EP1736528A2 - Process for increasing the oxidative stability of biodiesel. - Google Patents

Process for increasing the oxidative stability of biodiesel. Download PDF

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Publication number
EP1736528A2
EP1736528A2 EP06101504A EP06101504A EP1736528A2 EP 1736528 A2 EP1736528 A2 EP 1736528A2 EP 06101504 A EP06101504 A EP 06101504A EP 06101504 A EP06101504 A EP 06101504A EP 1736528 A2 EP1736528 A2 EP 1736528A2
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EP
European Patent Office
Prior art keywords
tert
butyl
biodiesel
primary antioxidant
methylphenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06101504A
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German (de)
French (fr)
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EP1736528A3 (en
Inventor
Hark-Oluf Asbahr
Thomas Bomba
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Filing date
Publication date
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Publication of EP1736528A2 publication Critical patent/EP1736528A2/en
Publication of EP1736528A3 publication Critical patent/EP1736528A3/en
Withdrawn legal-status Critical Current

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D1/00—Water flushing devices with cisterns ; Setting up a range of flushing devices or water-closets; Combinations of several flushing devices
    • E03D1/02—High-level flushing systems
    • E03D1/14—Cisterns discharging variable quantities of water also cisterns with bell siphons in combination with flushing valves
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • 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
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D1/00—Water flushing devices with cisterns ; Setting up a range of flushing devices or water-closets; Combinations of several flushing devices
    • E03D1/30—Valves for high or low level cisterns; Their arrangement ; Flushing mechanisms in the cistern, optionally with provisions for a pre-or a post- flushing and for cutting off the flushing mechanism in case of leakage
    • E03D1/34—Flushing valves for outlets; Arrangement of outlet valves
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D5/00—Special constructions of flushing devices, e.g. closed flushing system
    • E03D5/10—Special constructions of flushing devices, e.g. closed flushing system operated electrically, e.g. by a photo-cell; also combined with devices for opening or closing shutters in the bowl outlet and/or with devices for raising/or lowering seat and cover and/or for swiveling the bowl
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D1/00—Water flushing devices with cisterns ; Setting up a range of flushing devices or water-closets; Combinations of several flushing devices
    • E03D1/02—High-level flushing systems
    • E03D1/14—Cisterns discharging variable quantities of water also cisterns with bell siphons in combination with flushing valves
    • E03D2001/147—Cisterns discharging variable quantities of water also cisterns with bell siphons in combination with flushing valves having provisions for active interruption of flushing

