CN101899331A - 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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- CN101899331A CN101899331A CN2009100857254A CN200910085725A CN101899331A CN 101899331 A CN101899331 A CN 101899331A CN 2009100857254 A CN2009100857254 A CN 2009100857254A CN 200910085725 A CN200910085725 A CN 200910085725A CN 101899331 A CN101899331 A CN 101899331A
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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 the method for a kind of Dresel fuel compositions and raising oxidation stability of biodiesel.
Background technology
Quickening along with vehicle diesel oil trend in the world wide, the demand of diesel oil can be more and more big, and the raising of exhausted day by day and people's environmental consciousness of petroleum resources, promoted countries in the world to accelerate the exploitation paces of diesel oil alternative fuel greatly, biofuel has been subjected to the attention of various countries with its superior environmental-protecting performance and recyclability.
Biofuel (BD100) claims fatty acid methyl ester (Fatty Acid Methyl Ester) again, be that grease and the animal grease with oil plant waterplant such as oil-yielding shrubs fruit, engineering microalgae such as oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistaches, the food and drink wet goods that gives up are made raw material, obtaining through transesterification reaction with alcohols (methyl alcohol, ethanol), is a kind of biofuel of cleaning.That biofuel has is renewable, cleaning and safety three big advantages, and China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment are had very great strategic importance.And China is a net import of oil state at present, and prospective oil is very limited again, and a large amount of Imported oils threaten to the energy security of China; Therefore, the research of biofuel and production have important practical sense to China.
But because raw material and complete processing, the oxidation stability of some biofuel is very poor, using and store and all cause very big difficulty biofuel.The biofuel of oxidation stability difference easily generates following ageing products: 1) insoluble polymer (colloid and greasy filth), and this can cause the engine filter screen to stop up and the squirt pump coking, and causes smoke evacuation to increase, start difficulty; 2) soluble polymer, it can form resinous substance in engine, may cause flame-out and the startup difficulty; 3) aging acid, this can cause the engine metal component corrosion; 4) superoxide, this can cause aging the becoming fragile of rubber components and cause fuel leakage etc.
Europe biofuel standard EN 14214:2003, Australian biofuel standard (Draft2003), New Zealand biofuel standard NZS 7500:2005, Brazilian biofuel standard A NP255 (2003), India biofuel standard I S 15607:2005, South Africa biofuel standard SANS1935:2004 and China's diesel-fuel blending with biofuel (BD100) standard GB/T20828-2007 all the oxidation stability of regulation biofuel be to be not less than 6 hours inductive phase under 110 ℃, measuring method is EN 14112:2003.
As everyone knows, petroleum diesel (is the diesel oil of ordinary meaning, herein in order to distinguish mutually with biofuel, non-hydrocarbon compounds such as alkene, diolefin and the sulfide the special petroleum diesel of introducing), nitride are under the effect of oxygen, generate a series of intermediate oxidation product, and produce insoluble precipitation through condensation.These insoluble particles that generate in the petroleum diesel storage process can have influence on the use properties of fuel, cause filtering system to stop up, and cause the prime the fuel system unit failure; influence oil atomizing; cause incomplete combustion, even in engine, form too much carbon deposit, make spray nozzle clogging.And biofuel is because oxidation stability than petroleum diesel difference, and can increase the weight of the problems referred to above after the petroleum diesel blending.The most significantly performance is to contain the stability of the blending fuel of biofuel and detergent-dispersant performance than petroleum diesel difference.
The problems referred to above can additive solves or alleviation by adding.A kind of mode is to add oxidation inhibitor slowing down its oxidation in pure biofuel, thereby alleviates the harm of ageing products; Another kind of mode is to petroleum diesel or contains in the blending fuel of biofuel and add stablizer and detergent-dispersant additive, with stability and the detergent-dispersant performance that improves blending fuel.Stablizer can stop, weakens or disturb each kinds of oxidation reaction, to suppress oil deterioration, improves its stability; Detergent-dispersant additive can wash down established carbon deposit on the nozzle, and forms protective membrane at nozzle surface, prevents that new carbon deposit from producing, but established sediment in the dispersed oil also simultaneously improves purifier and spray nozzle clogging, and improves exhaust emissions.
CN 1742072A discloses a kind of method that improves storage stability of bio-diesel, this method comprises and is dissolved in 2 of biofuel with containing with what stoste was counted 15-60 weight %, the liquid stoste of 4-di-t-butyl hydroxy toluene joins in the biofuel for the treatment of stabilization, until total solution in biofuel, 2, the concentration of 4-di-t-butyl hydroxy toluene reaches 0.005-2 weight %.
CN 1847368A discloses a kind of method that improves the oxidative stability of biofuel, this method comprises bisphenol type oxidation inhibitor as 4,4`-methylene radical two [2, the 6-DI-tert-butylphenol compounds], 2,2`-methylene radical two [the 6-tertiary butyl-4-methylphenol] joins with the amount of 10-20000ppm (w/w) and treats in the stable biofuel.
CN 1847369A discloses a kind of method that improves the oxidative stability of biofuel, this method comprises that fusing point is less than or equal to 40 ℃ main anti-oxidant to join with the amount of 10-20000ppm (w/w) and treat that in the stable biofuel, wherein said main anti-oxidant contains alkylphenol.
US 2007/113467A1 discloses a kind of fuel composition with improved oxidative stability, said composition contains biofuel and at least a oxidation inhibitor, described oxidation inhibitor is selected from Tenox PG, 1,2,3-trihydroxybenzene, 2, a kind of in 6-di-tert-butyl methyl phenol, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, tocopherol, the quinoline.
Though more than the method for using traditional oxidation inhibitor to improve oxidation stability of biodiesel has certain effect, does not have peace and quiet dispersion effect for biofuel, for the diesel engine that uses pure biofuel, can not improve its detergency.Simultaneously to the stability of the blending fuel that contains biofuel and detergent-dispersant performance to improve effect also not so good.
Summary of the invention
The objective of the invention is for overcome above-mentioned prior art with pure biofuel be basic diesel oil Dresel fuel compositions oxidation stability and detergency is relatively poor and be the stability and the relatively poor shortcoming of detergent-dispersant performance of the Dresel fuel compositions of basic diesel oil with the blending fuel of biofuel and other diesel oil, provide a kind of oxidation stability and detergency all better or the equal Dresel fuel compositions and a kind of method that improves oxidation stability of biodiesel is provided preferably of stability and detergent-dispersant performance.
The invention provides a kind of Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, and wherein, described basic diesel oil 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 that improves oxidation stability of biodiesel simultaneously, this method comprises, in containing the basic diesel oil of biofuel, add additive, described additive contains component a and components b, and described components of additives 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.
