CN101993743B - Additive composition, diesel composition and method for improving oxidation stability of biodiesel - Google Patents
Additive composition, diesel composition and method for improving oxidation stability of biodiesel Download PDFInfo
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- CN101993743B CN101993743B CN 200910090511 CN200910090511A CN101993743B CN 101993743 B CN101993743 B CN 101993743B CN 200910090511 CN200910090511 CN 200910090511 CN 200910090511 A CN200910090511 A CN 200910090511A CN 101993743 B CN101993743 B CN 101993743B
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Abstract
The invention discloses an additive composition, a diesel composition comprising the additive composition and a method for improving oxidation stability of biodiesel by adopting the additive composition. The additive composition comprises a component a and a component b, wherein the component a is an arylamine antioxidant and/or a hindered phenol antioxidant, and the hindered phenol antioxidant is a bisphenol antioxidant and/or a polyphenol antioxidant which comprises at least three phenolic hydroxyls in the molecule; and the component b is a product of an ammonolysis reaction between an acylating agent comprising two acyl groups in the molecule and ammonia and/or amine according to a molar ratio of 1:(0.5-2), wherein the acylating agent comprising two acyl groups in the molecule is one or more of C6-C30 hydrocarbyl-substituted organic dicarboxylic acid, anhydride and half-ester. The additive composition also optionally comprises a component c, namely a metal passivator. The provided diesel composition has higher oxidation stability.
Description
Technical field
The invention relates to a kind of compositions of additives, contain the Dresel fuel compositions of this compositions of additives and improve the method for oxidation stability of biodiesel.
Background technology
Quickening along with diesel oil of vehicle trend in the world wide, the demand of diesel oil can be more and more large, and the raising of day by day exhausted and people's environmental consciousness of petroleum resources, greatly promoted countries in the world to accelerate the exploitation paces of Alternative Diesel Fuel, biofuel has been subject to the attention of various countries with its superior environmental-protecting performance and recyclability.
Biofuel (BD100) claims again fatty acid methyl ester (FattyAcid Methyl Ester), to make raw material with the greases of the oil plant waterplant such as oil-yielding shrubs fruit, the engineering microalgaes such as the oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistache and animal grease, biodiesel etc., obtaining through transesterification reaction with alcohols (methyl alcohol, ethanol), is a kind of biofuel of cleaning.That biofuel has is renewable, cleaning and safe three advantages, and China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment are had very great strategic importance.And China is a net import of oil state at present, and prospective oil is very limited again, and a large amount of Imported oils threaten to the energy security of China; Therefore, the research of biofuel and production have important realistic meaning to China.
But because raw material and complete processing, the oxidation stability of some biofuel is very poor, using and store and all cause very large difficulty biofuel.The poor biofuel of oxidation stability easily generates following ageing products: 1) insoluble polymer (colloid and greasy filth), and this can cause engine filter net jam and squirt pump coking, and causes smoke evacuation increase, difficulty in starting; 2) soluble polymer, it can form resinous substance in engine, may cause flame-out and difficulty in starting; 3) aging acid, this can cause the engine metal component corrosion; 4) superoxide, this can cause aging the becoming fragile of rubber components and cause fuel leakage etc.
Europe Biodiesel Standards EN 14214:2003, Australian Biodiesel Standards (Draft2003), New Zealand Biodiesel Standards NZS 7500:2005, Brazilian Biodiesel Standards ANP255 (2003), India Biodiesel Standards IS 15607:2005, South Africa Biodiesel Standards SANS1935:2004 and China's diesel-fuel blending with biofuel (BD100) standard GB/T/T20828-2007 all the oxidation stability of regulation biofuel be inductive phase under 110 ℃ to be not less than 6 hours, measuring method is EN 14112:2003.
As everyone knows, petroleum diesel (is the diesel oil of ordinary meaning, herein in order to distinguish mutually with biofuel, the non-hydrocarbon compounds such as alkene, diolefin and the sulfide the special petroleum diesel of introducing), nitride are under the effect of oxygen, generate a series of intermediate oxidation product, and produce insoluble precipitation through condensation.These insoluble particles that generate in the petroleum diesel storage process can have influence on the use properties of fuel, cause filtering system to stop up, and cause the prime the fuel system unit failure; affect oil atomizing; cause incomplete combustion, even in engine, form too much carbon deposit, make spray nozzle clogging.And biofuel is poorer than petroleum diesel owing to oxidation stability, can increase the weight of the problems referred to above after concocting with petroleum diesel.The most significantly performance is that to contain the stability of the blending fuel of biofuel poorer than petroleum diesel.
The problems referred to above can additive solves or alleviation by adding.A kind of mode is to add oxidation inhibitor in the pure biofuel slowing down its oxidation, thereby alleviates the harm of ageing products; Another kind of mode is to petroleum diesel or contains in the blending fuel of biofuel and add stablizer to improve the stability of blending fuel.Stablizer can stop, weakens or disturb each kinds of oxidation reaction, to suppress oil deterioration, improves its stability.
CN1742072A discloses a kind of method that improves storage stability of bio-diesel, the method comprises and is dissolved in 2 of biofuel with containing with what stoste was counted the 15-60 % by weight, the liquid stoste of 4-di-t-butyl hydroxy toluene joins in the biofuel for the treatment of stabilization, until in total solution of biofuel, the concentration of 2,4-di-t-butyl hydroxy toluene reaches the 0.005-2 % by weight.
CN1847368A discloses a kind of method that improves the oxidative stability of biofuel, the method comprises bisphenol type oxidation inhibitor such as 4,4`-methylene radical two [2, the 6-DI-tert-butylphenol compounds], 2,2`-methylene radical two [6-tert-butyl-4-methyl-Phenol] joins with the amount of 10-20000ppm (w/w) and treats in the stable biofuel.
CN1847369A discloses a kind of method that improves the oxidative stability of biofuel, the method comprises that fusing point is less than or equal to 40 ℃ main anti-oxidant to be joined with the amount of 10-20000ppm (w/w) and treat that in the stable biofuel, wherein said main anti-oxidant contains alkylphenol.
US2007/113467A1 discloses a kind of fuel composition with improved oxidative stability, said composition contains biofuel and at least a oxidation inhibitor, described oxidation inhibitor is selected from Tenox PG, 1,2, a kind of in 3-trihydroxybenzene, BHT, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, tocopherol, the quinoline.
Although the oxidation inhibitor that above usefulness is traditional improves the method for oxidation stability of biodiesel certain effect is arranged, consumption is all larger, simultaneously to the stability of the blending fuel that contains biofuel to improve effect also not so good.
Summary of the invention
The objective of the invention is the relatively poor shortcoming of improved stability effect large for the oxidation inhibitor consumption that overcomes above-mentioned prior art and that contain the blending fuel of biofuel, provide a kind of and can improve preferably compositions of additives and contain the Dresel fuel compositions of this compositions of additives and a kind of method that improves oxidation stability of biodiesel is provided of oxidation stability of biodiesel or stability.
The invention provides a kind of compositions of additives, described compositions of additives contains component a and components b, described component a is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and described hindered phenol type antioxidant is the polyphenol type oxidation inhibitor that contains at least three phenolic hydroxyl groups in bisphenol type oxidation inhibitor and/or the molecule; Described components b is to contain the acylating agent of two acyl groups and ammonia and/or amine in the molecule with mol ratio 1: ammonolysis reaction product (0.5-2), the acylating agent that contains two acyl groups in the described molecule are one or more in the alkyl of the C6-C30 Dicarboxylic Acids, acid anhydrides and the half ester that replace.
The present invention also provides a kind of Dresel fuel compositions, and described Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, described basic diesel oil contains biofuel, and described additive is compositions of additives provided by the invention.
The present invention also provides a kind of method that improves oxidation stability of biodiesel, and the method comprises, in containing the basic diesel oil of biofuel, adds additive, and wherein, described additive is compositions of additives provided by the invention.