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 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 become increasingly important 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 prior art, the biodiesel as primary antioxidant preferably 2,6-di-tert-butyl-4-methylphenol (BHT) is added to meet the required in the standard DIN EN 14214 oxidation stability.
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • 2,6-di-tert-butyl-4-methylphenol as antioxidants describes the European Patent EP 0 189 049 , Described herein is the use of 2,6-di-tert-butyl-4-methylphenol in amounts of 10 to 100 ppm as the only stabilizer in palm kernel fatty acid methyl esters of the C 12 -C 18 fatty acid range.
  • WO 2004/044104 describes a method 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, comprising the preparation of a liquid stock solution containing from 15 to 60% by weight of 2,4-di-tert-butylhydroxytoluene dissolved in biodiesel, to biodiesel to be stabilized up to a concentration of 0.005 to 2 wt .-% of 2,4-di-tert-butylhydroxytoluene, based on the total solution of biodiesel, metered.
  • the primary antioxidant used in the process according to the invention is characterized by a low melting point, ie a melting point of less than or equal to 40.degree. Because of its low melting point, this primary antioxidant can be added as a liquid in the process of the invention directly to the biodiesel, without this primary antioxidant must first be dissolved in a solvent such as alcohol, or in biodiesel. Thus, the preparation of a masterbatch of these primary antioxidants in biodiesel can be dispensed with.
  • the masterbatches are usually produced with the biodiesel, for which the masterbatch should also be used later. Especially in the case of long distances between biodiesel and antioxidant manufacturers, this leads to high costs for storage and transport in the case of primary antioxidants according to the prior art.
  • the primary antioxidant used in the process of the invention thus leads to low production costs of the oxidation-stabilized biodiesel, since on the one hand can be dispensed with the preparation of solutions or masterbatches with the drug primary antioxidant, on the other hand, the present method shows that a product mixture from the manufacturing process of Substituted alkylphenols can be used without expensive separation and purification steps.
  • Another advantage of the method according to the invention is that the preparation of the oxidation-stabilized biodiesel can be carried out at lower temperatures and within a shorter time.
  • the inventive method thus enables an improvement in the economy in the production of oxidation-stabilized biodiesel.
  • the active ingredient content of the liquid primary antioxidant of the present invention is 100% versus 20% of the prior art liquid primary antioxidants because the liquid typically has only about 20% by weight of the active ingredient antioxidant.
  • transport and storage costs can also be saved due to the high active ingredient content of primary antioxidants per liter.
  • the use of a liquid primary antioxidant according to the method according to the invention also leads to a lower crystallization of the primary antioxidant at low temperatures in biodiesel or in plant components.
  • Another object of the invention is the use of a primary antioxidant having a melting point of less than or equal to 40 ° C and at least one compound according to the structure
  • R 1 , R 2 hydrogen, linear alkyl group having a carbon number of 1 to 20 or where * is a carbon atom of the aromatic ring system
  • R 3 , R 5 hydrogen, linear alkyl group having a carbon number of 1 to 20
  • R 4 hydrogen, linear alkyl group with a carbon number of 1 to 40, wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different, to increase the oxidation stability of biodiesel.
  • the invention likewise relates to an oxidation-stabilized biodiesel characterized in that the biodiesel has from 10 to 20,000 ppm (w / w) of a primary antioxidant, wherein the primary antioxidant has a melting point of less than or equal to 40 ° C and at least one compound according to the structure
  • R 1 , R 2 hydrogen, linear alkyl group having a carbon number of 1 to 20 or where * is a carbon atom of the aromatic ring system
  • R 3 , R 5 hydrogen, linear alkyl group having a carbon number of 1 to 20
  • R 4 hydrogen, linear alkyl group with a carbon number of 1 to 40, wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different.
  • the process according to the invention for increasing the oxidation stability of biodiesel is characterized in that a primary antioxidant having a melting point of less than or equal to 40 ° C. is added to the biodiesel to be stabilized in an amount of from 10 to 20,000 ppm (w / w) primary antioxidants at least one compound according to the structure
  • R 1 , R 2 hydrogen, linear alkyl group having a carbon number of 1 to 20 or where * is a carbon atom of the aromatic ring system
  • R 3 , R 5 hydrogen, linear alkyl group having a carbon number of 1 to 20
  • R 4 hydrogen, linear alkyl group with a carbon number of 1 to 40, wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different.
  • the primary antioxidant used in the inventive method has neither organic solvents, such as alcohols, or biodiesel, as for example in Trap of a masterbatch is on.
  • the primary antioxidant used therefore preferably has exclusively alkylphenols and / or substituted alkylphenols.
  • a mixture is used as the primary antioxidant, this mixture having various substituted and / or unsubstituted alkylphenols, preferably a mixture is used as the primary antioxidant, from 0.1 to 99.9 wt .-%, preferably from 50 to 99 wt .-% and particularly preferably from 55 to 90 wt .-% of one or more compounds according to structure I.
  • a mixture as the primary antioxidant which has exclusively compounds according to structure I.
  • This mixture has the advantage of having only compounds according to structure I , all of which have an oxidation-stabilizing effect on biodiesel.
  • a primary antioxidant which comprises at least one compound according to structure III is preferably added to the biodiesel having.
  • a primary antioxidant which contains at least one compound according to structure IV having.
  • the primary antioxidant used in the process according to the invention has a melting point of ⁇ 40 ° C., preferably of ⁇ 39 ° C. and particularly preferably of ⁇ 38 ° C.
  • biodiesel is to be understood as meaning all saturated and / or unsaturated fatty acid alkyl esters, in particular fatty acid methyl esters, usable as energy carriers Fatty acid ethyl ester, understood.
  • 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 for use as automotive fuel .
  • the biodiesel used in the process according to the invention has, in particular, C 12 -C 24 fatty acid alkyl esters, preferably C 12 -C 24 fatty acid methyl esters or C 12 -C 24 fatty acid ethyl esters, 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 customary additives, such as, for example, 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 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, 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.
  • the method according to the invention can be used as biodiesel mixtures of saturated and / or unsaturated fatty acid alkyl esters with liquid fuels, such as diesel fuel, fuel oil.
  • liquid fuels such as diesel fuel, fuel oil.
  • a mixture of diesel fuel and from 0.1 to 99.9% by volume, in particular from 2 to 10% by volume and preferably from 3 to 5% by volume, of saturated and / or unsaturated fatty acid alkyl esters.
  • the oxidation-stabilized biodiesel can be present in an amount of from 0.1 to 99.9% by volume, in particular from 1 to 20% by volume, preferably from 2 to 10% by volume and more preferably from 3 to 5 vol .-% of a liquid energy carrier, in particular diesel fuel or fuel oil, are added.
  • a liquid energy carrier in particular diesel fuel or fuel oil
  • the primary antioxidant is preferably directly in the process of the invention added, in particular in an amount of 10 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), wherein a direct addition is understood to mean no preparation of a solution or a masterbatch of the primary antioxidants was carried out in a preceding process step.
  • secondary antioxidants may also be added to the biodiesel in an amount of from 10 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).
  • the primary antioxidant is dissolved with stirring at a temperature of 18 ° C to 60 ° C, preferably at 20 ° C to 40 ° C, in the biodiesel.
  • the subject matter of the invention is the use of a primary antioxidant which has a melting point of less than or equal to 40 ° C. and at least one compound according to the structure I for increasing the oxidation stability of biodiesel.
  • a mixture as the primary antioxidant which comprises exclusively compounds according to structure I.
  • This mixture has the advantage of having only compounds according to structure I , all of which have an oxidation-stabilizing effect on biodiesel.
  • a primary antioxidant is used which has at least one compound according to structure II .
  • a primary antioxidant is used which comprises at least one compound according to structure III .
  • a primary antioxidant is used which has at least one compound according to structure IV .
  • the oxidation-stabilized biodiesel according to the invention is characterized in that this biodiesel has from 10 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) of a primary antioxidant which has a melting point less than or equal to 40 ° C and at least one compound according to structure I.
  • the primary antioxidant of the oxidation-stabilized biodiesel according to the invention therefore preferably comprises exclusively alkyphenols and / or substituted alkylphenols.
  • the oxidation-stabilized biodiesel according to the invention has a mixture as the primary antioxidant, this mixture having various substituted and / or unsubstituted alkylphenols.
  • the biodiesel according to the invention preferably has a primary antioxidant which contains from 0.1 to 99.9% by weight, preferably from 50 to 99% by weight and more preferably from 55 to 99% by weight, of one or more compounds according to Structure I has.
  • the biodiesel according to the invention particularly preferably has a mixture as the primary antioxidant, which comprises exclusively compounds according to structure I.
  • the biodiesel according to the invention preferably has a primary antioxidant which has at least one compound according to structure II .
  • the biodiesel according to the invention preferably has a primary antioxidant which has at least one compound according to structure III .
  • the biodiesel according to the invention particularly preferably has a primary antioxidant which has at least one compound according to structure IV .
  • the biodiesel according to the invention has, in particular, C 12 -C 24 fatty acid alkyl esters, preferably C 12 -C 24 fatty acid methyl esters or C 12 -C 24 fatty acid ethyl esters, 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, secondary antioxidants, defoamers.
  • the biodiesel according to the invention preferably comprises transesterification products of rapeseed oil, soybean oil, sunflower oil, palm kernel oil, coconut oil, jatropha oil and / or used cooking oils.
  • the inventive biodiesel on transesterification products which are obtained by the transesterification of rapeseed 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 of the present invention may have these secondary antioxidants in an amount of 10 to 20,000 ppm (w / w), preferably 50 to 12,000 ppm (w / w), and preferably 100 to 8,000 ppm (w / w).
  • the biodiesel according to the invention is preferably prepared according to the process of the invention.
  • the primary antioxidant is dissolved in biodiesel at 20 ° C with stirring, stirring is continued until a clear solution of the primary antioxidant in the biodiesel is obtained.
  • the primary antioxidants used as well as the biodiesel used, as well as the proportions are shown in Table 1.
  • Primary Antioxidants 1 obtained from Degussa AG under the trade name IONOL 99: > 99.0% by weight 2,6-di-tert-butyl phenol ⁇ 0.5% by weight 2-tert-butylphenol ⁇ 0.5% by weight 2,4-di-tert-butylphenol
  • Primary antioxidant 2 obtained from Degussa AG under the trade name IONOL K98: > 98.5% by weight 6-tert-butyl-2,4-dimethylphenol ⁇ 1.5% by weight 4-tert-butyl-2,6-dimethylphenol and di-tert-butylmethylphenols
  • Primary Antioxidants 3 obtained from Degussa AG under the trade name IONOL K65: > 55% by weight 6-tert-butyl-2,4-dimethylphenol > 15% by weight 2,6-di-tert-butyl-4-methylphenol 18-22% by weight tert-butyl-2,5-dimethylphenol ⁇ 1% by weight 4,6-di-tert-butyl-2-methylphenol ⁇ 3.5% by weight Di-tert-butyl-3-methylphenol ⁇ 3.5% by weight 2,5-di-tert-butyl-4-methylphenol
  • Primary antioxidants 4 obtained from Degussa AG under the trade name IONOL 75: > 75% by weight 2,6-di-tert-butyl phenol ⁇ 5% by weight 2-tert-butylphenol ⁇ 0.5% by weight 4-tert-butylphenol ⁇ 3% by weight 2,4-di-tert-butylphenol ⁇ 1% by weight 2,5-di-tert-butylphenol ⁇ 15.5% by weight 2,4,6 tri-tert-butylphenol
  • Example 1 The samples prepared according to Example 1 were tested in accordance with the test method DIN EN 14112 with respect to their oxidation stability at a test temperature of 110 ° C.
  • Table 1 antioxidants Amount of liquid antioxidants in ppm oxidation stability [in h at 110 ° C] Rapsölmethylester - - 5.1 1 500 6.7 2 500 6.5 3 500 6.6 4 500 6.7 Baynox * 2500 7.1 Altspeisefettemethylester - - 4.0 1 2000 9.7 2 2000 9.5 3 2000 9.1 4 2000 9.4 Baynox * 10000 12.0 Sojaölmethylester - - 3.6 1 2000 7.3 2 2000 6.6 3 2000 6.3 4 2000 7.1 Baynox * 10000 8.8 Sonnenblumenölmethylester - - 1.6 1 4000 8.8 2 4000 7.8 3 4000 6.9 4 4000 8.0 Baynox * 20000 9.0 * Baynox is an antioxidant from Lanxess and is a solution of the distilled, high-purity active ingredient in biodiesel.
  • the active ingredient content is adjusted to 20% g / l.
  • 11 Baynox ® correspond to 200 g of active ingredient. Analysis studies have shown that it is the active ingredient in Baynox ® 2.6-di-tert-butyl-4-hydroxytoluene.

