CN104371775A - Additive composition, diesel oil composition and method for improving biodiesel oxidation stability - Google Patents

Abstract

The invention provides an additive composition, a diesel oil composition containing the additive composition and a method for improving biodiesel oxidation stability by the additive composition. The additive composition comprises an ingredient a and an ingredient b. The ingredient a is a product of a condensation reaction of amino polybasic acid and organic amine and the ingredient b comprises one or more of an arylamine-type anti-oxidant and gallic acid amide. The diesel oil composition has good oxidation stability.

Description

A kind of 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 and the Dresel fuel compositions containing this compositions of additives and use this compositions of additives to improve the method for 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 facilitate the exploitation paces that Alternative Diesel Fuel is accelerated in countries in the world, biofuel receives the attention of various countries with its superior environmental-protecting performance and recyclability.

Biofuel (BD100) is also known as fatty acid methyl ester (Fatty Acid Methyl Ester), make raw material with the grease of the oil plant waterplant such as oil-yielding shrubs fruit, engineering microalgae 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.Biofuel has renewable, clean and safe three advantages, has very great strategic importance to China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment.And China is a net import of oil state at present, prospective oil is very limited again, and the energy security of a large amount of Imported oil to China threatens; Therefore, biofuel research and produce 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 biofuel of oxidation stability difference 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 within the 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 EN14214:2003, Australian Biodiesel Standards (Draft2003), New Zealand Biodiesel Standards NZS7500:2005, Brazilian Biodiesel Standards ANP255(2003), the oxidation stability of India Biodiesel Standards IS15607:2005, South Africa Biodiesel Standards SANS1935:2004 and China diesel-fuel blending biofuel (BD100) standard GB/T/T20828-2007 all regulation biofuel is inductive phase at 110 DEG C be not less than 6 hours, measuring method is EN14112:2003.

CN1742072A discloses a kind of method improving storage stability of bio-diesel, the method comprises and will be dissolved in 2 of biofuel containing what count 15-60 % by weight with stoste, the liquid stoste of 4-di-t-butyl hydroxy toluene (BHT) joins in biofuel to be stabilized, until in total solution of biofuel, the concentration of 2,4-di-t-butyl hydroxy toluene reaches 0.005-2 % by weight.

CN1847368A discloses a kind of method improving the oxidative stability of 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] are with 10-20000ppm(w/w) amount join and treat in stable biofuel.

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

US2007/113467A1 discloses a kind of fuel composition with the oxidative stability of improvement, 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.

Traditional oxidation inhibitor is more than used to have certain effect to the method improving oxidation stability of biodiesel, but effect not too obviously or need the oxidation inhibitor of larger consumption to obtain significantly to improve effect, especially to waste grease, if sewer oil, acidification oil, hogwash fat are raw material production, biofuel effect is poorer.

CN101144040A disclose use arylamine kind antioxidant especially phenylenediamine oxidation inhibitor to improve the method for biofuel oxidative stability, the arylamine kind antioxidant especially improvement effect of phenylenediamine oxidation inhibitor to oxidation stability of biodiesel is better than phenol type antioxidant, but this compounds generally has certain toxicity, corrodibility and dyeability, add the color burn that dosage may make biofuel during the effect obtained, affect the outward appearance of biodiesel oil product.

Summary of the invention

The method effect oxidation inhibitor that is not too obvious or the larger consumption of needs that the object of the invention is to improve to overcome above-mentioned prior art oxidation stability of biodiesel could obtain the shortcoming significantly improving effect, a kind of oxidation stability obviously can improving fuel containing biodiesel when less consumption is provided, overcome simultaneously and be used alone aryl diamine type or Nutgalls oxidation inhibitor to the compositions of additives of the disadvantageous effect that biofuel color burn causes and the Dresel fuel compositions containing this compositions of additives and provide a kind of method improving oxidation stability of biodiesel.

The invention provides a kind of compositions of additives, it is characterized in that, this compositions of additives contains component a and components b, and described component a is the reaction product of amino polyprotonic acid and organic amine; Described components b is one or more in arylamine type oxidation inhibitor and gallamide.

Present invention also offers a kind of Dresel fuel compositions, this Dresel fuel compositions contains Base Diesel and additive, and described Base Diesel contains biofuel, and wherein, described additive is above-mentioned compositions of additives provided by the invention.

The present invention also provides a kind of method improving oxidation stability of biodiesel simultaneously, and the method comprises, and containing in the Base Diesel of biofuel, adds additive, and wherein, described additive is above-mentioned compositions of additives provided by the invention.

The compositions of additives that the application of the invention provides, no matter diesel oil or by containing diesel oil based on the blending fuel of biofuel based on pure biofuel, excellent oxidation stability can be obtained under less consumption, amazingly between component a and components b occur synergistic effect, it is well a lot of that antioxidant effect ratio is used alone oxidation inhibitor.Component a 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 requiring, the amount of components b in biodiesel composition can greatly reduce, especially under components b is expensive especially or components b has certain toxicity, dyeability or corrosive situation, decrease its consumption and there is very large meaning, not only reduce toxicity and the corrodibility of additive, and the consumption reducing components b can make the color burn degree of biofuel greatly reduce.Meanwhile, because the cost of component a is much less than components b, therefore, the present invention also greatly reduces the cost of biological diesel oil anti-oxidant.

