CN101928614B - 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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- CN101928614B CN101928614B CN 200910087970 CN200910087970A CN101928614B CN 101928614 B CN101928614 B CN 101928614B CN 200910087970 CN200910087970 CN 200910087970 CN 200910087970 A CN200910087970 A CN 200910087970A CN 101928614 B CN101928614 B CN 101928614B
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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 a kind of method of Dresel fuel compositions and raising oxidation stability of biodiesel.
Background technology
Quickening along with diesel oil of vehicle trend in world wide, the demand of diesel oil can be more and more large, and the raising of day by day exhausted and people's environmental consciousness of petroleum resources, greatly promoted countries in the world to accelerate the exploitation paces of Alternative Diesel Fuel, the environmental-protecting performance that biofuel is superior with it and recyclability have been subject to the attention of various countries.
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., with alcohols (methyl alcohol, ethanol), through transesterification reaction, obtaining, is a kind of biofuel of cleaning.That biofuel has is renewable, clean and safe three advantages, and China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment are had to very great strategic importance.And China is a net import of oil state at present, prospective oil is very limited again, and a large amount of Imported oils threaten to the energy security of China; Therefore, the research of biofuel and production have important realistic meaning to China.
But, due to raw material and complete processing, the oxidation stability of some biofuel is very poor, using and storing and all cause very large difficulty biofuel.The poor biofuel of oxidation stability easily generates following ageing products: 1) insoluble polymer (colloid and greasy filth), and this can cause engine filter net jam and squirt pump coking, and causes smoke evacuation increase, difficulty in starting; 2) soluble polymer, it can form resinous substance in engine, may cause flame-out and difficulty in starting; 3) aging acid, this can cause 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 due to oxidation stability, after concocting with petroleum diesel, can increase the weight of the problems referred to above.The most obvious performance is more far short of what is expected than petroleum diesel containing stability and the detergent-dispersant performance of the blending fuel of biofuel.
The problems referred to above can be by adding additive to solve or alleviating.A kind of mode is in pure biofuel, to add oxidation inhibitor to slow down its oxidation, thereby alleviates the harm of ageing products; Another kind of mode is to add stablizer and detergent-dispersant additive to petroleum diesel or containing in the blending fuel of biofuel, 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 nozzle, and forms protective membrane at nozzle surface, prevents that new carbon deposit from producing, but established sediment in 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, the method comprise by contain count the 15-60 % by weight with stoste be dissolved in 2 of biofuel, the liquid stoste of 4-di-t-butyl hydroxy toluene joins in the biofuel for the treatment of stabilization, until in total solution of biofuel, the concentration of 2,4-di-t-butyl hydroxy toluene reaches 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 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 and treats in stable biofuel with the amount of 10-20000ppm (w/w).
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 the main anti-oxidant of 40 ℃ to be joined and treat that, in stable biofuel, wherein said main anti-oxidant contains alkylphenol with the amount of 10-20000ppm (w/w).
US2007/113467A1 discloses a kind of fuel composition with improved oxidative stability, said composition contains biofuel and at least one oxidation inhibitor, described oxidation inhibitor is selected from Tenox PG, 1,2, a kind of in 3-trihydroxybenzene, BHT, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, tocopherol, quinoline.
Although the oxidation inhibitor that above use is traditional improves the method for oxidation stability of biodiesel, certain effect is arranged, consumption is all larger, simultaneously to the stability containing the blending fuel of biofuel to improve effect also not so good.
Summary of the invention
The objective of the invention is oxidation stability in order to overcome the Dresel fuel compositions that the pure biofuel of take of above-mentioned prior art is basic diesel oil poor and take the shortcoming of less stable of the Dresel fuel compositions that the blending fuel of biofuel and other diesel oil is basic diesel oil, 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, the 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 usining 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 components b, and 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 corrosive situation, reduced its consumption and there is very large meaning.When usining the blending fuel during as basic diesel oil that contains biofuel, the stability of this Dresel fuel compositions is better.Particularly according to preferred implementation provided by the invention, when described additive contains component a, components b simultaneously, while perhaps also containing optional amount of component b, due to obvious synergistic effect between each additive, the antioxygen of Dresel fuel compositions provided by the invention obviously improves simultaneously.
Embodiment
According 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, 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 one or more in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position of a tertiary butyl at least, further preferred described component a contains the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 and one or more in the bisphenol type oxidation inhibitor be connected by methylene radical or sulphur.
Described arylamine type oxidation inhibitor as component a can be selected from least one in naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, quinoline.
