CN101353601B - Method for improving biodiesel antioxygen property - Google Patents
Method for improving biodiesel antioxygen property Download PDFInfo
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- CN101353601B CN101353601B CN 200710119551 CN200710119551A CN101353601B CN 101353601 B CN101353601 B CN 101353601B CN 200710119551 CN200710119551 CN 200710119551 CN 200710119551 A CN200710119551 A CN 200710119551A CN 101353601 B CN101353601 B CN 101353601B
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Abstract
The invention provides a method for enhancing the anti-oxygen performance of biodiesel, which comprises the following steps: an arylamine antioxidant with the content of 20 to 20000mg/kg is added into the biodiesel. The arylamine antioxidant is selected from at least one of naphthylamine derivative, diphenylamine derivative, ursol derivative and quinoline derivative. According to the method provided by the invention, a phenol antioxidant can also be added into the biodiesel, and the mass ratio between the phenol antioxidant and the arylamine antioxidant is 1:0.05 to 20. The method provided bythe invention can obviously improve the oxidative stability of the biodiesel.
Description
Technical field
The present invention relates to improve the method for antioxygen property of biodiesel.
Background technology
Quickening along with vehicle diesel oil trend in the world wide, the demand of diesel oil can be more and more big, and the raising of exhausted day by day and people's environmental consciousness of petroleum resources, promoted countries in the world to accelerate the exploitation paces of diesel oil alternative fuel greatly, biofuel has been subjected to the attention of various countries with its superior environmental-protecting performance and recyclability.
Biofuel (BD100) claims that again fatty acid methyl ester (Fatty Acid Methyl Ester) is that grease and the animal grease with oil plant waterplant such as oil-yielding shrubs fruit, engineering microalgae such as oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistaches, the food and drink wet goods that gives up are made raw material, obtaining through transesterification reaction (Transesterification reaction) with alcohols (methyl alcohol, ethanol), is a kind of biofuel of cleaning.That biofuel has is renewable, cleaning and safety three big advantages, and China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment are had very great strategic importance.And China is a net import of oil state at present, and prospective oil is very limited again, and a large amount of Imported oils threaten to the energy security of China; Therefore, the research of biofuel and production have important practical sense to China.
Compare with conventional diesel oil, biofuel has following incomparable performance: (1) has good environmental protection characteristic.Because sulphur content is low in the biofuel, makes that the discharging of sulfurous gas and sulfide is low, can reduce about 30% (being 70% when catalyzer is arranged); Do not contain the aromatic hydrocarbons that can pollute environment in the biofuel, thereby waste gas is lower than diesel oil to human body infringement.According to the EPA report, biofuel can make HC reduction by 67%, CO reduction by 48%, PM reduction by 47% in the exhaust gas from diesel vehicle.Other detection shows, compares with ordinary diesel oil, uses biofuel can reduce by 90% air toxicity, reduces by 94% cancer rate; Because biofuel oxygen level height, smoke evacuation is lacked when making its burning, and the discharging of carbon monoxide is compared with diesel oil and reduced about 10% (being 95% when catalyzer is arranged); The biological degradability height of biofuel; (2) has lubricity preferably.Make the wear rate of oil injection pump, engine cylinder-body and connecting rod low, long service life; (3) has good safety performance.Because the flash-point height, biofuel does not belong to hazardous substance.Therefore, when transportation, storage, use, all compare safety; (4) cetane value height; (5) has renewable performance.And since the carbonic acid gas of biofuel when burning discharging far below the carbonic acid gas that absorbs in the growing process, thereby improve since the Global warming that emission of carbon-dioxide causes this be harmful to the mankind's great environmental problem.Thereby biofuel is a kind of real green diesel.
But because raw material and complete processing, the oxidation stability of some biofuel is very poor, to use, the storage of biofuel with all cause very big difficulty.The biofuel of oxidation stability difference easily generates following ageing products: 1) insoluble polymer (colloid and greasy filth), and this can cause the engine filter screen to stop up and the squirt pump coking, and causes smoke evacuation to increase, start difficulty; 2) soluble polymer, it can form resinous substance in engine, may cause flame-out and the startup difficulty; 3) aging acid, this can cause the engine metal component corrosion; 4) superoxide, this can cause aging the becoming fragile of rubber components and cause fuel leakage etc.
