CN101899331B - Diesel composition and method for improving oxidation stability of biodiesel - Google Patents
Diesel composition and method for improving oxidation stability of biodiesel Download PDFInfo
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- CN101899331B CN101899331B CN200910085725.4A CN200910085725A CN101899331B CN 101899331 B CN101899331 B CN 101899331B CN 200910085725 A CN200910085725 A CN 200910085725A CN 101899331 B CN101899331 B CN 101899331B
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- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention provides a diesel composition. The diesel composition contains base diesel and an additive, wherein the base diesel contains biodiesel; the additive contains a component a and a component b; the component a contains alkenyl succinimide and/or alkenyl succinic acid amide; and the component b is an arylamine antioxidant and/or a hindered phenol antioxidant. The additive also optionally contains a component c which is a metal passivator. The invention also provides a method for improving oxidation stability of biodiesel. With the pure biodiesel as the base diesel, the diesel composition provided by the invention has better oxidation stability, and with the blend fuel containing biodiesel as the base diesel, the diesel composition has better stability and detergency and dispersibility.
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, 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-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.
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.Simultaneously to containing the stability of blending fuel of biofuel and the improvement effect of detergent-dispersant performance also not so good.
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 and provide a kind of method improving oxidation stability of biodiesel all preferably.
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 components b, and described component a contains allyl butyrate imide and/or alkenyl succinic acid acid amides; Described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant.
The present invention also provides a kind of method improving oxidation stability of biodiesel simultaneously, the method comprises, containing in the Base Diesel of biofuel, add additive, described additive contains component a and components b, and the component a of described additive contains allyl butyrate imide and/or alkenyl succinic acid acid amides; 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, amazingly between component a and components b occurs synergistic effect, and it is well a lot of that antioxidant effect ratio is used alone oxidation inhibitor.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.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 and 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.
Embodiment
According in Dresel fuel compositions provided by the invention, the content of described additive can be selected in a big way, such as, can be 10-10000ppm relative to the content of Base Diesel, is preferably 50-8000ppm.
The weight ratio of described components b and component a can be 0.01-100: 1, is preferably 0.1-10: 1, more preferably 0.2-5: 1.
Component a
Described component a contains allyl butyrate imide and/or alkenyl succinic acid acid amides
.
In the present invention, described allyl butyrate imide and/or alkenyl succinic acid acid amides can be the various polyolefine containing succimide base and/or alkenyl succinic acid acid amides, and such as described alkenyl succinic acid acid amides is one or more in polyisobutenyl succinamide, polypropylene-base succinamide, random or block polyethylene-propenyl succinamide, polyisopreneyl succinamide.Described allyl butyrate imide is one or more in polyisobutylene succinamide, polypropylene-base succimide, random or block polyethylene-propenyl succimide, polyisopreneyl succimide.These allyl butyrate imide and/or alkenyl succinic acid acid amides can be obtained by various method, such as can be prepared by existing various method, also can be commercially available, 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.Preparation method can obtain for carrying out dehydration reaction by polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried and amine, the mol ratio that the condition of described dehydration reaction comprises amine and polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried total amount is 1: 0.1-2.5, temperature of reaction can be 40-250 DEG C, reaction times can be 1-10 hour, and the medium of reaction is benzene,toluene,xylene, C
9one or more in heavy aromatics, industrial naptha and mineral oil, described C
9the boiling range of heavy aromatics is 159-185 DEG C, and the boiling point of described mineral oil is more than 120 DEG C.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.
Described concentration calculates according to gross weight × 100% of concentration (% by weight)=(water separated in the add-on-reaction of the add-on+amine of polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried and quantity of solvent)/diluent.In the present invention, unless stated otherwise, the content of described component a for benchmark, is also that the amount of above-mentioned solvent is also as a part of component a with the amount of above-mentioned diluent.
Preferred amines and polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried mol ratio are 1: 0.2-1.5, temperature of reaction is 50-200 DEG C, the reaction times is 2-8 hour.Described amine is preferably polyamines, especially preferably polyamines polyene and the amine containing polyamines polyene.
