CN101928614A - Diesel composite and method for improving oxidation stability of biodiesel - Google Patents
Diesel composite and method for improving oxidation stability of biodiesel Download PDFInfo
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- CN101928614A CN101928614A CN2009100879709A CN200910087970A CN101928614A CN 101928614 A CN101928614 A CN 101928614A CN 2009100879709 A CN2009100879709 A CN 2009100879709A CN 200910087970 A CN200910087970 A CN 200910087970A CN 101928614 A CN101928614 A CN 101928614A
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Abstract
The invention provides a diesel composite which comprises base diesel and addition agent, wherein the base diesel comprises biodiesel, the addition agent comprises a component a and a component b; the component a comprises arylamine type antioxidant and/or hindered phenol type antioxidant, the component b comprises organic amine different from arylamine serving as the component a. The addition agent also optionally comprises a component c, the component c is metal deactivator which can react with the metal surface and/or metal chelator which can react or combine with metal or metal ions. The diesel composite of the invention features in good oxidation stability. The invention also provides a method for improving the oxidation stability of the biodiesel.
Description
Technical field
The invention relates to the method for a kind of Dresel fuel compositions and raising oxidation stability of biodiesel.
Background technology
Quickening along with vehicle diesel oil trend in the world wide, the demand of diesel oil can be more and more big, and the raising of exhausted day by day and people's environmental consciousness of petroleum resources, promoted countries in the world to accelerate the exploitation paces of diesel oil alternative fuel greatly, biofuel has been subjected to the attention of various countries with its superior environmental-protecting performance and recyclability.
Biofuel (BD100) claims fatty acid methyl ester (Fatty Acid Methyl Ester) again, be that grease and the animal grease with oil plant waterplant such as oil-yielding shrubs fruit, engineering microalgae such as oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistaches, the food and drink wet goods that gives up are made raw material, obtaining through transesterification reaction with alcohols (methyl alcohol, ethanol), is a kind of biofuel of cleaning.That biofuel has is renewable, cleaning and safety three big advantages, and China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment are had very great strategic importance.And China is a net import of oil state at present, and prospective oil is very limited again, and a large amount of Imported oils threaten to the energy security of China; Therefore, the research of biofuel and production have important practical sense to China.
But because raw material and complete processing, the oxidation stability of some biofuel is very poor, using and store and all cause very big difficulty biofuel.The biofuel of oxidation stability difference easily generates following ageing products: 1) insoluble polymer (colloid and greasy filth), and this can cause the engine filter screen to stop up and the squirt pump coking, and causes smoke evacuation to increase, start difficulty; 2) soluble polymer, it can form resinous substance in engine, may cause flame-out and the startup difficulty; 3) aging acid, this can cause the engine metal component corrosion; 4) superoxide, this can cause aging the becoming fragile of rubber components and cause fuel leakage etc.
Europe biofuel standard EN 14214:2003, Australian biofuel standard (Draft2003), New Zealand biofuel standard NZS 7500:2005, Brazilian biofuel standard A NP255 (2003), India biofuel standard I S 15607:2005, South Africa biofuel standard SANS1935:2004 and China's diesel-fuel blending with biofuel (BD100) standard GB/T20828-2007 all the oxidation stability of regulation biofuel be to be not less than 6 hours inductive phase under 110 ℃, 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, non-hydrocarbon compounds such as alkene, diolefin and the sulfide the special petroleum diesel of introducing), nitride are under the effect of oxygen, generate a series of intermediate oxidation product, and produce insoluble precipitation through condensation.These insoluble particles that generate in the petroleum diesel storage process can have influence on the use properties of fuel, cause filtering system to stop up, and cause the prime the fuel system unit failure; influence oil atomizing; cause incomplete combustion, even in engine, form too much carbon deposit, make spray nozzle clogging.And biofuel is because oxidation stability than petroleum diesel difference, and can increase the weight of the problems referred to above after the petroleum diesel blending.The most significantly performance is that to contain the stability and the detergent-dispersant performance of the blending fuel of biofuel more far short of what is expected than petroleum diesel.
The problems referred to above can additive solves or alleviation by adding.A kind of mode is to add oxidation inhibitor slowing down its oxidation in pure biofuel, thereby alleviates the harm of ageing products; Another kind of mode is to petroleum diesel or contains in the blending fuel of biofuel and add stablizer and detergent-dispersant additive, with stability and the detergent-dispersant performance that improves 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 the nozzle, and forms protective membrane at nozzle surface, prevents that new carbon deposit from producing, but established sediment in the dispersed oil also simultaneously improves purifier and spray nozzle clogging, and improves exhaust emissions.
CN1742072A discloses a kind of method that improves storage stability of bio-diesel, this method comprises and is dissolved in 2 of biofuel with containing with what stoste was counted 15-60 weight %, the liquid stoste of 4-di-t-butyl hydroxy toluene joins in the biofuel for the treatment of stabilization, until total solution in biofuel, 2, the concentration of 4-di-t-butyl hydroxy toluene reaches 0.005-2 weight %.
CN1847368A discloses a kind of method that improves the oxidative stability of biofuel, this method comprises bisphenol type oxidation inhibitor as 4,4`-methylene radical two [2, the 6-DI-tert-butylphenol compounds], 2,2`-methylene radical two [the 6-tertiary butyl-4-methylphenol] joins with the amount of 10-20000ppm (w/w) and treats in the stable biofuel.
CN1847369A discloses a kind of method that improves the oxidative stability of biofuel, this method comprises that fusing point is less than or equal to 40 ℃ main anti-oxidant to join with the amount of 10-20000ppm (w/w) and treat that in the stable biofuel, wherein said main anti-oxidant contains alkylphenol.
US2007/113467A1 discloses a kind of fuel composition with improved oxidative stability, said composition contains biofuel and at least a oxidation inhibitor, described oxidation inhibitor is selected from Tenox PG, 1,2,3-trihydroxybenzene, 2, a kind of in 6-di-tert-butyl methyl phenol, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, tocopherol, the quinoline.