Dresel fuel compositions provided by the invention, when with pure biofuel during as basic diesel oil, this Dresel fuel compositions has oxidation stability preferably, the amazing synergistic effect that occurs between component a and the components b, and antioxidant effect will be got well much than independent use oxidation inhibitor.Component a can be regarded as auxiliary antioxidant, and it can make the effect of oxidation inhibitor unexpectedly strengthen greatly.Therefore, when reaching identical oxidation stability and require, the amount of components b in biodiesel composition can significantly reduce, and especially has under certain toxicity or the corrosive situation in components b costliness especially or components b, reduced its consumption and had very big meaning.When with the blending fuel that contains biofuel during as basic diesel oil, the stability of this Dresel fuel compositions and detergent-dispersant performance are all better.Particularly according to preferred implementation provided by the invention, when described additive contains component a, components b and amount of component b simultaneously, because obvious synergistic effect between each additive, the antioxygen and the detergent-dispersant performance of Dresel fuel compositions provided by the invention obviously improve.
Embodiment
In Dresel fuel compositions provided by the invention, described content of additive can be selected in a big way, and for example the content with respect to basic diesel oil can be 10-10000ppm, is preferably 50-8000ppm.
The weight ratio of described components b and component a can be 0.01-100: 1, be preferably 0.1-10: and 1,0.2-5 more preferably: 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 that contain succimide base and/or alkenyl succinic acid acid amides, and for example described alkenyl succinic acid acid amides is one or more in polyisobutenyl succinamide, polypropylene-base succinamide, random or block polyethylene-propenyl succinamide, the polyisopreneyl succinamide.Described allyl butyrate imide is one or more in polyisobutenyl succimide, polypropylene-base succimide, random or block polyethylene-propenyl succimide, the polyisopreneyl succimide.These allyl butyrate imide and/or alkenyl succinic acid acid amides can obtain by the whole bag of tricks, for example can obtain by existing prepared in various methods, also can be commercially available, be T151A (mono butonediimide), T151B (mono butonediimide), T152 (two succimide), T154 (two succimide), T155 (poly succimide) and/or T161 (poly succimide) etc. as homemade trade names.Import additive such as OLOA-1200, LZ894, Infineum C9238,9237, Hitec 644 etc.The preparation method can obtain for carrying out dehydration reaction by polyolefin-based Succinic Acid and/or polyolefin-based Succinic anhydried and amine, the condition of described dehydration reaction comprises that the mol ratio of 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 ℃, reaction times can be 1-10 hour, and the medium of reaction is benzene,toluene,xylene, C
9In heavy aromatics, industrial naptha and the mineral oil one or more, described C
9The boiling range of heavy aromatics is 159-185 ℃, and the boiling point of described mineral oil is more than 120 ℃.Solvent load generally is the 30-150 weight % of monomer material gross weight.For the ease of postorder operation and storage, last product can be made into the diluent of about 50 weight % with the aromatic hydrocarbons thinning oil.
Described concentration calculates according to gross weight * 100% of concentration (weight %)=(water and the quantity of solvent told in the add-on-reaction of the add-on+amine of polyolefin-based Succinic Acid and/or polyolefin-based Succinic anhydried)/diluent.Among the present invention, unless stated otherwise, the content of described component a is benchmark with the amount of above-mentioned diluent, and the amount that also is above-mentioned solvent is also as the part of component a.
Preferred amines and polyolefin-based Succinic Acid and/or polyolefin-based Succinic anhydried mol ratio are 1: 0.2-1.5, temperature of reaction are that 50-200 ℃, reaction times are 2-8 hour.Described amine is preferably polyamines, especially preferred polyamines polyene and the amine that contains polyamines polyene.
Polyolefin-based Succinic Acid and polyolefin-based Succinic anhydried are called as " acylating agent " in this area, this acylating agent and amine can carry out acylation reaction.According to the reaction conditions difference, the product of generation is also different, promptly generates respectively the product based on allyl butyrate imide or alkenyl succinic acid acid amides.For example, temperature of reaction low, generate product when amine is excessive based on the alkenyl succinic acid acid amides; Generate product when temperature of reaction is high based on the allyl butyrate imide; Polyolefin-based Succinic Acid or polyolefin-based Succinic anhydried and amine reaction mol ratio is different, and can to generate monobutane diacid acid amides or mono butonediimide, two succinamide or two succimide and many succinamides or many succimides respectively be main product.
Described polyolefin-based can be various C
3-C
4The multipolymer of monoolefine or the substituting group of homopolymer for example can be a kind of in polyisobutenyl, polypropylene-base, random or block polyethylene-propenyl, the polyisopreneyl.Preferred polyisobutenyl.Wherein polyolefin-based number-average molecular weight is preferably 300-5000, is preferably 500-2500, more preferably 800-2000; Each polyolefin-based substitution value of going up succinyl is preferably 0.5-1.0.The described polyolefin-based polyisobutenyl that number-average molecular weight is 500-2500 that is preferably.
Described amine can be the organic amine with structure shown in the formula (A):
(1) R
1, R
2Can respectively do for oneself H or carbonatoms is 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, can be the alkyl of 1-30 for carbonatoms perhaps, and promptly organic amine can be a primary amine, also can be secondary amine." alkyl " refers to hydrocarbon substituent, i.e. aliphatics, alicyclic, aromatics and cyclic substituent.Aliphatic alkyl can be saturated also can be two keys of undersaturated band or triple-linked alkyl.Wherein primary amine can be that carbonatoms is the aliphatic amide of 1-30, also can be that carbonatoms is the arylamine of 1-30, preferred fat amine, can the aliphatic amide of straight chain in the 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, positive amino dodecane (lauryl amine), positive tetradecy lamine, positive cetylamine, positive stearylamine, positive 20 amine, in positive two amino dodecanes one or more, it also can be the fat primary amine that has side chain, these fat primary amines that have side chain are various isomer of above-mentioned straight chain fat primary amine, Isopropylamine for example, 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, in different 20 amine one or more.Fat primary amine can also be to have the amine of cycloaliphatic ring such as cyclopentamine, hexahydroaniline.Also can be to contain unsaturated double-bond or triple-linked fat primary amine such as oleyl amine (octadecenyl amine), palm oleyl amine (hexadecylene amine) in the carbochain, can also be the primene JM-T, for example Rohm﹠amp; The trade names that Haas company produces are the primene JM-T of Primere 81R.
If secondary amine, wherein R
1, R
2Can be identical, also can be different, can be normal chain alkyl such as methyl separately, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl (lauryl), the n-tetradecane base, n-hexadecyl, the Octadecane base, NSC 62789 base or n-docosane base, also can be isomery alkyl such as the sec.-propyl that has side chain, isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl, isodecyl, the Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base or Isoeicosane base.
(2) R
1, R
2Can respectively do for oneself H or carbonatoms is the heteroatomic group of being with of 1-30.
Here being with heteroatomic group can be carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido or amino.
The amine that contains hydroxyl is thanomin, diethanolamine, N-alkyl ethanol amine, N-vinyl-ethyl alcohol amine, N-alkyl Yi Bingchunan, N-thiazolinyl Yi Bingchunan, Yi Bingchunan, diisopropanolamine (DIPA), Tutofusin tris, 3-amino-1 for example, 2-propylene glycol, 2-amino-1, one or more in ammediol, 3-aminopropanol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol and the 4-amino-phenol.
