CN104371775B - A kind of method of compositions of additives and Dresel fuel compositions and raising oxidation stability of biodiesel - Google Patents
A kind of method of compositions of additives and Dresel fuel compositions and raising oxidation stability of biodiesel Download PDFInfo
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- CN104371775B CN104371775B CN201310357645.6A CN201310357645A CN104371775B CN 104371775 B CN104371775 B CN 104371775B CN 201310357645 A CN201310357645 A CN 201310357645A CN 104371775 B CN104371775 B CN 104371775B
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Abstract
The invention provides a kind of compositions of additives and the Dresel fuel compositions that contains this compositions of additives and use this compositions of additives to improve the method for oxidation stability of biodiesel. Described compositions of additives contains component a and components b, and described component a is the condensation reaction products of amino polyacid and organic amine; Described components b is one or more in arylamine type antioxidant, gallamide. Dresel fuel compositions provided by the invention has good oxidation stability.
Description
Technical field
The Dresel fuel compositions and the use that the invention relates to a kind of compositions of additives and contain this compositions of additivesThis compositions of additives improves the method for 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 petroleum resourcesThe raising of day by day exhausted and people's environmental consciousness, greatly promoted the exploitation paces of countries in the world quickening Alternative Diesel Fuel,Biodiesel has been subject to the attention of various countries with its superior environmental-protecting performance and recyclability.
Biodiesel (BD100) claims again fatty acid methyl ester (FattyAcidMethylEster), is with soybean and rapeGrease and the animal of the oil plant water plants such as oil-yielding shrubs fruit, engineering microalgae such as the oil crops such as seed, oil palm and Chinese pistacheGrease, biodiesel etc. are made raw material, obtain through ester exchange reaction with alcohols (methyl alcohol, ethanol), and be a kind of bio-fuel of cleaning.That biodiesel has is renewable, clean and safe three advantages, and China Agricultural Structure Adjustment, energy security and ecological environment are combinedClose to administer and have very great strategic importance. And China is a net import of oil state at present, petroleum reserves is very limited again, a large amount ofImported oil threatens to the energy security of China; Therefore, the research of biodiesel and production have important showing to ChinaSincere justice.
But due to raw material and processing technology, the oxidation stability of some biodiesel is very poor, to biodieselUse and store and all cause very large difficulty. The poor biodiesel of oxidation stability easily generates following ageing products: 1) insolubleProperty polymer (colloid and greasy filth), this can cause engine filter net jam and jet pump coking, and causes smoke evacuation to increase, start tiredDifficult; 2) soluble polymer, it can form resinoid in engine, may cause flame-out and difficulty in starting; 3) oldChange acid, this can cause engine metal component corrosion; 4) peroxide, this can cause aging the becoming fragile of rubber components and cause combustionMaterial leakage etc.
Europe Biodiesel Standards EN14214:2003, Australian Biodiesel Standards (Draft2003), New Zealand's lifeThing diesel oil standard NZS7500:2005, Brazilian Biodiesel Standards ANP255(2003), India Biodiesel Standards IS15607:2005, South Africa Biodiesel Standards SANS1935:2004 and diesel fuel blending biodiesel (BD100) country of ChinaThe standard GB/T20828-2007 oxidation stability of regulation biodiesel is induction period at 110 DEG C to be not less than 6 hours, surveysThe method of determining is EN14112:2003.
CN1742072A discloses a kind of method that improves storage stability of bio-diesel, and the method comprises and will contain with formerWhat liquid was counted 15-60 % by weight is dissolved in 2 of biodiesel, the liquid stoste of 4-di-t-butyl hydroxy toluene (BHT) join treats steadyIn the biodiesel of fixedization, until in total solution of biodiesel, the concentration of 2,4-di-t-butyl hydroxy toluene reaches 0.005-2% by weight.
CN1847368A discloses a kind of method of the oxidation stability that improves biodiesel, and the method comprises bisphenol typeAntioxidant is as 4,4`-methylene two [2,6-DI-tert-butylphenol compounds], 2,2`-methylene two [6-tert-butyl-4-methyl-Phenol] withAmount 10-20000ppm(w/w) joins to be treated in stable biodiesel.
CN1847369A discloses a kind of method of the oxidation stability that improves biodiesel, and the method comprises fusing point littleIn or equal the main anti-oxidant of 40 DEG C with 10-20000ppm(w/w) amount join and treat in stable biodiesel, Qi ZhongsuoState main anti-oxidant and contain alkyl phenol.
US2007/113467A1 discloses a kind of fuel composition with improved oxidation stability, and said composition containsHave biodiesel and at least one antioxidant, described antioxidant is selected from n-propyl gallate, Pyrogallic acid, 2,6-bis-unclesOne in butyl p-methyl phenol, butylated hydroxy anisole (BHA), dilauryl thiodipropionate, tocopherol, quinoline.
More than have certain effect by the method that traditional antioxidant improves oxidation stability of biodiesel, but effect is notToo obviously or need the antioxidant of larger consumption to obtain significantly to improve effect, especially to waste grease as trenchOil, acidification oil, hogwash fat are that the biodiesel effect of raw material production is poorer.
CN101144040A discloses and has improved biodiesel with arylamine kind antioxidant especially phenylenediamine antioxidantThe method of oxidation stability, arylamine kind antioxidant is the improvement effect of phenylenediamine antioxidant to oxidation stability of biodiesel especiallyFruit is better than phenol type antioxidant, but this compounds generally has certain toxicity, corrosivity and dyeability, when the effect that obtainAdd the color burn that dosage may make biodiesel, affect the outward appearance of biodiesel product.
Summary of the invention
The object of the invention is in order to overcome method effect that above-mentioned prior art improves oxidation stability of biodiesel notAntioxidant too obvious or the larger consumption of needs could obtain the shortcoming of significantly improving effect, provides a kind of at less consumptionSituation under can obviously improve the oxidation stability of fuel containing biodiesel, overcome independent use aryl diamine type or food no simultaneouslyThe compositions of additives of the adverse effect that sub-antioxidant causes biodiesel color burn and contain this compositions of additivesDresel fuel compositions and a kind of method that improves oxidation stability of biodiesel is provided.
The invention provides a kind of compositions of additives, it is characterized in that, this compositions of additives contains component a and componentB, described component a is the product of amino polyacid and organic amine; Described components b is arylamine type antioxidant and gallic acid acylOne or more in amine.
The present invention also provides a kind of Dresel fuel compositions, and this Dresel fuel compositions contains basic diesel oil and additive, described basePlinth diesel oil contains biodiesel, and wherein, described additive is above-mentioned compositions of additives provided by the invention.
The present invention also provides a kind of method that improves oxidation stability of biodiesel simultaneously, and the method comprises, is containing lifeIn the basic diesel oil of thing diesel oil, add additive, wherein, described additive is above-mentioned compositions of additives provided by the invention.
The compositions of additives that the application of the invention provides, be no matter using pure biodiesel as basic diesel oil or withThe blending fuel that contains biodiesel, as basic diesel oil, can obtain excellent oxidation stability, group under less consumptionDivide the amazing cooperative effect that occurs between a and components b, antioxidant effect is well more a lot of than independent use antioxidant. Component aCan be regarded as auxiliary antioxidant, it can make the effect of antioxidant unexpectedly greatly strengthen. Therefore, reaching identicalWhen oxidation stability requires, the amount of components b in biodiesel composition can greatly reduce, especially high especially in components bExpensive or components b has in certain toxicity, dyeability or corrosive situation, has reduced its consumption and has had very large meaning, not only reducesToxicity and the corrosivity of additive, and reduce the consumption of components b and can make the color burn degree of biodiesel greatly reduce.Meanwhile, because the cost of component a is little more a lot of than components b, therefore, the present invention also greatly reduces the one-tenth of biological diesel oil anti-oxidantThis.
