CN102936521B - Diesel oil composition and method for improving biodiesel oxidation stability - Google Patents
Diesel oil composition and method for improving biodiesel oxidation stability Download PDFInfo
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- CN102936521B CN102936521B CN201110233548.7A CN201110233548A CN102936521B CN 102936521 B CN102936521 B CN 102936521B CN 201110233548 A CN201110233548 A CN 201110233548A CN 102936521 B CN102936521 B CN 102936521B
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Abstract
The invention provides a diesel oil composition, which contains base diesel oil and an additive. Specifically, the base diesel oil contains biodiesel, and the additive contains component a, which is an amination or ammonolysis reaction product of maleic anhydride-oil soluble polymer grafted copolymer. The additive also optionally includes component b, which is an arylamine antioxidant and/or a hindered phenol antioxidant. The invention also provides a method for improving biodiesel oxidation stability. The diesel oil composition provided in the invention has good oxidation stability and low temperature fluidity when taking pure biodiesel as the base diesel oil, and can have good stability and low temperature fluidity when taking a biodiesel-containing blended fuel as the base diesel oil.
Description
Technical field
The invention relates to a kind of method of Dresel fuel compositions and raising oxidation stability of biodiesel.
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 EN 14214:2003, Australian Biodiesel Standards (Draft2003), New Zealand Biodiesel Standards NZS 7500:2005, Brazilian Biodiesel Standards ANP255 (2003), India Biodiesel Standards IS 15607:2005, South Africa Biodiesel Standards SANS1935:2004 and China diesel-fuel blending biofuel (BD100) standard GB/T/T20828-2007 all regulation biofuel is be not less than 6 hours the inductive phase at 110 DEG C, and measuring method is EN 14112:2003.
As everyone knows, petroleum diesel (the i.e. diesel oil of ordinary meaning, herein in order to distinguish mutually with biofuel, the special concept introducing 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-tert-butyl-4-methyl-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.
The reaction product of succinic acylating agent and polyalkylene amine that CN101058774A discloses the replacement of a kind of alkyl is optionally with 2; being combined in of 5-di-tert-butyl hydroquinone prevents or postpones the purposes in liquid composition oxidation, and wherein said liquid composition contains the oil being derived from plant or animal of at least 2 % by weight.
Although more than use traditional oxidation inhibitor to have certain effect to the method improving oxidation stability of biodiesel, but DeGrain is improved for the oxidation stability of pure biofuel basis diesel oil, also not so good with the improvement effect of the stability of the blending fuel of other diesel oil for biofuel.
Summary of the invention
The object of the invention is the oxidation stability of the Dresel fuel compositions of diesel oil based on pure biofuel in order to overcome above-mentioned prior art shortcoming that the is poor and less stable of the Dresel fuel compositions of diesel oil based on the blending fuel of biofuel and other diesel oil, a kind of oxidation stability or the good Dresel fuel compositions of stability being provided and a kind of method improving oxidation stability of biodiesel is provided.
The invention provides a kind of Dresel fuel compositions, this Dresel fuel compositions contains Base Diesel and additive, and wherein, described Base Diesel contains biofuel, described additive contains component a, and described component a is amination or the ammonia solution thing of the multipolymer of maleic anhydride graft oil-soluble polymers.
The present invention also provides a kind of method improving oxidation stability of biodiesel simultaneously, the method comprises, and containing in the Base Diesel of biofuel, adds additive, described additive contains component a, and described component a is amination or the ammonia solution thing of the multipolymer of maleic anhydride graft oil-soluble polymers.
Dresel fuel compositions provided by the invention, when based on pure biofuel during diesel oil, this Dresel fuel compositions has good oxidation stability, and when by containing based on the blending fuel of biofuel during diesel oil, the stability of this Dresel fuel compositions is better.And the low-temperature fluidity of Dresel fuel compositions provided by the invention also significantly improves.Particularly according to preferred implementation provided by the invention, when described additive is simultaneously containing component a, components b, there is synergistic effect due to amazing between each additive, will get well a lot when antioxidant effect ratio is used alone said components a, b.Component a and components b used in combination time, component a can be regarded as auxiliary antioxidant, and it can make the effect of oxidation inhibitor unexpectedly greatly strengthen.Therefore, when reaching identical oxidation stability and requiring, the amount of components b in biodiesel composition can greatly reduce, and especially under components b is expensive especially or components b has certain toxicity or corrosive situation, decreases its consumption and has very large meaning.
Embodiment
According to Dresel fuel compositions provided by the invention, the content of described additive can be selected in a big way, such as, can be 500-5000ppm relative to the content of Base Diesel, is preferably 1000-3000ppm.
Component a
The number-average molecular weight of the polymkeric substance in described component a can be 500-100,000, be preferably 1000-50,000.The percentage of grafting of the polymkeric substance in described component a is 0.5-10, is preferably 1-5.