The amine that contains amido or amino can be polyamine compounds, and the polyamines here refers to contain in the molecule amine of two or more nitrogen-atoms, is H as structural formula
2N-R
3-NHR
4Amine, the R here
3Can be that carbon number is the alkylidene group of 1-30, thiazolinyl, cycloalkyl, aryl or polyether-based; R
4Can be that hydrogen or carbon number are the alkyl of 1-30.For example 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, one or more in the 3-propylene diamine.Can also be as shown in the formula the polyether diamine shown in the A1:
Wherein x1 is the integer of 1-5, R
4Can be that hydrogen, carbon number are the alkyl of 1-30; R
5Be hydrogen or methyl.
Polyamines can also be a 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, is preferably 2 or 3, y1 can be the integer of 1-8, R
6Can be that hydrogen, carbon number are the alkyl of 1-30.For example, work as R
6During for H, described polyamines polyene can be in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, seven ethene, eight amine, propylene diamine, two propylene triamines, three propylene tetramines, tetrapropylene five amine and five propylene hexamines, six propylene, seven amine, seven propylene, eight amine one or more.Work as R
6When being the alkyl of 1-30, be preferably the alkyl of C4-C22 for carbon number.This alkyl can be saturated alkyl, also can be the aryl that has the thiazolinyl of two keys or have phenyl ring.Alkyl can be the straight chain normal chain alkyl, also can be the isomery alkyl that has 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; 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 the Isoeicosane base one or more.The example of thiazolinyl comprises 9-octadecylene base.The example that has an aryl of phenyl ring comprises one or more in phenmethyl (benzyl), styroyl and the hydrocinnamyl.Wherein, more preferably one or more in the alkyl of C6-C20.
The polyamines here can also be the amine of nitrogenous heterocyclic amine such as but not limited to imidazoline type, piperazine type and piperidines type.
The imidazoline type polyamines is as shown in the formula shown in the A2:
Wherein y2 is 0 to 5 integer, R
7Be C
1-C
24Alkyl.Be preferably C
4-C
22Alkyl.This alkyl can be saturated alkyl, also can be the aryl that has the thiazolinyl of two keys or have phenyl ring.Alkyl can be the straight chain normal chain alkyl, also can be the isomery alkyl that has 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 the Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.The example that has an aryl of phenyl ring comprises one or more in phenmethyl (benzyl), styroyl and the hydrocinnamyl.Wherein, further preferred y2 is the integer of 1-3, R
7Be C
6-C
20Alkyl or alkenyl.
Piperazine type polyamines is as shown in the formula shown in the A3:
R wherein
8Be the alkyl of H or C1-C24, x3 is 0 to 5 integer.Preferred typical piperazine type polyamines is N-(2-amino-ethyl) piperazine.
The polyamines of piperidines type such as 4-amino-2,2,6,6-tetramethyl piperidine, 4-amino-1,2,2,6,6-pentamethyl-piperidines etc.
The polyamines here can also be suc as formula the polyamines that contains tertiary amine shown in A4, the A5.
R wherein
9, R
10For or the alkyl of C1-C24, x4 is 0 to 10 integer.Preferred R
9, R
10Be the alkyl of C1-C10 independently of one another, x4 is 1 to 8 integer.N for example, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dimethyl-1, one or more in the 6-hexanediamine.
Wherein x5 is 1 to 10 integer, is preferably 2 to 6 integer, for example three (2-amino-ethyl) amine.
Polyamines can also be that structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene and the condenses of oxyethane, propylene oxide.Wherein, x2 can be the integer of 2-4, is preferably 2 or 3, and y1 can be the integer of 1-8, R
6Can be that hydrogen, carbon number are the alkyl of 1-30.
Amine with acylation reaction among the component a of the present invention preferably contains polyamines, further preferably contains polyamines, the especially polyamines polyene of at least one primary amine group or contains the mixed amine of polyamines polyene.
The concrete operation method for preparing described allyl butyrate imide and/or alkenyl succinic acid acid amides is for conventionally known to one of skill in the art, for example can be referring to US 2,992, and 708, US3,172,892, US3,272,746, US 5,286,823 documents such as grade are not given unnecessary details at this.
The allyl butyrate imide that is used for component a of the present invention is mono butonediimide more preferably; The alkenyl succinic acid acid amides is the monobutane diacid acid amides more preferably.
Component a of the present invention removes and to contain allyl butyrate imide and/or basic succinamide and further also can contain one or more of other type ashless dispersant known in the field, and these ashless dispersants comprise mannich base type ashless dispersant, polyetheramine type ashless dispersant and polyalkene amines type ashless dispersant.Described mannich base type ashless dispersant for example molecular-weight average at the polyolefin-based phenol of 500-3000 and the condensation product of formaldehyde and amine; Described polyetheramine type ashless dispersant for example behind C8-C30 alkylphenol and oxyethane or the 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 polyalkene amines type ashless dispersant is the polyolefin-based amine that generates of chlorinatedpolyolefins and amine reaction for example.Here all preferred polyamines of said amine, said especially as mentioned polyamines polyene.
Components b
Components b is arylamine type oxidation inhibitor and/or hindered phenol type antioxidant.
Can be selected from least a in naphthylamine derivative, diphenylamine derivatives, p-phenylene diamine derivative, the quinoline as the described arylamine type oxidation inhibitor of components b.
Wherein naphthylamine derivative includes but not limited to one or more in the following material:
Phenyl-a-naphthylamine (oxidation inhibitor T531, antioxidant A);
Phenyl beta naphthylamine (antioxidant d);
N-p-methoxyphenyl alpha-naphthylamine (anti-aging agent 102);
To hydroxyphenyl-beta-naphthylamine (antioxidant D-OH);
Aldol-alpha-naphthylamine (antioxidant A P)
2-hydroxyl-1, two [to (beta-naphthylamine) phenoxy group] propane (anti-aging agent C-49) of 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 '-two [to (beta-naphthylamine) phenoxy group] diethyl ether (anti-aging agent C-41-ether).
Wherein, the preferred nonox of naphthylamine derivative, for example one or more in phenyl-a-naphthylamine, Phenyl beta naphthylamine, the N-p-methoxyphenyl alpha-naphthylamine.Especially preferred phenyl-a-naphthylamine.