Though the method for more than using traditional oxidation inhibitor to improve oxidation stability of biodiesel has certain effect, consumption is all bigger, simultaneously to the stability of the blending fuel that contains biofuel to improve effect also not so good.
Summary of the invention
The objective of the invention is for what overcome above-mentioned prior art is that the oxidation stability of Dresel fuel compositions of basic diesel oil is relatively poor and be the shortcoming of less stable of the Dresel fuel compositions of basic diesel oil with the blending fuel of biofuel and other diesel oil with pure biofuel, and a kind of oxidation stability or stability Dresel fuel compositions and a kind of method that improves oxidation stability of biodiesel is provided preferably is provided.
The invention provides a kind of Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, and wherein, described basic diesel oil contains biofuel, described additive contains component a and components b, and described component a contains arylamine type oxidation inhibitor and/or hindered phenol type antioxidant; Described components b contains the organic amine that is different from component a arylamine.
The present invention also provides a kind of method that improves oxidation stability of biodiesel simultaneously, this method comprises, in containing the basic diesel oil of biofuel, adds additive, described additive contains component a and components b, and described component a contains arylamine type oxidation inhibitor and/or hindered phenol type antioxidant; Described components b contains the organic amine that is different from component a.
Dresel fuel compositions provided by the invention, when with pure biofuel during as basic diesel oil, this Dresel fuel compositions has oxidation stability preferably, the amazing synergistic effect that occurs between component a and the components b, and antioxidant effect will be got well much than independent use oxidation inhibitor.Components b can be regarded as auxiliary antioxidant, and it can make the effect of oxidation inhibitor unexpectedly strengthen greatly.Therefore, when reaching identical oxidation stability and require, the amount of component a in biodiesel composition can significantly reduce, especially component a especially costliness or component a have under certain toxicity or the corrosive situation, reduced its consumption and had very big meaning.When with the blending fuel that contains biofuel during as basic diesel oil, the stability of this Dresel fuel compositions better.Particularly according to preferred implementation provided by the invention, when described additive contains component a, components b simultaneously, when perhaps also containing optional amount of component b simultaneously, because obvious synergistic effect between each additive, the antioxygen of Dresel fuel compositions provided by the invention obviously improves.
Embodiment
In Dresel fuel compositions provided by the invention, described content of additive can be selected in a big way, and for example the content with respect to basic diesel oil can be 50-10000ppm, is preferably 80-5000ppm, more preferably 100-3000ppm.
The weight ratio of described components b and component a can be 0.01-100: 1, be preferably 0.1-10: and 1,0.05-5 more preferably: 1, further be preferably 0.2-5: 1.
Component a
Component a is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, preferably contain Ursol D type oxidation inhibitor, have a tertiary butyl one or more in phenolic hydroxyl group adjacent hindered phenol type antioxidant at least, further preferred described component a contains one or more in the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 and the bisphenol type oxidation inhibitor that links to each other by methylene radical or sulphur.
Can be selected from least a in naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, the quinoline as the described arylamine type oxidation inhibitor of component a.
Wherein naphthylamine derivative includes but not limited to one or more in the following material:
Phenyl-a-naphthylamine (oxidation inhibitor T531, antioxidant A);
Phenyl beta naphthylamine (antioxidant d);
N-p-methoxyphenyl alpha-naphthylamine (anti-aging agent 102);
To hydroxyphenyl-beta-naphthylamine (antioxidant D-OH);
Aldol-alpha-naphthylamine (antioxidant A P)
2-hydroxyl-1, two [to (beta-naphthylamine) phenoxy group] propane (anti-aging agent C-49) of 3-;
Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41) of dimethyl;
Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41-ethyl) of diethyl;
2,2 '-two [to (beta-naphthylamine) phenoxy group] diethyl ether (anti-aging agent C-41-ether).
Wherein, the preferred nonox of naphthylamine derivative, for example one or more in phenyl-a-naphthylamine, Phenyl beta naphthylamine, the N-p-methoxyphenyl alpha-naphthylamine.Especially preferred phenyl-a-naphthylamine.
Wherein diphenylamine derivatives includes but not limited to one or more in the following material:
4,4 '-diamino-diphenylamine (antioxidant A PA);
Right, to '-the dimethoxy pentanoic;
N, N, N ', N '-tetraphenyl diamines methane (anti-aging agent 350);
N, N '-diphenyl ethylene diamine;
N, N '-diphenylprop diamines;
N, N '-di-o-tolyl-ethylene-diamine;
2-hydroxyl-1,3-pair-(to the aniline phenoxy group) propane (anti-aging agent C-47);
2,2 '-two (to the aniline phenoxy group)-diethyl ether (antioxidant H-1);
Two (to aniline-phenoxy group)-silane (anti-aging agent C-1) of dimethyl;
P-isopropoxy-diphenylamine (anti-aging agent ISO);
Right, to '-diisopropoxy pentanoic (antioxidant D ISO);
4,4 '-two (α, α '-dimethyl benzyl) pentanoic (anti-aging agent KY-405);
P-hydroxydiphenylamine (antioxidant A O3920);
Two-(1,1,3,3-tetramethyl-ethyl) pentanoic (anti-aging agent ODA);
4,4 '-dioctyl diphenylamine;
4,4 '-di-iso-octyldiphenylamine;
4,4 '-diheptyl pentanoic;
4,4 '-dinonyldiphenylamine;
Octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines, anti-aging agent OD);
Octyl group/butyl pentanoic (oxidation inhibitor L-57);
Styrenated diphenylamine (antioxidant D FL, DFC-34);
And the mixture of alkylated diphenylamine, wherein alkyl can be heptyl, octyl group, in the nonyl one or more, the example of its Industrial products has U.S. Pennwalt company commodity to be called Pennox A, Pennox A-" S ", American National Instrument polychem company commodity are called Wytox ADP, ADP-X, U.S. Vanderbilt company commodity are called Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, U.S. Uniroyal company commodity are called Polylite, Antioxidant 445, and domestic code name is the antioxidant product of T534.
