CN101987980B - Additive composition and diesel fuel composition as well as method for improving oxidation stability of biodiesel - Google Patents

Abstract

The invention relates to an additive composition and a method for improving the oxidation stability of biodiesel. The additive composition comprises a component (a) and a component (b), wherein the component (a) is an aromatic amine-type antioxidant and/or a hindered phenol antioxidant which is a bisphenol-type antioxidant and/or a polyphenol-type antioxidant containing at least three phenolic hydroxyls in a molecule, and the component (b) is an ammonolysis reaction product between one or more of fatty acids, fatty acyl halide and fatty acid alkyl ester and ammonia and/or amine. The additive also composition selectively contains a component (c) which is a metal passivant. The invention also provides a diesel fuel composition containing the additive composition. The diesel fuel composition provided by the invention has more favorable oxidation stability.

Description

The method of compositions of additives and Dresel fuel compositions and raising oxidation stability of biodiesel

Technical field

The invention relates to a kind of compositions of additives, contain the Dresel fuel compositions of this compositions of additives and improve the method for oxidation stability of biodiesel.

Background technology

Quickening along with diesel oil of vehicle trend in the world wide, the demand of diesel oil can be more and more large, and the raising of day by day exhausted and people's environmental consciousness of petroleum resources, greatly promoted countries in the world to accelerate the exploitation paces of Alternative Diesel Fuel, biofuel has been subject to the attention of various countries with its superior environmental-protecting performance and recyclability.

Biofuel (BD100) claims again fatty acid methyl ester (Fatty Acid Methyl Ester), to make raw material with the greases of the oil plant waterplant such as oil-yielding shrubs fruit, the engineering microalgaes such as the oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistache and animal grease, biodiesel etc., obtaining through transesterification reaction with alcohols (methyl alcohol, ethanol), is a kind of biofuel of cleaning.That biofuel has is renewable, cleaning and safe three advantages, and China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment are had very great strategic importance.And China is a net import of oil state at present, and prospective oil is very limited again, and a large amount of Imported oils threaten to the energy security of China; Therefore, the research of biofuel and production have important realistic meaning to China.

But because raw material and complete processing, the oxidation stability of some biofuel is very poor, using and store and all cause very large difficulty biofuel.The poor biofuel of oxidation stability easily generates following ageing products: 1) insoluble polymer (colloid and greasy filth), and this can cause engine filter net jam and squirt pump coking, and causes smoke evacuation increase, difficulty in starting; 2) soluble polymer, it can form resinous substance in engine, may cause flame-out and difficulty in starting; 3) aging acid, this can cause the engine metal component corrosion; 4) superoxide, this can cause aging the becoming fragile of rubber components and cause fuel leakage etc.

Europe Biodiesel Standards EN 14214:2003, Australian Biodiesel Standards (Draft2003), New Zealand Biodiesel Standards NZS 7500:2005, Brazilian Biodiesel Standards ANP255 (2003), India Biodiesel Standards IS 15607:2005, South Africa Biodiesel Standards SANS1935:2004 and China's diesel-fuel blending with biofuel (BD100) standard GB/T/T20828-2007 all the oxidation stability of regulation biofuel be inductive phase under 110 ℃ to be not less than 6 hours, measuring method is EN 14112:2003.

As everyone knows, petroleum diesel (is the diesel oil of ordinary meaning, herein in order to distinguish mutually with biofuel, the non-hydrocarbon compounds such as alkene, diolefin and the sulfide the special petroleum diesel of introducing), nitride are under the effect of oxygen, generate a series of intermediate oxidation product, and produce insoluble precipitation through condensation.These insoluble particles that generate in the petroleum diesel storage process can have influence on the use properties of fuel, cause filtering system to stop up, and cause the prime the fuel system unit failure; affect oil atomizing; cause incomplete combustion, even in engine, form too much carbon deposit, make spray nozzle clogging.And biofuel is poorer than petroleum diesel owing to oxidation stability, can increase the weight of the problems referred to above after concocting with petroleum diesel.The most significantly performance is that to contain the stability of the blending fuel of biofuel poorer than petroleum diesel.

The problems referred to above can additive solves or alleviation by adding.A kind of mode is to add oxidation inhibitor in the pure biofuel slowing down its oxidation, thereby alleviates the harm of ageing products; Another kind of mode is to petroleum diesel or contains in the blending fuel of biofuel and add stablizer to improve the stability of blending fuel.Stablizer can stop, weakens or disturb each kinds of oxidation reaction, to suppress oil deterioration, improves its stability.

CN1742072A discloses a kind of method that improves storage stability of bio-diesel, the method comprises and is dissolved in 2 of biofuel with containing with what stoste was counted the 15-60 % by weight, the liquid stoste of 4-di-t-butyl hydroxy toluene joins in the biofuel for the treatment of stabilization, until in total solution of biofuel, the concentration of 2,4-di-t-butyl hydroxy toluene reaches the 0.005-2 % by weight.

CN1847368A discloses a kind of method that improves the oxidative stability of biofuel, the method comprises bisphenol type oxidation inhibitor such as 4,4`-methylene radical two [2, the 6-DI-tert-butylphenol compounds], 2,2`-methylene radical two [6-tert-butyl-4-methyl-Phenol] joins with the amount of 10-20000ppm (w/w) and treats in the stable biofuel.

CN1847369A discloses a kind of method that improves the oxidative stability of biofuel, the method comprises that fusing point is less than or equal to 40 ℃ main anti-oxidant to be joined with the amount of 10-20000ppm (w/w) and treat that in the stable biofuel, wherein said main anti-oxidant contains alkylphenol.

US2007/113467A1 discloses a kind of fuel composition with improved oxidative stability, said composition contains biofuel and at least a oxidation inhibitor, described oxidation inhibitor is selected from Tenox PG, 1,2, a kind of in 3-trihydroxybenzene, BHT, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, tocopherol, the quinoline.

Although the oxidation inhibitor that above usefulness is traditional improves the method for oxidation stability of biodiesel certain effect is arranged, consumption is all larger, simultaneously to the stability of the blending fuel that contains biofuel to improve effect also not so good.

Summary of the invention

The objective of the invention is the relatively poor shortcoming of improved stability effect large for the oxidation inhibitor consumption that overcomes above-mentioned prior art and that contain the blending fuel of biofuel, provide a kind of and can improve preferably compositions of additives and contain the Dresel fuel compositions of this compositions of additives and a kind of method that improves oxidation stability of biodiesel is provided of oxidation stability of biodiesel or stability.

The invention provides a kind of compositions of additives, wherein, described compositions of additives contains component a and components b, described component a is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and described hindered phenol type antioxidant is the polyphenol type oxidation inhibitor that contains at least three phenolic hydroxyl groups in bisphenol type oxidation inhibitor and/or the molecule; Described components b is one or more and the ammonolysis reaction product of ammonia and/or amine in lipid acid, fatty carboxylic acid halides, the fatty acid alkyl ester.

The present invention also provides a kind of Dresel fuel compositions, and described Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, described basic diesel oil contains biofuel, and described additive is compositions of additives provided by the invention.

The present invention also provides a kind of method that improves oxidation stability of biodiesel, and the method comprises, in containing the basic diesel oil of biofuel, adds additive, and wherein, described additive is compositions of additives provided by the invention.

