JP2965764B2 - Hydrocarbon fuels and their additives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a liquid fuel composition having enhanced use characteristics, particularly combustion characteristics and stability characteristics.

Hitherto, it has been found that certain organometallic compounds are effective as combustion improvers for distilled fuels such as household heating fuels. For example, US Pat.
No. 2,789 describes the use of cyclopentadienyl manganese tricarbonyl for this purpose, the compound methylcyclopentadienyl manganese tricarbonyl (MMT) being a fuel improver for this type of distilled fuel. As a solution in a hydrocarbon diluent. Bis- (cyclopentadienyl) iron has also been recommended and is commercially available as a combustion improver for use in such fuels.

[0003] Keszthelyi et al. Polytech. Chem. En
g. Journal, Vol. 21, No. 1, pp. 79-93 (1977) shows that 0.025% cyclopentadienyl manganese tricarbonyl is effective in reducing soot in the combustion of light fuel oil in evaporative burners Has been reported. Nauka of Mosquea, published in 1971 by A.N. Nesumenov
yanov) Edited by Margansevye Antideto
pp. 192-199, Makhov et al. report test results showing that the addition of cyclopentadienyl manganese tricarbonyl in diesel oil reduces the level of smoke in the waste gas.

[0004] Rybn. Khoz (Moscow) Magazine 9
Vol. 52-4 (1977).
arev) reports the results of adding cyclopentadienyl manganese tricarbonyl (CMT) alone or as a formulation containing "detergents and solvents" to a mixture of diesel fuel oil and marine residue. CMT
It has been shown that while alone reduces carbon deposition in intake valves, it does not on engine surfaces and reduces smoke. The CMT formulation ("Ts8") has been shown to more effectively reduce carbon deposition, particularly at intake valves, cylinder heads and piston heads.

In Canadian Patent No. 1,188,891, additives to fuel oils and diesel fuels, as well as other liquid fuels and motor fuels with improved flammability, reduce soot formation and improve storage stability. It is stated to increase. Such additives include at least one transition metal or alkaline earth metal oil-soluble or oil-dispersible organic compound, and at least one hydrocarbon stable oxidation and polymerization inhibitor at a temperature of at least 300 ° C. Made up of According to this patent, the presence of compounds of transition metals such as copper, manganese, cobalt, nickel and iron in such fuels promotes fuel degradation in accelerated stabilization tests performed at 149 ° C. in air. You. MMT, ferrocene, naphthalene copper,
Compounds such as naphthalene iron and naphthalene manganese are high temperature (eg, 300 ° C.) stabilizers such as heat stable alkylphenols, amines, aminophenols, dithiophosphates, dithiocarbamates and imidazoles, and oxides of aluminum, magnesium or silicon Alternatively, it is indicated as a compound which causes the above-mentioned degradation in the absence of an inorganic inhibitor in the form of a hydroxide. EP 0078249 B1 describes a similar general effect, stating that the additive can be a combination of a transition metal compound and an alkaline earth metal compound, or either. ing.

[0006] German Patent 1,413,323 describes a multi-component diesel fuel additive for avoiding or suppressing the formation of deposits on injectors. These additives are, in particular, esters of oleic acid or naphthenic acid having an acid value of less than 200; naphthenic esters of cresol; alkoxyalkyl esters of aliphatic carboxylic acids; organometallic tricarbonylcyclopentadiene compounds, for example cyclopentadienyl manganese tricarbonyl An amide derivative of a polyolefin obtained by reacting a polyolefin-substituted succinic acid or acid anhydride with a polyamine; a copolymer of ethylene and a vinyl (or hydrocarbyl-substituted vinyl) ester of carboxylic acid having a number average molecular weight higher than 3000; It consists of a re-odorizer of a mixture of natural or synthetic alcohols, ketones and ethers; kerosene; and petroleum distillate.

US Pat. No. 4,505,718 describes a combination of a transition metal salt, such as manganese carboxylate and a hydrocarbon-soluble ashless dispersant.
It is said that an optimal balance between beneficial and adverse effects is achieved in oils of lubricant viscosity and hydrocarbon fuels.

Additions based on or based on one or more fuel-soluble manganese carbonyl compounds and one or more fuel-soluble alkali and / or alkaline earth metal-containing detergents The agent composition has been found to significantly improve the combustion characteristics of various hydrocarbon fuels. Unfortunately, however, such combinations of additives often cause fuel instability. That is, the hydrocarbon fuel blended with these additives is more prone to instability when exposed to air or oxygen at high temperatures than fuels without these additives.

Accordingly, an effective method for preventing fuel instability without impairing the combustibility improving effect obtained by such a combination of additives and without substantially increasing the cost of the combination of additives. It is desired to find out. According to the present invention, it is believed that such a requirement is achieved in the most effective manner.

According to the present invention, there is provided a liquid hydrocarbon comprising a combination of one or more fuel-soluble manganese carbonyl compounds and one or more fuel-soluble alkali or alkaline earth metal-containing detergents. The instability of the volatile fuel is prevented by including in the fuel at least one chelating metal quencher soluble in the fuel, ie, a metal quenching agent capable of forming a complex with the dissolved metal or metal ion. Is done.

According to one embodiment of the present invention, there is provided an additive composition for a hydrocarbon fuel. The additive composition comprises: (a) a manganese carbonyl compound soluble in one or more fuels; (b) an alkali or alkaline earth metal-containing detergent soluble in one or more fuels, such as at least One sulfonic acid, and / or at least one carboxylic acid, and / or at least one salicylic acid, and / or at least one organic phosphorus acid containing at least one carbon-phosphorus bond; One or more salts of a neutral or basic alkali or alkaline earth metal; and (c) one or more fuel-soluble chelating metal deactivators. Accordingly, the additive composition of the present invention is comprised of three different substantial or essential components, namely (a), (b) and (c).

In another embodiment of the present invention, there is provided a fuel composition which is predominantly a liquid hydrocarbon fuel and contains a small amount of components (a), (b) and (c) above.

In accordance with a preferred embodiment of the present invention, the additive composition and the fuel composition are substantially, ie, contain no more than 10 ppm, if any, halogen.

The preferred manganese carbonyl compound of component (a) is a cyclopentadienyl manganese tricarbonyl compound. The preferred salts of component (b) are sulfonic acids, alkylphenols, sulfurized alkylphenols, and carboxylic acids, especially Sodium, potassium, calcium and magnesium salts of aromatic carboxylic acids. Suitable metal deactivators used as component (c) are of the formula

[0015]

Embedded image

Is a Schiff base soluble in fuels having one or more chelating centers. The aromatic ring in the above formula may or may not further have a substituent,
When it has a substituent, the number thereof is 1 to 4 (other than a hydrogen atom), and these substituents inhibit the complex forming ability of the metal deactivator with the dissolved metal or metal ion, or Any type of organic or inorganic substituents that do not render the metal deactivator useless, for example, by rendering it unstable, flammable, highly toxic, explosive, or fuel insoluble. be able to. In other words, it does not matter much what substituents are present on the ring.

A feature of the present invention is that even when the metal deactivator is present in an amount less than equimolar for either the manganese carbonyl compound or the metal detergent, fuel destabilization can be effectively prevented. It is in the discovery that. Another feature of the present invention is that the metal deactivator can effectively prevent fuel instability even when other additive components such as ashless dispersants, amine stabilizers, and demulsifiers are present. That is the discovery.

The compositions used for heating gas oils and similar burner fuels contain, in addition to components (a), (b) and (c), one or more of the following:

(D) at least one ashless dispersant; (e) at least one fuel-soluble demulsifier; and (f ) at least one aliphatic or cycloaliphatic amine.

Compositions used in automotive diesel fuels and similar medium fuels comprise, in addition to components (a), (b) and (c) above, component (d), ie at least one ashless dispersant And / or component (e), ie at least one
Contains demulsifiers soluble in some fuels.

The above and other embodiments of the present invention will be apparent from the following description and the appended claims.

As used herein, the term "fuel soluble" refers to the compound or component in question at normal ambient temperature at least at the lowest concentration in the concentration range specified for the compound or component. Has sufficient solubility in hydrocarbons to give a homogeneous solution containing

Manganese carbonyl compound. The manganese compound of the composition according to the invention, i.e. component (a), is characterized in that it is soluble in fuel and has at least one carbonyl group bonded to a manganese atom.