Wherein diphenylamine derivatives includes but not limited to one or more in the following material:
4,4 '-diamino-diphenylamine (antioxidant A PA);
Right, to '-the dimethoxy pentanoic;
N, N, N ', N '-tetraphenyl diamines methane (anti-aging agent 350);
N, N '-diphenyl ethylene diamine;
N, N '-diphenylprop diamines;
N, N '-di-o-tolyl-ethylene-diamine;
2-hydroxyl-1,3-pair-(to the aniline phenoxy group) propane (anti-aging agent C-47);
2,2 '-two (to the 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 '-two (α, α-Er Jiajibianji) pentanoic (anti-aging agent KY-405);
P-hydroxydiphenylamine (antioxidant A O3920);
Two-(1,1,3,3-tetramethyl-ethyl) pentanoic (anti-aging agent ODA);
4,4 '-dioctyl diphenylamine;
4,4 '-di-iso-octyldiphenylamine;
4,4 '-diheptyl pentanoic;
4,4 '-dinonyldiphenylamine;
Octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines, anti-aging agent OD);
Octyl group/butyl pentanoic (oxidation inhibitor L-57);
Styrenated diphenylamine (antioxidant D FL, DFC-34);
And the mixture of alkylated diphenylamine, wherein alkyl can be heptyl, octyl group, in the nonyl one or more, the example of its Industrial products has U.S. Pennwalt company commodity to be called Pennox A, Pennox A-" S ", American National Instrument polychem company commodity are called Wytox ADP, ADP-X, U.S. Vanderbilt company commodity are called Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, U.S. Uniroyal company 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 among 4 '-dinonyldiphenylamine, octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines), octyl group/butyl pentanoic, the commodity oxidation inhibitor T534.
Wherein p-phenylene diamine derivative's type oxidation inhibitor comprises but is not limited in the following material one or more:
N-phenyl-N '-cyclohexyl Ursol D (antioxidant 4010);
N, N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent 4020);
N, N '-two-(1,4-dimethyl amyl group) Ursol D (anti-aging agent 4030);
N-p-methylphenyl-N '-(1, the 3-dimethylbutyl) Ursol D (anti-aging agent 4040);
N, N '-diheptyl Ursol D (anti-aging agent 788);
N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);
N-sec.-propyl-N '-p-methylphenyl Ursol D (anti-aging agent methyl 4010NA);
N, N '-di tolyl p phenylenediamine (anti-aging agent PPD-A);
N, N '-diphenyl-para-phenylene diamine (antioxidant H);
N, N '-two-(betanaphthyl) Ursol D (antioxidant D NP);
N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5);
N, N '-dioctyl-p-phenylenediamine (anti-aging agent 88);
N, N '-two-(1-methylheptyl) Ursol D (anti-aging agent 288);
N, N '-two-(1-ethyl-3-methyl amyl) Ursol D (anti-aging agent 8L);
N, N '-two-(1, the 4-dimethylbutyl) Ursol D (anti-aging agent 66);
N-octyl group-N '-diphenyl-para-phenylene diamine (anti-aging agent 688);
N-isobutyl--N '-diphenyl-para-phenylene diamine (anti-aging agent 5L);
N, N '-dimethyl-N, N '-two-(1-first propyl group) Ursol D (anti-aging agent 32);
N-(p-methylphenyl alkylsulfonyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent TPPD);
N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent G-1);
N-(3-anilino phenyl) Methacrylamide;
N-hexyl-N '-diphenyl-para-phenylene diamine;
The preferred dialkyl group Ursol D of p-phenylene diamine derivative's type oxidation inhibitor, the dialkyl group Ursol D of preferred alkyl carbonatoms between 4-10 especially, as: N, N '-diheptyl Ursol D; N, N '-di-sec-butyl-p-phenyl enediamine; N, N '-dioctyl-p-phenylenediamine; N, one or more in N '-two-(1-methylheptyl) Ursol D.
Quinoline wherein includes but not limited to:
6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W);
6-phenyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (anti-aging agent PMQ);
6-dodecyl-2,2,4-trimethylammonium-1,2-dihyaroquinoline (antioxidant D D);
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD, anti-aging agent 124);
Pentanoic and acetone low-temp reaction product (anti-aging agent BAS);
Pentanoic and acetone high-temperature reaction product (antioxidant BLE);
The reaction product of pentanoic and acetone and aldehyde (anti-aging agent BXA);
The reaction product of Phenyl beta naphthylamine and acetone (antioxidant A PN, antioxidant A M).
The preferred Ursol D class of arylamine antioxidant arylamine antioxidant.
Phenol type antioxidant described in the components b can be single phenol, bis-phenol or polyphenol, also can be the mixture of their arbitrary proportions.
Wherein single phenol be have a phenyl ring/and phenyl ring on the phenol of the replacement of a hydroxyl is arranged, and have at least one to be the tertiary butyl in the substituting group, other substituting group can be alkyl or contain heteroatomic substituting group that alkyl wherein is selected from C
1-C
10Alkyl, for example methyl, ethyl, allyl group, normal-butyl, sec-butyl, nonyl etc. contain heteroatomic substituting group and are selected from methyl, methylol, nitrogenous substituting group such as the alpha, alpha-dimethyl aminomethyl that oxygen containing substituting group such as methoxyl group, methoxyl group replace.For example can be single phenol of following structure: o-tert-butylphenol, p-tert-butylphenol, the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol; The 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol; 2,4-DI-tert-butylphenol compounds, 2,5-DI-tert-butylphenol compounds, 2,6 di t butyl phenol; 2,5-di-tert-butyl-4-methy phenol, 2,6 di tert butyl 4 methyl phenol (BHT, oxidation inhibitor T501), 4,6-di-t-butyl-2-methylphenol; 2,4,6-tri-butyl-phenol, 2 allyl 4 methyl 6 tert butyl phenol, 2-sec-butyl-4-tert.-butyl phenol, 4-sec-butyl-2,6-DI-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 acid amides etc.
Wherein single phenol oxidation inhibitor preferably has a tertiary butyl at least at phenolic hydroxyl group adjacent single phenol that is obstructed, as:
The 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2, the 4-xylenol, 2, the 6-DI-tert-butylphenol compounds, 2,6-di-tert-butyl-4-methy phenol (BHT, oxidation inhibitor T501), 2,4, the 6-tri-butyl-phenol, 4-sec-butyl-2, the 6-DI-tert-butylphenol compounds, 4-nonyl-2, the 6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-ethylphenol (oxidation inhibitor DBEP), butylhydroxy anisole (BHA), 2,6-di-t-butyl-α-methoxyl group-p-cresol (BHT-MO), 4-methylol-2,6-DI-tert-butylphenol compounds (oxidation inhibitor 754), 2, one or more in the 6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol (oxidation inhibitor 703).
Bis-phenol is meant the phenol type antioxidant that is linked to each other by sulphur or carbon atom by two single phenol, for example:
(1) bis-phenol that links to each other by carbon atom
4,4 '-isopropylidene bis-phenol (dihydroxyphenyl propane);
2,2 '-two-(3-methyl-4 hydroxy phenyl) propane (bisphenol-c);
4,4 '-dihydroxybiphenyl (oxidation inhibitor DOD);
4,4 '-dihydroxyl-3,3 ', 5,5 '-four-tertiary butyl biphenyl (oxidation inhibitor 712);
2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol) (oxidation inhibitor bis-phenol 2246);
4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol) (oxidation inhibitor methene 736);
2,2 '-methylene radical-two-(4-ethyl-6-tert.-butyl phenol) (oxidation inhibitor 425);
2,2 '-methylene radical-two-(4-methyl-6-cyclohexylphenol) (oxidation inhibitor ZKF);
2,2 '-methylene radical-two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol] (oxidation inhibitor WSP);
2,2 '-methylene radical-two-(6-α-Jia Jibianji p-cresol);
4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-two-(2-tert.-butyl phenol) (oxidation inhibitor 702);
2,2 '-ethylidene-two-(4-methyl-6-tert butyl phenol);
4,4 '-ethylidene-two-(2-methyl-6-tert butyl phenol);
4,4 '-ethylidene-two-(2,6 di t butyl phenol);
4,4 '-butylidene-two-(the 6-tertiary butyl-meta-cresol) (oxidation inhibitor BBM, oxidation inhibitor TCA);
4,4 '-isobutylidene-two-(2,6 di t butyl phenol) etc.
