JPH04272995A - Fuel composition having mild effect on environment, and additive for it - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

This invention relates to middle distillate fuel compositions with improved combustion properties, such as diesel fuels, home heating oils, kerosene, jet fuels, aviation fuels, gas turbine engine fuels, light cycle oils, and the like.

It has long been known that small amounts of various additives are used to improve the properties and/or performance characteristics of middle distillate fuels. For example, small amounts of dispersants are used to improve engine or burner cleanliness, thereby reducing the amount of harmful emissions produced during fuel combustion over time. Similarly, antioxidants, corrosion inhibitors, defoamers, demulsifiers and similar types of additives have been used in the fuels.

The present invention provides middle distillate fuel compositions that, upon combustion, produce an almost immediate and substantial reduction in harmful emissions, such as unburned hydrocarbons, particulates, and/or carbon monoxide. This is accompanied by the surprising discovery that this is possible. Furthermore, it has been found that the above fuel compositions can provide substantial improvements in fuel economy during, for example, diesel engine operation.

[0004] In the practice of this invention, higher concentrations of fuel soluble ashless dispersants are used than are normally used in conventional fuels. In addition, the fuel composition preferably comprises:
one or more sterically hindered phenolic compounds, most preferably 2,6-dihydrocarbyl-α-dihydrocarbylamino-p-cresol, such as 2,6-di-tert-butyl-α-dimethylamino- p-Cresol (which is used as ETHYLER Antioxidant 703)
Corporation).

[0005] Therefore, in one embodiment of the present invention,
The present invention provides a method for carbonizing a liquid middle distillate containing at least one fuel soluble ashless dispersant in an amount of at least 50 ppm sufficient to rapidly reduce emissions released during combustion of the fuel composition. A fuel composition comprising a hydrogen-based fuel is provided. Preferably, the fuel contains 75 to 1,000 ppm,
Most preferably it contains 100-250 ppm of ashless dispersant.

Another embodiment of the invention comprises blending into said fuel an ashless dispersant in an amount of at least 50 ppm sufficient to achieve said reduction in emissions. A method of achieving an almost immediate reduction in the amount of harmful emissions produced during the combustion of a range of hydrocarbon-based fuels.

Other embodiments of the invention will become apparent from the description and the appended claims.

Ashless dispersant. Although ashless dispersants have been described in numerous patent specifications primarily as additives for use in lubricating compositions, their use in hydrocarbon fuels has also been described. Ashless dispersants leave little or no metal-containing residue upon combustion. These generally contain only carbon, hydrogen, oxygen and often nitrogen, but sometimes also contain non-metallic elements such as phosphorus, sulfur or boron.

Suitable ashless dispersants are amine alkenyl succinimides having at least one primary amino group capable of giving rise to imide groups. Typical examples are U.S. Patent Nos. 3,172,892; 3,202,678; 3,
216,936; 3,219,666; 3,254
,025; 3,272,746; and 4,234,
435. The alkenyl succinimides can be prepared by conventional methods such as heating alkenyl succinic anhydrides, acids, acid-esters, acid halides, or lower alkyl esters with amines having at least one primary amino group. It may be manufactured by This alkenylsuccinic anhydride can be easily produced by heating a mixture of olefin and maleic anhydride to about 180-220°C. The olefin is preferably a polymer or copolymer of lower monoolefins, such as ethylene, propylene, isobutene, and the like. A more preferred source of alkenyl groups is 10,0
It is obtained from polyisobutene having a molecular weight of 0.00 or less or more. In an even more preferred embodiment, the alkenyl group has about 500 to 5,000,
Preferably about 700 to 2,000, especially about 800 to 1,20
It is a polyisobutenyl group with a molecular weight of 0. The isobutene used to produce this polyisobutene is usually (
(but not necessarily), a mixture of isobutene and other C4 isomers, such as 1-butene. Therefore, strictly speaking,
An acylating agent made from maleic anhydride and a "polyisobutene" made from the above mixture of isobutene and other C4 isomers, such as 1-butene, can be referred to as "polybutenylsuccinic anhydride"; And succinimide produced using it can be called "polybutenyl succinimide." However, it is common to refer to the above materials as "polyisobutenylsuccinic anhydride" and "polyisobutenylsuccinimide", respectively. "Polyisobutenyl" and "polybutenyl" used here are high-purity isobutene or isobutene and 1
- used interchangeably to represent an alkenyl moiety, whether or not prepared from a lower purity mixture with other C4 isomers such as butene.

The amines that can be used to prepare the ashless dispersant may be any amine having at least one primary amino group that can react to form an imide group. Some representative examples are methylamine, 2-ethylhexylamine, n-dodecylamine, stearylamine, N,N-dimethylpropanediamine, N-(3-aminopropyl)morpholine, N-dodecylpropanediamine, -aminopropyl-piperazine, 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 amines are of the formula

[0013]

##STR1## These are ethylene polyamines that can be represented by H2N(CH2CH2NH)nH, where n is an integer from 1 to about 10. These include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc., and mixtures thereof, where n is the average value of the mixture. These ethylene polyamines have a primary amine group at each end, and therefore,
Mono-alkenyl succinimides and bis-alkenyl succinimides can be produced. Commercially available ethylene polyamine mixtures typically contain small amounts of branched and cyclic species, such as N-aminoethylpiperazine, N,N'-bis(aminoethyl)piperazine, N,N'-bis-(piperazinyl)ethane, etc. Contains the following compounds. Suitable commercially available mixtures have approximate overall compositions in the range corresponding to diethylenetriamine to pentaethylenehexamine, with mixtures whose overall composition generally corresponds to tetraethylenepentamine being the most suitable.