The most preferred general type of manganese carbonyl compound used in the present invention is an organic manganese polycarbonyl compound. For best results see US Pat. Nos. 2,818,417 and 3,127,35.
Cyclopentadienyl manganese tricarbonyl compounds of the type described in item 1 must be used. That is, cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese trimethyl, propylcyclopentadienyl manganese Trimethyl, isopropylcyclopentadienyl manganese tricarbonyl, butylcyclopentadienyl manganese tricarbonyl, pentyl cyclopentadienyl manganese tricarbonyl, hexylcyclopentadienyl manganese tricarbonyl, ethylmethylcyclopentadienyl manganese tricarbonyl, dimethyloctyl Cyclopentadienyl manganese tricarbonyl, dodecyl cyclopentadienyl manganese trica Boniru, indenyl manganese tricarbonyl,
And similar compounds wherein the cyclopentadienyl moiety contains up to about 18 carbon atoms.

A preferred organomanganese compound is cyclopentadienyl manganese tricarbonyl. Most preferred for use in the present invention is methylcyclopentadienyl manganese tricarbonyl.

The synthesis of cyclopentadienylmanganesetricarbonyl is known in the literature. For example, U.S. Pat. Nos. 2,818,417 and 3,127,351 mentioned above.
No. 2,868,816, U.S. Pat.
Nos. 898,354, 2,960,514 and 2,987,529.

Other less preferred but usable organomanganese compounds include nonionic diaminemanganesetricarbonyl halide compounds such as bromomanganese dianiline tricarbonyl and bromomanganese described in US Pat. No. 2,902,489. Dipyridinetricarbonyl; acylmanganesetricarbonyl, such as methylacetylcyclopentadienylmanganesetricarbonyl and benzoylmethylcyclopentadienylmanganesetricarbonyl as described in US Pat. No. 2,959,604; arylmanganesepentacarbonyl, such as US Pat. No. 3,007,953, phenylmanganese pentacarbonyl; aromatic cyanomanganese dicarbonyl, for example, mesitylene cyanomanganese dica described in U.S. Pat. No. 3,042,693. Boniru are included. Similarly, the formula RM
n (CO) ₂ L cyclopentadienyl manganese dicarbonyl compound can be used. Here, R is a substituted or unsubstituted cyclopentadienyl group having 5 to 18 carbon atoms, and L is a ligand such as olefin, amine, phosphine, SO ₂ , tetrahydrofuran and the like. Such compounds are described, for example, in Amsterdam (Am
Sterdam) Elsevier
r) Publisher, published in 1967, M. Herberhold, Metal π Complex (Met
al π-Complex ”, Vol. 2, and also PJ Giordano and MS Weighton.
Inorg. Chem. 19 (1977) 16
See the article on page 0. Manganese pentacarbonyl dimer (dimanganese decacarbonyl) can also be used.

Metal-containing detergent. Examples of metal-containing detergents are neutral or basic salts (or mixtures thereof) of oil-soluble alkali or alkaline earth metals with one or more of the following acidic substances: (1) sulfonic acid,
(2) carboxylic acid, (3) salicylic acid, (4) alkylphenol, (5) sulfurized alkylphenol,
(6) Organic phosphorus acids having at least one carbon-phosphorus bond. Such organic phosphorus acids include olefin polymers (for example, polyisobutylene having a molecular weight of 1000) as phosphating agents, such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, and white phosphorus. Includes those made by treatment with sulfur halides or phosphorothioic acid chloride. The most commonly used salts of such acids are the sodium, potassium, lithium, calcium, magnesium, strontium, and barium salts.

The term "basic salt" means a metal salt in which the metal is present in a stoichiometrically greater amount than the organic acid group. The most commonly used method for producing basic salts is to prepare a solution of the acid mineral oil in a stoichiometric excess of a metal neutralizing agent such as a metal oxide, hydroxide, carbonate, bicarbonate. ,
Alternatively, the sulfide is heated at a temperature of about 50 ° C., and the obtained product is filtered. It is also known to use a "promoter" in the neutralization step to incorporate a large excess of metal. Examples of compounds used as accelerators include phenolic substances such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and condensation products of formaldehyde with phenolic substances; alcohols such as methanol, 2- There are propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine. A particularly effective method of making basic salts is to mix the acid with an excess of a basic alkaline earth metal neutralizer and at least one alcohol promoter and mix the mixture with 60-20
This is a method of carbonation at a high temperature such as 0 ° C.

Examples of suitable metal-containing detergents include lithium phenate, sodium phenate, potassium phenate, calcium phenate, magnesium phenate,
Sulfurized lithium phenate, sulfided sodium phenate, sulfided potassium phenate, sulfided calcium phenate, and sulfided magnesium phenate in which each aromatic group is one or more aliphatic With a solubility in hydrocarbons; any of the above phenols or basic salts of sulfurized phenols (often "overbased" phenates or "overbased" sulfurized Lithium sulfonate, sodium sulfonate, potassium sulfonate, calcium sulfonate, and magnesium sulfonate link each sulfonic acid moiety to an aromatic nucleus, which is typically one or more aromatic nuclei. Having an aliphatic group and imparting solubility to hydrocarbons A basic salt of any of the above sulfonic acids (often referred to as the "overbased"sulfonate); lithium salicylate, sodium salicylate, potassium salicylate, calcium salicylate, and magnesium salicylate, each salicylic acid moiety being bound to an aromatic nucleus. The aromatic nucleus usually having one or more aliphatic groups and imparted with solubility in hydrocarbons; any of the above basic salts of salicylic acid (often referred to as "overbased" salicylates) C10-200)
Lithium, sodium, potassium, calcium and magnesium salts of a hydrolyzed and phosphorylated olefin of 0 or a hydrolyzed and phosphorylated alcohol and / or aliphatic group-substituted phenol having 10 to 2000 carbon atoms; Lithium, sodium, potassium, calcium and magnesium salts of aliphatic carboxylic acids and aliphatic group-substituted cycloaliphatic carboxylic acids; basic salts of any of the above carboxylic acids (often with "overbased" carboxylic acid salts) And many other similar alkali and alkaline earth metal salts of oil-soluble organic acids, but are not limited thereto. Mixtures of two or more different alkali and / or alkaline earth metal salts can also be used. Similarly, a mixture of two or more different acids or salts of two or more different acids (eg, a mixture of one or more calcium phenates and one or more calcium sulfonates) Mixtures) can also be used. Rubidium, cesium and strontium can also be used, but are expensive and not practical for most applications. Similarly, barium salts are effective, but barium is considered to be toxic as a heavy metal, so the use of barium salts at the present stage is not suitable.

Metal deactivator. Component (c), the third essential component of the composition according to the invention, is a chelating metal quencher, ie one or more substances capable of reacting or complexing with dissolved metals and / or metal ions. It is.
Examples of chelating type metal deactivators include 8-hydroxyquinoline, ethylenediaminetetracarboxylic acid, β-diketones such as acetylacetone and β-ketoesters such as octyl acetoacetate. Suitable metal deactivators generally recognized as chelating agents are Schiff bases such as N, N'-salicylidene-1,2-ethanediamine, N, N'-disalicylidene-1,2-propanediamine, N , N'-Disalicylidene-1,3-propanediamine, N, N'-disalicylidene-1,2-cyclohexanediamine, N, N "-disalicylidene-
N'-methyldipropylenetriamine, 3'-ethoxy-5,2 ', 6'-trimethyl-N, N'-disalicylidene-biphenyl-2,4'-diyldiamine, 5'-
Ethoxy-3,5,2'-lolymethyl-N, N'-disalicylidenebiphenyl-2,4'-diyldiamine, and wherein one or more salicylidene groups is alkyl,
Similar compounds substituted with an inert group such as alkoxy, alkylthio, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkoxyalkyl, aralkyl, carboxy, esterified carboxy and the like. Accordingly, a wide range of known metal deactivators can be used as component (c) when practicing the present invention. The most preferred metal deactivators are N, N'-disalicylidene-1,2-alkanediamine and N, N'-disalicylidene-1,2-.
Cycloalkanediamines, especially N, N'-disalicylidene-1,2-propanediamine. Mixtures of metal deactivators can also be used.