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Abstract

Method for increasing oxidation stability of biodiesel, comprises adding a phenyl compound (I), as primary antioxidant, with a melting point of smaller than 40[deg]C to a biodiesel (10-20000 ppm (w/w)). Method for increasing oxidation stability of biodiesel, comprises adding a phenyl compound of formula (I), as primary antioxidant, with a melting point of smaller than 40[deg]C to a biodiesel (10-20000 ppm (w/w)). R 1>, R 2>H or 1-20C linear alkyl group or a-C(R 3>)(R 4>)(R 5>); R 3>, R 5>H or 1-20C linear alkyl group; and R 4>H or 1-40C linear alkyl group. An INDEPENDENT is included for an oxidation stable biodiesel. [Image].

Description

Die Erfindung betrifft ein Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel.The invention relates to a method for increasing the oxidation stability of biodiesel.

Eine Alternative zum herkömmlichen Dieselkraftstoff wird heutzutage in zunehmenden Maße Biodiesel eingesetzt, welcher aus Monoalkylestern von Pflanzenölen, Tierfetten und auch Altspeisefetten besteht. Gewonnen wird Biodiesel durch Umesterung von Ölen, wie beispielsweise Rapsöl, Sojaöl oder Sonnenblumenöl aber auch Altspeiseöle, mit einem Alkohol in Gegenwart eines Katalysators.An alternative to conventional diesel fuel is nowadays increasingly used biodiesel, which consists of monoalkyl esters of vegetable oils, animal fats and 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.

Da die Bedeutung von Biodiesel in jüngster Zeit als alternativer Dieselkraftstoff im PKW-Bereich immer mehr an Bedeutung gewinnt, hat im entsprechenden Maße auch die Produktion von Biodiesel in den letzten Jahren zugenommen. Biodiesel weist einen hohen Gehalt an ungesättigten Fettsäureestern auf, die leicht durch Luftsauerstoff oxidiert werden können. Die dabei gebildeten Produkte (u.a. Säuren, Harze) können zu Korrosionen und Verstopfungen in Einspritzpumpen und/oder Zuleitungen führen. Der zunehmende Einsatz der Alternative Biodiesel als Automobilkraftstoff führt zu einem Bedarf an oxidationsstabilisierten Biodiesel. Gemäß dem Stand der Technik wird dem Biodiesel als primäres Antioxidants vorzugsweise 2,6-Di-tert.-butyl-4-methylphenol (BHT) zugesetzt, um die in der Norm DIN EN 14214 geforderte Oxidationsstabilität zu erfüllen.Since the importance of biodiesel has recently become increasingly important 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 prior art, the biodiesel as primary antioxidant preferably 2,6-di-tert-butyl-4-methylphenol (BHT) is added to meet the required in the standard DIN EN 14214 oxidation stability.

Den Einsatz von 2,6-Di-tert.-butyl-4-methylphenol als Antioxidants beschreibt die europäische Patentschrift EP 0 189 049 . Hierin wird die Verwendung von 2,6-Di-tert.-butyl-4-methylphenol in Mengen von 10 bis 100 ppm als ausschließliches Stabilisierungsmittel in Palmkernfettsäuremethylestern des C12-C18-Fettsäurebereichs beschrieben.The use of 2,6-di-tert-butyl-4-methylphenol as antioxidants describes the European Patent EP 0 189 049 , Described herein is the use of 2,6-di-tert-butyl-4-methylphenol in amounts of 10 to 100 ppm as the only stabilizer in palm kernel fatty acid methyl esters of the C 12 -C 18 fatty acid range.

