CN100357408C - Diesel fuel composition and a method to improve filterability of diesel fuel - Google Patents

Abstract

Disclosed is a stabilized diesel fuel composition comprising a) a diesel fuel with a cetane number less than or equal to 50, b) an effective amount of at least one compound selected from the group consisting of the cetane improvers and c) i) an effective stabilizing amount of at least one compound selected from the group consisting of the stable nitroxide compounds or ii) an effective synergistic stabilizing amount of at least one compound selected from the group consisting of the stable nitroxide compounds and at least one antioxidant compound selected from the group consisting of the aromatic amine antioxidants and the hindered phenolic antioxidants. The cetane improvers are for example nitrate esters. The diesel fuel compositions exhibit improved filterability.

Description

The method of the filtration capacity of diesel fuel composition and raising diesel oil fuel

The present invention relates to comprise the stabilize diesel fuels composition of cetane improver.The stabilize diesel fuels composition has improved filtration capacity.Diesel fuel composition comprises stablizer and optional aromatic amine and the hindered phenolic antioxidants that is selected from stable nitroxide compounds.Cetane improver is, for example, and nitric ether.

But this composition forms the clog fuel lines of minimizing and the soluble material of strainer.

Diesel oil fuel is the fuel that is used for oil engine second more.It is widely used in truck, bus, and heavy equipment, and sea-freight and stationary applica-tions.Its application in passenger vehicle also constantly increases owing to the higher fuel efficiency of the relative spark ignition engines of compression ignition engine.

In diesel motor, fuel in the pressure stroke process owing to the heat that compression produced of air in cylinder is lighted.When fuel is injected into cylinder and the thermal conductance that produced of compression have for some time between when causing fuel combustion.This time is known as ignition delay, and if oversize, diesel knock can appear.Other influence of long ignition delay is a power loss, the increase that carbon monoxide produces and cause increasing hydrocarbon and particulate incomplete combustion in the waste gas.Recently, regulations department has required to reduce these environmental pollutant.

Special fuel shows an index how in compression ignition engine be cetane value.Bad fuel with long ignition delay has low cetane value, and fuel has higher cetane value preferably.Representative value is 40-48 (for commercial diesel fuel) and greater than 50 (for insurance products).Except environmental benefit, high n-Hexadecane fuel can reduce engine deposits and help cold-starting.

Because being used for the purposes of diesel oil fuel, increase in demand, cracking material increase.Regrettably, cat cracker, hydrocracker and coker overhead product have low cetane value.In some cases, cetane value is lower than 40, and this is the minimum cetane number that diesel fuel specifications allows.Having developed can be with the additive that be called cetane improver of diesel oil fuel cetane number boost to acceptable level.

Nitrate ester cetane improvers for example is disclosed in U.S. patent specification Nos.4,705,534,5,258,049 and 5,482,518.

But cetane improver destabilize diesel fuel.In typical heat stability test (ASTM D6468), fuel wore out 1.5 or 3.0 hours down at 150 degrees centigrade (302_).Under these conditions, heat-staple low cetane fuel can produce considerably less settling.If add the commercial cetane promotor, as nitric acid 2-(ethyl hexyl) ester, the fuel mass aspect burning increases, but forms more settling in heat stability test.In the engine of reality, these settlings can cause fuel circuit to stop up and fuel filter stops up.

EP-A-0947577 has proposed a kind of fuel composition that comprises cetane improver and alkyl amine thermo-stabilizer.U.S.App.No.2002/0026743 (publishing) discloses the heterocycle with big hydrocarbyl group, is used for increasing the purposes of cetane improver in the thermostability of fuel composition as polyisobutenyl succinimide.

Although make great efforts to prevent to form the soluble material that causes by cetane improver, still need more effectively stabilize diesel fuels.Those fuel more responsive to the harmful effect of cetane improver more need this.

Find shockingly that steric hindrance nitro oxide stablizer especially is suitable for the additive that work increases the thermostability of the diesel oil fuel that comprises cetane improver.Steric hindrance nitro oxide stablizer is used for reduce forming soluble material, or the settling in the diesel oil fuel and therefore increase filtration capacity and prevent that fuel filter from stopping up.