In the present invention, described " amination of the multipolymer of maleic anhydride graft oil-soluble polymers or ammonia solution thing " is obtained by condensation reaction by maleic anhydride graft oil-soluble polymers and the ammonia containing-NH functional group and/or organic amine.Maleic anhydride graft oil-soluble polymers with containing the ammonia of-NH functional group and/or organic amine generation condensation reaction (also claim the ammonia (amine) of carboxylic acid derivative to separate to react or ammonia (amine) change react).
In the present invention, the monomer of described " oil-soluble polymers " is ethylenically unsaturated monomers, more preferably carbonatoms is the ethylenically unsaturated monomers of 2-30, is further preferably one or more in ethene, propylene, butylene, divinyl, vinyl cyanide, vinylformic acid C1-C22 alkyl ester, methacrylic acid C1-C22 alkyl ester, acrylamide, Methacrylamide, vinyl acetate, vinylbenzene, the alpha-olefin of C6-C24, maleic anhydride, toxilic acid, maleic acid ester, maleimide, fumarate, vinyl pyridine, alkyl vinyl ether.Described oil-soluble polymers can be the homopolymer of aforementioned monomer, binary, ternary or multiple copolymer.The number-average molecular weight of described oil-soluble polymers is preferably 500-100000, more preferably 1000-50000.Described oil-soluble polymers can be existing commercial polymer, such as, be ethylene-vinyl acetate copolymer (EVA), Voncoat R 3310, methacrylate homopolymer, (methyl) acrylate-maleic imide copolymer, (methyl) acrylate-maleic ester copolymer as diesel flow improver; As one or more in the ethylene-propylene copolymer of lubricating oil viscosity index improver, polymethacrylate, vinylbenzene-diene copolymer; As one or more in the poly-alpha olefins of pour depressant for lubricating oil, poly-(methyl) acrylate, vinyl acetate-fumarate copolymer; As ethylene-vinyl acetate copolymer (EVA), (methyl) acrylate copolymer of pour point depressant for crude oil.The oil-soluble polymers meeting above-mentioned condition can be such as the commercial additive T602 of Shanghai Gaoqiao petrochemical industry branch office of China Petrochemical Industry refinery production and the diesel oil commodity pour point depressant T1804C of Beijing Organic Chemical Plant production.
The multipolymer of maleic anhydride graft oil-soluble polymers is product maleic anhydride and above-mentioned oil-soluble polymers being carried out graft polymerization.Quality of material ratio when maleic anhydride and above-mentioned oil-soluble polymers carry out graft polymerization is generally 0.005-0.2: 1, preferred 0.01-0.1: 1.Carrying out graft polymerization to polymkeric substance is technology well known in the art, and general employing adds initiator thus Inducing Graft Polymerization reaction in the solution.It is 40-250 DEG C that described graft polymerization condition comprises polymerization temperature, and the reaction times is 1-10 hour.Initiator used can be superoxide or azo compound, as fine in ditertiary butyl peroxide, dilauryl peroxide, benzoyl peroxide, azo two isobutyl, dilauroyl peroxide, isopropyl benzene hydroperoxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate etc.; The inorganic initiator such as Potassium Persulphate, thiosulphate can also be used.The consumption of initiator is generally the 0.5-2% of reactant gross weight.Described solvent can be toluene, dimethylbenzene, ethylbenzene, normal hexane, hexanaphthene etc., and also can be aromatic diluent oil, boiling range be 159-185 DEG C, is preferably the aromatic diluent oil that boiling range is 159-185 DEG C.Solvent load is generally the 30-150% of monomer material gross weight.The feed way of initiator can be once all add, and also can add by separated in time several times.Reaction product can be removed solvent or not remove solvent and directly carry out the next step, is preferably the product removing unreacted maleic anhydride.The method removing unreacted maleic anhydride can be by nitrogen purging or underpressure distillation, or is precipitated out in methyl alcohol or acetone by polymkeric substance.Reaction product is more preferably to be removed after unreacted maleic anhydride and product containing about 50 % by weight solvents.
The amination of described maleic anhydride grafted polymer or ammonolysis reaction product refer to that above-mentioned graft copolymer reacts with the ammonia containing-NH functional group and/or organic amine, can obtain one or more in ammonium salt, acid amides and imide.