Embodiment

According to compositions of additives provided by the invention, the weight ratio of described components b and component a can be 0.01-100:1, is preferably 0.1-10:1, more preferably 0.2-5:1.

Component a

In the present invention, component a is the reaction product of amino polyprotonic acid and amine.

Described " amino polyprotonic acid " refers to that, containing amino polycarboxylic acid in molecule, preferably amino number is 1-5, is more preferably 1-3.Described amino is all preferably that uncle is amino.The number of the hydroxy-acid group (-COOH) in described aminopolycarboxylic acid can be 2-6, is more preferably 2-5.Described hydroxy-acid group be more preferably in formyloxy, acetoxyl, propionyloxy and butyric acid base one or more, be particularly preferably acetoxyl and/or propionyloxy.The total number of carbon atoms of described amino polyprotonic acid is preferably 2-20, is more preferably 4-14.The specific examples of described aminopolycarboxylic acid includes but not limited to iminodiethanoic acid, complexon I, ethylenediamine tetraacetic acid (EDTA) (EDTA), ethylenediamine tetrapropionic acid(EDTP) (EDTP), 1,2-trimethylenedinitrilo-tertraacetic acid, 1,3-trimethylenedinitrilo-tertraacetic acid (PDTA), diethylene triamine pentacetic acid (DTPA) (DTPA), 1, one or more in 6-hexamethylene dinitrilo-tetraacetic acid, CDTA.

Described organic amine can be the various organic amines that can form amide structure with the carboxyl generation condensation reaction in amino polyprotonic acid, such as, can be have the structure shown in formula (1)

In formula (1), R ₁and R ₂be the group shown in H, formula (2), formula (3) or (4) independently, and R ₁and R ₂be asynchronously H.

In formula (2), x be 2 or 3, y be the integer of 0 to 5, R ₃for C ₁-C ₃₀alkyl; Preferred y is the integer of 1 to 4, R ₃for C ₆-C ₂₄alkyl.

In formula (3), x1 be 2 or 3, y1 be the integer of 0 to 5, R ₄for C ₁-C ₃₀alkyl; Preferred y1 is the integer of 1 to 4, R ₄for C ₆-C ₂₄alkyl.

In formula (4), y2 is the integer of 0 to 5, R ₅for C ₁-C ₂₆alkyl.

For formula (2), preferably y is the integer of 1 to 3 further, R ₃for C ₈-C ₂₂alkyl.This alkyl can be saturated alkyl, also can be the thiazolinyl with double bond or the aryl with 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 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 (i.e. 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.

When y equals 1, formula (2) is-CH ₂cH ₂nHR ₃or-CH ₂cH ₂cH ₂nHR ₃, preferably-CH ₂cH ₂cH ₂nHR ₃group, R ₃definition same as described above.The group of such as formula (2) can be,

-CH ₂cH ₂cH ₂nHC ₁₀h ₂₁(3-(the positive last of the ten Heavenly stems is amino) propyl group),

-CH ₂cH ₂cH ₂nHC ₁₂h ₂₅(3-(positive ten diamino) propyl group),

-CH ₂cH ₂cH ₂nHC ₁₄h ₂₉(3-(positive ten tetraminos) propyl group),

-CH ₂cH ₂cH ₂nHC ₁₆h ₃₃(3-(positive 16 is amino) propyl group),

-CH ₂cH ₂cH ₂nHC ₁₈h ₃₇(3-(positive 18 amino) propyl group) and

-CH ₂cH ₂cH ₂nHC ₁₈h ₃₅(3-(oil is amino) propyl group).

According to the present invention, for formula (3), preferred y1 is the integer of 1-5.The further preferably integer of x1 to be 2, y1 be 1-4, R ₄with above-mentioned R ₃definition identical.The group of such as formula (3) can be:

-CH ₂CH ₂NHCOC ₁₁H ₂₃，

-CH ₂CH ₂NHCOC ₁₃H ₂₇，

-CH ₂CH ₂NHCOC ₁₅H ₃₁，

-CH ₂CH ₂NHCOC ₁₇H ₃₅，

-CH ₂CH ₂NHCOC ₁₇H ₃₃，

-CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₁H ₂₃，

-CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₃H ₂₇，

-CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₅H ₃₁，

-CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₅，

-CH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃，

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

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

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

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

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

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

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

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

-CH ₂cH ₂nHCH ₂cH ₂nHCH ₂cH ₂nHCH ₂cH ₂nHCOC ₁₇h ₃₅with

-CH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCH ₂CH ₂NHCOC ₁₇H ₃₃。

According to composition provided by the invention, for formula (4), preferred y2 is the integer of 0-2.R ₅with above-mentioned R ₃definition identical.The group of such as formula (4) can be:

The preferred described organic amine of the present invention contains at least two NH groups or contains at least one NH and at least one C=C.Described NH group can be primary amino NH ₂, also can be secondary amino group.Further preferably, described organic amine is NH ₂(CH ₂) _mnHR ', NH ₂r ' ' and NH ₂(CH ₂) _nnH ₂in the acid amides that formed of one or more and R ' ' ' COOH in one or more, wherein, m and n is 1-4 separately, is preferably 2 or 3; R ', R ' ' and R ' ' ' are separately for carbon atom is the alkyl of 5-25, and described alkyl is further preferably containing at least one C=C, and being further preferably R ', R ' ' and R ' ' ' is cocoyl or 9-octadecylene base separately.