Detailed description of the invention
According to compositions of additives provided by the invention, the weight ratio of described components b and component a can be 0.01-100:1, be preferably 0.1-10:1, more preferably 0.2-5:1.
Component a
In the present invention, component a is the product of amino polyacid and amine.
Described " amino polyacid " refers to contain amino polybasic carboxylic acid in molecule, and preferably amino number is 1-5, more excellentElect 1-3 as. Described amino is preferably all tertiary amino. The number of the hydroxy-acid group (COOH) in described amino polybasic carboxylic acid canThink 2-6, more preferably 2-5. Described hydroxy-acid group is the one in formyl, acetate, propionyloxy and butyric acid base more preferablyOr multiple, be particularly preferably acetate and/or propionyloxy. The total number of carbon atoms of described amino polyacid is preferably 2-20, more excellentElect 4-14 as. The instantiation of described amino polybasic carboxylic acid includes but not limited to iminodiacetic acid, complexon I, second twoAmine tetraacethyl (EDTA), ethylenediamine tetrapropionic acid (EDTP), 1,2-trimethylen-edinitrilo-tetraacetic acid, 1,3-trimethylen-edinitrilo-tetraacetic acid (PDTA), twoEthene pentaacetic acid (DTPA), 1, one or more in 6-hexamethylene tetraacetic acid, CDTA.
Described organic amine can be various can with amino polyacid in carboxyl generation condensation reaction form amide structureOrganic amine, for example, can be to there is the structure shown in formula (1)
In formula (1), R1And R2Be the group shown in H, formula (2), formula (3) or (4) independently, and R1And R2When different, be H.
In formula (2), x be 2 or 3, y be 0 to 5 integer, R3For C1-C30Alkyl; Preferably y is 1 to 4 integer, R3ForC6-C24Alkyl.
In formula (3), x1 be 2 or 3, y1 be 0 to 5 integer, R4For C1-C30Alkyl; Preferably y1 is 1 to 4 integer, R4For C6-C24Alkyl.
In formula (4), y2 is 0 to 5 integer, R5For C1-C26Alkyl.
For formula (2), further preferred y is 1 to 3 integer, R3For C8-C22Alkyl. This alkyl can be saturatedAlkyl can be also with the thiazolinyl of two keys or with the aryl of phenyl ring. Alkyl can be straight chain normal chain alkyl, can be also bandHave the isomery alkyl of side chain, the example of this alkyl comprise n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl,N-tetradecane base, n-hexadecyl, n-octadecane base, n-eicosane base, n-docosane base; Isobutyl group, the tert-butyl group, isoamylBase, neopentyl, isohesyl, different heptyl, iso-octyl (being 2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A base, different 14Alkyl, isocetyl, isooctadecane base and Isoeicosane base. The example of thiazolinyl comprises 9-octadecylene base. With the virtue of phenyl ringThe example of base comprises benzyl (benzyl), phenethyl and phenylpropyl.
In the time that y equals 1, formula (2) is-CH2CH2NHR3Or-CH2CH2CH2NHR3, preferably-CH2CH2CH2NHR3Group, R3'sDefine same as described above. The group of for example formula (2) can be,
-CH2CH2CH2NHC10H21(3-(positive the last of the ten Heavenly stems amino) propyl group),
-CH2CH2CH2NHC12H25(3-(positive ten diaminourea) propyl group),
-CH2CH2CH2NHC14H29(3-(positive ten tetraminos) propyl group),
-CH2CH2CH2NHC16H33(3-(positive 16 amino) propyl group),
-CH2CH2CH2NHC18H37(3-(positive 18 amino) propyl group) and
-CH2CH2CH2NHC18H35(3-(oil is amino) propyl group).
According to the present invention, for formula (3), the integer that preferably y1 is 1-5. Further preferably x1 is that 2, y1 is the integer of 1-4,R4With above-mentioned R3Definition identical. The group of for example formula (3) can be:
-CH2CH2NHCOC11H23，
-CH2CH2NHCOC13H27，
-CH2CH2NHCOC15H31，
-CH2CH2NHCOC17H35，
-CH2CH2NHCOC17H33，
-CH2CH2NHCH2CH2NHCOC11H23，
-CH2CH2NHCH2CH2NHCOC13H27，
-CH2CH2NHCH2CH2NHCOC15H31，
-CH2CH2NHCH2CH2NHCOC17H35，
-CH2CH2NHCH2CH2NHCOC17H33，
-CH2CH2NHCH2CH2NHCH2CH2NHCOC11H23，
-CH2CH2NHCH2CH2NHCH2CH2NHCOC13H27，
-CH2CH2NHCH2CH2NHCH2CH2NHCOC15H31，
-CH2CH2NHCH2CH2NHCH2CH2NHCOC17H35，
-CH2CH2NHCH2CH2NHCH2CH2NHCOC17H33，
-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCOC11H23，
-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCOC13H27，
-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCOC15H31，
-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCOC17H35With
-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCOC17H33。
According to composition provided by the invention, for formula (4), the integer that preferably y2 is 0-2. R5With above-mentioned R3Definition phaseWith. The group of for example formula (4) can be:
The preferred described organic amine of the present invention contains at least two NH groups or contains at least one NH and at least one C=C. Described NH group can be primary amino radical NH2, can be also secondary amino group. Further preferably, described organic amine is NH2(CH2)mNHR’、NH2R ' ' and NH2(CH2)nNH2In the acid amides that forms of one or more and R ' ' ' COOH in one or more, itsIn, m and the n 1-4 that respectively does for oneself, is preferably 2 or 3; R ', R ' ' and the R ' ' ' carbon atom of respectively doing for oneself is the alkyl of 5-25, and described alkyl enters oneStep preferably contains at least one C=C, is further preferably R ', R ' ' and R ' ' ' respectively do for oneself cocoyl or 9-octadecylene base.
The present invention particularly preferably described organic amine is N-cocoyl ethylene diamin(e), N-cocoyl-1,3-trimethylene diamines, N-oilBase ethylene diamin(e), N-oil base-1,1:0.5-1 is anti-in molar ratio for 3-trimethylene diamines, 9-octadecenyl amine, coconut oil and diethylenetriamineThe acid amides that should form, coconut oil and triethylene tetramine in molar ratio 1:0.3-1 react the acid amides, oleic acid and the diethylenetriamine that formAcid amides that 1:0.5-1 reaction in molar ratio forms, oleic acid and triethylene tetramine in molar ratio 1:0.3-1 react in the acid amides of formationOne or more.