Polyolefin-based succinic acid and polyolefin-based Succinic anhydried are called as " acylating agent " in this area, and this acylating agent and amine can carry out acylation reaction.Different according to reaction conditions, the product of generation is also different, namely generates the product respectively based on allyl butyrate imide or alkenyl succinic acid acid amides.Such as, generate based on the product of alkenyl succinic acid acid amides when low, the amine of temperature of reaction is excessive; Generate based on the product of allyl butyrate imide during temperature of reaction height; Polyolefin-based succinic acid or polyolefin-based Succinic anhydried and amine react mol ratio, and different can to generate monobutane diacid acid amides or mono butonediimide, two succinamide or two succimide and many succinamides or many succimides be respectively main product.
Described polyolefin-based can be various C
3-C
4the multipolymer of monoolefine or the substituting group of homopolymer can be such as the one in polyisobutenyl, polypropylene-base, random or block polyethylene-propenyl, polyisopreneyl.Preferred polyisobutenyl.Wherein polyolefin-based number-average molecular weight is preferably 300-5000, is preferably 500-2500, is more preferably 800-2000; The substitution value of each polyolefin-based upper succinyl is preferably 0.5-1.0.Described polyolefin-based preferably number-average molecular weight is the polyisobutenyl of 500-2500.
Described amine can be the organic amine with structure shown in formula (A):
(1) R
1, R
2can separately for H or carbonatoms be the alkyl of 1-30.
R
1, R
2one of them can be H, and another one can be the alkyl of 1-30 for carbonatoms, or can be the alkyl of 1-30 for carbonatoms, and namely organic amine can be primary amine, also can be secondary amine." alkyl " refers to hydrocarbon substituent, i.e. aliphatics, alicyclic, aromatics and cyclic substituent.The alkyl of aliphatic alkyl can be saturated also can be undersaturated band double bond or triple bond.The wherein aliphatic amide of primary amine 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, one or more in positive two amino dodecanes, 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, one or more in different 20 amine.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.
If secondary amine, wherein R
1, R
2can be identical, also can be different, can be that normal chain alkyl is as methyl separately, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl (lauryl), n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base or n-docosane base, also can be as sec.-propyl with the isomery alkyl of side chain, 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 or Isoeicosane base.
(2) R
1, R
2can be the heteroatomic group of band that H or carbonatoms are 1-30 separately.
Here heteroatomic group is with can be carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino.
Amine containing hydroxyl is thanomin, diethanolamine, N-alkyl ethanol amine, N-vinyl-ethyl alcohol amine, N-alkyl α-amino isopropyl alcohol, N-thiazolinyl α-amino isopropyl alcohol, α-amino isopropyl alcohol, diisopropanolamine (DIPA), Tutofusin tris, 3-amino-1 such as, one or more in 2-propylene glycol, 2-amino-1,3-propanediol, 3-aminopropanol, 4-amino-n-butyl alcohol, 5-amino-1-amylalcohol, 6-amino-1-hexanol and PAP.
Amine containing amido or amino can be polyamine compounds, and polyamines here refers to the amine containing two or more nitrogen-atoms in molecule, if structural formula is H
2n-R
3-NHR
4amine, R here
3the alkylidene group of can be carbon number be 1-30, thiazolinyl, cycloalkyl, aryl or polyether-based; R
4can be hydrogen or carbon number be the alkyl of 1-30.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 A1:
Wherein x1 is the integer of 1-5, R
4can be hydrogen, carbon number is the alkyl of 1-30; R
5hydrogen or methyl.