Next, the components (d), (e) and (f) which are optionally used in the composition of the present invention and are preferably used.
Will be described. As mentioned above, these optional components do not substantially hinder the improvement in fuel stability obtained by combining component (c) with components (a) and (b). The following description will be made from such a viewpoint.

Ashless dispersant. -Ashless dispersants are said to be used primarily in lubricant compositions in many patents, but examples are also given for use in hydrocarbon fuels. Ashless dispersants leave little or no residue containing metals when burned. These dispersants generally contain only carbon, hydrogen, oxygen and, in most cases, nitrogen, but often also contain non-metallic elements such as phosphorus, sulfur or boron.

A preferred ashless dispersant is an alkenyl succinimide of an amine having at least one primary amino group capable of forming an imide group. Representative examples are U.S. Pat. Nos. 3,172,892, 3,202,678, 3,216,936, and 3,219,666;
Nos. 3,254,025, 3,272,746 and 4,234,435. The alkenyl succinimide can be prepared by conventional methods, for example, by heating an alkenyl succinic anhydride, acid, acid ester, acid chloride, or lower alkyl ester with an amine containing at least one primary amino group. it can. Alkenyl succinic anhydrides are easily obtained by heating the olefin and maleic anhydride to about 180-220 ° C. The olefin is preferably a lower monoolefin,
For example, polymers or copolymers of ethylene, propylene, isobutene, and the like. A further preferred source of alkenyl groups is polyisobutene having a molecular weight of 10,000 or more.
In a more preferred embodiment, the alkenyl group has a molecular weight of about 500-5,000, preferably about 900-2.0.
00, especially 900 to 1,200 polyisobutenes.

The amines that can be used in the ashless dispersant include any amine containing at least one primary amino group that can react to form an imide group. The following are a few typical examples. Methylamine, 2-ethylhexylamine, n-dodecylamine, stearylamine,
N, N-dimethylpropanediamine, N- (3-aminopropyl) morpholine, N-dodecylpropanediamine, N-aminopropylpiperazine, ethanolamine, N-ethanolethylenediamine, and the like.

Suitable amines are alkylene polyamines such as propylene diamine, dipropylene triamine, di- (1,2-butylene) triamine, and tetra-
(1,2-propylene) pentamine.

The most preferred amine has the formula

[0038]

Embedded image H ₂ N (CH ₂ CH ₂ NH) _n H is an ethylene polyamine. Here, n is an integer of 1 to about 10. These include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like, and mixtures thereof. In the case of a mixture, n is the average value of the mixture. These ethylene polyamines are flanked by primary amine groups and can thus form monoalkenylsuccinimides and bis-alkenylsuccinimides. Commercially available ethylene polyamine mixtures are generally branched and cyclic species, such as N-aminoethylpiperazine, N, N'-bis (aminoethyl) piperazine, N, N'-bis (piperazinyl) ethane and the like. Contains small amounts of important compounds. Preferred commercial mixtures have an approximate overall composition in the range corresponding to diethylenetriamine or tetraethylenepentamine, with the mixture generally corresponding to tetraethylenepentamine generally being most preferred.

Thus, particularly suitable ashless dispersants for use in the present invention are polyolefins, preferably having a number average molecular weight of 50.
0 to 5,000, more preferably 900 to 2,000
0, especially 900 to 1200 polyisobutene and an unsaturated polycarboxylic acid or anhydride such as maleic anhydride, maleic acid, fumaric acid, etc., a polyethylene polyamine, such as triethylenetetramine or tetraethylenepentane. Reaction products of amines with hydrocarbon-substituted carboxylic acids or anhydrides;
It is a mixture of species or more.

Another class of useful ashless dispersants includes alkenyl succinates and diesters of alcohols having 1 to 20 carbon atoms and having 1 to 6 hydroxyl groups. A representative example is U.S. Pat. No. 3,331,77.
No. 6, No. 3,381,022 and No. 3,52
No. 2,179. The alkenyl succinic moiety of these esters corresponds to the alkenyl succinic moiety of the same preferred and most preferred subgenus, such as the succinimides described above, including polyisobutenyl succinic acid, where the number average molecular weight of the polyisobutenyl groups 500-5,000
0, preferably 900-2,000, especially 900-1,
200.

The alcohol used for producing the ester includes methanol, ethanol, isobutanol, octadecanol, eicosanol, ethylene glycol, diethylene glycol, tetraethylene glycol, diethylene glycol monoethyl ether, propylene glycol, tripropylene glycol, and glycerin. Sorbitol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 1,1,1-
Trimethylolbutane, pentaerythritol, dipentaerythritol and the like.

Succinates are readily prepared by simply distilling off water or lower alkanols while simply heating the alkenyl succinic acid, anhydride or lower alkyl (eg, C ₁ -C ₄ ) ester with the alcohol. In the case of acid esters, use less alcohol. In fact, acid esters made from alkenyl succinic anhydrides do not generate water. In another method, it is only necessary to react the alkenyl succinic acid or anhydride with a suitable alkylene oxide, such as ethylene oxide, propylene oxide, and the like, and mixtures thereof.

In another embodiment, the ashless dispersant is an alkenyl succinate / amide mixture. These can be prepared by heating the above alkenyl succinic acids, anhydrides or lower alkyl esters with alcohols and amines either sequentially or as a mixture. The alcohols and amines described above are also useful in this embodiment. Alternatively, amino alcohols alone or with alcohols and / or amines can be used to make ester / amide mixtures. The amino alcohol has 1 to 20 carbon atoms and may contain 1 to 6 hydroxy groups and 1 to 4 amine nitrogen atoms.
Examples are ethanolamine, diethanolamine, N
-Ethanol-diethylenetriamine and trimethylolaminomethane.

Representative examples of suitable acid / amide mixtures are described in US Pat. Nos. 3,184,474 and 3,576,743.
No. 3,632,511, No. 3,804,76
No. 3, No. 3,836,471, No. 3,862,9
No. 81, No. 3,936,480, No. 3,948,
No. 800, No. 3,950,341, No. 3,95
No. 7,854, No. 3,957,855, No. 3,9
Nos. 91,098, 4,071,548 and 4,173,540.

Such ashless dispersants containing alkenyl succinic acid residues can be subsequently reacted with boron compounds, phosphorus derivatives and / or carboxylic acylating agents such as maleic anhydride, as is known.

Another useful class of ashless dispersants include hydrocarbyl-substituted phenols, formaldehyde or formaldehyde precursors (eg, paraformaldehyde) and at least one primary amine group having from 1 to 1
It includes a Mannich condensate of an amine having 0 amine groups and 1 to 20 carbon atoms. Mannich condensates useful in the present invention are disclosed in U.S. Pat. No. 3,442,80.
No. 8, No. 3,448,047 and No. 3,539, 6
No. 33, No. 3,591,598, No. 3,600,
No. 372, No. 3,634,515 and No. 3,69
No. 7,574, No. 3,703,536, No. 3,7
No. 04,308, No. 3,725,480, No. 3,
Nos. 726,882, 3,736,357, 3,751,365, 3,756,953, 3,793,202, 3,798,165,
Nos. 3,798,247 and 3,803,039
And No. 3,413,347.

Further preferred Mannich condensates are polyisobutenylphenols having a polyisobutyl group number average molecular weight of about 800 to 3,000 and formaldehyde or a formaldehyde precursor and a compound of the formula

[0048]

Embedded image embedded image Condensed with ethylene polyamine of H ₂ N (CH ₂ CH ₂ NH) _n H. In the above formula, n is an integer of 1 to 10, and especially in the case of a mixture, n has an average value of 3 to 5.

Typical ashless dispersants such as succinimides and Mannich condensates are described in US Pat.
No. 003, No. 3,087,936, No. 3,20
No. 0,107, No. 3,216,936, No. 3,2
No. 54,025, No. 3,256,185, No. 3,
No. 278,550, No. 3,280,234, No. 3,281,428, No. 3,282,955, No. 3,312,619, No. 3,366,569,
No. 3,367,943, No. 3,373,111
No. 3,403,102, No. 3,442,80
No. 8, No. 3,455, 831, No. 3,455, 8
No. 32, No. 3,493,520, No. 3,502,
677, 3,513,093 and 3,53
No. 3,945, No. 3,539,633, No. 3,5
No. 73,010, No. 3,579,450, No. 3,
Nos. 591,598, 3,600,372, 3,639,242, 3,649,229, 3,649,659, 3,658,846.
No. 3,697,574, No. 3,702,575
No. 3,703,536, No. 3,704,30
No. 8, No. 3,708,422 and No. 4,85
No. 7,214.