Wherein naphthylamine derivative includes but not limited to one or more in following material:
Phenyl-a-naphthylamine (oxidation inhibitor T531, antioxidant A);
Phenyl beta naphthylamine (antioxidant d);
N-p-methoxyphenyl alpha-naphthylamine (anti-aging agent 102);
To hydroxyphenyl-beta-naphthylamine (antioxidant D-OH);
Aldol-alpha-naphthylamine (antioxidant A P)
2-hydroxyl-1, two [to (beta-naphthylamine) phenoxy group] propane (anti-aging agent C-49) of 3-;
Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41) of dimethyl;
Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41-ethyl) of diethyl;
2,2 '-bis-[to (beta-naphthylamine) phenoxy group] diethyl ether (anti-aging agent C-41-ether).
Wherein, the preferred nonox of naphthylamine derivative, for example one or more in phenyl-a-naphthylamine, Phenyl beta naphthylamine, N-p-methoxyphenyl alpha-naphthylamine.Especially preferred phenyl-a-naphthylamine.
Wherein diphenylamine derivatives includes but not limited to one or more in following material:
4,4 '-diamino-diphenylamine (antioxidant A PA);
Right, to '-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 '-bis-(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 '-bis-(α, α '-dimethyl benzyl) pentanoic (anti-aging agent KY-405);
P-hydroxydiphenylamine (antioxidant A O3920);
Two-(1,1,3,3-tetramethyl-ethyl) pentanoic (anti-aging agent ODA);
4,4 '-dioctyl diphenylamine;
4,4 '-di-iso-octyldiphenylamine;
4,4 '-diheptyl pentanoic;
4,4 '-dinonyldiphenylamine;
Octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines, anti-aging agent OD);
Octyl group/butyl pentanoic (oxidation inhibitor L-57);
Styrenated diphenylamine (antioxidant D FL, DFC-34);
And the mixture of alkylated diphenylamine, wherein alkyl can be heptyl, octyl group, one or more in nonyl, the example of its Industrial products has 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 the domestic code name antioxidant product that is T534.
Diphenylamine derivatives type oxidation inhibitor preferred alkyl diphenylamines and composition thereof, especially preferred alkyl carbonatoms alkylated diphenylamine between 4-10 and composition thereof, as: 4,4 '-dioctyl diphenylamine, 4,4 '-di-iso-octyldiphenylamine, 4,4 '-diheptyl pentanoic, 4, one or more in 4 '-dinonyldiphenylamine, octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines), octyl group/butyl pentanoic, commodity oxidation inhibitor T534.
Wherein p-phenylene diamine derivative's type oxidation inhibitor comprises but is not limited to one or more in following material:
N phenyl-N '-cyclohexyl Ursol D (antioxidant 4010);
N, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (antioxidant 4020);
N, N '-bis--(Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D (anti-aging agent 4030);
N-p-methylphenyl-N '-(1,3-dimethylbutyl) Ursol D (anti-aging agent 4040);
N, N '-diheptyl Ursol D (anti-aging agent 788);
N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);
N-sec.-propyl-N '-p-methylphenyl Ursol D (anti-aging agent methyl 4010NA);
N, N '-di tolyl p phenylenediamine (anti-aging agent PPD-A);
N, N '-diphenyl-para-phenylene diamine (antioxidant H);
N, N '-bis--(betanaphthyl) Ursol D (antioxidant D NP);
N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5);
N, N '-dioctyl-p-phenylenediamine (anti-aging agent 88);
N, N '-bis--(1-methylheptyl) Ursol D (anti-aging agent 288);
N, N '-bis--(1-ethyl-3-methyl amyl) Ursol D (anti-aging agent 8L);
N, N '-bis--(Isosorbide-5-Nitrae-dimethylbutyl) Ursol D (anti-aging agent 66);
N-Octyl-N '-diphenyl-para-phenylene diamine (anti-aging agent 688);
N-isobutyl--N '-diphenyl-para-phenylene diamine (anti-aging agent 5L);
N, N '-dimethyl-N, N '-bis--(1-first propyl group) Ursol D (anti-aging agent 32);
N-(p-methylphenyl alkylsulfonyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent TPPD);
N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent G-1);
N-(3-anilino phenyl) Methacrylamide;
N-hexyl-N '-diphenyl-para-phenylene diamine;
The preferred dialkyl group Ursol D of p-phenylene diamine derivative's type oxidation inhibitor, the 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 '-bis--(1-methylheptyl) Ursol D.
