WO2007115844A1 - Procede d'augmentation de la stabilite a l'oxydation de biodiesel - Google Patents

Procede d'augmentation de la stabilite a l'oxydation de biodiesel Download PDF

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Publication number
WO2007115844A1
WO2007115844A1 PCT/EP2007/051110 EP2007051110W WO2007115844A1 WO 2007115844 A1 WO2007115844 A1 WO 2007115844A1 EP 2007051110 W EP2007051110 W EP 2007051110W WO 2007115844 A1 WO2007115844 A1 WO 2007115844A1
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Prior art keywords
butyl
tert
biodiesel
bis
type
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PCT/EP2007/051110
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German (de)
English (en)
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Hark-Oluf Asbahr
Thomas Bomba
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Oxiris Chemicals S.A.
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Priority to BRPI0710150-3A priority Critical patent/BRPI0710150A2/pt
Priority to US12/296,616 priority patent/US20090158644A1/en
Priority to EP07726312A priority patent/EP2007859A1/fr
Publication of WO2007115844A1 publication Critical patent/WO2007115844A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to a method for increasing the oxidation stability of biodiesel.
  • Biodiesel which consists of monoalkyl esters of vegetable oils, animal fats and also used cooking oils.
  • Biodiesel is obtained by transesterification of oils, such as rapeseed oil, soybean oil or sunflower oil, but also used cooking oils, with an alcohol in the presence of a catalyst.
  • Biodiesel Since the importance of biodiesel has recently gained increasing importance as an alternative diesel fuel in the passenger car sector, the production of biodiesel has also increased in recent years. Biodiesel has a high content of unsaturated fatty acid esters that can be easily oxidized by atmospheric oxygen. The products formed thereby (among other things acids, resins) can lead to corrosion and blockages in injection pumps and / or supply lines. The increasing use of alternative biodiesel as automotive fuel leads to a need for oxidation-stabilized biodiesel. According to the state of the art, it is preferable to add 2,6-di-tert-butyl-4-methylphenol (BHT) to the biodiesel as the primary antioxidant in order to fulfill the oxidation stability required by the DIN EN 14214 standard.
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • 2,6-di-tert-butyl-4-methylphenol as antioxidant is described by the European patent EP 0 189 049.
  • 2,6-di-tert-butyl-4-. methylphenol in amounts of from 10 to 100 ppm described as exclusive stabilizer in palm kernel fatty acid methyl esters of Ci 2 -Ci 8 fatty acid range.
  • DE 102 52 714 and WO 2004/044104 also describe a process for increasing the oxidation stability of biodiesel by adding di-2,6-tert.-butyl-4-hydroxytoluene.
  • a liquid stock solution containing from 15 to 60% by weight of mono- or dialkylhydroxytoluene dissolved in biodiesel is added to the biodiesel to be stabilized up to a concentration of 0.005 to 2% by weight of mono- or dialkylhydroxytoluene, based on the total solution Biodiesel added.
  • DE 102 52 715 describes a method for increasing the storage stability of biodiesel, in which a liquid stock solution containing from 15 to 60 wt .-% 2,4-di-tert-butylhydroxytoluene dissolved in biodiesel, to be stabilized biodiesel until to a concentration of 0.005 to 2 wt .-% of 2,4-di-tert-butylhydroxytoluene, based on the total solution of biodiesel, metered.
  • phenylenediamines as well as the diphenylamines, which are commonly used as antiozonants for rubber or as stabilizers for synthetic lubricants and fossil fuels, have an effectiveness for the stabilization of biodiesel.
  • the effectiveness of this class of phenylenediamine compounds is in many cases higher than the phenolic antioxidants used hitherto, while the effectiveness of the diphenylamines is comparable to the effectiveness of the phenolic antioxidants. Due to the significantly higher efficiency significantly lower amounts can be added to achieve the same stability of the biodiesel.
  • the present invention therefore provides a process for increasing the oxidation stability of biodiesel, which is characterized in that at least one antidegradant according to the structure I
  • R hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylaryl, arylalkyl,
  • Cycloalkyl, hydroxy or aryl group A R 5 (AI) or -NRiR 2 (All) and
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylaryl, arylalkyl, cycloalkyl, hydroxy or aryl group, are the same or different and the phenyl or naphthyl structural unit in structure I, BII and BIII has one, two or three substituents of the type R 3 , R 4 and / or R 5 ,
  • Another object of the invention is the use of compounds according to the structure I as an anti-aging agent to increase the oxidation stability of biodiesel.