Auch die DE 102 52 714 bzw. WO 2004/044104 beschreibt ein Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel durch Zugabe von Di-2,6-tert.-butyl-4-hydroxytoluol. Eine flüssige Stammlösung, die von 15 bis 60 Gew.-% an Mono- oder Dialkylhydroxytoluol in Biodiesel gelöst enthält, wird zum zu stabilisierenden Biodiesel bis zu einer Konzentration von 0,005 bis 2 Gew.-% Mono- oder Dialkylhydroxytoluol bezogen auf die gesamte Lösung an Biodiesel zudosiert.Also the DE 102 52 714 respectively. WO 2004/044104 describes a method 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 beschreibt ein Verfahren zur Erhöhung der Lagerstabilität von Biodiesel, bei dem man eine flüssige Stammlösung, welche von 15 bis 60 Gew.-% 2,4-Di-tert.-butylhydroxytoluol in Biodiesel gelöst enthält, zum zu stabilisierenden Biodiesel bis zu einer Konzentration von 0,005 bis 2 Gew.-% an 2,4-Di-tert.-butylhydroxytoluol, bezogen auf die gesamte Lösung an Biodiesel, zudosiert. DE 102 52 715 describes a method for increasing the storage stability of biodiesel, comprising the preparation of a liquid stock solution containing from 15 to 60% by weight of 2,4-di-tert-butylhydroxytoluene dissolved in biodiesel, to biodiesel to be stabilized up to a concentration of 0.005 to 2 wt .-% of 2,4-di-tert-butylhydroxytoluene, based on the total solution of biodiesel, metered.

Es war die Aufgabe der vorliegenden Erfindung ein verbessertes Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel zur Verfügung zu stellen, insbesondere war es die Aufgabe die Verarbeitbarkeit des primären Antioxidants in Biodiesel zu verbessern und damit die Wirtschaftlichkeit bzgl. dem Einsatz von primären Antioxidantien in Biodiesel zu erhöhen.It was the object of the present invention to provide an improved process for increasing the oxidation stability of biodiesel, in particular the object was to improve the processability of the primary antioxidant in biodiesel and thus to increase the efficiency with regard to the use of primary antioxidants in biodiesel ,

Überraschenderweise wurde gefunden, dass die Zugabe eines flüssigen primären Antioxidants basierend auf substituierten Alkylphenolen gemäß der Struktur I zu Biodiesel eine Verbesserung der Handhabbarkeit der primären Antioxidantien in Biodiesel ermöglicht. Das in dem erfindungsgemäßen Verfahren eingesetzte primäre Antioxidants zeichnet sich durch einen niedrigen Schmelzpunkt, d.h. einen Schmelzpunkt kleiner gleich 40°C aus. Aufgrund seines niedrigen Schmelzpunktes kann dieses primäre Antioxidants als Flüssigkeit in dem erfindungsgemäßen Verfahren direkt dem Biodiesel zugemischt werden, ohne dass dieses primäre Antioxidants zuerst in einem Lösemittel, wie beispielsweise Alkohol, oder in Biodiesel gelöst werden muss. Somit kann auf die Herstellung eines Masterbatches dieser primären Antioxidants in Biodiesel verzichtet werden. Die Masterbatches werden i.d.R. mit dem Biodiesel hergestellt, für den der Masterbatch später auch verwendet werden soll. Gerade bei großen Entfernungen zwischen Biodiesel- und Antioxidantshersteller führt dies bei primären Antioxidantien gemäß dem Stand der Technik zu hohen Kosten für Lager und Transport. Das in dem erfindungsgemäßen Verfahren eingesetzte primäre Antioxidants führt somit zu niedrigen Herstellungskosten des oxidationsstabilisierten Biodiesels, da zum einen auf die Herstellung von Lösungen oder Masterbatches mit dem Wirkstoff primäres Antioxidants verzichtet werden kann, zum anderen zeigt das vorliegende Verfahren, dass ein Produktgemisch aus dem Herstellungsprozess von substituierten Alkylphenolen ohne aufwändige Trenn- und Reinigungsstufen eingesetzt werden kann. Weiterer Vorteil des erfindungsgemäßen Verfahrens ist, dass die Herstellung des oxidationsstabilisierten Biodiesels bei geringeren Temperaturen und innerhalb kürzerer Zeit erfolgen kann. Das erfindungsgemäße Verfahren ermöglicht somit eine Verbesserung der Wirtschaftlichkeit bei der Herstellung von oxidationsstabilisierten Biodiesel. Der Wirkstoffgehalt des flüssigen primären Antioxidants der vorliegenden Erfindung liegt bei 100 % gegenüber 20 % der flüssigen primären Antioxidantien gemäß dem Stand der Technik, da die Flüssigkeit in der Regel nur ca. 20 Gew.-% an dem Wirkstoff Antioxidants aufweist. Durch den Einsatz eines flüssigen primären Antioxidants gemäß dem erfindungsgemäßen Verfahren kann aufgrund des hohen Wirkstoffgehalts an primären Antioxidants pro Liter ebenfalls Transport- und Lagerungskosten eingespart werden. Die Verwendung eines flüssigen primären Antioxidants gemäß dem erfindungsgemäßen Verfahren führt auch zu einer geringeren Auskristallisation des primären Antioxidants bei niedrigen Temperaturen im Biodiesel bzw. in Anlagenbauteilen.Surprisingly, it has been found that the addition of a liquid primary antioxidant based on substituted alkylphenols according to structure I to biodiesel makes it possible to improve the handling of the primary antioxidants in biodiesel. The primary antioxidant used in the process according to the invention is characterized by a low melting point, ie a melting point of less than or equal to 40.degree. Because of its low melting point, this primary antioxidant can be added as a liquid in the process of the invention directly to the biodiesel, without this primary antioxidant must first be dissolved in a solvent such as alcohol, or in biodiesel. Thus, the preparation of a masterbatch of these primary antioxidants in biodiesel can be dispensed with. The masterbatches are usually produced with the biodiesel, for which the masterbatch should also be used later. Especially in the case of long distances between biodiesel and antioxidant manufacturers, this leads to high costs for storage and transport in the case of primary antioxidants according to the prior art. The primary antioxidant used in the process of the invention thus leads to low production costs of the oxidation-stabilized biodiesel, since on the one hand can be dispensed with the preparation of solutions or masterbatches with the drug primary antioxidant, on the other hand, the present method shows that a product mixture from the manufacturing process of Substituted alkylphenols can be used without expensive separation and purification steps. Another advantage of the method according to the invention is that the preparation of the oxidation-stabilized biodiesel can be carried out at lower temperatures and within a shorter time. The inventive method thus enables an improvement in the economy in the production of oxidation-stabilized biodiesel. The active ingredient content of the liquid primary antioxidant of the present invention is 100% versus 20% of the prior art liquid primary antioxidants because the liquid typically has only about 20% by weight of the active ingredient antioxidant. By using a liquid primary antioxidant according to the method of the invention, transport and storage costs can also be saved due to the high active ingredient content of primary antioxidants per liter. The use of a liquid primary antioxidant according to the method according to the invention also leads to a lower crystallization of the primary antioxidant at low temperatures in biodiesel or in plant components.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel, das sich dadurch auszeichnet, dass ein primäres Antioxidants mit einem Schmelzpunkt kleiner gleich 40°C zu dem zu stabilisierenden Biodiesel in einer Menge von 10 bis 20000 ppm (w/w) zugegeben wird, wobei das primäre Antioxidants zumindest eine Verbindung gemäß der Struktur

