of the aforedescribed salt/dispersant/antioxidant composi-tions), as well as additive concentrate compositions, are 15 also within the scope of the invention.
Detailed Description of the Invention (A) The transition metal salts.
The transition metals in the organic salts of this invention are chosen from the group consisting o copper, 20 scandium, titanium, vanadium, chromium, manganese, iron, co-bal~, nickel and mixtures of two or more of these. Mangan-ese salts and salts containing manganese in admixture with other metals are most commonly u~ed. Often sal~s containing only manganese are used. Lead salts can also be used.
- The organic acids used to make the transition metal salts used in this invention con~ain carbon atoms and include carboxylic acids, particularly those containing from 1 to 30 carbon atoms, sulfonic acids, particularly those containing an aromatic ring structure (e.g., benzene ring) 30 substituted with one or more alkyl groups of 4 to about 22 carbon atoms, and phosphorus acids, containing within their structures one or more organic groups of 1 to about 30 or more carbon atoms.
Such carboxylic, sulfonic and phosphorus acids are 35 well known to the art. Tha carboxylic acids can be mono- or polycarboxylic acids (if the latter, typically they are di-or tricarboxylic acids). Monocarboxylic acids include Cl-7 lower acids (acetic, propionic, etc.) and higher C8+

acids (e.g., octanoic, decanoic, etc.) as well as the well known fatty acids o:E about 12-30 carbon atoms. The fatty acids are often mixtures of straight and branched chain acids containing, for example, from 5 to about 30% straight chain acids and about 70 to about 95% (mole) branched chain acids. Other commercially available fatty acid mixtures containing much higher proportions of straight chain acids are also useful. Mixtures produced from dimerization of unsaturated fatty acids can also be used.
Higher carboxylic acids include the well known dicarboxylic acids made by alkylating maleic anhydride or its derivatives. The products of such reactions are hydro-carbon substi~uted succinic acids, anhydrides, and the like.
Lower molecular weight dicarboxylic acids, such as the polymethylene bridged acids (glutaric, adipic, and the like), can also be used to make the salts of this invention as well as the lower molecular weight substituted succinic acids such as -tetrapropenyl succinic acid and its analogs of to about C30 substituted acids.
Higher molecular weight substituted succinic anhydrides, acids, and analogs useful in making the salts of this invention have been described in a number of patents, particularly those dealing with acylated compounds useful as dispersants. Typical high molecular weight acids are those made by reacting a poly(isobutene) fraction having between 30 and 400 (usually 50-250) carbon atoms with maleic anhydride. Such materials are described in U.S. Patents 3,172,892, 3,219,666, and 3,272,746. Other mono-carboxylic acids of similar molecular weight can be made by alkylating acrylic acid and its analogs. Mixtures of such acids can also be used.
Useful salts can also be made from carbocycli~
carboxylic acid and even acidic hydroxy compounds such as alkylated phenols. Such materials are disclosed in U . S .
Patent 4,100,082, particularly columns 15-17.

The '082 patent just idPntified also describes a number of sulfonic acids which are useful in making the salts of this invention particularly in col~s 12-14.
Transition metal salts made from phosphorus acids are also useful in this invention. Such phosphorus acids have been disclosed in a number of U.S. patents and other literature. Exemplary of the former is U.S. Patent 4,191,658 which discloses pho~phorus acid salts of the formula x3 Rl(Xl)~
P-X M
R2 (X2) b/

wherein M i9 a transition metal as described above; each and R2 is a hydrocarbon radical; each of Xl, x2, X3 and X4 is oxygen or sulfur; and each of a and b is 0 or 1.
Typically, the organic acids used to make the salts of this invention are carboxylic acid, sulfonic acid, or mixtures thereof. A particularly useful group of such salts are those described in U.S. Patent 4,162,986 to A~kaitis, et al.
It should be noted that the transition metal salts used in this invention are often overbased; that is, they ~5 contain more khan sufficien~ m~tal to neutralize the acid present. In other words, they contain in excess of one equivalent of metal per equivalent of acid derived moiety.

