CN102453553B - Diesel composition and method for improving oxidation stability of biodiesel - Google Patents

Abstract

The invention provides a diesel composition, which comprises base diesel and additives, wherein the base diesel comprises biodiesel, the additives comprise ingredients a, the ingredients a comprise polymers of unsaturated dicarboxylic acid and one kind or several kinds of amides from anhydride, monoester and diester of the unsaturated dicarboxylic acid, the additives also optionally comprise ingredients b and/or ingredients c, the ingredients b are arylamine antioxidants and/or hindered phenol antioxidants, and the ingredients c are metal passivators. The invention also provides a method for improving the oxidation stability of the biodiesel. According to the diesel composition provided by the invention, when using pure biodiesel as the base diesel, the diesel composition has good oxidation stability and low-temperature flowability; and when using mixed fuel containing the biodiesel as the base diesel, the diesel composition has good stability and low-temperature flowability.

Description

A kind of method of Dresel fuel compositions and raising oxidation stability of biodiesel

Technical field

The invention relates to a kind of method of Dresel fuel compositions and raising oxidation stability of biodiesel.

Background technology

Along with the quickening of diesel oil of vehicle trend in 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, clean and safe three advantages, and China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment are had to very great strategic importance.And China is a net import of oil state at present, 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 due to raw material and complete processing, the oxidation stability of some biofuel is very poor, using and storing 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 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 at 110 DEG C 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 special petroleum diesel of introducing) in the non-hydrocarbon compound such as alkene, diolefin and sulfide, nitride under the effect of oxygen, generate a series of intermediate oxidation product, and produce insoluble precipitation through condensation.These insoluble particles that generate in petroleum diesel storage process can have influence on the use properties of fuel, cause filtering system to stop up, and cause 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 because oxidation stability is poorer than petroleum diesel, after concocting with petroleum diesel, can increase the weight of the problems referred to above.The most obvious performance is poorer than petroleum diesel containing stability and the detergent-dispersant performance of the blending fuel of biofuel.

The problems referred to above can be by adding additive to solve or alleviating.Mode is in pure biofuel, to add oxidation inhibitor to slow down its oxidation, thereby alleviates the harm of ageing products; Another kind of mode is to add stablizer and detergent-dispersant additive to petroleum diesel or containing in the blending fuel of biofuel, to improve stability and the detergent-dispersant performance of blending fuel.Stablizer can stop, weakens or disturb each kinds of oxidation reaction, to suppress oil deterioration, improves its stability; Detergent-dispersant additive can wash down established carbon deposit on nozzle, and forms protective membrane at nozzle surface, prevents that new carbon deposit from producing, and also dispersibles established sediment in oil simultaneously, improves purifier and spray nozzle clogging, and improves exhaust emissions.

CN 1742072A discloses a kind of method that improves storage stability of bio-diesel, the method comprise by contain count 15-60 % by weight with stoste be dissolved in 2 of biofuel, 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 0.005-2 % by weight.

CN 1847368A discloses a kind of method of the oxidative stability that improves biofuel, the method comprises bisphenol type oxidation inhibitor as 4,4`-methylene radical two [2,6-DI-tert-butylphenol compounds], 2,2`-methylene radical two [6-tert-butyl-4-methyl-Phenol] joins and treats in stable biofuel with the amount of 10-20000ppm (w/w).

CN 1847369A discloses a kind of method of the oxidative stability that improves biofuel, the method comprises that fusing point is less than or equal to the main anti-oxidant of 40 DEG C to be joined and treat that, in stable biofuel, wherein said main anti-oxidant contains alkylphenol with the amount of 10-20000ppm (w/w).

US 2007/113467A1 discloses a kind of fuel composition with improved oxidative stability, said composition contains biofuel and at least one oxidation inhibitor, described oxidation inhibitor is selected from Tenox PG, 1,2, one in 3-trihydroxybenzene, BHT, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, tocopherol, quinoline.

CN101058774A discloses the reaction product of succinic acylating agent that a kind of alkyl replaces and polyalkylene amine optionally with 2; being combined in of 5-di-tert-butyl hydroquinone prevents or postpones the purposes in liquid composition oxidation, the oil of the plant-derived or animal that wherein said liquid composition contains at least 2 % by weight.

Although more than have certain effect by the method that traditional oxidation inhibitor improves oxidation stability of biodiesel, but the oxidation stability for pure biofuel basis diesel oil improves DeGrain, for the stability of the blending fuel of biofuel and other diesel oil to improve effect also not so good.

Summary of the invention

The object of the invention is the poor and shortcoming taking the blending fuel of biofuel and other diesel oil as the less stable of the Dresel fuel compositions of basic diesel oil of the oxidation stability of the Dresel fuel compositions taking pure biofuel as basic diesel oil in order to overcome above-mentioned prior art, the Dresel fuel compositions that a kind of oxidation stability or stability are better and low-temperature fluidity is good is provided and a kind of method that improves oxidation stability of biodiesel is provided.

The invention provides a kind of Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, wherein, described basic diesel oil contains biofuel, described additive contains component a, and described component a contains one or more the polymkeric substance of aminate in unsaturated dicarboxylic acid and acid anhydrides, half ester and dibasic acid esters.

The present invention also provides a kind of method that improves oxidation stability of biodiesel simultaneously, the method comprises, in the basic diesel oil that contains biofuel, add additive, described additive contains component a, and the component a of described additive contains one or more the polymkeric substance of aminate in unsaturated dicarboxylic acid and acid anhydrides, half ester and dibasic acid esters.

Dresel fuel compositions provided by the invention, when using pure biofuel as basic diesel oil, this Dresel fuel compositions has good oxidation stability, and when the blending fuel to contain biofuel is during as basic diesel oil, the stability of this Dresel fuel compositions is better.And the low-temperature fluidity of Dresel fuel compositions provided by the invention has also obviously improved.Particularly according to preferred implementation provided by the invention, in the time that described additive contains component a, components b and amount of component b simultaneously, due to the amazing synergistic effect that occurs between each additive, antioxidant effect is well a lot of during than independent use said components a, b or c.Mix with components b and/or amount of component b at component a while use, component a can be regarded as auxiliary antioxidant, and it can make the effect of oxidation inhibitor unexpectedly greatly strengthen.Therefore,, in the time reaching identical oxidation stability and require, the amount of components b in biodiesel composition can greatly reduce, and especially has in certain toxicity or corrosive situation in components b especially costliness or components b, reduced its consumption and had very large meaning.

Embodiment

According in Dresel fuel compositions provided by the invention, the content of described additive can be selected in a big way, for example, can be 50-12000ppm with respect to the content of basic diesel oil, is preferably 100-8000ppm.