Another class of ashless dispersants which can be used are monomers which can be solubilized in oils, such as dodecyl methacrylate, vinyl decyl ether and monomers containing high molecular weight olefins and polar substituents, such as acrylic acid Consists of an interpolymer of aminoalkyl or acrylamide and a poly (oxyethylene) substituted acrylate.
These polymers are characterized as "polymer dispersants", examples of which are U.S. Patent Nos. 3,329,658; 3,449,250; 3,519,565; , 666,730, and 3,687,849,
And No. 3,702,300.

Another type of ashless dispersant that can be advantageously used in the fuel composition of the present invention is

[0052]

Embedded image

An imidazoline dispersant which can be represented by Here, R ₁ is a hydrocarbon group having 1 to 30 carbon atoms, for example, an alkyl or alkenyl group having 7 to 22 carbon atoms, and R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or 2 carbon atoms.
-50 aminoalkyl, acylaminoalkyl or hydroxyalkyl groups. Such long-chain alkyl (or long-chain alkenyl) imidazoline compounds can be made by reacting a corresponding long-chain fatty acid (formula R ₁ -COOH), for example, oleic acid with a suitable polyamine. The imidazoline thus formed is usually referred to as, for example, oleyl imidazoline, wherein R ₁ represents the oleyl residue of oleic acid. The imidazoline 2-
Examples of other suitable alkyl substituents for substituting at position include undecyl, heptadecyl, lauryl and erucyl. Suitable N- substituents imidazoline (i.e. group R ₂₎ in the hydrocarbyl group, a hydroxyalkyl group,
Includes aminoalkyl groups and acylaminoalkyl groups. Examples of these groups are methyl, butyl, decyl, cyclohexyl, phenyl, benzyl, tolyl, hydroxyethyl, aminoethyl, oleylaminoethyl, and stearylaminoethyl.

Other suitable ashless dispersants which can be incorporated into the fuel composition of the present invention include cyclic anhydrides and

[0055]

Embedded image Condensation products of R— (NH—R′—) _n NH ₂ with linear N-alkylpolyamines are included. Here, n is at least 1, usually an integer of 3 to 5, R is a saturated or unsaturated linear hydrocarbon group having 10 to 22 carbon atoms, R ′ is a divalent alkylene having 1 to 6 carbon atoms or An alkylidene group. Examples of such polyamines include N-oleyl-1,3-propanediamine, N-
Stearyl-1,3-propanediamine, N-oleyl-1,3-butanediamine, N-oleyl-2-methyl-1,3propanediamine, N-oleyl-1,3-pentanediamine, N-oleyl-2 -Ethyl-1,3-
Propanediamine, N-stearyl-1,3-butanediamine, N-stearyl-2-methyl-1,3-propanediamine, N-stearyl-1,3-pentanediamine, N-stearyl-2-ethyl-1, Includes 3-propanediamine, N-oleyl-1,3-dipropylenetriamine and N-stearyldipropylenetriamine. Such linear N-alkyl polyamines condense with, for example, succinic, maleic, phthalic, or hexahydrophthalic anhydride, which can substitute one or more of the groups having up to 5 carbon atoms.

Other ashless dispersants which can be incorporated into the compositions of the present invention include ethoxylated amines formed by the reaction of ammonia with ethylene oxide and C8-30 carbons.
Is a reaction product of the above with a carboxylic acid. The ethoxylated amine can be, for example, a mono-, di- or tri-ethanolamine or a polyethoxylated derivative thereof;
Can be linear or branched fatty acids, naphthenic acids, resin acids, or alkylaryl carboxylic acids.

Another type of ashless dispersant that can be used in practicing the present invention is an α-olefin / maleimide copolymer as described in US Pat. No. 3,909,215. Such a copolymer is an alternating copolymer of an N-substituted maleimide and an aliphatic α-olefin having 8 to 30 carbon atoms. This copolymer can have an average of 4 to 20 maleic imide groups in one molecule. The substituents on the maleimide imide nitrogen can be the same or different and have substantially 3 to 6 carbon atoms including carbon, hydrogen and nitrogen.
It is an organic group of 0. A commercially available material very suitable for use in the present invention is Chevron OFA425
B and this material is believed to consist of an α-olefin maleic imide copolymer of the type described in US Pat. No. 3,909,215. It works very well, whatever its composition.

All of the above types of ashless dispersants are described in the literature and many are commercially available. Of course, mixtures of various types of ashless dispersants can be used.

For environmental considerations, it is desirable to use an ashless dispersant containing almost no halogen atoms such as chlorine atoms. Therefore, in order to satisfy such conditions, it is desirable to select an ashless dispersant (as well as other components used in the composition of the present invention) so that the total halogen content of the entire fuel composition does not exceed 10 ppm. (However, it is not always necessary from the viewpoint of operating characteristics). In fact, the lower the halogen content, the better. Most desirably, the additive composition does not contain detectable amounts of halogen.

Typical ashless dispersants without halogen (chlorine) suitable for use in the compositions of the present invention include those of the various types mentioned above, as well as the recent publication WO 90033.
59 and EP 365 288.

Demulsifier. -Various demulsifiers can be used in the fuels and fuel compositions of the present invention. Demulsifiers improve the water tolerance of fuel compositions by preventing or minimizing excessive formation of emulsions.

Examples of demulsifiers used in practicing the present invention include poly (alkylphenol) formaldehyde condensates and polyalkyleneoxy-modified reaction products thereof. After these compounds obtained by reacting alkylphenols with formaldehyde, the reaction product C ₂ -C ₆ alkylene oxide is produced by, for example, reacting it with ethylene oxide or propylene oxide. This demulsifier has a general structural formula

[0063]

Embedded image

Has the following. Here, U is an alkylene having 2 to 6 carbon atoms, y is an integer of 4 to 10 on average, x is an integer of 4 to 10 on average, and R ₅ is alkyl of 4 to 15 carbon atoms.

A preferred demulsifier of the above formula is a poly (alkylphenol) polymer having a methylene bridge modified with a polyethyleneoxy group, wherein the polyethyleneoxy chain has 8 to 20, preferably 10 to 16, carbon atoms. At least 75% of the number of oxy chains fall within the above range. The methylene-bridged poly (alkylphenol) moiety of this polymer has 4 to 10, preferably 5 to 8, methylene-bridged alkylphenol repeating units.
And the alkyl group has 4 to 15, preferably 6 to 12 carbon atoms. In a preferred embodiment, the alkyl group is a mixture of C12 alkyl.

Examples of the alkylphenol include p-isobutylphenol, p-diisobutylphenol and p-isobutylphenol.
Hexylphenol, p-heptylphenol, p-octylphenol, p-tripropylenephenol, and p-dipropylenephenol are included.

Another type of demulsifier component is a sulfonated alkyl phenol neutralized with ammonia. These compounds have the general structural formula

[0068]

Embedded image

Has the following. Here, R ₁ has 4 to ₁ carbon atoms.
5, preferably 6 to 12 hydrocarbyl groups.

These compounds are made by sulfonating an alkylated phenol and then neutralizing the sulfonated product with ammonia.

Another class of demulsifiers is oxyalkylated glycols. These compounds are made by reacting a polyhydroxy alcohol, such as ethylene glycol, trimethylene glycol, etc., with ethylene or propylene oxide. Many of these compounds are available from BS F. Wyandotte Chemical
Company (BASF Wayandotte Che
medicalCompany) to Pluronic (PL)
URONIC). These compounds are hydroxyl-terminated polyethers,
It is produced by block copolymerization of ethylene oxide and propylene oxide. The ethylene oxide block acts as a hydrophilic part and the propylene oxide block acts as a hydrophobic part. A wide range of molecular weights with different ratios of ethylene oxide to propylene oxide are available.