Compositions of additives provided by the invention, when cooperating when obtaining Dresel fuel compositions as basic diesel oil with pure biofuel, this Dresel fuel compositions has preferably oxidation stability, the amazing synergistic effect that occurs between component a and the components b, antioxidant effect is well more a lot of than independent use oxidation inhibitor.Components b can be regarded as auxiliary antioxidant, and it can make the effect of oxidation inhibitor unexpectedly greatly strengthen.Therefore, when reaching identical oxidation stability and require, the amount of component a in biodiesel composition can greatly reduce, especially component a especially costliness or component a have in certain toxicity or the corrosive situation, reduced its consumption and had very large meaning.When this compositions of additives with cooperate when obtaining Dresel fuel compositions as basic diesel oil with the blending fuel that contains biofuel, the stability of this Dresel fuel compositions is better.Particularly according to preferred implementation provided by the invention, when described additive contained component a, components b and amount of component b simultaneously, because obvious synergistic effect between each additive, the antioxygen of Dresel fuel compositions provided by the invention obviously improved.

Embodiment

In Dresel fuel compositions provided by the invention, the content of described additive can be selected in a big way, and for example the content with respect to basic diesel oil can be 50-10000ppm, preferred 80-8000ppm, more preferably 100-5000ppm.

The weight ratio of described components b and component a can be 0.01-100: 1, be preferably 0.02-50: and 1,0.05-10 more preferably: 1, further be preferably 0.2-5: 1.

Component a

Described component a is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, described arylamine type oxidation inhibitor can be selected from least a in the quinoline of Ursol D, replacement of pentanoic, the replacement of naphthylamines, the replacement of replacement, and described hindered phenol type antioxidant is the polyphenol type oxidation inhibitor that contains at least three phenolic hydroxyl groups in bisphenol type oxidation inhibitor and/or the molecule.

The naphthylamines that wherein replaces includes but not limited to one or more in the following material:

Phenyl-a-naphthylamine (oxidation inhibitor T531, antioxidant A);

Phenyl beta naphthylamine (antioxidant d);

N-p-methoxyphenyl alpha-naphthylamine (anti-aging agent 102);

To hydroxyphenyl-beta-naphthylamine (antioxidant D-OH);

Aldol-alpha-naphthylamine (antioxidant A P)

2-hydroxyl-1, two [to (beta-naphthylamine) phenoxy group] propane (anti-aging agent C-49) of 3-;

Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41) of dimethyl;

Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41-ethyl) of diethyl;

2,2 '-two [to (beta-naphthylamine) phenoxy group] diethyl ether (anti-aging agent C-41-ether).

Wherein, the preferred nonox of the naphthylamines of replacement, for example one or more in phenyl-a-naphthylamine, Phenyl beta naphthylamine, the N-p-methoxyphenyl alpha-naphthylamine.Especially preferred phenyl-a-naphthylamine.

The pentanoic that wherein replaces includes but not limited to one or more in the following material:

4,4 '-diamino-diphenylamine (antioxidant A PA);

Right, to '-the dimethoxy pentanoic;

N, N, N ', N '-tetraphenyl diamines methane (anti-aging agent 350);

N, N '-diphenyl ethylene diamine;

N, N '-diphenylprop diamines;

N, N '-di-o-tolyl-ethylene-diamine;

2-hydroxyl-1,3-pair-(to the aniline phenoxy group) propane (anti-aging agent C-47);

2,2 '-two (to the aniline phenoxy group)-diethyl ether (antioxidant H-1);

Two (to aniline-phenoxy group)-silane (anti-aging agent C-1) of dimethyl;

P-isopropoxy-diphenylamine (anti-aging agent ISO);

Right, to '-diisopropoxy pentanoic (antioxidant D ISO);

4,4 '-two (α, α '-dimethyl benzyl) pentanoic (anti-aging agent KY-405);

P-hydroxydiphenylamine (antioxidant A O3920);

Two-(1,1,3,3-tetramethyl-ethyl) pentanoic (anti-aging agent ODA);

4,4 '-dioctyl diphenylamine;

4,4 '-di-iso-octyldiphenylamine;

4,4 '-diheptyl pentanoic;

4,4 '-dinonyldiphenylamine;

Octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines, anti-aging agent OD);

Octyl group/butyl pentanoic (oxidation inhibitor L-57);

Styrenated diphenylamine (antioxidant D FL, DFC-34);

And the mixture of alkylated diphenylamine, wherein alkyl can be heptyl, octyl group, in the nonyl one or more, the example of its Industrial products has U.S. Pennwalt company commodity to be called Pennox A, PennoxA-" S ", American National Instrument polychem company commodity are called Wytox ADP, ADP-X, U.S. Vanderbilt company commodity are called Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, U.S. Uniroyal company commodity are called Polylite, Antioxidant 445, and domestic code name is the antioxidant product of T534.

Pentanoic type oxidation inhibitor preferred alkyl diphenylamines that replaces and composition thereof, especially preferred alkyl carbonatoms alkylated diphenylamine between 4-10 and composition thereof, as: 4,4 '-dioctyl diphenylamine, 4,4 '-di-iso-octyldiphenylamine, 4,4 '-diheptyl pentanoic, 4, one or more among 4 '-dinonyldiphenylamine, octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines), octyl group/butyl pentanoic, the commodity oxidation inhibitor T534.

The Ursol D type oxidation inhibitor that wherein replaces comprises but is not limited in the following material one or more:

N phenyl-N '-cyclohexyl Ursol D (antioxidant 4010);

N, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (antioxidant 4020);

N, N '-two-(Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D (anti-aging agent 4030);

N-p-methylphenyl-N '-(1,3-dimethylbutyl) Ursol D (anti-aging agent 4040);

N, N '-diheptyl Ursol D (anti-aging agent 788);

N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);

N-sec.-propyl-N '-p-methylphenyl Ursol D (anti-aging agent methyl 4010NA);

N, N '-di tolyl p phenylenediamine (anti-aging agent PPD-A);

N, N '-diphenyl-para-phenylene diamine (antioxidant H);

N, N '-two-(betanaphthyl) Ursol D (antioxidant D NP);

N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5);

N, N '-dioctyl-p-phenylenediamine (anti-aging agent 88);

N, N '-two-(1-methylheptyl) Ursol D (anti-aging agent 288);

N, N '-two-(1-ethyl-3-methyl amyl) Ursol D (anti-aging agent 8L);

N, N '-two-(Isosorbide-5-Nitrae-dimethylbutyl) Ursol D (anti-aging agent 66);

N-Octyl-N '-diphenyl-para-phenylene diamine (anti-aging agent 688);

N-isobutyl--N '-diphenyl-para-phenylene diamine (anti-aging agent 5L);

N, N '-dimethyl-N, N '-two-(1-first propyl group) Ursol D (anti-aging agent 32);

N-(p-methylphenyl alkylsulfonyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent TPPD);

N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent G-1);

N-(3-anilino phenyl) Methacrylamide;

N-hexyl-N '-diphenyl-para-phenylene diamine;

The preferred dialkyl group Ursol D of Ursol D type oxidation inhibitor that replaces, the dialkyl group Ursol D of preferred alkyl carbonatoms between 4-10 especially, as: N, N '-diheptyl Ursol D; N, N '-di-sec-butyl-p-phenyl enediamine; N, N '-dioctyl-p-phenylenediamine; N, one or more in N '-two-(1-methylheptyl) Ursol D.

The quinoline type oxidation inhibitor of replacement wherein comprises but is not limited to:

6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W);

6-phenyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (anti-aging agent PMQ);

6-dodecyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant D D);

2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD, anti-aging agent 124);

Pentanoic and acetone low-temp reaction product (anti-aging agent BAS);

Pentanoic and acetone high-temperature reaction product (antioxidant BLE);

The reaction product of pentanoic and acetone and aldehyde (anti-aging agent BXA);

The reaction product of Phenyl beta naphthylamine and acetone (antioxidant A PN, antioxidant A M).