[0014] Particularly suitable ashless dispersants for use in the present invention therefore include polyethylene polyamines such as triethylenetetramine or tetraethylenepentamine;
a hydrocarbon-substituted carboxylic acid or anhydride [which is a polyolefin, preferably having a number average molecular weight of 500 to 5,00
0, preferably 700 to 2,000, especially 800 to 1,2
00 polyisobutene with an unsaturated polycarboxylic acid or anhydride, such as maleic anhydride, maleic acid, fumaric acid, etc., and a mixture of two or more of the above substances. It is a product.

The term "succinimide" as used herein is meant to include the complete reaction product resulting from the reaction between components (i) and (ii) and includes a primary amino group. It is intended to include compounds in which the product may have amide, amidine and/or salt bonds in addition to imide bonds of the type that result from the reaction of the anhydride moiety with the anhydride moiety.

Another class of useful ashless dispersants include:
Included are alkenylsuccinic esters and diesters of alcohols having 1 to 20 carbon atoms and 1 to 6 hydroxyl groups. Representative examples are described in US Patent Nos. 3,331,776; 3,381,022; and 3,522,179. The alkenylsuccinic acid moiety of these esters may be of the same preferred and most preferred subgenus, e.g.
5,000, preferably 700-2,000, especially 800
It corresponds to the alkenylsuccinic acid moiety of the above succinimide containing polyisobutenylsuccinic acid having a number average molecular weight of ~1,200.

Alcohols useful in the preparation of these esters include methanol, ethanol, isobutanol,
Octadecanol, eicosanol, ethylene glycol, diethylene glycol, tetraethylene glycol, diethylene glycol monoethyl ether, propylene glycol, tripropylene glycol, glycerol, sorbitol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane , 1, 1, 1-
Includes trimethylolbutane, pentaerythritol, dipentaerythritol, etc.

These succinic esters are alkenylsuccinic acids, anhydrides or lower alkyls (eg C1-
C4) It is easily prepared by simply heating a mixture of the ester and the alcohol while distilling the water or lower alkanol. In the case of acid-esters, smaller amounts of alcohol are used. In fact, acid-esters made from alkenylsuccinic anhydrides do not evolve water. In another method, the alkenylsuccinic acid or anhydride is treated with a suitable alkylene oxide, such as ethylene oxide, propylene oxide, etc.
as well as mixtures thereof.

In another embodiment, the ashless dispersant is an alkenyl succinic ester-amide mixture. These may be prepared by heating the alkenyl succinic acids, anhydrides or lower alkyl esters mentioned above together with alcohols and amines, either sequentially or in a mixture. The alcohols and amides mentioned above are also useful in this embodiment. Alternatively, amino alcohols may be used alone or with said alcohol and/or
Alternatively, it can be used with amines to form the ester-amide mixture. The amino alcohol can have 1 to 20 carbon atoms, 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 ester-amide mixtures include US Pat. No. 3,184,474; 3,576
,743; 3,632,511; 3,804,76
3; 3,836,471; 3,862,981;
3,936,480; 3,948,800; 3,9
50,341; 3,957,854; 3,957,
855; 3,991,098; 4,071,548;
and 4,173,540.

The above-mentioned ashless dispersants containing alkenylsuccinic acid residues can be post-reacted with boron compounds, phosphorus derivatives and/or carboxylic acylating agents such as maleic anhydride, as is well known. It's okay.

Another useful class of ashless dispersants includes:
hydrocarbyl-substituted phenols, formaldehyde or formaldehyde precursors (e.g., paraformaldehyde) and having at least one primary amine group and 1 to 10 amine groups and 1 to
Included are Mannich condensates of amines having 20 carbon atoms. Mannich condensates useful in the present invention include U.S. Patent Nos. 3,442,808; 3,448,047;
3,539,633; 3,591,598; 3,
600,372; 3,634,515; 3,697
,574; 3,703,536; 3,704,30
8; 3,725,480; 3,726,882;
3,736,357; 3,751,365; 3,7
56,953; 3,793,202; 3,798,1
65; 3,798,247; 3,803,039;
and No. 3,413,347.

The most preferred Mannich condensate is a polyisobutenylphenol in which the polyisobutenyl group has an average molecular weight of about 800 to 3,000, formaldehyde or a formaldehyde precursor and the formula:

[0024]

[Image Omitted] Ethylene polyamine having H2N(CH2CH2NH)nH [wherein n is an integer from 1 to 10],
Alternatively, it is a condensate prepared by condensing mixtures thereof, especially with ethylene polyamines in which n has an average value of 3 to 5.

Typical post-treated ashless dispersants such as succinimides and Mannich condensates are described in US Pat.
36,003; 3,087,936; 3,200,
107; 3,216,936; 3,254,025
; 3,256,185; 3,278,550; 3
,280,234; 3,281,428; 3,28
2,955; 3,312,619; 3,366,5
69; 3,367,943; 3,373,111;
3,403,102; 3,442,808; 3,4
55,831; 3,455,832; 3,493,
520; 3,502,677; 3,513,093
; 3,533,945; 3,539,633; 3,
573,010; 3,579,450; 3,591
,598; 3,600,372; 3,639,24
2; 3,649,229; 3,649,659;
3,658,846; 3,697,574; 3,7
02,575; 3,703,536; 3,704,
308; 3,708,422; and 4,578,
214.