  • an oxidation-stabilized biodiesel which is distinguished by the fact that the biodiesel has from 5 to 20,000 ppm (w / w) at least one antidegradant according to structure I.
  • the inventive method for increasing the oxidation stability of biodiesel is characterized in that at least one anti-aging agent according to the structure I
  • R hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylaryl, arylalkyl,
  • Cycloalkyl, hydroxy or aryl group A R 5 (AI) or -NRiR 2 (All) and
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylaryl, arylalkyl, cycloalkyl, hydroxy or aryl group, are the same or different and the phenyl or naphthyl structural unit in structure I, BII and BIII has one, two or three substituents of the type R 3 , R 4 and / or R 5 ,
  • w / w is added to the biodiesel to be stabilized in an amount of 5 to 20,000 ppm (w / w), preferably 50 to 12,000 ppm (w / w), and preferably 100 to 8,000 ppm (w / w).
  • At least one anti-aging agent according to structure II is preferred.
  • R, Ri, R 2 and R 6 are hydrogen, alkyl, cycloalkyl and / or aryl group, wherein the substituents of the type R, R 1 , R 2 and R 6 are identical or different, used, particularly preferably at least one anti-aging agent is used according to structure III:
  • R, Ri, R 2 and R 6 are hydrogen, alkyl, cycloalkyl and / or aryl group, wherein the substituents of the type R, R 1 , R 2 and R 6 are identical or different.
  • At least one anti-aging agent of structure III which has as substituents of the R, R 1 , R 2 and R 6 type alkyl, cycloalkyl and / or aryl groups with a number of carbon atoms of 1 to 20 , preferably from 1 to 10, or hydrogen.
  • the alkyl groups of the substituents of the R, R 1 , R 2 and R 6 type may in this case be both linear and branched.
  • the alkyl groups of the substituents of the type R, R 1 , R 2 and R 6 are unsubstituted.
  • Particularly preferred are alkyl groups selected from iso-propyl, 1-methylethyl, sec-butyl, 1,3-dimethylbutyl, 1, 4-dimethylpentyl, 1-ethyl-3-methylpentyl and 1-methyl heptyl group, as substituents of the type R, R 1 , R 2 and R 6 .
  • the cyclohexyl group is preferably suitable for the substituents of the R, R 1 , R 2 and R 6 type.
  • the aryl group of the substituents R, R 1 , R 2 and R 6 is preferably phenyl, tolyl or naphthyl, which aryl groups may be substituted or unsubstituted.
  • at least one anti-aging agent according to structure III is added in the process according to the invention, wherein the substituents R and Ri are hydrogen, preferably an anti-aging agent according to structure III is added, wherein the substituents of the type R and Ri are hydrogen and the substituents of the type R 2 and R 6 are the same.
  • Anti-aging agents selected from N, N'-dialkyl-p-phenylenediamines, such as N, N'-diisopropyl-p-phenylenediamine, N, N-di-SeL-butyl-p-phenylenediamine (44PD), N, N'- Bis (1,4-dimethylpentyl) -p-phenylenediamine (77PD), N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine (DOPD) or N, N'-bis (1-methyl) heptyl) -p-phenylenediamine, N, N'-dicycloalkyl-p-phenylenediamines, such as, for example, N, N'-dicyclohexyl-p-phenylenediamine, and N, N'-diaryl-p-phenylenediamines, such as, for example, N, N'- Diphen
  • aging inhibitors according to structure III can be added in the process according to the invention, but here too the substituents of the R and Ri types are hydrogen, but the two substituents of the R 2 and R 6 types are different from one another.
  • anti-aging agents selected from N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (6PPD), N- (l- Methylethyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl -p-phenylenediamine and N, N'-diaryl-p-phen
  • this aging inhibitors selected from diphenylamine, alkylated diphenylamines, in particular, these alkyl groups on the Phenyl Modellismeen of 1 to 10 carbon atoms, preferably 4 to 9 carbon atoms, and, styrenated diphenylamines used.