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 among 4 '-dinonyldiphenylamine, octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines), octyl group/butyl pentanoic, the commodity oxidation inhibitor T534.
Wherein p-phenylene diamine derivative's type oxidation inhibitor comprises but is not limited in the following material one or more:
N phenyl-N '-cyclohexyl Ursol D (antioxidant 4010);
N, N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent 4020);
N, N '-two-(1,4-dimethyl amyl group) Ursol D (anti-aging agent 4030);
N-p-methylphenyl-N '-(1, the 3-dimethylbutyl) Ursol D (anti-aging agent 4040);
N, N '-diheptyl Ursol D (anti-aging agent 788);
N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);
N-sec.-propyl-N '-p-methylphenyl Ursol D (anti-aging agent methyl 4010NA);
N, N '-di tolyl p phenylenediamine (anti-aging agent PPD-A);
N, N '-diphenyl-para-phenylene diamine (antioxidant H);
N, N '-two-(betanaphthyl) Ursol D (antioxidant D NP);
N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5);
N, N '-dioctyl-p-phenylenediamine (anti-aging agent 88);
N, N '-two-(1-methylheptyl) Ursol D (anti-aging agent 288);
N, N '-two-(1-ethyl-3-methyl amyl) Ursol D (anti-aging agent 8L);
N, N '-two-(1, the 4-dimethylbutyl) Ursol D (anti-aging agent 66);
N-octyl group-N '-diphenyl-para-phenylene diamine (anti-aging agent 688);
N-isobutyl--N '-diphenyl-para-phenylene diamine (anti-aging agent 5L);
N, N '-dimethyl-N, N '-two-(1-first propyl group) Ursol D (anti-aging agent 32);
N-(p-methylphenyl alkylsulfonyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent TPPD);
N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent G-1);
N-(3-anilino phenyl) Methacrylamide;
N-hexyl-N '-diphenyl-para-phenylene diamine;
The preferred dialkyl group Ursol D of p-phenylene diamine derivative's type oxidation inhibitor, the dialkyl group Ursol D of preferred alkyl carbonatoms between 4-10 especially, as: N, N '-diheptyl Ursol D; N, N '-di-sec-butyl-p-phenyl enediamine; N, N '-dioctyl-p-phenylenediamine; N, one or more in N '-two-(1-methylheptyl) Ursol D.
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 of pentanoic and acetone and aldehyde (anti-aging agent BXA);
The reaction product of Phenyl beta naphthylamine and acetone (antioxidant A PN, antioxidant A M).
The preferred Ursol D class of arylamine antioxidant arylamine antioxidant.
Phenol type antioxidant described in the component a can be single phenol, bis-phenol, diphenol and polyphenol, also can be the mixture of their arbitrary proportions.
Wherein single phenol be have a phenyl ring/and phenyl ring on the phenol of the replacement of a hydroxyl is arranged, and have at least one to be the tertiary butyl in the substituting group, other substituting group can be alkyl or contain heteroatomic substituting group that alkyl wherein is selected from C
1-C
10Alkyl, for example methyl, ethyl, allyl group, normal-butyl, sec-butyl, nonyl etc. contain heteroatomic substituting group and are selected from methyl, methylol, nitrogenous substituting group such as the alpha, alpha-dimethyl aminomethyl that oxygen containing substituting group such as methoxyl group, methoxyl group replace.For example can be single phenol of following structure: o-tert-butylphenol, p-tert-butylphenol, the 2-tertiary butyl-4-methylphenol, 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-DI-tert-butylphenol compounds, 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-tert.-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), 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 phenolic hydroxyl group adjacent single phenol that is obstructed, as:
The 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2, the 4-xylenol, 2, the 6-DI-tert-butylphenol compounds, 2,6-di-tert-butyl-4-methy phenol (BHT, oxidation inhibitor T501), 2,4, the 6-tri-butyl-phenol, 4-sec-butyl-2, the 6-DI-tert-butylphenol compounds, 4-nonyl-2, the 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 the 6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703).
Bis-phenol is meant the phenol type antioxidant that is linked to each other by sulphur or carbon atom by two single phenol, for example:
(1) bis-phenol that links to each other by carbon atom
4,4 '-isopropylidene bis-phenol (dihydroxyphenyl propane);
2,2 '-two-(3-methyl-4 hydroxy phenyl) propane (bisphenol-c);
4,4 '-dihydroxybiphenyl (oxidation inhibitor DOD);
4,4 '-dihydroxyl-3,3 ', 5,5 '-four-tertiary butyl biphenyl (oxidation inhibitor 712);
2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol) (oxidation inhibitor bis-phenol 2246);
4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol) (oxidation inhibitor methene 736);
2,2 '-methylene radical-two-(4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);
2,2 '-methylene radical-two-(4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);
2,2 '-methylene radical-two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);
2,2 '-methylene radical-two-(6-α-Jia Jibianji p-cresol);
4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-two-(2-tert.-butyl phenol) (oxidation inhibitor 702);
2,2 '-ethylidene-two-(4-methyl-6-tert butyl phenol);
4,4 '-ethylidene-two-(2-methyl-6-tert butyl phenol);
4,4 '-ethylidene-two-(2,6 di t butyl phenol);
4,4 '-butylidene-two-(the 6-tertiary butyl-meta-cresol) (oxidation inhibitor BBM, oxidation inhibitor TCA);
4,4 '-isobutylidene-two-(2,6 di t butyl phenol) etc.