Compositions of additives provided by the invention, when cooperating when obtaining Dresel fuel compositions as basic diesel oil with pure biofuel, this Dresel fuel compositions has preferably oxidation stability, the amazing synergistic effect that occurs between component a and the components b, antioxidant effect is well more a lot of than independent use oxidation inhibitor.Components b can be regarded as auxiliary antioxidant, and it can make the effect of oxidation inhibitor unexpectedly greatly strengthen.Therefore, when reaching identical oxidation stability and require, the amount of component a in biodiesel composition can greatly reduce, especially component a especially costliness or component a have in certain toxicity or the corrosive situation, reduced its consumption and had very large meaning.When this compositions of additives and the blending fuel that contains biofuel cooperate when obtaining Dresel fuel compositions as basic diesel oil, the stability of this Dresel fuel compositions better.Particularly according to preferred implementation provided by the invention, when described additive contained component a, components b and amount of component b simultaneously, because obvious synergistic effect between each additive, the antioxygen of Dresel fuel compositions provided by the invention obviously improved.
Embodiment
In Dresel fuel compositions provided by the invention, the content of described additive can be selected in a big way, and for example the content with respect to basic diesel oil can be 50-10000ppm, preferred 80-8000ppm, more preferably 100-5000ppm.
The weight ratio of described components b and component a can be 0.01-100: 1, be preferably 0.02-50: and 1,0.05-10 more preferably: 1, further be preferably 0.2-5: 1.
Component a
Described component a is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, described arylamine type oxidation inhibitor can be selected from least a in the quinoline of Ursol D, replacement of pentanoic, the replacement of naphthylamines, the replacement of replacement, and described hindered phenol type antioxidant is the polyphenol type oxidation inhibitor that contains at least three phenolic hydroxyl groups in bisphenol type oxidation inhibitor and/or the molecule.
The naphthylamines that wherein replaces includes but not limited to one or more in the following material:
Phenyl-a-naphthylamine (oxidation inhibitor T531, antioxidant A);
Phenyl beta naphthylamine (antioxidant d);
N-p-methoxyphenyl alpha-naphthylamine (anti-aging agent 102);
To hydroxyphenyl-beta-naphthylamine (antioxidant D-OH);
Aldol-alpha-naphthylamine (antioxidant A P)
2-hydroxyl-1, two [to (beta-naphthylamine) phenoxy group] propane (anti-aging agent C-49) of 3-;
Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41) of dimethyl;
Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41-ethyl) of diethyl;
2,2 '-two [to (beta-naphthylamine) phenoxy group] diethyl ether (anti-aging agent C-41-ether).
Wherein, the preferred nonox of the naphthylamines of replacement, for example one or more in phenyl-a-naphthylamine, Phenyl beta naphthylamine, the N-p-methoxyphenyl alpha-naphthylamine.Especially preferred phenyl-a-naphthylamine.
The pentanoic that wherein replaces includes but not limited to one or more in the following material:
4,4 '-diamino-diphenylamine (antioxidant A PA);
Right, to '-the dimethoxy pentanoic;
N, N, N ', N '-tetraphenyl diamines methane (anti-aging agent 350);
N, N '-diphenyl ethylene diamine;
N, N '-diphenylprop diamines;
N, N '-di-o-tolyl-ethylene-diamine;
2-hydroxyl-1,3-pair-(to the aniline phenoxy group) propane (anti-aging agent C-47);
2,2 '-two (to the aniline phenoxy group)-diethyl ether (antioxidant H-1);
Two (to aniline-phenoxy group)-silane (anti-aging agent C-1) of dimethyl;
P-isopropoxy-diphenylamine (anti-aging agent ISO);
Right, to '-diisopropoxy pentanoic (antioxidant D ISO);
4,4 '-two (α, α '-dimethyl benzyl) pentanoic (anti-aging agent KY-405);
P-hydroxydiphenylamine (antioxidant A O3920);
Two-(1,1,3,3-tetramethyl-ethyl) pentanoic (anti-aging agent ODA);
4,4 '-dioctyl diphenylamine;
4,4 '-di-iso-octyldiphenylamine;
4,4 '-diheptyl pentanoic;
4,4 '-dinonyldiphenylamine;
Octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines, anti-aging agent OD);
Octyl group/butyl pentanoic (oxidation inhibitor L-57);
Styrenated diphenylamine (antioxidant D FL, DFC-34);
And the mixture of alkylated diphenylamine, wherein alkyl can be heptyl, octyl group, in the nonyl one or more, the example of its Industrial products has U.S. Pennwalt company commodity to be called Pennox A, PennoxA-" S ", American National Instrument polychem company commodity are called WytoxADP, ADP-X, U.S. Vanderbilt company commodity are called Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, U.S. Uniroyal company commodity are called Polylite, Antioxidant 445, and domestic code name is the antioxidant product of T534.
Pentanoic type oxidation inhibitor preferred alkyl diphenylamines that replaces and composition thereof, especially preferred alkyl carbonatoms alkylated diphenylamine between 4-10 and composition thereof, as: 4,4 '-dioctyl diphenylamine, 4,4 '-di-iso-octyldiphenylamine, 4,4 '-diheptyl pentanoic, 4, one or more among 4 '-dinonyldiphenylamine, octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines), octyl group/butyl pentanoic, the commodity oxidation inhibitor T534.
The Ursol D type oxidation inhibitor of wherein said replacement can be the amido (NH of Ursol D
2) in the product of hydrogen atom after being replaced by in one or more alkyl, aryl, aralkyl, alkylaryl, alkyl acyl group, alkyl alkylsulfonyl, the alkyl acyloxy one or more; when two hydrogen atoms in the amido are substituted; it can be the hydrogen atom that replaces on the same amido; it also can be the hydrogen atom that replaces on two amidos; and when being two above substituting groups; can be identical between each substituting group, also can be different.That is to say; the Ursol D type oxidation inhibitor of described replacement can be the Ursol D that monoalkyl replaces; the Ursol D that single aryl replaces; the Ursol D that the monoalkyl aryl replaces; the Ursol D that single arylalkyl replaces; the Ursol D of single alkyl acyl substituted; the Ursol D that single alkyl alkylsulfonyl replaces; the Ursol D that single alkyl acyloxy replaces; the Ursol D that N-alkyl-N '-alkyl replaces; the Ursol D that N-aryl-N '-alkyl replaces; the Ursol D that N-alkyl-N '-alkylaryl replaces; the Ursol D that N-aryl-N '-alkyl replaces; the Ursol D that N-arylalkyl-N '-alkyl replaces; the Ursol D that N-arylalkyl-N '-aryl replaces; the Ursol D of N-arylalkyl-N '-alkyl acyl substituted; the Ursol D that N-arylalkyl-N '-alkyl alkylsulfonyl replaces; the Ursol D that N-arylalkyl-N '-alkyl acyloxy replaces; the Ursol D of N-aryl-N '-alkyl acyl substituted; the Ursol D that N-alkyl-N '-alkyl alkylsulfonyl replaces; the Ursol D of Ursol D N-aryl-N ' that N-alkyl-N '-alkyl acyloxy replaces-alkyl acyl substituted; the Ursol D that N-alkyl-N '-alkyl alkylsulfonyl replaces; the Ursol D that N-alkyl-N '-alkyl acyloxy replaces; the Ursol D of N-alkylaryl-N '-alkyl acyl substituted; the Ursol D that N-alkylaryl-N '-alkyl alkylsulfonyl replaces; the Ursol D that N-alkylaryl-N '-alkyl acyloxy replaces; N; the Ursol D that the two alkyl of N-replace; N; the Ursol D that the two aryl of N replace; N; the Ursol D that the two alkylaryls of N-replace; N; the Ursol D that the two arylalkyls of N-replace; N; the Ursol D that the two alkyl alkylsulfonyls of N-replace; N; the Ursol D of the two alkyl acyl substituted of N-; N, one or more in the Ursol D that the two alkyl acyloxy of N-replace.Each substituent carbonatoms is preferably 1-20, and for alkyl substituent, preferred carbonatoms is 4-10.