The present invention particularly preferably described organic amine is N-cocoyl Edamine, N-cocoyl-1,3-trimethylene diamines, N-oil base Edamine, N-oil base-1,3-trimethylene diamines, 9-octadecenyl amine, coconut oil and diethylenetriamine in molar ratio 1:0.5-1 react the acid amides, coconut oil and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react the acid amides, oleic acid and the diethylenetriamine that are formed in molar ratio 1:0.5-1 react the acid amides, oleic acid and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react in the acid amides formed one or more.

The condensation reaction of amino polyprotonic acid and organic amine is generally 1:0.2-5 according to the number of carboxyl in amino polyprotonic acid and the mol ratio of organic amine, preferably 1:0.6-1.5.Temperature of reaction is generally 80-300 DEG C, preferred within 120-250 DEG C of scope further, preferably within 180-220 DEG C of scope.Reaction times is as the criterion to react fully, and can determine to react the degree of carrying out according to point water yield, the preferred reaction time is 5-30 hour.Reaction medium can be aromatic solvent as dimethylbenzene, ethylbenzene, aromatic diluent oil (boiling range is 159-185 DEG C), mineral oil (boiling point is more than 120 DEG C), naphthane, or their mixture.Solvent load is generally the 30-150 % by weight of reaction mass gross weight.Reaction also can without solvent.Available nitrogen protection in reaction system, or allow system carry out under reflux water-dividing condition.Reaction can without catalyzer, also can carry out 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., and basic catalyst is as NaOH, KOH, Ca (OH) ₂, Mg (OH) ₂, sodium methylate, potassium methylate, organic amine etc.Also can steam solvent at the end of reaction, then be deployed into heavy aromatic solvent the diluent use that solvent is 20-50 % by weight.In the present invention, the addition unification in compositions of additives and diesel oil is adjusted (i.e. not solvent-laden add-on) with dry dosage.

NH ₂(CH ₂) _nnH ₂the acid amides formed with R ' ' ' COOH can be obtained by various mode, such as can be commercially available, also can be obtained by condensation reaction according to existing method, the concrete operations of condensation reaction can with reference to the carrying out of above-mentioned amino polyprotonic acid and organic amine generation condensation reaction, can carry out with reference to known method, the present invention does not repeat them here yet.

Components b

Components b is one or more in arylamine type oxidation inhibitor, gallamide.

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)

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

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, such as, 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 dioctylated pentanoic, 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, Antioxidant445, and domestic code name is the antioxidant product of 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 (octylated diphenylamine and/or dioctylated pentanoic), octyl group/butyl pentanoic, commodity oxidation inhibitor T534.

Wherein p-phenylene diamine derivative's type oxidation inhibitor includes but 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 '-two-(betanaphthyl) Ursol D (antioxidant D NP);

N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5, oxidation inhibitor 44PD);

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-aniiinophenyl) Methacrylamide;

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

The preferred dialkyl-pphenylenediamines of p-phenylene diamine derivative's type oxidation inhibitor, the especially dialkyl-pphenylenediamines 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, N ' one or more in-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.

Above-mentioned arylamine type oxidation inhibitor can be used alone a kind of or used in combination two or more.

A kind of preferred implementation of the present invention is that arylamine antioxidant comprises Ursol D class arylamine antioxidant.

Another kind of preferred embodiment of the present invention to be arylamine antioxidant the be naphthylamines of above-mentioned replacement and the diphenylamine oxidation inhibitor of replacement are with the mixed aromatic diamine oxidation inhibitor of mass ratio 1:0.1 ~ 10.

Gallamide as described components b can be the acid amides that gallic acid and various ammonia and/or amine are formed, specifically can see CN101613630A.Under preferable case, described Nutgalls acid amides is one or more in the gallamide shown in following formula (I),

In formula (I), R ₁and R ₂be the group shown in H, formula (2) independently.

In formula (2), x be 2 or 3, y be the integer of 0 to 5, R ₃for C ₁-C ₃₀alkyl; Preferred y is the integer of 0 to 3, R ₃for C ₆-C ₂₄alkyl.

When y equals 0, formula (2) is R ₃, i.e. C ₁-C ₃₀alkyl, be preferably C ₆-C ₂₄alkyl.This alkyl can be saturated alkyl, also can be the thiazolinyl with double bond or the aryl with 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, more preferably C ₆-C ₂₀alkyl.

When y equals 1, formula (2) is-CH ₂cH ₂nHR ₃or-CH ₂cH ₂cH ₂nHR ₃, preferably-CH ₂cH ₂cH ₂nHR ₃group, R ₃definition same as described above.The group of such as formula (2) can be,

-CH ₂cH ₂cH ₂nHC ₁₀h ₂₁(3-(the positive last of the ten Heavenly stems is amino) propyl group),

-CH ₂cH ₂cH ₂nHC ₁₂h ₂₅(3-(positive ten diamino) propyl group),

-CH ₂cH ₂cH ₂nHC ₁₄h ₂₉(3-(positive ten tetraminos) propyl group),

-CH ₂cH ₂cH ₂nHC ₁₆h ₃₃(3-(positive 16 is amino) propyl group),

-CH ₂cH ₂cH ₂nHC ₁₈h ₃₇(3-(positive 18 amino) propyl group) and

-CH ₂cH ₂cH ₂nHC ₁₈h ₃₅(3-(oil is amino) propyl group).