Polyamines can also be polyamines polyene, and the structural formula of polyamines polyene is H
2n [(CH
2)
x2nH]
y1r
6, wherein, x2 can be the integer of 2-4, be preferably 2 or 3, y1 can be the integer of 1-8, R
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.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; One or more in 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 one or more in phenmethyl (benzyl), styroyl and hydrocinnamyl.Wherein, one or more in 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 A2:
Wherein y2 is the integer of 0 to 5, R
7for C
1-C
24alkyl.Be preferably C
4-C
22alkyl.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, one or more in isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Example with the aryl of phenyl ring comprises one or more in phenmethyl (benzyl), styroyl and hydrocinnamyl.Wherein, preferably y2 is the integer of 1-3 further, R
7for C
6-C
20alkyl or alkenyl.
Piperazine polyamine is as shown in the formula shown in A3:
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 is as 4-amino-2,2,6,6-tetramethylpiperidine, amino-1,2,2,6, the 6-pentamethvl of 4-etc.
Here polyamines can also be such as formula the polyamines containing tertiary amine shown in A4, A5.
Wherein R
9, R
10for or the alkyl of C1-C24, x4 is the integer of 0 to 10.Preferred R
9, R
10be the alkyl of C1-C10 independently of one another, x4 is the integer of 1 to 8.Such as, in N, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dimethyl-Putriscine, N, N-diethyl-Putriscine, N, N-dimethyl-1,6-hexanediamine one or more.
Wherein x5 is the integer of 1 to 10, is preferably the integer of 2 to 6, such as three (2-amino-ethyl) amine.
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.
Preferably polyamines is contained with the amine of acylation reaction in instant component a, further preferably containing the polyamines of at least one primary amine group, especially polyamines polyene or the mixed amine containing polyamines polyene.
The concrete operation method preparing described allyl butyrate imide and/or alkenyl succinic acid acid amides, such as can see US 2 for conventionally known to one of skill in the art, and 992,708, US3,172,892, US3,272,746, US 5,286,823 documents such as grade, are not repeated herein.
For the allyl butyrate imide more preferably mono butonediimide of instant component a; Alkenyl succinic acid acid amides is monobutane diacid acid amides more preferably.
Instant component a further also can containing one or more of other type ashless dispersant known in the field except containing allyl butyrate imide and/or base succinamide, and these ashless dispersants comprise mannich base type ashless dispersant, polyethers amine type ashless dispersant and polyolefine amine type ashless dispersant.The polyolefin-based phenol of described mannich base type ashless dispersant such as molecular-weight average 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 all preferably, especially as said polyamines polyene above.
Components b
Components b is 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 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-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.
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 (Schiff bases), 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.
In the present invention, preferred described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide are formed, the product (such as commodity are called the commercial additive of T551) that 124 Triazole, formaldehyde and aliphatic amide are obtained by mannich reaction, Schiff's base and organic polycarboxylic acid and with one or more in the condensation reaction products (i.e. amides, the ester derivative of organic polycarboxylic acid) of aliphatic amide or fatty alcohol.
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) (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, and described biofuel refers to that grease and low-carbon alcohol are (as C
1-C
5fatty alcohol) fatty acid ester of low-carbon alcohol 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 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 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 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, containing in the diesel component of biofuel, add additive, described additive contains component a and components b, and the component a of described additive contains allyl butyrate imide and/or alkenyl succinic acid acid amides; Described components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant.
Under preferable case, the method for raising oxidation stability of biodiesel provided by the invention, described additive is also containing amount of component b, and described amount of component b is metal passivator, and the weight ratio of the component a of described additive and the amount of component b of described additive is 1: 0.01-1.
The amount of component b of the component a of described additive, the components b of additive and additive is identical with amount of component b 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 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.
Embodiment 1-3 is for illustration of the preparation of allyl butyrate imide and/or alkenyl succinic acid acid amides.