A further class of ashless dispersants that can be used are oil-solubilizing monomers such as decyl methacrylate,
It consists of interpolymers of vinyl decyl ether and high molecular weight olefins with polar substituent-containing monomers such as aminoalkyl acrylates or acrylamide and poly(oxyethylene) substituted acrylates. These are characterized as "polymeric dispersants" and examples thereof include the following US Patent Nos.: 3,329,658; 3,449,250;
3,519,565; 3,666,730; 3,6
87,849; and 3,702,300.

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

[0028]

[Chemical formula 3]

[wherein R1 represents a hydrocarbon group having 1 to 30 carbon atoms, for example an alkyl or alkenyl group having 7 to 22 carbon atoms, and R2 is a hydrogen atom or 1 - represents a hydrocarbon group having 22 carbon atoms, or an aminoalkyl, acylaminoalkyl or hydroxyalkyl group having 2 to 50 carbon atoms]. The long chain alkyl (or long chain alkenyl) imidazoline compound described above is a corresponding long chain fatty acid (formula R1-CO
OH), for example oleic acid, and a suitable polyamine. The imidazolines produced are therefore usually referred to as olelimidazolines, for example where the group R1 represents the oleyl residue of oleic acid. Other suitable alkyl substituents at the 2-position of these imidazolines include undecyl, heptadecyl, lauryl and erucyl. Suitable N-substituents (ie, groups R2) for these imidazolines include hydrocarbyl, hydroxyalkyl, aminoalkyl, and acylaminoalkyl groups. Examples of said groups include:
Methyl, butyl, decyl, cyclohexyl, phenyl,
benzyl, tolyl, hydroxyethyl, aminoethyl,
Includes oleylaminoethyl and stearylaminoethyl.

Other suitable ashless dispersants that can be incorporated into the fuel compositions of this invention include cyclic acid anhydrides and

[
0031

[Formula 4] R-(NH-R'-)n-NH2 [wherein n is an integer at least equal to 1, usually 3 to 5, and R is 10
a saturated or unsaturated linear hydrocarbon group having ~22 carbon atoms, and R' is a divalent alkylene or alkylidene group having 1 to 6 carbon atoms]
and a linear N-alkyl polyamine. Examples of the polyamines include N-oleyl-1,
3-propanediamine, N-stearyl-1,3-propanediamine, N-oleyl-1,3-butanediamine, N-oleyl-2-methyl-1,3-propanediamine, 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-1,3-propanediamine, N-oleyl-
Includes dipropylene triamine and N-stearyl-dipropylene triamine. The above linear N-alkylpolyamines are condensed with succinic, maleic, phthalic or hexahydrophthalic anhydride, each optionally substituted with one or more groups having up to 5 carbon atoms. .

Another class of ashless dispersants that can be incorporated into the compositions of the present invention are ethoxylated amines prepared by the reaction of ammonia with ethylene oxide and carbon atoms having from 8 to 30 carbon atoms. acid and
is the reaction product of The ethoxylated amine may be, for example, a mono-, di- or tri-ethanolamine, or a polyethoxylated derivative thereof, and the carboxylic acid may have, for example, 10 to 22 carbon atoms. It may be a linear or branched fatty acid, a naphthenic acid, a resin acid, or an alkylarylcarboxylic acid.

Yet another type of ashless dispersant that can be used in the practice of this invention is described in US Pat. No. 3,909,215.
α-olefin-maleimide copolymers as described in . The copolymer comprises an N-substituted maleimide and an aliphatic α having 8 to 30 carbon atoms.
- Alternating copolymers with olefins. These copolymers may have an average of 4 to 20 maleimide groups per molecule. The substituents on the maleimide nitrogen may be the same or different and consist essentially of carbon, hydrogen and nitrogen, totaling 3 to 6
It is an organic group with 0 carbon atoms. A commercially available material that is highly suitable for use in the present invention is Chevron OFA 4
25B, and this material is described in U.S. Patent No. 3,909,
It is believed to be or consist of an alpha-olefin maleimide copolymer of the type described in No. 215.

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

[0035] Because of environmental concerns, it is desirable to use ashless dispersants that contain little, if any, halogen atoms, such as chlorine atoms. Therefore, to satisfy the above concerns, it is desirable to select an ashless dispersant (as well as other components used in the compositions of the present invention) such that the total halogen content of the total fuel composition does not exceed 10 ppm (performance Although it is not necessarily necessary from this point of view). In fact, the lower the better. Most desirably, the additive composition does not contain any detectable amounts of halogen.

Typical halogen-free (chlorine) ashless dispersants suitable for use in the compositions of the present invention include those described in the recently published applications below, in addition to the various types mentioned above. Includes: WO 9003359 and EP
365288.

[0037] Hindered phenolic antioxidant. As indicated above, it is preferred to include at least one fuel-soluble hindered phenolic antioxidant in the fuel composition. One suitable class of compounds has the formula

00
38]

[C5]

[wherein R1 is a hydrocarbyl group having 1 to 12 carbon atoms, R2 is a secondary or tertiary hydrocarbyl group having 3 to 12 carbon atoms, and R3 is a hydrocarbyl group or

[0040]

[C6]

and R4 is a hydrocarbyl group. When R3 and R4 are hydrocarbyl groups, they are 50
It usually has 18 or fewer carbon atoms, although it can have 18 or more carbon atoms. A method applicable to the synthesis of the above compounds is described in U.S. Pat.
962,531.