U.S. patent specification No.5,711,767 disclose the purposes .U.S. patent specification No.5 that goo that stable nitroxide compounds is used to reduce gasoline forms, and 460,634 have proposed the purposes that stable nitroxide compounds is used to reduce the discharge that fuel combustion produces.

The present invention relates to the stabilize diesel fuels composition, comprise

A) cetane value is less than or equal to 50 diesel oil fuel;

B) at least a compound that is selected from cetane improver of significant quantity; With

C) i) effectively stabilization amount at least a be selected from stable nitroxide compounds compound or

The ii) at least a compound and at least a anti-oxidant compounds that is selected from aromatic amine antioxidant and hindered phenolic antioxidants that is selected from stable nitroxide compounds of effective Synergistically stabilized amount.

Amount of component b) the stable nitroxide and the additive combination of antioxidant have synergy to thermostability is provided.

Diesel oil fuel exists as main component, and amount is greater than 50% weight of total prescription.

Hydrocarbon based diesel fuels is in general by falling into the diesel oil fuel boiling spread, and about 160 degrees centigrade to about 370 degrees centigrade usually, for example the mixture of the hydrocarbon of 90% distillation point 282 degrees centigrade to 338 degrees centigrade (ASTMD-396 and D-975) is formed.The specification of diesel oil fuel can comprise 38 degrees centigrade of minimum flash point.Diesel oil fuel is middle overhead product fuel, because they are included in gasoline distilled fraction afterwards.Diesel oil fuel of the present invention has low sulfur content, for example is no more than 500ppm weight, for example is no more than 100ppm or is no more than the sulphur of 60ppm weight.Aromatic content is the 10-50% volume, for example about 10-35% volume.Lower sulphur content causes lower aromatics.

Typical cetane number values is 40-48 (for a commercial diesel fuel).This diesel oil fuel has and is lower than 50 cetane value.That is, this diesel oil fuel has and is lower than 50 intrinsic cetane value (before adding any cetane improver).

Cetane improver for example is selected from superoxide, two-t-butylperoxide for example, sulfo-aldehyde, primary t-alkyl-amine, cross ketal (perketal) and (for example be disclosed in U.S. patent specification No.5,011,503, alkyl oxide/peroxide blends (for example is disclosed in U.S. patent specification No.5,520,710), peracid (for example being disclosed in EP-A-0537931), tetrazolium and triazole (for example are disclosed in U.S. patent specification No.4,632,674), N, the dibasic organic nitro oxide of N-(for example is disclosed in U.S. patent specification No.4,398,505), organic nitrates and its mixture.U.S. the disclosure of patent is to incorporate the present invention as a reference at this.

Cetane improver is organic nitrates especially, for example nitric ether, or alkyl nitrate ester selected.Nitrate ester cetane improvers for example is disclosed in U.S. patent specification Nos.4, and 705,534,5,258,049 and 5,482,518, its disclosure is to incorporate the present invention as a reference at this.

Nitric ether is a nitric acid hydrocarbyl carbonate for example, wherein alkyl is the straight or branched alkyl with 1 to 24 carbon atom, have 2 to 24 by the straight or branched alkyl of the carbon atom of 1-3 Sauerstoffatom interruption, straight or branched alkenyl with 3 to 24 carbon atoms has the cycloalkyl of 5 to 12 carbon atoms or has the C of 5 to 12 carbon atoms ₁-C ₄The cycloalkyl of alkyl-replacement.

The example of alkyl is a methyl, ethyl, n-propyl group, sec.-propyl, butyl, amyl group, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, nonyl, decyl, allyl group, cyclopentyl, cyclohexyl, methylcyclohexyl, cyclo-dodecyl, 2-ethoxyethyl group and 2-(2-ethoxy ethoxy) ethyl.

For example, preferred nitric ether is a nitric acid 2-(ethyl hexyl) ester.

Nitro oxide of the present invention is for example to be disclosed in U.S. patent specification Nos.5,711,767 and 5,460, and those of 634, its disclosure is incorporated into as a reference at this.