Described ammonia and/or the polyamine compounds of organic amine preferably containing-NH functional group containing-NH functional group, polyamines here refers to the amine containing two or more nitrogen-atoms in molecule, if structural formula is R
1hN-R
2-NHR
3amine, R here
1and R
3can be hydrogen, carbon number is the alkyl of 1-30, R
3the alkylidene group of can be carbon number be 1-30, thiazolinyl, cycloalkyl, aryl or polyether-based etc.; " alkyl " refers to hydrocarbon substituent, one or more namely in aliphatics, alicyclic, aromatics and cyclic substituent.Such as, in quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, decamethylene diamine, coconut oil base 1,3-propylene diamine, oil base 1,3-propylene diamine, tallow base 1,3-propylene diamine one or more.Can also be as shown in the formula the polyether diamine shown in 1:
Wherein x1 is the integer of 1-50, R
4can be hydrogen, carbon number is the alkyl of 1-30; R
5hydrogen or methyl.Such as No. CAS for 9046-10-0, number equal relative molecular mass be the polyetheramine of 400.
Polyamines can also be polyamines polyene, and the structural formula of polyamines polyene is H
2n [(CH
2)
x2nH]
y1r
6, wherein, x2 can be the integer of 2-4, be preferably 2 or 3, y1 can be the integer of 1-8, R
6can be hydrogen, carbon number is the alkyl of 1-30.Such as, R is worked as
6during for H, described polyamines polyene can be one or more in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene seven amine, seven ethene eight amine, propylene diamine, dipropylenetriamine, three propylene tetramines, tetrapropylene five amine and five propylene hexamines, six propylene seven amine, seven propylene eight amine and N-(2-amino-ethyl)-1,3-propylene diamine.Work as R
6for carbon number be the alkyl of 1-30 time, be preferably the alkyl of C4-C22.This alkyl can be saturated alkyl, also can be the thiazolinyl with double bond or the aryl with phenyl ring.Alkyl can be straight chain normal chain alkyl, also can be the isomery alkyl with side chain, the example of this alkyl comprises normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; Isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Example with the aryl of phenyl ring comprises phenmethyl (benzyl), styroyl and hydrocinnamyl.Wherein, the alkyl of more preferably C6-C20.
Here polyamines can also be the amine of nitrogenous heterocyclic amine such as but not limited to imidazoline type, piperazine and piperidines type.
Imidazoline type polyamines is as shown in the formula shown in 2:
Wherein y2 is the integer of 0 to 5, R
7for the alkyl of C1-C24.Be preferably the alkyl of C4-C22.This alkyl can be saturated alkyl, also can be the thiazolinyl with double bond or the aryl with phenyl ring.Alkyl can be straight chain normal chain alkyl, also can be the isomery alkyl with side chain, the example of this alkyl comprises normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; Isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Example with the aryl of phenyl ring comprises phenmethyl (benzyl), styroyl and hydrocinnamyl.Wherein, preferably y2 is the integer of 1-3 further, R
7for the alkyl or alkenyl of C6-C20.
Piperazine polyamine is as shown in the formula shown in 3:
Wherein R
8for the alkyl of H or C1-C24, x3 is the integer of 0 to 5.Preferably typical piperazine polyamine is N-(2-amino-ethyl) piperazine.
The polyamines of piperidines type as 4-amino-2,2,6,6-tetramethylpiperidine, amino-1,2,2,6, the 6-pentamethvl of 4-, 1-(2-aminoethyl) piperidines etc.
Here polyamines can also be such as formula 4, the polyamines containing tertiary amine shown in 5 and 6.
Wherein R
9, R
10for the alkyl of C1-C24, x4 is the integer of 0 to 10.Preferred R
9, R
10for the alkyl of C1-C10, x4 is the integer of 1 to 8.Such as N, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dimethyl-Putriscine, N, N-diethyl-1,4-butanediamine, N, N-dimethyl-1,6-hexanediamine, 3-diethyl amino propylamine (DEAPA), 3-dimethylaminopropylamine (DMAPA), 3-(dibutylamino) propylamine (CAS 102-83-0) etc.
Wherein x5 is the integer of 1 to 10, is preferably the integer of 2 to 6, such as three (2-amino-ethyl) amine.
Wherein R
11for the alkyl of C1-C24, x6 is the integer of 1 to 10, is preferably the integer of 2 to 6, two (3-aminopropyl) methylamine of such as N, N-.
Polyamines can also be structural formula is H
2n [(CH
2)
x2nH]
y1r
6polyamines polyene and oxyethane, propylene oxide condenses.Wherein, x2 can be the integer of 2-4, be preferably 2 or 3, y1 can be the integer of 1-8, R
6can be hydrogen, carbon number is the alkyl of 1-30.