Concrete, the Ursol D type oxidation inhibitor of described replacement comprises but is not limited in the following material one or more:
N phenyl-N '-cyclohexyl Ursol D (antioxidant 4010);
N, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (antioxidant 4020);
N, N '-two-(Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D (anti-aging agent 4030);
N-p-methylphenyl-N '-(1,3-dimethylbutyl) Ursol D (anti-aging agent 4040);
N, N '-diheptyl Ursol D (anti-aging agent 788);
N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);
N-sec.-propyl-N '-p-methylphenyl Ursol D (anti-aging agent methyl 4010NA);
N, N '-di tolyl p phenylenediamine (anti-aging agent PPD-A);
N, N '-diphenyl-para-phenylene diamine (antioxidant H);
N, N '-two-(betanaphthyl) Ursol D (antioxidant D NP);
N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5);
N, N '-dioctyl-p-phenylenediamine (anti-aging agent 88);
N, N '-two-(1-methylheptyl) Ursol D (anti-aging agent 288);
N, N '-two-(1-ethyl-3-methyl amyl) Ursol D (anti-aging agent 8L);
N, N '-two-(Isosorbide-5-Nitrae-dimethylbutyl) Ursol D (anti-aging agent 66);
N-Octyl-N '-diphenyl-para-phenylene diamine (anti-aging agent 688);
N-isobutyl--N '-diphenyl-para-phenylene diamine (anti-aging agent 5L);
N, N '-dimethyl-N, N '-two-(1-first propyl group) Ursol D (anti-aging agent 32);
N-(p-methylphenyl alkylsulfonyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent TPPD);
N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent G-1);
N-(3-anilino phenyl) Methacrylamide;
N-hexyl-N '-diphenyl-para-phenylene diamine;
Among the present invention, the Ursol D type oxidation inhibitor that replaces is preferably one or more in the dialkyl group Ursol D that the hydrogen atom in the amido of Ursol D replaced by two alkyl or two aryl or aryl of an alkyl, two amidos of especially preferred Ursol D respectively by a carbonatoms between 4-10 alkyl or one or more in the dialkyl group Ursol D of one or more replacements in the Ursol D that replaces of the carbonatoms aryl that is 6-15, as: N, N '-diheptyl Ursol D; N, N '-di-sec-butyl-p-phenyl enediamine; N, N '-dioctyl-p-phenylenediamine; N, one or more in N '-two-(1-methylheptyl) Ursol D.
The quinoline type oxidation inhibitor of replacement wherein comprises but is not limited to:
6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W);
6-phenyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (anti-aging agent PMQ);
6-dodecyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant D D);
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD, anti-aging agent 124);
Pentanoic and acetone low-temp reaction product (anti-aging agent BAS);
Pentanoic and acetone high-temperature reaction product (antioxidant BLE);
The reaction product of pentanoic and acetone and aldehyde (anti-aging agent BXA);
The reaction product of Phenyl beta naphthylamine and acetone (antioxidant A PN, antioxidant A M).
The Ursol D type arylamine antioxidant that arylamine antioxidant preferably replaces.
Among the present invention, described bisphenol type oxidation inhibitor is the bis-phenol that is linked to each other and formed by two single phenol, preferably refers to the bisphenol type oxidation inhibitor that is linked to each other by sulphur or carbon atom by two single phenol.The described bisphenol type oxidation inhibitor that is linked to each other by sulphur or carbon atom by two single phenol can be one or more in following:
(1) bis-phenol that is linked to each other by carbon atom
4,4 '-isopropylidene bis-phenol (dihydroxyphenyl propane);
2,2 '-two-(3-methyl-4 hydroxy phenyl) propane (bisphenol-c);
4,4 '-dihydroxybiphenyl (oxidation inhibitor DOD);
4,4 '-dihydroxyl-3,3 ', 5,5 '-four-tertiary butyl biphenyl (oxidation inhibitor 712);
2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol) (oxidation inhibitor bis-phenol 2246);
4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);
2,2 '-methylene radical-two-(4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);
2,2 '-methylene radical-two-(4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);
2,2 '-methylene radical-two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);
2,2 '-methylene radical-two-(6-α-methylbenzyl p-cresol);
4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-two-(2-TBP) (oxidation inhibitor 702);
2,2 '-ethylidene-two-(4-methyl-6-tert-butylphenol);
4,4 '-ethylidene-two-(2-methyl-6-tert-butylphenol);
4,4 '-ethylidene-two-(2,6 di t butyl phenol);
4,4 '-butylidene-two-(the 6-tertiary butyl-meta-cresol) (oxidation inhibitor BBM, oxidation inhibitor TCA);
4,4 '-isobutylidene-two-(2,6 di t butyl phenol) etc.
(2) bis-phenol that is linked to each other by sulphur atom
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2, and 2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);
4,4 '-thiobis-(5-methyl-2-TBP);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
2,2 '-thiobis-(4-octyl phenol) etc.
(3) linked to each other by carbon atom but contain heteroatomic bis-phenol
N, N '-hexamethylene is two-(3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) (oxidation inhibitor 1098);
Hexylene glycol two [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 259);
Two-(3,5-di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine (oxidation inhibitor BPP);
Two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S);
2,2 '-sulfurous ethyl glycol two [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 1035);
Triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (oxidation inhibitor 245) etc.
Bisphenol type oxidation inhibitor is preferably by two bis-phenols that have at least the single phenol of a tertiary butyl at the phenolic hydroxyl group ortho position to link to each other by methylene radical or sulphur, for example one or more in the following substances:
2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol) (antioxidant 2246);
4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);
4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-two-(2-TBP) (oxidation inhibitor 702);
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2, and 2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
Two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.
Described polyphenol type oxidation inhibitor refers to contain in the same phenol type antioxidant molecule phenol of a plurality of phenolic hydroxyl groups, the number of phenolic hydroxyl group is more than three or three, a plurality of phenolic hydroxyl groups can be positioned on the same phenyl ring, also can be positioned on the different phenyl ring, the preferred described polyphenol type oxidation inhibitor of the present invention is to contain the macromole oxidation inhibitor that at least three single phenolic group are rolled into a ball in the molecule, namely contain at least three phenyl ring in a phenol type antioxidant, and have at least on three phenyl ring and have separately at least one phenolic hydroxyl group, preferred described polyphenol type oxidation inhibitor is served as reasons and is had at least a tertiary butyl to roll into a ball the polyphenol that forms at single phenolic group at phenolic hydroxyl group ortho position, especially preferably have two tertiary butyls in the polyphenol that is obstructed at phenolic hydroxyl group ortho position, for example one or more in the following substances:
1,3,5-trimethylammonium-2,4,6-three-(4 '-hydroxyl-3 ', 5 '-di-t-butyl) benzene (antioxidant 330);
Three [2-(3,5-di-tert-butyl-hydroxy phenyl) propionyl oxygen ethyl] isocyanic ester (oxidation inhibitor 3125);
Four (3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester (antioxidant 1010);
1,3,5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) (antioxidant 3114);
1,1,3-three-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA);
1,3,5-three (2, the 6-dimethyl-4-tertiary butyl-3-hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) (oxidation inhibitor 1790);
Two [3,3-pair-(3 '-tertiary butyl-4 '-hydroxybenzyl) butyric acid] glycol ester etc.
The polyphenol here can also be in the phenyl ring with the phenol of three hydroxyls, such as pyrogallol, gallic acid ester such as methyl gallate, Progallin A, Tenox PG, butyl gallate, gallic acid pentyl ester, the own ester of gallic acid, gallic acid heptyl ester, Stabilizer GA 8, gallic acid ester in the ninth of the ten Heavenly Stems, gallic acid ester in the last of the ten Heavenly stems, lauryl gallate, gallic acid 14 esters, gallic acid hexadecyl ester, gallic acid octadecyl ester, gallic acid octadecylene ester etc.; And the disclosed gallamide of CN200810115581.8 or ammonia salt.The esterification products of the preferred gallic acid-derivate of polyphenol type oxidation inhibitor such as gallic acid is Tenox PG especially.
The bisphenol type oxidation inhibitor that phenol type antioxidant of the present invention is preferably linked to each other by sulphur or carbon atom by two single phenol and one or more in the polyphenol that is obstructed at phenolic hydroxyl group ortho position of two tertiary butyls are arranged.The present invention most preferably described phenol type antioxidant is selected from 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-TBP), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2, the 6-DI-tert-butylphenol compounds), in two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
Component a can also be the composite antioxidant of described phenol type antioxidant and arylamine type oxidation inhibitor, and the weight ratio of described phenol type antioxidant and arylamine type oxidation inhibitor is preferably 0-10: 1, and 0.2-5 more preferably: 1.