Nitro oxide can be several different types.Aromatics and aliphatic series (bulky amine usually) nitro oxide all shows in this composition effectively.The bulky amine nitro oxide is valuable especially, promptly has the compound of the nitroxyl part that connects with two tertiary carbon atom sides.The tertiary carbon atom that side connects can further connect to form ring texture by various bridge joint groups, as six-first piperidines, and piperazine, five-first tetramethyleneimine and analogue.

Can be used for nitro oxide stablizer of the present invention and for example have structural formula

Or comprise the compound of one or more following formula groups

Wherein R is respectively that methyl or ethyl and T finish 5-or the required group of 6-unit ring independently.

Two or more nitro oxide groups can be present in in a part by the T part keyed jointing that use is exemplified below, and wherein E is a linking group.

Stable nitroxide compounds for example is selected from sebacic acid two (1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) ester, 4-hydroxyl-1-oxygen base-2,2; 6,6-tetramethyl piperidine, 4-oxyethyl group-1-oxygen base-2; 2,6, the 6-tetramethyl piperidine; 4-propoxy--1-oxygen base-2,2,6; 6-tetramethyl--piperidines, 4-acetylaminohydroxyphenylarsonic acid 1-oxygen base-2,2; 6,6-tetramethyl piperidine, 1-oxygen base-2; 2,6, the 6-tetramethyl piperidine; 1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-ketone, acetate 1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-base ester, 2 ethyl hexanoic acid 1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-base ester; stearic acid 1-oxygen base-2,2,6; 6-tetramethyl--piperidin-4-yl ester, phenylformic acid 1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-base ester, 4-t-butylbenzoic acid 1-oxygen base-2; 2,6,6-four-methyl piperidine-4-base ester; succsinic acid two (1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) ester, hexanodioic acid two (1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-yl) ester, propanedioic acid two (1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-yl) the n-butyl ester; phthalic acid two (1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) ester, m-phthalic acid two (1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-yl) ester, terephthalic acid two (1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-yl) ester; six hydrogen terephthalic acids two (1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) ester, N, N '-two (1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-yl) hexanediamide; N-(1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) hexanolactam; N-(1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) dodecyl succinimide; 2,4,6-three-[N-butyl-N-(1-oxygen base-2; 2; 6,6-tetramethyl piperidine-4-yl)]-the s-triazine, 4; 4 '-ethylene (1-oxygen base-2; 2,6,6-four-methylpiperazine-3-ketone); the 2-Oxy-1; 1,3,3-tetramethyl--2-isoindole; 1-oxygen base-2; 2,5,5-four-crassitude; N; N-two-(1,1,3; the 3-tetramethyl butyl) nitro oxide; N, N-phenylbenzene nitroxyl, single-and the dialkyl group tertiary butyl/uncle octyl group-N; the mixture of N-phenylbenzene nitroxyl and list-and dialkyl group nonyl-N, the mixture of N-phenylbenzene nitroxyl.

Stable nitroxide compounds is two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebate for example, 4-hydroxyl-1-oxygen base-2,2,6,6-tetramethyl piperidine, 4-oxyethyl group-1-oxygen base-2,2,6,6-four-methyl piperidine, 4-propoxy--1-oxygen base-2,2,6, the 6-tetramethyl piperidine, 4-ethylamino-1-oxygen base-2,2,6, the 6-tetramethyl piperidine, 1-oxygen base-2,2,6,6-tetramethyl piperidine or 1-oxygen base-2,2,6,6-tetramethyl piperidine-4-ketone.

Particular is that wherein nitroxide compound is two (1-oxygen base-2,2,6,6-tetramethyl--piperidin-4-yl) sebates or 4-hydroxyl-1-oxygen base-2,2,6, the 6-tetramethyl piperidine.