Organic amine of the present invention, except containing except above-mentioned polyamines, also can contain monoamine again.Here monoamine can be primary amine, also can be secondary amine.Preferred primary amine.The aliphatic amide of can be carbonatoms be 1-30, the arylamine of also can be carbonatoms be 1-30, preferred fat amine, it can be the aliphatic amide of straight chain in fat primary amine, as methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, n-dodecylamine (lauryl amine), positive tetradecy lamine, hexadecylamine, octadecyl amine, positive 20 amine, positive two amino dodecanes and composition thereof, also can be the fat primary amine with side chain, these fat primary amines with side chain are various isomer of above-mentioned straight chain fatty primary amine, such as Isopropylamine, isobutylamine, TERTIARY BUTYL AMINE, isobutylcarbylamine, neopentyl amine, dissident's amine, tuaminoheptane, octodrine (2 ethyl hexylamine), different nonyl amine, isodecyl amine, different amino dodecane, different tetradecy lamine, different cetylamine, different stearylamine, different 20 amine and composition thereof.Fat primary amine can also be as cyclopentamine, hexahydroaniline with the amine of cycloaliphatic ring.Also can be contain the fat primary amine of unsaturated double-bond or triple bond in carbochain as oleyl amine (octadecenyl amine), palm oleyl amine (hexadecylene amine), can also be the primene JM-T, the trade names that such as Rohm & Haas company produces be the primene JM-T of Primere 81R.
The organic amine reacted with maleic anhydride grafted polymer of the present invention, preferably containing polyamines, preferably contains the polyamines of at least one primary amine group further, especially preferably polyamines polyene.
Above-mentioned maleic anhydride grafted polymer contains the ammonia of-NH functional group and/or organic amine reaction for conventionally known to one of skill in the art, such as can without catalyzer, above-mentioned maleic anhydride grafted polymer is mixed with organic amine, reflux water-dividing or to be dewatered by nitrogen purging or except methyl alcohol in the presence of solvent, ethanol generates, or under acidity or basic catalyst effect, carry out above-mentioned reaction, an acidic catalyst is as sulfuric acid, phosphoric acid, tosic acid, acidic ion exchange resin, heteropolyacid, solid super-strong acid, acidic white earth, acidic molecular sieve etc., basic catalyst is as NaOH, KOH, Ca (OH)
2, Mg (OH)
2, sodium methylate, potassium methylate, organic amine etc., specifically do not repeat them here.
When the graftomer of described maleic anhydride and oil-soluble polymers carries out amination or ammonolysis reaction, maleic anhydride can for 1: 0.5-5 with the mol ratio of the ammonia and/or organic amine that contain-NH functional group in-NH.
In the present invention, unless stated otherwise, preferably through removing the amount of step of maleic anhydride for benchmark after the content of described component a does not remove solvent with products therefrom after above-mentioned reaction, also namely the amount of above-mentioned solvent also as a part of component a.
Example as the concrete graftomer of component a has a lot, but scope of the present invention is not by the restriction of these examples:
The amination reaction product of poly-(methyl) vinylformic acid C6-C22 alkyl ester copolymer of maleic anhydride graft and the organic amine containing polyamines; The amination reaction product of maleic anhydride graft C6-C24 alpha-olefin copolymer and the organic amine containing polyamines; The amination reaction product of maleic anhydride grafted polystyrene multipolymer and the organic amine containing polyamines; The amination reaction product of maleated ethylene vinyl acetate copolyme and the organic amine containing polyamines.
Additive of the present invention, except containing except component a, preferably also contains components b.The weight ratio of components b and component a can be 0.01-10: 1, is preferably 0.05-5: 1.
Components b
Components b can be arylamine type oxidation inhibitor and/or hindered phenol type antioxidant.
Described arylamine type oxidation inhibitor as components b can be selected from least one in naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, quinoline.
Wherein naphthylamine derivative includes but not limited to one or more in following material:
Phenyl-a-naphthylamine (oxidation inhibitor T531, antioxidant A);
Phenyl beta naphthylamine (antioxidant d);
N-p-methoxyphenyl alpha-naphthylamine (anti-aging agent 102);
To hydroxyphenyl-beta-naphthylamine (antioxidant D-OH);
Aldol-alpha-naphthylamine (antioxidant A P)
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 '-bis--(Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D (anti-aging agent 4030);
N-p-methylphenyl-N '-(1,3-dimethylbutyl) Ursol D (anti-aging agent 4040);
N, N '-diheptyl Ursol D (anti-aging agent 788);
N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);
N-sec.-propyl-N '-p-methylphenyl Ursol D (anti-aging agent methyl 4010NA);
N, N '-di tolyl p phenylenediamine (anti-aging agent PPD-A);
N, N '-diphenyl-para-phenylene diamine (antioxidant H);
N, N '-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.
Arylamine antioxidant preferred Ursol D class arylamine antioxidant.
Phenol type antioxidant described in components b can be single phenol, bis-phenol or 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 in substituting group, have at least one to be the tertiary butyl, other substituting group can be alkyl or contain heteroatomic substituting group, alkyl is wherein selected from C1-C10 alkyl, 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-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703), various 3,5-di-tert-butyl-hydroxy phenyl propionic ester and 3,5-di-tert-butyl-hydroxy phenyl propionic acid 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).