(2) bis-phenol that links to each other by sulphur atom
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2, and 2 '-thiobis-(4-methyl-6-tert butyl phenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert butyl phenol) (oxidation inhibitor 736);
4,4 '-thiobis-(5-methyl-2-tert.-butyl phenol);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
2,2 '-thiobis-(4-octyl phenol) etc.
(3) link to each other by carbon atom but contain heteroatomic bis-phenol
N, N '-hexamethylene is two-(3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) (oxidation inhibitor 1098);
Hexylene glycol two [β-(3, the 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, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S);
2,2 '-sulfurous ethyl glycol two [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 1035);
Triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (oxidation inhibitor 245) etc.
Bisphenol type oxidation inhibitor is preferably by the bis-phenol that has at least a tertiary butyl to link to each other by methylene radical or sulphur at phenolic hydroxyl group adjacent list phenol, for example:
2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol) (antioxidant 2246);
4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol) (oxidation inhibitor methene 736);
4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-two-(2-tert.-butyl phenol) (oxidation inhibitor 702);
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2, and 2 '-thiobis-(4-methyl-6-tert butyl phenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert butyl phenol) (oxidation inhibitor 736);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
Two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.
The diphenol here is meant the phenol type antioxidant that two hydroxyls are arranged on the phenyl ring, can be the diphenol of following structure: Resorcinol, Tert. Butyl Hydroquinone (TBHQ), 2,5-di-tert-butyl hydroquinone, 2, one or more in the 5-two tert-pentyl Resorcinol.
Described polyphenol antioxidant refers in the molecule macromole oxidation inhibitor by at least three single phenolic group groups preferably by having a tertiary butyl at least at the polyphenol that phenolic hydroxyl group adjacent list phenolic group group forms, and especially preferably has two tertiary butyls at the phenolic hydroxyl group adjacent polyphenol that is obstructed, for example:
1,3,5-trimethylammonium-2,4,6-three-(4 '-hydroxyl-3 ', 5 '-di-t-butyl) benzene (antioxidant 330);
Three [2-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl oxygen ethyl] isocyanic ester (oxidation inhibitor 3125);
Four (3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester (antioxidant 1010);
1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) (antioxidant 3114);
1,1,3-three-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA);
1,3,5-three (2, the 6-dimethyl-4-tertiary butyl-3-hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) (oxidation inhibitor 1790);
Two [3,3-pair-(3 '-tertiary butyl-4 '-hydroxybenzyl) butyric acid] glycol ester etc.
The polyphenol here can also be the phenol that has three hydroxyls in the phenyl ring, for example pyrogallol, gallic acid ester such as methyl gallate, Progallin A, Tenox PG, gallic acid butyl ester, 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 disclosed gallamide of CN200810115581.8 or ammonia salt.The preferred gallic acid-derivate of polyphenol type oxidation inhibitor is Tenox PG especially.
Above-mentioned phenol type antioxidant preferably has a tertiary butyl at least at phenolic hydroxyl group adjacent bisphenol type oxidation inhibitor, particularly by methylene radical or the continuous bisphenol type oxidation inhibitor of sulphur, Tert. Butyl Hydroquinone and/or 2 most preferably in the bisphenol type oxidation inhibitor, 5-di-tert-butyl hydroquinone, and one or more in the ammonia salt of gallic acid ester, gallamide and gallic acid most preferably in the polyphenol antioxidant.
Component a can also be the composite antioxidant of above-mentioned arylamine type oxidation inhibitor and above-mentioned phenol type antioxidant.The most preferably described component a 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 '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-tert.-butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
Components b
Described components b contains the organic amine of the structure shown in (A) that has structural formula:
(1) R
1, R
2Can respectively do for oneself H or carbonatoms is the alkyl of 1-30.
R
1, R
2One of them can be H, and another one can be the alkyl of 1-30 for carbonatoms, can be the alkyl of 1-30 for carbonatoms perhaps, and promptly organic amine can be a primary amine, also can be secondary amine." alkyl " refers to hydrocarbon substituent, i.e. a kind of in aliphatics, alicyclic, aromatics and the cyclic substituent.Aliphatic alkyl can be saturated also can be two keys of undersaturated band or triple-linked alkyl.Wherein 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, further preferred fat primary amine, described 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, positive amino dodecane (lauryl amine), positive tetradecy lamine, positive cetylamine, positive stearylamine, positive 20 amine, in positive two amino dodecanes one or more, it also can be the fat primary amine that has side chain, these fat primary amines that have side chain are various isomer of above-mentioned straight chain fat primary amine, Isopropylamine for example, isobutylamine, TERTIARY BUTYL AMINE, isobutylcarbylamine, neopentyl amine, dissident's amine, tuaminoheptane, octodrine (2 ethyl hexylamine), different nonyl amine, isodecyl amine, different amino dodecane, different tetradecy lamine, different cetylamine, different stearylamine, in different 20 amine one or more.Fat primary amine can also be to have the amine of cycloaliphatic ring such as cyclopentamine, hexahydroaniline.Also can be to contain unsaturated double-bond or triple-linked fat primary amine such as oleyl amine (octadecenyl amine), palm oleyl amine (hexadecylene amine) in the carbochain, can also be the primene JM-T, for example Rohm﹠amp; The trade names that Haas company produces are the primene JM-T of Primere 81R.
If secondary amine, wherein R
1, R
2Can be identical, also can be different, can be normal chain alkyl such as methyl separately, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl (lauryl), the n-tetradecane base, n-hexadecyl, the Octadecane base, NSC 62789 base or n-docosane base, also can be isomery alkyl such as the sec.-propyl that has side chain, isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, the Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base or Isoeicosane base.
(2) R
1, R
2Can respectively do for oneself H or carbonatoms is the heteroatomic group of being with of 1-30.
Here being with heteroatomic group can be carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino etc.