Europe biofuel standard EN 14214:2003, Australian biofuel standard (Draft2003), New Zealand biofuel standard NZS 7500:2005, Brazilian biofuel standard A NP255 (2003), India biofuel standard I S 15607:2005, South Africa biofuel standard SANS1935:2004 and China's diesel-fuel blending with biofuel (BD100) standard GB/T20828-2007 all the oxidation stability of regulation biofuel be to be not less than 6 hours inductive phase under 110 ℃, measuring method is EN14112:2003.
US20060096159 openly handles coarse biodiesel to improve the stability of biofuel with strong acid such as sulfuric acid, corrodes and increased production cost but use present method that equipment is had.
CN1742072A openly uses oxidation inhibitor 2, and 6-di-tert-butyl methyl phenol (BHT) improves the method for biofuel stability, dosage 0.005～2% (weight).
CN1847368A openly uses bisphenols oxidation inhibitor as 4,4`-methylene radical two [2,6 di t butyl phenol], 2, and 2`-methylene radical two [6-di-tert-butyl-4-methy phenol] etc. improve the method for biofuel stability, dosage 0.001～2% (weight).
CN1847369A openly improves the method for biofuel stability, dosage 0.001～2% (weight) with induced by alkyl hydroxybenzene oxidation inhibitor.
Summary of the invention
The present invention provides a kind of method that improves antioxygen property of biodiesel based on prior art.
Method provided by the invention comprises: add the arylamine kind antioxidant in biofuel, the content of arylamine kind antioxidant in biofuel is 20～20000mg/kg.
Said arylamine kind antioxidant is selected from least a in naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, the quinoline, at least a among preferred naphthylamine derivative, diphenylamine derivatives, the p-phenylene diamine derivative.
According to method provided by the invention, preferably in biofuel, add by naphthylamine derivative and diphenylamine derivatives according to mass ratio 1:0.05～20 oxidation inhibitor of preferred 1:0.1～10 compositions.
Naphthylamine derivative wherein 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-1,3-pair-[right-(beta-naphthylamine)-phenoxy group] propane (anti-aging agent C-49);
Dimethyl-two-[right-(beta-naphthylamine)-phenoxy group] silane (anti-aging agent C-41);
Diethyl-two-[right-(beta-naphthylamine)-phenoxy group] silane (anti-aging agent C-41-ethyl);
2,2 '-one or more compositions in two-[right-(beta-naphthylamine)-phenoxy group] diethyl ether (anti-aging agent C-41-ether).
Wherein, the preferred nonox of naphthylamine derivative, for example one or more in phenyl-a-naphthylamine, Phenyl beta naphthylamine, the N-p-methoxyphenyl alpha-naphthylamine.Especially preferred phenyl-a-naphthylamine.
Diphenylamine derivatives wherein includes but not limited to one or more in the following material:
4,4 '-diamino-pentanoic (antioxidant A PA);
Right, right '-dimethoxy-pentanoic;
N, N, N, N '-tetraphenyl-diamines methane (anti-aging agent 350);
N, N '-phenylbenzene-quadrol;
N, N '-phenylbenzene-propylene diamine;
N, N '-di-o-tolyl-quadrol;
2-hydroxyl-1,3-pair-(to the aniline phenoxy group) propane (anti-aging agent C-47);
2,2 '-two-(right-the aniline phenoxy group)-diethyl ether (antioxidant H-1);
Dimethyl-two-(right-aniline-phenoxy group)-silane (anti-aging agent C-1);
Right-isopropoxy-pentanoic (anti-aging agent ISO);
Right, right '-diisopropoxy-pentanoic (antioxidant D ISO);
4,4 '-two-(α, α '-dimethyl benzyl)-pentanoic (anti-aging agent KY-405);
Right-hydroxy diphenylamine (antioxidant A O3920);
Two-(1,1,3,3-tetramethyl-ethyl)-pentanoic (anti-aging agent ODA);
4,4 '-dioctyl-pentanoic;
4,4 '-diisooctyl-pentanoic;
4,4 '-diheptyl-pentanoic;
4,4 '-dinonyl-pentanoic;
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 is heptyl, octyl group, nonyl etc., 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 Wytox ADP, ADP-X, U.S. Vanderbilt company commodity are called Agerite Stalite, Agerite Stalite S, AgeriteNepa, Agerite Gel, and U.S. Uniroyal company commodity Polylite, Antioxidant445 by name and domestic code name are the antioxidant product of T534.