Among the present invention, most preferably described component a is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-TBP), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2, the 6-DI-tert-butylphenol compounds), in two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
Components b
Described components b is that carbonatoms is to contain the acylating agent of two acyl groups (C=O) and ammonia in the molecule of 6-34 with mol ratio 1: ammonolysis reaction product (0.5-2) and/or amine are with mol ratio 1: ammonolysis reaction product (0.5-2), the acylating agent that contains two acyl groups in the described molecule are one or more in C6-C30 the alkyl Dicarboxylic Acids, acid anhydrides and the half ester that replace.Described ammonolysis reaction refers to the reaction that one or more and ammonia in lipid acid, fatty carboxylic acid halides, the fatty acid alkyl ester and/or amine generation metathesis obtain acid amides.Above-mentioned reaction product can without separation and purification directly as described components b, also can only be used as components b with amidate wherein behind the separating-purifying.If do not separate purification, the main component of this mixture is imide or/and amidate also contains the unreacted raw material of part and other reaction product such as ammonium salt or alcohol etc. usually, specifically forms the visual response condition different and slightly different.
Among the present invention, the Dicarboxylic Acids of described C6-C30 alkyl replacement can be one or more in the toxilic acid of C6-C30 alkyl replacement, Succinic Acid (succsinic acid), fumaric acid, methylene-succinic acid, citraconic acid, clothing holder acid, the phthalic acid; The acid anhydrides that described C6-C30 alkyl replaces can be one or more in the maleic anhydride that replaces of C6-C30 alkyl, Succinic anhydried (succinyl oxide), itaconic anhydride, citraconic anhydride, isatoic anhydride, the Tetra hydro Phthalic anhydride; The half ester that described C6-C30 alkyl replaces can be the Dicarboxylic Acids of above-mentioned C6-C30 alkyl replacement or the partial esterification thing of acid anhydrides and pure preferred fat alcohol, be in two carbonyls in above-mentioned Dicarboxylic Acids or the acid anhydrides one and with alcohol esterification occured, the product of esterification does not occur in another carbonyl.The acylating agent that contains two acyl groups in the preferred described molecule of the present invention is one or more in the Succinic anhydried that replaces of the Succinic Acid that replaces of C6-C30 alkyl and C6-C30 alkyl.The structural formula of the Succinic Acid that the alkyl of preferred C6-C30 replaces is suc as formula shown in the B1, and the structural formula of the Succinic anhydried that the C6-C30 alkyl replaces is shown in B2:
Wherein, R is that carbonatoms is the alkyl of 6-30, and " alkyl " refers to hydrocarbon substituent, i.e. aliphatics, alicyclic, aromatics and cyclic substituent.Aliphatic alkyl can be saturated also can be the alkyl of the two keys of undersaturated band or triple bond.Preferred R is that carbonatoms is the alkyl or alkenyl of the aliphatic alkyl of 8-24, especially straight chain.
The Dicarboxylic Acids that typically can replace as the C6-C30 alkyl of acylating agent of the present invention can be the nonyl Succinic Acid; the decyl Succinic Acid; the dodecyl Succinic Acid; the tridecyl Succinic Acid; the tetradecyl Succinic Acid; the pentadecyl Succinic Acid; the hexadecyl Succinic Acid; the octadecyl Succinic Acid; nonenyl succinic acid; decene base Succinic Acid; dodecenylsuccinic acid; tetradecene base Succinic Acid; hexadecylene base Succinic Acid; octadecylene base Succinic Acid; in the docosene base Succinic Acid one or more.
The acid anhydrides that typically can replace as the C6-C30 alkyl of acylating agent of the present invention can be nonyl succinic anhydride; decyl succinic anhydride; dodecyl succinic anhydride; the tridecyl succinyl oxide; the tetradecyl succinyl oxide; the pentadecyl succinyl oxide; the hexadecyl succinyl oxide; the octadecyl succinyl oxide; the nonenyl succinic acid acid anhydride; decene base succinyl oxide; dodecenylsuccinic anhydride; tetradecene base succinyl oxide; hexadecylene base succinyl oxide; octadecylene base succinyl oxide; in the docosene base succinyl oxide one or more.
The preparation method of the succinyl oxide that above-mentioned C6-C30 alkyl replaces has belonged to known technology in this area, for example polyolefine and the maleic anhydride with respective chain length carries out heat polymerization, perhaps carries out substitution reaction with chlorinated hydrocarbon such as chlorinatedpolyolefins and maleic anhydride.Specifically can be with reference to the description among US3361673, US3676089 and the US3172892.
The succsinic acid (Succinic Acid) that above-mentioned alkyl replaces is available commercially, also can by this area known the whole bag of tricks make, for example can after being hydrolyzed with water or steam treatment, obtain by the succinyl oxide that corresponding alkyl replaces.The actual conditions of hydrolysis and operation have been as well known to those skilled in the art.
Described amine is suc as formula the organic amine shown in the B3
R wherein
1And R
2Can be the alkyl of 1-30 or be with heteroatomic group, perhaps R for carbonatoms separately
1And R
2One of them is H; another is the alkyl of 1-30 for carbonatoms or is with heteroatomic group, and described can be to contain carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino group with heteroatomic group.Being that B3 can be primary amine, can also be secondary amine, also can be one or more mixture in ammonia, primary amine and the secondary amine." alkyl " refers to hydrocarbon substituent, i.e. aliphatics, alicyclic, aromatics and heterocyclic substituent.Aliphatic alkyl can be saturated also can be the alkyl of the two keys of undersaturated band or triple bond.
(1) works as R
1And R
2One of them is H, when another for carbonatoms is the primary amine of alkyl of 1-30, this primary amine can be that carbonatoms is the aliphatic amide of 1-30, also can be that carbonatoms is the arylamine of 6-30, preferred carbonatoms is the aliphatic amide of 1-24, fat primary amine can be the aliphatic amide of straight chain, such as methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, n-dodecylamine (lauryl amine), positive tetradecy lamine, hexadecylamine, octadecyl amine, positive 20 amine, in positive two amino dodecanes one or more, it also can be the fat primary amine with side chain, these fat primary amines with side chain are the various isomer of above-mentioned straight chain fat primary amine, for example Isopropylamine, isobutylamine, TERTIARY BUTYL AMINE, isobutylcarbylamine, neopentyl amine, dissident's amine, tuaminoheptane, octodrine (2 ethyl hexylamine), different nonyl amine, isodecyl amine, different amino dodecane, different tetradecy lamine, different cetylamine, different stearylamine, in different 20 amine one or more.Fat primary amine can also be the amine with cycloaliphatic ring, such as cyclopentamine and/or hexahydroaniline, also can be the fat primary amine that contains unsaturated double-bond or triple bond in the carbochain, such as oleyl amine (octadecenyl amine), palm oleyl amine (hexadecylene amine), can also be the primene JM-T, for example Rohm﹠amp; The trade names that Haas company produces are the primene JM-T of Primere 81R.
If secondary amine, wherein R
1, R
2Can be identical, also can be different, preferred can be that carbonatoms is the normal chain alkyl of 1-24 separately, such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl (lauryl), the n-tetradecane base, n-hexadecyl, the Octadecane base, NSC 62789 base or n-docosane base, also can be that carbonatoms with side chain is the isomery alkyl of 1-24, such as sec.-propyl, isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, the Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base or Isoeicosane base.
(2) R
1, R
2At least one is that carbonatoms is the heteroatomic group of being with of 1-30, and another is that H or carbonatoms are the alkyl of 1-30.
The amine that wherein contains hydroxyl can be hydramine or amino phenol, for example thanomin, diethanolamine, N-alkyl ethanol amine, N-vinyl-ethyl alcohol amine, N-alkyl α-amino isopropyl alcohol, N-thiazolinyl α-amino isopropyl alcohol, α-amino isopropyl alcohol, diisopropanolamine (DIPA), Tutofusin tris, 3-amino-1, in 2-propylene glycol, 2-amino-1,3-propanediol, 3-aminopropanol, 4-amino-n-butyl alcohol, 5-amino-1-amylalcohol, 6-amino-1-hexanol, the PAP one or more.