The Ursol D type arylamine antioxidant that arylamine antioxidant preferably replaces.

Among the present invention, described bisphenol type oxidation inhibitor is the bis-phenol that is linked to each other and formed by two single phenol, preferably refers to the bisphenol type oxidation inhibitor that is linked to each other by sulphur or carbon atom by two single phenol.The described bisphenol type oxidation inhibitor that is linked to each other by sulphur or carbon atom by two single phenol can be one or more in following:

(1) bis-phenol that is linked to each other by carbon atom

4,4 '-isopropylidene bis-phenol (dihydroxyphenyl propane);

2,2 '-two-(3-methyl-4 hydroxy phenyl) propane (bisphenol-c);

4,4 '-dihydroxybiphenyl (oxidation inhibitor DOD);

4,4 '-dihydroxyl-3,3 ', 5,5 '-four-tertiary butyl biphenyl (oxidation inhibitor 712);

2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol) (oxidation inhibitor bis-phenol 2246);

4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);

2,2 '-methylene radical-two-(4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);

2,2 '-methylene radical-two-(4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);

2,2 '-methylene radical-two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);

2,2 '-methylene radical-two-(6-α-methylbenzyl p-cresol);

4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);

4,4 '-methylene radical-two-(2-TBP) (oxidation inhibitor 702);

2,2 '-ethylidene-two-(4-methyl-6-tert-butylphenol);

4,4 '-ethylidene-two-(2-methyl-6-tert-butylphenol);

4,4 '-ethylidene-two-(2,6 di t butyl phenol);

4,4 '-butylidene-two-(the 6-tertiary butyl-meta-cresol) (oxidation inhibitor BBM, oxidation inhibitor TCA);

4,4 '-isobutylidene-two-(2,6 di t butyl phenol) etc.

(2) bis-phenol that is linked to each other by sulphur atom

4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);

2, and 2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);

4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);

4,4 '-thiobis-(5-methyl-2-TBP);

4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);

2,2 '-thiobis-(4-octyl phenol) etc.

(3) linked to each other by carbon atom but contain heteroatomic bis-phenol

N, N '-hexamethylene is two-(3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) (oxidation inhibitor 1098);

Hexylene glycol two [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 259);

Two-(3,5-di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine (oxidation inhibitor BPP);

Two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S);

2,2 '-sulfurous ethyl glycol two [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 1035);

Triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (oxidation inhibitor 245) etc.

Bisphenol type oxidation inhibitor is preferably by two bis-phenols that have at least the single phenol of a tertiary butyl at the phenolic hydroxyl group ortho position to link to each other by methylene radical or sulphur, for example one or more in the following substances:

2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol) (antioxidant 2246);

4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);

4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);

4,4 '-methylene radical-two-(2-TBP) (oxidation inhibitor 702);

4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);

2, and 2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);

4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);

4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);

Two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.

Described polyphenol type oxidation inhibitor refers to contain in the same phenol type antioxidant molecule phenol of a plurality of phenolic hydroxyl groups, the number of phenolic hydroxyl group is more than three or three, a plurality of phenolic hydroxyl groups can be positioned on the same phenyl ring, also can be positioned on the different phenyl ring, the preferred described polyphenol type oxidation inhibitor of the present invention is to contain the macromole oxidation inhibitor that at least three single phenolic group are rolled into a ball in the molecule, namely contain at least three phenyl ring in a phenol type antioxidant, and have at least on three phenyl ring and have separately at least one phenolic hydroxyl group, preferred described polyphenol type oxidation inhibitor is served as reasons and is had at least a tertiary butyl to roll into a ball the polyphenol that forms at single phenolic group at phenolic hydroxyl group ortho position, especially preferably have two tertiary butyls in the polyphenol that is obstructed at phenolic hydroxyl group ortho position, for example one or more in the following substances:

1,3,5-trimethylammonium-2,4,6-three-(4 '-hydroxyl-3 ', 5 '-di-t-butyl) benzene (antioxidant 330);

Three [2-(3,5-di-tert-butyl-hydroxy phenyl) propionyl oxygen ethyl] isocyanic ester (oxidation inhibitor 3125);

Four (3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester (antioxidant 1010);

1,3,5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) (antioxidant 3114);

1,1,3-three-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA);

1,3,5-three (2, the 6-dimethyl-4-tertiary butyl-3-hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) (oxidation inhibitor 1790);

Two [3,3-pair-(3 '-tertiary butyl-4 '-hydroxybenzyl) butyric acid] glycol ester etc.

The polyphenol here can also be in the phenyl ring with the phenol of three hydroxyls, such as pyrogallol, gallic acid ester such as methyl gallate, Progallin A, Tenox PG, butyl gallate, gallic acid pentyl ester, the own ester of gallic acid, gallic acid heptyl ester, Stabilizer GA 8, gallic acid ester in the ninth of the ten Heavenly Stems, gallic acid ester in the last of the ten Heavenly stems, lauryl gallate, gallic acid 14 esters, gallic acid hexadecyl ester, gallic acid octadecyl ester, gallic acid octadecylene ester etc.; And the disclosed gallamide of CN200810115581.8 or ammonia salt.The esterification products of the preferred gallic acid-derivate of polyphenol type oxidation inhibitor such as gallic acid is Tenox PG especially.

The bisphenol type oxidation inhibitor that phenol type antioxidant of the present invention is preferably linked to each other by sulphur or carbon atom by two single phenol and one or more in the polyphenol that is obstructed at phenolic hydroxyl group ortho position of two tertiary butyls are arranged.The present invention most preferably described phenol type antioxidant is selected from 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-TBP), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2, the 6-DI-tert-butylphenol compounds), in two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.

Component a can also be the composite antioxidant of described phenol type antioxidant and arylamine type oxidation inhibitor, and the weight ratio of described phenol type antioxidant and arylamine type oxidation inhibitor is preferably 0-10: 1, and 0.2-5 more preferably: 1.

Among the present invention, most preferably described component a is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-TBP), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2, the 6-DI-tert-butylphenol compounds), in two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.

Components b

Described components b is one or more and the ammonolysis reaction product of ammonia and/or amine in lipid acid, fatty carboxylic acid halides, the fatty acid alkyl ester, further preferably one or more in organic unary fatty acid, fatty carboxylic acid halides, the fatty acid alkyl ester and the ammonolysis reaction product of ammonia and/or amine.Described ammonolysis reaction refers to the reaction that one or more and ammonia in lipid acid, fatty carboxylic acid halides, the fatty acid alkyl ester and/or amine generation metathesis obtain acid amides.Above-mentioned reaction product can without separation and purification directly as described components b, also can only be used as components b with amidate wherein behind the separating-purifying.If do not separate purification, the main component of this mixture is amidate, usually also contains the unreacted raw material of part and other reaction product such as ammonium salt or alcohol etc., specifically forms the visual response condition different and slightly different.

Amidate of the present invention can be commercially available, and also can be obtained by various known amidate action, for example can be by the ester shown in the acid shown in the B1 or the B2 and the ammonia shown in the B3 and/or amine with mol ratio 1: (0.5-2) pass through ammonolysis reaction and get.In the described ammonolysis reaction, the stoichiometries or excessive a little such as ammonia or amine and acid, carboxylic acid halides or ester, for example the ammonia shown in the organic monocarboxylic ester shown in the organic monocarboxylic acid shown in the B1 or the B2 and the B3 or amine are with mol ratio 1: (1-2) reaction, the product behind the preferred ammonolysis reaction without separating-purifying directly as components b of the present invention.