The condensation reaction of amino polyacid and organic amine is generally according to the number of carboxyl in amino polyacid and organic amineMol ratio is 1:0.2-5, is preferably 1:0.6-1.5. Reaction temperature is generally 80-300 DEG C, further preferably at 120-250 DEG CWithin scope, within being preferably in 180-220 DEG C of scope. Reaction time is as the criterion to react fully, can be according to a point water yieldDetermine the degree that reaction is carried out, the preferred reaction time is 5-30 hour. Reaction medium can be that aromatic solvent is as dimethylbenzene, secondBenzene, aromatic hydrocarbons flux oil (boiling range is 159-185 DEG C), mineral oil (boiling point is more than 120 DEG C), decahydronaphthalenes, or theyMixture. Solvent load is generally the 30-150 % by weight of reaction mass gross weight. Reaction also can be without solvent. Reaction systemInterior available nitrogen protection, or allow system carry out under reflux water-dividing condition. Reaction can be without catalyst, also can be in acidityOr carry out under base catalyst effect, acidic catalyst is as sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, acid-exchange resin, assorted manyAcid, solid super-strong acid, Emathlite, acidic molecular sieve etc., base catalyst is as NaOH, KOH, Ca (OH)2、Mg(OH)2, methyl alcoholSodium, potassium methoxide, organic amine etc. Reaction also can steam solvent while end, then to be deployed into solvent with heavy aromatic solvent be 20-The dilution of 50 % by weight uses. In the present invention, the addition unification in compositions of additives and diesel oil is adjusted with dry dosage(i.e. not solvent-laden addition).
NH2(CH2)nNH2The acid amides forming with R ' ' ' COOH can obtain by variety of way, for example can be commercially available,Also can obtain by condensation reaction according to existing method, the concrete operations of condensation reaction can be with reference to above-mentioned amino polyacidWith the carrying out of organic amine generation condensation reaction, also can carry out with reference to known method, the present invention does not repeat them here.
Components b
Components b is one or more in arylamine type antioxidant, gallamide.
Can be selected from naphthylamine derivative, diphenylamine derivatives, p-phenylenediamine (PPD) as the described arylamine type antioxidant of components b spreads outAt least one in biology, quinoline.
Wherein naphthylamine derivative includes but not limited to one or more in following material:
PA (antioxidant T531, antioxidant A);
PBNA (antioxidant d);
N-p-methoxyphenyl alpha-naphthylamine (age resistor 102);
To hydroxyphenyl-beta-naphthylamine (antioxidant D-OH);
Acetaldol-alpha-naphthylamine (antioxidant A P)
2-hydroxyl-1, two [to (beta-naphthylamine) phenoxy group] propane (age resistor C-49) of 3-;
Two [to (beta-naphthylamine) phenoxy group] silane (age resistor C-41) of dimethyl;
Two [to (beta-naphthylamine) phenoxy group] silane (age resistor C-41-ethyl) of diethyl;
2,2 '-bis-[to (beta-naphthylamine) phenoxy group] diethyl ether (age resistor C-41-ether).
Wherein, the preferred nonox of naphthylamine derivative, for example PA, PBNA, N-are to methoxybenzeneOne or more in base alpha-naphthylamine. Especially preferably PA.
Wherein diphenylamine derivatives includes but not limited to one or more in following material:
4,4 '-diamino-diphenylamine (antioxidant A PA);
Right, to '-dimethoxy diphenylamines;
N, N, N ', N '-tetraphenyl diamines methane (age resistor 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 (age resistor C-47);
2,2 '-bis-(to aniline phenoxy group)-diethyl ether (antioxidant H-1);
Two (to aniline-phenoxy group)-silane (age resistor C-1) of dimethyl;
P-isopropoxy-diphenylamine (age resistor ISO);
Right, to '-diisopropoxy diphenylamines (antioxidant D ISO);
4,4 '-bis-(α, α ' '-dimethyl benzyl) diphenylamines (age resistor KY-405);
Parahydroxydi-phenylamine (antioxidant A O3920);
Two-(1,1,3,3-tetramethyl ethyl) diphenylamines (age resistor ODA);
4,4 '-dioctyl diphenylamine;
4,4 '-di-iso-octyldiphenylamine;
4,4 '-diheptyl diphenylamines;
4,4 '-dinonyldiphenylamine;
Octylated diphenylamine (mixture of an octylated diphenylamine and dioctyl diphenylamines, age resistor OD);
Octyl group/butyl diphenylamines (antioxidant L-57);
Styrenated diphenylamine (antioxidant D FL, DFC-34);
And the mixture of alkylated diphenylamine, wherein alkyl can be one or more in heptyl, octyl group, nonyl,The example of its industrial products has Pennwalt company of U.S. commodity to be called PennoxA, PennoxA-" S ", American National InstrumentPolychem company commodity are called WytoxADP, ADP-X, and Vanderbilt company of U.S. commodity are called AgeriteStalite, AgeriteStaliteS, AgeriteNepa, AgeriteGel, Uniroyal company of U.S. commodity are by nameThe antioxidant product that Polylite, Antioxidant445 and domestic code name are T534.
Diphenylamine derivatives type antioxidant preferred alkyl diphenylamines and composition thereof, especially preferred alkyl carbon number existsAlkylated diphenylamine between 4-10 and composition thereof, as: 4,4 '-dioctyl diphenylamine, 4,4 '-di-iso-octyldiphenylamine, 4,4 '-diheptyl diphenylamines, 4,4 '-dinonyldiphenylamine, octylated diphenylamine (octylated diphenylamine and/or dioctylization twoAniline), one or more in octyl group/butyl diphenylamines, commodity antioxidant T534.
Wherein p-phenylene diamine derivative's type antioxidant comprises but is not limited to one or more in following material:
N-phenyl-N '-cyclohexyl p-phenylenediamine (PPD) (antioxidant 4010);
N, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (antioxidant 4020);
N, N '-bis--(Isosorbide-5-Nitrae-dimethyl amyl group) p-phenylenediamine (PPD) (age resistor 4030);
N-p-methylphenyl-N '-(1,3-dimethylbutyl) p-phenylenediamine (PPD) (age resistor 4040);
N, N '-diheptyl p-phenylenediamine (PPD) (age resistor 788);
N-isopropyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA);
N-isopropyl-N '-p-methylphenyl p-phenylenediamine (PPD) (age resistor methyl 4010NA);
N, N '-DTPD di tolyl p phenylenediamine (age resistor PPD-A);
N, N '-diphenyl-para-phenylene diamine (antioxidant H);
N, N '-bis--(betanaphthyl) p-phenylenediamine (PPD) (antioxidant D NP);
N, N '-di-sec-butyl-p-phenyl enediamine (age resistor U-5, antioxidant 44PD);
N, N '-dioctyl-p-phenylenediamine (age resistor 88);
N, N '-bis--(1-methylheptyl) p-phenylenediamine (PPD) (age resistor 288);
N, N '-bis--(1-ethyl-3-methyl amyl) p-phenylenediamine (PPD) (age resistor 8L);
N, N '-bis--(Isosorbide-5-Nitrae-dimethylbutyl) p-phenylenediamine (PPD) (age resistor 66);
N-Octyl-N '-diphenyl-para-phenylene diamine (age resistor 688);
N-isobutyl group-N '-diphenyl-para-phenylene diamine (age resistor 5L);
N, N '-dimethyl-N, N '-bis--(1-first propyl group) p-phenylenediamine (PPD) (age resistor 32);
N-(p-methylphenyl sulfonyl)-N '-diphenyl-para-phenylene diamine (age resistor TPPD);
N-(3-methylpropenyl acyl-oxygen generation-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine (age resistor G-1);
N-(3-anilino-phenyl) Methacrylamide;
N-hexyl-N '-diphenyl-para-phenylene diamine;
The preferred dialkyl group p-phenylenediamine (PPD) of p-phenylene diamine derivative's type antioxidant, especially preferred alkyl carbon number 4-10 itBetween dialkyl group p-phenylenediamine (PPD), as N, N '-diheptyl p-phenylenediamine (PPD); N, N '-di-sec-butyl-p-phenyl enediamine; N, N '-dioctyl pairPhenylenediamine; N, one or more in N '-bis--(1-methylheptyl) p-phenylenediamine (PPD).