R
1, R
2At least one is that amido or amino amine are polyamine compounds, and the polyamines here refers to contain in the molecule amine of two or more nitrogen-atoms, is H such as structural formula
2N-R
3-NHR
4Amine, the R here
3Can be that carbon number is the alkylidene group of 1-30, thiazolinyl, cycloalkyl, aryl or polyether-based etc.; R
4Can be that hydrogen, carbon number are the alkyl of 1-30.For example quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, decamethylene diamine, coconut oil base 1,3-propylene diamine, oil base 1,3-propylene diamine, tallow base 1,3-propylene diamine.Can also be as shown in the formula the polyether diamine shown in the B4:
Wherein x1 is the integer of 1-5, R
4Can be that hydrogen, carbon number are the alkyl of 1-30; R
5Hydrogen or methyl.
Polyamines can also be polyamines polyene, and the structural formula of polyamines polyene is H
2N[(CH
2)
X2NH]
Y1R
6, wherein, x2 can be the integer of 2-4, be preferably 2 or 3, y1 can be the integer of 1-8, R
6Can be that hydrogen, carbon number are the alkyl of 1-30.For example, work as R
6During for H, described polyamines polyene can be in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, seven ethene, eight amine, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines, six propylene, seven amine, seven propylene, eight amine one or more.Work as R
6When being the alkyl of 1-30 for carbonatoms, be preferably the alkyl that carbonatoms is 4-22.This alkyl can be saturated alkyl, also can be with the thiazolinyl of two keys or with the aryl of phenyl ring.Alkyl can be the straight chain normal chain alkyl, also can be the isomery alkyl with side chain, this alkyl can be normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; Isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, one or more in isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and the Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Can be in phenmethyl (benzyl), styroyl and the hydrocinnamyl one or more with the aryl of phenyl ring.Wherein, the more preferably alkyl of C6-C20.
The polyamines here can also be nitrogenous heterocyclic amine, includes but not limited in the amine of imidazoline type, piperazine type and piperidines type one or more.
The imidazoline type polyamines is as shown in the formula shown in the B5:
Wherein y2 is the integer of 0-5, R
7Be C
1-C
24Alkyl.Be preferably C
4-C
22Alkyl.This alkyl can be saturated alkyl, also can be with the thiazolinyl of two keys or with the aryl of phenyl ring.Alkyl can be the straight chain normal chain alkyl, also can be the isomery alkyl with side chain, this alkyl can be normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tetradecane base, n-hexadecyl, the Octadecane base, the NSC 62789 base, the n-docosane base, isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, the Permethyl 99A. base, different tetradecyl, isocetyl, in isooctadecane base and the Isoeicosane base one or more.The example of thiazolinyl comprises 9-octadecylene base.Can be in phenmethyl (benzyl), styroyl and the hydrocinnamyl one or more with the aryl of phenyl ring.Wherein, further preferred y2 is the integer of 1-3, R
7Be C
6-C
20Alkyl or alkenyl.
Piperazine type polyamines is as shown in the formula shown in the B6:
R wherein
8Be the alkyl of H or C1-C24, x3 is the integer of 0-5.Preferred typical piperazine type polyamines is N-(2-amino-ethyl) piperazine.
The polyamines of piperidines type such as 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethyl-piperidines etc.
The polyamines here can also be suc as formula the polyamines that contains tertiary amine shown in B7, the B8.
R wherein
9, R
10For or the alkyl of C1-C24, x4 is the integer of 0-10.Preferred R
9, R
10Be the alkyl of C1-C10, x4 is the integer of 1-8.N for example, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dimethyl-Putriscine, N, N-diethyl-Putriscine, N, N-dimethyl-1, one or more in the 6-hexanediamine.
Wherein x5 is the integer of 1-10, is preferably the integer of 2-6, for example three (2-amino-ethyl) amine.
Polyamines can also be that structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene and the condenses of oxyethane, propylene oxide.Wherein, x2 can be the integer of 2-4, be preferably 2 or 3, y1 can be the integer of 1-8, R
6Can be that hydrogen, carbon number are the alkyl of 1-30.
The described amine of B3 of the present invention is preferably polyamines, the polyamines that further preferably contains at least one primary amine group, in the amine of especially preferred above-mentioned polyamines polyene, imidazoline type, piperazine type and piperidines type one or more, particularly preferably one or more in polyamines polyene and the piperazine type polyamines.
The succsinic acid that above-mentioned alkyl replaces and/or the ammonolysis reaction of succinyl oxide and ammonia and/or amine also belong to techniques well known, do not repeat them here.
The succsinic acid that alkyl replaces and/or the ammonolysis reaction product of succinyl oxide and ammonia and/or amine and the mol ratio of temperature of reaction and reactant have relation.(about 100 ℃) reaction generated the product that acid amides is the master when in general, temperature of reaction was low; (about 150 ℃) reaction generated the product that imide is the master when temperature of reaction was high.When succsinic acid and/or succinyl oxide were excessive, two or more succsinic acids and/or succinyl oxide can react with same polyamines, generated the reaction product of so-called " two extension " or " hang " more.The preferred polyamines of the present invention is excessive, namely generates take " the single extension " as main reaction product.
Amount of component b
Under the preferable case, compositions of additives provided by the invention also contains amount of component b, described amount of component b can for various can with the metal passivator of metallic surface reaction and/or with the metal chelator of metal or metal ion reaction or combination.The weight ratio of described component a and amount of component b can be 1: 0-1, the weight ratio of preferred described component a and described amount of component b is 1: 0.01-1, more preferably 1: 0.01-0.5 further is preferably 1: 0.02-0.2.
Concrete, described amount of component b can be in 124 Triazole and derivative, thiadiazoles and derivative thereof, oxine, ethylenediamine tetraacetic carboxylic acid, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base (Schiff bases), organic polycarboxylic acid and the derivative thereof one or more.Because this solvability in biofuel of 124 Triazole is very unexcellent, therefore, in order to increase its solvability in biofuel, usually 124 Triazole is carried out modification, modification is mainly by introducing oil-soluble group such as long chain hydrocarbon groups in 124 Triazole.Therefore, described 124 Triazole derivative can be various solvabilities in the biofuel various derivatives good than 124 Triazole itself.Concrete, one or more in the described 124 Triazole derivative product that can be 124 Triazole obtain by mannich reaction with the ammonium salt of aliphatic amide formation and 124 Triazole, formaldehyde and aliphatic amide.Described ethylenediamine tetraacetic carboxylic acid can be ethylenediamine tetraacetic acid (EDTA) (EDTA), and described hydrazides can be N-salicylidene-N '-salicylyl hydrazine and/or N, N '-diacetyl adipyl two hydrazides.Described beta-diketon such as methyl ethyl diketone, described 'beta '-ketoester such as etheric acid monooctyl ester.Described Schiff's base can be N, N '-two salicylidenes-1，2-diaminoethane, N, N '-two salicylidene-1,2-propylene diamine, N, N '-two salicylidene-1,2-cyclohexanediamine, N, one or more in N '-two salicylidenes-N '-methyl two propylene triamines.Described organic polycarboxylic acid and derivative thereof are such as being in citric acid, tartrate, oxysuccinic acid, succsinic acid (Succinic Acid), toxilic acid, phytic acid etc. and the derivative thereof one or more.
Among the present invention, preferred described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction (for example commercial additive of commodity T551 by name), Schiff's base and organic polycarboxylic acid and with the condensation reaction products (being amides, the ester derivative of organic polycarboxylic acid) of aliphatic amide or Fatty Alcohol(C12-C14 and C12-C18) in one or more.
According to using needs, compositions of additives provided by the invention can also contain other additive, such as in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, the emulsion splitter etc. one or more.