Another example for use in the practice of the present invention
One preferred class of phenolic antioxidants consists of phenolic compounds with methylene bridges, including: 2,2'-methylenebis(4,
6-dihydroxycarbylphenol), 4,4'-methylenebis(2,6-dihydroxycarbylphenol), and various alkylphenols with methylene bridges such as those described in U.S. Patent No. 3,211,652. A mixture of. Typical 2,2'-methylenebis(4,6-dihydroxycarbylphenol) includes 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl -6-tert-butylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), and the like. Examples of 4,4'-methylenebis(2,6-dihydroxycarbylphenol) include 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol),
'-methylenebis(2-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-diisopropyl-phenol), 4,4'-methylenebis(2-tert-amyl-o-cresol), and Includes similar compounds. The synthesis of the above compounds is described, for example, in U.S. Pat.
807,653. Commercially available alkylphenols with methylene bridges include ETHYLR
Antioxidant 728 and ETHYLR Antioxidant 702 (both available from Ethyl Corporation) are included.

Other sterically hindered phenolic antioxidants that can be used include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6
-tri-tert-butylphenol, 2-tert-butylphenol, 2,6-diisopropylphenol, 2-methyl-6-tert-butylphenol, 2,4-dimethyl-6-
Includes tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 2-methyl-6-styrylphenol, 2,6-di-styryl-4-nonylphenol, and analogs and congeners thereof. . Mixtures of two or more of the above phenolic compounds are also suitable, such as ETHYLR Antioxidant 733 available from Ethyl Corporation.

In preferred embodiments of the invention, one or more additional components are included in the fuel composition. These include demulsifiers, metal deactivators, antifoam agents, corrosion inhibitors, lubrication additives, friction modifiers, and/or solvents.

Demulsifier. The demulsifier improves the water tolerance level of the fuel composition by minimizing or preventing excessive emulsion formation.

Examples of demulsifiers that may be utilized in the practice of this invention include poly(alkylphenol) formaldehyde condensates and polyalkyleneoxy-modified reaction products thereof. These compounds are produced by reacting an alkylphenol with formaldehyde and then reacting the reaction product with a C2-C6 alkylene oxide, such as ethylene oxide and propylene oxide. These demulsifiers have the general structural formula

[0047]

[C7]

[wherein U is alkylene having 2 to 6 carbon atoms, y is an integer with an average of 4 to 10, x is an integer with an average of 4 to 10, and R5 is an integer with an average of 4 to 15 is an alkyl having 5 carbon atoms.

Preferred demulsifiers described by the above formula are polyethylene oxy chains having from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms, and in which at least about 75 percent of the polyethylene oxy chains are within the specified range. Polyethyleneoxy-modified methylene-bridged poly(alkylphenol) polymers having the following properties. The methylene-bridged poly(alkylphenol) portion of this polymer is a repeating methylene-bridged alkylphenol having 4 to 10 carbon atoms, preferably 5 to 8 carbon atoms in the alkyl group, preferably 6 to 12 carbon atoms in the alkyl group. It has a unit. In preferred embodiments, the alkyl group is a mixture of alkyls having 4 to 12 carbon atoms.

Illustrative alkylphenols include p-isobutylphenol, p-diisobutylphenol, p-diisobutylphenol,
-hexylphenol, p-heptylphenol, p-
Octylphenol, p-tripropylenephenol,
and p-dipropylenephenol.

Another type of demulsifier component is a sulfonated alkylphenol neutralized with ammonia. These compounds have the general structure:

[0052]

[Chemical formula 8]

[In the formula, R1 is 4 to 15, preferably 6
is a hydrocarbyl group having ~12 carbon atoms]
has.

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

Another class of demulsifiers are glycols that are oxyalkylated. These compounds are produced by reacting polyhydroxy alcohols such as ethylene glycol, trimethylene glycol, etc. with ethylene or propylene oxide. Many of these compounds are sold under the trademark PLURONIC by BASF-Wyandotte Chemica.
It is commercially available by I Company. These are hydroxy-terminated polyethers and are produced by block copolymerization of ethylene oxide and propylene oxide. These ethylene oxide blocks act as hydrophiles and the propylene oxide blocks act as hydrophobic bodies. These are available in a wide range of molecular weights and with varying ratios of ethylene oxide to propylene oxide.

A further class of commercially available demulsifiers consists of alkylaryl sulfonates, polyoxyalkylene glycols, and oxyalkylated alkylphenolic resins. The above products are sold under the TOLAD trademark.
trolite Corporation. One suitable above product is TOLAD 2
86K, which is understood to be a mixture of these components dissolved in a solvent consisting of alkylbenzene. A related product, TOLAD 286, is also suitable. In this case, the product apparently contains the same type of active material dissolved in a solvent consisting of heavy aromatic naphtha and isopropanol. However, other known demulsifiers can also be used.