Quinoline wherein includes but not limited to:
6-ethyoxyl-2,2,4-trimethyl-1,2-dihyaroquinoline (antioxidant A W);
6-phenyl-2,2,4-trimethyl-1,2-dihyaroquinoline (age resistor PMQ);
6-dodecyl-2,2,4-trimethyl-1,2-dihyaroquinoline (antioxidant D D);
2,2,4-trimethyl-1,2-dihyaroquinoline condensate (anti-aging agent RD, age resistor 124);
Diphenylamines and acetone low-temp reaction product (age resistor BAS);
Diphenylamines and acetone high-temperature reaction product (antioxidant BLE);
The product (age resistor BXA) of diphenylamines and acetone and aldehyde;
The product (antioxidant A PN, antioxidant A M) of PBNA and acetone.
Above-mentioned arylamine type antioxidant can use separately one or mix and use two or more.
A kind of preferred embodiment of the present invention is that arylamine antioxidant comprises p-phenylenediamine (PPD) class arylamine antioxidant.
Another kind of preferred embodiment of the present invention is that arylamine antioxidant is the naphthylamines of above-mentioned replacement and the diphenylamines of replacementKind antioxidant is with the mixed aromatic diamine antioxidant of mass ratio 1:0.1～10.
Can be the acid amides of gallic acid and various ammonia and/or amine formation as the gallamide of described components b, toolBody can be referring to CN101613630A. Under preferable case, described nutgall acid amides is in the gallamide shown in following formula (I)One or more,
In formula (I), R1And R2Be the group shown in H, formula (2) independently.
In formula (2), x be 2 or 3, y be 0 to 5 integer, R3For C1-C30Alkyl; Preferably y is 0 to 3 integer, R3ForC6-C24Alkyl.
In the time that y equals 0, formula (2) is R3, i.e. C1-C30Alkyl, be preferably C6-C24Alkyl. This alkyl can be saturatedAlkyl, can be also with the thiazolinyl of two keys or with the aryl of phenyl ring. Alkyl can be straight chain normal chain alkyl, can be alsoWith the isomery alkyl of side chain, the example of this alkyl comprise normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl,Positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, n-octadecane base, n-eicosane base, positive twoDodecyl; Isobutyl group, the tert-butyl group, isopentyl, neopentyl, isohesyl, different heptyl, iso-octyl (2-ethylhexyl), different nonyl,Isodecyl, Permethyl 99A base, different myristyl, isocetyl, isooctadecane base and Isoeicosane base. The example of thiazolinyl comprises9-octadecylene base. Example with the aryl of phenyl ring comprises benzyl (benzyl), phenethyl and phenylpropyl. Wherein, more preferably C6-C20Alkyl.
In the time that y equals 1, formula (2) is-CH2CH2NHR3Or-CH2CH2CH2NHR3, preferably-CH2CH2CH2NHR3Group, R3'sDefine same as described above. The group of for example formula (2) can be,
-CH2CH2CH2NHC10H21(3-(positive the last of the ten Heavenly stems amino) propyl group),
-CH2CH2CH2NHC12H25(3-(positive ten diaminourea) propyl group),
-CH2CH2CH2NHC14H29(3-(positive ten tetraminos) propyl group),
-CH2CH2CH2NHC16H33(3-(positive 16 amino) propyl group),
-CH2CH2CH2NHC18H37(3-(positive 18 amino) propyl group) and
-CH2CH2CH2NHC18H35(3-(oil is amino) propyl group).
Further preferably gallamide be gallic acid caprylamide, gallic acid pelargonamide, gallic acid decyl amide,Gallic acid lauramide, gallic acid myristamide, gallic acid palmitamide, gallic acid stearamide, gallic acidOil base acid amides, gallic acid (N-coco group) propionamide, gallic acid (N-tallow base) propionamide, gallic acid (N-hydrogenation oxFat base) one or more in propionamide and gallic acid (N-oil base) propionamide.
The present invention further preferred described components b is N, N '-diheptyl p-phenylenediamine (PPD), N, N '-di-sec-butyl-p-phenyl enediamine,N, N '-dioctyl-p-phenylenediamine, N, N '-bis--(1-methylheptyl) p-phenylenediamine (PPD), gallic acid caprylamide, gallic acid nonanoylAmine, gallic acid decyl amide, gallic acid lauramide, gallic acid myristamide, gallic acid palmitamide, gallic acidStearamide, gallic acid oil base acid amides, gallic acid (N-coco group) propionamide, gallic acid (N-tallow base) propionamide,One or more in gallic acid (N-hydrogenated-tallow group) propionamide and gallic acid (N-oil base) propionamide. Further excellentChoose that to state p-phenylene diamine derivative's (p-phenylenediamine (PPD) of replacement) and above-mentioned gallamide compound with mass ratio 1:0.1～10.
, after described component a and said components b are compound, there is obvious cooperative effect, to containing in the discovery that the inventor is pleasantly surprisedThe improvement effect of biodiesel fuel oxidation stability strengthens greatly. Meanwhile, add containing component a and the compound additive of components bAfter, the color of biodiesel fuel is shallow a lot of will reach same antioxidant effect than independent use components b time.
According to use needs, Dresel fuel compositions provided by the invention can also contain other additive, as phenol type antioxidant,Macromolecule amine type ashless dispersant, flow improving agent, cetane number improver, matal deactivator, antistatic additive, anticorrisive agent, anti-One or more in rust agent, demulsifier etc.
Described macromolecule amine type ashless dispersant comprises allyl butyrate imidodicarbonic diamide and/or alkenyl succinic acid acid amides, Manny westOne or more in alkali type ashless dispersant, polyetheramine type ashless dispersant and polyalkene amines type ashless dispersant. Described alkeneBase succimide and/or base succinamide ashless dispersant for example number-average molecular weight in the polyolefin-based fourth two of 500-3000The product of acid anhydrides and/or succinic acid and amine, if domestic trade names are T151A(mono butonediimide), T151B(only sonImidodicarbonic diamide), the two succimides of T152(), the two succimides of T154(), T155(poly succimide) and/or T161(poly succimide) etc. Import additive is as OLOA-1200, LZ894, InfineumC9238,9237, Hitec644Deng. Mannich base type ashless dispersant for example number-average molecular weight in the condensation of polyolefin-based phenol and formaldehyde and the amine of 500-3000Product; After for example C8-C30 alkyl phenol of described polyetheramine type ashless dispersant and oxirane or expoxy propane adduction, contract with amine againAfter the product closing or C8-C30 alcohol and oxirane or expoxy propane adduction again with the product of amine condensation; Described polyalkene aminesFor example chloridized polyolefin of type ashless dispersant reacts the polyolefin-based amine generating with amine.