Component a

The equal relative molecular weight of number of described component a can be 500-100000, is preferably 1000-50000.

In the present invention, described " containing one or more the polymkeric substance of aminate in unsaturated dicarboxylic acid and acid anhydrides thereof, half ester and dibasic acid esters " refer to by one or more in the acid anhydrides of unsaturated dicarboxylic acid, unsaturated dicarboxylic acid and the half ester of unsaturated dicarboxylic acid and carry out the multipolymer of polyreaction with the ammonia of contain-NH functional group and/or organic amine generation condensation reaction (also claim the ammonia (amine) of carboxylic acid derivative to separate react or ammonia (amine) change react) and with other unsaturated monomer.Can first there is condensation reaction, also can first polymerization reaction take place, can also be simultaneously by unsaturated dicarboxylic acid and acid anhydrides, half ester and dibasic acid esters one or more, the ammonia of contain-NH functional group and/or organic amine and other unsaturated monomer be placed in same reactor and react.Product of each reaction gained can separate or be directly used in next step reaction or directly as component a after separating.Therefore, in the not separated situation of each step gained reaction product, described component a conventionally contain in solvent, unsaturated dicarboxylic acid and acid anhydrides thereof, half ester and dibasic acid esters, dibasic acid esters one or more homopolymer and/or the aminate of multipolymer, the homopolymer of other unsaturated monomer and/or multipolymer, one or more and other homopolymer of unsaturated monomer and/or the aminate of multipolymer in unsaturated dicarboxylic acid and acid anhydrides thereof, half ester and dibasic acid esters, dibasic acid esters.

Carboxylic acid in " one or more in unsaturated dicarboxylic acid and acid anhydrides thereof, half ester and dibasic acid esters, dibasic acid esters " is preferably the di-carboxylic acid containing unsaturated link(age) that carbonatoms is 4-10, can be for example one or more in toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, be preferably toxilic acid and/or fumaric acid; The acid anhydrides of unsaturated dicarboxylic acid is preferably the acid anhydrides that above-mentioned carbonatoms is the dehydration of the di-carboxylic acid containing the unsaturated link(age) formation of 4-10, for example, can be one or more in maleic anhydride, itaconic anhydride, citraconic anhydride, preferably maleic anhydride; Unsaturated dicarboxylic acid half ester can be that above-mentioned carbonatoms is the partial esterification thing of the fatty alcohol that is 1-10 containing the di-carboxylic acid of unsaturated link(age) and/or acid anhydrides and the preferred carbonatoms of alcohol of 4-10, the carbonatoms that is described unsaturated dicarboxylic acid half ester is preferably 5-20, more preferably 5-10, is particularly preferably one or more in monomethyl maleate, ethyl maleate, monomethyl fumarate, monomethyl ester, monomethyl itaconate, methylene-succinic acid mono ethyl ester, citraconic acid mono-methyl, citraconic acid mono ethyl ester.Unsaturated dicarboxylic acid dibasic acid esters can be that above-mentioned carbonatoms is the dibasic acid esters compound of the di-carboxylic acid containing unsaturated link(age) and/or acid anhydrides and the fatty alcohol that preferably carbonatoms is 1-10 of 4-10, is preferably one or more in dimethyl maleate, ethyl maleate, dimethyl fumarate, DEF, dimethyl itaconate, diethyl itaconate, citraconic acid dimethyl ester, citraconic acid diethyl ester.

The ammonia of one or more in unsaturated dicarboxylic acid, acid anhydrides, half ester and dibasic acid esters, dibasic acid esters and contain-NH functional group and/or organic amine react and can obtain one or more in ammonium salt, acid amides and imide.

The polyamine compounds of preferably contain-NH of ammonia and/or the organic amine functional group of described containing-NH functional group, the polyamines here refers to the amine that contains two or more nitrogen-atoms in molecule, if structural formula is R ₁hN-R ₂-NHR ₃amine, the R here ₁and R ₃can be the alkyl that hydrogen, carbon number are 1-30, R ₂can be that carbon number is the alkylidene group of 1-30, thiazolinyl, cycloalkyl, aryl or polyether-based etc.; " alkyl " refers to hydrocarbon substituent, i.e. one or more in aliphatics, alicyclic, aromatics and cyclic substituent.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, one or more in 3-propylene diamine.Can also be as shown in the formula the polyether diamine shown in 1:

Wherein x1 is mean polymerisation degree, is 1-50, R ₄it can be the alkyl that hydrogen, carbon number are 1-30; R ₅hydrogen or methyl.It is for No. CAS for example the polyetheramine that 9046-10-0, number-average molecular weight are 400.

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 ₆it can be the alkyl that hydrogen, carbon number are 1-30.For example, work as R ₆during for H, described polyamines polyene can be 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 and five propylene hexamines, six propylene seven amine, seven propylene eight amine and N-(2-amino-ethyl)-1, one or more in 3-propylene diamine.When R6 is carbon number while being the alkyl of 1-30, be preferably the alkyl of C4-C22.This alkyl can be saturated alkyl, can be also with the thiazolinyl of two keys or with the aryl of phenyl ring.Alkyl can be straight chain normal chain alkyl, also can be the isomery alkyl with side chain, the example of this alkyl comprises 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, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Example with the aryl of phenyl ring comprises phenmethyl (benzyl), styroyl and hydrocinnamyl.Wherein, the more preferably alkyl of C6-C20.

The polyamines here can also be the amine of nitrogenous heterocyclic amine such as but not limited to imidazoline type, piperazine type and piperidines type.

Imidazoline type polyamines is as shown in the formula shown in 2:

Wherein y2 is 0 to 5 integer, R ₇for C ₁-C ₂₄alkyl.Be preferably C ₄-C ₂₂alkyl.This alkyl can be saturated alkyl, can be also with the thiazolinyl of two keys or with the aryl of phenyl ring.Alkyl can be straight chain normal chain alkyl, also can be the isomery alkyl with side chain, the example of this alkyl comprises 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, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Example with the aryl of phenyl ring comprises phenmethyl (benzyl), styroyl and hydrocinnamyl.Wherein, the integer that further preferably y2 is 1-3, R ₇for C ₆-C ₂₀alkyl or alkenyl.

Piperazine type polyamines is as shown in the formula shown in 3:

Wherein R ₈for the alkyl of H or C1-C24, x3 is 0 to 5 integer.Preferably typical piperazine type polyamines is N-(2-amino-ethyl) piperazine.

The polyamines of piperidines type is as 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethyl-piperidines, 1-(2-aminoethyl) piperidines etc.

The polyamines here can also be suc as formula the polyamines containing tertiary amine shown in 4,5 and 6.