(2) bis-phenol that links to each other by sulphur atom
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2, and 2 '-thiobis-(4-methyl-6-tert butyl phenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert butyl phenol) (oxidation inhibitor 736);
4,4 '-thiobis-(5-methyl-2-tert.-butyl phenol);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
2,2 '-thiobis-(4-octyl phenol) etc.
(3) link to each other by carbon atom but contain heteroatomic bis-phenol
N, N '-hexamethylene is two-(3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) (oxidation inhibitor 1098);
Hexylene glycol two [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 259);
Two-(3,5-di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine (oxidation inhibitor BPP);
Two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S);
2,2 '-sulfurous ethyl glycol two [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (oxidation inhibitor 1035);
Triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (oxidation inhibitor 245) etc.
Bisphenol type oxidation inhibitor is preferably by the bis-phenol that has at least a tertiary butyl to link to each other by methylene radical or sulphur at phenolic hydroxyl group adjacent list phenol, for example:
2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol) (antioxidant 2246);
4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol) (oxidation inhibitor methene 736);
4,4 '-methylene radical-two-(2,6 di t butyl phenol) (oxidation inhibitor T511);
4,4 '-methylene radical-two-(2-tert.-butyl phenol) (oxidation inhibitor 702);
4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1);
2, and 2 '-thiobis-(4-methyl-6-tert butyl phenol) (antioxidant 2246-S);
4,4 '-thiobis-(2-methyl-6-tert butyl phenol) (oxidation inhibitor 736);
4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300);
Two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether (oxidation inhibitor methene 4426-S) etc.
Described polyphenol antioxidant refers in the molecule macromole oxidation inhibitor by at least three single phenolic group groups preferably by having a tertiary butyl at least at the polyphenol that phenolic hydroxyl group adjacent list phenolic group group forms, and especially preferably has two tertiary butyls at the phenolic hydroxyl group adjacent polyphenol that is obstructed, for example:
1,3,5-trimethylammonium-2,4,6-three-(4 '-hydroxyl-3 ', 5 '-di-t-butyl) benzene (antioxidant 330);
Three [2-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl oxygen ethyl] isocyanic ester (oxidation inhibitor 3125);
Four (3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester (antioxidant 1010);
1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) (antioxidant 3114);
1,1,3-three-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA);
1,3,5-three (2, the 6-dimethyl-4-tertiary butyl-3-hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) (oxidation inhibitor 1790);
Two [3,3-pair-(3 '-tertiary butyl-4 '-hydroxybenzyl) butyric acid] glycol ester etc.
The polyphenol here can also be the phenol that has three hydroxyls in the phenyl ring, for example pyrogallol, gallic acid ester such as methyl gallate, Progallin A, Tenox PG, gallic acid butyl ester, 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 esters, gallic acid hexadecyl ester, gallic acid octadecyl ester, gallic acid octadecylene ester etc.; And Chinese patent application number 200810115581.8 disclosed gallamides or ammonia salt.The preferred gallic acid-derivate of polyphenol type oxidation inhibitor is Tenox PG especially.
Above-mentioned phenol type antioxidant preferably has a tertiary butyl at least at phenolic hydroxyl group adjacent bisphenol type oxidation inhibitor, particularly passes through gallic acid ester, gallamide or ammonia salt in continuous bisphenol type oxidation inhibitor of methylene radical or sulphur and the polyphenol antioxidant.
Components b can also be the composite antioxidant of above-mentioned arylamine type oxidation inhibitor and above-mentioned phenol type antioxidant.
The also optional amount of component b that contains of Dresel fuel compositions provided by the invention.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 further is preferably 1: 0.02-0.2.
Described amount of component b can be reacted or the bonded metal chelator with the metal passivator of metallic surface reaction and/or with metal or metal ion for various.
Concrete, described amount of component b can be 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 the derivative thereof one or more.Because this solvability in biofuel of 124 Triazole is very unexcellent, therefore, in order to increase its solvability in biofuel, usually 124 Triazole is carried out modification, the method for modification is mainly by introducing oil-soluble group such as long chain hydrocarbon groups in 124 Triazole.Therefore, described 124 Triazole derivative can be various solvabilities in the biofuel various derivatives good than 124 Triazole itself.Concrete, one or more in the described 124 Triazole derivative product that can be 124 Triazole obtain by mannich reaction with the ammonium salt of aliphatic amide formation and 124 Triazole, formaldehyde and aliphatic amide.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 such as methyl ethyl diketone, described 'beta '-ketoester such as etheric acid monooctyl ester.Described Schiff's base can be N, N '-two salicylidenes-1, N, N '-two salicylidene-1,2-propylene diamine, N, N '-two salicylidene-1,2-cyclohexanediamine, N, one or more in N '-two salicylidenes-N '-methyl two propylene triamines.Described organic polycarboxylic acid and derivative thereof for example can be one or more in citric acid, tartrate, oxysuccinic acid, succsinic acid (Succinic Acid), toxilic acid, phytic acid etc. and the derivative thereof.
Among the present invention, preferred described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction (for example commercial additive of commodity T551 by name), Schiff's base and organic polycarboxylic acid and with the condensation reaction products (being amides, the ester derivative of organic polycarboxylic acid) of aliphatic amide or Fatty Alcohol(C12-C14 and C12-C18) in one or more.
According to using needs, Dresel fuel compositions provided by the invention can also contain other additive, as in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, the emulsion splitter etc. one or more.
The preparation of Dresel fuel compositions provided by the invention is simple, and each component that only need form Dresel fuel compositions mixes and gets final product.Can directly each additive component be mixed with basic diesel oil, also can earlier various additive components be mixed, obtain additive after, again the gained additive is mixed with basic diesel oil.For easy to operate, when various additive components are mixed, can in the presence of solvent, carry out, the solvent here can be polar solvent such as N, dinethylformamide (DMF), 1, one or more in 4-dioxane, tetrahydrofuran (THF) (THF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidone and the methyl-2-pyrrolidone.Also can be especially aromatic hydrocarbons such as benzene,toluene,xylene, aromatic hydrocarbons thinning oil and composition thereof of hydro carbons, can also be biofuel.
In the present invention, described basic diesel oil can be pure biofuel, and described biofuel is meant that grease and low-carbon alcohol are (as C
1-C
5Fatty Alcohol(C12-C14 and C12-C18)) fatty acid ester of low-carbon alcohol that generates through transesterify (alcoholysis) reaction is generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.