Figure imgb0001
mit:
R1, R2 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20 oder
Figure imgb0002
 wobei * für ein Kohlenstoffatom des aromatischen Ringssystems steht,
R3, R5 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20,
R4 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 40,
wobei sowohl die Substituenten vom Typ R1 und R2 als auch vom Typ R3 und R5 gleich oder verschieden sind, aufweist.The present invention is a process for increasing the oxidation stability of biodiesel, which is characterized in that a primary antioxidant having a melting point of less than or equal to 40 ° C added to the biodiesel to be stabilized in an amount of 10 to 20,000 ppm (w / w) wherein the primary antioxidant is at least one compound according to the structure
Figure imgb0001
 With:
R 1 , R 2 = hydrogen, linear alkyl group having a carbon number of 1 to 20 or
Figure imgb0002
 where * is a carbon atom of the aromatic ring system,
R 3 , R 5 = hydrogen, linear alkyl group having a carbon number of 1 to 20,
R 4 = hydrogen, linear alkyl group with a carbon number of 1 to 40,
wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different.

Weiterer Gegenstand der Erfindung ist die Verwendung eines primären Antioxidants, das einen Schmelzpunkt kleiner gleich 40°C und zumindest eine Verbindung gemäß der Struktur

Figure imgb0003
mit:
R1, R2 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20 oder
Figure imgb0004
 wobei * für ein Kohlenstoffatom des aromatischen Ringssystems steht,
R3, R5 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20,
R4 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 40,
wobei sowohl die Substituenten vom Typ R1 und R2 als auch vom Typ R3 und R5 gleich oder verschieden sind, aufweist, zur Erhöhung der Oxidationsstabilität von Biodiesel.Another object of the invention is the use of a primary antioxidant having a melting point of less than or equal to 40 ° C and at least one compound according to the structure
Figure imgb0003
 With:
R 1 , R 2 = hydrogen, linear alkyl group having a carbon number of 1 to 20 or
Figure imgb0004
 where * is a carbon atom of the aromatic ring system,
R 3 , R 5 = hydrogen, linear alkyl group having a carbon number of 1 to 20,
R 4 = hydrogen, linear alkyl group with a carbon number of 1 to 40,
wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different, to increase the oxidation stability of biodiesel.

Ebenfalls Gegenstand der Erfindung ist ein oxidationsstabilisierter Biodiesel, der sich dadurch auszeichnet, dass der Biodiesel von 10 bis 20000 ppm (w/w) eines primären Antioxidants aufweist, wobei das primäre Antioxidants einen Schmelzpunkt kleiner gleich 40°C und zumindest eine Verbindung gemäß der Struktur

Figure imgb0005
mit:
R1, R2 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20 oder
Figure imgb0006
 wobei * für ein Kohlenstoffatom des aromatischen Ringssystems steht,
R3, R5 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20,
R4 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 40,
wobei sowohl die Substituenten vom Typ R1 und R2 als auch vom Typ R3 und R5 gleich oder verschieden sind, aufweist.The invention likewise relates to an oxidation-stabilized biodiesel characterized in that the biodiesel has from 10 to 20,000 ppm (w / w) of a primary antioxidant, wherein the primary antioxidant has a melting point of less than or equal to 40 ° C and at least one compound according to the structure
Figure imgb0005
 With:
R 1 , R 2 = hydrogen, linear alkyl group having a carbon number of 1 to 20 or
Figure imgb0006
 where * is a carbon atom of the aromatic ring system,
R 3 , R 5 = hydrogen, linear alkyl group having a carbon number of 1 to 20,
R 4 = hydrogen, linear alkyl group with a carbon number of 1 to 40,
wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different.

Das erfindungsgemäße Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel, zeichnet sich dadurch aus, dass ein primäres Antioxidants mit einem Schmelzpunkt kleiner gleich 40°C zu dem zu stabilisierenden Biodiesel in einer Menge von 10 bis 20000 ppm (w/w) zugegeben wird, wobei das primäre Antioxidants zumindest eine Verbindung gemäß der Struktur

Figure imgb0007
mit:
R1, R2 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20 oder
Figure imgb0008
 wobei * für ein Kohlenstoffatom des aromatischen Ringssystems steht,
R3, R5 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20,
R4 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 40,
wobei sowohl die Substituenten vom Typ R1 und R2 als auch vom Typ R3 und R5 gleich oder verschieden sind, aufweist.The process according to the invention for increasing the oxidation stability of biodiesel is characterized in that a primary antioxidant having a melting point of less than or equal to 40 ° C. is added to the biodiesel to be stabilized in an amount of from 10 to 20,000 ppm (w / w) primary antioxidants at least one compound according to the structure
Figure imgb0007
 With:
R 1 , R 2 = hydrogen, linear alkyl group having a carbon number of 1 to 20 or
Figure imgb0008
 where * is a carbon atom of the aromatic ring system,
R 3 , R 5 = hydrogen, linear alkyl group having a carbon number of 1 to 20,
R 4 = hydrogen, linear alkyl group with a carbon number of 1 to 40,
wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different.

Unter primären Antioxidantien werden im Sinne dieser Erfindung Verbindungen oder Mischungen solcher Verbindungen verstanden, die unerwünschte durch Sauerstoff verursachte Abbaureaktionen in Biodiesel hemmen oder verhindern. Die Wirkungsweise dieser primären Antioxidantien im Biodiesel ist in dem folgenden Reaktionsschema beschrieben, wobei R und R' für einen organischen Rest und AOH für ein in dem erfindungsgemäßen Verfahren eingesetztes primäres Antioxidants steht.