Preferably gallamide is one or more in gallic acid decoylamide, gallic acid pelargonamide, gallic acid decyl amide, gallic acid laurylamide, gallic acid myristamide, gallic acid palmitamide, gallic acid stearylamide, gallic acid oil base acid amides, gallic acid (N-coco group) propionic acid amide, gallic acid (N-tallow base) propionic acid amide, gallic acid (N-hydrogenated-tallow group) propionic acid amide and gallic acid (N-oil base) propionic acid amide further.

The further preferred described components b of the present invention 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, gallic acid decoylamide, gallic acid pelargonamide, gallic acid decyl amide, gallic acid laurylamide, gallic acid myristamide, gallic acid palmitamide, gallic acid stearylamide, gallic acid oil base acid amides, gallic acid (N-coco group) propionic acid amide, gallic acid (N-tallow base) propionic acid amide, one or more in gallic acid (N-hydrogenated-tallow group) propionic acid amide and gallic acid (N-oil base) propionic acid amide.Further preferred above-mentioned p-phenylene diamine derivative (Ursol D of replacement) and above-mentioned gallamide are with mass ratio 1:0.1 ~ 10 compound.

, after described component a and said components b compound, there is obvious synergistic effect, the improvement result of oxidation stability of fuel containing biodiesel strengthened greatly in the discovery that the present inventor is pleasantly surprised.Meanwhile, after adding the additive containing component a and components b compound, the color ratio of biodiesel fuel is used alone when components b will reach same antioxidant effect a lot shallow.

According to use needs, Dresel fuel compositions provided by the invention can also contain other additive, as one or more in phenol type antioxidant, polymer amine type ashless dispersant, FLOW IMPROVERS, cetane number improver, metal passivator, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc.

Described polymer amine type ashless dispersant comprise in allyl butyrate imide and/or alkenyl succinic acid acid amides, mannich base type ashless dispersant, polyethers amine type ashless dispersant and polyolefine amine type ashless dispersant one or more.Described allyl butyrate imide and/or the polyolefin-based Succinic anhydried of base succinamide ashless dispersant such as number-average molecular weight at 500-3000 and/or the reaction product of succinic acid and amine, if domestic trade names are T151A(mono butonediimide), T151B(mono butonediimide), the two succimide of T152(), the two succimide of T154(), T155(poly succimide) and/or T161(poly succimide) etc.Import additive as OLOA-1200, LZ894, Infineum C9238,9237, Hitec644 etc.The polyolefin-based phenol of mannich base type ashless dispersant such as number-average molecular weight at 500-3000 and the condensation product of formaldehyde and amine; After described polyethers amine type ashless dispersant such as C8-C30 alkylphenol 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; Described polyolefine amine type ashless dispersant such as chlorinatedpolyolefins and amine react the polyolefin-based amine generated.

Described FLOW IMPROVERS is preferably containing the polymkeric substance of (methyl) acrylate.Cetane number improver can be nitric ether or superoxide, as one or more in isooctyl ester nitrate, ditertiary butyl peroxide.Metal passivator can be that 124 Triazole and derivative, thiadiazoles and derivative thereof are as one or more in TH561, oxine, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base (Schiff bases), organic polycarboxylic acid and derivative thereof.Because this solvability in biofuel of 124 Triazole is very unexcellent, therefore, in order to increase its solvability in biofuel, usually carry out modification to 124 Triazole, the method for modification mainly through introducing oil-soluble group as long chain hydrocarbon groups in 124 Triazole.Therefore, described 124 Triazole derivative can be the various derivatives that various solvability in biofuel is good compared with 124 Triazole itself.Concrete, one or more in the described 124 Triazole derivative product that can be the ammonium salt that formed of 124 Triazole and aliphatic amide and 124 Triazole, formaldehyde and aliphatic amide be obtained by mannich reaction.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 one or more in N, N '-two salicylidene-1，2-diaminoethane, N, N '-two salicylidene-1,2-propylene diamine, N, N '-two salicylidene-1,2-cyclohexanediamine, N, N '-two salicylidene-N '-methyl dipropylenetriamine.Described organic polycarboxylic acid and derivative thereof can be such as one or more in citric acid, tartrate, oxysuccinic acid, succsinic acid (succinic acid), toxilic acid, phytic acid etc. and derivative thereof.Concrete, metal passivator can be the ammonium salt that 124 Triazole and aliphatic amide are formed, the product that 124 Triazole, formaldehyde and aliphatic amide are obtained by mannich reaction, one or more in Schiff's base and organic polycarboxylic acid.

The preparation of compositions of additives provided by the invention is simple, only each component of composition compositions of additives need be mixed.

Compositions of additives provided by the invention preferably with the content relative to Base Diesel for 50-10000 weight ppm(mg/kg), more preferably 50-5000 weight ppm, further preferably the consumption of 100-3000 weight ppm uses, and especially preferably the consumption of 150-800 weight ppm uses.