Metal deactivator. Generally speaking, metal deactivators can be broadly divided into two categories. One category is passivators, which are believed to react with the surface of the metal, thereby passivating it.
tor). Another category consists of chelating agents, ie, substances that have the ability to react with or form complexes with dissolved metals and/or metal ions. Examples of this passivating agent type are thiadiazoles, such as H
ITECR 314 additive (Ethyl Petrol
eum Additives, Ltd. ;Ethyl
Petroleum Additives, Inc.
). Examples of chelating-type metal deactivators include 8-hydroxyquinoline, ethylenediaminetetraacetic acid, β-diketones such as acetylacetone, β-ketoesters such as octyl acetoacetate, and the like. Suitable metal deactivators, which are generally considered as chelating agents, include Schiff bases, such as N,N'-disalicylidene-1,2-ethanediamine, N,N'-disalicylidene-1,2-propanediamine, N,N'-disalicylidene-1,2-cyclohexane-diamine, and N,N"-disalicylidene-N'-methyl-dipropylene-triamine. Thus, for the use of the compositions of the present invention, a wide variety of A number of known metal deactivators are available.Mixtures of metal deactivators can also be used.

[0058] Antifoaming agent. Suitable defoamers include silicones and organic polymers such as acrylate polymers. Various defoamers are available from H. T. Kerne
"Foam Control Agent" by R.
ents) (Noyes Data Corporation
ion, 1976, pp. 125-176). The use of commercially available silicone oils is generally preferred.

Corrosion inhibitor. It is also suitable according to the present invention to use appropriate amounts of corrosion or rust inhibitors in the present fuel compositions. This may be a single compound or a mixture of compounds that has the property of inhibiting corrosion of metal surfaces. In some cases, it is used not only as a corrosion inhibitor;
Compounds that also act as metal deactivators that suppress corrosion by passivating the surface of metals are also known.

Among the corrosion inhibitors suitable for use in accordance with preferred embodiments of the invention are thiazoles, triazoles and thiadiazoles. Examples of the above compounds include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole,
2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5
-Hydrocarbylthio-1,3,4-thiadiazoles, 2-mercapto-5-hydrocarbyldithio-1,3
, 4-thiadiazoles, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and 2,
Includes 5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles. Many of these materials are commercially available.

Other types of useful corrosion inhibitors include those made from dimeric and trimeric acids such as tall oil fatty acids, oleic acid, linoleic acid, and the like; alkenylsuccinic acids and alkenylsuccinic acids. Included are anhydride corrosion inhibitors such as tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, dodecenylsuccinic acid, dodecenylsuccinic anhydride, hexadecenylsuccinic acid, and similar compounds. Also useful are derivatives of alkenylsuccinic acids and anhydrides, half-esters of alkenylsuccinic acids having 8 to 24 carbon atoms in the alkenyl group, as well as alcohols such as diols and polyglycols, and Imides and amides of alkenyl succinic acids and anhydrides having 8 to 24 carbon atoms in the alkenyl group, such as dodecyl succinic acid or anhydride, are reacted with polyethylene polyamine and then further reacted with a fatty acid such as oleic acid. This is the reaction product of the reaction. Also useful is the formula

[0062]

[Chemical formula 9]

[In the formula, R1, R2, R5, R6 and R
Each of 7 is independently a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms, and each of R3 and R4 is independently a hydrogen atom, a hydrocarbyl group having 1 to 30 carbon atoms. or an acyl group having 1 to 30 carbon atoms] or derivatives thereof. These groups R1
, R2, R3, R4, R5, R6 and R7, when they are in the form of hydrocarbyl groups, can be, for example, alkyl, cycloalkyl or aromatic-containing groups. Suitably R1 and R5 are identical or different straight-chain or branched hydrocarbon radicals having 1 to 20 carbon atoms. Most preferably R1 and R5 are saturated hydrocarbon groups having 3 to 6 carbon atoms. Either R2, R3 or R4, and R6 and R7, when they are in the form of hydrocarbyl groups, are preferably the same or different straight-chain or branched saturated hydrocarbon groups. Preferably, R1 and R5 are the same or different alkyl groups having 3 to 6 carbon atoms, R2 is a hydrogen atom, and either R3 or R4 is 15 to 20
Dialkyl esters of aminosuccinic acid are used, which are alkyl groups having 2 to 10 carbon atoms or acyl groups derived from saturated or unsaturated carboxylic acids having 2 to 10 carbon atoms.

The most preferred aminosuccinic acid derivative is one in which R1 and R5 are isobutyl, R2 is a hydrogen atom, R3 is octadecyl and/or octadecenyl, and R4 is 3-carboxy-1-oxo A dialkyl ester of aminosuccinic acid having the above formula, which is -2-propenyl. In the above ester, R6 and R7 are most preferably hydrogen atoms.

Lubricant. The compositions of the invention may also contain lubricants such as sulfurized fats, sulfurized isobutylene, dialkyl polysulfides, and sulfur-bridged phenols such as nonylphenol polysulfide. Also useful as lubricants are fatty acids and their derivatives, such as dimeric or trimeric acids, such as tall oil fatty acids, oleic acid, linoleic acid, and the like.

Friction modifier. Another class of additives that may be included in the compositions of the invention are friction modifiers, such as aliphatic amines or ethoxylated aliphatic amines, fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic acid esters, aliphatic carboxylic acid ester-amides, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates, etc., where the aliphatic group typically refers to a hydrocarbon suitable for the compound. (having about 8 or more carbon atoms, so as to make it solubilized). Also suitable are aliphatic substituted succinic acids or anhydrides prepared by reacting one or more aliphatic succinic acids or anhydrides with ammonia as described in EP 20,037. It is a succinimide.