Quinoline wherein includes but not limited to:
6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W);
6-phenyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (anti-aging agent PMQ);
6-dodecyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant D D);
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD, anti-aging agent 124);
Pentanoic and acetone low-temp reaction product (anti-aging agent BAS);
Pentanoic and acetone high-temperature reaction product (antioxidant BLE);
The reaction product 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 component a can be single phenol, bis-phenol, diphenol and polyphenol, can be also 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 in substituting group, have at least one to be the tertiary butyl, other substituting group can be alkyl or contain heteroatomic substituting group, alkyl wherein is selected from C
1-C
10alkyl, such as methyl, ethyl, allyl group, normal-butyl, sec-butyl, nonyl etc., contain heteroatomic substituting group to be selected from methyl, the methylol of oxygen containing substituting group as methoxyl group, methoxy substitution, and nitrogenous substituting group is as the alpha, alpha-dimethyl aminomethyl.Can be for example single phenol of following structure: o-tert-butylphenol, p-tert-butylphenol, 2-tert-butyl-4-methyl-Phenol, the 6-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol; The 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol; 2,4-DTBP, 2,5-DI-tert-butylphenol compounds, 2,6 di t butyl phenol; 2,5-di-tert-butyl-4-methy phenol, 2,6 di tert butyl 4 methyl phenol (BHT, oxidation inhibitor T501), 4,6-di-t-butyl-2-methylphenol; 2,4,6-tri-butyl-phenol, 2 allyl 4 methyl 6 tert butyl phenol, 2-sec-butyl-4-TBP, 4-sec-butyl-2,6-DI-tert-butylphenol compounds, 4-nonyl-2,6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-ethylphenol (oxidation inhibitor DBEP), 2,6-di-t-butyl-4-normal-butyl phenol (oxidation inhibitor 678); Butylhydroxy anisole (BHA), 2,6-di-t-butyl-α-methoxyl group-p-cresol (BHT-MO), 4-methylol-2,6-DI-tert-butylphenol compounds (oxidation inhibitor 754), 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703), various 3,5-di-tert-butyl-hydroxy phenyl propionic ester and 3,5-di-tert-butyl-hydroxy phenyl propionic acid acid amides etc.
Wherein single phenol oxidation inhibitor preferably has a tertiary butyl at least at the single phenol of being obstructed of phenolic hydroxyl group ortho position, as:
The 2-tert-butyl-4-methyl-Phenol, 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 6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703).
Bis-phenol for example refers to by two single phenol, by sulphur or the connected phenol type antioxidant of carbon atom:
(1) the connected bis-phenol by carbon atom
4,4 '-isopropylidene bis-phenol (dihydroxyphenyl propane);
2,2 '-bis--(3-methyl-4 hydroxy phenyl) propane (bisphenol-c);
4,4 '-dihydroxybiphenyl (oxidation inhibitor DOD);
4,4 '-dihydroxyl-3,3 ', 5,5 '-tetra--tertiary butyl biphenyl (oxidation inhibitor 712);
2,2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol) (oxidation inhibitor bis-phenol 2246);
4,4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);
2,2 '-methylene radical-bis--(4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);
2,2 '-methylene radical-bis--(4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);
2,2 '-methylene radical-bis-[4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);
2,2 '-methylene radical-bis--(6-α-methylbenzyl p-cresol);
4,4 '-methylene radical-bis--(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-bis--(2-TBP) (oxidation inhibitor 702);
2,2 '-ethylidene-bis--(4-methyl-6-tert-butylphenol);
4,4 '-ethylidene-bis--(2-methyl-6-tert-butylphenol);
4,4 '-ethylidene-bis--(2,6 di t butyl phenol);
4,4 '-butylidene-bis--(the 6-tertiary butyl-meta-cresol) (oxidation inhibitor BBM, oxidation inhibitor TCA);
4,4 '-isobutylidene-bis--(2,6 di t butyl phenol) etc.
(2) the connected bis-phenol by sulphur atom
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2,2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);
4,4 '-thiobis-(5-methyl-2-TBP);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
2,2 '-thiobis-(4-octyl phenol) etc.
(3) be connected but contain heteroatomic bis-phenol by carbon atom
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 preferably passes through methylene radical or the connected bis-phenol of sulphur by the single phenol that has at least a tertiary butyl at the phenolic hydroxyl group ortho position, for example:
2,2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol) (antioxidant 2246);
4,4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);
4,4 '-methylene radical-bis--(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-bis--(2-TBP) (oxidation inhibitor 702);
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2,2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
Two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.
The diphenol here refers to the phenol type antioxidant that two hydroxyls are arranged on a 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 5-bis-tert-pentyl Resorcinol.