~8~3~7 -- 6 ~

Such salts are known to the art. See, for example, the just cited ~,162,986 patent as well as the :Eollowing U~S.
Patents: 3,~27,979 to Plotrowski, et. al., 3,312,618 to LeSuer, et. al., 3,616,904 and 3,616,905 to Asseff, et. al.,

2,595,790 to Norman, et. al., and 3,725,~1 to Murphy, et.
al (B) The ashless dispersants.
The ashless dispersants useful in the present invention are known to the art and are those dispersants commonly used in lubricants based on oils of lubricating viscosity and hydrocarbon fuels such as normally li~uid hydrocarbon fuels. Ashless dispersants are those which leave little or no (metallic) residuQ or ash on combustion.
Generally, this means that they are substantially metal free though they may contain, in addition to carbon, oxygen, hydrogen and, often, nitrogen elements such as phosphorus, sulfur, boron, etc.
Generally, the ashless dispersants of the present invention contain only C, H, O, and N. Occasionally, ester type dispersants (see below) can contain only C, H, and O.
More complex ashless dispersants, while still metal free, may also contain other elements, such as sulfur, boron r phosphorus, and the like. Typically, however, the ashless dispersants used in this invention are of the nitrogen-containing or nitrogen-free ester type.
Many types of ashless dispersants are known; see, for example, the descriptions in ~lLubricant Additives -Recent Developments" and the earlier "Lubricant Additives", both by M.W. Ranney, published by Noyes Data Corporation, Park Ridge, New Jersey, 1978 and 1973, respectively.
Among the more commonly available and, therefore, useful hydrocarbon-soluble ashless dispersants are:

~c~

3~

(1) Acylated nitrogen-containing dispersants such as those described in U.S. Patent 4,100,082, particularly those at columns 18-20.
These dispersants are made by reaction of an acylating agent (e.g. carboxylic acid or anhydride) with an amino compound such as an amine, polyamine, or other compound containing an -~H- group. Typical acylating agents include the substituted succinic acids described above and in the '082 patent. Other useful acylating agents have been described in detail in many other patents, such as UOS. Patent 4,234,435 which describes in detail both acylating agents and amino-containing and non-amino-containing compounds which can be used to prepare ashless dispersants.
The acylated ashless dispersants useful in the present invention can be of either the high or low molecular weight type. In addition to portions from amino compounds, they may also incorporate portions from mono- and poly- alcohols, including amino hydroxy compound groups such as the well known amino alcohols. Typical ashless dispersants include those made from alkylene polyamines having 2 to 7 amino groups and 1 to 6 alkylene groups, each containing 2 to 4 carbon atoms. The commercially available ethylene polyamines are useful reagents in this regard.
Lower molecular weight acylated nitrogen-containing compounds are also useful as dispersants in the compositions of this invention. Such compounds are made from the aforedescribed amino compounds and mono- and dicarboxylic acid acylating agents containing about 12 to about 20 carbon atoms. Such dispersants often contain imida~oline groups and are known to the art; see, for example, U.S. Patents 3,405,064 and 3,240,575.

.~

High molecular weight acylated nitrogen-containing ashless dispersants wherein an amino and alcohol compound (or amino-alcohol) both are acylated are also known and useful in the compositions of this invention; these are described in U.S. Patent 4,136,043.
(2) High molecular weight nitrogen-free esters.
These esters, as indicated above, are made by reactlng the aforedescribed acylating agents (e.g. poly-(isobutene)) succinic anhydride with polyols and mono-alcohols and are well known; see, for example, U.S. Patent 3,522,179 A
(3) Hydrocarbyl substituted amines.
Hydrocarbyl substituted amines useful as ashless dispersants are known in the art; see, for example, U.S.
15 Patents 3,275,554, 3,438,7~7, 3,454,555, and 3,565,804.
A discussion of such materials also appears in the aforementioned '082 patent.