  • the anti-aging agents according to the structure I to III can be used both as sole anti-aging agent and as a mixture of different compounds according to the structures I to III in the inventive method.
  • primary and / or secondary antioxidants as a pure substance or as a mixture of different primary and secondary antioxidants, are used.
  • primary antioxidants are compounds which are capable of stopping radical degradation reactions by chain termination reactions as free-radical scavengers.
  • hindered phenols preferably selected from alkylated monophenols, preferably 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6- Di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4 - /, s-butylphenol,
  • nonylphenols where the nonyl group may be linear or branched, such as, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1-methyl-undec-1-yl ) phenol, 2,4-dimethyl-6- (r-methyl-heptadec-1-yl) -phenol, 2,4-dimethyl-6- (1-methyl-tridec-1-yl) -phenol, tri- t-butylphenols, in particular 2,4,6-tri-tert-butylphenol, di-tert-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di t-butylphenol, 2,6-di-t-butylphenol, di-te / t-butylmethylphenols, especially 2,5-di-tert-butyl-4-methylphenol, 2.6 Di-tert-butyl-4-methylphenol,
  • Butyldimethylphenole esp 4-tert.-butyl-2,6-dimethylphenol, 6-butanol-2,4-dimethylphenol, 1-butyl-2,5-dimethylphenol, tert-butylphenol, in particular 2-Butylphenol, 4-tert-butylphenol, di-sec-butylphenols, sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol , 4-5'-L-butyl-2,6-di-tert-butylphenol, tert-amylphenols, in particular 2-tert-amyl-phole, di-tert-amylphenols, in particular 2,4-di- ert-amylphenol, 2- Isopropylphenol, 4-octylphenol, 4-nonylphenols, especially 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol,
  • Alkylthiomethylphenols preferably 2,4-dioctylthiomethyl-6-tert.-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
  • Hydroquinones and alkylated hydroquinones preferably 2,6-di-tert-butyl-4-methoxyphenol, tert-butylhydroquinone (TBHQ), especially 2,5-di-tert-butyl-hydroquinone, 2 , 6-di-tert-butyl-hydroquinone, 2,5-di-L-L-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, butylated hydroxyanisole (BHA), especially 2,5-diene tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis (3,5-di-tert-butyl-4-hydroxyanisole) te / t.-butyl-4-hydroxyphenyl) adipate; Tocopherols, preferably ⁇ -,
  • O-, N- and S-benzyl compounds preferably 3,5,3 ', 5'-tetra-te / t.-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
  • Tridecyl-4-hydroxy-3,5-di-? -? - butylbenzylmercaptoacetate tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-) hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxy-benzyl) -sulfide, SO 2-octyl-3,5-di-tert-butyl-butyl 4-hydroxybenzylmercaptoacetate; hydroxybenzylated malonates, preferably dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5 - methylbenzyl) malonate, didodecyl-mercaptoethyl-2,
  • Triazine compounds preferably 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, I, 3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-
  • Acylaminophenols preferably 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate; Esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, ⁇ - (5-butyl-4-hydroxy-3-methylphenyl) propionic acid, ⁇ - (3 , 5-dicyclohexyl-4-hydroxyphenyl) propionic acid and / or 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, wherein the alcohol component in each case methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1, 6 Hexanediol, 1.9- Nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
  • Amides of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine; - ascorbic acid (vitamin C);
  • Pentaerythritol tetrakis [3 - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] (IRGANOX 1010), N, N'-hexane-1,6-diyl-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide)] (IRGANOX 1098), ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ( IRGANOX 245) and mixtures of these compounds are added to the biodiesel to be stabilized.
  • secondary antioxidants are compounds which are capable of reducing hydroperoxide groups directly under reduction without any further formation of radicals.
  • alkylthiomethylphenols preferably selected from
  • Triphenyl phosphite - diphenylalkyl phosphites
  • Trioctadecyl phosphite distearyl pentaerythritol diphosphite
  • biodiesel is understood as meaning all saturated and / or unsaturated fatty acid alkyl esters, in particular fatty acid methyl esters or fatty acid ethyl esters, which can be used as energy carriers.
  • energy sources are both fuels, such as heating material, and fuels, for example for automobiles, trucks, ships or aircraft.