Diphenylamine derivatives kind antioxidant preferred alkyl diphenylamines and composition thereof, preferred alkyl carbon number alkylated diphenylamine between 4～10 and composition thereof especially, as: 4,4 '-dioctyl diphenylamine; 4,4 '-di-iso-octyldiphenylamine; 4,4 '-the diheptyl pentanoic; 4,4 '-dinonyldiphenylamine; Octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines); Octyl group/butyl pentanoic, one or more among the commodity oxidation inhibitor T534.
P-phenylene diamine derivative's kind antioxidant wherein includes but not limited to one or more in the following material:
N-phenyl-N '-cyclohexyl-Ursol D (antioxidant 4010);
N-(1,3-dimethylbutyl)-N '-phenyl-Ursol D (anti-aging agent 4020);
N, N '-two-(1,4-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 '-phenyl-Ursol D (antioxidant 4010NA);
N-sec.-propyl-N '-p-methylphenyl-Ursol D (anti-aging agent methyl 4010NA);
N, N '-two-tolyl-Ursol D (anti-aging agent PPD-A);
N, N '-phenylbenzene-Ursol D (antioxidant H);
N, N '-two-betanaphthyl-Ursol D (antioxidant D NP);
N, N '-two-sec-butyl-Ursol D (anti-aging agent U-5);
N, N '-dioctyl-Ursol D (anti-aging agent 88);
N, N '-two-(1-methylheptyl)-Ursol D (anti-aging agent 288);
N, N '-two-(1-ethyl-3-methyl amyl)-Ursol D (anti-aging agent 8L);
N, N '-two-(1,4-dimethylbutyl)-Ursol D (anti-aging agent 66);
N-octyl group-N '-phenyl-Ursol D (anti-aging agent 688);
N-isobutyl--N '-phenyl-Ursol D (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 '-phenyl-Ursol D (anti-aging agent TPPD);
N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-phenyl-Ursol D (anti-aging agent G-1);
N-(3-anilino phenyl) Methacrylamide;
N-hexyl-N '-phenyl-Ursol D;
The preferred dialkyl group Ursol D of p-phenylene diamine derivative's kind antioxidant, the dialkyl group Ursol D of preferred alkyl carbon number between 4～10 especially, as: N, N '-diheptyl-Ursol D; N, N '-two-sec-butyl-Ursol D; N, N '-dioctyl-Ursol D; N, one or more in N '-two-(1-methylheptyl)-Ursol D.
Quinoline wherein includes but not limited to:
6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W);
6-phenyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (anti-aging agent PMQ);
6-dodecyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant D D);
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD, anti-aging agent 124);
Pentanoic and acetone low-temp reaction product (anti-aging agent BAS);
Pentanoic and acetone high-temperature reaction product (antioxidant BLE);
The reaction product of pentanoic and acetone and aldehyde (anti-aging agent BXA);
The reaction product of Phenyl beta naphthylamine and acetone (antioxidant A PN, antioxidant A M).
According to method provided by the invention, can also in biofuel, add phenol type antioxidant, the mass ratio of phenol type antioxidant and arylamine type oxidation inhibitor is 1:0.05～20, preferred 1:0.1～10.
Said phenol type antioxidant can be single phenol, diphenol, bis-phenol and polyphenol, also can be the mixture of their arbitrary proportions.Preferred single phenol, diphenol and bisphenols oxidation inhibitor especially preferably have a tertiary butyl at least at the hindered phenol at phenolic hydroxyl group ortho position.