  1. 1. Kettenstart

             R―H → R· + H·

             R―H + O2 → R· + HO2 ·

  2. 2. Kettenfoftpflanzung

             R· + O2 → RO2 ·

             RO2 · + R'― H → ROOH + R'·

  3. 3. Kettenabbruch

             RO2 · + AOH → ROOH + AO·

             AO· + R· → AOR

For the purposes of this invention, primary antioxidants are compounds or mixtures of compounds which inhibit or prevent undesired oxygen-induced degradation reactions in biodiesel. The mode of action of these primary antioxidants in biodiesel is described in the following reaction scheme, wherein R and R 'are an organic radical and AOH is a primary antioxidant used in the process of the present invention.
  1. 1st chain start

    R-H → R · + H ·

    R-H + O 2 → R · + HO 2 ·

  2. 2. Kettenfoftpflanzung

    R · + O 2 → RO 2 ·

    RO 2 · + R'-H → ROOH + R ' ·

  3. 3. chain termination

    RO 2 · + AOH → ROOH + AO ·

    AO · + R · → AOR

Neben den oben genannten Reaktionen können auch Reaktionen an den Doppelbindungen der Fettsäurealkylester erfolgen, die ebenfalls durch Sauerstoff ausgelöst werden können. Hierbei wird durch den Sauerstoff vorzugsweise die Kohlenstoff-Wasserstoff-Bindung, die in Allyl-Stellung zur Doppelbindungen sich befindet, angegriffen:

Figure imgb0009
In addition to the abovementioned reactions, it is also possible for reactions to take place on the double bonds of the fatty acid alkyl esters, which can likewise be triggered by oxygen. In this case, the oxygen preferably attacks the carbon-hydrogen bond which is in the allyl position relative to the double bonds:
Figure imgb0009

Das in dem erfmdungsgemäßen Verfahren eingesetzte primäre Antioxidants weist weder organische Lösemittel, wie beispielsweise Alkohole, noch Biodiesel, wie es beispielsweise im Falle eines Masterbatches ist, auf. Das eingesetzte primäre Antioxidants weist daher vorzugsweise ausschließlich Alkylphenole und/oder substituierte Alkylphenole auf. Insbesondere wird in dem erfindungsgemäßen Verfahren eine Mischung als primäres Antioxidants eingesetzt, wobei diese Mischung verschiedene substituierte und/oder unsubstituierte Alkylphenole aufweist, vorzugsweise wird eine Mischung als primäres Antioxidants eingesetzt, die von 0,1 bis 99,9 Gew.-%, bevorzugt von 50 bis 99 Gew.-% und besonders bevorzugt von 55 bis 90 Gew.-% einer oder mehrerer Verbindungen gemäß Struktur I aufweist.The primary antioxidant used in the inventive method has neither organic solvents, such as alcohols, or biodiesel, as for example in Trap of a masterbatch is on. The primary antioxidant used therefore preferably has exclusively alkylphenols and / or substituted alkylphenols. In particular, in the process according to the invention a mixture is used as the primary antioxidant, this mixture having various substituted and / or unsubstituted alkylphenols, preferably a mixture is used as the primary antioxidant, from 0.1 to 99.9 wt .-%, preferably from 50 to 99 wt .-% and particularly preferably from 55 to 90 wt .-% of one or more compounds according to structure I.

Besonders bevorzugt wird in dem erfindungsgemäßen Verfahren eine Mischung als primäres Antioxidants eingesetzt, die ausschließlich Verbindungen gemäß der Struktur I aufweist. Diese Mischung hat den Vorteil, dass sie ausschließlich Verbindungen gemäß der Struktur I aufweist, die alle eine oxidationsstabilisierende Wirkung gegenüber Biodiesel aufweisen.In the process according to the invention, it is particularly preferable to use a mixture as the primary antioxidant which has exclusively compounds according to structure I. This mixture has the advantage of having only compounds according to structure I , all of which have an oxidation-stabilizing effect on biodiesel.

In dem erfindungsgemäßen Verfahren wird vorzugsweise ein primäres Antioxidants eingesetzt, das zumindest eine Verbindung gemäß der Struktur II

Figure imgb0010
mit:
R1, R2 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 4 oder
Figure imgb0011
 wobei * für ein Kohlenstoffatom des aromatischen Ringssystems steht,
R3, R5 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 4,
R4 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 4,
wobei sowohl die Substituenten vom Typ R1 und R2 als auch vom Typ R3 und R5 gleich oder verschieden sind, aufweist.In the method according to the invention preferably a primary antioxidant is used which comprises at least one compound according to the structure II
Figure imgb0010
 With:
R 1 , R 2 = hydrogen, linear alkyl group having a carbon number of 1 to 4 or
Figure imgb0011
 where * is a carbon atom of the aromatic ring system,
R 3 , R 5 = hydrogen, linear alkyl group having a carbon number of 1 to 4,
R 4 = hydrogen, linear alkyl group having a carbon number of 1 to 4,
wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different.

Bevorzugt werden in dem erfindungsgemäßen Verfahren dem Biodiesel ein primäres Antioxidants zugegeben, das zumindest eine Verbindung gemäß der Struktur III

Figure imgb0012
aufweist.In the process according to the invention, a primary antioxidant which comprises at least one compound according to structure III is preferably added to the biodiesel
Figure imgb0012
 having.

Besonders bevorzugt wird in dem erfmdungsgemäßen Verfahren dem Biodiesel ein primäres Antioxidants zugegeben, das zumindest eine Verbindung gemäß der Struktur IV

Figure imgb0013
aufweist.In the process according to the invention, it is particularly preferred to add to the biodiesel a primary antioxidant which contains at least one compound according to structure IV
Figure imgb0013
 having.