  • a biodiesel is preferably used which is usually offered under the term biodiesel in Germany for use as automotive fuel.
  • the biodiesel used in the inventive process has, in particular C 12 -C 24 - fatty acid alkyl ester, preferably C 2 -C 24 fatty acid methyl esters or C 2 -C 24 -Fettklareethylester, on which may be present in pure form or as a mixture.
  • the biodiesel used in the process according to the invention may moreover contain all conventional additives, such as, for example, primary and / or secondary antioxidants, defoamers, cold flow improvers.
  • Biodiesel which is produced from vegetable and / or animal oils by a transesterification process with an alcohol, preferably methanol or ethanol, particularly preferably methanol, is preferably used in the process according to the invention.
  • Biodiesel consisting of transesterification products of rapeseed oil, soybean oil, sunflower oil, palm oil, palm kernel oil, coconut oil, jatropha oil, cotton kernel oil, peanut kernel oil, corn kernel oil and / or used cooking oils is preferably used in the process according to the invention.
  • biodiesel is particularly preferably used, which is obtained by said transesterification from rapeseed oil, palm oil, sunflower oil or soybean oil.
  • Mixtures of the transesterification products of various vegetable and / or animal oils can also be used in the process according to the invention.
  • biodiesel mixtures also known as blends
  • Be present fatty acid alkyl esters with liquid fuels, such as mineral diesel fuel, fuel oil, are used. Particularly preferred is a
  • the oxidation-stabilized biodiesel can be used in an amount of 0.1 to 99.9 vol .-%, in particular 1 to 50 vol .-% and preferably from 2 to 25 vol .-% of a liquid energy carrier, in particular mineral diesel fuel or fuel oil, are added.
  • a liquid energy carrier in particular mineral diesel fuel or fuel oil
  • the anti-aging agents may in the process according to the invention in an amount of 5 to 20,000 ppm (w / w), preferably from 50 to 12,000 ppm (w / w) and preferably from 100 to 8000 ppm (w / w) as a solid or as a liquid Biodiesel be added.
  • biodiesel may also contain primary and / or secondary antioxidants in an amount of from 5 to 20,000 ppm (w / w), preferably from 50 to 12,000 ppm (w / w) and preferably from 100 to 8,000 ppm (w / w). be added.
  • the aging inhibitors which are present as a solid at room temperature, in the inventive method with stirring at a temperature of 18 ° C to 80 0 C, preferably at 20 0 C to 35 ° C, dissolved in the biodiesel.
  • Anti-aging agents which are present as a liquid at room temperature, can be mixed homogeneously without stirring with an increase in temperature with the biodiesel to be stabilized.
  • the aging inhibitor is dissolved in biodiesel before it is added to the energy carrier biodiesel to produce a masterbatch.
  • a masterbatch preferably initially from 2 to 99% by weight, preferably from 15 to 70% by weight, particularly preferably from 20 to 60% by weight, of the anti-aging agent is dissolved in biodiesel.
  • this masterbatch can be added to the energy carrier biodiesel, preferably this is done with stirring at a temperature of 18 ° C to 80 0 C, preferably at 20 0 C to 35 ° C.
  • the aging inhibitor if present as a solid at room temperature, is dissolved in an organic solvent, preferably in an alcohol or in an aromatic, before being added to the biodiesel.
  • an organic solvent preferably in an alcohol or in an aromatic
  • you can the solution of the anti-aging agent is added to the energy carrier biodiesel, preferably this is done with stirring at a temperature of 18 ° C to 80 0 C, preferably at 20 0 C to 35 ° C.
  • the anti-aging agent may be added directly in the process of the present invention when the anti-aging agent is a liquid, especially in an amount of 5 to 20,000 ppm (w / w), preferably 50 to 12,000 ppm (w / w), and preferably 100 to 8000 ppm (w / w), wherein a direct addition means that no preparation of a solution or a masterbatch of the anti-aging agent has taken place in a preceding process step.
  • the biodiesel may additionally contain primary and secondary antioxidants in an amount of from 5 to 20,000 ppm (w / w), preferably from 50 to 12,000 ppm (w / w) and preferably from 100 to 8,000 ppm (w / w), be added.