Solvent. Various types of solvents or carriers are available for use in formulating the compositions of the present invention. These include hydrocarbons of suitable viscosity and boiling range, such as high-boiling aromatic naphthas, processing oils, kerosene, etc., as well as oligomers and hydrogenated oligomers of alkenes, such as hydrogenated decene-1 This includes dimers or trimers of. Also of interest are alcohols and esters, especially higher alcohols, such as liquid alkanols having at least 8 carbon atoms. A particularly useful solvent is isodecanol.

[0068] Further other ingredients may be utilized in the compositions of the present invention in their conventional amounts. These include:
Aromatic amine antioxidants or stabilizers, such as N,N'
-di-s-butyl-p-phenylenediamine, phenyl-alpha-naphthylamine, and 4-isopropylaminodiphenylamine; cetane improvers, such as organic nitrate esters or fuel-soluble peroxides, hydroperoxides or peroxyesters ; metal-containing combustion modifiers such as ferrocene and ferrocene derivatives, cyclopentadienylmanganese carbonyl compounds such as cyclopentadienylmanganese tricarbonyl and methylcyclopentadienylmanganese tricarbonyl, and metal salts such as manganese oleate, naphthenic acid; Iron, copper naphthenate, cobalt naphthenate, nickel oleate, and manganese naphthenate; dyes; and the like.

Concentrations and ratios. As shown above,
The key to this invention is to use a sufficiently high concentration of combustion soluble ashless dispersant to achieve rapid reduction of harmful emissions during fuel combustion. In other words, rather than relying on the engine or burner parts to be slowly cleaned with a concomitant gradual reduction in emissions,
The present invention, due to the high concentration of ashless dispersant used in this fuel, eliminates harmful emissions virtually immediately.
This results in a dramatic reduction. The minimum amount of ashless dispersant necessary to achieve a substantially immediate reduction in such emissions will vary somewhat depending on the characteristics and composition of the hydrocarbon-based middle distillate fuel in which the dispersant is being used. . However, generally speaking, this minimum amount is 5
It is in the range of 0 to 60 ppm. Usually this fuel is about 5,
000 ppm of dispersant, although higher concentrations may be used if such high concentrations are warranted or required.

Generally, the other additive components of the compositions of this invention are used in minimum amounts sufficient to improve the performance characteristics and properties of the base fuel. These amounts will therefore vary according to the type of base fuel, the type of intended use of the fuel composition, and the desired performance characteristics in the final fuel. However, generally speaking, the following concentrations (ppm by weight) are typical for the components (active materials) in this fuel:

[0071]

[Table 1]
Typical Range Preferred Range Hindered Phenolic Antioxidant 0-3
00 5-50 Demulsifier
0~
300 2-75 Metal deactivator 0-10
0 0.5-25 foam suppressor
0-100
0.5-50 corrosion inhibitor
0-100
0.5-50 Lubricating additive
0-100
The individual components used can be blended into this fuel separately or, if desired, in various subcombinations. Generally, the particular order of the blending steps is not important. Furthermore, the above ingredients are
They can be blended in the form of individual solutions in diluents. However, it is preferred to blend the ingredients used in the form of additive concentrates of the present invention, since this simplifies the blending operation, reduces the susceptibility to blending errors, and This is because it takes advantage of the compatibility and solubility properties provided by this total concentrate.

The additive concentrate of the present invention contains components in amounts formulated to produce a final fuel consistent with the concentrations shown in the table above. In most cases, the additive concentrate contains one or more diluents, such as light mineral oils and/or higher alcohols, to facilitate handling and blending of the concentrate. in this way,
Concentrates containing up to 90% by weight of one or more diluents or solvents can be used.

Hydrocarbon fuel. In principle, the advantages of the invention can be achieved in any distilled or distillable liquid hydrocarbon fuel derived from petroleum, coal, shale and/or tar sands. In most cases, at least under current circumstances, this base fuel is primarily, if not exclusively, derived from petroleum.

Therefore, the present invention provides kerosene, jet fuel,
aviation fuel, diesel fuel, home heating oil,
Light cycle oil, heavy cycle oil, light gas oil,
Heavy gas oils and generally any liquid carbonization suitable for combustion either in engines (e.g. diesel fuel, gas turbine fuel, etc.) or in burner equipment (e.g. gas oil, home heating oil, etc.) Applicable to hydrogen-based products. Other suitable fuels include liquid fuels derived from biomass, e.g. vegetable oils (e.g. rapeseed oil, jojoba oil, cottonseed oil, etc.); or liquid fuels derived from refuse, e.g. municipal and/or industrial waste. or waste oil and/or liquid waste biomass and derivatives thereof; or mixtures of any of the foregoing materials.

In many cases specifications exist for various hydrocarbon fuels or classes thereof, and in any case the properties and characteristics of said fuels are well known and reported in the literature. ing. Generally speaking, so-called middle distillate fuels have temperatures ranging from about 140°C to about 400°C.
Boiling within the range of °C.

The implementation and advantages of the invention will become even more apparent from the following illustrative examples. Here, all percentages are by weight.