(4) Nitrogen-containing condensates of phenols, aldehydes and amino compounds.
Condensates made from reacting a phenol, aldehyde (such as formaldehyde) and amino compounds ~such as those described above) are useful as ashless dispersants in the compositions of this invention. These materials are often generically known as Mannich condensates. Generally, they are made from reacting a hydrocarbon suhstituted phenol (e.g., an alkylated phenol having an alkyl group of about 34-400 carbon atoms), formaldehyde and an amino or poly-amino compound having at least one -NH- group. A number of such materials are known to the art; see, for example, the aforementioned '082 patent, particularly columns 21-22, and the references cited therein.

1~

3~7 (C) The phenolic antioxidants As noted throughvut this specifica~ion and ap-pended claims, the compositions of the present invention are hydrocarbon soluble. To ensure this solubility, it is necessary that the antioxidants used in combination with the above descxibed tran~ition metal salts of organic acids, component (A) and the ashle~s dispersants, component (~), be compatible with said components and not cau~e precipita~ion of the compo~ition~ and particularly the tran~ition metal alt component. Antioxidants which were fo~nd to be com-patible with the other components in the composition~
described and claimed herein and not cause precipitation of the transition metal ~alt component comprise the class of antioxidants commonly referred to as phenolic antioxidants and preferably th~ hindered phenoli antioxidants. As used herein, tne term "hindered phenolic antioxidants" means phenolic antioxidant~ characterized by having at least one substituent in at least one position oxtho to the phenolic hydroxyl group. Specifically, the hindered phenols useful in preparing the organo transition metal salt/ashless de-tergent-di~persant/ phenolic antioxidant combination~ of this invention ar~ hindered phenols and hindered bisphenols corresponding to the general formulae ~H