The amine that contains hydroxyl is thanomin, diethanolamine, N-alkyl ethanol amine, N-vinyl-ethyl alcohol amine, N-alkyl Yi Bingchunan, N-thiazolinyl Yi Bingchunan, Yi Bingchunan, diisopropanolamine (DIPA), Tutofusin tris, 3-amino-1 for example, 2-propylene glycol, 2-amino-1, one or more in ammediol, 3-aminopropanol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, the 4-amino-phenol.
The amine that contains amido or amino is polyamine compounds, and the polyamines here refers to contain in the molecule amine of two or more nitrogen-atoms, is H as structural formula
2N-R
3-NHR
4Amine, the R here
3Can be that carbon number is alkylidene group, thiazolinyl, cycloalkyl, aryl or the polyether-based of 1-30; R
4Can be that hydrogen, carbon number are the alkyl of 1-30.For example quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, decamethylene diamine, coconut oil base 1,3-propylene diamine, oil base 1,3-propylene diamine, tallow base 1,3-propylene diamine.Can also be as shown in the formula the polyether diamine shown in the A1:
Wherein x1 is the integer of 1-5, R
4Can be that hydrogen, carbon number are the alkyl of 1-30; R
5Be hydrogen or methyl.
Polyamines can also be a 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, is preferably 2 or 3, y1 can be the integer of 1-8, R
6Can be that hydrogen, carbon number are the alkyl of 1-30.For example, work as R
6During for H, described polyamines polyene can be in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, seven ethene, eight amine, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines, six propylene, seven amine, seven propylene, eight amine one or more.Work as R
6When being the alkyl of 1-30, be preferably the alkyl of C4-C22 for carbon number.This alkyl can be saturated alkyl, also can be the aryl that has the thiazolinyl of two keys or have phenyl ring.Alkyl can be the straight chain normal chain alkyl, also can be the isomery alkyl that has side chain, this alkyl can be normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; Isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, one or more in isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and the Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.The aryl that has phenyl ring can be one or more in phenmethyl (benzyl), styroyl and the hydrocinnamyl.Wherein, the more preferably alkyl of C6-C20.
The polyamines here can also be nitrogenous heterocyclic amine, such as but not limited in the amine of the amine of the amine of imidazoline type, piperazine type and piperidines type one or more.
The imidazoline type polyamines is as shown in the formula shown in the A2:
Wherein y2 is the integer of 0-5, R
7Be C
1-C
24Alkyl.Be preferably C
4-C
22Alkyl.This alkyl can be saturated alkyl, also can be the aryl that has the thiazolinyl of two keys or have phenyl ring.Alkyl can be the straight chain normal chain alkyl, also can be the isomery alkyl that has side chain, this alkyl can be normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; Isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, one or more in isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and the Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.The aryl that has phenyl ring can be one or more in phenmethyl (benzyl), styroyl and the hydrocinnamyl.Wherein, further preferred y2 is the integer of 1-3, R
7Be C
6-C
20Alkyl or alkenyl.
Piperazine type polyamines is as shown in the formula shown in the A3:
R wherein
8Be the alkyl of H or C1-C24, x3 is the integer of 0-5.Preferred typical piperazine type polyamines is N-(2-amino-ethyl) piperazine, N-(2-aminoethyl)-1,4-piperazine two basic diethylamine etc.
The polyamines of piperidines type such as 4-amino-2,2,6,6-tetramethyl piperidine, 4-amino-1,2,2,6,6-pentamethyl-piperidines etc.
The polyamines here can also be suc as formula the polyamines that contains tertiary amine shown in A4, the A5.
R wherein
9, R
10For or the alkyl of C1-C24, x4 is the integer of 0-10.Preferred R
9, R
10Be the alkyl of C1-C10, x4 is the integer of 1-8.N for example, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dimethyl-1, one or more in the 6-hexanediamine.
Wherein x5 is the integer of 1-10, is preferably the integer of 2-6, for example three (2-amino-ethyl) amine.
Polyamines can also be that structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene and the condenses of oxyethane, propylene oxide.Wherein, x2 can be the integer of 2-4, is preferably 2 or 3, and y1 can be the integer of 1-8, R
6Can be that hydrogen or carbon number are the alkyl of 1-30.
Described organic amine as components b of the present invention is preferably polyamines, further preferably contains the polyamines of at least one primary amine group.
Components b of the present invention also can further contain one or more in the following polymer amine type ashless dispersant except that containing above-mentioned organic amine, the mass ratio of the two is preferably 1: 0.1-10.These polymer amine type ashless dispersants comprise allyl butyrate imide and/or alkenyl succinic acid acid amides, mannich base type ashless dispersant, polyetheramine type ashless dispersant and polyalkene amines type ashless dispersant.Described allyl butyrate imide and/or basic 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; 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; Described polyetheramine type ashless dispersant for example behind C8-C30 alkylphenol and oxyethane or the 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 polyalkene amines type ashless dispersant is the polyolefin-based amine that generates of chlorinatedpolyolefins and amine reaction for example.Here all preferred polyamines of said amine, said especially as mentioned polyamines polyene.
Amount of component b
Under the preferable case, Dresel fuel compositions provided by the invention also contains amount of component b, and described amount of component b can be reacted or the bonded metal chelator with the metal passivator of metallic surface reaction and/or with metal or metal ion for various.The weight ratio of described component a and amount of component b can be 1: 0-1, the weight ratio of preferred described component a and described amount of component b is 1: 0.01-1, more preferably 1: 0.01-0.5 further is preferably 1: 0.02-0.2.