Embodiment 1
In three-necked bottle, add the C that 200 grams of (about 0.14mol) polyisobutylene butanedioic anhydrides (polyisobutene number-average molecular weight is 1200, and saponification value is 80 milligrams of KOH/ gram, and substitution value is 1.0) and 200 grams of boiling ranges are 159-185 DEG C
9heavy aromatics (platinum reforming still bed material); be heated to 80 DEG C stir; slowly add 20.2 grams of (0.138mol) triethylene tetramines; be warming up to 150 DEG C of dehydration reactions 6 hours under nitrogen protection; separate the water of about 2.4 grams; obtain polyisobutene succinimide, recording its nitrogen content by SH/T 0224 method is 1.9 % by weight.Add 25 grams of above-mentioned C again
9heavy aromatics is made into the diluent of about 50 % by weight, as component a (in following table 1, the amount of component a refers to the amount of diluent) for subsequent use.
Embodiment 2
In three-necked bottle, add the C that 18.2 grams of (0.096mol) tetraethylene pentamine, 20 grams of toluene and 200 grams of boiling ranges are 159-185 DEG C
9heavy aromatics (platinum reforming still bed material), heated and stirred to 50 DEG C, in the presence of nitrogen, 200 grams of (0.107mol) polyisobutylene butanedioic anhydrides (polyisobutene number average molecular weight Mn=900, saponification value 60 milligrams of KOH/ gram are slowly added, substitution value is 0.65), be warming up to 110 DEG C of reactions 3 hours, heating steams toluene, reacts 2 hours again at 145 DEG C, obtain polyisobutene succinimide, recording its nitrogen content by SH/T 0224 method is 2.0 % by weight.Then 20 grams of C are added
9heavy aromatics is made into the diluent of about 50 % by weight, for subsequent use as component a.
Embodiment 3
Add 112 grams of (about 0.1mol) polyisobutylene butanedioic anhydrides (polyisobutene number-average molecular weight is 1000) and 120 grams of 150SN mineral oil, be heated to 80 DEG C stir, slowly add 25.5 gram of five ethene hexamine, (mixed amine is by five ethene hexamines to the mixed amine of 10.4 grams of tetraethylene pentamine and 7.1 grams of N-(2-amino-ethyl) piperazine compositions, tetraethylene pentamine and N-(2-amino-ethyl) piperazine mix with mol ratio 1: 0.5: 0.5, about 0.22mol), be warming up to 100 DEG C of dehydration reactions 4 hours under nitrogen protection, obtain alkenyl succinic acid acid amides, add the diluent that 35 grams of above-mentioned 150SN mineral oil are made into about 50 % by weight again, for subsequent use as component a.
Embodiment 4-11
Embodiment 4-11 is for illustration of the composition of additive.
To the component a of embodiment 1-3 and components b and c be selected from according to the weight ratio mixing shown in table 1.
Table 1
| Embodiment | Component a | Components b | Amount of component b | A: b: c (weight ratio) |
| Embodiment 4 | Embodiment 1 | N, N '-di-sec-butyl-p-phenyl enediamine | - | 1∶0.5∶0 |
| Embodiment 5 | Embodiment 1 | N, N '-di-sec-butyl-p-phenyl enediamine | N, N '-two salicylidene-1,2-propylene diamine | 1∶0.5∶0.09 |
| Embodiment 6 | Embodiment 2 | Oxidation inhibitor T511 | - | 1∶3∶0 |
| Embodiment 7 | Embodiment 2 | Oxidation inhibitor T511 | T551 | 1∶3∶0.2 |
| Embodiment 8 | Embodiment 3 | Antioxidant 4020 | - | 1∶2∶0 |
| Embodiment 9 | T151A | Antioxidant 4020 | - | 1∶1∶0 |
| Embodiment 10 | T151A | Antioxidant 2246 | - | 1∶1∶0 |
| Embodiment 11 | T154 | N, N '-di-sec-butyl-p-phenyl enediamine | - | 1∶0.5∶0 |
| Comparative example 1 | Embodiment 1 | - | - | 1∶0∶0 |
| Comparative example 2 | - | N, N '-di-sec-butyl-p-phenyl enediamine | - | 0∶1∶0 |
| Comparative example 3 | Embodiment 2 | - | - | 1∶0∶0 |
| Comparative example 4 | - | T 511 | - | 0∶1∶0 |
| Comparative example 5 | Embodiment 3 | - | - | 1∶0∶0 |
| Comparative example 6 | T151A | - | - | 1∶0∶0 |
| Comparative example 7 | - | Antioxidant 4020 | - | 0∶1∶0 |
| Comparative example 8 | - | Antioxidant 2246 | - | 0∶1∶0 |
| Comparative example 9 | T151A | 2,5 di tert butylhydroquinone | - | 1∶1∶0 |
| Comparative example 10 | - | - | N, N '-two salicylidene-1,2-propylene diamine | 0∶0∶1 |
Performance test
Below in test, Oleum Gossypii semen biofuel used is the biodiesel oil product that Shijiazhuang refinery branch office of China Petrochemical Industry provides, sewer 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) 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.Its test result is shown in table 2 and following table 3.