Described flow improving agent preferably contains the polymer of (methyl) acrylate. Cetane number improver can be nitrateOr peroxide, as one or more in isooctyl ester nitrate, di-tert-butyl peroxide. Matal deactivator can be benzene threeAzoles and derivative thereof, thiadiazoles and derivative thereof are as TH561, oxine, hydrazides, beta-diketon, 'beta '-ketoester, schiff bases(Schiffbases), one or more in organic polycarboxylic acid and derivative thereof. Because 124 Triazole is originally in biodieselIn dissolubility very unexcellent, therefore, in order to increase its dissolubility in biodiesel, conventionally 124 Triazole is changedProperty, the method for modification mainly by introducing oil-soluble group as long chain hydrocarbon groups in 124 Triazole. Therefore, described 124 Triazole derivativeCan be the various derivatives that various dissolubilities in biodiesel are good compared with 124 Triazole itself. Concrete, described 124 Triazole spreads outBiology can be that ammonium salt and 124 Triazole, formaldehyde and the fatty amine that 124 Triazole and fatty amine form obtains by mannich reactionOne or more in product. Described ethylenediamine tetraacetic carboxylic acid can be ethylenediamine tetra-acetic acid (EDTA), and described hydrazides can be N-Salicylidene-N '-salicylyl hydrazine and/or N, N '-diacetyl adipyl base two hydrazides. Described beta-diketon is as acetylacetone,2,4-pentanedione, described in'beta '-ketoester is as acetoacetate monooctyl ester. Described schiff bases can be N, N '-bis-salicylidene-1, and 2-ethylenediamine, N, N '-bis-salicylidene-1,2-propane diamine, N, N '-bis-salicylidene-1,2-cyclohexanediamine, N, the one in N '-bis-salicylidene-N '-methyl two propylene triaminesOr multiple. Described organic polycarboxylic acid and derivative thereof can be for example citric acid, tartaric acid, malic acid, butanedioic acid (fourth twoAcid), one or more in maleic acid, phytic acid etc. and derivative thereof. Concrete, matal deactivator can be 124 Triazole and fatThe ammonium salt that amine forms, the product that 124 Triazole, formaldehyde and fatty amine obtain by mannich reaction, schiff bases and organic polycarboxylic acidIn one or more.
The preparation of compositions of additives provided by the invention is simple, only each component of composition compositions of additives need be mixedEvenly.
Compositions of additives provided by the invention is preferably taking the content with respect to basic diesel oil as 50-10000 ppm by weight(mg/kg), more preferably 50-5000 ppm by weight, further preferably the consumption of 100-3000 ppm by weight uses, especially preferredThe consumption of 150-800 ppm by weight uses.
According to Dresel fuel compositions provided by the invention, this Dresel fuel compositions contains basic diesel oil and additive, described basisDiesel oil contains biodiesel, and wherein, described additive is above-mentioned compositions of additives provided by the invention.
In the present invention, described basic diesel oil can be all biodiesel, can be partly also biodiesel, also contains simultaneouslyHave other diesel oil, described other diesel oil is petroleum diesel, Fischer-Tropsch combined diesel oil, hydrocracking biodiesel, contains oxygen diesel oil blendingOne or more in thing. Under preferable case, the volume ratio of described biodiesel and other diesel oil is 1:2-99.
The preparation of Dresel fuel compositions provided by the invention is simple, only each component of composition Dresel fuel compositions need be mixed. Can directly each additive component be mixed with basic diesel oil, also can first various additive components be mixed,After compositions of additives, then gained compositions of additives is mixed with basic diesel oil. For easy to operate, by various interpolationsWhen agent composition mixes, can solvent exist under carry out, the solvent here can be polar solvent as N, N-dimethyl methylAcid amides (DMF), Isosorbide-5-Nitrae-dioxane, oxolane (THF), dimethyl sulfoxide (DMSO) (DMSO), pyrrolidones and methyl pyrrolidoneIn one or more. Also can be hydro carbons especially aromatic hydrocarbons as benzene,toluene,xylene, aromatic hydrocarbons flux oil and composition thereof, alsoIt can be biodiesel.
In the present invention, described biodiesel refers to that grease and low-carbon alcohols are (as C1-C5Fatty alcohol) anti-through ester exchange (alcoholysis)The fatty acid ester of low-carbon alcohol of answering and generate, is generally fatty acid methyl ester, i.e. the ester exchange offspring of grease and methyl alcohol.
Described trans-esterification processes can be that any known or unknown ester exchange of passing through grease and low-carbon alcohols is anti-Should obtain the process of biodiesel, for example acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, etc. Specifically canWith 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 fatty acid glycerineThree esters. What general normal temperature was liquid is called oil, and normal temperature is solid or the semisolid fat (abbreviation fat) that is called. Described grease comprisesVegetable oil and animal oil, in addition, also comprise from the oil plant in the material such as microorganism, algae, can also be even waste oil,The used grease of acidifying wet goods or the rotten grease of for example waste cooking oil, waste oil, swill oil, grease factory. Described plantOil can be that herbaceous plant oil can be also xylophyta oil, as peanut oil, corn oil, cottonseed oil, rape seed oil, soybean oil, palm fibrePalmitic acid oil, safflower oil, linseed oil, coconut oil, Oak Tree oil, apricot kernel oil, walnut oil, castor oil, sesame oil, olive oil, tall oil(TallOil), sunflower oil, curcas oil, tung oil, shinyleaf yellowhorn oil, coptis wood oil, halophytes are as kostelezkya virginica, oily Sha's beansDeng the oil of plant. Described animal oil can be lard, chicken fat, duck oil, goose oil, sheep oil, house oil, butter, haco oil, shark oilDeng.
In biodiesel composition of the present invention, described basic diesel oil also can contain other diesel oil, described other bavinOil is petroleum diesel, Fischer-Tropsch combined diesel oil, hydrocracking biodiesel, containing one or more in oxygen diesel oil blending thing, described inThe volume ratio of biodiesel and other diesel oil is preferably 1:2-99.
Wherein petroleum diesel refer to crude oil (oil) through the decompression as usual of various refining process, the catalytic cracking of oil plant, urgeChange the cut of the device boiling ranges after treatment such as reformation, coking, hydrofinishing, hydrocracking between 160-380 DEG C, and through toningJoining the compression ignition engine that meets ordinary diesel oil standard GB/T 252 or derv fuel standard GB/T/T19147 forming usesFuel.
Fischer-Tropsch combined diesel oil mainly refers to the GTL producing through Fischer-Tropsch (F-T) synthetic method as raw material taking natural gas or coalDiesel oil (GasToLiquid) or CTL diesel oil (CoalToLiquid) can also be that string is through Fischer-Tropsch synthetic methodAnd the BTL diesel oil (BiomassToLiquid) of producing. Fischer-Tropsch combined diesel oil does not basically contain sulphur and aromatic hydrocarbons, is very cleanFuel, but its lubricity extreme difference, greatly improve, but the oxidation stability of tempered oil has with lubricity after biodiesel blendingPossible deviation, therefore also needs to add antioxidant containing the blending fuel of biodiesel.
Hydrocracking biodiesel, also referred to as second generation biodiesel, refers to by animal and plant fat anti-through hydrogenation and crackingShould generate afterwards with C8-C24Alkane is main, especially with C12-C20N-alkane is the product of main component, this hydrogenationCracking biodiesel Cetane number is high, and sulphur and arene content are extremely low, can greatly fall as diesel motor fuel or blending componentThe discharge of low diesel engine pollutant.
Refer to and can be deployed into the oxidation that contains that meets certain code requirement with various diesel fuels containing oxygen diesel oil blending componentThe mixture of compound or oxygenatedchemicals, normally alcohols and ethers or its mixture, alcohols is C such as1-C18Fatty alcohol, preferredC1-C12Unitary fatty alcohol, as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecylenic alcohol,Laruyl alcohol and various isomers thereof. Ethers can be dimethyl ether, methyl tertiary butyl ether(MTBE), ethyl tert-butyl ether (ETBE), C6-C14Poly alkyl alcoholOxygen vinethene, C6-C14Fatty alcohol polyoxypropylene ether, C6-C14APES, C6-C14Alkyl phenol polyethenoxy ether, poly-Oxidation methylene dimethyl ether (PolyoxymethyleneDimethylEthers, CH3O(CH2O)xCH3, x=1-8) etc. andMixture.