Concrete, described amount of component b can be in 124 Triazole and derivative, thiadiazoles and derivative thereof, oxine, ethylenediamine tetraacetic carboxylic acid, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base (Schiff bases), organic polycarboxylic acid and the derivative thereof one or more.Because this solvability in biofuel of 124 Triazole is very unexcellent, therefore, in order to increase its solvability in biofuel, usually 124 Triazole is carried out modification, the method for modification is mainly by introducing oil-soluble group such as long chain hydrocarbon groups in 124 Triazole.Therefore, described 124 Triazole derivative can be various solvabilities in the biofuel various derivatives good than 124 Triazole itself.Concrete, one or more in the described 124 Triazole derivative product that can be 124 Triazole obtain by mannich reaction with the ammonium salt of aliphatic amide formation and 124 Triazole, formaldehyde and aliphatic amide.Described ethylenediamine tetraacetic carboxylic acid can be ethylenediamine tetraacetic acid (EDTA) (EDTA), and described hydrazides can be N-salicylidene-N '-salicylyl hydrazine and/or N, N '-diacetyl adipyl two hydrazides.Described beta-diketon such as methyl ethyl diketone, described 'beta '-ketoester such as etheric acid monooctyl ester.Described Schiff's base can be N, N '-two salicylidenes-1, N, N '-two salicylidene-1,2-propylene diamine, N, N '-two salicylidene-1,2-cyclohexanediamine, N, one or more in N '-two salicylidenes-N '-methyl two propylene triamines.Described organic polycarboxylic acid and derivative thereof for example can be one or more in citric acid, tartrate, oxysuccinic acid, succsinic acid (Succinic Acid), toxilic acid, phytic acid etc. and the derivative thereof.
Among the present invention, preferred described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction (for example commercial additive of commodity T551 by name), Schiff's base and organic polycarboxylic acid and with the condensation reaction products (being amides, the ester derivative of organic polycarboxylic acid) of aliphatic amide or Fatty Alcohol(C12-C14 and C12-C18) in one or more.
According to using needs, Dresel fuel compositions provided by the invention can also contain other additive, as in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, the emulsion splitter etc. one or more.
The preparation of Dresel fuel compositions provided by the invention is simple, and each component that only need form Dresel fuel compositions mixes and gets final product.Can directly each additive component be mixed with the various compositions of basic diesel oil, also can earlier various additive components be mixed, obtain additive after, again the gained additive is mixed with the various compositions of basic diesel oil or basic diesel oil.For easy to operate, when various additive components are mixed, can in the presence of solvent, carry out, the solvent here can be polar solvent such as N, dinethylformamide (DMF), 1, one or more in 4-dioxane, tetrahydrofuran (THF) (DHF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidone and the methyl-2-pyrrolidone.Also can be especially aromatic hydrocarbons such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil and composition thereof of hydro carbons, can also be biofuel.
In the present invention, described basic diesel oil can be pure biofuel, and described biofuel is meant that grease and low-carbon alcohol are (as C
1-C
5Fatty Alcohol(C12-C14 and C12-C18)) fatty acid ester of low-carbon alcohol that generates through transesterify (alcoholysis) reaction is generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.
Described trans-esterification processes can be the processing method that any known or unknown transesterification reaction of passing through grease and low-carbon alcohol obtains biofuel, for example acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, or the like.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 a fatty acid triglycercide.General normal temperature is the oil that is called of liquid, and normal temperature is solid or the semisolid fat (abbreviation fat) that is called.Described grease comprises vegetables oil and animal oil, in addition, also comprise from the oil plant in the materials such as microorganism, algae, even can also be waste oil, for example the used grease of acidifying wet goods or the rotten grease of waste cooking oil, sewer oil, swill oil, grease factory.Described vegetables oil can be that herbaceous plant oil also can be xylophyta oil, as the oil of peanut oil, Semen Maydis oil, Oleum Gossypii semen, rape seed oil, soybean oil, plam oil, Thistle oil, linseed oil, Oleum Cocois, Oak Tree oil, Prunus amygdalus oil, walnut oil, Viscotrol C, sesame oil, sweet oil, Yatall MA (Tall Oil), sunflower oil, curcas oil, tung oil, shinyleaf yellowhorn oil, coptis wood oil, halophytes such as plants 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, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of described biofuel and other diesel oil is preferably 1: 2-99.
Wherein petroleum diesel is meant boiling range the cut 160-380 ℃ between of crude oil (oil) after devices such as the various refining process decompression as usual of refinery, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking are handled, and the compression ignition engine fuel that satisfies solar oil standard GB 252 or derv fuel oil standard GB 19147 that forms through allotment.
The fischer-tropsch combined diesel oil refers to that mainly with Sweet natural gas or coal be GTL diesel oil (Gas To Liquid) or the CTL diesel oil (Coal To Liquid) that raw material funds-Tuo (F-T) synthetic method is produced, and can also be vegetable fibre funds-Tuo synthetic method and the BTL diesel oil (Biomass To Liquid) produced.The fischer-tropsch combined diesel oil is substantially free of sulphur and aromatic hydrocarbons, be very clean fuel, but its oilness extreme difference improve greatly with biofuel blending back oilness, but the possible variation of the oxidation stability of tempered oil, the blending fuel that therefore contains biofuel also needs to add oxidation inhibitor.
The hydrocracking biofuel is also referred to as s-generation biofuel, be meant by animal-plant oil through generate after hydrogenation and the cracking reaction with C
8-C
24Alkane is main, especially with C
12-C
20Normal paraffin is the reaction product of main component, this hydrocracking biofuel cetane value height, and sulphur and aromaticity content are extremely low, can reduce the discharging of diesel engine pollutent greatly as diesel motor fuel or blending component.
Contain oxygen diesel oil blending component and be meant and can be deployed into the oxygenatedchemicals that meets certain code requirement or the mixture of oxygenatedchemicals with various diesel-fuels, normally alcohols and ethers or its mixture, alcohols is C for example
1-C
18Fatty Alcohol(C12-C14 and C12-C18), preferred C
1-C
12Unitary fatty alcohol is 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) wait and composition thereof.