Described trans-esterification processes can be the processing method that any known or unknown transesterification reaction of passing through grease and low-carbon alcohol obtains biofuel, for example acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, or the like.Specifically can be with reference to documents such as CN1473907A, DE3444893, CN1472280A, CN1142993C, CN1111591C, CN1594504A.
Described grease has general sense well known in the art, is the general name of oil and fat, and main component is a fatty acid triglycercide.General normal temperature is the oil that is called of liquid, and normal temperature is solid or the semisolid fat (abbreviation fat) that is called.Described grease comprises vegetables oil and animal oil, in addition, also comprise from the oil plant in the materials such as microorganism, algae, even can also be waste oil, for example the used grease of acidifying wet goods or the rotten grease of waste cooking oil, sewer oil, swill oil, grease factory.Described vegetables oil can be that herbaceous plant oil also can be xylophyta oil, as the oil of peanut oil, Semen Maydis oil, Oleum Gossypii semen, rape seed oil, soybean oil, plam oil, Thistle oil, linseed oil, Oleum Cocois, Oak Tree oil, Prunus amygdalus oil, walnut oil, Viscotrol C, sesame oil, sweet oil, Yatall MA (Tall Oil), sunflower oil, curcas oil, tung oil, shinyleaf yellowhorn oil, coptis wood oil, halophytes such as plants such as kostelezkya virginica, cyperus esculentus.Described animal oil can be lard, chicken fat, duck oil, goose oil, sheep oil, house oil, butter, haco oil, shark wet goods.
In biodiesel composition of the present invention, described basic diesel oil also can contain other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of described biofuel and other diesel oil is preferably 1: 2-99.
Wherein petroleum diesel is meant boiling range the cut 160-380 ℃ between of crude oil (oil) after devices such as the various refining process decompression as usual of refinery, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking are handled, and the compression ignition engine fuel that satisfies solar oil standard GB 252-2000 or derv fuel oil standard GB/T 19147-2003 that forms through allotment.
The fischer-tropsch combined diesel oil refers to that mainly with Sweet natural gas or coal be GTL diesel oil (Gas To Liquid) or the CTL diesel oil (Coal To Liquid) that raw material funds-Tuo (F-T) synthetic method is produced, and can also be vegetable fibre funds-Tuo synthetic method and the BTL diesel oil (Biomass To Liquid) produced.The fischer-tropsch combined diesel oil is substantially free of sulphur and aromatic hydrocarbons, be very clean fuel, but its oilness extreme difference improve greatly with biofuel blending back oilness, but the possible variation of the oxidation stability of tempered oil, the blending fuel that therefore contains biofuel also needs to add oxidation inhibitor.
The hydrocracking biofuel is also referred to as s-generation biofuel, be meant by animal-plant oil through generate after hydrogenation and the cracking reaction with C
8-C
24Alkane is main, especially with C
12-C
20Normal paraffin is the reaction product of main component, this hydrocracking biofuel cetane value height, and sulphur and aromaticity content are extremely low, can reduce the discharging of diesel engine pollutent greatly as diesel motor fuel or blending component.
Contain oxygen diesel oil blending component and be meant and can be deployed into the oxygenatedchemicals that meets certain code requirement or the mixture of oxygenatedchemicals with various diesel-fuels, normally alcohols and ethers or its mixture, alcohols is C for example
1-C
18Fatty Alcohol(C12-C14 and C12-C18), preferred C
1-C
12Unitary fatty alcohol is 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) wait and composition thereof.
Among the present invention, described basic diesel oil is when containing the blending fuel of biofuel, described Dresel fuel compositions can obtain by described additive, biofuel and other diesel oil are directly mixed, and also can earlier described additive be mixed with biofuel, and then obtain with other diesel oil blending.The various components of additive directly can be mixed with basic diesel oil, also can be earlier the various components of additive be pre-mixed, obtain behind the additive agent mixture again and basic diesel oil.The various components of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various orders.The blended condition can be carried out under the various conditions that Dresel fuel compositions do not caused disadvantageous effect, for example, can mix at ambient temperature.
The method of raising oxidation stability of biodiesel provided by the invention comprises, in containing the diesel component of biofuel, add additive, described additive contains component a and components b, and described components of additives 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.
Under the preferable case, the method for raising oxidation stability of biodiesel provided by the invention, described additive also contains amount of component b, and described amount of component b is a metal passivator, and the weight ratio of described components of additives a and described components of additives c is 1: 0.01-1.
Described components of additives a, components of additives b and components of additives c are identical with component a, components b and amount of component b in the above-mentioned Dresel fuel compositions separately, and its kind and consumption are described at preamble, do not repeat them here.
Under the preferable case, the method of raising oxidation stability of biodiesel provided by the invention also is included in the basic diesel oil that contains biofuel, add other additive, as in FLOW IMPROVERS, cetane number improver, static inhibitor, sanitas, rust-preventive agent, the emulsion splitter etc. one or more.
The various components of additive and the order by merging of biofuel and other diesel oil are not particularly limited, can mix with various orders.The blended condition can be carried out under the various conditions that Dresel fuel compositions do not caused disadvantageous effect, for example, can mix at ambient temperature.
Described biofuel both can be aforementioned pure biofuel, also can be the aforementioned blending fuel that contains biofuel.
The following examples will the present invention is described further.
Embodiment 1-3 is used to illustrate the preparation of allyl butyrate imide and/or alkenyl succinic acid acid amides.
Embodiment 1
In three-necked bottle, adding 200 gram (about 0.14mol) polyisobutylene butanedioic anhydrides (the polyisobutene number-average molecular weight is 1200, and saponification value is 80 milligrams of KOH/ grams, and substitution value is 1.0) and 200 gram boiling ranges are 159-185 ℃ C
9Heavy aromatics (platinum reforming still bed material); being heated to 80 ℃ stirs; slowly add 20.2 gram (0.138mol) triethylene tetramines; under nitrogen protection, be warming up to 150 ℃ of dehydration reactions 6 hours; tell the water of about 2.4 grams; obtain polyisobutene succinimide, recording its nitrogen content with SH/T 0224 method is 1.9 weight %.Add the above-mentioned C of 25 grams again
9Heavy aromatics is made into the diluent of about 50 weight %, as component a standby (amount of component a is meant the amount of diluent in the following table 1).
Embodiment 2
In three-necked bottle, adding 18.2 gram (0.096mol) tetraethylene pentamine, 20 gram toluene and 200 gram boiling ranges are 159-185 ℃ C
9Heavy aromatics (platinum reforming still bed material), heated and stirred to 50 ℃, in the presence of nitrogen, slowly add 200 gram (0.107mol) polyisobutylene butanedioic anhydrides (polyisobutenyl number-average molecular weight Mn=900,60 milligrams of KOH/ grams of saponification value, substitution value is 0.65), be warming up to 110 ℃ of reactions 3 hours, heating steams toluene, reacts 2 hours at 145 ℃ again, obtain polyisobutene succinimide, recording its nitrogen content with SH/T 0224 method is 2.0 weight %.Add 20 gram C then
9Heavy aromatics is made into the diluent of about 50 weight %, and a is standby as component.