In the present invention, described basic diesel oil is that while containing the blending fuel of biodiesel, described Dresel fuel compositions can pass throughDescribed additive, biodiesel and other diesel oil are directly obtained by mixing, also can be first by described additive and biodieselMix, and then obtain with other diesel oil blending. The various components of additive directly can be mixed with basic diesel oil, also canFirst the various components of additive are pre-mixed, obtain after additive agent mixture again and basic diesel oil. Various to additiveThe order by merging of component and biodiesel and other diesel oil is not particularly limited, and can mix with various orders. The bar mixingPart can carry out under the various conditions that Dresel fuel compositions do not caused adverse effect, for example, can mix at ambient temperature.
The method of raising oxidation stability of biodiesel provided by the invention comprises, is containing the basic diesel oil of biodieselIn, adding additive, described additive is above-mentioned compositions of additives provided by the invention.
Under preferable case, described additive is 50-10000 ppm by weight (mg/kg) with respect to the addition of basic diesel oil,More preferably 50-5000 ppm by weight, further preferred 100-3000 ppm by weight, especially preferably 150-800 ppm by weight.
Be described above about basic diesel oil and compositions of additives, the present invention does not repeat them here.
The present invention is described further for the following examples.
Preparation example 1-5 is for illustrating synthesizing of component a.
Preparation example 1
In three-necked bottle, add 116.2gN-cocoyl-1,3-trimethylene diamines and 35.0g ethylenediamine tetra-acetic acid (EDTA),Wherein N-cocoyl-1, the mol ratio of 3-trimethylene diamines and ethylenediamine tetra-acetic acid is 4:1, i.e. carboxyl in amine and amino polyacidMol ratio 1:1. Heating is stirred to 190 DEG C, passes into nitrogen reaction 20h, and collects the water generating with collector, then cools to120 DEG C, take out a small amount of water of 2h to generate except dereaction with vavuum pump decompression, collect altogether watery thing 13.6g, obtain product125.2g。
Preparation example 2
In three-necked bottle, add 129.8gN-oil base-1,3-trimethylene diamines and 38.2g complexon I (NTA), itsMiddle N-oil base-1, the mol ratio of 3-trimethylene diamines and complexon I is 2:1, i.e. carboxyl mol ratio in amine and amino polyacid1:1.5. Heating is stirred to 170 DEG C, passes into nitrogen reaction 18h, and collects the water generating with collector, then cools to 110 DEG C,Take out a small amount of water of 2h to generate except dereaction with vavuum pump decompression, collect altogether watery thing 6.6g, obtain product 149.4g.
Preparation example 3
In three-necked bottle, add 133.8g oleyl amine and 38.3g1,3-trimethylen-edinitrilo-tetraacetic acid (PDTA), wherein oleyl amine and 1,3-The mol ratio of trimethylen-edinitrilo-tetraacetic acid is 4:1, i.e. carboxyl mol ratio 1:1 in amine and amino polyacid. Heating is stirred to 200 DEG C, logicalEnter nitrogen reaction 25h, and collect the water generating with collector, then cool to 120 DEG C, take out 2h with vavuum pump decompression anti-to removeA small amount of water that should generate, collects watery thing 10.1g altogether, obtains product 149.4g.
Preparation example 4
In three-necked bottle, add 186.2g oleic acid to react the acid amides and the 35.0g ethylenediamine tetrem that form with triethylene tetramineAcid (EDTA), wherein oleic acid react with triethylene tetramine formation acid amides and the mol ratio of ethylenediamine tetra-acetic acid be 3:1, organicThe mol ratio 0.75:1 of carboxyl in amine and amino polyacid. Heating is stirred to 200 DEG C, passes into nitrogen reaction 20h, and uses collectorCollect the water generating, then cool to 120 DEG C, take out a small amount of water of 2h to generate except dereaction with vavuum pump decompression, collect altogetherWatery thing 12.8g, obtains product 162.2g.
Wherein, oleic acid react with triethylene tetramine form acid amides prepare according to following step:
In a 500ml three-necked bottle, add 0.5mol oleic acid and the heating of 0.3mol triethylene tetramine to be stirred to 130 DEG C, logicalEnter nitrogen and blow water reaction 5 hours. Product after dewatering, by infrared analysis product, finds to have in product the spy of amide groupLevy peak. This product is directly reacted formation with triethylene tetramine acid amides as oleic acid is many for the preparation of amino of the present inventionThe condensation product of unit's acid and organic amine.
Preparation example 5
In three-necked bottle, add octadecylamine and 1,3-trimethylen-edinitrilo-tetraacetic acid (PDTA), wherein octadecylamine and 1,3-thirdThe mol ratio of ethylenediamine tetraacetic acid (EDTA) is 4:1, i.e. carboxyl mol ratio 1:1 in amine and amino polyacid. Heating is stirred to 200 DEG C, passes intoNitrogen reaction 25h, and collect the water generating with collector, then cool to 120 DEG C, reduce pressure and take out 2h to remove dereaction with vavuum pumpThe a small amount of water generating, obtains product 150.1g.
Embodiment 1-9 and comparative example 1-12 are for illustrating the composition of compositions of additives.
Prepare compositions of additives according to the weight ratio shown in table 1.
Table 1
Performance test
Below, in test, acidification oil biodiesel used is CNOOC New Energy (Hainan) Biological Energy Chemical Co., Ltd.The biodiesel product providing, waste oil biodiesel used is provided by the remarkable new forms of energy of Fujian Longyan Co., Ltd, oil bavinOil is the diesel oil that meets Beijing provincial standard DB11/239-2007 that Yanshan Mountain branch company of China Petrochemical Industry produces. Addition unification withDry dosage is adjusted (i.e. not solvent-laden addition).
(1) pure biodiesel is as the oxidation stability test of the biodiesel composition of basic diesel oil
Evaluate biodiesel oxidation peace the induction period at measuring 110 DEG C by EN14112:2003 method (Racimat method)Qualitative, use the 743 type oil oxidative stability analyzers that instrument is Wan Tong company of Switzerland, wherein, longer explanation induction periodThe non-oxidizability of Dresel fuel compositions is better, otherwise shorter illustrate that the non-oxidizability of Dresel fuel compositions is poorer induction period. Colourity is usedASTMD1500 method is measured, and the little explanation of chroma data is of light color. Its test result is shown in table 2, table 3.