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) (antioxidant 2246);
4,4 '-methylene radical-bis--(2-methyl-6-tert-butylphenol) (oxidation inhibitor methene 736);
4,4 '-methylene radical-bis--(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-bis--(2-TBP) (oxidation inhibitor 702);
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2,2 '-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert-butylphenol) (oxidation inhibitor 736);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
Two-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.
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.
Here polyphenol can also be the phenol with three hydroxyls in phenyl ring, and such as pyrogallol, gallic acid ester are as methyl gallate, Progallin A, Tenox PG, butyl gallate, gallic acid pentyl ester, the own ester of gallic acid, gallic acid heptyl ester, Stabilizer GA 8, gallic acid ester in the ninth of the ten Heavenly Stems, gallic acid ester in the last of the ten Heavenly stems, lauryl gallate, gallic acid 14 ester, gallic acid hexadecyl ester, gallic acid octadecyl ester, gallic acid octadecylene ester etc.; And gallamide disclosed in Chinese Patent Application No. 200810115581.8 or ammonia salt.The preferred gallic acid-derivate of many phenol type antioxidants especially Tenox PG.
Above-mentioned phenol type antioxidant preferably has a tertiary butyl at least at the bisphenol type oxidation inhibitor at phenolic hydroxyl group ortho position, gallic acid ester, gallamide or ammonia salt in the bisphenol type oxidation inhibitor be particularly connected by methylene radical or sulphur and polyphenol antioxidant.
Components b can also be the composite antioxidant of above-mentioned arylamine type oxidation inhibitor and above-mentioned phenol type antioxidant.The present invention most preferably described 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.
The present inventor surprisingly finds, after described component a and said components b compound, occurs obvious synergistic effect, greatly strengthens the improvement result of oxidation stability of fuel containing biodiesel.
According to use needs, Dresel fuel compositions provided by the invention can also contain other additive, as one or more in metal passivator, detergent-dispersant additive, FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc.
Described metal passivator can be one or more in 124 Triazole and derivative, thiadiazoles and derivative thereof, oxine, ethylenediamine tetraacetic carboxylic acid, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base (Schiffbases), organic polycarboxylic acid and derivative thereof.Because this solvability in biofuel of 124 Triazole is very unexcellent, therefore, in order to increase its solvability in biofuel, usually carry out modification to 124 Triazole, the method for modification mainly through introducing oil-soluble group as long chain hydrocarbon groups in 124 Triazole.Therefore, described 124 Triazole derivative can be the various derivatives that various solvability in biofuel is good compared with 124 Triazole itself.Concrete, one or more in the described 124 Triazole derivative product that can be the ammonium salt that formed of 124 Triazole and aliphatic amide and 124 Triazole, formaldehyde and aliphatic amide be obtained by mannich reaction.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.
The example of described detergent-dispersant additive can comprise succimide, mannich base, PIBA and polyetheramine; Described allyl butyrate imide and/or the polyolefin-based Succinic anhydried of base succinamide ashless dispersant such as number-average molecular weight at 500-3000 and/or the reaction product of succinic acid and amine, if domestic trade names are T151A (mono butonediimide), T151B (mono butonediimide), T152 (two succimide), T154 (two succimide), T155 (poly succimide) and/or T161 (poly succimide) etc.Import additive as OLOA-1200, LZ894, Infineum C9238,9237, Hitec 644 etc.The polyolefin-based phenol of mannich base type ashless dispersant such as number-average molecular weight at 500-3000 and the condensation product of formaldehyde and amine; After described polyethers amine type ashless dispersant such as C8-C30 alkylphenol and oxyethane or propylene oxide adduction again with the product of amine condensation or C8-C30 alcohol and oxyethane or propylene oxide adduction after again with the product of amine condensation; Described polyolefine amine type ashless dispersant such as chlorinatedpolyolefins and amine react the polyolefin-based amine generated.Amine mentioned here is polyamines, especially polyamines polyene all preferably.
The example of described cetane number improver can comprise organic nitrates if isooctyl ester nitrate (T2201), amyl nitrate and superoxide are as ditertiary butyl peroxide; The example of described defoamer can comprise T901, T911, T921 and T922 of being purchased; The example of described static inhibitor can comprise T1502, Stadis 425 and Stadis 450 of being purchased.