Wherein R ₉, R ₁₀for the alkyl of C1-C24, x4 is 0 to 10 integer.Preferably R ₉, R ₁₀for the alkyl of C1-C10, x4 is 1 to 8 integer.For example 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-1,6-hexanediamine, 3-diethyl amino propylamine (DEAPA), 3-dimethylaminopropylamine (DMAPA), 3-(dibutylamino) propylamine (CAS 102-83-0) etc.

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

Wherein R ₁₁for the alkyl of C1-C24, x6 is 1 to 10 integer, is preferably 2 to 6 integer, for example N, two (3-aminopropyl) methylamines of N-.

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 ₆it can be the alkyl that hydrogen, carbon number are 1-30.

Organic amine of the present invention, except containing above-mentioned polyamines, also can contain monoamine again.The monoamine here can be primary amine, can be also secondary amine.Preferably primary amine.Can be that carbonatoms is the aliphatic amide of 1-30, also can be that carbonatoms is the arylamine of 1-30, preferred fat amine, it in fat primary amine, can be the aliphatic amide of straight chain, 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, positive two amino dodecanes and composition thereof, also can be the fat primary amine with side chain, these fat primary amines with side chain are 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, different 20 amine and composition thereof.Fat primary amine can also be that amine with cycloaliphatic ring is as cyclopentamine, hexahydroaniline.Also can be in carbochain, contain unsaturated double-bond or triple bond fat primary amine as oleyl amine (octadecenyl amine), palm oleyl amine (hexadecylene amine), can also be the primene JM-T, the trade names that for example Rohm & Haas company produces be the primene JM-T of Primere 81R.

The organic amine reacting with unsaturated dicarboxylic acid, acid anhydrides or half ester, dibasic acid esters of the present invention preferably contains polyamines, further preferably containing the polyamines of at least one primary amine group, and especially preferred polyamines polyene.

Described other unsaturated monomer can be various can with above-mentioned unsaturated dicarboxylic acid, acid anhydrides, other monomer of unsaturated link(age) generation copolyreaction in one or more in half ester and dibasic acid esters, be preferably thiazolinyl unsaturated monomer, the alkene that more preferably carbonatoms is 2-30, olefin(e) acid ester, one or more in enol ester, further be preferably ethene, propylene, butylene, divinyl, vinyl cyanide, vinylformic acid C1-C22 alkyl ester, methacrylic acid C1-C22 alkyl ester, acrylamide, Methacrylamide, vinyl acetate, vinylbenzene, the alpha-olefin of C6-C24, vinyl pyridine, alkyl vinyl ether etc.Polyreaction can be binary copolymerization, and for example, in unsaturated dicarboxylic acid, acid anhydrides or half ester, dibasic acid esters aminate, a kind of and one that be selected from above-mentioned other thiazolinyl unsaturated monomer are carried out polyreaction, can be also multi-component copolymers.

Above-mentioned unsaturated dicarboxylic acid, acid anhydrides, half ester and dibasic acid esters, reacting with the ammonia of contain-NH functional group and/or organic amine before one or more in dibasic acid esters and other comonomer polymerizations or after polymerization is conventionally known to one of skill in the art, for example can be without catalyzer, by above-mentioned unsaturated dicarboxylic acid, acid anhydrides or half ester, dibasic acid esters mixes with organic amine, reflux water-dividing or dewater or except methyl alcohol by nitrogen purging under solvent exists, ethanol generates, or carry out above-mentioned reaction under acidity or basic catalyst effect, an acidic catalyst is as sulfuric acid, phosphoric acid, tosic acid, acidic ion exchange resin, heteropolyacid, solid super-strong acid, acidic white earth, acidic molecular sieve etc., basic catalyst is as NaOH, KOH, Ca (OH) ₂, Mg (OH) ₂, sodium methylate, potassium methylate, organic amine etc., specifically do not repeat them here.

The preparation of multipolymer, can be with reference to pertinent literature.Generally to carry out free radical solution polymerization reaction under the initiator effect that can produce free radical.

One or more in described unsaturated dicarboxylic acid, acid anhydrides, half ester and dibasic acid esters, dibasic acid esters and the ammonia of contain-NH functional group taking-NH and/or the mol ratio of organic amine can be as 1: 0.5-5.Concrete condition is known to the skilled person, for example can be without catalyzer, by above-mentioned unsaturated dicarboxylic acid, acid anhydrides, half ester and dibasic acid esters, one or more in dibasic acid esters mix with organic amine before polymerization or after polymerization, reflux water-dividing or methyl alcohol under solvent exists, ethanol or dewater or methyl alcohol by nitrogen purging, ethanol generates, or carry out above-mentioned reaction under acidity or basic catalyst effect, an acidic catalyst is as sulfuric acid, phosphoric acid, tosic acid, acidic ion exchange resin, heteropolyacid, solid super-strong acid, acidic white earth, acidic molecular sieve etc., basic catalyst is as NaOH, KOH, Ca (OH) ₂, Mg (OH) ₂, sodium methylate, potassium methylate, organic amine etc., specifically do not repeat them here.

The preferred described component a of the present invention by unsaturated dicarboxylic acid, acid anhydrides, half ester and dibasic acid esters, dibasic acid esters one or more be different from described unsaturated dicarboxylic acid, acid anhydrides, half ester and dibasic acid esters, dibasic acid esters one or more containing obtaining by condensation reaction with ammonia and/or the organic amine of contain-NH functional group after alkenyl monomer polymerization, for convenience of description, one or more in unsaturated dicarboxylic acid, acid anhydrides, half ester and dibasic acid esters, dibasic acid esters are called monomer A by the present invention, is called monomers B by what be different from described monomer A containing alkenyl monomer.Described monomers B can be also one or more in above-mentioned unsaturated dicarboxylic acid, acid anhydrides, half ester and dibasic acid esters, only otherwise with monomer A be same material simultaneously.The mol ratio of described monomer A and monomers B can be 1: 0.1-10, preferably 1: 0.2-5, more preferably 1: 0.5-1.5; Polymerizing condition makes the number-average molecular weight of the product after polymerization at 1000-50000, preferably 2000-30000, more preferably 5000-25000.

Under preferable case, described in be aggregated in solvent and initiator and carry out under existing, described polymerizing condition comprises that polymerization temperature is 40-250 DEG C, the reaction times is 1-10 hour.Initiator used can be superoxide or azo compound, as ditertiary butyl peroxide, dilauryl superoxide, benzoyl peroxide, Diisopropyl azodicarboxylate, dilauroyl peroxide, isopropyl benzene hydroperoxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate etc.; Can also use Potassium Persulphate, thiosulphate etc. without organic initiators.The consumption of initiator is generally the 0.5-2% of polymerization single polymerization monomer gross weight.Described solvent can be toluene, dimethylbenzene, ethylbenzene, normal hexane, hexanaphthene etc., can be also aromatic hydrocarbons thinning oil, and boiling range is 159-185 DEG C, heavy aromatic solvent (160～190 DEG C of boiling ranges), and the latter two are preferred.Solvent load is generally the 30-150% of monomer material gross weight.The feed way of reactant can be once all to add, can be also monomer high reactive behavior (as alkyl acrylate) is added in batches, and then back flow reaction 2-7 hour.Reaction product can be purified and also can directly be carried out the next step, and synthetic polymeric additive preferably contains the solvent of 50 % by weight left and right.