Table 2 waste oil biodiesel adds agent effect
| Additive source | Addition/(mg/kg) | 110 DEG C induction period/(hr) | Colourity/number |
| - | - | 1.0 | 1.0 |
| Embodiment 1 | 500 | 23.2 | 2.0 |
| Embodiment 1 | 250 | 15.3 | 1.5 |
| Comparative example 1 | 250 | 2.1 | 1.0 |
| Comparative example 1 | 500 | 3.4 | 1.5 |
| Comparative example 2 | 250 | 10.4 | 3.0 |
| Comparative example 2 | 500 | 15.1 | 3.5 |
| Embodiment 2 | 300 | 16.2 | 1.5 |
| Comparative example 3 | 200 | 2.7 | 1.5 |
| Comparative example 3 | 300 | 3.3 | 1.5 |
| Comparative example 4 | 100 | 5.4 | 1.5 |
| Comparative example 4 | 300 | 10.1 | 3.5 |
| Embodiment 3 | 450 | 20.1 | 2.5 |
| Comparative example 5 | 150 | 3.8 | 1.5 |
| Comparative example 5 | 450 | 5.3 | 2.0 13 --> |
| Comparative example 6 | 300 | 9.9 | 3.0 |
| Comparative example 6 | 450 | 14.6 | 3.5 |
| Embodiment 4 | 500 | 8.9 | 2.0 |
| Comparative example 7 | 500 | 5.7 | 3.0 |
| Embodiment 5 | 500 | 10.1 | 2.0 |
| Comparative example 8 | 500 | 6.8 | 3.0 |
| Embodiment 6 | 500 | 16.8 | 2.0 |
| Comparative example 9 | 500 | 10.8 | 3.0 |
| Embodiment 7 | 500 | 26.8 | 2.0 |
| Embodiment 7 | 250 | 18.1 | 1.5 |
| Comparative example 10 | 500 | 18.8 | 3.5 |
| Comparative example 10 | 250 | 11.5 | 2.5 |
| Embodiment 8 | 600 | 22.5 | 1.5 |
| Embodiment 8 | 300 | 15.8 | 1.0 |
| Comparative example 11 | 500 | 6.1 | 1.0 |
| Comparative example 11 | 600 | 7.8 | 1.0 |
| Comparative example 10 | 600 | 20.1 | 3.5 |
| Embodiment 9 | 600 | 24.1 | 2.5 |
| Comparative example 12 | 100 | 1.0 | 1.0 |
| Comparative example 12 | 600 | 3.2 | 1.0 |
Data from table 2 can be found out, the condensation reaction products list by amino polyacid and polyamines provided by the inventionThe private effect of making biological diesel oil anti-oxidant is poor, and as the one in component a and arylamine type antioxidant, gallamideOr multiple (components b) is compound rear oxidation stability of biodiesel is had to the good effect of improving, the two it is to occur unexpectedSynergy, the effect of improving of oxidation stability of biodiesel is greatly better than it and is used separately, simultaneously compound rear to biologyThe intensification degree of diesel colour is significantly less than components b and uses separately. Arylamine antioxidant, gallamide use biology separatelyOxidation stability of diesel oil have some improvement effect, especially p-phenylene diamine derivative (p-phenylenediamine (PPD) of replacement) and gallic acidAcid amides, but its consumption can cause biodiesel color greatly to be deepened when slightly large. From the effect of embodiment 1,2 and embodiment 4,5Can find out, p-phenylene diamine derivative's (p-phenylenediamine (PPD) of replacement) kind antioxidant is better than as components b and the compound effect of component aThe naphthylamines that diphenylamine derivatives (diphenylamines of replacement) and phenyl replace is compound as components b and component a separately respectively. From realityExecuting the effect of example 4,5,6 can find out, after naphthylamines that diphenylamine derivatives (diphenylamines of replacement) and phenyl replace is compoundBe better than with the compound effect of component a the naphthylamines that diphenylamine derivatives (diphenylamines of replacement) and phenyl replace again as components bCompound as components b and component a separately respectively. Effect by embodiment 1 and 7 can find out, p-phenylene diamine derivative be (replacementP-phenylenediamine (PPD)) kind antioxidant and gallamide compound rear more excellent with the compound effect of component a again as components b.
Table 3 acidification oil biodiesel adds agent effect
| Additive source | Addition/(mg/kg) | 110 DEG C induction period/(hr) | Colourity/number |
| - | - | 1.4 | 1.5 |
| Embodiment 1 | 400 | 16.9 | 2.5 14 --> |
| Comparative example 1 | 400 | 2.7 | 2.0 |
| Comparative example 2 | 400 | 9.9 | 3.5 |
| Embodiment 2 | 600 | 23.5 | 2.5 |
| Comparative example 4 | 600 | 4.7 | 2.5 |
| Comparative example 5 | 600 | 14.8 | 4.0 |
| Embodiment 3 | 300 | 15.9 | 2.5 |
| Comparative example 5 | 300 | 5.0 | 2.5 |
| Comparative example 6 | 300 | 8.9 | 3.5 |
| Embodiment 7 | 400 | 21.3 | 2.5 |
| Comparative example 10 | 400 | 11.4 | 3.5 |
| Embodiment 8 | 600 | 24.7 | 1.5 |
| Comparative example 11 | 500 | 7.0 | 1.0 |
| Comparative example 11 | 600 | 8.3 | 1.0 |
| Comparative example 10 | 600 | 22.8 | 3.5 |
| Embodiment 9 | 600 | 25.9 | 3.0 |
| Comparative example 12 | 100 | 1.3 | 1.0 |
| Comparative example 12 | 600 | 2.8 | 1.0 |
Data from table 3 can find out, the condensation reaction products by amino polyacid and polyamines provided by the invention is doneFor one or more (components b) in component a and arylamine type antioxidant, gallamide compound rear to acidification oil biodieselOxidation stability has the good effect of improving, and the two occurs unexpected synergy, stable to biodiesel oxidationProperty the effect of improving be greatly better than it and use separately, the compound rear intensification degree to biodiesel color is significantly less than component simultaneouslyB uses separately.
(2) stability using the mixture of biodiesel and petroleum diesel as the concocted diesel oil composition of basic diesel oilTest, biodiesel used is acidification oil biodiesel.
Adopt the method for EN15751:2009 to measure respectively each Dresel fuel compositions, petroleum diesel and concocted diesel oil at 110 DEG CUnder induction period, to use instrument be Wan Tong company of Switzerland 743 type oil oxidative stability analyzers, longer explanation induction periodThe non-oxidizability of biodiesel composition is better, on the contrary induction period the shorter non-oxidizability that biodiesel composition is described morePoor. Its test result is shown in Table 4.
Table 4
Result by table 4 can be found out, adds after biodiesel, contains the oxidation stability of the blending fuel of biodieselPoor, the invention provides by the condensation reaction products of amino polyacid and polyamines as component a and arylamine type antioxidant, gallic acidOne or more (being components b) in acid amides are compound has good effect afterwards to improving biodiesel blend fuels oxidation stabilityReally, be obviously better than using separately the effect of components b.
Table 3, table 4 also can be found out, can be found out p-phenylene diamine derivative (replacement right by the effect of embodiment 1 and 7Phenylenediamine) kind antioxidant and gallamide compound rear more excellent with the compound effect of component a again as components b.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited in above-mentioned embodimentDetail, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, thisA little simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characterictic described in above-mentioned detailed description of the invention, at lance notIn the situation of shield, can combine by any suitable mode. For fear of unnecessary repetition, the present invention to various canThe combination explanation no longer separately of energy.
In addition, between various embodiment of the present invention, also can be combined, as long as it is without prejudice to thisThe thought of invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a compositions of additives, is characterized in that, this compositions of additives contains component a and components b, and described component a isThe condensation reaction products of amino polyacid and organic amine; Described components b is p-phenylene diamine derivative's type antioxidant and gallic acidOne or more in acid amides; Described organic amine contains at least two NH groups; The weight ratio of described components b and component a is0.01-10：1。
2. compositions of additives according to claim 1, wherein, number 1-5 amino in described amino polyacid is individual, carboxylicThe number of acid groups is 2-6, and described amino is tertiary amino.