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) (THF), 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 the present invention, described Base Diesel can be pure biofuel, described biofuel refers to the fatty acid ester of low-carbon alcohol that grease and low-carbon alcohol (as C1-C5 fatty alcohol) are reacted through transesterify (alcoholysis) and generated, 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 biodiesel composition of the present invention, described Base Diesel also can contain other diesel oil, 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 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 is also referred to as s-generation biofuel, refer to by animal-plant oil generate after hydrogenation and cracking reaction based on C8-C24 alkane, especially with the reaction product that C12-C20 normal paraffin is main component, this hydrocracking biofuel cetane value is high, 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 C1-C18 fatty alcohol, preferably C1-C12 unitary fatty alcohol such as, 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, C6-C14 fatty alcohol-polyoxyethylene ether, C6-C14 fatty alcohol polyoxypropylene ether, C6-C14 alkylphenol polyoxyethylene, C6-C14 alkylphenol polyethenoxy ether, polyoxymethylene dme (Polyoxymethylene Dimethyl Ethers, CH3O (CH2O) xCH3, 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 various components of additive directly can be mixed with Base Diesel, also can first the various components of additive be pre-mixed, to obtain after additive agent mixture again with Base Diesel.The various component of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various order.Mixing condition can various Dresel fuel compositions is not caused to the condition of disadvantageous effect under carry out, such as, can mix at ambient temperature.
The method of raising oxidation stability of biodiesel provided by the invention comprises, and containing in the diesel component of biofuel, adds additive, and described additive contains component a and components b.
The component a of described additive, the components b of additive are identical with the component a in above-mentioned Dresel fuel compositions, components b separately, and its kind and consumption describe above, do not repeat them here.
Under preferable case, the method of raising oxidation stability of biodiesel provided by the invention is also included in the Base Diesel containing biofuel, add other additive, as one or more in detergent-dispersant additive, FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc.
The various component of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various order.Mixing condition can various Dresel fuel compositions is not caused to the condition of disadvantageous effect under carry out, such as, can mix at ambient temperature.
Described biofuel both can be aforementioned pure biofuel, also can be the aforementioned blending fuel containing biofuel.
The present invention is described further for the following examples.
In following examples, the percentage of grafting of sample adopts determination of acid-basetitration, the method of test is specially: graft polymerization matter sample about the 0.5g after precise purification, be dissolved in appropriate dimethylbenzene, be cooled to 70 DEG C after backflow 15min, the potassium hydroxide-ethanol then adding 0.1mol/L carries out saponification backflow, after 1h, use phenolphthalein-thymolphthalein mixture indicator again, use the acetic acid-xylene solution back titration of 0.1mol/L while hot to terminal.The calculation formula of percentage of grafting is:
Wherein, M is maleic anhydride molecule quality (98.06); N
hACfor the concentration (mol/L) of acetic acid-xylene solution; V
0for during blank titration consume the volume (mL) of acetic acid-xylene solution; V for containing titration during product consume the volume (mL) of acetic acid-xylene solution; W is the weight (g) of sample.
Preparation example 1
By 200g polymethacrylate (commercial additive T602, Shanghai Gaoqiao petrochemical industry branch office of China Petrochemical Industry refinery is produced), 20g maleic anhydride and 200g aromatic diluent Oil solvent are placed in one and electric mixer are housed, thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, pass into nitrogen 5-10 minute, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 140-150 DEG C, point 3 instillation reactors from dropping funnel by 2.2g ditertiary butyl peroxide and 20g aromatic diluent oil mixt, drip off in 1.5 hours, keep temperature 140-150 DEG C, back flow reaction 3 hours, strengthen nitrogen flow, 150 DEG C of logical nitrogen 2 hours to remove unreacted maleic anhydride, cool to 50 DEG C, add acetone and separate out product, suction filtration, then acetone elution is used after washing, in vacuum drying oven, constant weight is dried to 80 DEG C time, obtain maleic anhydride-polymethacrylate graft copolymer 108.8g, percentage of grafting is 5.7.
Preparation example 2
By 200g EVA (diesel oil commodity pour point depressant T1804C, Beijing Organic Chemical Plant produces), 12g maleic anhydride and 100g toluene solvant are placed in one and electric mixer are housed, thermometer, reflux condensing tube, in the reactor of dropping funnel and nitrogen ingress pipe, pass into nitrogen 5-10 minute, and in reaction process, keep faint nitrogen gas stream, heated and stirred is warming up to 80 DEG C, 3.0g benzoyl peroxide and 20g toluene mixture are divided from dropping funnel and is added dropwise to reactor 3 times, drip off in 1.5 hours, keep temperature 85 DEG C, react 4 hours, underpressure distillation removes unreacted maleic anhydride and solvent, cool to 50 DEG C, add methyl alcohol and separate out product, suction filtration, after washing, in vacuum drying oven, constant weight is dried to 80 DEG C time, obtain maleic anhydride-EVA graft copolymer 103.2g, percentage of grafting is 4.2.
Embodiment 1-2 is for illustration of the synthesis of component a of the present invention.
Embodiment 1
Embodiment 1 is the aminate of maleic anhydride-polymethacrylate graft copolymer and polyamines.