In the present invention, unless stated otherwise, the content of described component a is taking the amount of above-mentioned diluent as benchmark, is also that the amount of above-mentioned solvent is also as a part of component a.

Example as the concrete polymkeric substance of component a has a lot, be described as follows, but scope of the present invention is not subject to the restriction of these examples as an example of copolymer example:

The amination reaction product of (methyl) vinylformic acid C6～C22 alkyl ester-copolymer-maleic anhydride and the organic amine that contains polyamines; (methyl) vinylformic acid C6～C22 alkyl ester-toxilic acid monoesters and amination reaction product containing the organic amine of polyamines; (methyl) vinylformic acid C6～C22 alkyl ester-fumaric acid polymkeric substance and amination reaction product containing the organic amine of polyamines; (methyl) vinylformic acid C6～C22 alkyl ester-fumaric monoalkylester and amination reaction product containing the organic amine of polyamines; (methyl) vinylformic acid C6～C22 alkyl ester-fumaric acid diester and amination reaction product containing the organic amine of polyamines; The amination reaction product of C6～C24 alpha-olefin-copolymer-maleic anhydride and the organic amine that contains polyamines; C6～C24 alpha-olefin-toxilic acid monoesters and amination reaction product containing the organic amine of polyamines; C6～C24 alpha-olefin-fumaric acid polymkeric substance and amination reaction product containing the organic amine of polyamines; C6～C24 alpha-olefin-fumaric monoalkylester and amination reaction product containing the organic amine of polyamines; The amination reaction product of styrene-maleic anhydride copolymer and the organic amine that contains polyamines; Styrene-maleic acid monoesters and amination reaction product containing the organic amine of polyamines; Vinyl acetate-fumaric acid polymkeric substance and amination reaction product containing the organic amine of polyamines; Vinyl acetate-fumaric monoalkylester and amination reaction product containing the organic amine of polyamines etc.

Additive of the present invention, except containing component a, preferably also contains components b and/or amount of component b.The weight ratio of components b and component a can be 0.01-10: 1, be preferably 0.05-5: 1.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, is further preferably 1: 0.02-0.2.

Components b

Components b can be arylamine type oxidation inhibitor and/or hindered phenol type antioxidant.

Described arylamine type oxidation inhibitor as components b can be selected from least one in naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, quinoline.

Wherein naphthylamine derivative includes but not limited to one or more in 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 '-bis-[to (beta-naphthylamine) phenoxy group] diethyl ether (anti-aging agent C-41-ether).

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

Wherein diphenylamine derivatives includes but not limited to one or more in following material:

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

Right, to '-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 aniline phenoxy group) propane (anti-aging agent C-47);

2,2 '-bis-(to 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 '-bis-(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, one or more in nonyl, the example of its Industrial products has Pennwalt company of U.S. commodity to be called Pennox A, Pennox A-" S ", American National Instrument polychem company commodity are called Wytox ADP, ADP-X, Vanderbilt company of U.S. commodity are called Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, Uniroyal company of U.S. commodity are called Polylite, Antioxidant 445, and the domestic code name antioxidant product that is T534.

Diphenylamine derivatives type oxidation inhibitor preferred alkyl diphenylamines 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 in 4 '-dinonyldiphenylamine, octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines), octyl group/butyl pentanoic, commodity oxidation inhibitor T534.

Wherein p-phenylene diamine derivative's type oxidation inhibitor comprises but is not limited to one or more in following material:

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

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

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

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

N, N '-bis--(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 '-bis--(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 p-phenylene diamine derivative's type oxidation inhibitor, the especially dialkyl group Ursol D of preferred alkyl carbonatoms between 4-10, 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 '-bis--(1-methylheptyl) Ursol D.

Quinoline wherein includes but 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 (anti-aging agent BXA) of pentanoic and acetone and aldehyde;

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

The preferred Ursol D class of arylamine antioxidant arylamine antioxidant.

Phenol type antioxidant described in components b can be single phenol, bis-phenol or polyphenol, can be also the mixture of their arbitrary proportions.

Wherein single phenol be have a phenyl ring/and phenyl ring on have the phenol of the replacement of a hydroxyl, and in substituting group, have at least one to be the tertiary butyl, other substituting group can be alkyl or contain heteroatomic substituting group, alkyl is wherein selected from C ₁-C ₁₀alkyl, such as methyl, ethyl, allyl group, normal-butyl, sec-butyl, nonyl etc., contain heteroatomic substituting group to be selected from oxygen containing substituting group as the methyl of methoxyl group, methoxy substitution, methylol, and nitrogenous substituting group is as alpha, alpha-dimethyl aminomethyl.Can be for example single phenol of structure below: o-tert-butylphenol, p-tert-butylphenol, 2-tert-butyl-4-methyl-Phenol, the 6-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol; The 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol; 2,4-DTBP, 2,5-DI-tert-butylphenol compounds, 2,6 di t butyl phenol; 2,5-di-tert-butyl-4-methy phenol, 2,6 di tert butyl 4 methyl phenol (BHT, oxidation inhibitor T501), 4,6-di-t-butyl-2-methylphenol; 2,4,6-tri-butyl-phenol, 2 allyl 4 methyl 6 tert butyl phenol, 2-sec-butyl-4-TBP, 4-sec-butyl-2,6-DI-tert-butylphenol compounds, 4-nonyl-2,6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-ethylphenol (oxidation inhibitor DBEP), 2,6-di-t-butyl-4-normal-butyl phenol (oxidation inhibitor 678); Butylhydroxy anisole (BHA), 2,6-di-t-butyl-α-methoxyl group-p-cresol (BHT-MO), 4-methylol-2,6-DI-tert-butylphenol compounds (oxidation inhibitor 754), 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703), various 3,5-di-tert-butyl-hydroxy phenyl propionic ester and 3,5-di-tert-butyl-hydroxy phenyl propionic acid acid amides etc.