The preparation of compositions of additives provided by the invention is simple, and each component that only need form compositions of additives mixes and gets final product.These components can directly be mixed, also can in the presence of solvent, mix, the solvent here can be polar solvent such as N, in dinethylformamide (DMF), Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF) (DHF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidone and the methyl-2-pyrrolidone one or more.Also can be especially aromatic hydrocarbons such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil and composition thereof of hydro carbons, can also be biofuel.
In Dresel fuel compositions provided by the invention, described basic diesel oil can be pure biofuel, and described biofuel refers to that grease and low-carbon alcohol are (such as C
1-C
5Fatty Alcohol(C12-C14 and C12-C18)) fatty acid ester of low-carbon alcohol that generates through transesterify (alcoholysis) reaction is generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.
Described trans-esterification processes can be the processing method that any known or unknown transesterification reaction of passing through grease and low-carbon alcohol obtains biofuel, for example acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, etc.Specifically can be with reference to documents such as CN1473907A, DE3444893, CN1472280A, CN1142993C, CN1111591C, CN1594504A.
Described grease has general sense well known in the art, is the general name of oil and fat, and main component is fatty acid triglycercide.General normal temperature is the oil that is called of liquid, and normal temperature is solid or the semisolid fat (abbreviation fat) that is called.Described grease comprises vegetables oil and animal oil, in addition, also comprise from the oil plant in the materials such as microorganism, algae, even can also be waste oil, for example the used grease of acidifying wet goods or the rotten grease of waste cooking oil, sewer oil, swill oil, grease factory.Described vegetables oil can be that herbaceous plant oil also can be xylophyta oil, such as the oil of peanut oil, Semen Maydis oil, Oleum Gossypii semen, rape seed oil, soybean oil, plam oil, Thistle oil, linseed oil, Oleum Cocois, Oak Tree oil, Prunus amygdalus oil, walnut oil, Viscotrol C, sesame oil, sweet oil, Yatall MA (Tall Oil), sunflower oil, curcas oil, tung oil, shinyleaf yellowhorn oil, coptis wood oil, halophytes such as the plants such as kostelezkya virginica, cyperus esculentus.Described animal oil can be lard, chicken fat, duck oil, goose is oily, sheep is oily, house oil, butter, haco oil, shark wet goods.
In biodiesel composition of the present invention, described basic diesel oil also can contain other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contains one or more in the oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is preferably 1: 2-99.
Wherein petroleum diesel refers to boiling range the cut 160-380 ℃ between of crude oil (oil) after the devices such as the various refining process decompression as usual of refinery, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking are processed, and the compression ignition engine fuel that satisfies solar oil standard GB/T 252 or derv fuel oil standard GB/T 19147 that forms through allotment.
The fischer-tropsch combined diesel oil mainly refers to GTL diesel oil (Gas To Liquid) or the CTL diesel oil (Coal To Liquid) produced as raw material funds-Tuo (F-T) synthetic method take Sweet natural gas or coal, can also be vegetable fibre funds-Tuo synthetic method and the BTL diesel oil (Biomass To Liquid) produced.The fischer-tropsch combined diesel oil is substantially free of sulphur and aromatic hydrocarbons, be very clean fuel, but its oilness extreme difference improve greatly with oilness after the biofuel blending, but the possible variation of the oxidation stability of tempered oil, the blending fuel that therefore contains biofuel also needs to add oxidation inhibitor.
The hydrocracking biofuel is also referred to as s-generation biofuel, refer to by animal-plant oil through generate after hydrogenation and the cracking reaction with C
8-C
24Alkane is main, especially with C
12-C
20Normal paraffin is the reaction product of main component, and this hydrocracking biofuel cetane value is high, and sulphur and aromaticity content are extremely low, can greatly reduce the discharging of diesel engine pollutent as diesel motor fuel or blending component.
Contain oxygen diesel oil blending component and refer to and can be deployed into the oxygenatedchemicals that meets certain code requirement or the mixture of oxygenatedchemicals with various diesel-fuels, normally alcohols and ethers or its mixture, alcohols is C for example
1-C
18Fatty Alcohol(C12-C14 and C12-C18), preferred C
1-C
12Unitary fatty alcohol is such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecylenic alcohol, lauryl alcohol and various isomer thereof.Ethers can be dme, methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, C
6-C
14Fatty alcohol-polyoxyethylene ether, C
6-C
14Fatty alcohol polyoxypropylene ether, C
6-C
14Alkylphenol polyoxyethylene, C
6-C
14Alkylphenol polyethenoxy ether, polyoxymethylene dme (Polyoxymethylene Dimethyl Ethers, CH
3O (CH
2O)
xCH
3, x=1-8) etc. and composition thereof.
Among the present invention, described basic diesel oil is when containing the blending fuel of biofuel, described Dresel fuel compositions can obtain by described additive, biofuel and other diesel oil are directly mixed, and also can first described additive be mixed with biofuel, and then obtain with other diesel oil blending.The various components of additive directly can be mixed with the various compositions of basic diesel oil, also can be first the various components of additive be pre-mixed, obtain mixing with the various compositions of basic diesel oil or basic diesel oil again behind the additive agent mixture.The various components of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various orders.The condition of mixing can be carried out under the various conditions that compositions of additives and Dresel fuel compositions do not caused disadvantageous effect, for example, can mix at ambient temperature.
The method of raising oxidation stability of biodiesel provided by the invention comprises, in containing the diesel component of biofuel, adds additive, and wherein, described additive is above-mentioned compositions of additives provided by the invention.
The present invention is described further for the following examples.
Preparation example 1-4 is used for the synthetic of explanation components b.
Preparation example 1
In a 500ml three-necked bottle, add 56.7g tetraethylene pentamine (0.3mol) and 96.5g hexadecylene base Succinic anhydried (0.3mol) and 136.5g dimethylbenzene, heated and stirred reflux water-dividing 5 hours, tell approximately 5g water, the mixture that is approximately contained the ammonolysis reaction product of 50 % by weight, this ammonolysis reaction product is take hexadecylene base succimide as main, and this mixture is directly stand-by as components b.
Preparation example 2
In a 500ml three-necked bottle, add 46.4g five ethene hexamines (0.2mol), 25.8gN-(2-amino-ethyl) piperazine (0.2mol), 56.8g dodecenylsuccinic acid (0.2mol) and 130g toluene, heated and stirred reflux water-dividing reaction 6 hours, toluene is removed in underpressure distillation, obtain take laurylene base succinic diamide as main ammonolysis reaction product 121g, the aromatic hydrocarbons thinning oil that adds the 123g boiling range again and be 159-185 ℃ is made into diluent, and this diluent is directly stand-by as components b.
Preparation example 3
In a 500ml three-necked bottle, adding 100g dodecenylsuccinic acid half ester (is the additive product of T747 with trade names, the chemical plant, Lvshun produces, acid number is about 180mgKOH/g), 46.9g triethylene tetramine (calculates according to the T747 acid number, the carboxyl mol ratio is 1: 1 in triethylene tetramine and the dodecenylsuccinic acid half ester), and the 150g boiling range is 159-185 ℃ aromatic hydrocarbons thinning oil, heated and stirred, under 110 ℃, blew water 5 hours with nitrogen, tell approximately 5g water, products therefrom is directly stand-by as components b.
Preparation example 4
In a 500ml three-necked bottle, adding 56.7g tetraethylene pentamine (0.3mol) and 79.8g dodecenylsuccinic acid acid anhydride (0.3mol) and 136.5g boiling range are 159-185 ℃ aromatic hydrocarbons thinning oil, heated and stirred, under 150 ℃, blew water 5 hours with nitrogen, tell approximately 5g water, the mixture that is approximately contained the ammonolysis reaction product of 50 % by weight, this ammonolysis reaction product is take single laurylene base succimide as main, and this mixture is directly stand-by as components b.
Preparation example 5
Method preparation according to preparation example 4, difference is, replace 56.7g tetraethylene pentamine (0.3mol) with 28.4g tetraethylene pentamine (0.15mol), and be that 159-185 ℃ aromatic hydrocarbons thinning oil replacement 136.5g boiling range is 159-185 ℃ aromatic hydrocarbons thinning oil with the 108.2g boiling range.The two laurylene base succimides that approximately contained 50 % by weight are main ammonolysis reaction mixture, and this ammonolysis reaction mixture is directly stand-by as components b.