  • the aging inhibitor is dissolved with stirring at a temperature of 18 ° C to 80 0 C, preferably at 20 0 C to 40 0 C, in the biodiesel.
  • Another object of the invention is the use of compounds according to the structure I.
  • R hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylaryl, arylalkyl, cycloalkyl, hydroxy or aryl group
  • A R 5 (AI) or -NRiR 2 (All) and
  • At least one anti-aging agent consisting of phenylenediamines according to structure II is preferred
  • R, Ri, R 2 and R 5 hydrogen, alkyl, cycloalkyl and / or aryl group, wherein the substituents of the type R, R 1 , R 2 and R 5 are identical or different.
  • At least one anti-aging agent is used according to structure III:
  • R, R 1 , R 2 and R 6 hydrogen, alkyl, cycloalkyl and / or aryl group, wherein the substituents of the type R, R 1 , R 2 and R 6 are identical or different.
  • At least one aging inhibitor of the structure III which has as substituents of the R, R 1 , R 2 and R 6 type alkyl, cycloalkyl and / or aryl groups with a number of carbon atoms of 1 to 20 and preferably from 1 to 10 or hydrogen.
  • the alkyl groups of the substituents of the R, R 1 , R 2 and R 6 type may in this case be both linear and branched.
  • the alkyl groups of the substituents of the type R, R 1 , R 2 and R 6 are unsubstituted.
  • Particularly preferred are alkyl groups selected from iso-propyl, 1-methylethyl, sec-butyl, 1,3-dimethylbutyl, 1, 4-dimethylpentyl, 1-ethyl-3-methylpentyl and 1-methyl heptyl group, as substituents of the type R, R 1 , R 2 and R 6 .
  • the cyclohexyl group is preferably suitable for the substituents of the R, R 1 , R 2 and R 6 type.
  • the aryl group of the substituents R, R 1 , R 2 and R 6 is preferably phenyl, tolyl or naphthyl, which aryl groups may be substituted or unsubstituted.
  • At least one anti-aging agent according to structure III is added to the biodiesel to be stabilized, the substituents of the R and Ri types being, preferably being, hydrogen an anti-aging agent according to the structure III is added, wherein the substituents of the type R and Ri are hydrogen and the substituents of the type R 2 and R 6 are the same.
  • Anti-aging agents selected from N, N'-dialkyl-p-phenylenediamines, such as N, N'-diisopropyl-p-phenylenediamine, N, N-di-SeL-butyl-p-phenylenediamine (44PD), N, N'- Bis (1,4-dimethylpentyl) -p-phenylenediamine (77PD), N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine (DOPD) or N, N'-bis (1-methyl) heptyl) -p-phenylenediamine, N, N'-dicycloalkyl-p-phenylenediamines, such as, for example, N, N'-dicyclohexyl-p-phenylenediamine, and N, N'-diaryl-p-phenylenediamines, such as, for example, N, N'- Diphen
  • aging inhibitors according to structure III can be added in the use according to the invention, whereby here too the substituents of the type R and Ri
  • the two substituents of the type R 2 and R 6 are different from each other.
  • aging inhibitors selected from N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N- (1, 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine
  • N- (1-methylethyl) -N'-phenyl-p-phenylenediamine N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine , N-cyclohexyl-N'-phenyl-p-phenylenediamine and N, N'-diaryl-p-phenylenediamine derivatives.
  • this aging inhibitors selected from diphenylamine, alkylated diphenylamines, in particular, these alkyl groups on the Phenyl Modellismeen of 1 to 10 carbon atoms, preferably 4 to 9 carbon atoms, and, styrenated diphenylamines used.
  • the anti-aging agents according to the structure I to III can be used both as sole anti-aging agent and as a mixture of different compounds according to the structures I to III in the inventive use.
  • the invention likewise relates to oxidation-stabilized biodiesel, which is characterized in that the biodiesel is from 5 to 20,000 ppm (w / w), preferably from 50 to 12,000 ppm (w / w) and preferably from 100 to 8,000 ppm (w / w). at least one anti-aging agent according to the structure I
  • R hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylaryl, arylalkyl,
  • Cycloalkyl, hydroxy or aryl group A R 5 (AI) or -NRiR 2 (All) and
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylaryl, arylalkyl, cycloalkyl, hydroxy or aryl group, are the same or different and the phenyl or naphthyl structural unit in structure I, BII and BIII has one, two or three substituents of the type R 3 , R 4 and / or R 5 ,
  • the biodiesel according to the invention preferably has at least one anti-aging agent according to structure II
  • R, R 1 , R 2 and R 6 hydrogen, alkyl, cycloalkyl and / or aryl group, wherein the substituents of the type R, R 1 , R 2 and R 6 are identical or different.