Embodiment 3
Add 112 gram (about 0.1mol) polyisobutylene butanedioic anhydrides (the polyisobutene number-average molecular weight is 1000) and 120 gram 150SN mineral oil; being heated to 80 ℃ stirs; slowly add 25.5 grams, five ethene hexamines; 10.4 (mixed amine is by five ethene hexamines to the mixed amine that gram tetraethylene pentamine and 7.1 gram N-(2-amino-ethyl) piperazines are formed; tetraethylene pentamine and N-(2-amino-ethyl) piperazine mixes with mol ratio at 1: 0.5: 0.5; about 0.22mol); under nitrogen protection, be warming up to 100 ℃ of dehydration reactions 4 hours; obtain the alkenyl succinic acid acid amides; add the diluent that the above-mentioned 150SN mineral oil of 35 grams is made into about 50 weight % again, a is standby as component.
Embodiment 4-11
Embodiment 4-11 is used to illustrate the composition of additive.
Mix according to the weight ratio shown in the table 1 being selected from the component a of embodiment 1-3 and components b and c.
Table 1
Performance test
Below in the test, used Oleum Gossypii semen biofuel is the biofuel product that Shijiazhuang refinery branch office of China Petrochemical Industry provides, used sewer oil biofuel provides by the remarkable new forms of energy in Longyan, Fujian company limited, and petroleum diesel is the capital mark B diesel oil that Yanshan Mountain branch office of China Petrochemical Industry produces.
(1) evaluates oxidation stability of biodiesel the inductive phase under pure biofuel is measured 110 ℃ as the oxidation stability test of the biodiesel composition of basic diesel oil with EN14112:2003 method (Racimat method), use the 743 type oil oxidative stability determinators of instrument as Switzerland Wan Tong company, wherein, inductive phase is long more to illustrate that then the oxidation-resistance of Dresel fuel compositions is good more, otherwise short more illustrate that then the oxidation-resistance of Dresel fuel compositions is poor more inductive phase.Its test result is shown in table 2 and the following table 3.
Table 2
Table 3
Data from table 2 and table 3 are compared with Comparative Examples as can be seen, and biodiesel composition provided by the invention has obviously better oxidation stability.Succimide or succinamide (component a) with the components b mating reaction after, the oxidation stability of biodiesel composition will be got well much than the effect sum of independent use component a, components b, this shows to have occurred synergy clearly between component a, the b astoundingly.After optional amount of component b added, effect further strengthened.
By Comparative Examples 1,3,5,6 results as can be seen, add component a separately, the oxidation stability of biofuel does not almost improve, but after the compound use of the oxidation inhibitor of component a and components b, the beat all enhancing of effect, shown in embodiment 4,6,8,9,10, promptly component a can make the performance of oxidation inhibitor strengthen greatly.
Compare as can be seen with embodiment 11 by embodiment 4, when using the preferred mono butonediimide of the present invention as component a, the oxidation stability of gained Dresel fuel compositions is better during as component a than two succimides.
Compare as can be seen with Comparative Examples 9 by embodiment 9, embodiment 10, the oxidation stability of biodiesel composition of the present invention (embodiment 9) is than using 2,5-di-tert-butyl hydroquinone (2,5 di tert butyl hydroquinone) is well a lot of as the components b resultant composition; The oxidation stability of biodiesel composition of the present invention (embodiment 10) and use 2,5-di-tert-butyl hydroquinone (2, the 5-di-tert-butyl hydroquinone) is more or less the same as the components b resultant composition, but components b shown in the present is a bis-phenolic antioxidants, lower than 2,5 di tert butylhydroquinone cost.
By embodiment 4 compare with embodiment 5, embodiment 6 compares as can be seen with 7, select optional amount of component b for use after, the oxidation stability of gained biodiesel composition further strengthens.
(2) with the test as oxidation-resistance, stability and the detergent-dispersant performance of the concocted diesel oil composition of basic diesel oil of the mixture of biofuel and petroleum diesel, used biofuel is the sewer oil biofuel.
Adopt the method for Pr EN15751:2008 to measure each Dresel fuel compositions, petroleum diesel and concocted diesel oil inductive phase under 110 ℃ respectively, use the 743 type oil oxidative stability determinators of instrument as Switzerland Wan Tong company, inductive phase is long more to illustrate that then the oxidation-resistance of biodiesel composition is good more, otherwise short more illustrate that then the oxidation-resistance of biodiesel composition is poor more inductive phase.Its test result is shown in Table 4.
Adopt derv fuel oil detergency determinator (by the production of petrochemical industry instrument company of Lanzhou dimension section, L-3 type) to measure the detergent-dispersant performance of each concocted diesel oil composition respectively according to the disclosed method of CN 1940524A.Its concrete operations comprise: the weight of the sediment trap of weighing one cleaning, then this sediment trap is heated to 250 ℃, afterwards with the speed of 2 ml/min with the concocted diesel oil combined stream to the working face of sediment trap, form the even mobile oil film of one deck, after 50 minutes, the oil film on the sediment trap working face is toasted under 180 ℃ high temperature, oxidation generates one deck paint film, then this sediment trap be impregnated in the normal heptane 2 minutes, weighing is attached with the weight of sedimental sediment trap then, and the weightening finish of record sediment trap, be the deposition A (unit: mg) of sediment trap.Can evaluate the detergent-dispersant performance of concocted diesel oil composition according to the size of deposition, if the big more then detergent-dispersant performance of deposition is poor more, otherwise if the more little then detergent-dispersant performance of deposition is good more.Its test result is shown in Table 4.
In addition, adopt the detergent-dispersant performance of the disclosed tinsel sedimentation of CN1351132A according to the evaluation method evaluation concocted diesel oil composition of above-mentioned biofuel detergent-dispersant performance, the weightening finish that obtains steel disc is the deposition B (mg) of sediment trap.According to the detergent-dispersant performance of the size of deposition evaluation Dresel fuel compositions, if the big more then detergent-dispersant performance of deposition is poor more, otherwise if the more little then detergent-dispersant performance of deposition is good more.Its test result is shown in Table 4.
The method of employing SH/T 0175 is measured the amount (unit: mg/100mL), thereby evaluate their stability of various concocted diesel oil composition total insoluble substances.The big more then stability of the amount of total insoluble substance is poor more, otherwise if the more little then stability of amount of total insoluble substance is good more, its test result is shown in Table 4.
Table 4
By the result of table 4 as can be seen, add biofuel after, the oxidation stability, stability and the detergent-dispersant performance that contain the blending fuel of biofuel are compared all variation with petroleum diesel.The oxidation stability, stability and the dispersiveness that contain the biodiesel composition of the present invention that the mixture of component a and components b or component a and components b and amount of component b obtains as additive all have significantly to be improved, synergistic effect appears in component a and components b effect, and its effect obviously strengthens than Comparative Examples effect.And when only containing phenol type or amine type oxidation inhibitor as oxidation inhibitor, the stability of gained biofuel blending fuel and detergent-dispersant performance improve DeGrain.