[0077]

EXAMPLE An additive concentrate of the present invention was prepared by blending together the ingredients in the proportions specified below:
Succinimide ashless dispersant (1)
37.
50% 2,6-di-tert-butyl-α-dimethylamino-
p-Cresol 3.75%N,N'-disalicylidene-1,2-propanediamine (2) 0
．． 50% corrosion inhibitor (3)

3.75% Demulsifier (4)

4.25%
silicone foam suppressor

2.50% Lubricant Additive (5)

3.75% aromatic naphtha solvent

9.50% isodecanol solvent
34.
50%
(1) Polyisobutenyl succinimide of tetraethylenepentamine with a polyisobutenyl group having a number average molecular weight of about 950; used as a 75% solution in a highly aromatic solvent.

(2) Used as an 80% solution in xylene.

(3) Low molecular weight succinimide type corrosion inhibitor; used as a 50% solution in processing oil.

(4) Used as a 60% solution in kerosene.

(5) 61.5 in the mixture of processing oil and kerosene
Used as a % solution.

This additive concentrate was blended into commercial diesel fuel at a concentration of 400 ppm. Therefore, this fuel contains approximately 112.5 ppm of succinimide ashless dispersant (
active material) and 15 ppm of 2,6-di-tert-butyl-α-dimethylamino-p-cresol. These blended fuels were used in the operation of two different diesel engines. One was a Volvo TD121F 12 liter turbo internally cooled truck engine. The other engine was a 4-cylinder Mercedes-Benz 200D passenger car engine with a displacement of 1.997 liters and a rated power of 53 kW. The base fuel used in Volvo truck engine tests had a cetane number (A
STM D 976-80) is 48.9;
Density at 15°C (ASTM D 1298) is 0.853
with an API gravity of 34.2, a total sulfur content of 0.125 wt%, and an aromatics content (ASTM
D 1019-68 (Mod)) is 39% by volume,
The initial boiling point is 176°C and the final boiling point (ASTM
D86) was 362°C.

[0083] In this Volvo truck engine test, the ECE R49 13-mode repeat test was used, first on pure (additive-free) diesel fuel (the commercially available diesel fuel mentioned above) three times, and then immediately after that,
The above diesel fuel of the present invention was tested three times. Three further series of tests were then carried out on the added fuel, but for these three sets, measurements were taken only after 60 hours of running, and the test was only used for this 60 hour run. This iteration used typical 3 modes rather than the full 13 modes used in the previous two sets. A summary of the results thus obtained is listed in Table 1.

[0084]

[Table 2] Table 1 ECE R49-13 mode results of Volvo truck engine - horsepower/grams per hour
Fuel of the present invention
Pure Fuel Immediate Test After 60 Hours Test Emissions HC, Average % Change 0.619
0.546
0.487
-- -11.8
-21.3 NOX, average % change 8.91 8
．． 88 9.26
---
-0.8
+3.4CO, average % change
3.395 2.996
2.450
−− −
11.8 -27.8 fine particles, average % change 0.4804
0.4420 0.377
9
----8.0
-21.3 Fuel consumption BSFC*, average % change 161.47
159.52 1
59.02
-- -1.21
-1.52* Brake Standard Fuel Consumption It can be seen from Table 1 that the fuel of the present invention dramatically reduced hydrocarbon, CO and particulate emissions almost immediately. In addition, the fuel of the present invention provides almost immediately usable improvements in fuel economy. Furthermore, these improvements continued and in some cases were even further improved after 60 hours of testing.

In a test using a Mercedes-Benz 200D passenger car, 135
A road test was conducted using a car that had already been driven normally for 500 km and whose injectors had not been replaced. This fuel was switched to using the fuel of the invention and emissions and fuel consumption changes were measured both immediately after the trip and after a further 1,000 km. Four different standard run repetition systems, the so-called "Federal Test Operation 75"
” (Federal Test Procedure
75 (“FTP 75”)), “Federal Test Operations 72” (
Federal Test Procedure 72
(“FTP 72”), “Highway Fuel Economy Test”
st) (“HW FET”), and “ECE Rule 1
5-04” (ECE Regulation 15-0
4 ("ECE 15")). The results of these tests are summarized in Table 2.

[0086]

[Table 3]
Table 2
Mercedes Benz passenger car test results

Fuel of the present invention

Exam immediately after
FTP
75 FTP 72 HW FET
ECE 15 Emissions HC, % change
-16 -11 -29
-10CO,% change
-5 -6
-6 -6 Fine particles, % change
-15-
5 -10 +5 Fuel consumption Fuel consumption, % change -1.5
-2.5 -1
-2
Trial after 1000km
experience
FTP 75 FTP 72
HW FET ECE 15 Emission HC, % change
-20 -22 -48
-3CO,% change
-6 -8
-11 0 fine particles, % change
-11 -1
-2 +3 Fuel consumption Fuel consumption, % change -2
-4 -3
-4.5 Tests were also conducted using diesel fuels other than the present invention having additive compositions very similar to those described above, but with lower concentrations of ashless dispersant. In this test, a Peugeot 30 equipped with a 1,905 cc four-cylinder indirect injection diesel engine was tested.
9. Evaluation was made using a GLD diesel passenger car. The additive composition (which, if used at suitably high concentrations, appears to be suitable for the practice of this invention) was as follows: Succinimide Ashless Dispersant (1)
17.
0% 2,6-di-tert-butyl-α-dimethylamino-p
-Cresol 2.5% methylene bridged alkylphenol (2)
10.0% N,N'-disalicylidene-1,2-propanediamine (3) 1.0% Corrosion inhibitor (4)

5.0% demulsifier (5)

4.0% silicone foam suppressor

3.8% aromatic naphtha solvent
34.0%
isodecanol solvent
2
2.7%
(1) The number average molecular weight of the polyisobutenyl group is approximately 950
Polyisobutenyl succinimide of tetraethylene pentamine; used as a 77% solution in processing oil.