Described polyphenol antioxidant refers to that the macromole oxidation inhibitor of being rolled into a ball by least three single phenolic group in molecule, preferably by having at least a tertiary butyl to roll into a ball at single phenolic group at phenolic hydroxyl group ortho position the polyphenol formed, especially preferably has the be obstructed polyphenol of two tertiary butyls at the phenolic hydroxyl group ortho position, for example:
1,3,5-trimethylammonium-2,4,6-tri--(4 '-hydroxyl-3 ', 5 '-di-t-butyl) benzene (antioxidant 330);
Three [2-(3,5-di-tert-butyl-hydroxy phenyl) propionyl oxygen ethyl] isocyanic ester (oxidation inhibitor 3125);
Four (3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester (antioxidant 1010);
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) (antioxidant 3114);
1,1,3-tri--(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA);
1,3,5-tri-(2, the 6-dimethyl-4-tertiary butyl-3-hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) (oxidation inhibitor 1790);
Two [3,3-pair-(3 '-tertiary butyl-4 '-hydroxybenzyl) butyric acid] glycol ester etc.
The polyphenol here can also be in phenyl ring with the phenol of three hydroxyls, such as pyrogallol, gallic acid ester 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 preferred gallic acid-derivate of polyphenol type oxidation inhibitor is Tenox PG especially.
Above-mentioned phenol type antioxidant preferably has the bisphenol type oxidation inhibitor of a tertiary butyl at the phenolic hydroxyl group ortho position at least, particularly by methylene radical or the connected bisphenol type oxidation inhibitor of sulphur, Tert. Butyl Hydroquinone and/or 2 most preferably in 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 polyphenol antioxidant.
Component a can also be the composite antioxidant of above-mentioned arylamine type oxidation inhibitor and above-mentioned phenol type antioxidant.The present invention most preferably described component a is N, N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-bis--(1-methylheptyl) Ursol D, 2, 2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2, the 6-DI-tert-butylphenol compounds), 4, 4 '-methylene radical-bis--(2-TBP), 4, 4 '-thiobis-(3 methy 6 tert butyl phenol), 2, 2 '-thiobis-(4-methyl-6-tert-butylphenol), 4, 4 '-thiobis-(2-methyl-6-tert-butylphenol), 4, 4 '-thiobis-(2, the 6-DI-tert-butylphenol compounds), two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) one or more in thioether.
components b
The organic amine that described components b contains the structure shown in (A) that has structural formula:
(1) R
1, R
2the alkyl that H or carbonatoms be 1-30 of can respectively doing for oneself.
R
1, R
2one of them can be H, and another one can be the carbonatoms alkyl that is 1-30, or can be the carbonatoms alkyl that is 1-30, and organic amine can be primary amine, can be also secondary amine." alkyl " refers to hydrocarbon substituent, i.e. a kind of in aliphatics, alicyclic, aromatics and cyclic substituent.Aliphatic alkyl can be saturated can be also the alkyl of the two keys of undersaturated band or triple bond.Wherein primary amine can be the aliphatic amide that carbonatoms is 1-30, it can be also the arylamine that carbonatoms is 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, n-dodecylamine (lauryl amine), positive tetradecy lamine, hexadecylamine, octadecyl amine, positive 20 amine, one or more in positive two amino dodecanes, it can be also the fat primary amine with side chain, these fat primary amines with side chain are various isomer of above-mentioned straight chain fat primary amine, 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, one or more in different 20 amine.Fat primary amine can also be that amine with cycloaliphatic ring is as cyclopentamine, hexahydroaniline.Can be also contain unsaturated double-bond or triple bond in carbochain fat primary amine as oleyl amine (octadecenyl amine), palm oleyl amine (hexadecylene amine), can also be the primene JM-T, for example Rohm& The primene JM-T that the trade names that Haas company produces are Primere 81R.
If secondary amine, wherein R
1, R
2can be identical, also can be different, can be that normal chain alkyl is 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, can be also that isomery alkyl with side chain is 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
2the heteroatomic group of being with that H or carbonatoms be 1-30 of can respectively doing for oneself.
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 α-amino isopropyl alcohol, N-thiazolinyl α-amino isopropyl alcohol, α-amino isopropyl alcohol, diisopropanolamine (DIPA), Tutofusin tris, 3-amino-1 for example, one or more in 2-propylene glycol, 2-amino-1,3-propanediol, 3-aminopropanol, 4-amino-n-butyl alcohol, 5-amino-1-amylalcohol, 6-amino-1-hexanol, PAP.