Wherein single phenol oxidation inhibitor preferably has a tertiary butyl at least at the single phenol of being obstructed of phenolic hydroxyl group ortho position, as:

2-tert-butyl-4-methyl-Phenol, the 6-tertiary butyl-2, 4-xylenol, 2, 6-DI-tert-butylphenol compounds, 2, 6-di-tert-butyl-4-methy phenol (BHT, oxidation inhibitor T501), 2, 4, 6-tri-butyl-phenol, 4-sec-butyl-2, 6-DI-tert-butylphenol compounds, 4-nonyl-2, 6-DI-tert-butylphenol compounds, 2, 6-di-t-butyl-4-ethylphenol (oxidation inhibitor DBEP), butylhydroxy anisole (BHA), 2, 6-di-t-butyl-α-methoxyl group-p-cresol (BHT-MO), 4-methylol-2, 6-DI-tert-butylphenol compounds (oxidation inhibitor 754), 2, one or more in 6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703).

Bis-phenol for example refers to by two single phenol, by sulphur or the connected phenol type antioxidant of carbon atom:

(1) bis-phenol being connected by carbon atom

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(2) bis-phenol being connected by sulphur atom

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

2,2 '-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) be connected 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 for example, by having at least a tertiary butyl to pass through methylene radical or the connected bis-phenol of sulphur at single phenol at phenolic hydroxyl group ortho position:

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

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

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

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

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

2,2 '-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 antioxidant refers to that the macromole oxidation inhibitor of being rolled into a ball by least three single phenolic group in molecule, preferably by having at least a tertiary butyl to roll into a ball at single phenolic group at phenolic hydroxyl group ortho position the polyphenol forming, especially preferably has the be obstructed polyphenol of two tertiary butyls at phenolic hydroxyl group ortho position, for example:

1,3,5-trimethylammonium-2,4,6-tri--(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-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) (antioxidant 3114);

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

1,3,5-tri-(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 the phenol with three hydroxyls in phenyl ring, and such as pyrogallol, gallic acid ester are 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 Chinese Patent Application No. 200810115581.8 or ammonia salt.Especially Tenox PG of the preferred gallic acid-derivate of many phenol type antioxidants.

Above-mentioned phenol type antioxidant preferably has the bisphenol type oxidation inhibitor of a tertiary butyl at phenolic hydroxyl group ortho position at least, particularly passes through gallic acid ester, gallamide or ammonia salt in the connected bisphenol type oxidation inhibitor of methylene radical or sulphur and polyphenol antioxidant.

Components b can also be the composite antioxidant of above-mentioned arylamine type oxidation inhibitor and above-mentioned phenol type antioxidant.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 '-bis--(1-methylheptyl) Ursol D, 2, 2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2, 6-DI-tert-butylphenol compounds), 4, 4 '-methylene radical-bis--(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-tert-butylphenol compounds), two-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in thioether.

, after described component a and said components b are compound, there is obvious synergistic effect in the discovery that the inventor is pleasantly surprised, the improvement effect of oxidation stability of fuel containing biodiesel is strengthened greatly.

Amount of component b

Described amount of component b can be the various metal passivators that can react with metallic surface and/or react with metal or metal ion or the metal chelator of combination.

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

In the present invention, preferred described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide form, 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 in one or more.

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

The example of described detergent-dispersant additive can comprise succimide, mannich base, PIBA and polyetheramine; Described allyl butyrate imide and/or base succinamide ashless dispersant for example number-average molecular weight in the reaction product of polyolefin-based Succinic anhydried and/or succinic acid and the amine of 500-3000, if domestic trade names are T151A (mono butonediimide), T151B (mono butonediimide), T152 (two succimide), T154 (two succimide), T155 (poly succimide) and/or T161 (poly succimide) etc.Import additive is as OLOA-1200, LZ894, Infineum C9238,9237, Hitec 644 etc.Mannich base type ashless dispersant for example number-average molecular weight at the polyolefin-based phenol of 500-3000 and the condensation product of formaldehyde and amine; After for example C8-C30 alkylphenol of described polyetheramine type ashless dispersant and oxyethane or propylene oxide adduction again with the product of amine condensation or C8-C30 alcohol and oxyethane or propylene oxide adduction after again with the product of amine condensation; For example chlorinatedpolyolefins of described polyalkene amines type ashless dispersant reacts the polyolefin-based amine generating with amine.Here all preferred polyamines, especially polyamines polyenes of said amine.

The example of described cetane number improver can comprise that organic nitrates is if isooctyl ester nitrate (T2201), amyl nitrate and superoxide are as ditertiary butyl peroxide; The example of described defoamer can comprise T901, the T911, T921 and the T922 that are purchased; The example of described static inhibitor can comprise T1502, the Stadis 425 and the Stadis 450 that are purchased.

The preparation of Dresel fuel compositions provided by the invention is simple, only each component of composition Dresel fuel compositions need be mixed.Can directly each additive component be mixed with basic diesel oil, also can first various additive components be mixed, obtain after additive, then gained additive is mixed with basic diesel oil.For easy to operate, in the time that various additive components are mixed, can under existing, solvent carry out, the solvent here can be that polar solvent is as N, one or more in dinethylformamide (DMF), Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF) (THF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidone and methyl-2-pyrrolidone.Also can be hydro carbons especially aromatic hydrocarbons as benzene,toluene,xylene, aromatic hydrocarbons thinning oil and composition thereof, can also be biofuel.

In the present invention, described basic diesel oil can be pure biofuel, and described biofuel refers to that grease and low-carbon alcohol are (as C ₁-C ₅fatty alcohol) react and the fatty acid ester of low-carbon alcohol of generation through transesterify (alcoholysis), be 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.What general normal temperature was liquid is called oil, 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 comprising from the oil plant in the material such as microorganism, algae, can also be even waste oil, the used grease of acidifying wet goods or the rotten grease of for example waste cooking oil, sewer oil, swill oil, grease factory.Described vegetables oil can be that herbaceous plant oil can be also xylophyta oil, if 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 are as the oil of the plant such as kostelezkya virginica, cyperus esculentus.Described animal oil can be lard, chicken fat, duck oil, goose oil, sheep oil, 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 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 that crude oil (oil) is through the cut of the device boiling ranges after treatment such as the various refining process decompression as usual of refinery, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking between 160-380 DEG C, and the compression ignition engine fuel that meets solar oil standard GB/T 252-2000 or derv fuel oil standard GB/T/T 19147-2003 forming through allotment.

Fischer-tropsch combined diesel oil mainly refers to GTL diesel oil (Gas To Liquid) or the CTL diesel oil (Coal To Liquid) produced through fischer-tropsch (F-T) synthetic method as raw material taking Sweet natural gas or coal, can also be the BTL diesel oil (Biomass To Liquid) that vegetable fibre is produced through fischer-tropsch synthetic method.Fischer-tropsch combined diesel oil does not basically contain sulphur and aromatic hydrocarbons, be very clean fuel, but its oilness extreme difference improve greatly with oilness after biofuel blending, but likely variation of the oxidation stability of tempered oil, therefore also needs to add oxidation inhibitor containing the blending fuel of biofuel.

