CN101768482B - Diesel composition - Google Patents
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- CN101768482B CN101768482B CN2008102466848A CN200810246684A CN101768482B CN 101768482 B CN101768482 B CN 101768482B CN 2008102466848 A CN2008102466848 A CN 2008102466848A CN 200810246684 A CN200810246684 A CN 200810246684A CN 101768482 B CN101768482 B CN 101768482B
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Abstract
The invention provides a diesel composition which contains base diesel and an additive, wherein the base diesel contains biodiesel and the additive contains a component a and a component b. The component a is prepared by the following method: mixing alkenyl succinimide with low carbonic ester containing hindered phenol according to the molar ratio of the polyethylene polyamine in the alkenyl succinimide to the low carbonic ester containing hindered phenol to react at 60-200 DEG C for 0.5-20h in the presence of solvents, wherein the molar ratio is 1:0.5-5. The component b is an arylamine antioxidant and/or a hindered phenol antioxidant. The biodiesel composition provided by the invention has obviously improved stability, oxidation stability, detergency and dispersancy.
Description
Technical field
The present invention relates to a kind of Dresel fuel compositions.
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 received 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 oil and fat with oil plant waterplant such as oil-yielding shrubs fruit, engineering microalgae such as oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistaches, the food and drink wet goods that gives up are made raw material; Obtaining through transesterification reaction with alcohols (methyl alcohol, ethanol), is a kind of biofuel of cleaning.That biofuel has is renewable, cleaning and safety three big advantages, and China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment are had the great strategic importance of ten minutes.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.
Yet because raw material and complete processing, the oxidation stability of some biofuel is very poor, using and store and all cause very big difficulty biofuel.The biofuel of oxidation stability difference is prone to generate following ageing products: (1) insoluble polymer (colloid and greasy filth), and this can cause the mover 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 mover, 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 (Draft 2003), nz biofuel standard NZS 7500:2005, Brazilian biofuel standard A NP255 (2003), India biofuel standard I S 15607:2005, South Africa biofuel standard SANS 1935:2004 and China's diesel-fuel blending with biofuel (BD100) standard GB/T 20828-2007 all the oxidation stability of regulation biofuel be to be not less than 6 hours inductive phase under 110 ℃, measuring method is EN14112:2003.
As everyone knows, non-hydrocarbon compounds such as the alkene in the diesel oil, diolefin and sulfide, nitride generate a series of intermediate oxidation product, and produce insoluble deposition through condensation under the effect of oxygen.These insoluble particles that in the diesel oil storage process, generate can have influence on the use properties of fuel, cause filtering system to stop up, and cause the prime the fuel system unit failure; Influence oil atomizing; Cause incomplete combustion, even in mover, form too much carbon deposit, make spray nozzle clogging.And biofuel is because oxidation stability than petroleum diesel difference, and can increase the weight of the problems referred to above after the petroleum diesel blending.The most significantly performance is to contain the stability of the blending fuel of biofuel and detergent-dispersant performance than petroleum diesel difference.
The problems referred to above can additive solves or alleviation through adding.A kind of mode is in pure biofuel, to add oxidation inhibitor slowing down its oxidation, thereby alleviates the harm of ageing products; Another kind of mode is to petroleum diesel or contains adding stablizer and detergent-dispersant additive in the biofuel blending fuel, with stability and the detergent-dispersant performance that improves blending fuel.Stablizer can stop, weakens or disturb each kinds of oxidation reaction, to suppress oil deterioration, improves its stability; Detergent-dispersant additive can wash down established carbon deposit on the nozzle, and forms protective membrane at nozzle surface, prevents that new carbon deposit from producing, but established sediment in the dispersed oil also simultaneously improves purifier and spray nozzle clogging, and improves exhaust emissions.
CN 1742072A discloses a kind of method that improves storage stability of bio-diesel; This method comprises and is dissolved in 2 of biofuel with containing with what stoste was counted 15-60 weight %; The liquid stoste of 4-di-t-butyl hydroxy toluene joins in the biofuel of treating stabilization; Until total solution in biofuel, 2, the concentration of 4-di-t-butyl hydroxy toluene reaches 0.005-2 weight %.
CN 1847368A discloses a kind of method that improves the oxidative stability of biofuel; This method comprises bisphenols oxidation inhibitor as 4; 4`-methylene radical two [2; The 6-DI-tert-butylphenol compounds], 2,2`-methylene radical two [6-di-tert-butyl-4-methy phenol] joins with the amount of 10-20000ppm (w/w) and treats in the stable biofuel.
CN 1847369A discloses a kind of method that improves the oxidative stability of biofuel; This method comprises that fusing point is less than or equal to 40 ℃ primary antioxidant to join with the amount of 10-20000ppm (w/w) and treat that in the stable biofuel, wherein said primary antioxidant contains alkylphenol.
US 2007/113467A1 discloses a kind of fuel composition with improved oxidative stability; Said composition contains biofuel and at least a oxidation inhibitor; Said oxidation inhibitor is selected from Tenox PG, 1; 2,3-trihydroxybenzene, 2, a kind of in 6-di-tert-butyl methyl phenol, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, Viteolin, the quinoline.
Though the method for more than using traditional oxidation inhibitor to improve oxidation stability of biodiesel has certain effect, does not have peace and quiet dispersion effect for biofuel, for the oil motor that uses pure biofuel, can not improve its detergency.Simultaneously to the stability of the tempered oil that contains biofuel and detergent-dispersant performance to improve effect also bad.
Summary of the invention
The objective of the invention is for overcome above-mentioned prior art with pure biofuel be basic diesel oil Dresel fuel compositions oxidation stability and detergency is relatively poor and be the stability and the relatively poor shortcoming of detergent-dispersant performance of the Dresel fuel compositions of basic diesel oil with the blending fuel of biofuel and other diesel oil, provide a kind of oxidation stability and detergency all better or the equal Dresel fuel compositions preferably of stability and detergent-dispersant performance.
The invention provides a kind of Dresel fuel compositions; This Dresel fuel compositions contains basic diesel oil and additive; Wherein, Said basic diesel oil contains biofuel, and said additive contains component a and components b, and said component a prepares through following method: is 1 according to the polyamines polyene in the allyl butyrate imide with the mol ratio that contains the low-carbon ester of hindered phenol with the low-carbon ester that contains hindered phenol with the allyl butyrate imide: 0.5-5 reacted 0.5-20 hour in 60-200 ℃ in the presence of solvent; Said components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant.
Dresel fuel compositions provided by the invention, when with pure biofuel during as basic diesel oil, this Dresel fuel compositions has oxidation stability and detergency preferably; When with the blending fuel that contains biofuel during as basic diesel oil, the stability of this Dresel fuel compositions and detergent-dispersant performance are all better.Particularly according to preferred implementation provided by the invention; When said additive contains component a, components b simultaneously; When perhaps also containing optional amount of component b simultaneously, because obvious synergistic effect between each additive, the antioxygen property and the detergent-dispersant performance of Dresel fuel compositions provided by the invention obviously improve.For example; Can find out from the result of the table 2 that describes below; Dresel fuel compositions provided by the invention is under the situation of 3920mg/kg in additive amount; Up to 16.1 hours, deposition was reduced to 28.1mg by containing additive 72.5mg before by 110 ℃ of oxidation stabilities of representing inductive phase, and deposition improvement rate is up to 61.2%.
Embodiment
In Dresel fuel compositions provided by the invention, said content of additive can be conventional content, for example can be 50-10000ppm, is preferably 100-8000ppm.
The weight ratio of said components b and component a can be 0.01-10: 1, be preferably 0.05-5: and 1, further be preferably 0.1-3: 1.
Said component a prepares through following method:
Polyamines polyene with allyl butyrate imide and phenolic group organic acid during according to this allyl butyrate imide of preparation is 1 with the mol ratio that contains the low-carbon ester of hindered phenol: 0.5-5, preferred 1-4: 1 reacted down 0.5-20 hour, preferably 1-10 hour in 60-200 ℃, preferred 80-160 ℃ under solvent.Available nitrogen protection in the reaction system perhaps lets and carries out under the condition that is reflected at solvent refluxing.This reaction can not add catalyzer; Also can add a small amount of (for example with respect to allyl butyrate imide and the 0.01-1 weight % that contains the low-carbon ester gross weight of hindered phenol) acidic substance such as sulfuric acid, tosic acid or acidic white earth as catalyzer, so that fast reaction speed.Said reaction solvent is preferably hydrocarbon polymer such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil, industrial naptha or MO (boiling point is more than 120 ℃), or their mixture.Solvent load generally is the 30-150 weight % of monomer material gross weight.For the ease of postorder operation and storage, last product can be made into the diluent of the about 50 weight % of concentration with the aromatic hydrocarbons thinning oil.Said concentration calculates according to gross weight * 100% of concentration (weight %)=(water and the quantity of solvent told in the add-on-reaction of the low-carbon ester of the add-on of allyl butyrate imide+contain hindered phenol)/diluent or according to gross weight * 100% of (weight %)=(water and the quantity of solvent told in the add-on-reaction of the low-carbon ester of the add-on of the add-on+polyamines polyene of polyolefin-based Succinic Acid and/or polyolefin-based Succinic anhydried+contain hindered phenol)/diluent.Among the present invention, unless stated otherwise, the content of said component a is benchmark with the amount of above-mentioned diluent, and the amount that also is above-mentioned solvent is also as the part of component a.
In the present invention, the said low-carbon ester that contains hindered phenol has the described structure of following formula:
Wherein, R
1And R
2Can be the alkyl of 1-24 for H or carbonatoms separately, work as R
1, R
2When the carbonatoms of respectively doing for oneself is the alkyl of 1-8; Can be straight chain also can be the alkyl of side chain; For example methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, hexyl, heptyl, octyl group, 2-ethyl-butyl, 1-methyl amyl, 1,3-dimethylbutyl, 1,1; 3,3-tetramethyl butyl, 1-methyl hexyl, 1-methylheptyl, 2-ethylhexyl; The preferred carbonatoms of respectively doing for oneself is alkyl, cyclopentyl or the cyclohexyl of 1-8; Most preferably respectively the do for oneself methyl or the tertiary butyl.N can be the integer of 0-10, is preferably the integer of 0-7, most preferably is the integer of 1-4.R
3For carbonatoms is the alkyl of 1-20, be preferably the alkyl that carbonatoms is 1-5, most preferably be methyl or ethyl.For example, the said low-carbon ester that contains hindered phenol can be β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) methyl propionate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) ethyl propionate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propyl propionate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) isopropyl propionate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) n-butyl propionate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) isobutyl propionate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) amyl propionate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) isopentyl pyruvate, the β-just own ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid dissident ester, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) the positive heptyl ester of propionic acid, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) propionic acid n-octyl, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) different monooctyl ester of propionic acid, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid ester in the positive ninth of the ten Heavenly Stems, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) propionic acid ester in the positive last of the ten Heavenly stems, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) positive ten diester of propionic acid, β-positive 14 esters of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive hexadecyl ester of propionic acid, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, ethylene glycol bis [β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) propionic ester], butyleneglycol two [β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic ester], pinakon two [β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic ester], triglycol be two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, four [3-(4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic acid] pentaerythritol ester, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) methyl-butyrate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) ethyl n-butyrate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propyl butyrate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) methyl isobutyrate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) ethyl isobutyrate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propyl isobutyrate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) methyl valerate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) one or more in Valeric acid ethylester, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propyl valerate.
In the present invention; Said allyl butyrate imide can be the various polyolefine that contain the succimide base; Can obtain through the whole bag of tricks; For example can obtain through existing prepared in various methods, also can be commercially available, be among T151A (mono butonediimide), T151B (mono butonediimide), T152 (two succimide), T154 (two succimide), T155 (poly succimide) and the T161 (poly succimide) one or more like trade names.The preparation method can obtain for carrying out dehydration reaction by polyolefin-based Succinic Acid and/or polyolefin-based Succinic anhydried and polyamines; The condition of said dehydration reaction comprises that the mol ratio of polyamines and polyolefin-based Succinic Acid and polyolefin-based Succinic anhydried total amount can be 1: 1-2; Temperature of reaction can be 100-200 ℃; Reaction times can be 3-6 hour, and the medium of reaction is benzene,toluene,xylene, C
9In heavy aromatics, industrial naptha and the MO one or more, said C
9The boiling range of heavy aromatics is 159-185 ℃, and the boiling point of said MO is more than 120 ℃.Preferred temperature is that 50-200 ℃, reaction times are 2-10 hour.Said polyamines is preferably polyamines polyene.Said polyolefin-based can be various C
3-C
4The multipolymer of monoolefine or the group of homopolymer for example can be polyisobutenyl, polypropylene-base, random or block Vilaterm-propenyl, polyisopreneyl.Wherein polyolefin-based number-average molecular weight is preferably 300-5000, is preferably 500-2500, more preferably 800-2000; Each polyolefin-based substitution value of going up succinyl is preferably 0.5-1.0.That is, allyl butyrate imide according to the invention can be one or more in polyisobutenyl succimide, polypropylene-base succimide, random or block Vilaterm-propenyl succimide, the polyisopreneyl succimide.The structural formula of the polyamines polyene that adopts is H
2N [(CH
2)
nNH]
mH, wherein, n can be the integer of 2-4, is preferably 2 or 3, m can be the integer of 1-5, is preferably 3 or 4.For example, said polyamines polyene can be in quadrol, diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines, tn, two propylene triamines, three propylene tetramines, tetrapropylene five amine and the five propylene hexamines one or more.The concrete operation method for preparing said allyl butyrate imide is for conventionally known to one of skill in the art, for example can be referring to US 2,992, and 708, US3,172,892, US 3,272,746, US 5,286,823 documents such as grade, do not give unnecessary details at this.
Components b
Can be selected from least a in naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, the quinoline as the said arylamine type oxidation inhibitor of components b; At least a among preferred naphthylamine derivative, diphenylamine derivatives, the p-phenylene diamine derivative, especially preferred p-phenylene diamine derivative.
Wherein naphthylamine derivative includes but not limited to one or more in the following material:
PA (oxidation inhibitor T531, antioxidant A);
PBNA (antioxidant d);
N-p-methoxyphenyl alpha-naphthylamine (anti-aging agent 102);
To phenylor-beta-naphthylamine (antioxidant D-OH);
Aldol-alpha-naphthylamine (antioxidant A P)
2-hydroxyl-1, two [to (beta-naphthylamine) phenoxy] propane (anti-aging agent C-49) of 3-;
Two [to (beta-naphthylamine) phenoxy] silane (anti-aging agent C-41) of dimethyl-;
Two [to (beta-naphthylamine) phenoxy] silane (anti-aging agent C-41-ethyl) of diethylammonium;
2,2 '-two [to (beta-naphthylamine) phenoxy] diethyl ether (anti-aging agent C-41-ether).
Wherein, the preferred nonox of naphthylamine derivative, for example one or more in PA, PBNA, the N-p-methoxyphenyl alpha-naphthylamine.Especially preferred PA.
Wherein diphenylamine derivatives includes but not limited to one or more in the following material:
4,4 '-diamino-diphenylamine (antioxidant A PA);
Right, to '-the dimethoxy pentanoic;
N, N, N ', N '-tetraphenyl diamines methane (anti-aging agent 350);
N, N '-diphenyl ethylene diamine;
N, N '-diphenylprop diamines;
N, N '-di-o-tolyl-ethylene-diamine;
2-hydroxyl-1,3-pair-(to the aniline phenoxy) propane (anti-aging agent C-47);
2,2 '-two (to the aniline phenoxy)-diethyl ether (antioxidant H-1);
Two (to aniline-phenoxy)-silane (anti-aging agent C-1) of dimethyl-;
P-isopropoxy-diphenylamine (anti-aging agent ISO);
Right, to '-diisopropoxy pentanoic (antioxidant D ISO);
4,4 '-two (α, α '-dimethyl benzyl) pentanoic (anti-aging agent KY-405);
P-hydroxydiphenylamine (antioxidant A O3920);
Two (1,1,3,3-tetramethyl-ethyl) pentanoic (anti-aging agent ODA);
4,4 '-dioctyl diphenylamine;
4,4 '-di-iso-octyldiphenylamine;
4,4 '-diheptyl pentanoic;
4,4 '-dinonyldiphenylamine;
Octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines, anti-aging agent OD);
Octyl group/butyl pentanoic (oxidation inhibitor L-57);
Styrenated diphenylamine (antioxidant D FL, DFC-34);
And the mixture of alkylated diphenylamine; Wherein alkyl can be in heptyl, octyl group, the nonyl one or more; The example of its Industrial products has U.S. Pennwalt company commodity to be called Pennox A, Pennox A-" S "; American National Instrument polychem company commodity are called Wytox ADP, ADP-X; U.S. Vanderbilt company commodity are called Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, and it is the antioxidant product of T534 that U.S. Uniroyal company commodity are called Polylite, Antioxidant 445 and domestic code name.
Diphenylamine derivatives type oxidation inhibitor preferred alkyl diphenylamines and composition thereof; Especially preferred alkyl carbonatoms alkylated diphenylamine between 4-10 and composition thereof; As: 4,4 '-dioctyl diphenylamine, 4,4 '-di-iso-octyldiphenylamine, 4; 4 '-diheptyl pentanoic, 4, one or more among 4 '-dinonyldiphenylamine, octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines), octyl group/butyl pentanoic, the commodity oxidation inhibitor T534.
Wherein p-phenylene diamine derivative's type oxidation inhibitor comprises but is not limited in the following material one or more:
N phenyl-N '-cyclohexyl Ursol D (antioxidant 4010);
N, N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent 4020);
N, N '-two-(1,4-dimethyl-amyl group) Ursol D (anti-aging agent 4030);
N-p-methylphenyl-N '-(1, the 3-dimethylbutyl) Ursol D (anti-aging agent 4040);
N, N '-diheptyl Ursol D (anti-aging agent 788);
N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);
N-sec.-propyl-N '-p-methylphenyl Ursol D (anti-aging agent methyl 4010NA);
N, N '-DTPD di tolyl p phenylenediamine (anti-aging agent PPD-A);
N, N '-diphenyl-para-phenylene diamine (antioxidant H);
N, N '-two-(betanaphthyl) Ursol D (antioxidant D NP);
N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5);
N, N '-dioctyl-p-phenylenediamine (anti-aging agent 88);
N, N '-two-(1-methylheptyl) Ursol D (anti-aging agent 288);
N, N '-two-(1-ethyl-3-methyl amyl) Ursol D (anti-aging agent 8L);
N, N '-two-(1, the 4-dimethylbutyl) Ursol D (anti-aging agent 66);
N-octyl group-N '-diphenyl-para-phenylene diamine (anti-aging agent 688);
N-isobutyl--N '-diphenyl-para-phenylene diamine (anti-aging agent 5L);
N, N '-dimethyl--N, N '-two-(1-first propyl group) Ursol D (anti-aging agent 32);
N-(p-methylphenyl alkylsulfonyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent TPPD);
N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent G-1);
N-(3-anilino phenyl) USAF RH-1;
N-hexyl-N '-diphenyl-para-phenylene diamine;
The preferred dialkyl group Ursol D of p-phenylene diamine derivative's type oxidation inhibitor, the dialkyl group Ursol D of preferred alkyl carbonatoms between 4-10 especially, as: N, N '-diheptyl Ursol D; N, N '-di-sec-butyl-p-phenyl enediamine; N, N '-dioctyl-p-phenylenediamine; N, one or more in N '-two-(1-methylheptyl) Ursol D.
Quinoline wherein includes but not limited to:
6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W);
6-phenyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (anti-aging agent PMQ);
6-dodecyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant D D);
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD, anti-aging agent 124);
Pentanoic and acetone low-temp reaction product (anti-aging agent BAS);
Pentanoic and acetone high-temperature reaction product (antioxidant BLE);
The reaction product of pentanoic and acetone and aldehyde (anti-aging agent BXA);
The reaction product of PBNA and acetone (antioxidant A PN, antioxidant A M).
Phenol type antioxidant described in the components b can be single phenol, diphenol, bis-phenol and polyphenol, also can be the mixture of their arbitrary proportions.
Wherein single phenol be have a phenyl ring/and phenyl ring on the substituted phenol of a hydroxyl is arranged, and have at least one to be the tertiary butyl in the substituting group, other substituting group can be alkyl or contain heteroatomic substituting group that alkyl wherein is selected from C
1-C
10Alkyl, for example methyl, ethyl, allyl group, normal-butyl, sec.-butyl, nonyl etc. contain heteroatomic substituting group and are selected from oxygen containing substituting group such as methoxyl group, the substituted methyl of methoxyl group, methylol, nitrogenous substituting group such as alpha, alpha-dimethyl aminomethyl.For example can be single phenol of following structure: o-tert-butylphenol, p-tert-butylphenol, the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol; The 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol; 2,4-DI-tert-butylphenol compounds, 2,5-DI-tert-butylphenol compounds, 2,6 di t butyl phenol; 2,5-di-tert-butyl-4-methy phenol, 2,6 di tert butyl 4 methyl phenol (BHT, oxidation inhibitor T501), 4,6-di-t-butyl-2-methylphenol; 2; 4; 6-tri-butyl-phenol, 2 allyl 4 methyl 6 tert butyl phenol, 2-sec.-butyl-4-tert.-butyl phenol, 4-sec.-butyl-2,6 di t butyl phenol, 4-nonyl-2,6 di t butyl phenol, 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 phenolic hydroxyl group adjacent single phenol that is obstructed, as:
The 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2,4-xylenol, 2,6 di t butyl phenol, 2; 6-di-tert-butyl-4-methy phenol (BHT, oxidation inhibitor T501), 2,4; 6-tri-butyl-phenol, 4-sec.-butyl-2,6 di t butyl phenol, 4-nonyl-2,6 di t butyl phenol, 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, one or more in the 6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703).
The diphenol here is meant the phenol type antioxidant that two hydroxyls are arranged on the phenyl ring, can be the diphenol of following structure: Resorcinol, Tert. Butyl Hydroquinone (TBHQ), 2,5 di tert butyl hydroquinone, 2, one or more in the 5-two tert-pentyl Resorcinol.
Bis-phenol is meant the phenol type antioxidant that is linked to each other through sulphur or carbon atom by two single phenol, for example:
(1) bis-phenol that links to each other by carbon atom
4,4 '-isopropylidene bis-phenol (dihydroxyphenyl propane);
2,2 '-two (3-methyl-4 hydroxy phenyl) propane (bisphenol-c);
4,4 '-dihydroxybiphenyl (oxidation inhibitor DOD);
4,4 '-dihydroxyl-3,3 ', 5,5 '-four-tertiary butyl biphenyl (oxidation inhibitor 712);
2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol) (oxidation inhibitor bis-phenol 2246);
4,4 '-methylene radical-two (2-methyl-6-tert butyl phenol) (oxidation inhibitor methene 736);
2,2 '-methylene radical-two (4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);
2,2 '-methylene radical-two (4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);
2,2 '-methylene radical-two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);
2,2 '-methylene radical-two (6-α-Jia Jibianji p-cresol);
4,4 '-methylene radical-two (2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-two (2-tert.-butyl phenol) (oxidation inhibitor 702);
2,2 '-ethylidene-two (4-methyl-6-tert butyl phenol);
4,4 '-ethylidene-two (2-methyl-6-tert butyl phenol);
4,4 '-ethylidene-two (2,6 di t butyl phenol);
4,4 '-butylidene-two (the 6-tertiary butyl-meta-cresol) (oxidation inhibitor BBM, oxidation inhibitor TCA);
4,4 '-isobutylidene-two (2,6 di t butyl phenol) etc.
(2) bis-phenol that links to each other by sulphur atom
4,4 '-thiobis (3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2, and 2 '-thiobis (4-methyl-6-tert butyl phenol) (antioxidant 2246-S);
4,4 '-thiobis (2-methyl-6-tert butyl phenol) (oxidation inhibitor 736);
4,4 '-thiobis (5-methyl-2-tert.-butyl phenol);
4,4 '-thiobis (2,6 di t butyl phenol) (Nocrac 300);
2,2 '-thiobis (4-octyl phenol) etc.
(3) link to each other by carbon atom but contain heteroatomic bis-phenol
N, N '-hexamethylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) (oxidation inhibitor 1098);
Pinakon two [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 259);
Two (3,5-di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine (oxidation inhibitor BPP);
Two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioethers (oxidation inhibitor methene 4426-S);
2,2 '-sulfurous ethyl glycol two [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 1035);
Triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (oxidation inhibitor 245) etc.
Bisphenol type oxidation inhibitor is preferably by the bis-phenol that has at least a tertiary butyl to link to each other through methylene radical or sulphur at phenolic hydroxyl group adjacent list phenol, for example:
2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol) (antioxidant 2246);
4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol) (oxidation inhibitor methene 736);
4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-two-(2-tert.-butyl phenol) (oxidation inhibitor 702);
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2, and 2 '-thiobis-(4-methyl-6-tert butyl phenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert butyl phenol) (oxidation inhibitor 736);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
Two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.
Said polyphenol antioxidant refers in the molecule macromole oxidation inhibitor by at least three single phenolic group groups preferably by having a tertiary butyl at least at the polyphenol that phenolic hydroxyl group adjacent list phenolic group group forms, and especially preferably has two tertiary butyls at the phenolic hydroxyl group adjacent polyphenol that is obstructed, for example:
1,3,5-trimethylammonium-2,4,6-three-(4 '-hydroxyl-3 ', 5 '-di-t-butyl) benzene (antioxidant 330);
Three [2-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group oxygen ethyl] isocyanic ester (oxidation inhibitor 3125);
Four (3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester (antioxidant 1010);
1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) (antioxidant 3114);
1,1,3-three-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA);
1,3,5-three (2, the 6-dimethyl--4-tertiary butyl-3-hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) (oxidation inhibitor 1790);
Two [3, two (3 '-tertiary butyl-4 '-hydroxybenzyl) butyric acid of 3-] glycol ester etc.
The preferred single phenol of above-mentioned phenol type antioxidant, diphenol and bisphenol type oxidation inhibitor further preferably have a tertiary butyl at least at phenolic hydroxyl group adjacent hindered phenol.Especially preferably has a tertiary butyl at least at phenolic hydroxyl group adjacent bisphenol type oxidation inhibitor, the bisphenol type oxidation inhibitor that particularly links to each other through methylene radical or sulphur.
The also optional amount of component b that contains of Dresel fuel compositions provided by the invention.And the weight ratio of said component a and amount of component b can be 1: 0-1, the weight ratio of preferred said component a and said amount of component b is 1: 0.01-1 further is preferably 1: 0.01-0.5 further is preferably 1: 0.02-0.2.
Said amount of component b can be reacted or the bonded metal chelator with the metal passivator of metallic surface reaction and/or with metal or metals ion for various.
Concrete, said amount of component b can be in 124 Triazole and verivate, thiadiazoles and verivate thereof, oxine, ethylenediamine tetraacetic carboxylic acid, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base (Schiff bases), organic polycarboxylic acid and the verivate thereof one or more.Said ethylenediamine tetraacetic carboxylic acid can be YD 30 (EDTA), and said hydrazides can be N-salicylidene-N '-salicylyl hydrazine and/or N, N '-diacetyl adipyl two hydrazides.Said beta-diketon such as methyl ethyl diketone, said 'beta '-ketoester such as etheric acid monooctyl ester.Said Schiff's base can be N, N '-two salicylidenes-1, N, N '-two salicylidene-1,2-tn, N, N '-two salicylidene-1,2-cyclohexanediamine, N, one or more in N '-two salicylidenes-N '-methyl two propylene triamines.Said organic polycarboxylic acid and verivate thereof for example can be one or more in Hydrocerol A, tartrate, oxysuccinic acid, succsinic acid (Succinic Acid), toxilic acid, phytic acid etc. and the verivate thereof.
Among the present invention, preferred said amount of component b is one or more in 124 Triazole and verivate (the for example commodity of commodity T551 by name), Schiff's base and organic polycarboxylic acid and the verivate thereof.
According to the use needs, Dresel fuel compositions provided by the invention can also contain other additive, like in FLOW IMPROVERS, cetane number improver, static inhibitor, the sanitas etc. one or more.
The preparation of Dresel fuel compositions provided by the invention is simple, and each component that only need will form Dresel fuel compositions mixes and gets final product.Can directly each additive component be mixed with basic diesel oil, also can earlier various additive components be mixed, obtain additive after, again the gained additive is mixed with basic diesel oil.For easy to operate; When various additive components are mixed; Can in the presence of solvent, carry out; The solvent here can be polar solvent such as N, dinethylformamide (DMF), 1, one or more in 4-dioxane, THF (DHF), DMSO 99.8MIN. (DMSO), pyrrolidone and the SL 1332.Also can be especially aromatic hydrocarbons such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil and composition thereof of hydro carbons, can also be biofuel.
In the present invention, said basic diesel oil can be pure biofuel, and said biofuel is meant that grease and low-carbon alcohol are (like C
1-C
5Fatty Alcohol(C12-C14 and C12-C18)) fatty acid ester of low-carbon alcohol that generates through transesterify (alcoholysis) reaction is generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.
Described trans-esterification processes can be the process method that any known or unknown transesterification reaction of passing through grease and low-carbon alcohol obtains biofuel, for example acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, or the like.Specifically can be with reference to documents such as CN1473907A, DE3444893, CN1472280A, CN1142993C, CN1111591C, CN1594504A.
Described grease has general sense well known in the art, is the general name of oil and fat, and staple is a fatty acid triglycercide.General normal temperature is the oil that is called of liquid, and normal temperature is solid or the semisolid fat (abbreviation fat) that is called.Said grease comprises vegetables oil and animal oil; In addition; Also comprise from the oil plant in the materials such as mikrobe, 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 herbage oil also can be xylophyta oil, like the oil of peanut oil, Semen Maydis oil, Oleum Gossypii semen, Uni Ace R, VT 18, plam oil, Thistle oil, linseed oil, Oleum Cocois, Oak Tree oil, Prunus amygdalus oil, walnut oil, Viscotrol C, til, 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 is oily, sheep is oily, house oil, butter, haco oil, shark wet goods.
In biodiesel composition of the present invention; Said basic diesel oil also can contain other diesel oil; Said other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrogen cracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of said biofuel and other diesel oil is preferably 1: 2-99.
Wherein petroleum diesel is meant boiling range the cut 160-380 ℃ between of crude oil (oil) after apparatus processes such as the various refining process decompression as usual of refinery, catalytic cracking, CR, coking, unifining, hydrogen cracking, and uses fuel through the compression ignition engine that satisfies solar oil standard GB 252-2000 or derv fuel oil standard GB/T 19147-2003 that allotment forms.
The fischer-tropsch combined diesel oil refers to that mainly with Sweet natural gas or coal be GTL diesel oil (Gas To Liquid) or the CTL diesel oil (Coal To Liquid) that raw material funds-Tuo (F-T) compound method is produced, and can also be vegetable fibre funds-Tuo compound 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 with biofuel blending back oilness greatly; But the possible variation of the oxidation stability of tempered oil, the blending fuel that therefore contains biofuel also need add oxidation inhibitor.
The hydrogen cracking biofuel is also referred to as s-generation biofuel, be meant by animal-plant oil through generate after hydrogenation and the cracking reaction with C
8-C
24Alkane is main, especially with C
12-C
20Normal paraffin is the reaction product of staple, and this hydrogen cracking biofuel cetane value is high, and sulphur and aromaticity content are extremely low, can reduce the discharging of oil motor pollutent greatly as diesel motor fuel or blending component.
Contain oxygen diesel oil blending component and be meant and can be deployed into the oxygenatedchemicals that meets certain code requirement or the mixture of oxygenatedchemicals with various diesel-fuels, normally alcohols and ethers or its mixture, alcohols is C for example
1-C
18Fatty Alcohol(C12-C14 and C12-C18), preferred C
1-C
12Unitary fatty alcohol is like 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, MTBE, Ethyl Tertisry Butyl Ether, C
6-C
14AEO, C
6-C
14Fatty alcohol polyoxypropylene ether, C
6-C
14TX10, C
6-C
14Alkylphenol polyethenoxy ether, polyoxymethylene dme (Polyoxymethylene Dimethyl Ethers, CH
3O (CH
2O)
xCH
3, x=1-8) wait and composition thereof.
Among the present invention; Said basic diesel oil is when containing the blending fuel of biofuel; Said Dresel fuel compositions can obtain through said additive, biofuel and other diesel oil are directly mixed, and also can earlier said additive be mixed with biofuel, and then obtain with other diesel oil blending.
Following embodiment will do further explanation to the present invention.
Embodiment 1-2 is used to explain the preparation of allyl butyrate imide.
Embodiment 1
In three-necked bottle, adding 200 gram (about 0.14mol) polyisobutylene butanedioic anhydrides (the polyisobutene number-average molecular weight is 1200, and saponification value is 80 milligrams of KOH/ grams, and substitution value is 1.0) and 200 gram boiling ranges are 159-185 ℃ C
9Heavy aromatics (platinum reforming still bed material); Being heated to 80 ℃ stirs; Slowly add 20.2 gram (0.138mol) triethylene tetramines, under nitrogen protection, be warming up to 150 ℃ of dehydration reactions 6 hours, divide the water of about 2.4 grams; Obtain the allyl butyrate imide, using SH/T 0224 method to record its nitrogen content is 1.9 weight %.Add the above-mentioned C of 25 grams again
9Heavy aromatics is made into the diluent of about 50 weight %.
Embodiment 2
In three-necked bottle, adding 18.2 gram (0.096mol) TEPAs, 20 gram toluene and 200 gram boiling ranges are 159-185 ℃ C
9Heavy aromatics (platinum reforming still bed material), heated and stirred to 50 ℃ is in the presence of nitrogen; Slowly add 200 gram (0.107mol) polyisobutylene butanedioic anhydrides (substitution value is 0.65 for polyisobutenyl number-average molecular weight Mn=900,60 milligrams of KOH/ grams of saponification value); Be warming up to 110 ℃ of reactions 3 hours, heating steams toluene, reacts 2 hours at 145 ℃ again; Make intermediates 2, obtain the allyl butyrate imide, using SH/T 0224 method to record its nitrogen content is 2.0 weight %.Add 20 gram C then
9Heavy aromatics is made into the diluent of about 50 weight %.
Embodiment 3-6 is used to explain the preparation of component a
Embodiment 3
In three-necked bottle; Add allyl butyrate imide and 9.0 grams (3 of 50 grams by embodiment 1 preparation; The 5-di-tert-butyl-hydroxy phenyl) methyl propionate (Beijing China brightness chemical plant produces); (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and triethylene tetramine mol ratio are about 2: 1, add 10 gram C again
9Heavy aromatics and 0.7 gram tosic acid, logical nitrogen, the methyl alcohol of generation was removed in reaction in 5 hours under 130 ℃, added the Ca (OH) of 1.3 grams then
2Neutralization is cooled to 100 ℃ and adds 1.8 gram super-cell and filtered while hot, and the product that obtains is subsequent use as component a.
Embodiment 4
In three-necked bottle; Add 50 grams intermediates and 9.6 gram (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionates (former Beijing Chemical Factory No. 3 produces), (3 by embodiment 2 preparations; The 5-di-tert-butyl-hydroxy phenyl) methyl propionate and TEPA mol ratio are about 3: 1, add 10 gram C again
9Heavy aromatics and 1.1 gram acidic ion exchange resins (Rohm&Hass Company products Amberlyst 35); Logical nitrogen; The methyl alcohol of generation was removed in reaction in 4 hours under 140 ℃, was cooled to 100 ℃ and added 1.2 gram super-cell and filtered while hot, and the product that obtains is subsequent use as component a.
Embodiment 5
In three-necked bottle, add 50 gram T151A (mono butonediimide, the production of Suzhou specialty oil products factory; The polyisobutene number-average molecular weight is about 1300, and polyamines polyene is in TEPA, the about 50 weight % of succimide content) and 12.7 grams (3; The 5-di-tert-butyl-hydroxy phenyl) methyl valerate (former Beijing Chemical Factory No. 3 produces); The mol ratio of (3, the 5-di-tert-butyl-hydroxy phenyl) methyl valerate and mono butonediimide is about 2.5: 1, adds 15 gram C again
9Heavy aromatics and 1.2 gram acidic ion exchange resins (Rohm&Hass Company products Amberlyst 15); Logical nitrogen; The methyl alcohol of generation was removed in reaction in 6 hours under 130 ℃, was cooled to 100 ℃ and added 1.3 gram super-cell and filtered while hot, and the product that obtains is subsequent use as component a.
Embodiment 6
In three-necked bottle, add 50 gram T154 (two succimides, the production of Lanzhou petrochemical industry additive factory; The polyisobutene number-average molecular weight is in 1000, and polyamines polyene is in TEPA, the about 50 weight % of succimide content) and 5.7 grams (3; The 5-di-tert-butyl-hydroxy phenyl) methyl propionate (Beijing China brightness chemical plant produces); (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate is about 1.8: 1 with two succimide mol ratios, adds 10 gram YLENE and 1.0 gram acidic ion exchange resins (Rohm&Hass Company products Amberlyst 36) again; Logical nitrogen; The methyl alcohol of generation was removed in reaction in 7 hours under 120 ℃, added 1.1 gram super-cell and filtered while hot, and the product that obtains is subsequent use as component a.
Embodiment 7-14
Embodiment 7-14 is used to explain the composition of additive.
The component a that is selected from embodiment 3-6 and components b and c are mixed according to the weight ratio shown in the table 1.
Table 1
| Embodiment | Component a source | Components b | Amount of component b | A: b: c (weight ratio) |
| Embodiment 7 | Embodiment 3 | N, N '-di-sec-butyl-p-phenyl enediamine | - | 1∶0.2∶0 |
| Embodiment 8 | Embodiment 3 | N, N '-di-sec-butyl-p-phenyl enediamine | N, N '-two salicylidene-1,2-tn | 1∶0.2∶0.03 |
| Embodiment 9 | Embodiment 3 | PA | - | 1∶0.2∶0 |
| Embodiment 10 | Embodiment 4 | Oxidation inhibitor T501 (BHT) | - | 1∶0.9∶0 |
| Embodiment 11 | Embodiment 4 | Oxidation inhibitor T501 (BHT) | T551 | 1∶0.9∶0.06 |
| Embodiment 12 | Embodiment 4 | Oxidation inhibitor methene 736 | - | 1∶0.9∶0 |
| Embodiment 13 | Embodiment 5 | Antioxidant 2246 | - | 1∶0.4∶0 |
| Embodiment 14 | Embodiment 6 | 2,6 di t butyl phenol | 1∶2∶0 | |
| Comparative Examples 1 | Embodiment 3 | - | - | 1∶0∶0 |
| Comparative Examples 2 | Embodiment 4 | - | - | 1∶0∶0 |
| Comparative Examples 3 | Embodiment 5 | - | - | 1∶0∶0 |
| Comparative Examples 4 | Embodiment 6 | - | - | 1∶0∶0 |
| Comparative Examples 5 | ?- | N, N '-di-sec-butyl-p-phenyl enediamine | - | 0∶1∶0 |
| Comparative Examples 6 | ?- | PA | - | 0∶1∶0 |
| Comparative Examples 7 | ?- | Oxidation inhibitor T501 | - | 0∶1∶0 |
| Comparative Examples 8 | ?- | Oxidation inhibitor methene 736 | - | 0∶1∶0 |
| Comparative Examples 9 | ?- | Antioxidant 2246 | - | 0∶1∶0 |
| Comparative Examples 10 | ?- | 2,6 di t butyl phenol | - | 0∶1∶0 |
| Comparative Examples 11 | ?- | - | N, N '-two salicylidene-1,2-tn | 0∶0∶1 |
Performance test
Below in the test; Used Shijiazhuang refinery biofuel is that the Oleum Gossypii semen biofuel of being produced by the said firm and plam oil biofuel are with 60: 40 blended biofuel of volume ratio product; Sample is provided by Shijiazhuang refinery branch office of China Petrochemical Industry; Used acidifying oil biodiesel provides by the remarkable new forms of energy in Longyan, Fujian ltd, 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-resistance of the biodiesel composition of basic diesel oil and the test of detergent-dispersant performance
Evaluate oxidation stability of biodiesel the inductive phase under measuring 110 ℃ with EN14112:2003 method (Racimat method), uses the 743 type oil oxidative stability determinators of instrument as Switzerland Wan Tong company, wherein.Inductive phase is longer explains that then the oxidation-resistance of Dresel fuel compositions is good more, otherwise shorter explain that then the oxidation-resistance of Dresel fuel compositions is poor more inductive phase.Its test result is shown in Table 2.
With the disclosed tinsel sedimentation evaluation of CN1351132A detergent-dispersant performance; Concrete operations comprise: biodiesel composition (Shijiazhuang refinery biofuel or acidifying oil biodiesel and Dresel fuel compositions) and the Shijiazhuang refinery biofuel or the acidifying oil biodiesel (being blank) that do not add additive are injected glass inner tube to scale marks (40 milliliters) respectively; Hang and impregnated in the stainless steel substrates of weighing in advance and grinding in above-mentioned Dresel fuel compositions and the blank respectively; Sealing and oxygenation displacement is three times then, boosts to 0.8MPa, and is warming up to 160 ℃; Oxygen pressure in the assaying reaction device afterwards, and under this temperature, kept 6 hours.Be cooled to room temperature then and emit the overbottom pressure in the reactor drum, take out tinsel, clean, dry up, weigh up the weightening finish of steel disc, will be designated as W in the steel disc weightening finish that blank pilot scale test gets with 70 ℃ sherwood oils
0, the steel disc weightening finish that biodiesel composition pilot scale test is got is designated as W
1, and calculate the deposition improvement rate of each biodiesel composition according to following formula:
Deposition improvement rate=(W
0-W
1)/W
0* 100%
Wherein, the detergent-dispersant performance of the high more then biodiesel composition of deposition improvement rate is good more, and the detergent-dispersant performance of the low more then biodiesel composition of deposition improvement rate is poor more.Its test result is shown in Table 2.
Table 2
Data from table 2 can be found out, compare with Comparative Examples, and biodiesel composition provided by the invention has obviously better oxidation stability and detergent-dispersant performance.Succimide with contain the low-carbon ester of hindered phenol reaction product (component a) with the components b mating reaction after; The oxidation stability of biodiesel composition and detergent-dispersant performance will be got well much than the effect sum of independent use component a, components b, this shows to have occurred synergy clearly between component a, the b astoundingly.After optional amount of component b added, effect further strengthened.
Compare with embodiment 9 through embodiment 7; Embodiment 10 compares and can find out with embodiment 12; Use the dialkyl group Ursol D of the preferred alkyl carbon atoms number of the present invention between 4-10 with the bisphenol type oxidation inhibitor that links to each other through methylene radical during as components b, it is obviously better that the oxidation stability of gained Dresel fuel compositions and detergent-dispersant performance improve effect.
Through embodiment 7 compare with embodiment 8, embodiment 10 compares with 11 and can find out, select optional amount of component b for use after, the oxidation stability and the detergent-dispersant performance of gained biodiesel composition further strengthen.
(2) with the test as oxidation-resistance, stability and the detergent-dispersant performance of the concocted diesel oil compsn of basic diesel oil of the mixture of biofuel and petroleum diesel, used biofuel is the acidifying oil biodiesel.
Adopt the method for Pr EN15751:2008 to measure each Dresel fuel compositions, petroleum diesel and concocted diesel oil inductive phase under 110 ℃ respectively; Use the 743 type oil oxidative stability determinators of instrument as Switzerland Wan Tong company; Inductive phase is longer explains that then the oxidation-resistance of biodiesel composition is good more, otherwise shorter explain that then the oxidation-resistance of biodiesel composition is poor more inductive phase.Its test result is shown in Table 3.
Adopt derv fuel oil detergency determinator (by the production of petrochemical industry instrument company of Lanzhou dimension section, L-3 type) to measure the detergent-dispersant performance of each concocted diesel oil compsn respectively according to the disclosed method of CN 1940524A.Its concrete operations comprise: the weight of the sediment trap of weighing one cleaning; Then this sediment trap is heated to 250 ℃, afterwards with the speed of 2 ml/min with the concocted diesel oil combined stream to the workplace of sediment trap, form the even mobile oil film of one deck; After 50 minutes, the oil film on the sediment trap workplace is toasted under 180 ℃ high temperature; Oxidation generates one deck paint film, then this sediment trap impregnated in the normal heptane 2 minutes, and weighing is attached with the weight of sedimental sediment trap then; And the weightening finish of record sediment trap, be the deposition A (unit: mg) of sediment trap.Can evaluate the detergent-dispersant performance of concocted diesel oil compsn according to the size of deposition, more greatly then detergent-dispersant performance is poor more as if deposition, otherwise if the more little then detergent-dispersant performance of deposition is good more.Its test result is shown in Table 3.
In addition, adopt the detergent-dispersant performance of the disclosed tinsel sedimentation of CN1351132A according to the evaluation method evaluation concocted diesel oil compsn of above-mentioned biofuel detergent-dispersant performance, the weightening finish that obtains steel disc is the deposition B (mg) of sediment trap.According to the detergent-dispersant performance of the size of deposition evaluation Dresel fuel compositions, more greatly then detergent-dispersant performance is poor more as if deposition, otherwise good more as if the more little then detergent-dispersant performance of deposition.Its test result is shown in Table 3.
Adopt the method for SH/T 0175 to measure respectively and the amount (unit: mg/100mL), thereby evaluate their stability of the insolubles of concocted diesel oil compsn.The amount of insolubles more greatly then stability is poor more, otherwise if the more little then stability of amount of insolubles is good more, its test result is shown in Table 3.
Table 3
Result by table 3 can find out that after the adding biofuel, the oxidation stability, stability and the detergent-dispersant performance that contain the blending fuel of biofuel are compared all variation with petroleum diesel.The oxidation stability, stability and the dispersiveness that contain the biodiesel composition of the present invention that the mixture of component a and components b or component a and components b and amount of component b obtains as additive all have significantly to be improved; Synergistic effect appears in component a and components b effect, and its effect obviously strengthens than Comparative Examples effect.Succimide is to improving the DeGrain (embodiment 1) of biofuel blending fuel stability, and when only containing phenol type or amine type oxidation inhibitor as oxidation inhibitor, the stability of gained biofuel blending fuel and detergent-dispersant performance improve DeGrain.In addition, arylamine type oxidation inhibitor has certain carcinogenesis and stronger corrodibility and contaminative, and production cost is higher.
Claims (12)
1. Dresel fuel compositions; This Dresel fuel compositions contains basic diesel oil and additive; It is characterized in that; Said basic diesel oil contains biofuel, and said additive contains component a and components b, and said component a prepares through following method: is that 1:0.5-5 under solvent in 60-200 ℃ react 0.5-20 hour with the low-carbon ester that contains hindered phenol according to polyamines polyene in the allyl butyrate imide and the mol ratio that contains the low-carbon ester of hindered phenol with the allyl butyrate imide; Said components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant; Content of additive is 50-10000ppm in the said Dresel fuel compositions; The weight ratio of said components b and component a is 0.01-10:1.
2. Dresel fuel compositions according to claim 1, wherein, the weight ratio of said components b and component a is 0.05-5:1.
3. Dresel fuel compositions according to claim 1 and 2, wherein, said components b is p-phenylene diamine derivative's type oxidation inhibitor, have a tertiary butyl one or more in phenolic hydroxyl group adjacent hindered phenol type antioxidant at least.
4. Dresel fuel compositions according to claim 3, wherein, said components b be the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 with the bisphenol type oxidation inhibitor that links to each other through methylene radical or sulphur in one or more.
5. Dresel fuel compositions according to claim 4, wherein, said components b is N; N '-diheptyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N; N '-two (1-methylheptyl) Ursol D, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two (2-methyl-6-tert butyl phenol), 4; 4 '-methylene radical-two (2,6 di t butyl phenol), 4,4 '-methylene radical-two (2-tert.-butyl phenol), 4; 4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), 4,4 '-thiobis (2-methyl-6-tert butyl phenol), 4; In 4 '-thiobis (2,6 di t butyl phenol), two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
6. according to the Dresel fuel compositions described in the claim 1, wherein, the said low-carbon ester that contains hindered phenol has the described structure of following formula:
Wherein, R
1And R
2Respectively do for oneself H or carbonatoms is the alkyl of 1-24, and n is the integer of 0-10, R
3For carbonatoms is the alkyl of 1-20.
7. Dresel fuel compositions according to claim 6, wherein, in the structural formula of the said low-carbon ester that contains hindered phenol, R
1And R
2The carbonatoms of respectively doing for oneself is the alkyl of 1-8, cyclopentyl or cyclohexyl, and n is the integer of 0-7, R
3For carbonatoms is the alkyl of 1-5.
8. Dresel fuel compositions according to claim 7, wherein, the said low-carbon ester that contains hindered phenol is one or more in the following compound: β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) methyl propionate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) ethyl propionate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propyl propionate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) isopropyl propionate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) n-butyl propionate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) isobutyl propionate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) amyl propionate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) isopentyl pyruvate, the β-just own ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid dissident ester, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) the positive heptyl ester of propionic acid, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) propionic acid n-octyl, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) different monooctyl ester of propionic acid, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) methyl-butyrate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) ethyl n-butyrate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) propyl butyrate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) methyl isobutyrate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) ethyl isobutyrate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) propyl isobutyrate, β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) methyl valerate, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) Valeric acid ethylester, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propyl valerate.
9. Dresel fuel compositions according to claim 1, wherein, said additive also contains amount of component b, and said amount of component b is a metal passivator.
10. Dresel fuel compositions according to claim 9, wherein, the weight ratio of said component a and said amount of component b is 1:0.01-1.
11. Dresel fuel compositions according to claim 9, wherein, said amount of component b is one or more in 124 Triazole and verivate, Schiff's base and the organic polycarboxylic acid.
12. Dresel fuel compositions according to claim 1; Wherein, Said basic diesel oil also contains other diesel oil; Said other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrogen cracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of said biofuel and other diesel oil is 1:2-99.
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