The amine that contains amido or amino is polyamine compounds, and the polyamines here refers in molecule the amine that contains two or more nitrogen-atoms, as structural formula is H
2n-R
3-NHR
4amine, the R here
3can be alkylidene group, thiazolinyl, cycloalkyl, aryl or the polyether-based that carbon number is 1-30; R
4it can be the alkyl that hydrogen, carbon number are 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 A1:
The integer that wherein x1 is 1-5, R
4it can be the alkyl that hydrogen, carbon number are 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
6it can be the alkyl that hydrogen, carbon number are 1-30.For example, work as R
6during for H, described polyamines polyene can be one or more 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.Work as R
6during for the carbon number alkyl that is 1-30, be preferably the alkyl of C4-C22.This alkyl can be saturated alkyl, can be also with the thiazolinyl of two keys or with the aryl of phenyl ring.Alkyl can be the straight chain normal chain alkyl, can be also 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 Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Aryl with phenyl ring can be one or more in phenmethyl (benzyl), styroyl and hydrocinnamyl.Wherein, the more preferably alkyl of C6-C20.
The polyamines here can also be nitrogenous heterocyclic amine, such as but not limited to one or more in the amine of the amine of the amine of imidazoline type, piperazine type and piperidines type.
The imidazoline type polyamines is as shown in the formula shown in A2:
The integer that wherein y2 is 0-5, R
7for C
1-C
24alkyl.Be preferably C
4-C
22alkyl.This alkyl can be saturated alkyl, can be also with the thiazolinyl of two keys or with the aryl of phenyl ring.Alkyl can be the straight chain normal chain alkyl, can be also 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 Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Aryl with phenyl ring can be one or more in phenmethyl (benzyl), styroyl and hydrocinnamyl.Wherein, the integer that further preferably y2 is 1-3, R
7for C
6-C
20alkyl or alkenyl.
Piperazine type polyamines is as shown in the formula shown in A3:
R wherein
8for the alkyl of H or C1-C24, the integer that x3 is 0-5.Preferably typical piperazine type polyamines is N-(2-amino-ethyl) piperazine, N-(2-aminoethyl)-Isosorbide-5-Nitrae-piperazine two base diethylamine etc.
The polyamines of piperidines type is 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 containing tertiary amine shown in A4, A5.
R wherein
9, R
10for or the alkyl of C1-C24, the integer that x4 is 0-10.Preferred R
9, R
10for the alkyl of C1-C10, the integer that x4 is 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.
The integer that wherein x5 is 1-10, be 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
6it can be the alkyl that hydrogen or carbon number are 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 following polymer amine type ashless dispersant except containing above-mentioned organic amine, and 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 base succinamide ashless dispersant for example number-average molecular weight in the reaction product of polyolefin-based Succinic anhydried and/or succinic acid and the amine of 500-3000; 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 after C8-C30 alkylphenol and oxyethane or propylene oxide adduction again with the product of amine condensation or C8-C30 alcohol and oxyethane or propylene oxide adduction after again with the product of amine condensation; Described polyalkene amines type ashless dispersant for example chlorinatedpolyolefins reacts the polyolefin-based amine generated with amine.Here said amine preferred polyamines all, especially as above said polyamines polyene.
amount of component b
Under preferable case, Dresel fuel compositions provided by the invention also contains amount of component b, and described amount of component b can and/or be reacted with metal or metal ion or the metal chelator of combination for the various metal passivators that can react with metallic surface.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 one or more in 124 Triazole and derivative, thiadiazoles and derivative thereof, oxine, ethylenediamine tetraacetic carboxylic acid, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base (Schiffbases), organic polycarboxylic acid and derivative thereof.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 to modification, the method for modification mainly by introducing oil-soluble group as long chain hydrocarbon groups in 124 Triazole.Therefore, described 124 Triazole derivative can be the various derivatives that various solvabilities in biofuel are good 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 ammonium salt and 124 Triazole, formaldehyde and the aliphatic amide of aliphatic amide formation.Described ethylenediamine tetraacetic carboxylic acid can be ethylenediamine tetraacetic acid (EDTA) (EDTA), and described hydrazides can be N-salicylidene-N '-salicylyl hydrazine and/or N, N '-diacetyl adipyl two hydrazides.Described beta-diketon is as methyl ethyl diketone, and described 'beta '-ketoester is as the etheric acid monooctyl ester.Described Schiff's base can be N, N '-bis-salicylidenes-1，2-diaminoethane, N, N '-bis-salicylidene-1,2-propylene diamine, N, N '-bis-salicylidene-1,2-cyclohexanediamine, N, one or more in N '-bis-salicylidenes-N '-methyl two propylene triamines.Described organic polycarboxylic acid and derivative thereof are such as being one or more in citric acid, tartrate, oxysuccinic acid, succsinic acid (succinic acid), toxilic acid, phytic acid etc. and derivative thereof.