Table 2
Table 3
As can be seen from the data in table 2 and table 3, compared with comparative example, biodiesel composition provided by the invention has obviously better oxidation stability.Succimide or succinamide (component a) with components b mating reaction after, the oxidation stability of biodiesel composition 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.
As can be seen from comparative example 1,3,5,6 result, add component a separately, the oxidation stability of biofuel does not almost improve, but after the oxidation inhibitor compound use of component a and components b, effect is beat all enhancing, as shown in embodiment 4,6,8,9,10, namely component a can make the performance of oxidation inhibitor greatly strengthen.
Can be found out compared with embodiment 11 by embodiment 4, when using the present invention preferred mono butonediimide as component a, the oxidation stability of gained Dresel fuel compositions than two succimide as better during component a.
Can be found out compared with comparative example 9 by embodiment 9, embodiment 10, the oxidation stability of biodiesel composition of the present invention (embodiment 9) is than use 2, the composition that 5-di-tert-butyl hydroquinone (2,5 di tert butyl hydroquinone) obtains as components b is well a lot; Oxidation stability and the use 2 of biodiesel composition of the present invention (embodiment 10), 5-di-tert-butyl hydroquinone (2,5-di-tert-butyl hydroquinone) composition that obtains as components b is more or less the same, but illustrated components b is bis-phenolic antioxidants, lower than 2,5 di tert butylhydroquinone cost.
By embodiment 4 compared with embodiment 5, embodiment 6 can find out compared with 7, after selecting optional amount of component b, the oxidation stability of gained biodiesel composition strengthens further.
(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 sewer 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 4.
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 4.
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 4.
Adopt the method for SH/T 0175 to measure the amount (unit: mg/100mL) of various concocted diesel oil composition total insoluble substance, thus evaluate their stability.The larger then stability of amount of total insoluble substance is poorer, otherwise if the amount of total insoluble substance is less, stability is better, and its test result is shown in Table 4.
Table 4
As can be seen from the result of table 4, 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.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.
Claims (20)
1. a Dresel fuel compositions, this Dresel fuel compositions contains Base Diesel and additive, it is characterized in that, described Base Diesel contains biofuel, and described additive contains component a and components b, and described component a contains mono butonediimide and/or monobutane diacid acid amides; Described components b is the dialkyl-pphenylenediamines of atomic number of alkyl carbon between 4-10, and the weight ratio of described components b and component a is 0.2-5: 1.
2. Dresel fuel compositions according to claim 1, wherein, the content of described additive in Dresel fuel compositions is 50-10000ppm.
3. Dresel fuel compositions according to claim 1, wherein, described mono butonediimide and/or monobutane diacid acid amides carry out dehydration reaction by polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried and amine and obtain, the mol ratio that the condition of described dehydration reaction comprises amine and polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried total amount is 1: 0.1-2.5, temperature of reaction is 40-250 DEG C, and the reaction times is 1-10 hour.
4. Dresel fuel compositions according to claim 3, wherein, polyolefin-based in described polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried is the one in polyisobutenyl, polypropylene-base, random or block polyethylene-propenyl, polyisopreneyl, described polyolefin-based number-average molecular weight is 300-5000, and described amine is for having the organic amine of structure shown in structural formula (A):
Wherein R
1, R
2be separately the heteroatomic group of band of H, carbonatoms to be the alkyl of 1-30 or carbonatoms be 1-30, described is one or more in carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido, amino with heteroatomic group.