Ferner kann das in dem erfindungsgemäßen Verfahren eingesetzte primäre Antioxidants ausschließlich Verbindungen, ausgewählt aus

  • Tri-tert.-butylphenolen, insbesondere 2,4,6 Tri-tert.-butylphenol,
  • Di-tert.-butylphenolen, insbesondere 2,4-Di-tert.-butylphenol, 2,5-Di-tert.-butylphenol, 2,6-Di-tert.-butylphenol,
  • Di-tert.-butylmethylphenole, insbesondere 2,5-Di-tert.-butyl-4-methylphenol, 2,6-Di-tert.-butyl-4-methylphenol, 4,6-Di-tert.-butyl-2-methylphenol, Di-tert.-butyl-3-methylphenol,
  • tert.-Butylmethylphenole, insbesondere 2-tert.-Butyl-4-methylphenol, 6-tert.-Butyl-2-methylphenol, 4-tert.-Butyl-2-methylphenol, 6-tert.-Butyl-3-methylphenol,
  • tert.-Butyldimethylphenole, insbesondere 4-tert.-Butyl-2,6-dimethylphenol, 6-tert.-Butyl-2,4-dimethylphenol, tert.-Butyl-2,5-dimethylphenol,
  • tert.-Butylphenolen, insbesondere 2-tert.-Butylphenol, 4-tert.-Butylphenol,
  • Di-sec.-butylphenole,
  • sec.-Butylphenole, insbesondere 2-sec.-Butylphenol, 2-sec.-Butyl-4-tert.-butylphenol, 4-sec.-Butyl-2,6-di-tert.-butylphenol,
  • tert.-Amylphenole, insbesondere 2-tert.-Amylphenol,
  • Di-tert.-Amylphenole, insbesondere 2,4-Di-tert.-amylphenol,
  • 2-Isopropylphenol, 4-Octylphenol, 4-Nonylphenole, 2,6-Di-tert.-butyl-4-nonylphenol, 4-Dodecylphenol und/oder Octadecylphenol
oder eine Mischung dieser Verbindungen aufweisen, wobei dieses primäre Antioxidants einen Schmelzpunkt von kleiner gleich 40°C aufweist.Furthermore, the primary antioxidant used in the process according to the invention exclusively compounds selected from
  • Tri-tert-butylphenols, in particular 2,4,6-tri-tert-butylphenol,
  • Di-tert-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol,
  • Di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2 methylphenol, di-tert-butyl-3-methylphenol,
  • tert-butylmethylphenols, in particular 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol,
  • tert-butyldimethylphenols, in particular 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol,
  • tert-butylphenols, in particular 2-tert-butylphenol, 4-tert-butylphenol,
  • Di-sec-butyl phenols,
  • sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol,
  • tert-amylphenols, in particular 2-tert-amylphenol,
  • Di-tert-amylphenols, in particular 2,4-di-tert-amylphenol,
  • 2-isopropylphenol, 4-octylphenol, 4-nonylphenols, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol and / or octadecylphenol
or a mixture of these compounds, said primary antioxidant having a melting point of less than or equal to 40 ° C.

Reinsubstanzen oder Mischungen, die Verbindungen gemäß den Strukturen I bis IV sind oder aufweisen und einen Schmelzpunkt von größer 40°C aufweisen, sind von dieser Erfindung ausgenommen.Pure substances or mixtures which are or have compounds according to structures I to IV and have a melting point greater than 40 ° C. are excluded from this invention.

Das in dem erfindungsgemäßen Verfahren eingesetzte primäre Antioxidants weist einen Schmelzpunkt von ≤ 40°C, bevorzugt von ≤ 39°C und besonders bevorzugt von ≤ 38°C auf.The primary antioxidant used in the process according to the invention has a melting point of ≦ 40 ° C., preferably of ≦ 39 ° C. and particularly preferably of ≦ 38 ° C.

Als sekundäre Antioxidantien können in dem erfindungsgemäßen Verfahren Alkylthiomethylphenole, vorzugsweise ausgewählt aus

  • - 2,4-Di-((octylthio)methyl)-6-tert.-butylphenol,
  • - 2,4-Di-((octylthio)methyl)-6-methylphenol,
  • - 2,4-Di-((octylthio)methyl))-6-ethylphenol oder
  • - 2,6-Di-((dodecylthio)methyl)-4-nonylphenol, hydroxylierte Thiodiphenylether, vorzugsweise ausgewählt aus
  • - 2,2'-Thiobis[6-tert.-butyl-4-methylphenol],
  • - 2,2'-Thiobis[4-octylphenol],
  • - 4,4'-Thiobis[6-tert.-butyl-3-methylphenol],
  • - 4,4'-Thiobis[6-tert.-butyl-2-methylphenol],
  • - 4,4'-Thiobis[3,6-di-sec.-amylphenol] oder
  • - 4,4'-Bis[2,6-dimethyl-4-hydroxyphenyl]disulfid,
As secondary antioxidants in the process according to the invention alkylthiomethylphenols, preferably selected from
  • 2,4-di- ((octylthio) methyl) -6-tert-butylphenol,
  • 2,4-di- ((octylthio) methyl) -6-methylphenol,
  • - 2,4-di - ((octylthio) methyl)) - 6-ethylphenol or
  • - 2,6-di - ((dodecylthio) methyl) -4-nonylphenol, hydroxylated thiodiphenyl ethers, preferably selected from
  • 2,2'-thiobis [6-tert-butyl-4-methylphenol],
  • 2,2'-thiobis [4-octylphenol],
  • 4,4'-thiobis [6-tert-butyl-3-methylphenol],
  • 4,4'-thiobis [6-tert-butyl-2-methylphenol],
  • 4,4'-thiobis [3,6-di-sec-amylphenol] or
  • 4,4'-bis [2,6-dimethyl-4-hydroxyphenyl] disulfide,