In the present invention, preferred described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide form, 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 in one or more.
According to using needs, Dresel fuel compositions provided by the invention can also contain other additive, as one or more in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc.
The preparation of Dresel fuel compositions provided by the invention is simple, only each component that forms Dresel fuel compositions need be mixed and gets final product.Can directly each additive component be mixed with the various compositions of basic diesel oil, also can first various additive components be mixed, after obtaining additive, then the gained additive be mixed with the various compositions of basic diesel oil or basic diesel oil.For easy to operate, when various additive components are mixed, can under existing, solvent carry out, the solvent here can be that polar solvent is as N, one or more in dinethylformamide (DMF), Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF) (DHF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidone and methyl-2-pyrrolidone.Can be also hydro carbons especially aromatic hydrocarbons as benzene,toluene,xylene, aromatic hydrocarbons thinning oil and composition thereof, can also be biofuel.
In the present invention, described basic diesel oil can be pure biofuel, and described biofuel refers to that grease and low-carbon alcohol are (as C
1-C
5fatty alcohol) fatty acid ester of low-carbon alcohol generated through transesterify (alcoholysis) reaction, be generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.
Described trans-esterification processes can be the processing method that any known or unknown transesterification reaction 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 liquid is called oil, and normal temperature is solid or the semisolid fat (abbreviation fat) that is called.Described grease comprises vegetables oil and animal oil, in addition, also comprising from the oil plant in the materials such as microorganism, algae, can also be even 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 can be also xylophyta oil, as 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, the halophytes oil as 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 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 the boiling range 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 meets solar oil standard GB/T 252 or derv fuel oil standard GB/T 19147 formed through allotment.
The fischer-tropsch combined diesel oil mainly refers to take GTL diesel oil (Gas To Liquid) or the CTL diesel oil (Coal To Liquid) that Sweet natural gas or coal are produced as raw material funds-Tuo (F-T) synthetic method, 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 oxidation stability of tempered oil is variation likely, therefore the blending fuel containing biofuel also needs to add oxidation inhibitor.
The hydrocracking biofuel is also referred to as s-generation biofuel, refer to by animal-plant oil, after hydrogenation and cracking reaction, generated with C
8-C
24alkane is main, especially with C
12-C
20the reaction product that normal paraffin is main component, this hydrocracking biofuel cetane value is high, and sulphur and aromaticity content are extremely low, can greatly reduce the discharge of diesel engine pollutent as diesel motor fuel or blending component.
Refer to and can be deployed into the oxygenatedchemicals that meets certain code requirement or the mixture of oxygenatedchemicals with various diesel-fuels containing oxygen diesel oil blending component, normally alcohols and ethers or its mixture, alcohols is C for example
1-C
18fatty alcohol, preferred C
1-C
12unitary fatty alcohol, as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecylenic alcohol, lauryl alcohol and various isomer thereof.Ethers can be dme, methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, C
6-C
14fatty alcohol-polyoxyethylene ether, C
6-C
14fatty alcohol polyoxypropylene ether, C
6-C
14alkylphenol polyoxyethylene, C
6-C
14alkylphenol polyethenoxy ether, polyoxymethylene dme (Polyoxymethylene Dimethyl Ethers, CH
3o (CH
2o)
xcH
3, x=1-8) etc. and composition thereof.
In the present invention, described basic diesel oil is while containing the blending fuel of biofuel, described Dresel fuel compositions can, by described additive, biofuel and other diesel oil directly are obtained by mixing, also can first mix described additive, and then obtain with other diesel oil blending with biofuel.The various components of additive directly can be mixed with the various compositions of basic diesel oil, also can first the various components of additive be pre-mixed, obtain mixing with the various compositions of basic diesel oil or basic diesel oil again after 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 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 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 the metal passivator that can react with metallic surface and/or reacts with metal or metal ion or the metal chelator of combination.
The amount of component b of the component a of described additive, the components b of additive and additive is identical with component a, components b and amount of component b in above-mentioned Dresel fuel compositions separately, and its kind and consumption describing above, do not repeat them here.
Under preferable case, the method of raising oxidation stability of biodiesel provided by the invention also is included in the basic diesel oil that contains biofuel, add other additive, as one or more in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc.