The aromatic amine antioxidant for example is selected from 4-(p-toluene-sulfamyl) diphenylamine; diphenylamine; N-allyl group diphenylamine; 4-isopropoxy two-phenyl amine; the N-phenyl-1-naphthylamine; N-(uncle's 4-octyl phenyl)-1-ALPHA-NAPHTHYL AMINE; N-phenyl-2-ALPHA-NAPHTHYL AMINE, octyl group diphenylamine, for example 4; 4 '-two-uncle octyldiphenylamine; 4-n-butyl amino-phenol, 4-butyryl radicals amino-phenol, 4-nonanoyl amino-phenol; 4-lauroyl amino-phenol; 4-octadecanoyl amino-phenol, two (4-p-methoxy-phenyl) amine, 2; 6-two-tertiary butyl-4-dimethyl-amino methyl phenol; 2,4 '-diaminodiphenyl-methane, 4; 4 '-diaminodiphenyl-methane; N, N, N '; N '-tetramethyl--4; 4 '-diaminodiphenyl-methane, 1,2-two [(2-aminomethyl phenyl) amino] ethane; 1; 2-two (phenyl amino) propane, (o-tolyl) biguanides, two [4-(1 '; 3 '-dimethylbutyl) phenyl] amine; uncle's octyl group N-phenyl-1-naphthylamine, single-and the mixture of the dialkyl group tertiary butyl/uncle's octyl group-two-phenyl amine, single-and the mixture of dialkyl group nonyl diphenylamine; single-and the mixture of dialkyl group dodecyl diphenylamine; single-and the mixture of dialkyl group sec.-propyl/isohexyl diphenylamine, single-and the mixture of dialkyl group tert-butyl diphenyl amine, 2; 3-dihydro-3; 3-dimethyl-4H-1,4-benzothiazine, thiodiphenylamine; single-and the mixture of the dialkyl group tertiary butyl/uncle's octyl group thiodiphenylamine; single-and the mixture of dialkyl group uncle octyl group-thiodiphenylamine, N-allyl group thiodiphenylamine, N; N; N ', N '-tetraphenyl-1,4-diamino but-2-ene; phenylenediamine and N, N '-two-sec-butyl-phenylenediamine.

Hindered phenolic antioxidants for example is selected from the single phenols of alkylation, and for example 2,6-two-tertiary butyl-4-methylphenol, 2,6-two-tert.-butyl phenol, the 2-tertiary butyl-4, the 6-xylenol, 2,6-two-tertiary butyl-4-ethylphenol, 2,6-two-tertiary butyl-4-n-butylphenol, 2,6-two-tertiary butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4,6-xylenol, 2,6-two (octadecyl)-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-two-tertiary butyl-4-methoxymethyl phenol, straight chain or in side chain the nonylphenol class of branching, for example, 2,6-two-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methyl undecane-1-yl) phenol, 2,4-dimethyl-6-(1-methyl heptadecane-1-yl) phenol, 2,4-dimethyl-6-(1-methyl tridecane-1-yl) phenol or its mixture;

The alkylthiomethyl phenols, for example 2,4-dioctyl sulphomethyl-6-tert.-butyl phenol, 2,4-dioctyl-sulphomethyl-6-methylphenol, 2,4-dioctyl sulphomethyl-6-ethylphenol or 2,6-two-dodecyl sulphomethyl-4-nonylphenol;

The steric hindrance Resorcinol, for example 2,6-two-tertiary butyl-4-methoxyphenol, 2,5-two-Tert. Butyl Hydroquinone, 2,5-two-tert-pentyl Resorcinol, 2,6-phenylbenzene-4-octadecyl oxygen base phenol, 2,6-two-Tert. Butyl Hydroquinone, 2,5-two-tertiary butyl-4-hydroxy phenylmethylether, 3,5-two-tertiary butyl-4-hydroxy phenylmethylether, stearic acid 3,5-two-tert-butyl-hydroxy phenyl ester or hexanodioic acid two-(3,5-two-tert-butyl-hydroxy phenyl) ester;

Tocopherol, alpha-tocopherol for example, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol or its mixture (vitamin-E);