R is that carbonatoms is the alkyl of 6-40 among the B1, and preferred carbonatoms is the alkyl of 8-36.Described " alkyl " refers to hydrocarbon substituent, i.e. aliphatics, alicyclic, aromatics and heterocyclic substituent.Aliphatic alkyl can be saturated also can be the alkyl of the two keys of undersaturated band or triple bond.Be B1 can be lipid acid, naphthenic acid, aromatic acid, with substituent aromatic acid, preferred fatty acid can be monoprotic acid, also can be polyprotonic acid such as diprotic acid.Described acid can be a kind of acid, also can be mixing acid, a kind of and multiple as in various vegetable fatty acids such as palmitinic acid, soybean oleic acid, arachic acid, vegetable seed oleic acid, the tall oil acid preferably is a kind of and multiple in liquid acid such as oleic acid, linolic acid, linolenic acid, dimerization oleic acid, linoleic acid dimer, industrial dimeracid, soybean oleic acid, arachic acid, vegetable seed oleic acid, ricinolic acid, the tall oil acid under the normal temperature.The Whitfield's ointment that replaces such as the phenylformic acid that replaces and/or alkyl with substituent aromatic acid etc.Lipid acid of the present invention is C6～C40 lipid acid, preferred caproic acid, hexanodioic acid, sad, isocaprylic acid (2 ethyl hexanoic acid), capric acid, laurostearic acid, TETRADECONIC ACID, palmitic acid (Palmiticacid), stearic acid (stearic acid), oleic acid, linolic acid, linolenic acid, ricinoleate acid, eicosenoic acid, 20 acid, erucic acid, docosenoic acid, dimeracid (oleic acid and/or linoleic dimer), oleic acid, linolic acid, linolenic acid, dimerization oleic acid, linoleic acid dimer, the industry dimeracid, soybean oleic acid, arachic acid, vegetable seed oleic acid, ricinolic acid, in the tall oil acid one or more.

R ' is the alkyl of 1-5 for carbonatoms among the B2, preferable methyl, ethyl, propyl group or sec.-propyl.B2 is the carboxylate of the described acid of B1, and preferred B2 is methyl esters compound of the described acid of B1 and composition thereof, and especially preferred B2 is biofuel.

For the ammonia shown in the B3 and/or amine: R ₁, R ₂The H that can respectively do for oneself, or one of them is that carbonatoms is the alkyl of 1-30 or is with heteroatomic group at least.

(1) R ₁, R ₂Can be H separately, namely B3 is ammonia.

(2) R ₁, R ₂One of them can be H, and another one can be the alkyl of 1-30 for carbonatoms, can be the alkyl of 1-30 for carbonatoms perhaps, and namely B3 can be primary amine, also can be secondary amine, also can be the mixture of primary amine and secondary amine." alkyl " refers to hydrocarbon substituent, i.e. aliphatics, alicyclic, aromatics and heterocyclic substituent.Aliphatic alkyl can be saturated also can be the alkyl of the two keys of undersaturated band or triple bond.Wherein primary amine can be that carbonatoms is the aliphatic amide of 1-30, also can be that carbonatoms is the arylamine of 6-30, preferred carbonatoms is the aliphatic amide of 1-24, fat primary amine can be the aliphatic amide of straight chain, such as methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, n-dodecylamine (lauryl amine), positive tetradecy lamine, hexadecylamine, octadecyl amine, positive 20 amine, in positive two amino dodecanes one or more, it also can be the fat primary amine with side chain, these fat primary amines with side chain are the various isomer of above-mentioned straight chain fat primary amine, for example Isopropylamine, isobutylamine, TERTIARY BUTYL AMINE, isobutylcarbylamine, neopentyl amine, dissident's amine, tuaminoheptane, octodrine (2 ethyl hexylamine), different nonyl amine, isodecyl amine, different amino dodecane, different tetradecy lamine, different cetylamine, different stearylamine, in different 20 amine one or more.Fat primary amine can also be the amine with cycloaliphatic ring, such as cyclopentamine and/or hexahydroaniline, also can be the fat primary amine that contains unsaturated double-bond or triple bond in the carbochain, such as oleyl amine (octadecenyl amine), palm oleyl amine (hexadecylene amine), can also be the primene JM-T, for example Rohm﹠amp; The trade names that Haas company produces are the primene JM-T of Primere 81R.

If secondary amine, wherein R ₁, R ₂Can be identical, also can be different, preferred can be that carbonatoms is the normal chain alkyl of 1-24 separately, such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl (lauryl), the n-tetradecane base, n-hexadecyl, the Octadecane base, NSC 62789 base or n-docosane base, also can be that carbonatoms with side chain is the isomery alkyl of 1-24, such as sec.-propyl, isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, the Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base or Isoeicosane base.

(3) R ₁, R ₂At least one is that carbonatoms is the heteroatomic group of being with of 1-30.

Here can be to contain carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino group with heteroatomic group.

The amine that contains hydroxyl can be hydramine or amino phenol, for example thanomin, diethanolamine, N-alkyl ethanol amine, N-vinyl-ethyl alcohol amine, N-alkyl α-amino isopropyl alcohol, N-thiazolinyl α-amino isopropyl alcohol, α-amino isopropyl alcohol, diisopropanolamine (DIPA), Tutofusin tris, 3-amino-1, in 2-propylene glycol, 2-amino-1,3-propanediol, 3-aminopropanol, 4-amino-n-butyl alcohol, 5-amino-1-amylalcohol, 6-amino-1-hexanol, the PAP one or more.

R ₁, R ₂At least one is that amido or amino amine are polyamine compounds, and the polyamines here refers to contain in the molecule amine of two or more nitrogen-atoms, is H such as structural formula ₂N-R ₃-NHR ₄Amine, the R here ₃Can be that carbon number is the alkylidene group of 1-30, thiazolinyl, cycloalkyl, aryl or polyether-based etc.; R ₄Can be that hydrogen, carbon number are the alkyl of 1-30.For example quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, decamethylene diamine, coconut oil base 1,3-propylene diamine, oil base 1,3-propylene diamine, tallow base 1,3-propylene diamine.Can also be as shown in the formula the polyether diamine shown in the B4:

Wherein x1 is the integer of 1-5, R ₄Can be that hydrogen, carbon number are the alkyl of 1-30; R ₅Hydrogen or methyl.

Polyamines can also be polyamines polyene, and the structural formula of polyamines polyene is H ₂N[(CH ₂) _X2NH] _Y1R ₆, wherein, x2 can be the integer of 2-4, be preferably 2 or 3, y1 can be the integer of 1-8, R ₆Can be that hydrogen, carbon number are the alkyl of 1-30.For example, work as R ₆During for H, described polyamines polyene can be in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, seven ethene, eight amine, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines, six propylene, seven amine, seven propylene, eight amine one or more.Work as R ₆When being the alkyl of 1-30 for carbonatoms, be preferably the alkyl that carbonatoms is 4-22.This alkyl can be saturated alkyl, also can be with the thiazolinyl of two keys or with the aryl of phenyl ring.Alkyl can be the straight chain normal chain alkyl, also can be the isomery alkyl with side chain, this alkyl can be normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; Isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, one or more in isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and the Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Can be in phenmethyl (benzyl), styroyl and the hydrocinnamyl one or more with the aryl of phenyl ring.Wherein, the more preferably alkyl of C6-C20.

The polyamines here can also be nitrogenous heterocyclic amine, includes but not limited in the amine of imidazoline type, piperazine type and piperidines type one or more.