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 Dresel fuel compositions do not caused disadvantageous effect, for example, can mix at ambient temperature.
Described biofuel can be both aforementioned pure biofuel, can be also the aforementioned blending fuel containing biofuel.
The present invention is described further for the following examples.
Embodiment 1-7
Following examples are 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 table 1.
Table 1
| Embodiment | Component a | Components b | Amount of component b | A: b: c (weight ratio) |
| Embodiment 1 | N, N '-di-sec-butyl-p-phenyl enediamine | Lauryl amine | - | 1∶1∶0 |
| Embodiment 2 | Anti-aging agent 88 | Coconut oil base trimethylene diamines | - | 1∶1.2∶0 |
| Embodiment 3 | N, N '-di-sec-butyl-p-phenyl enediamine | Tetraethylene pentamine | - | 1∶1∶0 |
| Embodiment 4 | N, N '-di-sec-butyl-p-phenyl enediamine | Tetraethylene pentamine | N, N '-bis-salicylidene-1,2-propylene diamine | 1∶1∶0.06 |
| Embodiment 5 | Antioxidant 4020 | N, N-dimethyl-1,3-propylene diamine | - | 2∶1∶0 |
| Embodiment 6 | 2,5 di tert butyl hydroquinone | N-(2-amino-ethyl) piperazine | - | 1∶3∶0 |
| Embodiment 7 | Antioxidant 2246 | Five ethene hexamines | - | 3∶1∶0 |
Performance test
Below in the test, Oleum Gossypii semen biofuel used is the biofuel product that Shijiazhuang refinery branch office of China Petrochemical Industry provides, sewer oil biofuel used provides by the remarkable new forms of energy of Fujian Longyan company limited, 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
Measure and evaluate inductive phase under 110 ℃ oxidation stability of biodiesel by EN14112:2003 method (Rancimat method), use the 743 type oil oxidative stability determinators that instrument is Switzerland Wan Tong company, wherein, inductive phase is longer illustrates that the oxidation-resistance of Dresel fuel compositions is better, otherwise shorter illustrate that the oxidation-resistance of Dresel fuel compositions is poorer inductive phase.Its test result is shown in Table 2.
Table 2
Data from table 2 can find out, component a is common oxidation inhibitor, and oxidation stability of biodiesel is had to 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 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, has occurred astoundingly as can be seen here synergy clearly between component a, b.After optional amount of component b adds, effect further strengthens.
Result by embodiment 1 and 3 can find out, polyamines is more excellent as the effect of components b.Embodiment 3 compares and can find out with embodiment 4, and after selecting optional amount of component b, the oxidation stability of gained biodiesel composition further strengthens.
(2) using the mixture of biofuel and petroleum diesel as the test of oxidation-resistance, stability and the detergent-dispersant performance of the concocted diesel oil composition of basic diesel oil, biofuel used 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 the 743 type oil oxidative stability determinators that instrument is Switzerland Wan Tong company.Its test result is shown in Table 3.Inductive phase is longer illustrates that the oxidation-resistance of biodiesel composition is better, otherwise shorter illustrate that the oxidation-resistance of biodiesel composition is poorer inductive phase.
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 amount of total insoluble substance more stability is poorer, otherwise, if the less stability of the amount of total insoluble substance is better, its test result is shown in Table 3.
Table 3
Result by table 3 can find out, after adding biofuel, containing oxidation stability, the stability of the blending fuel of biofuel, compares all variation with petroleum diesel.Oxidation stability, the stability of the biodiesel composition of the present invention that the mixture that contains component a and components b obtains as additive has significantly to be improved, synergistic effect appears in component a and components b effect, and its effect obviously strengthens than independent Use Limitation fruit.
Claims (22)
1. a Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, described basic diesel oil contains biofuel, described additive contains component a and components b, and described component a contains Ursol D type oxidation inhibitor and has one or more in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position of a tertiary butyl at least; Described components b contains the polyamines that is different from component a, and described additive is 50-10000ppm with respect to the content of basic diesel oil, and the weight ratio of described components b and component a is 0.01-100:1.
2. Dresel fuel compositions according to claim 1, wherein, the weight ratio of described components b and component a is 0.05-5:1.
3. Dresel fuel compositions according to claim 1, wherein, described component a contains the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 and one or more in the bisphenol type oxidation inhibitor be connected by methylene radical or sulphur.