Hydroxylation sulfo-diphenyl ether, for example 2,2 '-sulfo-two (the 6-tertiary butyl-4-methylphenol), 2,2 '-sulfo-two (4-octyl phenol), 4,4 '-sulfo-two (the 6-tertiary butyl-3-methylphenol), 4,4 '-sulfo-two (the 6-tertiary butyl-2-methylphenol), 4,4 '-sulfo-two-(3,6-two-sec.-amyl sec-pentyl secondary amyl phenol) or 4,4 '-two (2,6-dimethyl-4-hydroxyl-phenyl) disulphide;

Alkylidene bisphenols, for example 2,2 '-methylene radical two (the 6-tertiary butyl-4-methylphenol) 2,2 '-methylene radical two (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene radical two [4-methyl-6-(Alpha-Methyl cyclohexyl)-phenol], 2,2 '-methylene radical two (4-methyl-6-cyclohexylphenol), 2,2 '-methylene radical two (6-nonyl-4-methylphenol), 2,2 '-methylene radical two (4,6-two-tert.-butyl phenol), 2,2 '-ethylene (4,6-two-tertiary butyl-phenol), 2,2 '-ethylene (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene radical two [6-(α-Jia Jibianji)-4-nonylphenol], 2,2 '-methylene radical two [6-(α, α-Er Jiajibianji) 4-nonylphenol], 4,4 '-methyl-Ji two (2,4,4 6-two-tert.-butyl phenol), '-methylene radical two (the 6-tertiary butyl-2-methylphenol), 1,1-two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 2,6-two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1,1-two (5-tertiary butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecyl sulfydryl butane, ethylene glycol bisthioglycolate [3,3-two (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric ester], two (3-tertiary butyl-4-hydroxy-5-methyl-phenyl) Dicyclopentadiene (DCPD), terephthalic acid two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-methyl-benzyl)-the 6-tertiary butyl-4-aminomethyl phenyl] ester, 1,1-two-(3,5-dimethyl-2-hydroxy phenyl) butane, 2,2-two-(3,5-two-tert-butyl-hydroxy phenyl) propane, 2,2-two-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-4-n-dodecyl-sulfydryl butane or 1,1,5,5-four-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane;

O-, N-and S-benzyl compounds, for example 3,5,3 ', 5 '-four-tertiary butyl-4,4 '-dihydroxyl two-benzylic ether, Thiovanic acid octadecyl-4-hydroxyl-3,5-dimethyl benzyl ester, Thiovanic acid tridecyl-4-hydroxyl-3,5-two-tertiary butyl benzyl ester, three (3,5-two-tertiary butyl-4-hydroxy benzyl) amine, dithio terephthalic acid two (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) ester, two (3,5-two-tertiary butyl-4-hydroxy benzyl) sulfide or Thiovanic acid iso-octyl 3,5-two-tertiary butyl-4-hydroxy benzyl ester;

The hydroxybenzyl malonic ester, propanedioic acid two (octadecyl) 2 for example, 2-two-(3,5-two-tertiary butyl-4-hydroxy-benzyl) ester, propanedioic acid two-octadecyl 2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl) ester, propanedioic acid two-dodecyl mercaptoethyl-2,2-two-(3,5-two-tertiary butyl-4-hydroxy benzyl) [4-(1 for ester or propanedioic acid two, 1,3,3-four-methyl butyl) phenyl] 2,2-two (3,5-two-tertiary butyl-4-hydroxy benzyl) ester;

The aromatic hydroxy benzyl compounds, for example 1,3,5-three-(3,5-two-tertiary butyl-4-hydroxy-benzyl)-2,4, the 6-Three methyl Benzene, 1,4-two (3,5-two-tertiary butyl-4-hydroxy benzyl)-2,3,5,6-tetramethyl--benzene or 2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) phenol.