(2) A 50% solution of a hindered phenol mixture containing 85% methylene bridged phenol and 2% solvent in processing oil.

(3) Used as an 80% solution in xylene.

(4) Low molecular weight succinimide type corrosion inhibitor; used as a 50% solution in processing oil.

(5) Used as a 60% solution in kerosene.

This additive concentrate was blended into the fuel at a concentration of 200 ppm. Therefore, this fuel is about 26.
2 ppm active ashless dispersant and 5.0 ppm 2,6
-di-tert-butyl-α-dimethylamino-p-cresol.

This test run involved a dynamometer mileage accumulation of 967 km using combined city/highway driving repetitions. Following this, ECE
Emission measurements were made according to the 15-04 replication. The results of two tests performed in this manner were expressed in grams of emissions per test as follows:

[0093]

[Table 4] Emissions Untreated fuel
Processed fuel CO 3.457
3.915HC
0.759 0.967 NOX
4.495 4.
608 It can be seen that in each case, fuels treated other than the present invention increased the amount of harmful emissions.

Features and aspects of the present invention are as follows.

1. at least 50p sufficient to rapidly reduce emissions released upon combustion of the fuel composition;
A fuel composition comprising a liquid middle distillate hydrocarbon-based fuel containing at least one fuel-soluble ashless dispersant in an amount of pm.

2. 2. The fuel composition of claim 1, wherein the amount of ashless dispersant in said fuel composition is in the range of 75 to 1,000 ppm.

3. 2. The fuel composition of claim 1, wherein the amount of ashless dispersant in the fuel composition is in the range of 100 to 250 ppm.

4. a first additionally containing at least one fuel-soluble hindered phenolic antioxidant;
The fuel composition according to any one of items 1 to 3.

5. Additionally, the expression

[0100]

[Chemical formula 10]

[wherein R1 is a hydrocarbyl group having 1 to 12 carbon atoms, R2 is a secondary or tertiary hydrocarbyl group having 3 to 12 carbon atoms, and R3 is a hydrocarbyl group or

[0102]

[Chemical formula 11]

and R4 is a hydrocarbyl group.

6. 4. The fuel composition according to any one of items 1 to 3, additionally containing 2,6-di-tert-butyl-α-dimethyl-amino-p-cresol.

7. Additionally, the following ingredients: a) at least one chelating fuel-soluble metal deactivator; b) at least one fuel-soluble demulsifier; c) at least one fuel-soluble antifoaming agent; d) at least one lubricating additive; e) at least one liquid alcohol and/or at least one liquid aromatic hydrocarbon as a solvent or carrier liquid; 6. The fuel composition according to any one of Item 6.

8. The ashless dispersant reacts at least one polybutenylsuccinic acylating agent with a mixture of cyclic and acyclic polyethylene polyamines having an approximate overall composition ranging from diethylene triamine to pentaethylene hexamine. 8. The fuel composition according to any one of items 1 to 7, which is a succinimide produced by.

9. blending into the fuel at least one ashless dispersant in an amount of at least 50 ppm sufficient to achieve the reduction in emissions;
A method for achieving an almost instantaneous reduction in the amount of harmful emissions produced during the combustion of hydrocarbon fuels in the boiling range of said middle distillates.

10.　　expression

[0109]

[Chemical formula 12]

[0110] Where R1 is a hydrocarbyl group having 1 to 12 carbon atoms, R2 is a secondary or tertiary hydrocarbyl group having 3 to 12 carbon atoms, and R3 is a hydrocarbyl group or

[0111]

[Chemical formula 13]

and R4 is a hydrocarbyl group.
The method described in section.

11. at least 1 in an amount of at least 50 ppm sufficient to minimize consumption of said fuel.
Minimizing the fuel consumption of a compression ignition engine operating on a liquid hydrocarbon compression ignition fuel comprising supplying the engine with a liquid hydrocarbon compression ignition fuel containing a seed ashless dispersant. Method.

12. The fuel supplied to the engine has the formula

[0115]

[Chemical formula 14]

[0116] Where R1 is a hydrocarbyl group having 1 to 12 carbon atoms, R2 is a secondary or tertiary hydrocarbyl group having 3 to 12 carbon atoms, and R3 is a hydrocarbyl group or

[0117]

[Chemical formula 15]

and R4 is a hydrocarbyl group.

Claims (3)

[Claims] 1. At least 50 ppm sufficient to rapidly reduce emissions released during combustion of the fuel composition.
A fuel composition comprising a liquid middle distillate hydrocarbon-based fuel containing at least one fuel-soluble ashless dispersant in an amount of . 2. Boiling range carbonization of said middle distillate comprising blending into said fuel at least one ashless dispersant in an amount of at least 50 ppm sufficient to achieve said reduction in emissions. A method of achieving an almost instantaneous reduction in the amount of harmful emissions produced during the combustion of hydrogen-based fuels. 3. Supplying the engine with a liquid hydrocarbon-based compression ignition fuel containing at least one ashless dispersant in an amount of at least 50 ppm sufficient to minimize consumption of said fuel. A method of minimizing fuel consumption in a compression ignition engine operating on a liquid hydrocarbon-based compression ignition fuel, comprising: