CN101768484B - Diesel composition - Google Patents
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- CN101768484B CN101768484B CN200810246846.8A CN200810246846A CN101768484B CN 101768484 B CN101768484 B CN 101768484B CN 200810246846 A CN200810246846 A CN 200810246846A CN 101768484 B CN101768484 B CN 101768484B
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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 Mannich base generated by reaction of polyolefin-based phenol, aldehyde with carbon number being 1-6 and polyethylene polyamine with organic acid containing phenolic groups according to the molar ratio of the polyethylene polyamine in the Mannich base to the organic acid containing phenolic groups to react at 50-200 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. When taking the pure biodiesel as the base diesel, the diesel composition of the invention has better oxidation stability and detergency, and when taking the blended fuel containing biodiesel as the base diesel, the diesel composition has better stability, detergency and dispersancy.
Description
Technical field
The invention relates to a kind of Dresel fuel compositions.
Background technology
Along with the quickening of diesel oil of vehicle trend in world wide, the demand of diesel oil can be more and more large, and the raising of day by day exhausted and people's environmental consciousness of petroleum resources, greatly facilitate the exploitation paces that Alternative Diesel Fuel is accelerated in countries in the world, biofuel receives the attention of various countries with its superior environmental-protecting performance and recyclability.
Biofuel (BD100) is also known as fatty acid methyl ester (Fatty Acid Methyl Ester), make raw material with the grease of the oil plant waterplant such as oil-yielding shrubs fruit, engineering microalgae such as the oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistache and animal grease, biodiesel etc., obtaining through transesterification reaction with alcohols (methyl alcohol, ethanol), is a kind of biofuel of cleaning.Biofuel has renewable, clean and safe three advantages, has very great strategic importance to China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment.And China is a net import of oil state at present, prospective oil is very limited again, and the energy security of a large amount of Imported oil to China threatens; Therefore, biofuel research and produce have important realistic meaning to China.
But due to raw material and complete processing, the oxidation stability of some biofuel is very poor, using and storing and all cause very large difficulty biofuel.The biofuel of oxidation stability difference easily generates following ageing products: 1) insoluble polymer (colloid and greasy filth), and this can cause engine filter net jam and squirt pump coking, and causes smoke evacuation increase, difficulty in starting; 2) soluble polymer, it can form resinous substance within the engine, may cause flame-out and difficulty in starting; 3) aging acid, this can cause engine metal component corrosion; 4) superoxide, this can cause aging the becoming fragile of rubber components and cause fuel leakage etc.
The oxidation stability of Europe Biodiesel Standards EN14214:2003, Australian Biodiesel Standards (Draft 2003), New Zealand Biodiesel Standards NZS 7500:2005, Brazilian Biodiesel Standards ANP255 (2003), India Biodiesel Standards IS 15607:2005, South Africa Biodiesel Standards SANS 1935:2004 and China diesel-fuel blending biofuel (BD100) standard GB/T/T 20828-2007 all regulation biofuel is be not less than 6 hours the inductive phase at 110 DEG C, and measuring method is EN14112:2003.
As everyone knows, petroleum diesel (the i.e. diesel oil of ordinary meaning, herein in order to distinguish mutually with biofuel, special introduce petroleum diesel) in alkene, diolefin and the non-hydrocarbon compound such as sulfide, nitride under the effect of the oxygen, generate a series of intermediate oxidation product, and produce insoluble precipitation through condensation.These insoluble particles generated in petroleum diesel storage process can have influence on the use properties of fuel, cause filtering system to block, cause fuel system component failures; affect oil atomizing; cause incomplete combustion, form too much carbon deposit even within the engine, make spray nozzle clogging.And biofuel due to oxidation stability poorer than petroleum diesel, can the problems referred to above be increased the weight of after concocting with petroleum diesel.The most significantly performance be containing the stability of the blending fuel of biofuel and detergent-dispersant performance poorer than petroleum diesel.
The problems referred to above solve by adding additive or alleviate.Mode in pure biofuel, adds oxidation inhibitor to slow down its oxidation, thus alleviate the harm of ageing products; Another kind of mode adds stablizer and detergent-dispersant additive, to improve stability and the detergent-dispersant performance of blending fuel to petroleum diesel or containing in the blending fuel of biofuel.Stablizer can stop, weakens or disturb each kinds of oxidation reaction, to suppress oil deterioration, improves its stability; Detergent-dispersant additive can wash down carbon deposit established on nozzle, and forms protective membrane at nozzle surface, prevents new carbon deposit from producing, also dispersibles established sediment in oil simultaneously, improve purifier and spray nozzle clogging, and improve exhaust emissions.
CN 1742072A discloses a kind of method improving storage stability of bio-diesel, the method comprises and will be dissolved in 2 of biofuel containing what count 15-60 % by weight with stoste, the liquid stoste of 4-di-t-butyl hydroxy toluene joins in biofuel to be stabilized, until in total solution of biofuel, the concentration of 2,4-di-t-butyl hydroxy toluene reaches 0.005-2 % by weight.
CN 1847368A discloses a kind of method improving the oxidative stability of biofuel, the method comprises bisphenol type oxidation inhibitor as 4,4`-methylene radical two [2,6-DI-tert-butylphenol compounds], 2,2`-methylene radical two [6-di-tert-butyl-4-methy phenol] join with the amount of 10-20000ppm (w/w) and treat in stable biofuel.
CN 1847369A discloses a kind of method improving the oxidative stability of biofuel, the method comprises main anti-oxidant fusing point being less than or equal to 40 DEG C and joins with the amount of 10-20000ppm (w/w) and treat that, in stable biofuel, wherein said main anti-oxidant contains alkylphenol.
US 2007/113467A1 discloses a kind of fuel composition with the oxidative stability of improvement, said composition contains biofuel and at least one oxidation inhibitor, described oxidation inhibitor is selected from Tenox PG, 1,2, one in 3-trihydroxybenzene, BHT, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, tocopherol, quinoline.
Although more than use traditional oxidation inhibitor to have certain effect to the method improving oxidation stability of biodiesel, peace and quiet dispersion effect be there is no for biofuel, for use pure biofuel diesel engine can not improve its detergency.Meanwhile, traditional oxidation inhibitor to containing the stability of blending fuel of biofuel and the improvement effect of detergent-dispersant performance also not so good.Also namely when above-mentioned oxidation inhibitor to coordinate with biofuel obtain Dresel fuel compositions time, the detergency of this Dresel fuel compositions is poor; When above-mentioned oxidation inhibitor to coordinate with containing the blending fuel of biofuel obtain Dresel fuel compositions time, stability and the detergent-dispersant performance of this Dresel fuel compositions are poor.
Summary of the invention
The object of the invention is in order to overcome above-mentioned prior art based on pure biofuel the Dresel fuel compositions of diesel oil oxidation stability and detergency is poor and the stability of the Dresel fuel compositions of diesel oil and the poor shortcoming of detergent-dispersant performance based on the blending fuel of biofuel and other diesel oil, provide a kind of oxidation stability and detergency all better or stability and detergent-dispersant performance Dresel fuel compositions all preferably.
The invention provides a kind of Dresel fuel compositions, this Dresel fuel compositions contains Base Diesel and additive, wherein, described Base Diesel is containing biofuel, described additive contains component a and components b, described component a is prepared by following method: be the aldehyde of 1-6 and the mannich base of polyamines polyene reaction generation by polyolefin-based phenol, carbonatoms and contain phenolic group organic acid according to the polyamines polyene in mannich base and the mixed in molar ratio containing phenolic group organic acid 1: 0.5-5, react 0.5-20 hour in the presence of the solvent in 50-200 DEG C; Described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant.
Dresel fuel compositions provided by the invention, when based on pure biofuel during diesel oil, this Dresel fuel compositions has good oxidation stability and detergency; When by containing based on the blending fuel of biofuel during 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 described additive is simultaneously containing component a, components b, or time also simultaneously containing optional amount of component b, due to synergistic effect obvious between each additive, antioxidant and the detergent-dispersant performance of Dresel fuel compositions provided by the invention significantly improve.Such as, as can be seen from the result of table 2 described below, Dresel fuel compositions provided by the invention is when additive amount is 3300mg/kg, the oxidation stability represented inductive phase by 110 DEG C was up to 24.1 hours, deposition is reduced to 29.0mg by containing the 74.7mg before additive, and deposition improvement rate is up to 61.2%.
Embodiment
According in Dresel fuel compositions provided by the invention, the content of described additive can be conventional content, such as, can be 50-10000ppm, is preferably 100-8000ppm.
The weight ratio of described components b and component a can be 0.01-10: 1, is preferably 0.05-5: 1, more preferably 0.1-3: 1.
According to Dresel fuel compositions provided by the invention, described component a is prepared by following method:
By mannich base with containing the mixed in molar ratio (mole number of mannich base with the molar basis of wherein polyamines polyene) of phenolic group organic acid according to 1: 0.5-5, preferably 1: 1-4, in the presence of the solvent in 50-200 DEG C, preferred 80-160 DEG C of reaction 0.5-20 hour, preferred 1-10 hour.Available nitrogen protection in reaction system, or allow reaction carry out under the condition of solvent refluxing.This reaction can not add catalyzer, also can add a small amount of (such as relative to mannich base and the 0.01-1 % by weight containing phenolic group organic acid gross weight) catalyzer, so that fast reaction speed.Catalyzer can be acid type or alkaline, as sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, acidic ion exchange resin, acidic white earth; Sodium hydroxide, potassium hydroxide, sodium methylate, deacidite etc.Described reaction solvent can be that hydrocarbon polymer is as benzene,toluene,xylene, aromatic diluent oil, industrial naptha or mineral oil (boiling point is more than 120 DEG C), also can be that polar solvent is as N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE, 1, one or more in 4-dioxane, tetrahydrofuran (THF) (DHF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidone and methyl-2-pyrrolidone, or their mixture.Solvent load is generally the 30-150 % by weight of monomer material gross weight.For the ease of subsequent operations and storage, last product can be made into the diluent of about 50 % by weight with aromatic diluent oil.
The described phenolic group organic acid that contains can be selected from Whitfield's ointment (i.e. salicylic acid), m-Salicylic acid, P-hydroxybenzoic acid, 3, 4-resorcylic acid, 3, 5-resorcylic acid, 2, 3-resorcylic acid, 2, 4-resorcylic acid, 2, 5-resorcylic acid, 2, 6-resorcylic acid, 3, 6-resorcylic acid, 4, 5-resorcylic acid, 4, 6-resorcylic acid, 3, 4, 5-trihydroxybenzoic acid (gallic acid), 3-hydroxy-2-naphthoic acid, 4, 4-is two-(4-hydroxyphenyl) valeric acid (diphenolic acid) and their mixture in one or more.One or more in preferred Whitfield's ointment, P-hydroxybenzoic acid, Gallic Acid.Especially preferably Gallic Acid.
Described mannich base reacts obtained by polyolefin-based phenol, aldehyde and polyamines polyene, and three's mol ratio is generally 1: 0.1-10: 0.1-10, is preferably 1: 1-4: 0.5-2.Mannich reaction temperature is generally 50-200 DEG C, preferably within 70-150 DEG C of scope.Reaction medium can be hydrocarbon polymer as benzene,toluene,xylene, aromatic diluent oil (boiling range is 159-185 DEG C), industrial naptha or mineral oil (boiling point is more than 120 DEG C), or their mixture.Solvent load is generally the 30-150 % by weight of monomer material gross weight.Available nitrogen protection in reaction system, or allow system carry out under the condition of solvent refluxing.Preparation method at US 3,413,347, US 3,649,229, US 3,798,165, US 4,116,644, US4, all have description in 553,979 patent documentations such as grade.
Polyolefin-based phenol wherein can be the macromolecular compound with following structure,
Wherein R can be various polyolefin-based, and as polypropylene, polybutene, polyisobutene or ethylene-propylene copolymer, the number-average molecular weight of R can be 300-3000, is preferably 500-2000.The preferred polyisobutene phenol of described polyolefin-based phenol.The preparation of polyolefin-based phenol can adopt existing alkylation of phenol technology.Such as, under a small amount of an acidic catalyst effect, 0.1-10 moles of phenol (being preferably 1-2.5 mole) and 1 mole of polyolefine are carried out alkylated reaction at 50-150 DEG C.An acidic catalyst can be sulfuric acid, phosphoric acid or Lewis acid, as BF
3-diethyl ether solution, BF
3-ethanolic soln, BF
3-phenol solution etc., preferred Lewis acid.Reaction terminates rear distilled water and washes away catalyzer, then underpressure distillation or wet distillation remove unreacted phenol.
Wherein C
1-C
6aldehyde can be one or more in formaldehyde, acetaldehyde, propionic aldehyde, hexamethylene aldehyde, preferred formaldehyde, 36 % by weight formaldehyde solution and paraformaldehyde in one or more.
The structural formula of polyamines polyene is wherein H
2n [(CH
2)
nnH]
mh, n are the integer of 2-4, preferably 2-3, and m is the integer of 1-5, preferred 3-4.Described polyamines polyene is specifically as follows one or more in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, propylene diamine, dipropylenetriamine, three propylene tetramines, tetrapropylene five amine, five propylene hexamines, one or more in preferred triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
About components b, described arylamine type oxidation inhibitor can be selected from least one in naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, quinoline, at least one in preferred naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, especially preferably p-phenylene diamine derivative.
Wherein naphthylamine derivative includes but not limited to one or more in following material:
Phenyl-a-naphthylamine (oxidation inhibitor T531, antioxidant A);
Phenyl beta naphthylamine (antioxidant d);
N-p-methoxyphenyl alpha-naphthylamine (anti-aging agent 102);
To hydroxyphenyl-beta-naphthylamine (antioxidant D-OH);
Aldol-alpha-naphthylamine (antioxidant A P)
Two [to (beta-naphthylamine) phenoxy group] propane (anti-aging agent C-49) of 2-hydroxyl-1,3-;
Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41) of dimethyl;
Two [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41-ethyl) of diethyl;
2,2 '-bis-[to (beta-naphthylamine) phenoxy group] diethyl ether (anti-aging agent C-41-ether).
Wherein, the preferred nonox of naphthylamine derivative, such as, in phenyl-a-naphthylamine, Phenyl beta naphthylamine, N-p-methoxyphenyl alpha-naphthylamine one or more.Especially preferably phenyl-a-naphthylamine.
Wherein diphenylamine derivatives includes but not limited to one or more in following material:
4,4 '-diamino-diphenylamine (antioxidant A PA);
Right, to '-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 aniline phenoxy group) propane (anti-aging agent C-47);
2,2 '-bis--(to aniline phenoxy group)-diethyl ether (antioxidant H-1);
Two (to aniline-phenoxy group)-silane (anti-aging agent C-1) of dimethyl;
P-isopropoxy-diphenylamine (anti-aging agent ISO);
Right, to '-diisopropoxy pentanoic (antioxidant D ISO);
4,4 '-bis--(α, α '-dimethyl benzyl) pentanoic (anti-aging agent KY-405);
P-hydroxydiphenylamine (antioxidant A O3920);
Two (1,1,3,3-tetramethyl-ethyl) pentanoic (anti-aging agent ODA);
4,4 '-dioctyl diphenylamine;
4,4 '-di-iso-octyldiphenylamine;
4,4 '-diheptyl pentanoic;
4,4 '-dinonyldiphenylamine;
Octylated diphenylamine (mixture of an octylated diphenylamine and dioctylated pentanoic, anti-aging agent OD);
Octyl group/butyl pentanoic (oxidation inhibitor L-57);
Styrenated diphenylamine (antioxidant D FL, DFC-34);
And the mixture of alkylated diphenylamine, wherein alkyl can be heptyl, octyl group, one or more in nonyl, the example of its Industrial products has Pennwalt company of U.S. commodity to be called Pennox A, Pennox A-" S ", American National Instrument polychem company commodity are called Wytox ADP, ADP-X, Vanderbilt company of U.S. commodity are called Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, Uniroyal company of U.S. commodity are called Polylite, Antioxidant 445, and domestic code name is the antioxidant product of T534.
Diphenylamine derivatives type oxidation inhibitor preferred alkyl diphenylamines and composition thereof, especially preferred alkyl carbonatoms alkylated diphenylamine between 4-10 and composition thereof, as: 4,4 '-dioctyl diphenylamine, 4,4 '-di-iso-octyldiphenylamine, 4,4 '-diheptyl pentanoic, 4, one or more in 4 '-dinonyldiphenylamine, octylated diphenylamine (mixture of an octylated diphenylamine and dioctylated pentanoic), octyl group/butyl pentanoic, commodity oxidation inhibitor T534.
Wherein p-phenylene diamine derivative's type oxidation inhibitor includes but not limited to one or more in following material:
N phenyl-N '-cyclohexyl Ursol D (antioxidant 4010);
N, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (antioxidant 4020);
N, N-pair-(Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D (anti-aging agent 4030);
N-p-methylphenyl-N '-(1,3-dimethylbutyl) Ursol D (anti-aging agent 4040);
N, N '-diheptyl Ursol D (anti-aging agent 788);
N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);
N-sec.-propyl-N '-p-methylphenyl Ursol D (anti-aging agent methyl 4010NA);
N, N '-di tolyl p phenylenediamine (anti-aging agent PPD-A);
N, N '-diphenyl-para-phenylene diamine (antioxidant H);
N, N '-two-(betanaphthyl) Ursol D (antioxidant D NP);
N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5);
N, N '-dioctyl-p-phenylenediamine (anti-aging agent 88);
N, N '-bis--(1-methylheptyl) Ursol D (anti-aging agent 288);
N, N '-bis--(1-ethyl-3-methyl amyl) Ursol D (anti-aging agent 8L);
N, N '-bis--(Isosorbide-5-Nitrae-dimethylbutyl) Ursol D (anti-aging agent 66);
N-Octyl-N '-diphenyl-para-phenylene diamine (anti-aging agent 688);
N-isobutyl--N '-diphenyl-para-phenylene diamine (anti-aging agent 5L);
N, N '-dimethyl-N, N '-bis--(1-first propyl group) Ursol D (anti-aging agent 32);
N-(p-methylphenyl alkylsulfonyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent TPPD);
N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent G-1);
N-(3-aniiinophenyl) Methacrylamide;
N-hexyl-N '-diphenyl-para-phenylene diamine;
The preferred dialkyl-pphenylenediamines of p-phenylene diamine derivative's type oxidation inhibitor, the especially dialkyl-pphenylenediamines of preferred alkyl carbonatoms between 4-10, as: N, N '-diheptyl Ursol D; N, N '-di-sec-butyl-p-phenyl enediamine; N, N '-dioctyl-p-phenylenediamine; N, N ' one or more in-bis--(1-methylheptyl) Ursol D.
Quinoline wherein includes but not limited to:
6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W);
6-phenyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (anti-aging agent PMQ);
6-dodecyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant D D);
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD, anti-aging agent 124);
Pentanoic and acetone low-temp reaction product (anti-aging agent BAS);
Pentanoic and acetone high-temperature reaction product (antioxidant BLE);
The reaction product (anti-aging agent BXA) of pentanoic and acetone and aldehyde;
The reaction product (antioxidant A PN, antioxidant A M) of Phenyl beta naphthylamine and acetone.
Phenol type antioxidant described in components b can be single phenol, diphenol, bis-phenol and polyphenol, also can be the mixture of their arbitrary proportions.
Wherein single phenol is the phenol having a phenyl ring/and phenyl ring has the replacement of a hydroxyl, and has at least one to be the tertiary butyl in substituting group, and other substituting group can be alkyl or contain heteroatomic substituting group, and alkyl is wherein selected from C
1-C
10alkyl, such as methyl, ethyl, allyl group, normal-butyl, sec-butyl, nonyl etc., be selected from methyl, the methylol of oxygen containing substituting group as methoxyl group, methoxy substitution containing heteroatomic substituting group, nitrogenous substituting group is as alpha, alpha-dimethyl aminomethyl.Can be such as single phenol of structure below: o-tert-butylphenol, p-tert-butylphenol, 2-tert-butyl-4-methyl-Phenol, the 6-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol; The 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol; 2,4-DTBP, 2,5-DI-tert-butylphenol compounds, 2,6 di t butyl phenol; 2,5-di-tert-butyl-4-methy phenol, 2,6 di tert butyl 4 methyl phenol (BHT, oxidation inhibitor T501), 4,6-di-t-butyl-2-methylphenols; 2,4,6-tri-butyl-phenol, 2 allyl 4 methyl 6 tert butyl phenol, 2-sec-butyl-4-TBP, 4-sec-butyl-2,6-DI-tert-butylphenol compounds, 4-nonyl-2,6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-ethylphenol (oxidation inhibitor DBEP), 2,6-di-t-butyl-4-normal-butyl phenol (oxidation inhibitor 678); Butylhydroxy anisole (BHA), 2,6-di-t-butyl-α-methoxyl group-p-cresol (BHT-MO), 4-methylol-2,6-DI-tert-butylphenol compounds (oxidation inhibitor 754), 2,6-di-t-butyls-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 that is obstructed at phenolic hydroxyl group ortho position, as:
2-tert-butyl-4-methyl-Phenol, the 6-tertiary butyl-2, 4-xylenol, 2, 6-DI-tert-butylphenol compounds, 2, 6-di-tert-butyl-4-methy phenol (BHT, oxidation inhibitor T501), 2, 4, 6-tri-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), butylhydroxy anisole (BHA), 2, 6-di-t-butyl-α-methoxyl group-p-cresol (BHT-MO), 4-methylol-2, 6-DI-tert-butylphenol compounds (oxidation inhibitor 754), 2, one or more in 6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703).
Here diphenol refers to a phenol type antioxidant phenyl ring having two hydroxyls, can be the diphenol of structure below: Resorcinol, Tert. Butyl Hydroquinone (TBHQ), 2, one or more in 5-di-tert-butyl hydroquinone, 2,5-bis-tert-pentyl Resorcinol.
Bis-phenol refers to the phenol type antioxidant be connected by sulphur or carbon atom by two single phenol, such as:
(1) bis-phenol be connected by carbon atom
4,4 '-isopropylidene bis-phenol (dihydroxyphenyl propane);
2,2 '-bis--(3-methyl-4 hydroxy phenyl) propane (bisphenol-c);
4,4 '-dihydroxybiphenyl (oxidation inhibitor DOD);
4,4 '-dihydroxyl-3,3 ', 5,5 '-four-tertiary butyl biphenyl (oxidation inhibitor 712);
2,2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol) (oxidation inhibitor bis-phenol 2246);
4,4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);
2,2 '-methylene radical-bis--(4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);
2,2 '-methylene radical-bis--(4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);
2,2 '-methylene radical-bis--[4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);
2,2 '-methylene radical-bis--(6-α-methylbenzyl p-cresol);
4,4 '-methylene radical-bis--(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-bis--(2-TBP) (oxidation inhibitor 702);
2,2 '-ethylidene-bis--(4-methyl-6-tert-butylphenol);
4,4 '-ethylidene-bis--(2-methyl-6-tert-butylphenol);
4,4 '-ethylidene-bis--(2,6 di t butyl phenol);
4,4 '-butylidene-bis--(the 6-tertiary butyl-meta-cresol) (oxidation inhibitor BBM, oxidation inhibitor TCA);
4,4 '-isobutylidene-bis--(2,6 di t butyl phenol) etc.
(2) bis-phenol be connected by sulphur atom
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2,2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);
4,4 '-thiobis-(5-methyl-2-TBP);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
2,2 '-thiobis-(4-octyl phenol) etc.
(3) be connected by carbon atom but contain heteroatomic bis-phenol
N, N '-hexamethylene is two-(3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) (oxidation inhibitor 1098);
Hexylene glycol two [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 259);
Two-(3,5-di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine (oxidation inhibitor BPP);
Two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S);
2,2 '-sulfurous ethyl glycol two [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 1035);
Two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic esters (oxidation inhibitor 245) of triglycol etc.
The bis-phenol that bisphenol type oxidation inhibitor is preferably connected by methylene radical or sulphur by the single phenol having at least a tertiary butyl at phenolic hydroxyl group ortho position, such as:
2,2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol) (oxidation inhibitor bis-phenol 2246);
4,4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);
2,2 '-methylene radical-bis--(4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);
2,2 '-methylene radical-bis--(4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);
2,2 '-methylene radical-bis-[4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);
2,2 '-methylene radical-bis--(6-α-methylbenzyl p-cresol);
4,4 '-methylene radical-bis--(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-bis--(2-TBP) (oxidation inhibitor 702);
2,2 '-ethylidene-bis--(4-methyl-6-tert-butylphenol);
4,4 '-ethylidene-bis--(2-methyl-6-tert-butylphenol);
4,4 '-ethylidene-bis--(2,6 di t butyl phenol);
4,4 '-butylidene-bis--(the 6-tertiary butyl-meta-cresol) (oxidation inhibitor BBM, oxidation inhibitor TCA);
4,4 '-isobutylidene-bis--(2,6 di t butyl phenol).
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2,2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
Two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.
Described polyphenol antioxidant refers to that the macromole oxidation inhibitor rolled into a ball by least three single phenolic group in molecule preferably rolls into a ball by the single phenolic group having at least a tertiary butyl at phenolic hydroxyl group ortho position the polyphenol formed, and especially preferably has the hindered polyphenol of two tertiary butyls at phenolic hydroxyl group ortho position, such as:
1,3,5-trimethylammonium-2,4,6-tri--(4 '-hydroxyl-3 ', 5 '-di-t-butyl) benzene (antioxidant 330);
Three [2-(3,5-di-tert-butyl-hydroxy phenyl) propionyl oxygen ethyl] isocyanic ester (oxidation inhibitor 3125);
Four (3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester (antioxidant 1010);
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) (antioxidant 3114);
1,1,3-tri--(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA);
1,3,5-tri-(2, the 6-dimethyl-4-tertiary butyl-3-hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) (oxidation inhibitor 1790);
Two [3,3-pair-(3 '-tertiary butyl-4 '-hydroxybenzyl) butyric acid] glycol ester etc.
The preferred single phenol of above-mentioned phenol type antioxidant, diphenol and bisphenol type oxidation inhibitor, preferably have the hindered phenol of a tertiary butyl at phenolic hydroxyl group ortho position further at least.Especially a tertiary butyl is preferably had at least at the bisphenol type oxidation inhibitor at phenolic hydroxyl group ortho position, particularly by bisphenol type oxidation inhibitor that methylene radical or sulphur are connected.
Dresel fuel compositions provided by the invention is also optionally containing amount of component b.And the weight ratio of described component a and amount of component b can be 1: 0-1, the weight ratio of preferred described component a and described amount of component b is 1: 0.01-1, more preferably 1: 0.01-0.5, be further preferably 1: 0.02-0.2.
Described amount of component b can be the various metal passivator that can react with metallic surface and/or the metal chelator reacting with metal or metal ion or combine.
Concrete, described amount of component b can be one or more in 124 Triazole and derivative, thiadiazoles and derivative thereof, oxine, ethylenediamine tetraacetic carboxylic acid, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base, organic polycarboxylic acid and derivative thereof.Described ethylenediamine tetraacetic carboxylic acid can be ethylenediamine tetraacetic acid (EDTA) (EDTA), and described hydrazides can be N-salicylidene-N '-salicylyl hydrazine and/or N, N '-diacetyl adipyl two hydrazides.Described beta-diketon is as methyl ethyl diketone, and described 'beta '-ketoester is as etheric acid monooctyl ester.Described Schiff's base can be one or more in N, N '-two salicylidene-1，2-diaminoethane, N, N '-two salicylidene-1,2-propylene diamine, N, N '-two salicylidene-1,2-cyclohexanediamine, N, N '-two salicylidene-N '-methyl dipropylenetriamine.Described organic polycarboxylic acid and derivative thereof can be such as one or more in citric acid, tartrate, oxysuccinic acid, succsinic acid (succinic acid), toxilic acid, phytic acid etc. and derivative thereof.
In the present invention, preferred described amount of component b is one or more in 124 Triazole and derivative (such as commodity are called the commercial additive of T551), Schiff's base and organic polycarboxylic acid and derivative thereof.
According to use needs, Dresel fuel compositions provided by the invention can also contain other additive, as one or more in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc.
The preparation of Dresel fuel compositions provided by the invention is simple, only each component of composition Dresel fuel compositions need be mixed.Directly each additive component can be mixed with Base Diesel, also can first various additive component be mixed, after obtaining additive, then gained additive be mixed with Base Diesel.In order to easy to operate, when various additive component is mixed, can carry out in the presence of solvent, here solvent can be that polar solvent is as N, one or more in dinethylformamide (DMF), Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF) (DHF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidone and methyl-2-pyrrolidone.Also can be hydro carbons especially aromatic hydrocarbons as benzene,toluene,xylene, aromatic diluent oil and composition thereof, can also be biofuel.
In Dresel fuel compositions of the present invention, described Base Diesel is biofuel.Described biofuel refers to that grease and low-carbon alcohol are (as C
1-C
5fatty alcohol) fatty acid ester of low-carbon alcohol of generation through transesterify (alcoholysis) reaction, be generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.
Described trans-esterification processes can be the processing method that any known or unknown transesterification reaction by grease and low-carbon alcohol obtains biofuel, such as acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, etc.Specifically can with reference to documents such as CN1473907A, DE3444893, CN1472280A, CN1142993C, CN1111591C, CN1594504A.
Described grease has general sense well known in the art, and be the general name of oil and fat, main component is fatty acid triglycercide.General normal temperature be liquid be called oil, normal temperature is solid or is semisolidly called fat (abbreviation fat).Described grease comprises vegetables oil and animal oil, in addition, also comprising from the oil plant in the material such as microorganism, algae, can also be even waste oil, the used grease of acidifying wet goods of such as waste cooking oil, sewer oil, swill oil, grease factory or rotten grease.Described vegetables oil can be herbaceous plant oil also can be xylophyta oil, if 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 are as the oil of the plant such as kostelezkya virginica, cyperus esculentus.Described animal oil can be lard, chicken fat, duck oil, goose is oily, sheep is oily, house oil, butter, haco oil, shark wet goods.
In Dresel fuel compositions of the present invention, described Base Diesel also can contain other diesel oil, other diesel oil described can be petroleum diesel, Fiscber-Tropscb synthesis diesel oil, hydrocracking biofuel, containing one or more in oxygen diesel oil blending thing, the volume ratio of described biofuel and other diesel oil is preferably 1: 2-99.
Wherein, petroleum diesel refers to that the various refining process of crude oil (oil) through refinery are as the cut of boiling range between 160-380 DEG C after the device process such as Atmospheric vacuum, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking, and the compression ignition engine fuel meeting solar oil standard GB/T 252-2000 or derv fuel oil standard GB/T/T 19147-2003 through allocating.
Fiscber-Tropscb synthesis diesel oil mainly refers to the GTL diesel oil (Gas To Liquid) produced through fischer-tropsch (F-T) synthetic method for raw material with Sweet natural gas or coal or CTL diesel oil (Coal To Liquid), can also be the BTL diesel oil (Biomass To Liquid) that vegetable fibre is produced through fischer-tropsch synthetic method.Fiscber-Tropscb synthesis diesel oil not sulfur-bearing and aromatic hydrocarbons substantially, very clean fuel, but its oilness extreme difference, after concocting with biofuel, oilness is improved greatly, but the oxidation stability of tempered oil is likely deteriorated, the blending fuel therefore containing biofuel also needs to add oxidation inhibitor.
Hydrocracking biofuel also referred to as s-generation biofuel, refer to by animal-plant oil generate after hydrogenation and cracking reaction with C
8-C
24alkane is main, especially with C
12-C
20normal paraffin is the reaction product of main component, and this hydrocracking biofuel cetane value is high, and sulphur and aromaticity content are extremely low, greatly can reduce the discharge of diesel engine pollutent as diesel motor fuel or blending component.
Refer to be deployed into various diesel-fuel containing oxygen diesel oil blending component and meet the oxygenatedchemicals of certain code requirement or the mixture of oxygenatedchemicals, normally alcohols and ethers or its mixture, alcohols is C such as
1-C
18fatty alcohol, preferably C
1-C
12unitary fatty alcohol, as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecylenic alcohol, lauryl alcohol and various isomer thereof.Ethers can be dme, methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, C
6-C
14fatty alcohol-polyoxyethylene ether, C
6-C
14fatty alcohol polyoxypropylene ether, C
6-C
14alkylphenol polyoxyethylene, C
6-C
14alkylphenol polyethenoxy ether, polyoxymethylene dme (Polyoxymethylene Dimethyl Ethers, CH
3o (CH
2o)
xcH
3, x=1-8) etc. and composition thereof.
In the present invention, when described Base Diesel is the blending fuel containing biofuel, described additive by described additive, biofuel and other diesel oil being directly obtained by mixing, also can first can mix with biofuel by described Dresel fuel compositions, and then with other diesel oil blending and obtaining.
The present invention is described further for the following examples.
Embodiment 1-2 is for illustration of the preparation of polyolefin-based phenol.
Embodiment 1
In 1000ml three-necked bottle, add 363.3 grams of polyisobutene (the equal relative molecular mass Mn=1100 of polyisobutene number, source are Jinzhou) and 62.1 grams of phenol, complete 50 DEG C of stirring heating, by 14.1 grams of BF
3-diethyl ether solution divides and is added drop-wise in reaction system at two hours for three times.Be warming up to 60 DEG C, clock reaction 4.5 hours.Stopped reaction, washes three times with the distillations of 40 DEG C, then underpressure distillation removes unreacted phenol.Adopting column chromatography analysis methods analyst to go out unreacted polyisobutene is 32%, and the alkylation transformation efficiency calculating polyisobutene is thus 68%.
Embodiment 2
In 500ml three-necked bottle, add 100 grams of polyisobutene (the equal relative molecular mass Mn=1000 of polyisobutene number, source are BASF Corp. of Germany) and 18.8 grams of phenol, be heated with stirring to 60 DEG C, by 4.3 grams of BF
3-diethyl ether solution divides and is added drop-wise in reaction system at two hours for three times.Be warming up to 70 DEG C, clock reaction 4 hours.Stopped reaction, washes three times with the distillations of 50 DEG C, then underpressure distillation removes unreacted phenol.Adopting column chromatography analysis methods analyst to go out unreacted polyisobutene is 30%, and the alkylation transformation efficiency calculating polyisobutene is thus 70%.
Embodiment 3-4 is for illustration of the synthesis of mannich base.
Embodiment 3
In three-necked bottle, add 100 grams of polyolefin-based phenol prepared by embodiment 1,9.4 grams of triethylene tetramines and 120 grams of toluene, heated and stirred to 70 DEG C, is added drop-wise to the formaldehyde solution of 13.4 gram 36 % by weight in 2 hours (mol ratio of polyolefin-based phenol, formaldehyde, triethylene tetramine is 1: 3: 1.2) in reaction system.100 DEG C are warmed up to after dripping off, and 100 DEG C of clock reactions 2 hours.Then with underpressure distillation removing toluene solvant and water, then add 50 grams of aromatic diluent oil, be made into the diluent of 50 % by weight.
Embodiment 4
In three-necked bottle, add 100 grams of polyolefin-based phenol prepared by embodiment 2,1.9 grams of paraformaldehydes, 11.8 grams of tetraethylene pentamine and 50 grams of aromatic diluent oil (mol ratio of polyolefin-based phenol, formaldehyde, tetraethylene pentamine is about 1: 1: 1), heated and stirred to 95 DEG C, react 6 hours under nitrogen purge, divide water outlet, add 5 grams of aromatic diluent oil again, be made into the diluent of 50 % by weight.
Embodiment 5-7 is for illustration of the preparation of component a.
Embodiment 5
In three-necked bottle, add 50 grams of mannich bases prepared by embodiment 4 and 3.9 grams of P-hydroxybenzoic acid and 5 grams of aromatic diluent oil (P-hydroxybenzoic acid and tetraethylene pentamine mol ratio are about 1.6: 1), in the presence of nitrogen in 80 DEG C of reactions 6 hours, then be cooled to room temperature, products therefrom is stand-by as component a of the present invention.
Embodiment 6
In three-necked bottle, add 50 grams of mannich bases prepared by embodiment 3 and 6.0 gram 3,4,5-trihydroxybenzoic acid (gallic acid, wherein gallic acid and triethylene tetramine mol ratio are about 1.8: 1), and 10 grams of aromatic diluent oil are in the presence of nitrogen in 120 DEG C of reactions 5 hours, be cooled to room temperature, products therefrom is stand-by as component a of the present invention.
Embodiment 7
In three-necked bottle, add 50 grams of mannich bases prepared by embodiment 4 and and 5 grams of aromatic diluent oil, by the N of 7.4 gram of one hydration gallic acid (gallic acid and tetraethylene pentamine mol ratio are about 2.1: 1) and 8g, dinethylformamide is slowly added in reaction flask, blow water in 100 DEG C in the presence of nitrogen and react 5 hours, be cooled to room temperature, products therefrom is stand-by as component a of the present invention.
Embodiment 8-17
Embodiment 8-17 is for illustration of the composition of additive.
To the component a of embodiment 5-7 and components b and c be selected from according to the weight ratio mixing shown in table 1.
Table 1
| Embodiment | Component a originates | Components b | Amount of component b | A: b: c (weight ratio) |
| Embodiment 8 | Embodiment 5 | N, N '-dioctyl-p-phenylenediamine | - | 1∶0.4∶0 |
| Embodiment 9 | Embodiment 5 | N, N '-dioctyl-p-phenylenediamine | N, N '-two salicylidene-1,2-propylene diamine | 1∶0.4∶0.04 |
| Embodiment 10 | Embodiment 6 | Oxidation inhibitor T501 (BHT) | - | 1∶1∶0 |
| Embodiment 11 | Embodiment 6 | Oxidation inhibitor T501 (BHT) | Citric acid (40 % by weight ethylene glycol solution) | 1∶1∶0.08 |
| Embodiment 12 | Embodiment 6 | Oxidation inhibitor methene 736 | - | 1∶1∶0 |
| Embodiment 13 | Embodiment 6 | Oxidation inhibitor methene 736 | T551 | 1∶0.6∶0.05 |
| Embodiment 14 | Embodiment 7 | Oxidation inhibitor bis-phenol 2246 | - | 1∶0.2∶0 |
| Embodiment 15 | Embodiment 7 | 2,6 di t butyl phenol | - | 1∶2∶0 |
| Embodiment 16 | Embodiment 7 | N, N '-di-sec-butyl-p-phenyl enediamine | - | 1∶0.3∶0 |
| Embodiment 17 | Embodiment 6 | N, N '-dioctyl-p-phenylenediamine | - | 1∶0.4∶0 |
| Comparative example 1 | Embodiment 5 | - | - | 1∶0∶0 |
| Comparative example 2 | Embodiment 6 | - | - | |
| Comparative example 3 | Embodiment 7 | - | - | 1∶0∶0 |
| Comparative example 4 | - | N, N '-dioctyl-p-phenylenediamine | - | 0∶1∶0 |
| Comparative example 5 | - | Oxidation inhibitor T501 | - | 0∶1∶0 |
| Comparative example 6 | - | Oxidation inhibitor methene 736 | - | 0∶1∶0 |
| Comparative example 7 | - | Oxidation inhibitor bis-phenol 2246 | - | 0∶1∶0 |
| Comparative example 8 | - | 2,6 di t butyl phenol | - | 0∶1∶0 |
| Comparative example 9 | - | N, N '-di-sec-butyl-p-phenyl enediamine | - | 0∶1∶0 |
| Comparative example 10 | - | - | N, N '-two salicylidene-1,2-propylene diamine | 0∶0∶1 |
Performance test
Below in test, Shijiazhuang used refinery biofuel is the biodiesel oil product that the Oleum Gossypii semen biofuel of being produced by the said firm and plam oil biofuel mix with volume ratio 60: 40, sample is provided by Shijiazhuang refinery branch office of China Petrochemical Industry, acidification oil biofuel used provides by the remarkable new forms of energy company limited of Fujian Longyan, and petroleum diesel is the capital mark B diesel oil that Yanshan Mountain branch office of China Petrochemical Industry produces.
(1) oxidation-resistance of biodiesel composition of diesel oil and the test of detergent-dispersant performance based on pure biofuel
Evaluate oxidation stability of biodiesel the inductive phase measured at 110 DEG C by EN14112:2003 method (Racimat method), use the 743 type oil oxidative stability determinators that instrument is Wan Tong company of Switzerland, wherein.Inductive phase is longer, illustrate that the oxidation-resistance of biodiesel composition is better, otherwise inductive phase is shorter, illustrates that the oxidation-resistance of biodiesel composition is poorer.Its test result is shown in Table 2.
With tinsel sedimentation evaluation detergent-dispersant performance disclosed in CN 1351132A, concrete operations comprise: by biodiesel composition (Shijiazhuang refinery biofuel or acidification oil biofuel and additive) and do not add additivated Shijiazhuang refinery biofuel or acidification oil biofuel (i.e. blank sample) respectively in implantation glass pipe to scale marks (40 milliliters), to weigh in advance and the stainless steel substrates of milled hangs respectively and impregnated in above-mentioned biodiesel composition and blank sample, then close also oxygenation and replace three times, boost to 0.8MPa, and be warming up to 160 DEG C, oxygen pressure in assaying reaction device afterwards, and keep 6 hours at this temperature.Then be cooled to room temperature and release the overbottom pressure in reactor, taking out tinsel, with the sherwood oil cleaning of 70 DEG C, drying up, weigh up the weightening finish (i.e. deposition) of steel disc, the steel disc obtained in blank sample pilot scale test weightening finish is designated as W
0, the steel disc obtained in biodiesel composition pilot scale test weightening finish is designated as W
1, and according to the deposition improvement rate of each biodiesel composition of following formulae discovery:
Deposition improvement rate=(W
0-W
1)/W
0× 100%
Wherein, the detergent-dispersant performance of the higher then biodiesel composition of deposition improvement rate is better, and the detergent-dispersant performance of the lower then biodiesel composition of deposition improvement rate is poorer.Its test result is shown in Table 2.
Table 2
Data as can be seen from table 2, compared with comparative example, biodiesel composition provided by the invention has obviously better oxidation stability and detergent-dispersant performance.Mannich base with containing phenol organic acid reaction product (component a) with components b mating reaction after, the oxidation stability of biodiesel composition and detergent-dispersant performance than be used alone component a, components b effect sum well a lot, there is synergy clearly between component a, b astoundingly as can be seen here.After optional amount of component b adds, effect strengthens further.
Can be found out with embodiment 16 by embodiment 10 and 12 and embodiment 15, when the bisphenol type oxidation inhibitor using the present invention to be connected preferably through methylene radical and the dialkyl-pphenylenediamines of atomic number of alkyl carbon between 4-10 are as components b, it is better that the oxidation stability of gained Dresel fuel compositions and detergent-dispersant performance improve successful.
Can be found out compared with embodiment 17 by embodiment 8, during by the reaction product of gallic acid and mannich base as component a, it is better that the oxidation stability of gained biodiesel composition and detergent-dispersant performance improve successful.
By embodiment 8 compared with embodiment 9, embodiment 10 compared with embodiment 11, can find out, after selecting optional amount of component b, oxidation stability and the detergent-dispersant performance of gained biodiesel composition are more excellent.
(2) test of the oxidation-resistance of the concocted diesel oil composition of diesel oil, stability and detergent-dispersant performance based on the mixture of biofuel and petroleum diesel, biofuel used is acidification oil biofuel.
The method of Pr EN15751:2008 is adopted to measure each Dresel fuel compositions, petroleum diesel and concocted diesel oil inductive phase at 110 DEG C respectively, use the 743 type oil oxidative stability determinators that instrument is Wan Tong company of Switzerland, inductive phase is longer, illustrate that the oxidation-resistance of biodiesel composition is better, otherwise inductive phase is shorter, illustrates that the oxidation-resistance of biodiesel composition is poorer.Its test result is shown in Table 3.
Derv fuel oil detergency determinator (by the production of Lanzhou Wei Ke petrochemical industry instrument company, L-3 type) is adopted to measure the detergent-dispersant performance of each concocted diesel oil composition respectively according to the method disclosed in CN 1940524A.Its concrete operations comprise: the weight weighing the sediment trap of a cleaning, then this sediment trap is heated to 250 DEG C, afterwards with the speed of 2 ml/min by concocted diesel oil combined stream on the working face of sediment trap, form the oil film of one deck Uniform Flow, after 50 minutes, the oil film on sediment trap working face is toasted under the high temperature of 180 DEG C, oxidation generates one deck paint film, then this sediment trap to be impregnated in normal heptane 2 minutes, then the weight being attached with sedimental sediment trap is weighed, and record the weightening finish of sediment trap, be the deposition A (unit: mg) of sediment trap.Can according to the detergent-dispersant performance of the size evaluation concocted diesel oil composition of deposition, if deposition is larger, detergent-dispersant performance is poorer, otherwise if deposition is less, detergent-dispersant performance is better.Its test result is shown in Table 3.
In addition, adopt tinsel sedimentation disclosed in CN1351132A according to the detergent-dispersant performance of the evaluation method evaluation concocted diesel oil composition of above-mentioned biofuel detergent-dispersant performance, the weightening finish obtaining steel disc is the deposition B (mg) of sediment trap.According to the detergent-dispersant performance of the size evaluation Dresel fuel compositions of deposition, if deposition is larger, detergent-dispersant performance is poorer, otherwise if deposition is less, detergent-dispersant performance is better.Its test result is shown in Table 3.
Adopt the method for SH/T 0175 to measure respectively and the amount (unit: mg/100mL) of the insolubles of concocted diesel oil composition, thus evaluate their stability.The larger then stability of amount of insolubles is poorer, otherwise if the amount of insolubles is less, stability is better, and its test result is shown in Table 3.
Table 3
As can be seen from the result of table 3, after adding biofuel, be all deteriorated compared with petroleum diesel containing the oxidation stability of the blending fuel of biofuel, stability and detergent-dispersant performance.The oxidation stability of the biodiesel composition of the present invention that the mixture containing component a and components b or component a and components b and amount of component b obtains as additive, stability and dispersiveness have to be improved significantly, there is synergistic effect in component a and components b effect, its effect strengthens than comparative example successful.Mannich base is to the DeGrain (embodiment 1) of stability improving biodiesel blend fuels, and only containing phenolic or amine type oxidation inhibitor as oxidation inhibitor time, the stability of gained biodiesel blend fuels and the improvement DeGrain of detergent-dispersant performance.In addition, arylamine type oxidation inhibitor has certain carcinogenesis and stronger corrodibility and contaminative, and production cost is higher.
Claims (12)
1. a Dresel fuel compositions, this Dresel fuel compositions contains Base Diesel and additive, it is characterized in that, described Base Diesel is containing biofuel, described additive contains component a and components b, described component a is prepared by following method: be the aldehyde of 1-6 and the mannich base of polyamines polyene reaction generation by polyolefin-based phenol, carbonatoms and contain phenolic group organic acid according to the polyamines polyene in mannich base and the mixed in molar ratio containing phenolic group organic acid 1: 0.5-5, react 0.5-20 hour in the presence of the solvent in 50-200 DEG C; Described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant; The weight ratio of described components b and component a is 0.01-10: 1; The content of described additive is 50-10000ppm; Described Base Diesel is also containing other diesel oil, and other diesel oil described is petroleum diesel, Fiscber-Tropscb synthesis diesel oil, hydrocracking biofuel, containing one or more in oxygen diesel oil blending thing, the volume ratio of described biofuel and other diesel oil is 1: 2-99.
2. Dresel fuel compositions according to claim 1, wherein, the weight ratio of described components b and component a is 0.05-5: 1.
3. Dresel fuel compositions according to claim 1 and 2, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, has one or more in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position of a tertiary butyl at least.
4. Dresel fuel compositions according to claim 3, wherein, described components b is one or more in the bisphenol type oxidation inhibitor that is connected with by methylene radical or sulphur of the dialkyl-pphenylenediamines of atomic number of alkyl carbon between 4-10.
5. Dresel fuel compositions according to claim 4, wherein, described components b is N, N '-diheptyl Ursol D, N, N,-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-bis--(1-methylheptyl) Ursol D, 2, 2 '-methylene radical-bis--(4-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol), 4, 4 '-methylene radical-bis--(2, 6-DI-tert-butylphenol compounds), 4, 4 '-methylene radical-bis--(2-TBP), 4, 4 '-thiobis-(3 methy 6 tert butyl phenol), 2, 2 '-thiobis-(4-methyl-6-tert-butylphenol), 4, 4 '-thiobis-(2-methyl-6-tert-butylphenol), 4, 4 '-thiobis-(2, 6-DI-tert-butylphenol compounds), two-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in thioether.
6. Dresel fuel compositions according to claim 1, wherein, the described phenolic group organic acid that contains is selected from Whitfield's ointment, m-Salicylic acid, P-hydroxybenzoic acid, 3-hydroxy-2-naphthoic acid, 3,4, one or more in 5-trihydroxybenzoic acid, 4,4-two-(4-hydroxyphenyl) valeric acid.
7. Dresel fuel compositions according to claim 1, wherein, described polyolefin-based phenol is polyisobutene phenol.
8. Dresel fuel compositions according to claim 1, wherein, described C
1-C
6aldehyde be one or more in formaldehyde, acetaldehyde, propionic aldehyde, hexamethylene aldehyde.
9. Dresel fuel compositions according to claim 1, wherein, the structural formula of described polyamines polyene is H
2n [(CH
2)
nnH]
mh, n are the integer of 2-4, and m is 1-5.
10. Dresel fuel compositions according to claim 1, wherein, described additive is also containing amount of component b, and described amount of component b is metal passivator.
11. Dresel fuel compositions according to claim 10, wherein, the weight ratio of described component a and described amount of component b is 1: 0.01-1.
12. Dresel fuel compositions according to claim 10, wherein, described amount of component b is one or more in 124 Triazole and derivative, Schiff's base and organic polycarboxylic acid.
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| FR2984918B1 (en) * | 2011-12-21 | 2014-08-01 | Total Raffinage Marketing | ADDITIVE COMPOSITIONS ENHANCING LACQUERING RESISTANCE OF HIGH-QUALITY DIESEL OR BIODIESEL FUEL |
| CN103664655B (en) * | 2012-09-26 | 2015-05-20 | 中国石油化工股份有限公司 | Mannich base detergent, preparation method thereof as well as detergent concentrate and fuel oil composition |
| CN103666564B (en) * | 2012-09-26 | 2015-07-01 | 中国石油化工股份有限公司 | Antiscale composition and application thereof |
| CN103666563B (en) * | 2012-09-26 | 2015-05-20 | 中国石油化工股份有限公司 | Antiscale composition and application thereof |
| CN104946350B (en) * | 2014-03-25 | 2017-06-30 | 中国石油化工股份有限公司 | Lubricant oil composite |
| CN104946351B (en) * | 2014-03-25 | 2017-10-03 | 中国石油化工股份有限公司 | Lubricant oil composite and the method for improving lubrication oil antiwear antifriction performance |
| CN104946352B (en) * | 2014-03-25 | 2017-11-03 | 中国石油化工股份有限公司 | Lubricant oil composite |
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