Embodiment 1-9
Embodiment 1-9 is used for the preparation of explanation compositions of additives of the present invention.
Component a and components b and amount of component b are mixed according to the weight ratio shown in the table 1.
Table 1
| Embodiment | Component a | Components b | Amount of component b | a∶b∶c |
| Embodiment 1 | Anti-aging agent 88 | Preparation example 1 | - | 2∶1 |
| Embodiment 2 | 4,4 '-dioctyl diphenylamine | Preparation example 1 | - | 2∶1 |
| Embodiment 3 | Oxidation inhibitor T511 | Preparation example 3 | - | 1∶2 |
| Embodiment 4 | N, N '-di-sec-butyl-p-phenyl enediamine | Preparation example 2 | - | 1∶1 |
| Embodiment 5 | N, N '-di-sec-butyl-p-phenyl enediamine | Preparation example 2 | N, N '-two salicylidene-1,2-propylene diamine | 1∶1∶0.06 |
| Embodiment 6 | Antioxidant 2246 | Preparation example 2 | - | 3∶1 |
| Embodiment 7 | N, N '-di-sec-butyl-p-phenyl enediamine+Tenox PG (weight ratio 5: 1) | Preparation example 2 | - | 1∶1 |
| Embodiment 8 | Anti-aging agent 688 | Preparation example 4 | - | 1∶1 |
| Embodiment 9 | Anti-aging agent 688 | Preparation example 5 | 1∶1 | |
| Comparative Examples 1 | Oxidation inhibitor T501 | Preparation example 2 | - | 3∶1 |
Performance test
Below in the test, used Rapeseed Biodiesel is the biofuel product that Shijiazhuang refinery branch office of China Petrochemical Industry provides, used sewer oil biofuel provides by the remarkable new forms of energy of Fujian Longyan company limited, and petroleum diesel is the capital mark B diesel oil that Yanshan Mountain branch office of China Petrochemical Industry produces.
(1) pure biofuel is as the oxidation stability test of the biodiesel composition of basic diesel oil
Evaluate oxidation stability of biodiesel the inductive phase under measuring 110 ℃ with EN14112:2003 method (Racimat method), use instrument to be 743 type oil oxidative stability determinators of Switzerland Wan Tong company, wherein, inductive phase is longer to illustrate that then the oxidation-resistance of Dresel fuel compositions is better, otherwise shorter illustrate that then the oxidation-resistance of Dresel fuel compositions is poorer inductive phase.Its test result is shown in Table 2.
Table 2
Data from table 2 can find out, component a is common oxidation inhibitor, and oxidation stability of biodiesel is had certain improvement, and 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 is well more a lot of than the effect sum of independent use component a, components b, this shows to have occurred astoundingly synergy clearly between component a, the b.After optional amount of component b added, effect further strengthened.
Embodiment 1 compares and can find out with embodiment 2, the Ursol D kind antioxidant is (such as N, N '-dioctyl-p-phenylenediamine) more excellent with the effect of components b after compound, effective a lot of after more compound than diphenylamine oxidation inhibitor (such as 4,4 '-dioctyl diphenylamine) and components b.
Embodiment 6 compares and can find out with Comparative Examples 1, and the effect after bisphenol type oxidation inhibitor (such as antioxidant 2246) is compound with components b is better than single phenol type antioxidant (such as oxidation inhibitor T501) greatly.
Embodiment 4 compares and can find out with embodiment 5, select optional amount of component b after, the oxidation stability of gained biodiesel composition further strengthens.
Embodiment 4 compares and can find out with embodiment 7, and when component a was the mixture of arylamine type oxidation inhibitor and hindered phenol type antioxidant, the oxidation stability of gained biodiesel composition further improved.
Embodiment 8 compares and can find out with embodiment 9, and components b is that to be better than components b be that diene base succimide (" two extension ") is compound with oxidation inhibitor to the antioxidant effect of mono alkenyl succimide (" single hang ") after compound with oxidation inhibitor.
(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 respectively each Dresel fuel compositions, petroleum diesel and concocted diesel oil inductive phase under 110 ℃, use instrument to be 743 type oil oxidative stability determinators of Switzerland Wan Tong company, inductive phase is longer to illustrate that then the oxidation-resistance of biodiesel composition is better, otherwise shorter illustrate that then the oxidation-resistance of biodiesel composition is poorer inductive phase.Its test result is shown in Table 3.
The method of employing SH/T 0175 is measured the amount (unit: mg/100mL), thereby evaluate their stability of various concocted diesel oil composition total insoluble substances.The larger then stability of the amount of total insoluble substance is poorer, otherwise if the less then stability of the amount of total insoluble substance is better, its test result is shown in Table 3.
Table 3
*Represent to form according to volume ratio blending in 15: 85 with the biofuel behind the additive that adds 600mg/kg embodiment 4 correspondences and petroleum diesel, calculating the blending fuel additive level is 90mg/kg.
Result by table 3 can find out, after the adding biofuel, contains the oxidation stability of the blending fuel of biofuel, stable all variation of comparing with petroleum diesel.The oxidation stability, the stability that contain the biodiesel composition of the present invention that the mixture of component a and components b obtains as additive have significantly to be improved, synergistic effect appears in component a and components b effect, and its effect obviously strengthens than independent Use Limitation fruit.After allocating with the biofuel that adds additive and petroleum diesel, need not add again its oxidation stability of oxidation inhibitor also fine.
Claims (24)
1. compositions of additives, it is characterized in that, described compositions of additives contains component a and components b, described component a is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and described hindered phenol type antioxidant is the polyphenol type oxidation inhibitor that contains at least three phenolic hydroxyl groups in bisphenol type oxidation inhibitor and/or the molecule; Described components b is to contain the acylating agent of two acyl groups and ammonia and/or amine in the molecule with mol ratio 1: ammonolysis reaction product (0.5-2), the acylating agent that contains two acyl groups in the described molecule are one or more in C6-C30 the alkyl Dicarboxylic Acids, acid anhydrides and the half ester that replace.
2. compositions of additives according to claim 1, wherein, the weight ratio of described components b and component a is 0.01-100: 1.
3. compositions of additives according to claim 2, wherein, the weight ratio of described components b and component a is 0.05-10: 1.
4. the described compositions of additives of any one according to claim 1-3, wherein, the described arylamine type oxidation inhibitor of component a is selected from least a in the quinoline of Ursol D, replacement of pentanoic, the replacement of naphthylamines, the replacement of replacement.
5. compositions of additives according to claim 4; wherein; the naphthylamines of described replacement is selected from phenyl-a-naphthylamine; Phenyl beta naphthylamine; in N-p-methoxyphenyl-alpha-naphthylamine one or more; the pentanoic that replaces is selected from one or more in the alkylated diphenylamine of alkyl carbon atoms number between 4-10; the Ursol D of described replacement is selected from hydrogen atom in the amido of Ursol D by one or more alkyl; aryl; arylalkyl; alkylaryl; the alkyl acyl group; the alkyl alkylsulfonyl; product after in the alkyl acyloxy one or more replace; the quinoline of described replacement is selected from 6-oxyethyl group-2; 2; 4-trimethylammonium-1; the 2-dihyaroquinoline; 6-phenyl-2; 2; 4-trimethylammonium-1; the 2-dihyaroquinoline; 6-dodecyl-2,2,4-trimethylammonium-1; the 2-dihyaroquinoline; 2; 2,4-trimethylammonium-1, one or more in the 2-dihyaroquinoline polymer.
6. compositions of additives according to claim 5, wherein, the Ursol D of described replacement be in two amidos of Ursol D a hydrogen atom respectively by a carbonatoms between 4-10 alkyl or one or more in the Ursol D that replaces of the carbonatoms aryl that is 6-15.
7. compositions of additives according to claim 6, wherein, the Ursol D of described replacement is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, one or more in N '-two-(1-methylheptyl) Ursol D.
8. the described compositions of additives of any one according to claim 1-3, wherein, the described phenol type antioxidant of component a is selected from the bisphenol type oxidation inhibitor that is linked to each other by sulphur or carbon atom by two single phenol and one or more in the polyphenol that is obstructed at phenolic hydroxyl group ortho position of two tertiary butyls is arranged.