According to Dresel fuel compositions provided by the invention, this Dresel fuel compositions contains Base Diesel and additive, and described Base Diesel contains biofuel, and wherein, described additive is above-mentioned compositions of additives provided by the invention.

In the present invention, described Base Diesel can be all biofuel, also can be partly biofuel, simultaneously also containing other diesel oil, other diesel oil described be petroleum diesel, Fiscber-Tropscb synthesis diesel oil, hydrocracking biofuel, containing one or more in oxygen diesel oil blending thing.Under preferable case, the volume ratio of described biofuel and other diesel oil is 1:2-99.

The preparation of Dresel fuel compositions provided by the invention is simple, only each component of composition Dresel fuel compositions need be mixed.Directly each additive component can be mixed with Base Diesel, also can first various additive component be mixed, after obtaining compositions of additives, then gained compositions of additives be mixed with Base Diesel.In order to easy to operate, when various additive component is mixed, can carry out in the presence of solvent, here solvent 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 diluent oil and composition thereof, can also be biofuel.

In the present invention, described biofuel refers to that grease and low-carbon alcohol are (as C ₁-C ₅fatty alcohol) fatty acid ester of low-carbon alcohol of generation through transesterify (alcoholysis) reaction, 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 by grease and low-carbon alcohol obtains biofuel, such as acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, etc.Specifically can with reference to documents such as CN1473907A, DE3444893, CN1472280A, CN1142993C, CN1111591C, CN1594504A.

Described grease has general sense well known in the art, and be the general name of oil and fat, main component is fatty acid triglycercide.General normal temperature be liquid be called oil, normal temperature is solid or is semisolidly called fat (abbreviation fat).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 of such as waste cooking oil, sewer oil, swill oil, grease factory or rotten grease.Described vegetables oil can be herbaceous plant oil also can be 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 is oily, sheep is oily, house oil, butter, haco oil, shark wet goods.

In biodiesel composition of the present invention, described Base Diesel also can contain other diesel oil, other diesel oil described is petroleum diesel, Fiscber-Tropscb synthesis diesel oil, hydrocracking biofuel, containing one or more in oxygen diesel oil blending thing, the volume ratio of described biofuel and other diesel oil is preferably 1:2-99.

Wherein petroleum diesel refers to that the various refining process of crude oil (oil) through refinery are as the cut of boiling range between 160-380 DEG C after the device process such as Atmospheric vacuum, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking, and the compression ignition engine fuel meeting ordinary diesel oil standard GB/T 252 or derv fuel oil standard GB/T/T19147 through allocating.

Fiscber-Tropscb synthesis diesel oil mainly refers to the GTL diesel oil (Gas To Liquid) produced through fischer-tropsch (F-T) synthetic method for raw material with Sweet natural gas or coal or CTL diesel oil (Coal To Liquid), can also be the BTL diesel oil (Biomass To Liquid) that vegetable fibre is produced through fischer-tropsch synthetic method.Fiscber-Tropscb synthesis diesel oil not sulfur-bearing and aromatic hydrocarbons substantially, very clean fuel, but its oilness extreme difference, after concocting with biofuel, oilness is improved greatly, but the oxidation stability of tempered oil is likely deteriorated, the blending fuel therefore containing biofuel also needs to add oxidation inhibitor.

Hydrocracking biofuel also referred to as s-generation biofuel, refer to by animal-plant oil generate after hydrogenation and 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, greatly can reduce the discharge of diesel engine pollutent as diesel motor fuel or blending component.

Refer to be deployed into various diesel-fuel containing oxygen diesel oil blending component and meet the oxygenatedchemicals of certain code requirement or the mixture of oxygenatedchemicals, normally alcohols and ethers or its mixture, alcohols is C such as ₁-C ₁₈fatty alcohol, preferably 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, when described Base Diesel is the blending fuel containing biofuel, described additive by described additive, biofuel and other diesel oil being directly obtained by mixing, also can first can mix with biofuel by described Dresel fuel compositions, and then with other diesel oil blending and obtaining.The various components of additive directly can be mixed with Base Diesel, also can first the various components of additive be pre-mixed, to obtain after additive agent mixture again with Base Diesel.The various component of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various order.Mixing condition can various Dresel fuel compositions is not caused to the condition of disadvantageous effect under carry out, such as, can mix at ambient temperature.

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

Under preferable case, described additive is 50-10000 weight ppm(mg/kg relative to the add-on of Base Diesel), more preferably 50-5000 weight ppm, further preferred 100-3000 weight ppm, especially preferably 150-800 weight ppm.

Be described above about Base Diesel and compositions of additives, the present invention does not repeat them here.

The present invention is described further for the following examples.

Preparation example 1-5 is for illustration of the synthesis of component a.

Preparation example 1

In three-necked bottle, add 116.2g N-cocoyl-1,3-trimethylene diamines and 35.0g ethylenediamine tetraacetic acid (EDTA) (EDTA), wherein the mol ratio of N-cocoyl-1,3-trimethylene diamines and ethylenediamine tetraacetic acid (EDTA) is 4:1, i.e. the mol ratio 1:1 of carboxyl in amine and amino polyprotonic acid.Heated and stirred to 190 DEG C, passes into nitrogen reaction 20h, and collects the water generated with collector, then cool to 120 DEG C, takes out 2h with a small amount of water generated except dereaction, collect watery thing 13.6g altogether, obtain reaction product 125.2g with vacuum pump pressure.