One of the commercially available demulsifiers consists of a mixture of an alkylaryl sulfonate, a polyoxyalkylene glycol and an oxyalkylated alkylphenol resin. Such products are available from Petrolite Corporation.
e Corporation) to Torad (TOLA)
It is commercially available under the trade name D). One such product, called Trad 286K, is said to have the above components dissolved in a solvent, alkylbenzene. This product is effective when used in the composition of the present invention. The associated product trad 286 is also suitable. In this case, the product apparently contains the same active ingredient dissolved in a solvent consisting of heavy aromatic naphtha and isopropanol. Other known demulsifiers can also be used.

Aliphatic or cycloaliphatic amines. If one or more amines are to be included in the composition of the invention, a wide range of suitable amines can be used. This component contributes to the stability of the system in which it is used. Typically component (e) is a monoamine, but polyamines can be used if desired. Among the many suitable amines, the amines described in U.S. Pat. No. 3,909,215, such as t-alkyl primary amines, including Primene 81R, and EP 188,0.
No. 42, that is, an alkyl group having 8 to 1 carbon atoms.
4, or a mixture thereof. Also, mixed alkylcycloalkylamines such as N-cyclohexyl-N-butylamine, N-methylcyclohexyl-N-octylamine and the like, and di- and tricycloalkylamines such as N, N-dicyclohexylamine, N, N-di- (Ethylcyclohexyl) amine, N, N, N-tricycloalkylamine and the like are also suitable. Suitable amines include N-cycloalkyl-N, N-dialkylamine and N-cycloalkenyl-N, N-dialkylamine such as N-cyclohexyl-N, N-diethylamine, N-cyclohexyl-N, N-dibutylamine , N-cycloheptyl-N,
Includes N-dimethylamine, N-cyclooctyl-N, N-dilaurylamine, N-cyclohexenyl-N, N-dipropylamine and similar compounds. Particularly preferred is N-cyclohexyl-N, N-dimethylamine. The various amino mixtures described above are also suitable for use in the present invention.

Hydrocarbon fuel. -In principle the advantages of the present invention can be achieved in any liquid hydrocarbon fuel derived from petroleum, coal, shale and / or tar sands. In most cases, at least in the current environment, the substrate fuel is mainly, but not entirely, derived from petroleum.

Accordingly, the present invention relates to kerosene, jet fuel,
Aviation fuel, diesel fuel, household heating oil, light motorcycle fuel, heavy motorcycle fuel, light gas
Oils, heavy gas oils, fuel oils, residual fuel oils, ultra-heavy fuel oils, and generally in engines (eg, diesel fuel, gas turbine fuels, etc.) or in burner systems (eg, gas oil, hinterland) Heavy fuel oils, residual fuel oils, visbreaker fuel oils, domestic heating oils, etc.). Any liquid (or flowable) hydrocarbonaceous product suitable for combustion. Other suitable fuels are liquid fuels derived from biomass, such as vegetable oils (such as seed oil, jojoba oil, cottonseed oil, etc.); or liquid fuels derived from waste, such as municipal waste and / or Or fuel derived from industrial waste; or waste oil and / or liquid waste biomass and its derivatives; or mixtures of any of the above.

There are often standards for various hydrocarbon fuels or their quality, and in each case the type and properties of such fuels are known and reported in the literature.

Components (a), (b) and (c) and at least one component (d), (e) and (f), preferably two types of components (d), (e) and (f) And most preferably all three additive compositions of components (d), (e) and (f) are used in gas oils and similar fuel oils and fuel oils for agricultural and industrial engines. Useful for Standards for such fuel oils include, for example, the British Standards Institution (British Standards I).
BS2869 issued in 1988:
It is described in Part 2. Components (a), (b),
Typical specifications for automotive diesel fuels for which the compositions consisting of (c) and (d) are particularly useful are described in British Standard Stander Institution 1988, BS 2869: Part 1. Clearly, there are numerous such standards in each country.

[0078] Concentrations and proportions. -Generally, the components of the additive composition are used in the fuel in small amounts sufficient to improve the combustion characteristics and properties of the base hydrocarbon fuel in which it is used. Thus, this amount will vary depending on factors such as the type of substrate fuel and the intended service conditions of the finished fuel. However, typical examples of the concentration of the component (active component) in the substrate fuel are shown below.

General range Preferred range More preferred range Particularly preferred range Component (a) 1.5 to 2.5 to 3 to 100 3 to 25 10,000 1,500 Component (b) 4 to 5 to 6 to 300 6 to 100 10,000 6,000 Component (c) 0.25 to 0.25 to 1 to 500 1.5 to 100 6,000 1,000 Further, components (d), (e) and (f) are added to 1 In the case of fuels containing more than one species, the following active ingredient concentrations (ppm) are typical.

General range Preferred range Particularly preferred range Component (d) 0 to 15,000 8 to 5,000 10 to 200 Component (e) 0 to 4,000 0.5 to 200 2 to 50 Component (f) 0 -10,000 5-200 10-100 The individual components (a), (b) and (c), and (d), (e) and / or (f) (if used) are separately added to the fuel. It can be compounded or can be compounded in various small combinations as needed. Usually the particular order in such compounding steps is not very strict. Such components can also be formulated in the form of a diluent solution. However, it is preferred that the components used are incorporated in the form of the additive concentrate of the invention. This has the advantage that this simplifies the compounding operation, reduces compounding errors and provides compatibility and solubility properties of the overall concentrate.

The additive concentrate of the present invention comprises component (a),
Providing a fuel formulation comprising (b) and (c), and optionally optionally one or more of components (d), (e) and (f), to meet the concentrations listed in the table above. Included in an amount proportional to In most cases, the additive concentrate will contain one or more diluents, such as light mineral oil, to facilitate handling and formulation of the concentrate. 1
Up to 90% by weight of one or more diluents or solvents
Concentrates are often used.

Other components. -One or more other components can be included in the compositions of the present invention if it is deemed desirable or helpful for a given condition. For example, the additive compositions and fuel compositions of the present invention may also include antioxidants, such as one or more phenolic antioxidants, aromatic amine antioxidants, sulfurized phenolic antioxidants, and organic phosphorous. Fight may be included. Examples of these are 2,6-di-
t-butylphenol, a liquid mixture of t-butylated phenols, 2,6-di-t-butyl-4-methylphenol, 4,4′-methylenebis (2,6-di-t
-Butylphenol,), 2,2′-methylenebis (4
-Methyl-6-t-butylphenol), mixed methylene-crosslinked polyalkylphenol, 4,4′-thiobis (2
-Methyl-6-t-butylphenol), N, N'-di-sec-butyl-p-phenylenediamine, 4-isopropylaminodiphenylamine, phenyl-α-naphthylamine, and phenyl-β-naphthylamine.

Another type of additive optionally used in the present invention is a corrosion inhibitor. That is, dimer and trimer acids,
For example, acids formed from tall oil fatty acids, oleic acid, linoleic acid, and the like can be used. Products of this kind have recently been obtained from a variety of commercial products, such as Witco
Chemical Corporation (WitcoChemic)
al Corporation) Hamco Chemical
Division (Humco Chemical Di)
vision) to high strength (HYSTRENE)
Emery Chemicals
Chemicals) under the trade name EMPOL. Other useful types of corrosion inhibitors used in practicing the present invention are alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors, such as tetrapropenyl succinic acid, tetrapropenyl succinic anhydride,
Tetradecenyl succinic acid, tetradecenyl succinic anhydride, hexadecenyl succinic acid, hexadecenyl succinic anhydride and the like. The alkenyl group has 8 to 24 carbon atoms.
Also useful are the half esters of the alkenyl succinic acids of the above with alcohols such as polyglycols. The preferred material is of the formula

[0084]

Embedded image

Or aminosuccinic acid or a derivative thereof. Here, R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms, and each R ³ and R ⁴ are each independently a hydrogen atom and 1 to 3 carbon atoms. It is a hydrocarbyl group having 30 or an acyl group having 1 to 30 carbon atoms.

The radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R
⁷ is in the form of a hydrocarbyl group, for example an alkyl, cycloalkyl or aromatic-containing group. Preferably, R ¹ and R ⁵ are the same or different linear or branched hydrocarbon groups having 1 to 20 carbon atoms. Most preferably, R ¹ and R ⁵ are a saturated hydrocarbon group having 3 to 6 carbon atoms. When R ² , any of R ³ and R ⁴ , and R ⁶ and R ⁷ are in the form of a hydrocarbyl group, they are preferably the same or different, linear or branched saturated hydrocarbon groups. Preferably, R ¹ and R ⁵ are the same or different alkyl groups having 3 to 6 carbon atoms, R ² is a hydrogen atom, and either R ³ or R ⁴ is an alkyl group having 15 to 20 carbon atoms or 2 carbon atoms. A dialkyl ester of aminosuccinic acid, which is an acyl group derived from 10 to 10 saturated or unsaturated carboxylic acids, is used.