Single phenol wherein is that a phenyl ring is arranged, and the phenol of the replacement of a hydroxyl is arranged on the phenyl ring, and has at least one to be the tertiary butyl in the substituting group, and other substituting group can be alkyl or contain heteroatomic substituting group that alkyl wherein is selected from C
1～C
10Alkyl, for example methyl, ethyl, allyl group, normal-butyl, sec-butyl, nonyl etc. contain heteroatomic substituting group and are selected from methyl, methylol, nitrogenous substituting group such as the alpha, alpha-dimethyl aminomethyl that oxygen containing substituting group such as methoxyl group, methoxyl group replace.For example can be single phenol of following structure: o-tert-butylphenol, p-tert-butylphenol, the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol; The 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol; 2,4-DI-tert-butylphenol compounds, 2,5-DI-tert-butylphenol compounds, 2,6 di t butyl phenol; 2,5-di-tert-butyl-4-methy phenol, 2,6 di tert butyl 4 methyl phenol (BHT), 4,6-di-t-butyl-2-methylphenol; 2,4,6-tri-butyl-phenol, 2 allyl 4 methyl 6 tert butyl phenol, 2-sec-butyl-4-tert.-butyl phenol, 4-sec-butyl-2,6-DI-tert-butylphenol compounds, 4-nonyl-2,6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-ethylphenol (oxidation inhibitor DBEP), 2,6-di-t-butyl-4-normal-butyl phenol (oxidation inhibitor 678); Butylhydroxy anisole (BHA), 2,6-di-t-butyl-α-methoxyl group-p-cresol (BHT-MO), 4-methylol-2,6 di t butyl phenol (oxidation inhibitor 754), 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703) etc.
Wherein single phenol oxidation inhibitor preferably has a tertiary butyl at least at single phenol at phenolic hydroxyl group ortho position, as:
The 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2, the 4-xylenol, 2, the 6-DI-tert-butylphenol compounds, 2,6-di-tert-butyl-4-methy phenol (BHT), 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 t butyl phenol (oxidation inhibitor 754), 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703) etc.
The diphenol here refers to have on the phenyl ring phenol type antioxidant of two hydroxyls, can be the diphenol of following structure: Resorcinol, Tert. Butyl Hydroquinone (TBHQ), 2,5 di tert butyl hydroquinone, 2,5-two tert-pentyl Resorcinol etc.
Bis-phenol refers to pass through sulphur or the continuous phenol type antioxidant of carbon atom by two single phenol, for example:
(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 butyl phenol) (oxidation inhibitor bis-phenols 2246);
4,4 '-methylene radical-two (2-methyl-6-tert butyl phenol) (oxidation inhibitor methenes 736);
2,2 '-methylene radical-two (4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);
2,2 '-methylene radical-two (4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);
2,2 '-methylene radical-two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);
2,2 '-methylene radical-two (6-α-Jia Jibianji p-cresol);
4,4 '-methylene radical-two (2,6 di t butyl phenols) are (T511);
4,4 '-methylene radical-two (2-tert.-butyl phenol) (oxidation inhibitor 702);
2,2 '-ethylidene-two (4-methyl-6-tert butyl phenol);
4,4 '-ethylidene-two (2-methyl-6-tert butyl phenol);
4,4 '-ethylidene-two (2,6 di t butyl phenols);
4,4 '-butylidene-two (the 6-tertiary butyl-meta-cresols) (oxidation inhibitor BBM, oxidation inhibitor TCA);
4,4 '-isobutylidene-two (2,6 di t butyl phenols) 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);
2,2 '-thiobis (4-methyl-6-tert butyl phenol) (antioxidant 2246-S);
4,4 '-thiobis (2-methyl-6-tert butyl phenol) (oxidation inhibitor 736);
4,4 '-thiobis (5-methyl-2-tert.-butyl phenol);
4,4 '-thiobis (2,6 di t butyl phenol) is (Nocrac300);
2,2 '-thiobis (4-octyl phenol) etc.
(3) linked to each other by carbon atom but contain heteroatomic bis-phenol
N, N '-hexamethylene 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.
The bis-phenol that bisphenols oxidation inhibitor is preferably linked to each other by methylene radical or 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-two (4-methyl-6-tert butyl phenol) (oxidation inhibitor bis-phenols 2246);
4,4 '-methylene radical-two (2-methyl-6-tert butyl phenol) (oxidation inhibitor methenes 736);
4,4 '-methylene radical-two (2,6 di t butyl phenols);
4,4 '-methylene radical-two (2-tert.-butyl phenol) (oxidation inhibitor 702);
4,4 '-thiobis (3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2,2 '-thiobis (4-methyl-6-tert butyl phenol) (antioxidant 2246-S);
4,4 '-thiobis (2-methyl-6-tert butyl phenol) (oxidation inhibitor 736);
4,4 '-thiobis (2,6 di t butyl phenol) (Nocrac 300);
Two (3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.