4. Dresel fuel compositions according to claim 3, 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 '-bis--(1-methylheptyl) Ursol D, 2, 2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2, the 6-DI-tert-butylphenol compounds), 4, 4 '-methylene radical-bis--(2-TBP), 4, 4 '-thiobis-(3 methy 6 tert butyl phenol), 2, 2 '-thiobis-(4-methyl-6-tert-butylphenol), 4, 4 '-thiobis-(2-methyl-6-tert-butylphenol), 4, 4 '-thiobis-(2, the 6-DI-tert-butylphenol compounds), two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) one or more in thioether.
5. Dresel fuel compositions according to claim 1 and 2, wherein, the described organic amine of polyamines for thering is structure shown in structural formula (A) that is different from component a:
R
1, R
2the heteroatomic group of being with that alkyl that H, carbonatoms be 1-30 or carbonatoms be 1-30 of respectively doing for oneself, described to be with heteroatomic group be carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino.
6. Dresel fuel compositions according to claim 5, wherein, the described polyamines that is different from component a is that structural formula is H
2n[(CH
2)
x2nH]
y1r
6polyamines polyene, wherein, the integer that x2 is 2-4, the integer that y1 is 1-8, R
6it is the alkyl that hydrogen or carbon number are 1-30.
7. Dresel fuel compositions according to claim 5, wherein, the described polyamines that is different from component a is N-(2-amino-ethyl) piperazine.
8. Dresel fuel compositions according to claim 1 and 2, wherein, described additive also contains amount of component b, and described amount of component b is the metal passivator that can react with metallic surface and/or reacts with metal or metal ion or the metal chelator of combination.
9. Dresel fuel compositions according to claim 8, wherein, the weight ratio of described component a and described amount of component b is 1:0.01-1.
10. Dresel fuel compositions according to claim 8, 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 organic polycarboxylic acid.
11. according to the described Dresel fuel compositions of any one in claim 1,2,3,4,6 and 7, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contains one or more in oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is 1:0-99.
A 12. method that improves oxidation stability of biodiesel, the method comprises, in containing the basic diesel oil of biofuel, add additive, described additive contains component a and components b, and described component a contains Ursol D type oxidation inhibitor and has one or more in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position of a tertiary butyl at least; Described components b contains the polyamines that is different from component a, and described additive is 50-10000ppm with respect to the content of basic diesel oil, and the weight ratio of described components b and component a is 0.01-100:1.
13. method according to claim 12, wherein, the weight ratio of described components b and component a is 0.05-5:1.
14., according to the described method of claim 12 or 13, wherein, described component a contains the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 and one or more in the bisphenol type oxidation inhibitor be connected by methylene radical or sulphur.
15. method according to claim 14, 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 '-bis--(1-methylheptyl) Ursol D, 2, 2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2, the 6-DI-tert-butylphenol compounds), 4, 4 '-methylene radical-bis--(2-TBP), 4, 4 '-thiobis-(3 methy 6 tert butyl phenol), 2, 2 '-thiobis-(4-methyl-6-tert-butylphenol), 4, 4 '-thiobis-(2-methyl-6-tert-butylphenol), 4, 4 '-thiobis-(2, the 6-DI-tert-butylphenol compounds), two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) one or more in thioether.
16. according to the described method of claim 12 or 13, wherein, the described organic amine of polyamines for thering is structure shown in structural formula (A) that is different from component a:
R
1, R
2the heteroatomic group of being with that alkyl that H, carbonatoms be 1-30 or carbonatoms be 1-30 of respectively doing for oneself, described to be with heteroatomic group be carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino.
17. method according to claim 16, wherein, the described polyamines that is different from component a is that structural formula is H
2n[(CH
2)
x2nH]
y1r
6polyamines polyene, wherein, the integer that x2 is 2-4, the integer that y1 is 1-8, R
6it is the alkyl that hydrogen or carbon number are 1-30.
18. method according to claim 16, wherein, the described polyamines that is different from component a is N-(2-amino-ethyl) piperazine.
19., according to the described method of claim 12 or 13, wherein, described additive also contains amount of component b, described amount of component b is the metal passivator that can react with metallic surface and/or reacts with metal or metal ion or the metal chelator of combination.
20. method according to claim 19, wherein, the weight ratio of described component a and described amount of component b is 1:0.01-1.
21. method according to claim 19, 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 organic polycarboxylic acid.
22. according to the described method of claim 12 or 13, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contains one or more in oxygen diesel oil blending thing, and the volume ratio of described biofuel and other diesel oil is 1:0-99.
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| CN 200910087970 CN101928614B (en) | 2009-06-26 | 2009-06-26 | Diesel composite and method for improving oxidation stability of biodiesel |
| BRPI1012681-3A BRPI1012681B1 (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 |
| 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 |
| 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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