The imidazoline type polyamines is as shown in the formula shown in the B5:

Wherein y2 is the integer of 0-5, R ₇Be C ₁-C ₂₄Alkyl.Be preferably C ₄-C ₂₂Alkyl.This alkyl can be saturated alkyl, also can be with the thiazolinyl of two keys or with the aryl of phenyl ring.Alkyl can be the straight chain normal chain alkyl, also can be the isomery alkyl with side chain, this alkyl can be normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tetradecane base, n-hexadecyl, the Octadecane base, the NSC 62789 base, the n-docosane base, isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, the Permethyl 99A. base, different tetradecyl, isocetyl, in isooctadecane base and the Isoeicosane base one or more.The example of thiazolinyl comprises 9-octadecylene base.Can be in phenmethyl (benzyl), styroyl and the hydrocinnamyl one or more with the aryl of phenyl ring.Wherein, further preferred y2 is the integer of 1-3, R ₇Be C ₆-C ₂₀Alkyl or alkenyl.

Piperazine type polyamines is as shown in the formula shown in the B6:

R wherein ₈Be the alkyl of H or C1-C24, x3 is the integer of 0-5.Preferred typical piperazine type polyamines is N-(2-amino-ethyl) piperazine.

The polyamines of piperidines type such as 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethyl-piperidines etc.

The polyamines here can also be suc as formula the polyamines that contains tertiary amine shown in B7, the B8.

R wherein ₉, R ₁₀For or the alkyl of C1-C24, x4 is the integer of 0-10.Preferred R ₉, R ₁₀Be the alkyl of C1-C10, x4 is the integer of 1-8.N for example, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dimethyl-Putriscine, N, N-diethyl-Putriscine, N, N-dimethyl-1, one or more in the 6-hexanediamine.

Wherein x5 is the integer of 1-10, is preferably the integer of 2-6, for example three (2-amino-ethyl) amine.

Polyamines can also be that structural formula is H ₂N[(CH ₂) _X2NH] _Y1R ₆Polyamines polyene and the condenses of oxyethane, propylene oxide.Wherein, x2 can be the integer of 2-4, be preferably 2 or 3, y1 can be the integer of 1-8, R ₆Can be that hydrogen, carbon number are the alkyl of 1-30.

The described amine of B3 of the present invention is preferably polyamines, the polyamines that further preferably contains at least one primary amine group, in the amine of especially preferred above-mentioned polyamines polyene, imidazoline type, piperazine type and piperidines type one or more, particularly preferably one or more in polyamines polyene and the piperazine type polyamines.

Preferred ingredient b contains one or more in the following amidate, and wherein the carbonatoms of the carbonyl moiety of acid amides is that 6-40 is preferably 8-36:

NH ₂[(CH ₂) _X2NH] _Y1COC ₇H ₁₅(sad or isocaprylic acid acid amides),

NH ₂[(CH ₂) _X2NH] _Y1COC ₈H ₁₇(n-nonanoic acid acid amides),

NH ₂[(CH ₂) _X2NH] _Y1COC ₉H ₁₉(capric acid acidamide),

NH ₂[(CH ₂) _X2NH] _Y1COC ₁₁H ₂₃(lauric amide),

NH ₂[(CH ₂) _X2NH] _Y1COC ₁₃H ₂₇(Myristic acid amide),

NH ₂[(CH ₂) _X2NH] _Y1COC ₁₅H ₃₁(Palmiticacid acid amides),

NH ₂[(CH ₂) _X2NH] _Y1COC ₁₇H ₃₅(stearic amide),

NH ₂[(CH ₂) _X2NH] _Y1COC ₁₇H ₃₃(amine hydroxybenzene),

NH ₂[(CH ₂) _X2NH] _Y1COC ₁₇H ₃₃O (ricinoleate acid acid amides),

NH ₂[(CH ₂) _X2NH] _Y1COC ₁₇H ₃₁(linolic acid acid amides),

NH ₂[(CH ₂) _X2NH] _Y1COC ₂₁H ₄₁(erucicamide).

Wherein x2 is the integer of 2-4, and y1 is the integer of 2-8, and further preferred x2 is 2, y1 is the integer of 2-5.Namely further preferred described components b contains one or more in the following amidate:

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₇H ₁₅，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₈H ₁₇，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₉H ₁₉，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₁H ₂₃，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₃H ₂₇，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₅H ₃₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₅，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃O，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCOC ₂₁H ₄₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₇H ₁₅，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₈H ₁₇，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₉H ₁₉，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₁H ₂₃，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₃H ₂₇，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₅H ₃₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₅，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃O，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₂₁H ₄₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₇H ₁₅，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₈H ₁₇，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₉H ₁₉，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₁H ₂₃，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₃H ₂₇，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₅H ₃₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₅，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃O，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₂₁H ₄₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₁H ₂₃，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₃H ₂₇，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₅H ₃₁，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₅，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃，

NH ₂CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₁，

(NH ₂CH ₂CH ₂) ₅NHCOC ₁₇H ₃₃O。

Amount of component b

Under the preferable case, compositions of additives provided by the invention also contains amount of component b, described amount of component b can for various can with the metal passivator of metallic surface reaction and/or with the metal chelator of metal or metal ion reaction or combination.The weight ratio of described component a and amount of component b can be 1: 0-1, the weight ratio of preferred described component a and described amount of component b is 1: 0.01-1, more preferably 1: 0.01-0.5 further is preferably 1: 0.02-0.2.

Concrete, described amount of component b can be in 124 Triazole and derivative, thiadiazoles and derivative thereof, oxine, ethylenediamine tetraacetic carboxylic acid, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base (Schiff bases), organic polycarboxylic acid and the derivative thereof one or more.Because this solvability in biofuel of 124 Triazole is very unexcellent, therefore, in order to increase its solvability in biofuel, usually 124 Triazole is carried out modification, modification is mainly by introducing oil-soluble group such as long chain hydrocarbon groups in 124 Triazole.Therefore, described 124 Triazole derivative can be various solvabilities in the biofuel various derivatives good than 124 Triazole itself.Concrete, one or more in the described 124 Triazole derivative product that can be 124 Triazole obtain by mannich reaction with the ammonium salt of aliphatic amide formation and 124 Triazole, formaldehyde and aliphatic amide.Described ethylenediamine tetraacetic carboxylic acid can be ethylenediamine tetraacetic acid (EDTA) (EDTA), and described hydrazides can be N-salicylidene-N '-salicylyl hydrazine and/or N, N '-diacetyl adipyl two hydrazides.Described beta-diketon such as methyl ethyl diketone, described 'beta '-ketoester such as etheric acid monooctyl ester.Described Schiff's base can be N, N '-two salicylidenes-1，2-diaminoethane, N, N '-two salicylidene-1,2-propylene diamine, N, N '-two salicylidene-1,2-cyclohexanediamine, N, one or more in N '-two salicylidenes-N '-methyl two propylene triamines.Described organic polycarboxylic acid and derivative thereof are such as being in citric acid, tartrate, oxysuccinic acid, succsinic acid (Succinic Acid), toxilic acid, phytic acid etc. and the derivative thereof one or more.

Among the present invention, preferred described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction (for example commercial additive of commodity T551 by name), Schiff's base and organic polycarboxylic acid and with the condensation reaction products (being amides, the ester derivative of organic polycarboxylic acid) of aliphatic amide or Fatty Alcohol(C12-C14 and C12-C18) in one or more.

According to using needs, compositions of additives provided by the invention can also contain other additive, such as in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, the emulsion splitter etc. one or more.