Preparation example 2

In three-necked bottle, add 129.8g N-oil base-1,3-trimethylene diamines and 38.2g complexon I (NTA), wherein the mol ratio of N-oil base-1,3-trimethylene diamines and complexon I is 2:1, i.e. carboxyl mol ratio 1:1.5 in amine and amino polyprotonic acid.Heated and stirred to 170 DEG C, passes into nitrogen reaction 18h, and collects the water generated with collector, then cool to 110 DEG C, takes out 2h with a small amount of water generated except dereaction, collect watery thing 6.6g altogether, obtain reaction product 149.4g with vacuum pump pressure.

Preparation example 3

In three-necked bottle, add 133.8g oleyl amine and 38.3g1,3-trimethylenedinitrilo-tertraacetic acid (PDTA), wherein the mol ratio of oleyl amine and 1,3-trimethylenedinitrilo-tertraacetic acid is 4:1, i.e. carboxyl mol ratio 1:1 in amine and amino polyprotonic acid.Heated and stirred to 200 DEG C, passes into nitrogen reaction 25h, and collects the water generated with collector, then cool to 120 DEG C, takes out 2h with a small amount of water generated except dereaction, collect watery thing 10.1g altogether, obtain reaction product 149.4g with vacuum pump pressure.

Preparation example 4

In three-necked bottle, add 186.2g oleic acid and triethylene tetramine reacts the acid amides and 35.0g ethylenediamine tetraacetic acid (EDTA) (EDTA) that are formed, wherein oleic acid and triethylene tetramine react the mol ratio of acid amides and the ethylenediamine tetraacetic acid (EDTA) formed is 3:1, i.e. the mol ratio 0.75:1 of carboxyl in organic amine and amino polyprotonic acid.Heated and stirred to 200 DEG C, passes into nitrogen reaction 20h, and collects the water generated with collector, then cool to 120 DEG C, takes out 2h with a small amount of water generated except dereaction, collect watery thing 12.8g altogether, obtain reaction product 162.2g with vacuum pump pressure.

Wherein, oleic acid and triethylene tetramine react the acid amides formed and prepare according to following step:

In a 500ml three-necked bottle, add 0.5mol oleic acid and 0.3mol triethylene tetramine heated and stirred to 130 DEG C, pass into nitrogen and blow water and react 5 hours.Product after dewatering, by infrared analysis product, finds the characteristic peak having amide group in reaction product.This reaction product directly reacts the acid amides that the formed condensation product for the preparation of amino polyprotonic acid of the present invention and organic amine as oleic acid and triethylene tetramine.

Preparation example 5

In three-necked bottle, add octadecylamine and 1,3-trimethylenedinitrilo-tertraacetic acid (PDTA), wherein the mol ratio of octadecylamine and 1,3-trimethylenedinitrilo-tertraacetic acid is 4:1, i.e. carboxyl mol ratio 1:1 in amine and amino polyprotonic acid.Heated and stirred to 200 DEG C, passes into nitrogen reaction 25h, and collects the water generated with collector, then cool to 120 DEG C, takes out 2h with a small amount of water generated except dereaction, obtain reaction product 150.1g with vacuum pump pressure.

Embodiment 1-9 and comparative example 1-12 is for illustration of the composition of compositions of additives.

Compositions of additives is prepared according to the weight ratio shown in table 1.

Table 1

Performance test

Below in test, acidification oil biofuel used is the biodiesel oil product that CNOOC New Energy (Hainan) Biological Energy Chemical Co., Ltd. provides, sewer oil biofuel used is provided by the remarkable new forms of energy company limited of Fujian Longyan, and petroleum diesel is the diesel oil meeting Beijing provincial standard DB11/239-2007 that Yanshan Mountain branch office of China Petrochemical Industry produces.Addition unification is adjusted (i.e. not solvent-laden add-on) with dry dosage.

(1) based on pure biofuel, the oxidation stability of the biodiesel composition of diesel oil is tested

Oxidation stability of biodiesel is evaluated the inductive phase measured at 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, illustrate that the oxidation-resistance of Dresel fuel compositions is better, otherwise inductive phase is shorter, illustrates that the oxidation-resistance of Dresel fuel compositions is poorer.Colourity ASTM D1500 method measures, and the little explanation of chroma data is of light color.Its test result is shown in table 2, table 3.