In the above formula, aminosuccinic acid wherein R ¹ and R ⁵ are isobutyl, R ² is a hydrogen atom, R ³ is octadecyl and / or octadecenyl, and R ⁴ is 3-carboxy-1-oxo-2-propenyl. Dialkyl esters are most preferred. In such esters R ⁶ and R ⁷ are most preferably hydrogen atoms.

The heavy fuels of the present invention can include low temperature flow improvers and pour point depressants, for example, olefin / vinyl acetate copolymers such as ethylene / vinyl acetate copolymers and polymethacrylates. . Antifoaming agents such as silicone; passivator type metal deactivators, for example Hitec ^{(HITEC) (R)} 314 [ethyl Petoreriumu-Aditivuzu Limited (Et
hyl Petrolimu Additives,
Ltd. ), Ethyl Petrellium Additives
Incorporated (Ethyl Petroliu)
mu Additives, Inc. )]; And dyes can also be used in the compositions of the present invention. Diesel fuels include cetane improvers such as peroxy compounds and organic nitrates (eg, amyl nitrate, hexyl nitrate, heptyl nitrate, octyl nitrate, and about 4 to 4 carbon atoms).
About 10 alkyl nitrates, and mixtures thereof). Some examples of such alkyl nitrates include cyclohexyl nitrate, methoxypropyl nitrate, a mixture of nitrates formed by nitrating fusel oil, 2-ethylhexyl nitrate, n-octyl nitrate, n-decyl nitrate, and the like. Typical peroxy compounds include acetyl peroxide, benzoyl peroxide, t-
Butyl peroxyacetate and cumene hydroperoxide are included.

All of the above optional ingredients are well known in the art and are used in conventional proportions. Care must be taken in selecting such optional ingredients to ensure that the selected materials or combinations thereof are compatible with the overall composition used with them.

The following examples illustrate the invention. These examples do not limit the invention. All percentages are by weight unless otherwise specified.

[0091]

EXAMPLES Example 1 An additive composition is prepared by mixing the following components in the amounts shown below.

4.0%: M as a formulation containing 62% methylcyclopentadienyl manganese tricarbonyl (MMT) and 38% diluent (primarily aromatic solvents)
MT.

6.0%: Typical TBN is 1 of 295
00 Solvent overbased calcium sulfonate blended with 44% neutral oil.

1.6%: N, N'-disalicylidene-
1,2-propanediamine, as an 80% xylene solution.

88.4%: Heavy aromatic naphtha.

This composition was added at a ratio of 250 to 37,00.
At 0 ppm, typically 500 ppm, it was very suitable for use in heating gas oils.

Example 2 The following components were blended in the following amounts to make an additive composition.

4.0%: M as a formulation containing 62% methylcyclopentadienyl manganese tricarbonyl (MMT) and 38% diluent (primarily aromatic solvents)
MT.

6.0%: Typical TBN is 1 of 295
00 Solvent overbased calcium sulfonate blended with 44% neutral oil.

1.2%: N, N'-disalicylidene-
1,2-propanediamine, as an 80% xylene solution.

88.8%: Heavy aromatic naphtha.

This composition may be added, for example, at an addition ratio of 250 to 3
At 7,000 ppm, typically 500 ppm, it was very suitable for use in heating gas oils.

Example 3 An additive composition was prepared by blending the following components in the amounts shown below.

4.0%: M as a formulation containing 62% methylcyclopentadienyl manganese tricarbonyl (MMT) and 38% diluent (primarily aromatic solvents).
MT 6.0%: Overbased calcium sulfonate blended with 44% of 100 solvent neutral oils of 295 typical TBN.

1.6%: N, N'-disalicylidene-
1,2-propanediamine, as an 80% xylene solution.

9.2: Chevron OFA425B, N
C ₁₃ / aminated with alkyl propylene diamine /
Ashless dispersant, believed to consist of C ₁₆ α-olefin-maleic anhydride copolymer, used as a 50% oil solution.

9.2%: N-cyclohexyl-N, N
-Dimethylamine.

70.0%: Heavy aromatic naphtha.

This composition has an added concentration of 250 to 37,00
At 0 ppm, typically 500 ppm, it was very suitable for use in heating gas oils.

Example 4 An additive composition was prepared by blending the following components in the amounts shown below.

4.0%: M as a formulation containing 62% methylcyclopentadienyl manganese tricarbonyl (MMT) and 38% diluent (primarily aromatic solvents)
MT 6.0%: Overbased calcium sulfonate blended with 44% of 100 solvent neutral oils of 295 typical TBN.

1.6%: N, N'-disalicylidene-
1,2-propanediamine, as an 80% xylene solution.

6.9%: Chevron OFA425B,
C ₁₃ which is aminated with N- alkyl propylenediamine
/ C ₁₆ α-olefin-maleic anhydride copolymer, ashless dispersant believed to consist of a 50% oil solution.

5.2%: N-cyclohexyl-N, N
-Dimethylamine.

76.3%: Heavy aromatic naphtha.

This composition has an added concentration of 250 to 37,00
At 0 ppm, typically 500 ppm, it was very suitable for use in heating gas oils.

Example 5 The method of Example 3 was repeated using the following proportions of the additive components.

4.0%: MMT formulation of Example 3.

6.0%: Overbased calcium sulfonate of the formulation of Example 3.

1.2%: N, N 'of the formulation of Example 3
-Disalicylidene-1,2-propanediamine.

6.9%: Chevron OFA425B of the solution of Example 3.

6.9%: N-cyclohexyl-N, N
-Dimethylamine.

75.0: Heavy aromatic naphtha diluent.

Example 6 The procedure of Example 3 was repeated using the following proportions of the additive components.

4.0%: MMT formulation of Example 3.

6.0%: The overbased calcium sulfonate of the formulation of Example 3.

1.2%: N, N 'of the formulation of Example 3
-Disalicylidene-1,2-propanediamine.

6.9%: Chevron OFA425B of the solution of Example 3.

5.2%: N-cyclohexyl-N, N
-Dimethylamine.

76.7%: Heavy aromatic naphtha diluent.

Example 7 An additive composition of the present invention was made using the following ingredients.

4.0%: MMT as a 62% diluent solution as described in Example 1.

6.0%: Overbased calcium sulfonate as a 100 solvent neutral oil formulation as described in Example 1.

1.6%: N, N'-disalicylidene-1,2-propanediamine as a 80% solution of heavy aromatic naphtha.

5.5%: Polyisobutenylsuccinimide of tetraethylenepentamine as a 25% oil solution (prepared from polybutene having a number average molecular weight of about 950).

1.4%: Axo Armogard (Ak)
zo Armogard) D5021 demulsifier, demulsifier substrate and surfactant in a aromatic solvent.

5.2%: N-cyclohexyl-N, N
-Dimethylamine.

76.3%: Heavy aromatic naphtha.

This composition is, for example, 250 to 37,000.
Useful concentrations in the heating gas oil are at a loading level of ppm, typically 500 pp.

Example 8 An additive composition of the present invention was made using the following ingredients.

4.5%: MMT formulation as described in Example 1.

33.0%: The overbased calcium sulfonate described in Example 1.

1.8%: N, N'-disalicylidene-1,2-butanediamine as a 75% solution of heavy aromatic naphtha.

22.7%: Polyisobutenylsuccinimide of tetraethylenepentamine as a 23% oil solution (prepared from polybutene having a number average molecular weight of about 950).

6.8%: demulsifier (trad 286)
K).

31.2%: heavy aromatic naphtha.

The additive composition is, for example, 200 to 26,
A loading of 500 ppm, typically 400 pp, is particularly suitable for improving the combustibility of diesel fuel for motor vehicles.

Example 9 An additive composition of the present invention was made using the following ingredients.

2.8%: MMT.

14.5%: Overbased calcium sulfonate formulation.

1.5%: N, N'-disalicylidene-1,2-cyclohexanediamine as a 60% solution of aromatic naphtha.