Among the present invention, described basic diesel oil is when containing the blending fuel of biofuel, described Dresel fuel compositions can obtain by described additive, biofuel and other diesel oil are directly mixed, and also can earlier described additive be mixed with biofuel, and then obtain with other diesel oil blending.The various components of additive directly can be mixed with the various compositions of basic diesel oil, also can be earlier the various components of additive be pre-mixed, obtain mixing with the various compositions of basic diesel oil or basic diesel oil again behind the additive agent mixture.The various components of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various orders.The blended condition 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 containing the diesel component of biofuel, adds additive, and described additive contains component a and components b, and described component a contains arylamine type oxidation inhibitor and/or hindered phenol type antioxidant; Described components b contains the organic amine that is different from component a.
Under the preferable case, the method of raising oxidation stability of biodiesel provided by the invention, described additive also contains amount of component b, and described amount of component b is to react or the bonded metal chelator with the metal passivator of metallic surface reaction and/or with metal or metal ion.
Described components of additives a, components of additives b and components of additives c are identical with component a, components b and amount of component b in the above-mentioned Dresel fuel compositions separately, and its kind and consumption are described at preamble, do not repeat them here.
Under the preferable case, the method of raising oxidation stability of biodiesel provided by the invention also is included in the basic diesel oil that contains biofuel, add other additive, as in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, the emulsion splitter etc. one or more.
The various components of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various orders.The blended condition 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 both can be aforementioned pure biofuel, also can be the aforementioned blending fuel that contains biofuel.
The following examples will the present invention is described further.
Embodiment 1-7
Following examples are used for illustrating the preparation of Dresel fuel compositions additive provided by the invention.
Component a and components b and c are mixed according to the weight ratio shown in the table 1.
Table 1
Performance test
Below in the test, used Oleum Gossypii semen biofuel is the biofuel product that Shijiazhuang refinery branch office of China Petrochemical Industry provides, used sewer oil biofuel provides by the remarkable new forms of energy in Longyan, Fujian company limited, and petroleum diesel is the capital mark B diesel oil that Yanshan Mountain branch office of China Petrochemical Industry produces.
(1) pure biofuel is as the oxidation stability test of the biodiesel composition of basic diesel oil
Evaluate oxidation stability of biodiesel the inductive phase under measuring 110 ℃ with EN14112:2003 method (Rancimat method), use the 743 type oil oxidative stability determinators of instrument as Switzerland Wan Tong company, wherein, inductive phase is long more to illustrate that then the oxidation-resistance of Dresel fuel compositions is good more, otherwise short more illustrate that then the oxidation-resistance of Dresel fuel compositions is poor more inductive phase.Its test result is shown in Table 2.
Table 2
Data from table 2 as can be seen, component a is common oxidation inhibitor, and oxidation stability of biodiesel is had certain improvement, components b is used does not separately have antioxidant effect, biodiesel composition provided by the invention to have obviously better oxidation stability.After component a and the components b mating reaction, the oxidation stability of biodiesel composition will be got well much than the effect sum of independent use component a, components b, this shows to have occurred synergy clearly between component a, the b astoundingly.After optional amount of component b added, effect further strengthened.
By the result of embodiment 1 and 3 as can be seen, polyamines is more excellent as the effect of components b.Embodiment 3 compares as can be seen with embodiment 4, select optional amount of component b for use after, the oxidation stability of gained biodiesel composition further strengthens.
(2) with the test as oxidation-resistance, stability and the detergent-dispersant performance of the concocted diesel oil composition of basic diesel oil of the mixture of biofuel and petroleum diesel, used biofuel is the sewer oil biofuel.
Adopt the method for Pr EN15751:2008 to measure each Dresel fuel compositions, petroleum diesel and concocted diesel oil inductive phase under 110 ℃ respectively, use the 743 type oil oxidative stability determinators of instrument as Switzerland Wan Tong company.Its test result is shown in Table 3.Inductive phase is long more to illustrate that then the oxidation-resistance of biodiesel composition is good more, otherwise short more illustrate that then the oxidation-resistance of biodiesel composition is poor more inductive phase.
The method of employing SH/T 0175 is measured the amount (unit: mg/100mL), thereby evaluate their stability of various concocted diesel oil composition total insoluble substances.The big more then stability of the amount of total insoluble substance is poor more, otherwise if the more little then stability of amount of total insoluble substance is good more, its test result is shown in Table 3.
Table 3
By the result of table 3 as can be seen, add biofuel after, the oxidation stability, the stability that contain the blending fuel of biofuel are compared all variation with petroleum diesel.The oxidation stability, the stability that contain the biodiesel composition of the present invention that the mixture of component a and components b obtains as additive all have significantly to be improved, synergistic effect appears in component a and components b effect, and its effect obviously strengthens than independent Use Limitation fruit.
Claims (28)
1. Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, and described basic diesel oil contains biofuel, and described additive contains component a and components b, and described component a contains arylamine type oxidation inhibitor and/or hindered phenol type antioxidant; Described components b contains the organic amine that is different from component a.
2. Dresel fuel compositions according to claim 1, wherein, described additive is 50-10000ppm with respect to the content of basic diesel oil.
3. Dresel fuel compositions according to claim 1, wherein, the weight ratio of described components b and component a is 0.01-100: 1.
4. Dresel fuel compositions according to claim 3, wherein, the weight ratio of described components b and component a is 0.05-5: 1.
5. according to any described Dresel fuel compositions among the claim 1-4, wherein, described component a contains Ursol D type oxidation inhibitor, have a tertiary butyl one or more in phenolic hydroxyl group adjacent hindered phenol type antioxidant at least.
6. Dresel fuel compositions according to claim 5, wherein, described component a contains one or more in the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 and the bisphenol type oxidation inhibitor that links to each other by methylene radical or sulphur.
7. Dresel fuel compositions according to claim 6, wherein, described component a is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-tert.-butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
8. according to any described Dresel fuel compositions among the claim 1-4, wherein, the described organic amine that is different from component a is the organic amine with structure shown in the structural formula (A):
R
1, R
2Respectively do for oneself H, carbonatoms is that alkyl or the carbonatoms of 1-30 is the heteroatomic group of being with of 1-30, and described to be with heteroatomic group be carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino.