The preparation of compositions of additives provided by the invention is simple, and each component that only need form compositions of additives mixes and gets final product.These components can directly be mixed, also can in the presence of solvent, mix, the solvent here can be polar solvent such as N, in dinethylformamide (DMF), Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF) (DHF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidone and the methyl-2-pyrrolidone one or more.Also can be especially aromatic hydrocarbons such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil and composition thereof of hydro carbons, can also be biofuel.

In Dresel fuel compositions provided by the invention, described basic diesel oil can be pure biofuel, and described biofuel refers to that grease and low-carbon alcohol are (such as C ₁-C ₅Fatty Alcohol(C12-C14 and C12-C18)) fatty acid ester of low-carbon alcohol that generates through transesterify (alcoholysis) reaction is generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.

Described trans-esterification processes can be the processing method that any known or unknown transesterification reaction of passing through grease and low-carbon alcohol obtains biofuel, for example acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, etc.Specifically can be with reference to documents such as CN1473907A, DE3444893, CN1472280A, CN1142993C, CN1111591C, CN1594504A.

Described grease has general sense well known in the art, is the general name of oil and fat, and main component is fatty acid triglycercide.General normal temperature is the oil that is called of liquid, and normal temperature is solid or the semisolid fat (abbreviation fat) that is called.Described grease comprises vegetables oil and animal oil, in addition, also comprise from the oil plant in the materials such as microorganism, algae, even can also be waste oil, for example the used grease of acidifying wet goods or the rotten grease of waste cooking oil, sewer oil, swill oil, grease factory.Described vegetables oil can be that herbaceous plant oil also can be xylophyta oil, such as the oil of peanut oil, Semen Maydis oil, Oleum Gossypii semen, rape seed oil, soybean oil, plam oil, Thistle oil, linseed oil, Oleum Cocois, Oak Tree oil, Prunus amygdalus oil, walnut oil, Viscotrol C, sesame oil, sweet oil, Yatall MA (Tall Oil), sunflower oil, curcas oil, tung oil, shinyleaf yellowhorn oil, coptis wood oil, halophytes such as the plants such as kostelezkya virginica, cyperus esculentus.Described animal oil can be lard, chicken fat, duck oil, goose is oily, sheep is oily, house oil, butter, haco oil, shark wet goods.

In biodiesel composition of the present invention, described basic diesel oil also can contain other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contains one or more in the oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is preferably 1: 2-99.

Wherein petroleum diesel refers to boiling range the cut 160-380 ℃ between of crude oil (oil) after the devices such as the various refining process decompression as usual of refinery, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking are processed, and the compression ignition engine fuel that satisfies solar oil standard GB/T 252 or derv fuel oil standard GB/T 19147 that forms through allotment.

The fischer-tropsch combined diesel oil mainly refers to GTL diesel oil (Gas To Liquid) or the CTL diesel oil (Coal To Liquid) produced as raw material funds-Tuo (F-T) synthetic method take Sweet natural gas or coal, can also be vegetable fibre funds-Tuo synthetic method and the BTL diesel oil (Biomass To Liquid) produced.The fischer-tropsch combined diesel oil is substantially free of sulphur and aromatic hydrocarbons, be very clean fuel, but its oilness extreme difference improve greatly with oilness after the biofuel blending, but the possible variation of the oxidation stability of tempered oil, the blending fuel that therefore contains biofuel also needs to add oxidation inhibitor.

The hydrocracking biofuel is also referred to as s-generation biofuel, refer to by animal-plant oil through generate after hydrogenation and the cracking reaction with C ₈-C ₂₄Alkane is main, especially with C ₁₂-C ₂₀Normal paraffin is the reaction product of main component, and this hydrocracking biofuel cetane value is high, and sulphur and aromaticity content are extremely low, can greatly reduce the discharging of diesel engine pollutent as diesel motor fuel or blending component.

Contain oxygen diesel oil blending component and refer to and can be deployed into the oxygenatedchemicals that meets certain code requirement or the mixture of oxygenatedchemicals with various diesel-fuels, normally alcohols and ethers or its mixture, alcohols is C for example ₁-C ₁₈Fatty Alcohol(C12-C14 and C12-C18), preferred C ₁-C ₁₂Unitary fatty alcohol is such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecylenic alcohol, lauryl alcohol and various isomer thereof.Ethers can be dme, methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, C ₆-C ₁₄Fatty alcohol-polyoxyethylene ether, C ₆-C ₁₄Fatty alcohol polyoxypropylene ether, C ₆-C ₁₄Alkylphenol polyoxyethylene, C ₆-C ₁₄Alkylphenol polyethenoxy ether, polyoxymethylene dme (Polyoxymethylene Dimethyl Ethers, CH ₃O (CH ₂O) _xCH ₃, x=1-8) etc. and composition thereof.

Among the present invention, described basic diesel oil is when containing the blending fuel of biofuel, described Dresel fuel compositions can obtain by described additive, biofuel and other diesel oil are directly mixed, and also can first described additive be mixed with biofuel, and then obtain with other diesel oil blending.The various components of additive directly can be mixed with the various compositions of basic diesel oil, also can be first the various components of additive be pre-mixed, obtain mixing with the various compositions of basic diesel oil or basic diesel oil again behind the additive agent mixture.The various components of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various orders.The condition of mixing can be carried out under the various conditions that compositions of additives and Dresel fuel compositions do not caused disadvantageous effect, for example, can mix at ambient temperature.

The method of raising oxidation stability of biodiesel provided by the invention comprises, in containing the diesel component of biofuel, adds additive, and wherein, described additive is above-mentioned compositions of additives provided by the invention.

The present invention is described further for the following examples.

Preparation example 1-6 is used for the preparation of explanation components b.

Preparation example 1

In a 500ml three-necked bottle, add 100g lauric acid (0.5mol) and 56.7g tetraethylene pentamine (0.3mol) heated and stirred to 130 ℃, pass into nitrogen and blow water and reacted 5 hours, tell watery thing 8.5g.By the infrared analysis product, find to have in the reaction product characteristic peak of amide group.This reaction product is directly as components b.

Preparation example 2

With preparation example 1, difference is that tetraethylene pentamine is 141.7g (0.75mol) in the reactant.This reaction product is directly as components b.

Preparation example 3

In a 500ml three-necked bottle, add 141g oleic acid (0.5mol), 77.4gN-(2-amino-ethyl) piperazine (0.3mol) and 150g toluene, heated and stirred reflux water-dividing approximately 6 hours is told watery thing 8.3g, and underpressure distillation is removed toluene and obtained reaction product.By the infrared analysis product, find to have in the reaction product characteristic peak of amide group.This reaction product is directly as components b.

Preparation example 4

In a 250ml three-necked bottle, (acid number is 197mgKOH/g to add the 100g dimeracid, the YH13 type high-purity dimeric acid that Jiangxi Province Yichun Yuanda Chemical Industry Co., Ltd. produces) and 82.0g five ethene hexamines (dimeracid calculated carboxyl and five ethene hexamine mol ratios 1: 1 according to acid number) heated and stirred to 140 ℃, passing into nitrogen blows water and reacts and obtained reaction product in 4 hours.By the infrared analysis product, find to have in the reaction product characteristic peak of amide group.This reaction product is directly as components b.

Preparation example 5

In a 250ml three-necked bottle, (acid number is 190mgKOH/g to add the 100g ready denier oil acid, Arizona company produces) and 59.4g three (2-amino-ethyl) amine (ready denier oil acid calculated carboxyl and three (2-amino-ethyl) amine mol ratio 1: 1.2 according to acid number) heated and stirred to 120 ℃, pass into nitrogen and blow water and react and obtained reaction product in 6 hours.By the infrared analysis product, find to have in the reaction product characteristic peak of amide group.This reaction product is directly as components b.