X ~R ( I I ) wherein said R groups are hydrogen cr aliphatic hydrocarbon radicals con aining from 1 to about 8 carbon atoms with the proviso that at least one of said R groups is said aliphatic nydrocarbon radical in a position ortho to the phenolic hy-droxyl group and wherein X is a radical selected from thegroup consisting of alkylidene radicals containing from 1 to about 4 carbon atoms and thio (-S-) and dithio (-S~S-) rad-icals.
With re~pect to the hindered phenols and hindered bisphenols defined immediately above the term "aliphatic hydrocarbon" means saturated alkyl and cycloalkyl hydro-carbons and by the term "alkylidene radical" is meant di-valent hydrocarbon radicals derived from alkyl radicals in which two hydrogen atoms are removed from the same carbon.
Among the hindered phenol~ and hindered bisphenols useful in preparing the compositions of the present inven-tion the preferred phenols are those in which at least one of ~aid R group~ in the formulae above is a branched-chain alkyl xadical, especially a~ the alpha carbon in said rad-ical, in a position ortho to the phenolic hydroxyl group.
Particularly preferred hinderad phenols and hindered bis-phenols are those in which two of ~aid R groups in the formula àbove are branched-chain alkyl radicals, especially at the alpha carbon in said radical, in both positions ortho to the phenolic hydroxyl group.
Representative, but non-limited examples of hindered phenols and hindered bisphenols corresponding to the above formulae and useful in preparing the hydrocarbon soluble compositions of this invention include 2-tert-butylphenol; 2~ethyl-6-methylphenol; 2,6-di-tert-butyl-phenol; 3-methyl-2,6-bis(l-methylethyl)phenol; 4-methyl-2,6-di-tert-butylphenol; 3-methyl-2,6-bis(l-methylpropyl)phenol;
2-butyl-6-ethylphenol; 4-butyl-2,6-di tert-butylphenol; 4-tert-butyl-2,6-dimethylphenol; 6-tert-butyl-2,3-d~methyl-phenol; 2-tert-butyl-4-methylphenol; 2-cyclohexyl-6-tert-butylphenol; 2-cyclohexyl-6-ter~-butyl-4-methylphenol; 2-tert-butyl 4,6-dimethylphenol; 2,2'-methylenebis(4,6-di-tert-bukylph~nol); 4,4'-methylenebis~2,6-di-tsrt~butyl phenol~; 2,2'-methylenebis ~4,6-bis~ dimethylpropyl)-phenolJ; 4,4'-methylenebis~2,6-bis(2-methylhexyl)phenol];
3,3'-m~thylenebis(2,6-di-tert-butyl-4-methylphenol); 4,4'-propylideneb~s(2~tert-butylphenol); 2,2l-propylidenebis(6-tert-butyl-4-methyl-phenol); 2,2'-ethylidenebls(4,6-di-~ert-butylphenol); 4,4'-ethylidenebis(2,6-di-tert-butylphenol)i 4,4'-ethylidenebis(2-tert-butyl~6-methylphenol~; 2,2'-butylidenebis(4,6-di-tert-butylphenol); 4,4'-butylidenebis-(2-tert-butyl-3-methylphenol); 4,4'-butylidenebis(2-tert-butyl-6-methylphenol); 2,4,6-~ri-tert-butylphenol; 2,4,6~
tris~l,l^dimethylbutyl)-~henol; 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-butyl-phenol); 4,4'-dithiobis(2,6-diisopropylphenol); 2,2'-di-thiobis-[6-tert-butyl-4-methylphenol); 4,4'-dithiobist2-tert-butyl-6-methylphenol) and the like.
The phenolic antioxidants described hereinabove can be employed either singularly or as mixtures of two or more of said phenolic antioxidants. Preferred phenolic antioxidants for use in preparing the composi~ions of this invention include 2,6-di-tert-bu~yl-4-methylphenol; 2,6-di-tert-butylphenol; 2,6-di-tert-butylphenol, 2-tert-butyl phenol; 4,4'-methylenebis(2,6-di-tert-butylphenol) and mix-tures thereof.
The hydrocarbon-soluble compositions of this in~
vention are made by combining (A3 one or more of the afore-descxibed transition metal salts of organic acids with (B)at least one of the aforedescribed hydrocarbon-soluble ash-less dispersants and the combination of (A) and (B) with (C) at least one of the aforedescribed phenolic antioxidants.
It should b.f~ noted that "hydrocarbon soluble" in describing this invention means that the material in ~uestion has a 3~7 solubility at 25C. of at least 0.001 part~ by weight in the hydrocarbon system in which it is to function. The combin-ation of the materials (A) and (~ can be e~fected in any convenient manner. Usually, it is advantageous to avoid combining the salt and the dispersant directly since pre-cipitation problems can thus be avoidedO Therefore, it is common to combine either the dispersant or the salt with an inert, solvent diluent and then combine this material with the other and/or auxiliary agents. The solvent/diluents used in the composition of this invention are usually hy-drocarbyl in nature although they may contain small amounts of other hetero elements and are often highly aromatic to promote solubility. Auxiliary agents used in the composi-tions of this invention include dyes, metal deactivators, and, particularly, demulsifying agents which inhibit the tendency of the dispersant and/or the salt to promote emul-sion formations in the vehicles it i5 used ~o treat, such as fuel oils, lubricants and the like. Many such demul-sifying agents are known; see, for example, Encyclopedia of Chemical Technology - Kirk-Othmer, Volume 8, pages 151 et seq. and Volume 19, pages 507 et seq. (1965). Typical de-mulsifying agents are surface active agents containing hy-drophilic and lipophilic portions in the molecule. Such agents are often made by reacting a hydroxy compound, such as a phenol or alcohol, with materials such as ethylene oxide and propylene oxide and ~heir mixtures in various proportions.
As indicated above, the compositions of this in-vention are used to treat lubricants based on lubricating oils of lubricating ivscosity and hydrocarbon fuels. The lubricating oils are typically hydrocarbon in nature al-though they n.ay contain non-hydrocarby portions, such as synthetic ester, ether, and similar oils.
The fuels treated with the compositions of thiq invention include both solid and normally liguid fuels.
Among the solid fuels are coal, shale, peat, wood, organic refuse, charcoal and the like. Liquid fuels encompass the lighter petroleum fractions such as gasoline, kero~ene, and the like, as well as other fractions such as middle dis-tillaie fuel oils. Typical middle distillate fuel oils which can be treated with the compositions in this invention include No. 1, 2, and 4 fuel oils as defined by ANSI/ASTM
Standard D-396-97 and other such materials. Combinations of such fuel oils with straight run, vacuum run, and other specially treated residual oils can also be advantageously treated with the combinations of the present invention, The concentration of the compositions of this in--vention in the treated lubricant or oil compositions is such that the trea~ed lubricant or oil compositions contain about 1-500, preferably 5-350 ppm (by weight) transition metal*, about 5-1000, preferably 10-800 ppm (by weiyht) ashless dispersant and about 1-50, preferably 1-25 ppm (by weight) phenolic antioxidant. In fuel oiLs, particularly, the composition is used to produce a transition metal concen-tration at about 5-200 ppm (by weight), an ashless dis-persant concentration of about 15-450 ppm (by weight) and a phenolic antioxidant concentration of about 1-15 ppm (by weight).
EXAMPLES