9. Dresel fuel compositions according to claim 8, wherein, the described organic amine that is different from component a is that structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene, wherein, x2 is the integer of 2-4, y1 is the integer of 1-8, R
6Be that hydrogen or carbon number are the alkyl of 1-30.
10. Dresel fuel compositions according to claim 8, wherein, the described organic amine that is different from component a is N-(2-amino-ethyl) piperazine.
11. according to any described Dresel fuel compositions among the claim 1-4, wherein, described additive also contains amount of component b, described amount of component b is to react or the bonded metal chelator with the metal passivator of metallic surface reaction and/or with metal or metal ion.
12. Dresel fuel compositions according to claim 11, wherein, the weight ratio of described component a and described amount of component b is 1: 0.01-1.
13. Dresel fuel compositions according to claim 11, wherein, described amount of component b is a 124 Triazole, the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction, one or more in Schiff's base and the organic polycarboxylic acid.
14. according to any described Dresel fuel compositions among the claim 1-4,6,7,9 and 10, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of described biofuel and other diesel oil is 1: 0-99.
15. a method that improves oxidation stability of biodiesel, this method comprise, in containing the basic diesel oil of biofuel, add additive, described additive contains component a and components b, and described component a contains arylamine type oxidation inhibitor and/or hindered phenol type antioxidant; Described components b contains the organic amine that is different from component a.
16. method according to claim 15, wherein, described additive is 50-10000ppm with respect to the content of basic diesel oil.
17. method according to claim 15, wherein, the weight ratio of described components b and component a is 0.01-100: 1.
18. method according to claim 17, wherein, the weight ratio of described components b and component a is 0.05-5: 1.
19. according to any described method among the claim 15-18, wherein, described component a contains Ursol D type oxidation inhibitor, have a tertiary butyl one or more in phenolic hydroxyl group adjacent hindered phenol type antioxidant at least.
20. method according to claim 19, wherein, described component a contains one or more in the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 and the bisphenol type oxidation inhibitor that links to each other by methylene radical or sulphur.
21. method according to claim 20, wherein, described component a contains N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-tert.-butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
22. according to any described method among the claim 15-18, wherein, the described organic amine of organic amine that is different from component a for having structure shown in the structural formula (A):
R
1, R
2Respectively do for oneself H, carbonatoms is that alkyl or the carbonatoms of 1-30 is the heteroatomic group of being with of 1-30, and described to be with heteroatomic group be carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino.
23. method according to claim 22, wherein, the described organic amine that is different from component a is that structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene, wherein, x2 is the integer of 2-4, y1 is the integer of 1-8, R
6Be that hydrogen or carbon number are the alkyl of 1-30.
24. method according to claim 22, wherein, the described organic amine that is different from component a is N-(2-amino-ethyl) piperazine.
25. according to any described method among the claim 15-18, wherein, described additive also contains amount of component b, described amount of component b is to react or the bonded metal chelator with the metal passivator of metallic surface reaction and/or with metal or metal ion.
26. method according to claim 25, wherein, the weight ratio of described component a and described amount of component b is 1: 0.01-1.
27. method according to claim 25, wherein, described amount of component b is a 124 Triazole, the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction, one or more in Schiff's base and the organic polycarboxylic acid.
28. according to any described method among the claim 15-18, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of described biofuel and other diesel oil is 1: 0-99.
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| CN 200910087970 CN101928614B (en) | 2009-06-26 | 2009-06-26 | Diesel composite and method for improving oxidation stability of biodiesel |
| ES10791159T ES2749879T3 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process to improve oxidation stability of biodiesel |
| EP10791159.6A EP2447344B1 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process for improving oxidation stability of biodiesel |
| US13/380,334 US20120124896A1 (en) | 2009-06-26 | 2010-06-25 | Diesel Composition and Method of Increasing Biodiesel Oxidation Stability |
| PCT/CN2010/000950 WO2010148652A1 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process for improving oxidation stability of biodiesel |
| BRPI1012681-3A BRPI1012681B1 (en) | 2009-06-26 | 2010-06-25 | DIESEL COMPOSITION AND METHOD OF INCREASING BIODIESEL OXIDATION STABILITY |
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| CN102757826A (en) * | 2011-04-27 | 2012-10-31 | 中国石油化工股份有限公司 | Diesel composition and method for improving oxidation stability of biodiesel |
| CN114410355A (en) * | 2022-01-24 | 2022-04-29 | 浙江大学 | Composite antioxidant and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314459A (en) * | 2000-03-20 | 2001-09-26 | 英菲诺姆国际有限公司 | Lubrication oil composition |
| CN1351132A (en) * | 2000-10-30 | 2002-05-29 | 中国石油化工股份有限公司 | Multi-effect additive of diesel oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102005015474A1 (en) * | 2005-04-04 | 2006-10-05 | Degussa Ag | Method for increasing oxidation stability of biodiesel, comprises adding a phenyl compound as primary antioxidant to the biodiesel |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314459A (en) * | 2000-03-20 | 2001-09-26 | 英菲诺姆国际有限公司 | Lubrication oil composition |
| CN1351132A (en) * | 2000-10-30 | 2002-05-29 | 中国石油化工股份有限公司 | Multi-effect additive of diesel oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757826A (en) * | 2011-04-27 | 2012-10-31 | 中国石油化工股份有限公司 | Diesel composition and method for improving oxidation stability of biodiesel |
| CN102757826B (en) * | 2011-04-27 | 2014-10-29 | 中国石油化工股份有限公司 | Diesel composition and method for improving oxidation stability of biodiesel |
| CN114410355A (en) * | 2022-01-24 | 2022-04-29 | 浙江大学 | Composite antioxidant and preparation method and application thereof |
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