Preparation example 6

In a 250ml three-necked bottle, add 100g Oleum Gossypii semen biofuel (production of Shijiazhuang refinery branch office of China Petrochemical Industry) and 24.7g triethylene tetramine and 21.8gN-(2-amino-ethyl) piperazine (fatty acid methyl ester of biofuel and triethylene tetramine and N-(2-amino-ethyl) piperazine mol ratio probably is 1: 0.5: 0.5), heated and stirred to 120 ℃ passes into nitrogen and blows the methyl alcohol reaction and obtained reaction product in 8 hours.This reaction product is directly as components b.

Embodiment 1-9

Following examples are used for illustrating the preparation of compositions of additives provided by the invention.

Component a and components b and c are mixed according to the mass ratio shown in the table 1.

Table 1

Embodiment	Component a	Components b	Amount of component b	a∶b∶c
					Embodiment 1	N, N '-di-sec-butyl-p-phenyl enediamine	Preparation example 1	-	2∶1∶0
Embodiment 2	N, N '-di-sec-butyl-p-phenyl enediamine	Preparation example 2	-	2∶1∶0
					Embodiment 3	Anti-aging agent 88	Preparation example 3	-	1∶3∶0
Embodiment 4	Oxidation inhibitor T511	Preparation example 3	-	1∶2∶0
					Embodiment 5	N, N '-di-sec-butyl-p-phenyl enediamine	Preparation example 4	-	1∶1∶0
Embodiment 6	N, N '-di-sec-butyl-p-phenyl enediamine	Preparation example 4	N, N '-two salicylidene-1,2-propylene diamine	1∶1∶0.06
					Embodiment 7	Antioxidant 2246	Preparation example 5	-	3∶1∶0
Embodiment 8	N, N '-dioctyl-p-phenylenediamine+Tenox PG (weight ratio 5: 1)	Preparation example 5	-	3∶1∶0
					Embodiment 9	N, N '-di-sec-butyl-p-phenyl enediamine	Preparation example 6	-	1∶5∶0
Comparative Examples 1	Oxidation inhibitor T501	Preparation example 5	-	3∶1∶0

Performance test

Below in the test, used Oleum Gossypii semen biofuel is the biofuel product that Shijiazhuang refinery branch office of China Petrochemical Industry provides, used sewer oil biofuel provides by the remarkable new forms of energy of Fujian Longyan company limited, and petroleum diesel is the capital mark B diesel oil that Yanshan Mountain branch office of China Petrochemical Industry produces.

(1) pure biofuel is as the oxidation stability test of the biodiesel composition of basic diesel oil

Evaluate oxidation stability of biodiesel the inductive phase under measuring 110 ℃ with EN14112:2003 method (Racimat method), use instrument to be 743 type oil oxidative stability determinators of Switzerland Wan Tong company, wherein, inductive phase is longer to illustrate that then the oxidation-resistance of Dresel fuel compositions is better, otherwise shorter illustrate that then the oxidation-resistance of Dresel fuel compositions is poorer inductive phase.Its test result is shown in Table 2.

Table 2

Data from table 2 can be found out, component a is common oxidation inhibitor, oxidation stability of biodiesel there is certain improvement, components b is used does not separately have antioxidant effect, biodiesel composition of the present invention has obviously better oxidation stability, after component a and components b mating reaction were described, the oxidation stability of biodiesel composition was well more a lot of than the effect sum of independent use component a, components b, this shows to have occurred astoundingly synergy clearly between component a, the b.After optional amount of component b added, effect further strengthened.

Embodiment 1 compares and can find out with embodiment 2, if slightly good in the effect of preparation excessive reaction product of amine during components b.Embodiment 5 compares and can find out with embodiment 6, select optional amount of component b after, the oxidation stability of gained biodiesel composition further strengthens.Embodiment 7 compares and can find out with Comparative Examples 1, and bisphenol type oxidation inhibitor is better than single phenol type antioxidant as the effect of component a.Ursol D type oxidation inhibitor is better than other type oxidation inhibitor as component a effect.Embodiment 8 compares and can find out with Comparative Examples 1, and the successful that component a contains arylamine type oxidation inhibitor is better than only with the situation of phenol type antioxidant as component a.

(2) with the test as the oxidation-resistance of the concocted diesel oil composition of basic diesel oil and stability of the mixture of biofuel and petroleum diesel, used biofuel is the sewer oil biofuel.

Adopt the method for Pr EN15751:2008 to measure respectively each Dresel fuel compositions, petroleum diesel and concocted diesel oil inductive phase under 110 ℃, use instrument to be 743 type oil oxidative stability determinators of Switzerland Wan Tong company, inductive phase is longer to illustrate that then the oxidation-resistance of biodiesel composition is better, otherwise shorter illustrate that then the oxidation-resistance of biodiesel composition is poorer inductive phase.Its test result is shown in Table 3.

The method of employing SH/T 0175 is measured the amount (unit: mg/100mL), thereby evaluate their stability of various concocted diesel oil composition total insoluble substances.The larger then stability of the amount of total insoluble substance is poorer, otherwise if the less then stability of the amount of total insoluble substance is better, its test result is shown in Table 3.

Table 3

Result by table 3 can find out, after the adding biofuel, contains the oxidation stability of the blending fuel of biofuel, stable all variation of comparing with petroleum diesel.The oxidation stability, the stability that contain the biodiesel composition of the present invention that the mixture of component a and components b obtains as additive have significantly to be improved, synergistic effect appears in component a and components b effect, and its effect obviously strengthens than independent Use Limitation fruit.

Claims (22)

1. compositions of additives, it is characterized in that, described compositions of additives contains component a and components b, described component a is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and described hindered phenol type antioxidant is the polyphenol type oxidation inhibitor that contains at least three phenolic hydroxyl groups in bisphenol type oxidation inhibitor and/or the molecule; Described components b is one or more and the ammonolysis reaction product of ammonia and/or amine in lipid acid, fatty carboxylic acid halides, the fatty acid alkyl ester; Described bisphenol type oxidation inhibitor is the bis-phenol that is linked to each other and formed by two single phenol.

2. compositions of additives according to claim 1, wherein, the weight ratio of described components b and component a is 0.01-100:1.

3. compositions of additives according to claim 2, wherein, the weight ratio of described components b and component a is 0.05-10:1.

4. the described compositions of additives of any one according to claim 1-3, wherein, the described arylamine type oxidation inhibitor of component a is selected from least a in the quinoline of Ursol D, replacement of pentanoic, the replacement of naphthylamines, the replacement of replacement.

5. compositions of additives according to claim 4, wherein, the naphthylamines of described replacement is selected from phenyl-a-naphthylamine, Phenyl beta naphthylamine, in N-p-methoxyphenyl-alpha-naphthylamine one or more, the pentanoic that replaces is selected from one or more in the alkylated diphenylamine of alkyl carbon atoms number between 4-10, the Ursol D that replaces is selected from one or more that contain in the dialkyl group Ursol D of alkyl carbon atoms number between 4-10, the quinoline that replaces is selected from 6-oxyethyl group-2,2,4-trimethylammonium-1, the 2-dihyaroquinoline, 6-phenyl-2,2,4-trimethylammonium-1, the 2-dihyaroquinoline, 6-dodecyl-2,2,4-trimethylammonium-1, the 2-dihyaroquinoline, 2,2,4-trimethylammonium-1, one or more in the 2-dihyaroquinoline polymer.