Triaizine compounds, for example 2,4-two (octyl group sulfydryl)-6-(3,5-two-tertiary butyl-4-hydroxy phenylamino)-1,3, the 5-triazine, 2-octyl group sulfydryl-4,6-two (3,5-two-tertiary butyl-4-hydroxy phenylamino)-and 1,3,5-triazines, 2-octyl group sulfydryl-4,6-two (3,5-two-tertiary butyl-4-hydroxy phenoxy group)-1,3,5-triazines, 2,4,6-three-(3,5-two-tertiary butyl-4-hydroxy phenoxy group)-1,2,3-triazine, 1,3,5-three-(3,5-two-tertiary butyl-4-hydroxy benzyl) chlorinated isocyanurates, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates, 2,4,6-three-(3,5-two-tert-butyl-hydroxy phenyl ethyl)-1,3,5-triazines, 1,3,5-three (3,5-two-tertiary butyl-4-hydroxy-phenyl propionyl)-six hydrogen-1,3,5-triazines or 1,3,5-three (3,5-dicyclohexyl-4-hydroxybenzyl) chlorinated isocyanurates;

The benzylphosphonic acid ester, for example the benzylphosphonic acid dimethyl 2,5-two-tertiary butyl-4-hydroxy ester, benzylphosphonic acid diethyl-3,5-two-tertiary butyl-4-hydroxy ester, benzylphosphonic acid two (octadecyl) 3,5-two-tertiary butyl-4-hydroxy ester, benzylphosphonic acid two (octadecyl) 5-tertiary butyl-4-hydroxy-3-methyl ester or 3, the calcium salt of single ethyl ester of 5-two-tertiary butyl-4-hydroxy benzylphosphonic acid;

The acyl amino phenols, 4-hydroxyl bay N-anilide for example, stearic N-anilide of 4-hydroxyl or carboxylamine octyl group N-(3,5-two-tertiary butyl 4-hydroxy phenyl) ester;

β-(3,5-two-tertiary butyl 4-hydroxy phenyl) propionic acid and single-or polyvalent alcohol, as with methyl alcohol, ethanol, butanols, n-octanol, isooctyl alcohol (mixture of octanol), stearyl alcohol, 1, the 6-hexane diol, 1,9-nonane glycol, ethylene glycol, 1, the 2-propane diol, dimethyltrimethylene glycol, thio-diethylene glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl)-chlorinated isocyanurates, N, N '-two (hydroxyethyl) oxamide, 3-thiophene undecyl alcohol, 3-thiophene pentadecanol, trimethyl cyclohexane glycol, TriMethylolPropane(TMP) or 4-hydroxymethyl-1-phospha-2,6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane;

β-(5-tertiary butyl 4-hydroxy-3-methyl phenyl) propionic acid and single-or polyvalent alcohol, as with methyl alcohol, ethanol, the n-octanol, isooctyl alcohol (mixture of octanol), stearyl alcohol, 1,6-hexane diol, 1,9-nonane glycol, ethylene glycol, 1, the 2-propane diol, dimethyltrimethylene glycol, thio-diethylene glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl)-chlorinated isocyanurates, N, N '-two (hydroxyethyl) oxamide, 3-thiophene undecyl alcohol, 3-thiophene pentadecanol, trimethyl cyclohexane glycol, TriMethylolPropane(TMP) or 4-hydroxymethyl-1-phospha-2,6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane;

β-(3,5-dicyclohexyl-4-hydroxy phenyl) propionic acid and single-or polyvalent alcohol, as with methyl alcohol, ethanol, octanol, isooctyl alcohol (mixture of octanol), stearyl alcohol, 1, the 6-hexane diol, 1,9-nonane glycol, ethylene glycol, 1,2-propane diol, dimethyltrimethylene glycol, thio-diethylene glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl)-chlorinated isocyanurates, N, N '-two (hydroxyethyl) oxamide, 3-thiophene undecyl alcohol, 3-thiophene pentadecanol, the trimethyl cyclohexane glycol, TriMethylolPropane(TMP) or 4-hydroxymethyl-1-phospha-2,6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane;

3,5-two-tert-butyl-hydroxy phenyl acetate and single-or polyvalent alcohol, as with methyl alcohol, ethanol, octanol, isooctyl alcohol (mixture of octanol), stearyl alcohol, 1, the 6-hexane diol, 1,9-nonane glycol, ethylene glycol, 1,2-propane diol, dimethyltrimethylene glycol, thio-diethylene glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) chlorinated isocyanurates, N, N '-two (hydroxyethyl) oxamide, 3-thiophene undecyl alcohol, 3-thiophene pentadecanol, the trimethyl cyclohexane glycol, TriMethylolPropane(TMP) or 4-hydroxymethyl-1-phospha-2,6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane; With