Hydrocracking biofuel is also referred to as s-generation biofuel, refer to generated after hydrogenation and cracking reaction by animal-plant oil 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 discharge of diesel engine pollutent as diesel motor fuel or blending component.

Refer to and can be deployed into and meet the oxygenatedchemicals of certain code requirement or the mixture of oxygenatedchemicals with various diesel-fuels containing oxygen diesel oil blending component, normally alcohols and ethers or its mixture, alcohols is C such as ₁-C ₁₈fatty alcohol, preferred C ₁-C ₁₂unitary fatty alcohol, 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.

In the present invention, described basic diesel oil is while containing the blending fuel of biofuel, described Dresel fuel compositions can, by described additive, biofuel and other diesel oil are directly obtained by mixing, also can first mix described additive, and then obtain with other diesel oil blending with biofuel.The various components of additive directly can be mixed with basic diesel oil, also can first the various components of additive be pre-mixed, obtain after additive agent mixture again and basic diesel oil.The order by merging of the various components to additive and biofuel and other diesel oil is not particularly limited, and can mix with various orders.The condition of mixing can be carried out under the various conditions that 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 the diesel component that contains biofuel, adds additive, and described additive contains component a and optionally contains components b and/or amount of component b.

The amount of component b of the component a of described additive, the components b of additive and additive is identical with component a, components b and amount of component b in above-mentioned Dresel fuel compositions separately, and its kind and consumption describing above, do not repeat them here.

Under preferable case, the method of raising oxidation stability of biodiesel provided by the invention is also included in the basic diesel oil that contains biofuel, add other additive, as one or more in detergent-dispersant additive, FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc.

The order by merging of the various components to additive and biofuel and other diesel oil is not particularly limited, and can mix with various orders.The condition of mixing can be carried out under the various conditions that Dresel fuel compositions do not caused disadvantageous effect, for example, can mix at ambient temperature.

Described biofuel can be both aforementioned pure biofuel, can be also the aforementioned blending fuel containing biofuel.

The present invention is described further for the following examples.

Embodiment 1-5 is for illustrating synthesizing of component a of the present invention.

Embodiment 1

Embodiment 1 is the aminate of Acrylic Ester-Maleic Anhydride and polyamines.

49.0g (0.5mol) maleic anhydride and 50g aromatic hydrocarbons thinning oil solvent are placed in to one electric mixer is housed, thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, pass into nitrogen 5-10 minute, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 140-150 DEG C, by 134.0g tetradecyl acrylate (being purchased from Shanghai Yao Xuan Industrial Co., Ltd.), 2.0g ditertiary butyl peroxide and 134g aromatic hydrocarbons thinning oil (are purchased from Tianjin Xiang Yu coating company limited, identical below) mixture from dropping funnel, splash into reactor (mol ratio of tetradecyl acrylate and maleic anhydride 1: 1), in 1.5 hours, drip off, keep temperature 140-150 DEG C, back flow reaction 5 hours, gained polymerisate is cooled to 95 DEG C, add the reaction of 92.5g amino dodecane after 2 hours, add again 94.5g tetraethylene pentamine, 187g aromatic hydrocarbons thinning oil, pass into nitrogen reaction 3 hours at 110 DEG C, obtain red oily liquids 730g, be component a of the present invention, by the number-average molecular weight of gel permeation chromatography (GPC) deduction solvent and unreacted monomer, recording polymkeric substance number-average molecular weight in component a is 12300 (with respect to polystyrene).

Embodiment 2

Embodiment 2 is aminates of α-hexadecylene-copolymer-maleic anhydride and polyamines.

24.5g (0.25mol) maleic anhydride and 25g xylene solvent are placed in to one electric mixer is housed, thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, pass into nitrogen 5-10 minute, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 85-95 DEG C, by 67.2g α-hexadecylene, 1.1g benzoyl peroxide and 67g xylene mixture splash into reactor (mol ratio of α-hexadecylene and maleic anhydride 1.2: 1) from dropping funnel, in 1.5 hours, drip off, keep temperature 85-95 DEG C, react 4 hours, underpressure distillation is except desolventizing and unreacted maleic anhydride, add 165g dimethylbenzene, 45.6gN-dodecyl-1, 3-propylene diamine reacts after 1 hour at 90 DEG C, add again 32.2g N-(2-aminoethyl) piperazine, pass into nitrogen reaction 3 hours at 100 DEG C, obtain red oily liquids 321.4g, be component a of the present invention, by the number-average molecular weight of gel permeation chromatography (GPC) deduction solvent and unreacted monomer, recording polymkeric substance number-average molecular weight in component a is 9890 (with respect to polystyrene).

Comparative example 1

Comparative example 1 is substantially the same manner as Example 2, is α-hexadecylene-copolymer-maleic anhydride, and difference is not react with amine.

24.5g (0.25mol) maleic anhydride and 25g xylene solvent are placed in to one electric mixer is housed, thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, pass into nitrogen 5-10 minute, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 85-95 DEG C, by 67.2g α-hexadecylene, 1.1g benzoyl peroxide and 67g xylene mixture splash into reactor (mol ratio of α-hexadecylene and maleic anhydride 1.2: 1) from dropping funnel, in 1.5 hours, drip off, keep temperature 85-95 DEG C, react 4 hours, underpressure distillation is except desolventizing and unreacted maleic anhydride, add again 92g dimethylbenzene wiring solution-forming, by the number-average molecular weight of gel permeation chromatography (GPC) deduction solvent and unreacted monomer, the number-average molecular weight that records polymkeric substance in solution is 6780 (with respect to polystyrene).

Embodiment 3

Embodiment 3 is aminates of vinyl acetate-fumaric monoalkylester multipolymer and polyamines.

36.0g monomethyl ester (0.25mol) and 36g xylene solvent are placed in to a reactor that electric mixer, thermometer, reflux condensing tube, dropping funnel and nitrogen ingress pipe be housed, pass into nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 70 DEG C, 21.5g (0.25mol) vinyl acetate, 1.2g Diisopropyl azodicarboxylate and 22g xylene mixture are splashed into reactor from dropping funnel, in 1 hour, drip off, maintain the temperature at 70 DEG C of left and right, react 6 hours.In this polymerisate, add 58g dimethylbenzene, 57.8g five ethene hexamines, pass into nitrogen at 110 DEG C and divide water reaction 3 hours, obtain red oily liquids 213.7g, be component a of the present invention, by the number-average molecular weight of gel permeation chromatography (GPC) deduction solvent and unreacted monomer, recording polymkeric substance number-average molecular weight in component a is 15850 (with respect to polystyrene).