  • this biodiesel has at least one anti-aging agent according to structure III:
  • R, Ri, R 2 and R 6 hydrogen, alkyl, cycloalkyl and / or aryl group, wherein the substituents of the type R, R 1 , R 2 and R 6 are the same or different.
  • the biodiesel according to the invention may comprise at least one structure III anti-aging agent having as substituents of the R, R 1 , R 2 and R 6 type alkyl, cycloalkyl and / or aryl groups having a number of carbon atoms of 1 to 20 and preferably of 1 to 10 or hydrogen.
  • the alkyl groups of the substituents of the R, R 1 , R 2 and R 6 type may in this case be both linear and branched.
  • the alkyl groups of the substituents of the type R, R 1 , R 2 and R 6 are unsubstituted.
  • alkyl groups selected from iso-propyl, 1-methylethyl, sec-butyl, 1,3-dimethylbutyl, 1, 4-dimethylpentyl, 1-ethyl-3-methylpentyl and 1-methyl heptyl group, as substituents of the type R, R 1 , R 2 and R 6 .
  • the cyclohexyl group is preferably suitable for the substituents of the R, R 1 , R 2 and R 6 type.
  • the aryl group of the substituents R, R 1 , R 2 and R 6 is preferably phenyl, tolyl or naphthyl, which aryl groups may be substituted or unsubstituted.
  • the biodiesel according to the invention comprises at least one anti-aging agent according to structure III, wherein the substituents of the R and Ri are hydrogen, preferably this Biodiesel at least one anti-aging agent according to the structure III, wherein the substituents of the type R and Ri are hydrogen and the substituents of the type R 2 and R 6 are the same.
  • Anti-aging agents selected from N, N'-dialkyl-p-phenylenediamines, such as N, N'-diisopropyl-p-phenylenediamine, N, N-di-SeL-butyl-p-phenylenediamine (44PD), N, N'- Bis (1,4-dimethylpentyl) -p-phenylenediamine (77PD), N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine (DOPD) or N, N'-bis (1-methyl) heptyl) -p-phenylenediamine, N, N'-dicycloalkyl-p-phenylenediamines, such as, for example, N, N'-dicyclohexyl-p-phenylenediamine, and N, N'-diaryl-p-phenylenediamines, such as, for example, N, N'- Diphen
  • the biodiesel according to the invention may have aging inhibitors in accordance with the structure III, but here too the substituents of the R and Ri types are hydrogen, but the two substituents of the R 2 and R 6 types are different from one another.
  • the biodiesel according to the invention preferably comprises aging inhibitors selected from N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (6PPD), N- ( 1-methylethyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine and N, N'-diary
  • Anti-aging agents selected from diphenylamine, alkylated diphenylamines, in particular, these alkyl groups on the Phenyl Modellumbleen from 1 to 10
  • Carbon atoms preferably 4 to 9 carbon atoms, on, and styrenated diphenylamines.
  • the biodiesel according to the invention can have both the compounds according to the structures I to III as pure substance as well as a mixture of different compounds according to the structures I to III as anti-aging agent.
  • the biodiesel invention comprises in particular C 2 -C 24 -Fettklarealkylester, preferably Ci 2 -C 24 fatty acid methyl esters or C 2 -C 24 -Fettklareethylester on, which may be present in pure form or as a mixture.
  • the biodiesel according to the invention may contain all customary additives, such as, for example, primary and / or secondary antioxidants, defoamers, cold flow improvers.
  • the biodiesel according to the invention preferably comprises transesterification products of rapeseed oil, soybean oil, sunflower oil, palm kernel oil, coconut oil, jatropha oil, cotton kernel oil, peanut kernel oil, corn kernel oil and / or used cooking oils.
  • the biodiesel according to the invention particularly preferably has transesterification products which are obtained by transesterification from rapeseed oil, palm oil, sunflower oil or soybean oil.