Claims (28)
1. Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, it is characterized in that, described basic diesel oil 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.
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, the weight ratio of described components b and component a is 0.01-10: 1.
4. Dresel fuel compositions according to claim 3, wherein, the weight ratio of described components b and component a is 0.2-5: 1.
5. Dresel fuel compositions according to claim 1, wherein, described allyl butyrate imide and/or alkenyl succinic acid acid amides carry out dehydration reaction by polyolefin-based Succinic Acid and/or polyolefin-based Succinic anhydried and amine and obtain, the condition of described dehydration reaction comprises that the mol ratio of 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 ℃, and the reaction times is 1-10 hour.
6. Dresel fuel compositions according to claim 5, wherein, polyolefin-based in described polyolefin-based Succinic Acid and/or the polyolefin-based Succinic anhydried is a kind of in polyisobutenyl, polypropylene-base, random or block polyethylene-propenyl, the polyisopreneyl, described polyolefin-based number-average molecular weight is 300-5000, and described amine is the organic amine of described amine for having structure shown in the structural formula (A):
R wherein
1, R
2Respectively do for oneself H, carbonatoms is that alkyl or the carbonatoms of 1-30 is the heteroatomic group of being with of 1-30, and described to have heteroatomic group be in carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido, the amino one or more.
7. Dresel fuel compositions according to claim 6, wherein, described polyolefin-based for number-average molecular weight is the polyisobutenyl of 500-2500, described amine is that structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene, wherein, x2 is the integer of 2-4, y1 is the integer of 1-8, R
6Be that hydrogen or carbon number are the alkyl of 1-30.
8. according to any described Dresel fuel compositions among the claim 1-4, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, have a tertiary butyl one or more in phenolic hydroxyl group adjacent hindered phenol type antioxidant at least.
9. Dresel fuel compositions according to claim 8, wherein, described components b be the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 with the bisphenol type oxidation inhibitor that links to each other by methylene radical or sulphur in one or more.
10. Dresel fuel compositions according to claim 9, 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 '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-tert.-butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
11. according to any described Dresel fuel compositions among the claim 1-4, wherein, described additive also contains amount of component b, described amount of component b is a metal passivator.
12. Dresel fuel compositions according to claim 11, wherein, the weight ratio of described component a and described amount of component b is 1: 0.01-1.
13. Dresel fuel compositions according to claim 11, wherein, described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction, one or more in Schiff's base and the organic polycarboxylic acid.
14. Dresel fuel compositions according to claim 1, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of described biofuel and other diesel oil is 1: 0-99.
15. method that improves oxidation stability of biodiesel, this method comprises, in containing the basic diesel oil of biofuel, adds additive, 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.
16. method according to claim 15, wherein, the total amount of described components of additives a, components b and amount of component b is 50-10000ppm with respect to the content of basic diesel oil.
17. method according to claim 16, wherein, the weight ratio of described components b and component a is 0.01-10: 1.
18. method according to claim 17, wherein, the weight ratio of described components b and component a is 0.2-5: 1.
19. method according to claim 15, wherein, described allyl butyrate imide and/or alkenyl succinic acid acid amides carry out dehydration reaction by polyolefin-based Succinic Acid and/or polyolefin-based Succinic anhydried and amine and obtain, the condition of described dehydration reaction comprises that the mol ratio of 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 ℃, and the reaction times is 1-10 hour.
20. method according to claim 19, wherein, polyolefin-based in described polyolefin-based Succinic Acid and/or the polyolefin-based Succinic anhydried is a kind of in polyisobutenyl, polypropylene-base, random or block polyethylene-propenyl, the polyisopreneyl, described polyolefin-based number-average molecular weight is 300-5000, and described amine is the organic amine of described amine for having structure shown in the structural formula (A):
R wherein
1, R
2Respectively do for oneself H, carbonatoms is that alkyl or the carbonatoms of 1-30 is the heteroatomic group of being with of 1-30, and described to have heteroatomic group be in carbonyl, hydroxyl, carboxyl, ester group, acyl group, alkoxyl group, nitro, cyano group, halogen, amido, the amino one or more.
21. method according to claim 20, wherein, described polyolefin-based number-average molecular weight is 500-2500, and described amine is that structural formula is H
2N[(CH
2)
X2NH]
Y1R
6Polyamines polyene, wherein, x2 is the integer of 2-4, y1 is the integer of 1-8, R
6Be that hydrogen or carbon number are the alkyl of 1-30.
22. according to any described method among the claim 15-18, wherein, described components b is p-phenylene diamine derivative's type oxidation inhibitor, have a tertiary butyl one or more in phenolic hydroxyl group adjacent hindered phenol type antioxidant at least.
23. method according to claim 22, wherein, described components b be the dialkyl group Ursol D of alkyl carbon atoms number between 4-10 with the bisphenol type oxidation inhibitor that links to each other by methylene radical or sulphur in one or more.
24. method 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 '-two-(1-methylheptyl) Ursol D, 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2-methyl-6-tert butyl phenol), 4,4 '-methylene radical-two-(2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical-two-(2-tert.-butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-thiobis-(4-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2-methyl-6-tert butyl phenol), 4,4 '-thiobis-(2,6 di t butyl phenol), in two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether one or more.
25. method according to claim 15, wherein, described additive also contains amount of component b, and described amount of component b is a metal passivator.
26. method according to claim 25, wherein, the weight ratio of described component a and described amount of component b is 1: 0.01-1.
27. according to claim 25 or 26 described methods, wherein, described amount of component b is the ammonium salt that 124 Triazole and aliphatic amide form, the product that 124 Triazole, formaldehyde and aliphatic amide obtain by mannich reaction, one or more in Schiff's base and the organic polycarboxylic acid.
28. method according to claim 15, wherein, described basic diesel oil also contains other diesel oil, described other diesel oil is petroleum diesel, fischer-tropsch combined diesel oil, hydrocracking biofuel, contain in the oxygen diesel oil blending thing one or more, and the volume ratio of described biofuel and other diesel oil is 1: 0-99.
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| CN116463160A (en) * | 2022-01-12 | 2023-07-21 | 中国石油天然气股份有限公司 | Ashless antioxidant additive, application thereof and composite lubricant |
| CN117343713A (en) * | 2023-12-06 | 2024-01-05 | 成都理工大学 | Broad-spectrum high-activity modifier, nano-sheet oil displacement agent and preparation method thereof |
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| CN105779085A (en) * | 2016-02-26 | 2016-07-20 | 北京雅士科莱恩石油化工有限公司 | Diesel oil clearing agent containing friction modifier and saving fuel oil and preparing method thereof |
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| CN112521992B (en) * | 2019-09-18 | 2022-10-21 | 中国石油化工股份有限公司 | Biodiesel antioxidant composition and preparation method and application thereof |
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