Embodiment 4

Embodiment 4 is aminates of methacrylic dodecyl gallate-α-octadecylene-maleic anhydride terpolymer and polyamines.

By 19.6g maleic anhydride (0.2mol), 26.4g (0.2mol) α-octadecylene and 46g heavy aromatic solvent (160 DEG C of initial boiling points) are placed in one electric mixer are housed, thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, pass into nitrogen 5-10 minute, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 140 DEG C, by 50.9g (0.2mol) methacrylic dodecyl gallate, the mixture of 1.3g ditertiary butyl peroxide and 51g heavy aromatic solvent splashes into reactor from dropping funnel, in 1 hour, drip off, maintain the temperature at 145 DEG C of left and right, react 6 hours, in this polymerisate, add 55g dimethylbenzene and 21.5g n-octyl amine, 100 DEG C of reactions 2 hours, add again the N of 19.3g, two (3-aminopropyl) methylamines of N-and 14.6g triethylene tetramine, pass into 110 DEG C of points of water reactions of nitrogen 3 hours, obtain red oily liquids 291.4g, be component a of the present invention, by the number-average molecular weight of gel permeation chromatography (GPC) deduction solvent and unreacted monomer, recording polymkeric substance number-average molecular weight in component a is 18910 (with respect to polystyrene).

Embodiment 5 is aminates of Process Conditions of Cetane Acrylate-fumaric acid diester multipolymer and polyamines.

19.2g dimethyl fumarate (0.13mol) and 20g heavy aromatic solvent (160～190 DEG C of boiling ranges) are placed in to one electric mixer is housed, thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, pass into nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 140 DEG C, by 59.3g (0.2mol) Process Conditions of Cetane Acrylate, 1.6g ditertiary butyl peroxide and 60g heavy aromatic solvent mixture splash into reactor from dropping funnel, in 1 hour, drip off, maintain the temperature at 145 DEG C of left and right, react 6 hours.In this polymerisate, add 24g amino dodecane, 30.2g five ethene hexamines, 54g heavy aromatic solvent, pass into nitrogen at 110 DEG C and divide water reaction 3 hours, obtain red oily liquids 258.8g, be component a of the present invention, by the number-average molecular weight of gel permeation chromatography (GPC) deduction solvent and unreacted monomer, recording polymkeric substance number-average molecular weight in component a is 16930 (with respect to polystyrene).

Comparative example 2

Comparative example 2 is substantially the same manner as Example 5, is Process Conditions of Cetane Acrylate-fumaric acid diester multipolymer, and difference is not react with polyamines.

19.2g dimethyl fumarate (0.13mol) and 20g heavy aromatic solvent (160～190 DEG C of boiling ranges) are placed in to one electric mixer is housed, thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, pass into nitrogen 5～10 minutes, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 140 DEG C, by 59.3g (0.2mol) Process Conditions of Cetane Acrylate, 1.6g ditertiary butyl peroxide and 60g heavy aromatic solvent mixture splash into reactor from dropping funnel, in 1 hour, drip off, maintain the temperature at 145 DEG C of left and right, react 6 hours.In this polymerisate, add 24g amino dodecane, 24g heavy aromatic solvent, pass into nitrogen at 110 DEG C and divide water reaction 3 hours, obtain red oily liquids, by the number-average molecular weight of gel permeation chromatography (GPC) deduction solvent and unreacted monomer, recording this redness oily liquid strain polymkeric substance number-average molecular weight is 12460 (with respect to polystyrene).

Performance test

Below in test, Oleum Gossypii semen biofuel used is the biofuel product that Shijiazhuang refinery branch office of China Petrochemical Industry provides, sewer oil biofuel used provides by the remarkable new forms of energy of Fujian Longyan company limited, acidification oil biofuel product is provided by Hainan bioenergy company limited of CNOOC, 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 at measuring 110 DEG C by EN14112:2003 method (Racimat method), use the 743 type oil oxidative stability determinators that instrument is Wan Tong company of Switzerland, wherein, inductive phase is longer illustrates that the oxidation-resistance of Dresel fuel compositions is better, otherwise shorter illustrate that the oxidation-resistance of Dresel fuel compositions is poorer inductive phase.Its test result is shown in table 1 and following table 2.Wherein table 1 is the test result of component a in biofuel, and table 2 is the test result in biofuel after component a coordinates with components b.

Table 1

Data from table 1 can be found out, add after component a of the present invention, and the oxidation stability of biofuel improves, and increase inductive phase, and meanwhile, cold filter clogging temperature reduces, the low-temperature fluidity that biofuel is described also improvement to a certain extent.Compared with the effect of embodiment and comparative example, can find out, the polymkeric substance antioxidant effect reacting with polyamines obviously strengthens.

Table 2

Data from table 2 can be found out, common oxidation inhibitor has certain improvement to oxidation stability of biodiesel, and a little less than polymkeric substance shown in the present uses separately in the time that addition is few antioxidant effect, and by after the two compound use, effect is beat all to be strengthened greatly, be that obvious synergistic effect appears in another embodiment of the present invention, there is better oxidation stability according to the biodiesel composition of this embodiment.

The component a that embodiment 1 makes can find out with the contrast of the compound rear effect of dissimilar arylamine antioxidant respectively, Ursol D kind antioxidant is (as N, N '-dioctyl-p-phenylenediamine) effect with component a thing of the present invention after compound is more excellent, effective a lot of after more compound than diphenylamine oxidation inhibitor (as 4,4 '-dioctyl diphenylamine) and modified polyamine polymkeric substance of the present invention.Embodiment 4 more also can find out with the compound rear effect of dissimilar phenol type antioxidant, and the effect after bisphenol type oxidation inhibitor (as antioxidant 2246) is compound with modified polyamine polymkeric substance of the present invention is better than the effect of single phenol type antioxidant (as oxidation inhibitor T501) after compound with modified polyamine polymkeric substance of the present invention.Comparative example 1,2 respectively compared with embodiment 2,5, compound with oxidation inhibitor after, embodiment successful is better than the composite effect of comparative example, illustrates that the compound synergistic effect of the polymkeric substance of polyamines amination and oxidation inhibitor is more obvious.

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

Adopt the method for EN 15751:2009 to measure respectively each Dresel fuel compositions, petroleum diesel and concocted diesel oil inductive phase at 110 DEG C, use the 743 type oil oxidative stability determinators that instrument is Wan Tong company of Switzerland, inductive phase is longer illustrates that the oxidation-resistance of biodiesel composition is better, otherwise shorter illustrate that the oxidation-resistance of biodiesel composition is poorer inductive phase.Adopt the method for SH/T 0248 to measure cold filter clogging temperature, GB/T510 method mensuration condensation point.Test result is all shown in Table 3.