The N-cocoyl-1 of the maleic anhydride that 50g preparation example 1 is obtained-polymethacrylate graft copolymer, 65g dimethylbenzene and 6.5g, 3-trimethylene diamines is placed in the reactor that is equipped with electric mixer, thermometer, reflux condensing tube, water trap and nitrogen ingress pipe, 100 DEG C of reactions 2 hours, add 4.3g triethylene tetramine again, pass into nitrogen 110 DEG C of points of water and react 3 hours, obtain red oil 118.5g, be component of the present invention, effective concentration is about 50%.
Embodiment 2
Embodiment 2 is aminates of maleated polyethylene-vinyl acetate between to for plastic ester graft copolymer and polyamines.
Obtained for 50g preparation example 2 maleic anhydride-EVA graft copolymer, 60g dimethylbenzene and 3.2g amino dodecane are placed in the reactor that is equipped with electric mixer, thermometer, reflux condensing tube, water trap and nitrogen ingress pipe, 100 DEG C of reactions 1 hour, add 4.9g tetraethylene pentamine again, pass into nitrogen 110 DEG C of points of water and react 4 hours, obtain red oil 108.4g, be component a of the present invention, effective concentration is about 50%.
Performance test
Below in test, sewer oil biofuel used provides by the remarkable new forms of energy company limited of Fujian Longyan, acidification oil biodiesel oil product is provided by Hainan bioenergy company limited of CNOOC, and petroleum diesel is the capital mark B diesel oil that Yanshan Mountain branch office of China Petrochemical Industry produces.
(1) based on pure biofuel, the oxidation stability of the biodiesel composition of diesel oil is tested
Oxidation stability of biodiesel is evaluated 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 Dresel fuel compositions is better, otherwise inductive phase is shorter, illustrates that the oxidation-resistance of Dresel fuel compositions is poorer.The method of SH/T 0248 is adopted to measure cold filter clogging temperature, ASTMD1500 method mensuration colourity.Its test result shows table 1 and table 2, and addition is all in dry agent.
Table 1
Table 2
As can be seen from the data in table 1 and table 2, after adding component a of the present invention, the oxidation stability of biofuel improves, and inductive phase increases, and meanwhile, cold filter clogging temperature reduces, the low-temperature fluidity that biofuel is described also improvement to a certain extent.Ursol D kind antioxidant is (as N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine) relatively good to the improvement result of oxidation stability of biodiesel, but its to biofuel cold filter clogging temperature without improving effect, this compounds has certain toxicity and dyeability simultaneously, join greatly in biofuel with dosage and can cause biofuel color burn, cetane value reduces, such as, in table 1, biofuel adds the N of 1000mg/kg, N '-di-sec-butyl-p-phenyl enediamine's colourity becomes 3.5, in table 2, biofuel adds the N of 1500mg/kg, N '-dioctyl-p-phenylenediamine's colourity becomes 4.0.Although Ursol D kind antioxidant, bisphenol type oxidation inhibitor have certain improvement to oxidation stability of biodiesel, it is more weak that illustrated polymkeric substance is used alone the antioxidant effect when addition is few, but after both compound use, effect is beat all to be strengthened greatly, namely there is obvious synergistic effect in another embodiment of the present invention, has better oxidation stability according to the biodiesel composition of this embodiment.The effect of working in coordination with after component a and amine type prepared by embodiment 1,2 or bisphenol type oxidation inhibitor compound is clearly, also very little on the impact of biofuel color.Although the obtained graftomer of preparation 1 and 2 have and certain fall cold filter clogging temperature effect, little to the improvement result of oxidation stability of biodiesel, simultaneously as synergy after component a and amine type or bisphenol type oxidation inhibitor compound or collaborative effect also not obvious.
(2) oxidation-resistance of concocted diesel oil composition of diesel oil, the test of low-temperature fluidity based on the mixture of biofuel and petroleum diesel, biofuel used is sewer oil biofuel.
The method of EN 15751:2009 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.The method of SH/T 0248 is adopted to measure cold filter clogging temperature, GB/T510 method mensuration condensation point.Test result is all 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, low-temperature fluidity.Component a of the present invention is used alone the low-temperature fluidity and oxidation stability that can improve biodiesel blend fuels, the oxidation stability of the biodiesel composition of the present invention obtained as additive by the mixture of component a and paraphenylene diamine's oxidation inhibitor compound, low-temperature fluidity have and improve greatly, there is synergistic effect in its effect, strengthens than successful when being used alone.After not carrying out the graftomer of amination reaction and oxidation inhibitor compound, successful is not as good with oxidation inhibitor composite effect after amination reaction.