3. compositions of additives according to claim 1 and 2, wherein, the total number of carbon atoms of described amino polyacid is 4-14, hydroxy-acid group is one or more in formyl, acetate, propionyloxy and butyric acid base, and described organic amine is NH2(CH2)mNHR ' and NH2(CH2)nNH2In one or more and R "’One or more in the acid amides that COOH forms, wherein, m and nThe 1-4 that respectively does for oneself, R ' and R "’The carbon atom of respectively doing for oneself is the alkyl of 5-25.
4. compositions of additives according to claim 2, wherein, number amino in described amino polyacid is 1-3, carboxylicThe number of acid groups is 2-5, and hydroxy-acid group is acetate and/or propionyloxy, R ' and R "’The cocoyl of respectively doing for oneself or 9-octadecyleneBase.
5. compositions of additives according to claim 3, wherein, number amino in described amino polyacid is 1-3, carboxylicThe number of acid groups is 2-5, and hydroxy-acid group is acetate and/or propionyloxy, R ' and R "’The cocoyl of respectively doing for oneself or 9-octadecyleneBase.
6. compositions of additives according to claim 1, wherein, described amino polyacid is iminodiacetic acid, inferior ammoniaBase triacetic acid, ethylenediamine tetra-acetic acid, ethylenediamine tetrapropionic acid, 1,2-trimethylen-edinitrilo-tetraacetic acid, 1,3-trimethylen-edinitrilo-tetraacetic acid, divinyl threeTriamine pentaacetic acid, 1, one or more in 6-hexamethylene tetraacetic acid, CDTA; Described organic amine is N-cocounut oilBase ethylene diamin(e), N-cocoyl-1,3-trimethylene diamines, N-oil base ethylene diamin(e), N-oil base-1,3-trimethylene diamines, 9-octadecyleneAmine, coconut oil and diethylenetriamine in molar ratio 1:0.5-1 react the acid amides, coconut oil and the triethylene tetramine that form in molar ratioAcid amides that 1:0.3-1 reaction forms, oleic acid and diethylenetriamine in molar ratio 1:0.5-1 react acid amides, the oleic acid and three of formationOne or more in the acid amides that the 1:0.3-1 reaction in molar ratio of ethene tetramine forms.
7. according to the compositions of additives described in any one in claim 2,4-6, wherein, with the carboxyl in amino polyacidThe described amino polyacid of meter and the mol ratio of organic amine are 1:0.6-1.5, and the temperature of condensation reaction is 80-300 DEG C, and condensation is anti-The time of answering is 5-30 hour.
8. compositions of additives according to claim 3 is wherein, many in the described amino of the carboxyl in amino polyacidUnit's acid is 1:0.6-1.5 with the mol ratio of organic amine, and the temperature of condensation reaction is 80-300 DEG C, and the time of condensation reaction is 5-30Hour.
9. according to the compositions of additives described in any one in claim 1,2,4-6 and 8, wherein, described components b is N,N '-diheptyl p-phenylenediamine (PPD), N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-bis--(1-methyl heptanBase) p-phenylenediamine (PPD), gallic acid caprylamide, gallic acid pelargonamide, gallic acid decyl amide, gallic acid lauramide, do not haveGallate-based myristamide, gallic acid palmitamide, gallic acid stearamide, gallic acid oil base acid amides, gallic acid (N-Coco group) propionamide, gallic acid (N-tallow base) propionamide, gallic acid (N-hydrogenated-tallow group) propionamide and gallic acidOne or more in (N-oil base) propionamide.
10. compositions of additives according to claim 3, wherein, described components b is N, N '-diheptyl p-phenylenediamine (PPD), N,N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-bis--(1-methylheptyl) p-phenylenediamine (PPD), gallic acidCaprylamide, gallic acid pelargonamide, gallic acid decyl amide, gallic acid lauramide, gallic acid myristamide, nutgallAcid palmitamide, gallic acid stearamide, gallic acid oil base acid amides, gallic acid (N-coco group) propionamide, nutgallIn acid (N-tallow base) propionamide, gallic acid (N-hydrogenated-tallow group) propionamide and gallic acid (N-oil base) propionamide oneKind or multiple.
11. compositions of additives according to claim 7, wherein, described components b is N, N '-diheptyl p-phenylenediamine (PPD), N,N '-di-sec-butyl-p-phenyl enediamine, N, N '-dioctyl-p-phenylenediamine, N, N '-bis--(1-methylheptyl) p-phenylenediamine (PPD), gallic acidCaprylamide, gallic acid pelargonamide, gallic acid decyl amide, gallic acid lauramide, gallic acid myristamide, nutgallAcid palmitamide, gallic acid stearamide, gallic acid oil base acid amides, gallic acid (N-coco group) propionamide, nutgallIn acid (N-tallow base) propionamide, gallic acid (N-hydrogenated-tallow group) propionamide and gallic acid (N-oil base) propionamide oneKind or multiple.
12. compositions of additives according to claim 1, wherein, this compositions of additives also contains other additive, instituteState other additive and be selected from phenol type antioxidant, macromolecule amine type ashless dispersant, flow improving agent, cetane number improver, goldOne or more in genus passivator, antistatic additive, anticorrisive agent, antirust agent, demulsifier.
13. 1 kinds of Dresel fuel compositions, this Dresel fuel compositions contains basic diesel oil and additive, and described basic diesel oil contains biological bavinOil, is characterized in that, described additive is the compositions of additives described in any one in claim 1-12.
14. Dresel fuel compositions according to claim 13, wherein, described additive with respect to the content of basic diesel oil is50-10000 ppm by weight.
15. according to the Dresel fuel compositions described in claim 13 or 14, and wherein, described basic diesel oil also contains other diesel oil, instituteState other diesel oil and be petroleum diesel, Fischer-Tropsch combined diesel oil, containing one or more in oxygen diesel oil blending thing, described biodieselWith the volume ratio of other diesel oil be 1:2-99.
16. 1 kinds are improved the method for oxidation stability of biodiesel, and the method comprises, in the basic diesel oil that contains biodieselAdd additive, it is characterized in that, described additive is the compositions of additives described in any one in claim 1-12.
17. methods according to claim 16, wherein, described additive is 50-with respect to the addition of basic diesel oil10000 ppm by weight.
18. according to the method described in claim 16 or 17, and wherein, described basic diesel oil also contains other diesel oil, described otherDiesel oil is petroleum diesel, Fischer-Tropsch combined diesel oil, containing one or more in oxygen diesel oil blending thing, described biodiesel and otherThe volume ratio of diesel oil is 1:2-99.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009108851A1 (en) * | 2008-02-29 | 2009-09-03 | Novus International Inc. | Biodiesel stabilizing compositions |
| CN102307974A (en) * | 2009-02-09 | 2012-01-04 | 英诺斯派有限公司 | Improvements in fuels |
| CN103215091A (en) * | 2008-06-25 | 2013-07-24 | 中国石油化工股份有限公司 | Biodiesel composition and method for increasing oxidation stability of biodiesel-containing fuel |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009108851A1 (en) * | 2008-02-29 | 2009-09-03 | Novus International Inc. | Biodiesel stabilizing compositions |
| CN103215091A (en) * | 2008-06-25 | 2013-07-24 | 中国石油化工股份有限公司 | Biodiesel composition and method for increasing oxidation stability of biodiesel-containing fuel |
| CN102307974A (en) * | 2009-02-09 | 2012-01-04 | 英诺斯派有限公司 | Improvements in fuels |
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