The acid amides such as the N of β-(3,5-two-tertiary butyl 4-hydroxy phenyl) propionic acid, N '-two (3; 5-two-tert-butyl-hydroxy phenyl propionyl) hexa-methylene diamide; N, N '-two (3,5-two-tert-butyl-hydroxy phenyl-propionyl) trimethylene diamide; N; N '-two (3,5-two-tert-butyl-hydroxy phenyl propionyl) hydrazides or N, N '-two [2-(3-[3; 5-two-tert-butyl-hydroxy phenyl] propionyl oxygen base) ethyl] oxamide (Naugard_XL-1 is supplied with by Uniroyal).

For example, anti-oxidant compounds is a diphenylamine, single-and the mixture of the dialkyl group tertiary butyl/uncle's octyl group-diphenylamine, single-and the mixture of dialkyl group nonyl diphenylamine, phenylenediamine or N, N '-two-sec-butyl-phenylenediamine.

Amount of component b) effective stabilization amount is about 0.05ppm to about 10, and 000ppm weight is based on the weight of fuel composition.Amount of component b for example) amount be about 0.1ppm to about 1000ppm, about 0.2ppm is about 100ppm extremely, or about 0.5ppm about 25ppm extremely.For example, amount of component b) amount be about 0.05ppm to about 1000ppm, about 0.05ppm is about 100ppm extremely, or about 0.05ppm about 25ppm extremely, based on whole fuel formulation.For example, amount of component b) amount is about 0.1ppm to about 10, and 000ppm, about 0.2ppm be to about 10,000ppm, or about 0.5ppm is extremely about 10, and 000ppm is based on the weight of whole fuel formulation.

The ratio of stable nitroxide and antioxidant is for example about 1: 99 to about 95: 5 weight part.For example, the weight ratio of stable nitroxide and antioxidant is about 1: 10 to about 10: 1, about 1: 5 to about 5: 1, and about 1: 3 to about 3: 1, or about 1: 1 weight part.The ratio of stable nitroxide and antioxidant is for example about 1: 4 weight part.

This stabilized composition has excellent filtration capacity.Therefore, provide a kind of method that is used to improve filtration capacity and improves the cetane value of diesel oil fuel, this method comprises that being less than or equal to 50 diesel oil fuel to cetane value adds,

B) significant quantity at least a be selected from cetane improver compound and

C) i) effectively stabilization amount at least a be selected from stable nitroxide compounds compound or

The ii) at least a compound and at least a anti-oxidant compounds that is selected from aromatic amine antioxidant and hindered phenolic antioxidants that is selected from stable nitroxide compounds of effective Synergistically stabilized amount.

Other additives known also can be present in the composition neutralization method of the present invention.Other additive comprises for example dispersion agent, for example the succinimide of alkyl-replacement or succinic diamide and alkyl polyamine; The metal matrix combustion improving agent, as ferrocene, corrosion inhibitor, other antioxidant, as amine-aldehyde products, defoamer, deodorizer, antiwear agents, FLOW IMPROVERS, the anti-sedimentation additive of wax or other operability improving agent, cloud point inhibitor, friction modifiers, solubilizing agent, funcitonal rust-proof agent, detergents lubricants, other thermo-stabilizer, and analogue.The amount of other additive can be that about 5ppm is to about 500ppm weight, based on the weight of whole prescription.

The present invention is by following indefiniteness embodiment explanation.Unless refer else, umber and percentage ratio are the weight meters.

Embodiment

The diesel oil fuel filtration capacity

Filtration capacity is determined according to ASTM methods of test D6468.Diesel fuel sample is heated to 150 degrees centigrade and reaches 90 or 180 minutes under air.Fuel is filtered subsequently, and by the sedimental amount on the measuring reflectance filter paper.The settling of catching on the filter paper is many more, and the reflectivity of filter pad is low more.Too many deposition can be in the use of reality blocking filter.