  • the biodiesel according to the invention may also comprise mixtures of the transesterification products of various vegetable and / or animal oils.
  • the biodiesel according to the invention can be sterically hindered
  • Phenols preferably selected from alkylated monophenols, preferably 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4- n-butylphenol, 2,6-di-tert-butyl-4 - /, s-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol, 2.6 - Dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols, where the nonyl group may be linear or branched, such as, for example, 2,6-dinonyl-4- methylphenol, 2,4-dimethyl-6- (r -methyl-undec-1-yl) -phenol, 2,
  • ert-amylphenols in particular 2,4-di-tert-amylphenol, 2-isopropylphenol, 4-octylphenol, 4-nonylphenols, in particular 2,6-di-tert-butyl-4-nonylphenol, 4- Dodecylphenol, octadecylphenol; Alkylthiomethylphenols, preferably 2,4-dioctylthiomethyl-6-? butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-
  • Hydroquinones and alkylated hydroquinones preferably 2,6-di-tert-butyl-4-methoxyphenol, tert-butylhydroquinone (TBHQ), in particular 2,5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-hydroquinone, 2,5-di-? -Amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, butylated hydroxyanisole (BHA), especially 2,5-di - tert. butyl 4-hydroxyanisole, 3, 5-di-tert. butyl 4-hydroxyanisole, 3, 5-di-tert.
  • BHA butylated hydroxyanisole
  • -butyl-4-hydroxyphenyl stearate bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate
  • Tocopherols preferably ⁇ -, ⁇ -, ⁇ - or ⁇ -tocopherols (vitamin E); hydroxylated thiodiphenyl ethers, preferably 2,2'-thiobis [4-octylphenol], 2,2'-thiobis [6-tert-butyl-4-methylphenol], 4,4'-bis [2,6-dimethyl-4 hydroxyphenyl] disulfide,
  • alkylated bisphenols preferably 2,2'-ethylidenebis [4,6-di-tert-butylphenol], 2,2'-ethylidenebis [6-tert.-butyl-4-isobutylphenol], 2,2 ' Isobutylidene bis [4,6-dimethylphenol], 2,2'-methylenebis [4,6-di-tert-butylphenol], 2,2'-methylenebis [4-methyl-6- ( ⁇ -methylcyclohexyl) phenol ], 2,2'-methylenebis [4-methyl-6-cyclohexylphenol], 2,2'-methylenebis [4-methyl-6-nonylphenol], 2,2'-methylenebis [6- ( ⁇ , ⁇ '-dimethylbenzyl ) -4-nonylphenol], 2,2'-methylenebis [6- ( ⁇ , ⁇ '-dimethylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6-
  • Triazine compounds preferably l, 3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, l, 3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (4-tert-butyl-3-) hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1, 3,5-triazine, 2,4,6-tris (
  • Acylaminophenols preferably 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate; Esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, ⁇ - (5-butyl-4-hydroxy-3-methyl-phenyl) -propionic acid, ⁇ - (3 , 5-dicyclohexyl-4-hydroxyphenyl) propionic acid and / or 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, wherein the alcohol component in each case methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1, 6 Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopent
  • IRGANOX 1098 ethylene bis (oxyethylene) bis [3- (5- tert -butyl-4-hydroxy-m-tolyl) propionate (IRGANOX 245) and mixtures of these compounds.
  • the biodiesel according to the invention can be alkylthiomethylphenols, preferably selected from - 2,4-di- ((octylthio) methyl) -6-tert-butylphenol,
  • Phosphites or phosphonites preferably selected from
  • Phenyl dialkyl phosphites tris [nonylphenyl] phosphite
  • Esters of ⁇ -thio-dipropionic acid preferably the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide or
  • these mixtures also called blends
  • the fatty acid alkyl esters may also be present as a mixture of different fatty acid alkyl esters, with liquid fuels, such as mineral diesel fuel, fuel oil exhibit.
  • the biodiesel according to the invention particularly preferably has a mixture of mineral diesel fuel and from 0.1 to 99.9% by volume, in particular 1 to 50% by volume and preferably from 2 to 25% by volume, of saturated and / or unsaturated Fatty acid alkyl esters on.