Table 2 sewer oil biofuel adds agent effect

Additive is originated	Addition/(mg/kg)	110 DEG C inductive phase/(hr)	Colourity/number
				-	-	1.0	1.0
Embodiment 1	500	23.2	2.0
				Embodiment 1	250	15.3	1.5
Comparative example 1	250	2.1	1.0
				Comparative example 1	500	3.4	1.5
Comparative example 2	250	10.4	3.0
				Comparative example 2	500	15.1	3.5
Embodiment 2	300	16.2	1.5
				Comparative example 3	200	2.7	1.5
Comparative example 3	300	3.3	1.5
				Comparative example 4	100	5.4	1.5
Comparative example 4	300	10.1	3.5
				Embodiment 3	450	20.1	2.5
Comparative example 5	150	3.8	1.5
				Comparative example 5	450	5.3	2.0
Comparative example 6	300	9.9	3.0
				Comparative example 6	450	14.6	3.5
Embodiment 4	500	8.9	2.0
				Comparative example 7	500	5.7	3.0
Embodiment 5	500	10.1	2.0
				Comparative example 8	500	6.8	3.0
Embodiment 6	500	16.8	2.0
				Comparative example 9	500	10.8	3.0
Embodiment 7	500	26.8	2.0
				Embodiment 7	250	18.1	1.5
Comparative example 10	500	18.8	3.5
				Comparative example 10	250	11.5	2.5
Embodiment 8	600	22.5	1.5

Embodiment 8	300	15.8	1.0
				Comparative example 11	500	6.1	1.0
Comparative example 11	600	7.8	1.0
				Comparative example 10	600	20.1	3.5
Embodiment 9	600	24.1	2.5
				Comparative example 12	100	1.0	1.0
Comparative example 12	600	3.2	1.0

Data as can be seen from table 2, the effect that condensation reaction products by amino polyprotonic acid and polyamines provided by the invention is used alone as biological diesel oil anti-oxidant is poor, and well improve effect as having oxidation stability of biodiesel after one or more (components b) compounds in component a and arylamine type oxidation inhibitor, gallamide, there is unexpected synergy in the two, greatly be better than it to the improvement effect of oxidation stability of biodiesel to be used alone, after compound, components b be significantly less than to the intensification degree of biofuel color simultaneously and be used alone.Arylamine antioxidant, gallamide are used alone and have some improvement effect to oxidation stability of biodiesel, especially p-phenylene diamine derivative's (Ursol D of replacement) and gallamide, but biofuel color when its consumption is slightly large, can be caused greatly to deepen.As can be seen from the effect of embodiment 1,2 and embodiment 4,5, p-phenylene diamine derivative's (Ursol D of replacement) kind antioxidant is better than naphthylamines that diphenylamine derivatives (pentanoic of replacement) and phenyl replace individually as components b and component a compound as the effect of components b and component a compound.As can be seen from the effect of embodiment 4,5,6, after the naphthylamines compound that diphenylamine derivatives (pentanoic of replacement) and phenyl replace, be better than naphthylamines that diphenylamine derivatives (pentanoic of replacement) and phenyl replace again with the effect of component a compound individually as components b and component a compound as components b.As can be seen from the effect of embodiment 1 and 7, more excellent with the effect of component a compound again as components b after p-phenylene diamine derivative's (Ursol D of replacement) kind antioxidant and gallamide compound.

Table 3 acidification oil biofuel adds agent effect

Additive is originated	Addition/(mg/kg)	110 DEG C inductive phase/(hr)	Colourity/number
				-	-	1.4	1.5
Embodiment 1	400	16.9	2.5
				Comparative example 1	400	2.7	2.0
Comparative example 2	400	9.9	3.5
				Embodiment 2	600	23.5	2.5
Comparative example 4	600	4.7	2.5
				Comparative example 5	600	14.8	4.0
Embodiment 3	300	15.9	2.5
				Comparative example 5	300	5.0	2.5
Comparative example 6	300	8.9	3.5
				Embodiment 7	400	21.3	2.5
Comparative example 10	400	11.4	3.5
				Embodiment 8	600	24.7	1.5
Comparative example 11	500	7.0	1.0
				Comparative example 11	600	8.3	1.0
Comparative example 10	600	22.8	3.5
				Embodiment 9	600	25.9	3.0
Comparative example 12	100	1.3	1.0
				Comparative example 12	600	2.8	1.0

Data as can be seen from table 3, condensation reaction products by amino polyprotonic acid and polyamines provided by the invention well improves effect as having acidification oil oxidation stability of biodiesel after one or more (components b) compounds in component a and arylamine type oxidation inhibitor, gallamide, there is unexpected synergy in the two, greatly be better than it to the improvement effect of oxidation stability of biodiesel to be used alone, after compound, components b be significantly less than to the intensification degree of biofuel color simultaneously and be used alone.

(2) test of the stability of the concocted diesel oil composition of diesel oil based on the mixture of biofuel and petroleum diesel, biofuel used is acidification oil biofuel.

The method of EN15751:2009 is adopted to measure each Dresel fuel compositions, petroleum diesel and concocted diesel oil inductive phase at 110 DEG C respectively, use the 743 type oil oxidative stability determinators that instrument is Wan Tong company of Switzerland, inductive phase is longer, illustrate that the oxidation-resistance of biodiesel composition is better, otherwise inductive phase is shorter, illustrates that the oxidation-resistance of biodiesel composition is poorer.Its test result is shown in Table 4.

Table 4

As can be seen from the result of table 4, after adding biofuel, oxidation stability containing the blending fuel of biofuel is poor, the invention provides and have good effect as after one or more (i.e. components b) compounds in component a and arylamine type oxidation inhibitor, gallamide to improving biodiesel blend fuels oxidation stability by the condensation reaction products of amino polyprotonic acid and polyamines, be obviously better than the effect being used alone components b.