9. compositions of additives according to claim 8, wherein, described phenol type antioxidant is selected from 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2-methyl-6-tert-butylphenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-TBP), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2-methyl-6-tert-butylphenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
10. compositions of additives according to claim 1; wherein, described acylating agent is one or more in C6-C30 the alkyl toxilic acid, Succinic Acid, fumaric acid, methylene-succinic acid, citraconic acid, clothing holder acid, phthalic acid, maleic anhydride, Succinic anhydried, itaconic anhydride, citraconic anhydride, isatoic anhydride, Tetra hydro Phthalic anhydride and their half ester that replace.
11. compositions of additives according to claim 10, wherein, described acylating agent is Succinic Acid, the Succinic anhydried of C6-C30 alkyl replacement and one or more in their half ester that the C6-C30 alkyl replaces.
12. compositions of additives according to claim 11; wherein, described acylating agent is the nonyl Succinic Acid; the decyl Succinic Acid; the dodecyl Succinic Acid; the tridecyl Succinic Acid; the tetradecyl Succinic Acid; the pentadecyl Succinic Acid; the hexadecyl Succinic Acid; the octadecyl Succinic Acid; nonenyl succinic acid; decene base Succinic Acid; dodecenylsuccinic acid; tetradecene base Succinic Acid; hexadecylene base Succinic Acid; octadecylene base Succinic Acid; docosene base Succinic Acid; nonyl succinic anhydride; decyl succinic anhydride; dodecyl succinic anhydride; the tridecyl succinyl oxide; the tetradecyl succinyl oxide; the pentadecyl succinyl oxide; the hexadecyl succinyl oxide; the octadecyl succinyl oxide; the nonenyl succinic acid acid anhydride; decene base succinyl oxide; dodecenylsuccinic anhydride; tetradecene base succinyl oxide; hexadecylene base succinyl oxide; octadecylene base succinyl oxide; in docosene base succinyl oxide and their half ester one or more.
13. compositions of additives according to claim 1, wherein, described amine is structural formula as shown in the formula the organic amine shown in the B3:
R wherein
1And R
2The carbonatoms of respectively doing for oneself is the alkyl of 1-30 or is with heteroatomic group, perhaps R
1And R
2One of them is H, and another is the alkyl of 1-30 for carbonatoms or is with heteroatomic group, and described is to contain carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino group with heteroatomic group.
14. compositions of additives according to claim 13, wherein, the amine shown in the formula B3 is one or more in the following amine:
Methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, n-dodecylamine, positive tetradecy lamine, hexadecylamine, octadecyl amine, positive 20 amine, positive two amino dodecanes, Isopropylamine, isobutylamine, TERTIARY BUTYL AMINE, isobutylcarbylamine, neopentyl amine, dissident's amine, tuaminoheptane, octodrine, different nonyl amine, isodecyl amine, different amino dodecane, different tetradecy lamine, different cetylamine, different stearylamine, different 20 amine, cyclopentamine, hexahydroaniline, oleyl amine, the palm oleyl amine, the primene JM-T; R
1, R
2The methyl of respectively doing for oneself, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tetradecane base, n-hexadecyl, the Octadecane base, the NSC 62789 base, the n-docosane base, sec.-propyl, isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl, different nonyl, isodecyl, the Permethyl 99A. base, different tetradecyl, isocetyl, the secondary amine of isooctadecane base or Isoeicosane base; Thanomin, diethanolamine, N-alkyl ethanol amine, N-vinyl-ethyl alcohol amine, N-alkyl α-amino isopropyl alcohol, N-thiazolinyl α-amino isopropyl alcohol, α-amino isopropyl alcohol, diisopropanolamine (DIPA), Tutofusin tris, 3-amino-1,2-propylene glycol, 2-amino-1,3-propanediol, 3-aminopropanol, 4-amino-n-butyl alcohol, 5-amino-1-amylalcohol, 6-amino-1-hexanol, PAP; Structural formula is H
2N-R
3-NHR
4Amine, R
3Be alkylidene group, thiazolinyl, cycloalkyl, aryl or the polyether-based of 1-30 for carbon number; Polyether diamine shown in the formula B4:
Wherein x1 is the integer of 1-5, R
4For hydrogen or carbon number are the alkyl of 1-30, R
5Hydrogen or methyl; Structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene and/or the condenses of this polyamines polyene and oxyethane and/or propylene oxide, wherein x2 is the integer of 2-4, y1 is the integer of 1-8, R
6For hydrogen or carbon number are the alkyl of 1-30; Imidazoline type polyamines shown in the following formula B5; Piperazine type polyamines shown in the following formula B6; The polyamines that contains tertiary amine shown in formula B7 or the formula B8;
Wherein y2 is the integer of 0-5, R
7Be C
1-C
24Alkyl;
R wherein
8Be the alkyl of H or C1-C24, x3 is the integer of 0-5;
R
9, R
10For or the alkyl of C1-C24, x4 is the integer of 0-10;
Wherein x5 is the integer of 1-10.
15. compositions of additives according to claim 14, wherein, described structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene be in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, seven ethene, eight amine, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine, five propylene hexamines, six propylene, seven amine, seven propylene, eight amine one or more, perhaps be R
6Be normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; In the polyamines polyene of isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl, different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base, Isoeicosane base, 9-octadecylene base, phenmethyl, styroyl or hydrocinnamyl one or more; Among the formula B5, y2 is the integer of 1-3, R
7Be C
6-C
20Alkyl or alkenyl; Piperazine type polyamines shown in the formula B6 is N-(2-amino-ethyl) piperazine, and described piperidines type polyamines is 4-amino-2,2,6,6-tetramethyl piperidine and/or 4-amino-1,2,2,6,6-pentamethyl-piperidines, the polyamines that contains tertiary amine shown in the formula B7 is N, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-Putriscine, N, N-dimethyl-1, in the 6-hexanediamine one or more, the polyamines that contains tertiary amine shown in the formula B8 are three (2-amino-ethyl) amine.
16. the described compositions of additives of any one according to claim 1-3, wherein, described compositions of additives also contains amount of component b, described amount of component b be can with the metal passivator of metallic surface reaction and/or with the metal chelator of metal or metal ion reaction or combination.
17. compositions of additives according to claim 16, wherein, the weight ratio of described component a and described amount of component b is 1: 0.01-1.
18. compositions of additives according to claim 17, wherein, described amount of component b is 124 Triazole, the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction, one or more in Schiff's base and the organic polycarboxylic acid.
19. a Dresel fuel compositions, described Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, described basic diesel oil contains biofuel, and described additive is the described compositions of additives of any one among the claim 1-18.
20. Dresel fuel compositions according to claim 19, wherein, described additive is 50-10000ppm with respect to the content of described basic diesel oil.
21. according to claim 19 or 20 described Dresel fuel compositions, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contains one or more in the oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is 1: 0-99.
22. a method that improves oxidation stability of biodiesel, the method comprise, in containing the basic diesel oil of biofuel, add additive, it is characterized in that, described additive is the described compositions of additives of any one among the claim 1-18.
23. method according to claim 22, wherein, described additive is 50-10000ppm with respect to the content of basic diesel oil.
24. according to claim 22 or 23 described methods, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contains one or more in the oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is 1: 0-99.
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| CN 200910090511 CN101993743B (en) | 2009-08-19 | 2009-08-19 | Additive composition, diesel composition and method 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 |
| ES10791159T ES2749879T3 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process to improve oxidation stability of biodiesel |
| US13/380,334 US20120124896A1 (en) | 2009-06-26 | 2010-06-25 | Diesel Composition and Method of Increasing Biodiesel Oxidation Stability |
| EP10791159.6A EP2447344B1 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process for improving oxidation stability of biodiesel |
| PCT/CN2010/000950 WO2010148652A1 (en) | 2009-06-26 | 2010-06-25 | Diesel composition and process for improving oxidation stability of biodiesel |
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| CN103205299B (en) * | 2012-12-17 | 2014-11-19 | 湖北航天化学技术研究所 | Deoxidant for liquid hydrocarbon fuel, and its application |
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