Following table has provided the result of two kinds of different low sulphur diesel fuels.% reflectivity is at being heated to 150 degrees centigrade of sample determinations that reach 90 minutes.Content is ppm, based on fuel formulation.

Prescription	2-EHN	Compound 1	Compound 2	Compound 3	Blend 1	The % reflectivity
							A B C D E F G H I K L M	0 1500 1500 1500 0 1500 1500 1500 1500 1500 1500 1500	- - 1.4 10.4 - - - - - - - -	- - - - - - 1.0 10.0 - - - -	- - - - - - 1.0 10.0 - -	- - - - - - - - - - 1.0 10.0	94 69 74 78 95 73 74 78 80 84 79 84

2-EHN: nitric acid 2-(ethyl hexyl) ester cetane improver;

Compound 1: sebacic acid two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) ester;

Compound 2:1-oxygen base-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine;

Compound 3:1-oxygen base-4-n-propoxy--2,2,6, the 6-tetramethyl piperidine;

The list of blend 1:14% compound 1,56% weight-and the dialkyl group tertiary butyl/uncle's octyl group-diphenylamine mixture, 30% inertia aromatic solvent (weight).

Prescription A-D uses diesel oil fuel 1. prescription E-M to use diesel oil fuel 2.Two kinds of fuel satisfy ASTM D975 specification (diesel fuel specifications) according to the present invention.

As can be seen, cetane improver obviously reduces the filtration capacity of diesel oil fuel.Even the content of added stable nitroxide compounds is 1ppm, throw out also obviously reduces, and this shows as the increase of surveying of filter pad reflectivity.Therefore, be used in combination separately or with antioxidant by nitro oxide, the tendency that diesel oil fuel forms the soluble material that can stop up fuel filter and circuit descends.

Claims (2)

1. a stabilize diesel fuels composition comprises

A) cetane value is less than or equal to 50 diesel oil fuel;

B) the nitric acid 2-(ethyl hexyl) ester of effective stabilization amount; With

C) i) based on fuel composition weight meter, 0.05-10000ppm at least a two (the 1-oxygen bases-2 that are selected from of weight, 2,6,6-tetramethyl piperidine-4-yl) sebate, 1-oxygen base-4-hydroxyl-2,2,6,6-tetramethyl piperidine and 1-oxygen base-4-just-propoxy--2,2,6, the nitroxide compound of 6-tetramethyl--piperidines; Or

Ii) based on fuel composition weight meter, 0.05-10000ppm at least a two (the 1-oxygen bases-2 that are selected from of weight, 2,6,6-tetramethyl piperidine-4-yl) sebate, 1-oxygen base-4-hydroxyl-2,2,6,6-tetramethyl piperidine and 1-oxygen base-4-positive propoxy-2,2,6,6-tetramethyl--piperidines and at least a list-and the nitroxide compound of the mixture of the dialkyl group tertiary butyl/uncle's octyldiphenylamine.

2. method that is used to improve filtration capacity and improves the cetane value of diesel oil fuel, this method comprise to cetane value be less than or equal to 50 diesel oil fuel add effective stabilization amount nitric acid 2-(ethyl hexyl) ester and

I) based on fuel composition weight meter, 0.05-10000ppm at least a two (the 1-oxygen bases-2 that are selected from of weight, 2,6,6-tetramethyl piperidine-4-yl) sebate, 1-oxygen base-4-hydroxyl-2,2,6,6-tetramethyl piperidine and 1-oxygen base-4-positive propoxy-2,2,6, the nitroxide compound of 6-tetramethyl--piperidines; Or

Ii) based on fuel composition weight meter, 0.05-10000ppm at least a two (the 1-oxygen bases-2 that are selected from of weight, 2,6,6-tetramethyl piperidine-4-yl) sebate, 1-oxygen base-4-hydroxyl-2,2,6,6-tetramethyl piperidine and 1-oxygen base-4-positive propoxy-2,2,6,6-tetramethyl--piperidines and at least a list-and the nitroxide compound of the mixture of the dialkyl group tertiary butyl/uncle's octyldiphenylamine.