17.1% Polyisobutenyl succinimide of an equivalent mixture of diethylenetriamine, triethylenetetramine and tetraethylenepentamine (prepared from polybutene having a number average molecular weight of about 1000).

64.1%: inert diluent (mainly 1
00 solvent neutral mineral oil).

Example 10 The following additive concentrate was prepared.

5.0%: cyclopentadienyl manganese tricarbonyl in a formulation containing 40% of an aromatic hydrocarbon solvent.

30.5%: overbased magnesium sulfonate.

1.8%: N, N'-disalicylidene-
1,2-propanediamine. 24.5%: Mannich condensation product of p- (polyisobutenyl) phenol (prepared from polybutene having a number average molecular weight of about 750), formaldehyde and triethylenetetramine.

5.6%: Axo Armoguard D50
21 demulsifier.

32.6%: Heavy aromatic naphtha diluent.

Example 11 The sulfonates of Examples 9 and 10 were replaced with overbased potassium sulfonate in the first case and overbased calcium phenate in the second case. Examples 9 and 10 were repeated.

Example 12 Instead of overbased calcium sulfonate, in the first case an equivalent amount of overbased magnesium sulfonate and in the second case an equivalent amount of overbased sodium phenate Examples 4, 7, and 8 were repeated using, in the third case, an equivalent amount of overbased potassium sulfonate.

Example 13 Instead of methylcyclopentadienylmanganesetricarbonyl, in the first case an equivalent amount of cyclopentadienylmanganesetricarbonyl and in the second case an equivalent amount of cyclopentadienylmanganesedicarbonyl. Carboxytriphenylphosphine, in the third case an equivalent amount of indenyl manganese tricarbonyl, in a fourth case an equivalent amount of dimanganese decacarbonyl, in a fifth case an equivalent amount of methylcyclopentane. Dienyl manganese tricarbonyl 90%
And cyclopentadienyl manganese tricarbonyl 1
Examples 1 to 9 and 12 were repeated using a mixture consisting of 0%.

Example 14 The compositions of Examples 4 and 7 were applied at concentrations of 300, 500 and 1,000 ppm at a specific gravity (DIN
51775) 0.845 g / ml, kinematic viscosity at 20 ° C. (DIN 51567) 5.3 mm 2 / sec, pour point (DINISO 3016) −9 ° C., sulfur content (D
IN 51400) 0.19%, distillation behavior (DIN 5
1751) was mixed with 27% by volume at 250 ° C. and 92% by volume at 350 ° C. of the heating gas oil.

Example 15 Example 14 was repeated except that the components of each of the compositions of Examples 4 and 7 were compounded in equal amounts, individually or in small combinations, in gas oil.

Example 16 A diesel fuel meeting the requirements of DIN 51601-DK (February 1986) was formulated with the composition of Example 8 at concentrations of 300, 500, 1,000 and 1,500 ppm.

Example 17 Example 16 was repeated, except that the components of the composition of Example 8 were compounded in equal amounts, individually or in small combinations, in gas oil.

Example 18 Examples 16 and 17 were repeated, but using commercially available diesel fuel suitable for diesel fuel for railways, diesel fuel for truckers, diesel fuel for off-roads and fuel for backwaters.

Example 19 Examples 14 and 15 were repeated, but with commercially available heavy fuel oils and residual oils (eg, industrial and refinery fuel oils), such as heavy fuel oils for backcountry, and hydrocarbon fuels. Marine fuel was used. The additive concentrations of the additives in these fuels were 500,800 and 1,500 ppm.

The enhanced stability properties of the compositions of the present invention
Illustrated by the results of a series of oxidation stability tests performed according to STM test method D2274. In these tests, two different commercially available substrate fuels were used. One of them is a diesel fuel with a cetane number of 52.7 (Fuel A).
And the other was a relatively unstable diesel fuel with a cetane number of 52.5 (Fuel B). Each of these fuels was tested twice without any additives. Furthermore, the same AS for fuels A and B with and without chelating metal deactivator in the additive mixture based on the combination of MMT and calcium sulfonate
A TM test was performed. The compositions tested and the results obtained are summarized in the table below. In this table, the additive components are as follows.

"MMT" is the same 62% formulation as in Example 1.

"Ca Det."
Calcium sulfonate as a 4% formulation.

The “metal deactivator” was the same as in Example 1,
N'-disalicylidene-1,2-propanediamine 80
% Metal deactivator in the form of a solution.

"Disp." Is a chevron OFA425B ashless dispersant in the form of a 50% solution as described in Example 3.

"Amine" is N-cyclohexyl-N, N
-Form of dimethylamine stabilizer.

"Dil." Is a diluent in the form of heavy aromatic naphtha.

All tests using the additive mixture were performed at a total additive concentration of 500 ppm in the fuel. In the following table, “−−” means “none”, the numerical value for the additive component is represented by% by weight of the above component, and
Expressed in mg of sediment per ml. Test number 1
6 is performed on fuel A, and test numbers 7 to 13 are performed on fuel B
Made about.

[0177]

Table 1 Thermal Oxidation Stability Test Test Ca Metal Deposit No. MMT Det. Deactivator Disp. Amine Dil. Mg / mL 1------0.28 2--- ----0.34 3 4 6--20 70 1.83 4 4 6 1.2 6.9 5.2 76.7 2.88 5 4 6 1.6 9.2 9.2 70 0.09 6 4 6 1.6 6.9 5.2 76.3 0.23 7---- ---1.31 8------1.86 9 4 6-7.5 6.9 75.6 2.06 10 4 6 1.2 6.9 6.9 75 0.34 11 4 6 1.2 6.9 5.2 76.7 0.09 12 4 6 1.6 9.2 9.4 70 0.03 13 4 6 1.6 9.2 9.2 70 0.06 As can be seen from the above table, in the relatively stable fuel A, the manganese compound and the detergent containing calcium were compared with the fuel without additives (Test Nos. 1 and 2). When added in combination (test number 3), the stability of the fuel is significantly reduced. It is also noted that despite the presence of the known fuel stabilizer N-cyclohexyl-N, N-dimethylamine at relatively high concentrations in the fuel, fuel destabilization occurs. From test number 4 it can be seen that the additive mixture (500 p.
It is found that it is not sufficient to mix 1.2% of the metal deactivator in pm). On the other hand, Test Nos. 5 and 6 show that the presence of 1.6% of the metal deactivator in the additive mixture (500 ppm) significantly improves the stability of the fuel composition. That is, for Fuel A, in this system tested at 500 ppm, there is a concentration threshold between 1.2% and 1.6% of the additive.

In the less stable fuel (Fuel B), as can be seen from Test No. 9, the combination of the manganese compound and the calcium-containing detergent was again the fuel containing no additive (Test Nos. 7 and 8). In addition, the stability of the fuel is further reduced. In addition, from Test Nos. 10 to 13, Fuel B had a concentration of 1 at 500 ppm of the additive mixture.
It can be seen that the presence of 2% and 1.6% metal deactivator both significantly improves the stability of the fuel. That is, in Fuel B, the threshold value of the concentration of the metal deactivator in the additive composition of this system at 500 ppm corresponds to a value lower than 1,2%.

The effects and advantages of the compositions of the present invention are illustrated by several standard tests. For example, an 81 kW gas-oil combustion type high-temperature water boiler is set to a flue gas temperature of 207.
The system was operated at a temperature of 120 ° C., a flue gas carbon dioxide content of 12.1%, and a flue gas carbon monoxide content of 100 ppm or more. The gas oil for heating the substrate is as described in Example 14. The operation of a boiler with gas oil without additives has a Bacharach soot index of 4.60.
However, for the same gas oil containing 500 ppm of the additive of Example 4, the Bacharach soot index is 2.70,
Decrease by 1%. When measuring the acidity of the soot (as an average of four measurements) the gas oil of the substrate without additives is pH
It can be seen that an average of 4.05 soot is produced. In contrast, the pH of soot obtained from the fuel of the present invention averaged 7.06.

A standard CFR engine test (ASTM D61) using two different diesel fuels having cetane numbers of 52.7 (Fuel A) and 52.5 (Fuel B) respectively.
3) was performed. 500 ppm of the composition of Example 1 as fuel A
Does not cause any change in the cetane number. Fuel B
In the above, when 500 ppm of the composition of Example 1 is added, the cetane number slightly decreases (from 52.5 to 51.6).