Table 3, table 4 also can be found out, as can be seen from the effect of embodiment 1 and 7, more excellent with the effect of component a compound again as components b after p-phenylene diamine derivative's (Ursol D of replacement) kind antioxidant and gallamide compound.

More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.

It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.

In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (15)

1. a compositions of additives, is characterized in that, this compositions of additives contains component a and components b, and described component a is the condensation reaction products of amino polyprotonic acid and organic amine; Described components b is one or more in arylamine type oxidation inhibitor and gallamide.

2. compositions of additives according to claim 1, wherein, the weight ratio of described components b and component a is 0.01-10:1.

3. compositions of additives according to claim 1 and 2, wherein, number 1-5 amino in described amino polyprotonic acid, the number of hydroxy-acid group is 2-6, and described amino is tertiary amino; Described organic amine contains at least two NH groups or contains at least one NH and at least one C=C.

4. according to the compositions of additives in claim 1-3 described in any one, wherein, the total number of carbon atoms of described amino polyprotonic acid is 4-14, and hydroxy-acid group is one or more in formyloxy, acetoxyl, propionyloxy and butyric acid base, and described organic amine is NH ₂(CH ₂) _mnHR ', NH ₂r ' ' and NH ₂(CH ₂) _nnH ₂in the acid amides that formed of one or more and R ' ' ' COOH in one or more, wherein, m and n is 1-4, R separately ', R ' ' and R ' ' ' is separately for carbon atom is the alkyl of 5-25.

5. the compositions of additives according to claim 3 or 4, wherein, number amino in described amino polyprotonic acid is 1-3, and the number of hydroxy-acid group is 2-5, hydroxy-acid group is acetoxyl and/or propionyloxy, and R ', R ' ' and R ' ' ' are cocoyl or 9-octadecylene base separately.

6. compositions of additives according to claim 1, wherein, described amino polyprotonic acid is iminodiethanoic acid, complexon I, ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetrapropionic acid(EDTP), 1,2-trimethylenedinitrilo-tertraacetic acid, 1,3-trimethylenedinitrilo-tertraacetic acid, diethylene triamine pentacetic acid (DTPA), 1, one or more in 6-hexamethylene dinitrilo-tetraacetic acid, CDTA; Described organic amine is N-cocoyl Edamine, N-cocoyl-1,3-trimethylene diamines, N-oil base Edamine, N-oil base-1,3-trimethylene diamines, 9-octadecenyl amine, coconut oil and diethylenetriamine in molar ratio 1:0.5-1 react the acid amides, coconut oil and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react the acid amides, oleic acid and the diethylenetriamine that are formed in molar ratio 1:0.5-1 react the acid amides, oleic acid and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react in the acid amides formed one or more.

7. according to the compositions of additives in claim 3-6 described in any one, wherein, in the mol ratio of the described amino polyprotonic acid of the carboxyl in amino polyprotonic acid and organic amine for 1:0.6-1.5, the temperature of condensation reaction is 80-300 DEG C, and the time of condensation reaction is 5-30 hour.

8. according to the compositions of additives in claim 1-7 described in any one, 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, gallic acid decoylamide, gallic acid pelargonamide, gallic acid decyl amide, gallic acid laurylamide, gallic acid myristamide, gallic acid palmitamide, gallic acid stearylamide, gallic acid oil base acid amides, gallic acid (N-coco group) propionic acid amide, gallic acid (N-tallow base) propionic acid amide, one or more in gallic acid (N-hydrogenated-tallow group) propionic acid amide and gallic acid (N-oil base) propionic acid amide.

9. compositions of additives according to claim 1, wherein, this compositions of additives also containing other additive, other additive described be selected from phenol type antioxidant, polymer amine type ashless dispersant, FLOW IMPROVERS, cetane number improver, metal passivator, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc. one or more.

10. a Dresel fuel compositions, this Dresel fuel compositions contains Base Diesel and additive, and described Base Diesel contains biofuel, it is characterized in that, described additive is the compositions of additives in claim 1-9 described in any one.

11. Dresel fuel compositions according to claim 10, wherein, described additive is 50-10000 weight ppm relative to the content of Base Diesel.

12. Dresel fuel compositions according to claim 10 or 11, wherein, described Base Diesel is also containing other diesel oil, other diesel oil described is petroleum diesel, Fiscber-Tropscb synthesis diesel oil, hydrocracking biofuel, containing one or more in oxygen diesel oil blending thing, the volume ratio of described biofuel and other diesel oil is 1:2-99.

13. 1 kinds of methods improving oxidation stability of biodiesel, the method comprises, and adds additive, it is characterized in that in containing the Base Diesel of biofuel, and described additive is the compositions of additives in claim 1-9 described in any one.

14. methods according to claim 13, wherein, described additive is 50-10000 weight ppm relative to the add-on of Base Diesel.

15. methods according to claim 13 or 14, wherein, described Base Diesel is also containing other diesel oil, other diesel oil described is petroleum diesel, Fiscber-Tropscb synthesis diesel oil, hydrocracking biofuel, containing one or more in oxygen diesel oil blending thing, the volume ratio of described biofuel and other diesel oil is 1:2-99.