A known ashless acylated nitrogen-containing dis-per~ant iQ prepared by reacting a mixture of poly(isobutene) :-~ substituted succinic anhydride acyla~ing agent (having a substituent wi~h an Mn equal to about 1,OOO) with a commer-cial mixture of ethylene polyamineQ averaging in composition triethylene tetra-amine. The reaction is carried out in aromatic solvent/diluent and the proportion of acid to polyamine, by weight, i9 approximately 100 to 9; water and other low-boiling products and impurities are removed by heating to give the desired ashless dispersant having a * The concentration of salt is expressed in terms of metal alone.

33~

nitrogen content of about 2% ~by weight).
Exam~le 2 An intermediate composition is prepared by com-bining by weight the following: an overbased manganese carboxylate* (containing 40% by weight Mn) - 10.82 parts, the ashless dispersan~ of Example 1 - 14.43 parts, a first demulsifier** - 0.18 parts, a second demulsifier (3) - 0.14 parts, and aromatic solvent (4) - 74.43 par-ts. * Sold by the Mooney Chemical Company as Mooney 910. ** An Ethoxylated/
Propylated Hydroxy Compound available as TOLAD 285 from The Tretolite Division of Petrolite Corporatio~, St. Louis, Missouri~ (3) ~n Ethoxylated Propoxylated Pentaerythritol available as NALCO 5RD-648 from the Nalco Chemical Company o~ Houston, Texas. (4) HI-SOL Aromatic Solvent having a Kauri Gum-Butanol value of 95, The above combination is made by using ~he aromatic solven~ in such a way as to avoid direct combination of the concentrated carboxylate and ashless dispersant. The combination has a specific gravity at 15.6 of 0.94, a pour point of -57C., and a manganese content of 4.3-4.6 percent by weight.
Example 3 A hydrocarbon soluble compo~ition is prepared by combining 475.0 parts by weight of the intermediate compo-sition of Example 2 with 25.0 parts by weight of the pheno~
lic an~ioxidant t 4,4'-methylenebis(2,6-di-tert-butylphenol) under constant agitation at room temperature. Ag~tation is continued until a clear solution is obtained.
~.
A hydrocarbon soluble composition is prepared by combining 4~7.5 parts by weight of the intermediate compo-sition of Example 2 with 12,5 parts by weight of the phe-nolic antioxidant, 2,6-di-tert-butyl 4-methylphenol under constant agi~ation at room tempera~urel Agitation is con-tinued until a clear solution is obtained.
~
Two hydrocarbon soluble compositions are prepared as follows: to one portion of 475.0 parts by weight of the composition of Example 2 is combined 25.0 parts by weight of a mixture of phenolic antioxidan~s comprised of 85.0 weight percent of 2,4,6-tri-tert-butylphenol and 11.0 weight per-cent of 2,6-di-ter~-butylphenol and available from the Ethyl Corporation as Ethyl 735 and to another portion of 475.0 parts by weight of the composition of Example 2 is combined 25.0 parts by weight of a mixture of phenolic antioxidants comprised of 75.0 weight percent of 2,4,6-di-tert-butyl-phenol, 12.0 weight percent of 2,6-di-tert-butylphenol and 7.4 weight percent of 2-tert-butylphenol and available from the Ethyl Corporation as Ethyl 733. In both preparations the blending is carried out under constant agitation at room temperature and said agitation is continued until clear solutions are obtained, ~
The compositions of Examples 3, 4, and 5 are used to treat a typical commercially available No. 2 middle dis-tillate fuel oil. The treatment level in each instance is 1 part composition to 4600 parts by weight of fuel oil. This treatment level is equivalent to 10.7 parts per million manganese per part of fuel. The treated fuel is used to op-erate a commercial boiler.