5. Dresel fuel compositions according to claim 4, wherein, described polyolefin-based for number-average molecular weight be the polyisobutenyl of 500-2500, described amine is structural formula is H
2n [(CH
2)
x2nH]
y1r
6polyamines polyene, wherein, x2 is the integer of 2-4, and y1 is the integer of 1-8, R
6the alkyl of to be hydrogen or carbon number be 1-30.
6. Dresel fuel compositions according to claim 1, wherein, described components b is N, N '-diheptyl Ursol D, N, one or more in N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine and N, N '-bis--(1-methylheptyl) Ursol D.
7. Dresel fuel compositions according to claim 1 and 2, wherein, described additive is also containing amount of component b, and described amount of component b is metal passivator.
8. Dresel fuel compositions according to claim 7, wherein, the weight ratio of described component a and described amount of component b is 1: 0.01-1.
9. Dresel fuel compositions according to claim 7, wherein, described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide are formed, the product that 124 Triazole, formaldehyde and aliphatic amide are obtained by mannich reaction, one or more in Schiff's base and organic polycarboxylic acid.
10. Dresel fuel compositions according to claim 1, wherein, described Base Diesel is also containing 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 1: 0-99.
11. 1 kinds of methods improving oxidation stability of biodiesel, the method comprises, and containing in the Base Diesel of biofuel, adds additive, and described additive contains component a and components b, and described component a contains mono butonediimide and/or monobutane diacid acid amides; Described components b is the dialkyl-pphenylenediamines of atomic number of alkyl carbon between 4-10, and the weight ratio of described components b and component a is 0.2-5: 1.
12. methods according to claim 11, wherein, described mono butonediimide and/or monobutane diacid acid amides carry out dehydration reaction by polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried and amine and obtain, the mol ratio that the condition of described dehydration reaction comprises amine and polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried total amount is 1: 0.1-2.5, temperature of reaction is 40-250 DEG C, and the reaction times is 1-10 hour.
13. methods according to claim 12, wherein, polyolefin-based in described polyolefin-based succinic acid and/or polyolefin-based Succinic anhydried is the one in polyisobutenyl, polypropylene-base, random or block polyethylene-propenyl, polyisopreneyl, described polyolefin-based number-average molecular weight is 300-5000, and described amine is for having the organic amine of structure shown in structural formula (A):
Wherein R
1, R
2be separately the heteroatomic group of band of H, carbonatoms to be the alkyl of 1-30 or carbonatoms be 1-30, described is one or more in carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido, amino with heteroatomic group.
14. methods according to claim 13, wherein, described polyolefin-based number-average molecular weight is 500-2500, and described amine is structural formula is H
2n [(CH
2)
x2nH]
y1r
6polyamines polyene, wherein, x2 is the integer of 2-4, and y1 is the integer of 1-8, R
6the alkyl of to be hydrogen or carbon number be 1-30.
15. methods according to claim 11, wherein, described components b is N, N '-diheptyl Ursol D, N, one or more in N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine and N, N '-bis--(1-methylheptyl) Ursol D.
16. methods according to claim 11, wherein, described additive is also containing amount of component b, and described amount of component b is metal passivator.
17. methods according to claim 16, wherein, the weight ratio of described component a and described amount of component b is 1: 0.01-1.
18. methods according to claim 16, wherein, the total amount of the component a of described additive, components b and amount of component b is 50-10000ppm relative to the content of Base Diesel.
19. according to the method in claim 16,17 and 18 described in any one, wherein, described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide are formed, the product that 124 Triazole, formaldehyde and aliphatic amide are obtained by mannich reaction, one or more in Schiff's base and organic polycarboxylic acid.
20. methods according to claim 11, wherein, described Base Diesel is also containing 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 1: 0-99.
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