The polyphenol antioxidant here refers in the molecule macromole oxidation inhibitor by at least three single phenolic group groups, and the preferred polyphenol of being made up of the single phenolic group group that has at least a tertiary butyl at the phenolic hydroxyl group ortho position especially preferably has two tertiary butyls at the polyphenol at phenolic hydroxyl group ortho position, for example:
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.
Can also further add little metal passivator during the compound use of arylamine kind antioxidant of the present invention and hindered phenol type antioxidant, the mass ratio of metal passivator and arylamine kind antioxidant is 0.005～0.5:1, preferred 0.01～0.1:1.
The metal passivator here can be metal passivator such as 124 Triazole and derivative, thiadiazoles and the derivative thereof that reacts with the metallic surface, also can be the metal chelator with metal or metal ion reaction or combination.The metal chelator here has oxine; ethylenediamine tetraacetic carboxylic acid such as ethylenediamine tetraacetic acid (EDTA) (EDTA); hydrazides such as N-salicylidene-N '-salicylyl hydrazine; N; N '-diacetyl adipyl two hydrazides; beta-diketon such as methyl ethyl diketone; 'beta '-ketoester such as etheric acid monooctyl ester; Schiff's base (Schiff bases) is as N; N '-two salicylidene-1; the 2-quadrol; N; N '-two salicylidene-1; the 2-propylene diamine; N; N '-two salicylidene-1; the 2-cyclohexanediamine; N, N '-two salicylidenes-N '-methyl-two propylene triamine etc.; organic polycarboxylic acid and derivative thereof such as citric acid; tartrate; oxysuccinic acid; succsinic acid (Succinic Acid); toxilic acid; phytic acid etc. and derivative thereof.Preferred Schiff's base and organic polycarboxylic acid and derivative thereof, as N, N '-two salicylidene-1,2-quadrol, N, N '-two salicylidene-1,2-propylene diamine, N, N '-two salicylidene-1,2-cyclohexanediamine, citric acid and derivative thereof, tartrate and derivative thereof, oxysuccinic acid and derivative thereof, succsinic acid (Succinic Acid) and derivative thereof.
Antioxidant composition shown in the present can also be deployed into diluent or liquid product with solvent, said solvent can be alcohols, ethers, ester class or hydro carbons with and composition thereof.Alcohols is C for example
1～C
18Fatty Alcohol(C12-C14 and C12-C18), preferred C
5～C
12Unitary fatty alcohol is as 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
14Aliphatic alcohol polyethenoxy (propylene) ether, C
6～C
14Alkylphenol-polyethenoxy (propylene) ether, polyoxymethylene dme (Polyoxymethylene Dimethyl Ethers, CH
3O (CH
2O)
xCH
3, x=1～8) etc. and composition thereof.The ester class can be aromatic esters, also can be fatty acid ester.The especially preferred phthalic ester of the preferred phthalic ester of aryl esters and isophthalic acid ester class such as phthalic acid two C
1～C
12Alkyl ester, for example dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dimixo-octyl phthalate, diheptyl phthalate etc.Fatty acid ester can be that monoesters also can be diester, the C of monoesters preferred fatty acid
1～C
12Alkyl ester, for example C
12～C
24Lipid acid C
1～C
4Ester (biofuel).The preferred adipic acid ester of diester, azelate and sebacic acid ester be Di-n-butyl Adipate, dihexyl azelate and dioctyl sebacate etc. for example.Preferred aromatic hydrocarbons such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil in the hydro carbons.Choice of Solvent will be as far as possible can not cause detrimentally affect to other physical and chemical index of biofuel.
Biofuel provided by the invention and contain in the blending fuel of biofuel and also can add various additives as required is as FLOW IMPROVERS, other oxidation inhibitor, metal passivator, detergent-dispersant additive, corrosion inhibitor, cetane number improver, defoamer, static inhibitor, sterilant etc.
Said biofuel refers to that grease and low-carbon alcohol are (as C
1～C
5Fatty Alcohol(C12-C14 and C12-C18)) fatty acid ester of low-carbon alcohol that generates through transesterify (alcoholysis) reaction is generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.