  • the biodiesel according to the invention has the anti-aging agents in an amount of from 5 to 20,000 ppm (w / w), preferably from 50 to 12,000 ppm (w / w) and preferably from 100 to 8,000 ppm (w / w). Furthermore, the biodiesel according to the invention may also have primary and / or secondary antioxidants in an amount of from 5 to 20,000 ppm (w / w), preferably from 50 to 12,000 ppm (w / w) and preferably from 100 to 8,000 ppm (w / w) ,
  • biodiesel according to the invention is preferably prepared according to the process of the invention.
  • the following examples are intended to explain the process according to the invention in more detail, without the invention being restricted to this embodiment.
  • Example 1 Preparation of the samples in a glass beaker is dissolved at 20 0 C with stirring, the anti-aging agent in biodiesel, while stirring until a solution is obtained.
  • the anti-aging agents used as well as the biodiesel used, as well as the proportions are shown in Table 1.
  • Example 1 The samples prepared according to Example 1 were prepared according to the test method DIN EN 14112 respect. Their oxidation stability tested at a test temperature of 110 0 C.
  • the anti-aging agent was composed as follows:
  • N- (l, 4-dimethylpentyl) -N'-phenyl-p-phenylenediamine 30-40% by weight of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine 0-3% by weight of N-phenyl-p-phenylenediamine 1% by weight of diphenylamine -1% by weight of N- (1-methylethyl) -N'-phenyl-p-phenylenediamine

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Abstract

L'invention concerne un procédé d'augmentation de la stabilité à l'oxydation de biodiesel, caractérisé en ce qu'au moins un agent anti-vieillissement de structure (I), avec : R = hydrogène, alkyle, alcényle, alcynyle, alcoxy, alkylaryle, arylalkyle, cycloalkyle, hydroxy ou aryle, A = R5 (AI) ou -NR1R2 (AII) et B= R6 (BI), structure (BII) ou structure (BIII), R1, R2, R3, R4, R5 et R6 = hydrogène, alkyle, alcényle, alcynyle, alcoxy, alkylaryle, arylalkyle, cycloalkyle, hydroxy ou aryle, étant identiques ou différents et l'unité phényle ou naphtyle dans la structure (I), (BII) et (BIII) comprenant un, deux ou trois substituants du type R3, R4 et/ou R5, est ajouté en une quantité comprise entre 5 et 20 000 ppm (p/p) au biodiesel à stabiliser. L'invention concerne également l'utilisation de cet agent anti-vieillissement pour l'augmentation de la stabilité à l'oxydation de biodiesel, ainsi que le biodiesel stable à l'oxydation correspondant.
PCT/EP2007/051110 2006-04-10 2007-02-06 Procede d'augmentation de la stabilite a l'oxydation de biodiesel WO2007115844A1 (fr)

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BRPI0710150-3A BRPI0710150A2 (pt) 2006-04-10 2007-02-06 processo para o aumento da estabilidade de oxidação de biodiesel
US12/296,616 US20090158644A1 (en) 2006-04-10 2007-02-06 Method of increasing the oxidation stability of biodiesel
EP07726312A EP2007859A1 (fr) 2006-04-10 2007-02-06 Procede d'augmentation de la stabilite a l'oxydation de biodiesel

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DE102006017105A DE102006017105A1 (de) 2006-04-10 2006-04-10 Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel
DE102006017105.5 2006-04-10

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US8367593B2 (en) 2009-10-02 2013-02-05 Exxonmobil Research And Engineering Company Method for improving the resistance to one or more of corrosion, oxidation, sludge and deposit formation of lubricating oil compositions for biodiesel fueled engines
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DK2396390T3 (en) * 2009-02-11 2017-01-16 Agowa Ip Aps Use of a preparation as a lamp fuel
EP2447344B1 (fr) 2009-06-26 2019-07-24 China Petroleum & Chemical Corporation Composition de diesel et procédé pour l'amélioration de la stabilité d'un biodiesel à l'oxydation
CN101760328B (zh) * 2009-12-31 2012-01-25 大连理工大学 一种支化生物柴油的生产方法
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BRPI0710150A2 (pt) 2011-08-02
ZA200808568B (en) 2009-06-24
EP2007859A1 (fr) 2008-12-31

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