6. compositions of additives according to claim 5, wherein, described arylamine type oxidation inhibitor is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, one or more in N '-two-(1-methylheptyl) Ursol D.

7. the described compositions of additives of any one according to claim 1-3, wherein, the described phenol type antioxidant of component a is selected from the bisphenol type oxidation inhibitor that is linked to each other by sulphur or carbon atom by two single phenol and one or more in the polyphenol that is obstructed at phenolic hydroxyl group ortho position of two tertiary butyls is arranged.

8. compositions of additives according to claim 7, wherein, described phenol type antioxidant is selected from 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-TBP), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.

9. the described compositions of additives of any one according to claim 1-3, wherein, described components b by the fatty acid alkyl ester shown in the lipid acid shown in the B1 and/or the B2 and the ammonia shown in the B3 and/or amine with mol ratio 1:(0.5-2) get by ammonolysis reaction:

Wherein, R is that carbonatoms is the alkyl of 6-40, and R ' is the alkyl of 1-5 for carbonatoms, and the total carbon atom number of R and R ' is 6-40 among the formula B2, R ₁, R ₂The H that respectively does for oneself, or one of them is the alkyl of 1-30 for carbonatoms or is with heteroatomic group, and described is to contain carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino group with heteroatomic group.

10. compositions of additives according to claim 9, wherein, the amine shown in the formula B3 is one or more in the following amine:

Methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, n-dodecylamine, positive tetradecy lamine, hexadecylamine, octadecyl amine, positive 20 amine, positive two amino dodecanes, Isopropylamine, isobutylamine, TERTIARY BUTYL AMINE, isobutylcarbylamine, neopentyl amine, dissident's amine, tuaminoheptane, octodrine, different nonyl amine, isodecyl amine, different amino dodecane, different tetradecy lamine, different cetylamine, different stearylamine, different 20 amine, cyclopentamine, hexahydroaniline, oleyl amine, the palm oleyl amine, the primene JM-T; R ₁, R ₂The methyl of respectively doing for oneself, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tetradecane base, n-hexadecyl, the Octadecane base, the NSC 62789 base, the n-docosane base, sec.-propyl, isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl, different nonyl, isodecyl, the Permethyl 99A. base, different tetradecyl, isocetyl, the secondary amine of isooctadecane base or Isoeicosane base; Thanomin, diethanolamine, N-alkyl ethanol amine, N-vinyl-ethyl alcohol amine, N-alkyl α-amino isopropyl alcohol, N-thiazolinyl α-amino isopropyl alcohol, α-amino isopropyl alcohol, diisopropanolamine (DIPA), Tutofusin tris, 3-amino-1,2-propylene glycol, 2-amino-1,3-propanediol, 3-aminopropanol, 4-amino-n-butyl alcohol, 5-amino-1-amylalcohol, 6-amino-1-hexanol, PAP; Structural formula is H ₂N-R ₃-NHR ₄Amine, R ₃Be alkylidene group, thiazolinyl, cycloalkyl, aryl or the polyether-based of 1-30 for carbon number; Polyether diamine shown in the formula B4:

Wherein x1 is the integer of 1-5, R ₄For hydrogen or carbon number are the alkyl of 1-30, R ₅Hydrogen or methyl; Structural formula is H ₂N[(CH ₂) _X2NH] _Y1R ₆Polyamines polyene and/or the condenses of this polyamines polyene and oxyethane and/or propylene oxide, wherein x2 is the integer of 2-4, y1 is the integer of 1-8, R ₆For hydrogen or carbon number are the alkyl of 1-30; Imidazoline type polyamines shown in the following formula B5; Piperazine type polyamines shown in the following formula B6; The polyamines that contains tertiary amine shown in formula B7 or the formula B8;

Wherein y2 is the integer of 0-5, R ₇Be C ₁-C ₂₄Alkyl;

R wherein ₈Be the alkyl of H or C1-C24, x3 is the integer of 0-5;

R ₉, R ₁₀For or the alkyl of C1-C24, x4 is the integer of 0-10;

Wherein x5 is the integer of 1-10.

11. compositions of additives according to claim 10, wherein, described structural formula is H ₂N[(CH ₂) _X2NH] _Y1R ₆Polyamines polyene be in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, seven ethene, eight amine, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines, six propylene, seven amine, seven propylene, eight amine one or more, perhaps be R ₆Be normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; In the polyamines polyene of isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl, different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base, Isoeicosane base, 9-octadecylene base, phenmethyl, styroyl or hydrocinnamyl one or more; Among the formula B5, y2 is the integer of 1-3, R ₇Be C ₆-C ₂₀Alkyl or alkenyl; Piperazine type polyamines shown in the formula B6 is N-(2-amino-ethyl) piperazine, and described piperidines type polyamines is 4-amino-2,2,6,6-tetramethyl piperidine and/or 4-amino-1,2,2,6,6-pentamethyl-piperidines, the polyamines that contains tertiary amine shown in the formula B7 is N, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-Putriscine, N, N-dimethyl-1, in the 6-hexanediamine one or more, the polyamines that contains tertiary amine shown in the formula B8 are three (2-amino-ethyl) amine.

12. compositions of additives according to claim 11, wherein, described components b contains one or more in the following amidate:

NH ₂[(CH ₂) _x2NH] _y1COC ₇H ₁₅，

NH ₂[(CH ₂) _x2NH] _y1COC ₈H ₁₇，

NH ₂[(CH ₂) _x2NH] _y1COC ₉H ₁₉，

NH ₂[(CH ₂) _x2NH] _y1COC ₁₁H ₂₃，

NH ₂[(CH ₂) _x2NH] _y1COC ₁₃H ₂₇，

NH ₂[(CH ₂) _x2NH] _y1COC ₁₅H ₃₁，

NH ₂[(CH ₂) _x2NH] _y1COC ₁₇H ₃₅，

NH ₂[(CH ₂) _x2NH] _y1COC ₁₇H ₃₃，

NH ₂[(CH ₂) _x2NH] _y1COC ₁₇H ₃₃O，

NH ₂[(CH ₂) _x2NH] _y1COC ₁₇H ₃₁，

NH ₂[(CH ₂) _x2NH] _y1COC ₂₁H ₄₁。

Wherein x2 is the integer of 2-4, and y1 is the integer of 2-8.

13. compositions of additives according to claim 12, wherein, x2 is 2, y1 is the integer of 2-5.

14. the described compositions of additives of any one according to claim 1-3, wherein, described compositions of additives also contains amount of component b, described amount of component b be can with the metal passivator of metallic surface reaction and/or with the metal chelator of metal or metal ion reaction or combination.

15. compositions of additives according to claim 14, wherein, the weight ratio of described component a and described amount of component b is 1:0.01-1.

16. compositions of additives according to claim 15, wherein, described amount of component b is 124 Triazole, the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction, one or more in Schiff's base and the organic polycarboxylic acid.

17. a Dresel fuel compositions, described Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, described basic diesel oil contains biofuel, and described additive is the described compositions of additives of any one among the claim 1-16.

18. biodiesel composition according to claim 17, wherein, described additive is 50-10000ppm with respect to the content of described basic diesel oil.

19. according to claim 17 or 18 described Dresel fuel compositions, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contains one or more in the oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is 1:0-99.

20. a method that improves oxidation stability of biodiesel, the method comprise, in containing the basic diesel oil of biofuel, add additive, it is characterized in that, described additive is the described compositions of additives of any one among the claim 1-16.

21. method according to claim 20, wherein, described additive is 50-10000ppm with respect to the content of basic diesel oil.

22. according to claim 20 or 21 described methods, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contains one or more in the oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is 1:0-99.