Said 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.Said vegetables oil can be that herbaceous plant oil also can be xylophyta oil, as the oil of peanut oil, Semen Maydis oil, Oleum Gossypii semen, rape seed oil, soybean oil, plam oil, Thistle oil, linseed oil, Oleum Cocois, Oak Tree oil, Prunus amygdalus oil, walnut oil, Viscotrol C, sesame oil, sweet oil, Yatall MA (Tall Oil), sunflower oil, curcas oil, tung oil, shinyleaf yellowhorn oil, coptis wood oil, halophytes such as plants such as kostelezkya virginica, cyperus esculentus.Said animal oil can be lard, chicken fat, duck oil, goose oil, sheep oil, house oil, butter, haco oil, shark wet goods.
Can also contain in the said biofuel and be selected from petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel and contain in the oxygen diesel oil blending component one or more.Wherein petroleum diesel refers to boiling range the cut 160～380 ℃ between of crude oil (oil) after devices such as the various refining process decompression as usual of refinery, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking are handled, and the compression ignition engine fuel that satisfies solar oil standard GB 252-2000 or derv fuel oil standard GB/T 19147-2003 that forms through allotment.The fischer-tropsch combined diesel oil refers to that mainly with Sweet natural gas or coal be GTL diesel oil (Gas To Liquid) or the CTL diesel oil (Coal ToLiquid) that raw material funds-Tuo (F-T) synthetic method is produced, and can also be vegetable fibre funds-Tuo synthetic method and the BTL diesel oil (Biomass To Liquid) produced.The fischer-tropsch combined diesel oil is substantially free of sulphur and aromatic hydrocarbons, be very clean fuel, but its oilness extreme difference improve greatly with biofuel blending back oilness, but the possible variation of the oxidation stability of blending fuel, 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, this hydrocracking biofuel cetane value height, and sulphur and aromaticity content are extremely low, can reduce the discharging of diesel engine pollutent greatly as diesel motor fuel or blending component.Contain oxygen diesel oil blending component and 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 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
14Aliphatic alcohol polyethenoxy (propylene) ether, C
6～C
14Alkylphenol-polyethenoxy (propylene) ether, polyoxymethylene dme (Polyoxymethylene Dimethyl Ethers, CH
3O (CH
2O)
xCH
3, x=1～8) etc. and composition thereof.
Embodiment
In an embodiment, the oxidation stability of the blending fuel of biofuel or biofuel and petroleum diesel, combined diesel oil is measured its inductive phase under 110 ℃ with EN14112:2003 method (Racimat method) and is evaluated, and uses instrument to be 743 type oil oxidative stability determinators of Switzerland Wan Tong company.
Embodiment 1～6
Present embodiment illustrates arylamine kind antioxidant compound composition of the present invention, and is as shown in table 1:
Table 1
Embodiment 7
The antioxidant effect of arylamine kind antioxidant in the biofuel that certain plam oil is produced that the present embodiment explanation is shown in the present, as shown in table 2:
Table 2
By table 2 as seen, add arylamine kind antioxidant shown in the present, the oxidation stability of the biofuel of being produced by plam oil be improved significantly, reach the required value of standard.
Embodiment 8
The antioxidant effect of present embodiment explanation arylamine kind antioxidant of the present invention in the biofuel that certain rapeseed oil is produced, as shown in table 3:
Table 3
By table 3 as seen, add arylamine kind antioxidant shown in the present, the oxidation stability of the biofuel of being produced by rapeseed oil also be improved significantly, reach the required value of standard.
Embodiment 9
Antioxidant effect in the fuel (B20) of present embodiment explanation arylamine kind antioxidant of the present invention after the biofuel of certain sewer oil production is concocted with volume ratio 20:80 with the petroleum diesel that satisfies GB 252-2000 solar oil standard, addition is with total fuel ga(u)ge, and is as shown in table 4:
Table 4
By table 4 as seen, oxidation inhibitor of the present invention not only improves significantly to the oxidation stability of pure biofuel (BD100), and the oxidation stability of the blending fuel of biofuel and petroleum diesel is also had good improved action.