Table 3

Result by table 3 can be found out, adds after biofuel, containing the oxidation stability of the blending fuel of biofuel, low-temperature fluidity variation all compared with petroleum diesel.Component a of the present invention can improve oxidation stability and the low-temperature fluidity of biodiesel blend fuels, oxidation stability, the low-temperature fluidity of the biodiesel composition of the present invention that component a and the compound mixture of Ursol D type oxidation inhibitor are obtained as additive have greatly and improve, there is synergistic effect in its effect, obviously strengthens than independent Use Limitation fruit.The polymkeric substance (comparative example) that does not carry out amination reaction and the compound rear successful of oxidation inhibitor not as embodiment and oxidation inhibitor composite effect good.

Claims (32)

1. a Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, described basic diesel oil contains biofuel, described additive contains component a, and described component a contains one or more the polymkeric substance of aminate in unsaturated dicarboxylic acid and acid anhydrides, half ester and dibasic acid esters; Described component a obtains by condensation reaction with the polyamine compounds of contain-NH functional group after by monomer A and monomers B polymerization; Described additive also contains components b, and described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and the weight ratio of components b and component a is 0.01-10:1; Described monomer A is one or more in unsaturated dicarboxylic acid and acid anhydrides, half ester and dibasic acid esters; Described monomers B is one or more in α-hexadecylene, α-octadecylene, vinyl acetate, propylene alcohol ester.

2. Dresel fuel compositions according to claim 1, wherein, described additive is 50-12000ppm with respect to the content of basic diesel oil.

3. Dresel fuel compositions according to claim 1, wherein, described additive is 100-8000ppm with respect to the content of basic diesel oil.

4. Dresel fuel compositions according to claim 1, wherein, the number-average molecular weight of described component a is 500-100000.

5. Dresel fuel compositions according to claim 4, wherein, the number-average molecular weight of described component a is 1000-50000.

6. Dresel fuel compositions according to claim 1, wherein, the mol ratio of described monomer A and monomers B is 1:0.1-10, it is 1000-50000 that polymerizing condition makes the product number-average molecular weight after polymerization.

7. Dresel fuel compositions according to claim 1, wherein, the carbonatoms of described monomer A is 4-10.

8. Dresel fuel compositions according to claim 7, wherein, described monomer A is one or more in toxilic acid, maleic anhydride, toxilic acid monoesters, fumaric acid, fumaric monoalkylester.

9. Dresel fuel compositions according to claim 1, wherein, described in be aggregated in solvent and initiator and carry out under existing, described polymerizing condition comprises that polymerization temperature is 40-250 DEG C, polymerization time is 1-10 hour.

10. Dresel fuel compositions according to claim 1, wherein, described monomer A and the ammonia of contain-NH functional group taking-NH and/or the mol ratio of organic amine are as 1:0.5-5.

11. Dresel fuel compositions according to claim 1, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, have one or more in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position of a tertiary butyl at least.

12. Dresel fuel compositions according to claim 11, wherein, described components b is the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 and one or more in the bisphenol type oxidation inhibitor being connected by methylene radical or sulphur.

13. Dresel fuel compositions according to claim 11, wherein, described components b is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-bis--(1-methylheptyl) Ursol D, 2, 2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2, 6-DI-tert-butylphenol compounds), 4, 4 '-methylene radical-bis--(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-tert-butylphenol compounds), two-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in thioether.

14. Dresel fuel compositions according to claim 1, wherein, described additive also contains amount of component b, and described amount of component b is metal passivator, and the weight ratio of described component a and described amount of component b is 1:0.01-1.

15. Dresel fuel compositions according to claim 14, wherein, 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, one or more in Schiff's base and organic polycarboxylic acid.

16. Dresel fuel compositions according to claim 1, 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 oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is 1:2-99.

17. 1 kinds are improved the method for oxidation stability of biodiesel, the method comprises, in the basic diesel oil that contains biofuel, add additive, described additive contains component a, and described component a contains one or more the polymkeric substance of aminate in unsaturated dicarboxylic acid and acid anhydrides, half ester and dibasic acid esters; Described component a obtains by condensation reaction with the polyamine compounds of contain-NH functional group after by monomer A and monomers B polymerization; Described additive also contains components b, and described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and the weight ratio of components b and component a is 0.01-10:1; Described monomer A is one or more in unsaturated dicarboxylic acid and acid anhydrides, half ester and dibasic acid esters; Described monomers B is one or more in α-hexadecylene, α-octadecylene, vinyl acetate, propylene alcohol ester.

18. methods according to claim 17, wherein, described additive is 50-12000ppm with respect to the content of basic diesel oil.

19. methods according to claim 18, wherein, described additive is 100-8000ppm with respect to the content of basic diesel oil.

20. methods according to claim 17, wherein, the equal relative molecular weight of the number of described component a is 500-100000.

21. methods according to claim 20, wherein, the equal relative molecular weight of the number of described component a is 1000-50000.

22. methods according to claim 17, wherein, the mol ratio of described monomer A and monomers B is 1:0.1-10, it is 1000-50000 that polymerizing condition makes the number-average molecular weight of the product after polymerization.

23. methods according to claim 17, wherein, the carbonatoms of described monomer A is 4-10.

24. methods according to claim 23, wherein, described monomer A is one or more in toxilic acid, maleic anhydride, toxilic acid monoesters, fumaric acid, fumaric monoalkylester.

25. methods according to claim 24, wherein, described in be aggregated in solvent and initiator and carry out under existing, described polymerizing condition comprises that polymerization temperature is 40-250 DEG C, polymerization time is 1-10 hour.

26. methods according to claim 17, wherein, described monomer A and the ammonia of contain-NH functional group taking-NH and/or the mol ratio of organic amine are as 1:0.5-5.

27. methods according to claim 17, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, have one or more in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position of a tertiary butyl at least.

28. methods according to claim 27, wherein, described components b is the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 and one or more in the bisphenol type oxidation inhibitor being connected by methylene radical or sulphur.

29. methods according to claim 28, wherein, described components b is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-bis--(1-methylheptyl) Ursol D, 2, 2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2, 6-DI-tert-butylphenol compounds), 4, 4 '-methylene radical-bis--(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-tert-butylphenol compounds), two-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in thioether.

30. methods according to claim 17, wherein, described additive also contains amount of component b, and described amount of component b is metal passivator, and the weight ratio of described component a and described amount of component b is 1:0.01-1.

31. methods according to claim 30, wherein, 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, one or more in Schiff's base and organic polycarboxylic acid.

32. methods according to claim 17, 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 oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is 1:2-99.