Claims (18)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A hydrocarbon-soluble composition comprising:
(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.

2. A composition as claimed in claim 1 wherein the organic acid is a carboxylic acid, phosphoric acid, sulfonic acid or mixture of two or more of these.

3. A composition as claimed in claim 2 wherein the organic acid contains at least about 7 carbon atoms.

4. A composition as claimed in claim 3 wherein the metal is chosen from the group consisting of copper, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and mixtures of two or more of these.

5. A composition as claimed in claim 4 wherein the acid is a carboxylic acid, sulfonic acid or mixture thereof.

6. A composition as claimed in claim 5 wherein the metal is manganese.

7. A composition as claimed in claim 6 wherein the salt (A) is an overbased salt.

8. A composition as claimed in claim 7 wherein the dispersant (B) is a nitrogen-containing dispersant, a nitrogen free ester dispersant or a mixture thereof.

9. A composition according to claim 1 wherein the phenolic antioxidant (C) is selected from the group consisting of hindered phenols and hindered bisphenols corresponding to the formulae:

(I) (II) wherein said R groups are independently hydrogen or aliphatic hydrocarbon radicals containing from 1 to about 8 carbon atoms with the proviso that at least one of said R
groups is said aliphatic hydrocarbon radical in a position ortho to the phenolic hydroxyl group and wherein X is a radical selected from the group consisting of alkylidene radicals containing from 1 to about 4 carbon atoms and thio and dithio radicals.

10. A composition according to claim 9 wherein the phenolic antioxidant is at least one hindered phenol corresponding to the formula (I) wherein two of said R
groups are aliphatic hydrocarbon radicals containing from 1 to about 8 carbon atoms and substituted in both positions ortho to the phenolic hydroxyl group.

11. A hydrocarbon-soluble composition comprising:
(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) at least one demulsifier; and (E) substantially inert solvent-diluent.

12. A composition as claimed in claim 11 where (A) is an overbased manganese salt of a carboxylic acid, a sulfonic acid or mixture thereof; (B) is an acylated nitrogen-containing dispersant; and (C) is a phenolic antioxidant substituted in at least one of the positions ortho to the phenolic hydroxyl group with a branched-chain alkyl radical containing from 1 to about 8 carbon atoms.

13. A fuel composition comprising a major amount of fuel and a minor amount of the composition of claim 1.

14. A fuel composition as claimed in claim 13 wherein the fuel is normally liquid.

15. A normally liquid fuel composition comprising a major amount of distillate fuel oil and an amount of those compositions of claim 1 sufficient to give the fuel composition a transition metal content of about 1-500 ppm.

16. A normally liquid fuel composition comprising a major amount of distillate fuel oil and an amount of those compositions of claim 12 sufficient to give the fuel composition a transition metal content of about 5-200 ppm.

17. An additive concentrate comprising about 10-99% by weight of the composition of claim 1 and a substantially inert, normally liquid organic diluent.

18. An additive concentrate comprising about 10-99% by weight of the composition of claim 11 and a substantially inert, normally liquid organic diluent.