Embodiment 10～15
The composition of present embodiment explanation antioxidant composition of the present invention, as shown in table 6:
Table 6
Embodiment 16
The antioxidant effect of antioxidant composition in the biofuel that certain plam oil is produced that the present embodiment explanation is shown in the present, as shown in table 7:
Table 7
By table 7 and table 2 as seen, add phenolic antioxidant separately as 2,6-di-tert-butyl-4-methy phenol (BHT), butylhydroxy anisole (BHA), perhaps add arylamine kind antioxidant such as phenyl-a-naphthylamine, octyl diphenylamine mixture separately, the oxidation stability of biofuel obtains raising to a certain degree, synergistic effect occurred and add composite antioxidant shown in the present, the oxidation stability of biofuel is greatly improved.
Embodiment 17
The antioxidant effect of present embodiment explanation antioxidant composition of the present invention in the biofuel that certain Oleum Gossypii semen is produced, as shown in table 8:
Table 8
By table 8 as seen, the oxidation stability that adds separately phenolic antioxidant or add arylamine kind antioxidant biofuel separately obtains raising to a certain degree, synergistic effect occurred and add composite antioxidant shown in the present, the oxidation stability of biofuel is greatly improved.
Embodiment 18
Antioxidant effect in the fuel (B10) of present embodiment explanation antioxidant composition of the present invention after the biofuel that certain sewer oil is produced is concocted with volume ratio 10:70:20 with petroleum diesel, GTL diesel oil, addition is with total fuel ga(u)ge, and is as shown in table 9:
Table 9
By table 9 as seen, antioxidant composition of the present invention not only improves significantly to the oxidation stability of pure biofuel (BD100), and the oxidation stability of the blending fuel of biofuel and petroleum diesel, GTL diesel oil is also had good improvement.
Claims (5)
1. method that improves antioxygen property of biodiesel, comprise: in biofuel, add arylamine kind antioxidant and phenol type antioxidant, the content of arylamine kind antioxidant in biofuel is 20～20000mg/kg, the mass ratio of phenol type antioxidant and arylamine type oxidation inhibitor is 1: 0.05～20, described arylamine kind antioxidant is selected from least a in nonox, alkylated diphenylamine and the dialkyl group Ursol D, described phenol type antioxidant is two (3,5-di-tert-butyl-4-hydroxyl benzyl) thioethers.
2. in accordance with the method for claim 1, it is characterized in that nonox is selected from one or more the nonox in phenyl-a-naphthylamine, Phenyl beta naphthylamine, the N-p-methoxyphenyl alpha-naphthylamine.
3. in accordance with the method for claim 1, it is characterized in that alkylated diphenylamine is selected from the alkylated diphenylamine of alkyl carbon number between 4～10.
4. in accordance with the method for claim 1, it is characterized in that said biofuel is fatty acid methyl ester.
5. in accordance with the method for claim 1, it is characterized in that, also contain in the said biofuel and be selected from petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel and contain in the oxygen diesel oil blending component one or more.
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| ES2749879T3 (en) | 2009-06-26 | 2020-03-24 | China Petroleum & Chem Corp | Diesel composition and process to improve oxidation stability of biodiesel |
| JP5921667B2 (en) | 2011-03-25 | 2016-05-24 | エボニック オイル アディティヴス ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｏｉｌ Ａｄｄｉｔｉｖｅｓ ＧｍｂＨ | Composition for improving oxidation stability of fuel oil |
| CN103454267A (en) * | 2012-06-02 | 2013-12-18 | 王军 | Edible oil security detection method |
| AU2013314451B2 (en) | 2012-09-13 | 2016-10-13 | Evonik Oil Additives Gmbh | A composition to improve low temperature properties and oxidation stability of vegetable oils and animal fats |
| CN105985865B (en) * | 2015-02-02 | 2019-07-05 | 中国石油天然气股份有限公司 | Storage method of inedible animal and vegetable oil |
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| CN101484555A (en) * | 2006-06-14 | 2009-07-15 | 科聚亚公司 | Antioxidant additive for biodiesel fuels |
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| US5509944A (en) * | 1994-08-09 | 1996-04-23 | Exxon Chemical Patents Inc. | Stabilization of gasoline and gasoline mixtures |
| CN101484555A (en) * | 2006-06-14 | 2009-07-15 | 科聚亚公司 | Antioxidant additive for biodiesel fuels |
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