A standard corrosion test (ASTM665A) was performed using the same pair of diesel fuels. Both fuels were tested with and without 500 ppm of the composition of Example 1. The results of this test are as follows.

Evaluation by ASTM665A Fuel A, without additive D, D Fuel A, with additive A, A Fuel B, without additive B, B + Fuel B, with additive A, A The present invention described in Example 7 Standard corrosion test (ASTM6) for diesel fuel with or without additive composition
65A) and (ASTM665B). The results are as follows.

ASTM665A Evaluation value by evaluation value according to ASTM665B Fuel A, without additive C, CE, E Fuel A, with additive A, AE, E Fuel B, without additive B +, B + D, D Fuel B, With Additives A, AD, D A thermal stability test was performed using the same composition. In this test, the sample was heated to 150 ° C. for 90 minutes, filtered through a filter, and the reflectance of the deposit on the filter was measured. Evaluation values range from 0 (fine) to 20 (black). An evaluation value of 7 or less is considered to be good. A thermal oxidation stability test according to ASTM D2274 was also performed on the same fuel. The results in this test are expressed in mg of deposit per 100 ml of fuel. The results are as follows.

Thermal Stability Thermal Oxidation Stability (Filter Test) (ASTM D2274) Fuel A, without additives 6 0.15 Fuel A, with additives 3 0.17 Fuel B, without additives 19 4.45 Fuel B with additives 6 0.14 Demulsifier test (ASTM D1) for the same four fuels
094) and the following results were obtained.

Interface evaluation value Separation evaluation value Aqueous phase volume (ml) Fuel A, without additive 4 3 17 Fuel A, with additive 3 3 18 Fuel B, without additive 4 3 7 Fuel B, with additive 3 Another test was conducted using 319 commercial household heating gas oil to determine the behavior of two different burners. One was a recent burner and the other was a burner manufactured 15 years ago. In each case the burners were adjusted to the manufacturer's specifications. Examples 4 and 7
A baseline experiment was performed on an additive-free substrate fuel and with no additive. The smoke index and carbon monoxide content of the flue gas were measured. The determination of the smoke index includes a scale ranging from 0 to 10 and applies this rating to the filter that passes the flue gas during operation. An evaluation value of 10 means black, so it is better that this number is lower. The evaluation value of carbon monoxide is represented by the value of ppm in flue gas. The following table summarizes the data.

Old burner New burner Smoke index CO Smoke index CO Substrate fuel without additives 5.5 80 1 90 Substrate fuel with additives ^a 5.5 43 --- Substrate fuel with additives ^b 4.0 40 018 Substrate fuel ^{c with} additives 4.5 4.50 20 Substrate fuel ^d with additives 3.5 4500 25-------- ^a Additive composition, 500 ppm.

^B Additive composition of Example 1, 1000 pp
m.

^C Additive composition of Example 2, 500 pp
m.

^D Additive composition of Example 2, 1000 pp
m.

As a result of these and other tests, the fuels of the present invention generally have enhanced combustion characteristics (ie, less smoke and less soot acidity) and better thermal stability than the corresponding untreated fuel. You can see that they have sex. The use of the fuel of the present invention also reduces the amount of sludge deposits produced on critical engine or burner parts or surfaces. Further, such fuels tend to emit less toxic emissions than the corresponding untreated substrate fuels. Further, according to the present invention, there is provided a fuel composition in which the demulsifying properties are enhanced, the corrosion properties are reduced, and the influence on other desired fuel properties is minimized. The results of the above tests also show that the additive composition of the present invention reduces the fuel consumption of diesel engines. The data also shows that not all fuels need respond to the same processing range as the additive system of the present invention. However, generally speaking, the fuel of the present invention has significantly improved properties.

As can be seen from the above description, the present invention includes, in its embodiments, (a) a manganese carbonyl compound soluble in at least one fuel, and (b) a soluble manganese compound in at least one fuel. the alkali or alkaline earth metal-containing detergent is blended in a combustion improving amount of small amounts, it blended with improved stability of (c) at least one fuel soluble chelated metal deactivators small amount to include methods in which at least main component to improve the combustion characteristics and stability of hydrocarbonaceous liquid fuel. Such compositions preferably contain one or more of the above components (d), (e) and (f).

The main features and aspects of the present invention are as follows. 1. (A) contains at least soluble manganese carbonyl compound into one of the fuel, and (b) at least one small quantity of the combustion improving amount of soluble alkali or alkaline earth metal-containing detergent in the fuel, and , (c) at least one fuel-soluble chelate metal deactivators, (d) optionally at least one fuel soluble demulsifiers include, and (e) at least one contained at any time containing soluble aliphatic or cycloaliphatic amine with improved stability of small amounts in the fuel
Contains a major amount of liquid hydrocarbon fuel characterized by the following:
It is that the fuel composition.

[0193] 2. Component (a) comprises at least one cyclopentadienyl manganese tricarbonyl compound,
A composition according to claim 1, which preferably consists essentially of methylcyclopentadienyl manganese tricarbonyl.

[0194] 3. Component (b) comprises at least one detergent containing an overbased alkali or alkaline earth metal,
Preferably the first or second salt is at least one sulfonate, especially an overbased calcium sulfonate.
The composition according to Item.

4. Component (c) has the formula

[0196]

Embedded image

Wherein the aromatic ring can have up to four inert substituents in place of a hydrogen atom, wherein at least one fuel-soluble Schiff having one or more chelating centers Bases, preferably salicylidenediamines, especially N, N'-disalicylidene-1,2-alkanediamine or N, N'-disalicylidene-1,2-cycloalkanediamine, for example N, N'-disalicylidene-1,2 4. The composition according to the above 1, 2, or 3 substantially consisting of propanediamine.

5. A composition according to any of the preceding claims, comprising as component (e) at least one fuel-soluble N-cycloalkyl-N, N-dialkylamine, for example N-cyclohexyl-N, N-dimethylamine.

6. The proportions of components (a), (b) and (c) are 1.5 to 10,000: 4 to 10,000 in parts by weight.
0: 5 to 15,000, preferably 2.5 to 1,50
0: 5-6,000: 0.5-1,000, more preferably 3-100: 6-300: 1-500, especially 3-
25: 6 to 100: the first to fifth, which are 1.5 to 100.
The composition according to Item.

[0200] 7. A composition according to any of the preceding claims wherein the halogen content is from 0 to 10 ppm, preferably free of detectable amounts of halogen.

8. Component (a) according to the above items 1 to 6,
A fuel additive composition comprising (b) and (c), and optionally (d), and optionally (e).

9. Component (a) according to the above items 1 to 6,
(B) and (c), and optionally (d), and to improve the combustion characteristics and stability of the fuel comprising any time (e) at least predominantly hydrocarbonaceous liquid fuel blended with a combustion improving amount of small amounts Method.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10L 1/22 C10L 1/22 C 1/24 1/24 1/30 1/30 Z 9/10 9/10 10/02 10 / 02 10/04 10/04 (56) References JP-A-4-234489 (JP, A) JP-A-4-226598 (JP, A) JP-A-4-211693 (JP, A) JP-A-4 −114090 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C10L 1/18 C10L 1/22 C10L 1/24 C10L 1/30 C10L 9/10 C10L 10/02

Claims (3)

(57) [Claims] 1. A (a) soluble manganese carbonyl compound to at least one fuel, and (b) at least one small quantity of the combustion improving amount of soluble alkali or alkaline earth metal-containing detergents in the fuel And (c) a chelating metal deactivator soluble in at least one fuel; (d) a demulsifier soluble in at least one fuel optionally included; and (e) optionally included. containing hydrocarbon fuels liquid major amount, characterized in that it contains a small amount of stability improving amount of soluble aliphatic or cycloaliphatic amine with at least one fuel
It is that the fuel composition. 2. A fuel additive comprising components (a), (b) and (c) according to claim 1, and optionally (d) and optionally (e). Composition. 3. Claims components of claim 1 wherein (a), the blending with (b) and (c), and optionally (d) and a small amount of combustion improving amount from time to time (e) method for improving at least primarily burning characteristics of <br/> fuel consisting of hydrocarbon liquid fuels and stability characterized.