Claims (25)
1. a Dresel fuel compositions, this Dresel fuel compositions contains Base Diesel and additive, it is characterized in that, described Base Diesel contains biofuel, described additive contains component a, and described component a is amination and/or the ammonolysis reaction product of the multipolymer of maleic anhydride graft oil-soluble polymers; The monomer of described oil-soluble polymers is one or more in propylene, butylene, divinyl, vinyl cyanide, vinylformic acid C1-C22 alkyl ester, methacrylic acid C1-C22 alkyl ester, acrylamide, Methacrylamide, vinylbenzene, the alpha-olefin of C6-C24, maleic anhydride, toxilic acid, maleic acid ester, maleimide, fumarate, vinyl pyridine, alkyl vinyl ether.
2. Dresel fuel compositions according to claim 1, wherein, described additive is 500-5000ppm relative to the content of Base Diesel.
3. Dresel fuel compositions according to claim 1, wherein, the percentage of grafting of the polymkeric substance in described component a is 0.5-10, and the number-average molecular weight of oil-soluble polymers is 1000-100000.
4. Dresel fuel compositions according to claim 1, wherein, described component a is obtained by condensation reaction with the ammonia containing-NH functional group and/or organic amine by after maleic anhydride graft oil-soluble polymers.
5. Dresel fuel compositions according to claim 4, wherein, the mol ratio of described maleic anhydride and oil-soluble polymers is 0.005-0.2:1.
6. according to the Dresel fuel compositions in claim 1-5 described in any one, wherein, the monomer of described oil-soluble polymers is ethylenically unsaturated monomers.
7. Dresel fuel compositions according to claim 4, wherein, it is 40-250 DEG C that the reaction conditions of described maleic anhydride graft oil-soluble polymers comprises polymerization temperature, and polymerization time is 1-10 hour.
8. Dresel fuel compositions according to claim 4, wherein, maleic anhydride with in-NH containing the ammonia of-NH functional group and/or the mol ratio of organic amine for 1:0.5-5.
9. Dresel fuel compositions according to claim 1, wherein, described additive is also containing components b, and described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and the weight ratio of components b and component a is 0.01-10:1.
10. Dresel fuel compositions according to claim 9, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, have one or more in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position of a tertiary butyl at least.
11. Dresel fuel compositions according to claim 10, 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.
12. Dresel fuel compositions according to claim 11, 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.
13. Dresel fuel compositions according to claim 1, wherein, described Base Diesel is also containing other diesel oil, and other diesel oil described is petroleum diesel and/or Fiscber-Tropscb synthesis diesel oil, and the volume ratio of described biofuel and other diesel oil is 1:0-99.
14. 1 kinds of methods improving oxidation stability of biodiesel, the method comprises, and containing in the Base Diesel of biofuel, adds additive, described additive contains component a, and described component a is amination or the ammonolysis reaction product of the multipolymer of maleic anhydride graft oil-soluble polymers; The monomer of described oil-soluble polymers is one or more in propylene, butylene, divinyl, vinyl cyanide, vinylformic acid C1-C22 alkyl ester, methacrylic acid C1-C22 alkyl ester, acrylamide, Methacrylamide, vinylbenzene, the alpha-olefin of C6-C24, maleic anhydride, toxilic acid, maleic acid ester, maleimide, fumarate, vinyl pyridine, alkyl vinyl ether.
15. methods according to claim 14, wherein, described additive is 500-5000ppm relative to the content of Base Diesel.
16. methods according to claim 14, wherein, the percentage of grafting of the polymkeric substance in described component a is 0.5-10, and the number-average molecular weight of oil-soluble polymers is 1000-100000.
17. according to the method in claim 14-16 described in any one, and wherein, described component a is obtained by condensation reaction with the ammonia containing-NH functional group and/or organic amine by after maleic anhydride graft oil-soluble polymers.
18. methods according to claim 17, wherein, the mol ratio of described maleic anhydride and oil-soluble polymers is 0.005-0.2:1.
19. methods according to claim 14, wherein, it is 40-250 DEG C that the reaction conditions of described maleic anhydride graft oil-soluble polymers comprises polymerization temperature, and polymerization time is 1-10 hour.
20. methods according to claim 17, wherein, described maleic anhydride with in-NH containing the ammonia of-NH functional group and/or the mol ratio of organic amine for 1:0.5-5.
21. methods according to claim 14, wherein, described additive is also containing components b, and described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant, and the weight ratio of components b and component a is 0.01-10:1.
22. methods according to claim 21, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, have one or more in the hindered phenol type antioxidant at phenolic hydroxyl group ortho position of a tertiary butyl at least.
23. methods according to claim 22, 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.
24. methods according to claim 23, 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.
25. methods according to claim 14, wherein, described Base Diesel is also containing other diesel oil, and other diesel oil described is petroleum diesel and/or Fiscber-Tropscb synthesis diesel oil, and the volume ratio of described biofuel and other diesel oil is 1:0-99.
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