Phosphite oder Phosphonite, vorzugsweise ausgewählt aus

  • Triphenylphosphit,
  • Diphenylalkylphosphite,
  • Phenyldialkylphosphite,
  • Tris[nonylphenyl]phosphit,
  • Trilaurylphosphit,
  • Trioctadecylphosphit,
  • Distearyl-pentaerythritdiphosphit,
  • Tris[2,4-di-tert.-butylphenyl]phosphit,
  • Düsodecylpentaerythrit-diphosphit,
  • Bis[2,4-di-tert.-butylphenyl]pentaerythritdiphosphit,
  • Bis[2,6-di-tert.-butyl-4-methylphenyl]pentaerythritdiphosphit,
  • Bis[isodecyloxy]pentaerythritdiphosphit,
  • Bis[2,4-di-tert.-butyl-6-methylphenyl]pentaerythritdiphosphit,
  • Bis[2,4,6-tri-tert.-butylphenyl]pentaerythritdiphosphit,
  • Tristearyl-sorbit-triphosphit,
  • Tetrakis[2,4-di-tert.-butylphenyl]-4,4'-biphenylen-diphosphonit,
  • 6-Isooctyloxy-2,4,8,10-tetra-tert.-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,
  • 6-Fluor-2,4,8, 10-tetra-tert.-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,
  • Bis[2,4-di-tert.-butyl-6-methylphenyl]methylphosphit oder
  • Bis[2,4-di-tert.-butyl-6-methylphenyl]ethylphosphit, oder peroxidzerstörende Verbindungen, vorzugsweise ausgewählt aus
  • Ester der β-Thio-dipropionsäure, bevorzugt der Lauryl-, Stearyl-, Myristyl- oder Tridecylester,
  • Mercaptobenzimidazol,
  • Zinksalz des 2-Mercaptobenzimidazols,
  • Zink-dibutyl-dithiocarbamat,
  • Dioctadecyldisulfid oder
  • Pentaerythrit-tetrakis[β-dodecylmercapto]propionat,
oder Mischungen dieser Verbindungen eingesetzt werden.Phosphites or phosphonites, preferably selected from
  • triphenylphosphite,
  • diphenyl,
  • phenyldialkylphosphites,
  • Tris [nonylphenyl] phosphite,
  • trilaurylphosphite,
  • trioctadecyl,
  • Distearyl pentaerythritol,
  • Tris [2,4-di-tert-butylphenyl] phosphite,
  • Düsodecylpentaerythrit diphosphite,
  • Bis [2,4-di-tert-butyl-phenyl] pentaerythritol,
  • Bis [2,6-di-tert-butyl-4-methyl-phenyl] pentaerythritol,
  • Bis [isodecyloxy] pentaerythritol,
  • Bis [2,4-di-tert-butyl-6-methylphenyl] pentaerythritol diphosphite,
  • Bis [2,4,6-tri-tert-butyl-phenyl] pentaerythritol,
  • Tristearyl sorbitol triphosphite,
  • Tetrakis [2,4-di-tert-butylphenyl] -4,4'-biphenylene diphosphonite,
  • 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin,
  • 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocine,
  • Bis [2,4-di-tert-butyl-6-methylphenyl] methyl phosphite or
  • Bis [2,4-di-tert-butyl-6-methylphenyl] ethyl phosphite, or peroxide-destroying compounds, preferably selected from
  • Esters of β-thio-dipropionic acid, preferably the lauryl, stearyl, myristyl or tridecyl ester,
  • mercaptobenzimidazole,
  • Zinc salt of 2-mercaptobenzimidazole,
  • Zinc dibutyldithiocarbamate,
  • Dioctadecyl disulfide or
  • Pentaerythritol tetrakis [β-dodecylmercapto] propionate,
or mixtures of these compounds are used.

Unter Biodiesel werden im Sinne dieser Erfindung alle als Energieträger einsetzbaren gesättigten und/oder ungesättigten Fettsäurealkylester, insbesondere Fettsäuremethylester oder Fettsäureethylester, verstanden. Als Energieträger sind im Sinne dieser Erfmdung sowohl Brennstoffe, wie beispielsweise Heizmaterial, als auch Kraftstoffe, beispielsweise für Automobile, Lastkraftwagen, Schiffe oder Flugzeuge, zu verstehen. Bevorzugt wird in dem erfindungsgemäßen Verfahren ein Biodiesel eingesetzt, der üblicherweise unter dem Begriff Biodiesel für den Einsatz als Automobilkraftstoff angeboten wird. Der in dem erfindungsgemäßen Verfahren eingesetzte Biodiesel weist insbesondere C12-C24-Fettsäurealkylester, bevorzugt C12-C24-Fettsäuremethylester oder C12-C24-Fettsäureethylester, auf, die rein oder auch als Gemisch vorliegen können. Der im erfindungsgemäßen Verfahren eingesetzte Biodiesel kann darüber hinaus alle üblichen Zusatzstoffe, wie beispielsweise sekundäre Antioxidantien, Entschäumer, Kältefließverbesserer enthalten. Vorzugsweise wird in dem erfindungsgemäßen Verfahren Biodiesel eingesetzt, der aus pflanzlichen und/oder tierischen Ölen durch ein Umesterungsverfahren mit einem Alkohol, bevorzugt Methanol oder Ethanol, besonders bevorzugt Methanol, hergestellt wird. Bevorzugt wird in dem erfindungsgemäßen Verfahren Biodiesel bestehend aus Umesterungsprodukte von Rapsöl, Sojaöl, Sonnenblumenöl, Palmkernöl, Kokosöl, Jatrophaöl, Baumwollkernöl, Erdnusskernöl, Maiskernöl und/oder Altspeiseölen eingesetzt. Besonders bevorzugt wird jedoch Biodiesel eingesetzt, welcher durch die genannte Umesterung aus Rapsöl, Sonnenblumenöl oder Sojaöl gewonnen wird. In dem erfindungsgemäßen Verfahren können auch Mischungen der Umesterungsprodukte von verschiedenen pflanzlichen und/oder tierischen Ölen eingesetzt werden.In the context of this invention, biodiesel is to be understood as meaning all saturated and / or unsaturated fatty acid alkyl esters, in particular fatty acid methyl esters, usable as energy carriers Fatty acid ethyl ester, understood. For the purposes of this invention, energy sources are both fuels, such as heating material, and fuels, for example for automobiles, trucks, ships or aircraft. In the process according to the invention, a biodiesel is preferably used, which is usually offered under the term biodiesel for use as automotive fuel . The biodiesel used in the process according to the invention has, in particular, C 12 -C 24 fatty acid alkyl esters, preferably C 12 -C 24 fatty acid methyl esters or C 12 -C 24 fatty acid ethyl esters, 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 customary additives, such as, for example, 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 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. However, biodiesel is particularly preferably used, which is obtained by said transesterification from rapeseed 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.

In einer besonderen Ausführungsform des erfindungsgemäßen Verfahrens können als Biodiesel Gemische aus gesättigten und/oder ungesättigten Fettsäurealkylester mit flüssigen Energieträgern, wie beispielsweise Dieselkraftstoff, Heizöl, eingesetzt werden. Besonders bevorzugt wird eine Mischung aus Dieselkraftstoff und von 0,1 bis 99,9 Vol.-%, insbesondere 2 bis 10 Vol.-% und bevorzugt von 3 bis 5 Vol.-%, an gesättigten und/oder ungesättigten Fettsäurealkylester eingesetzt. In einem nachgeschalteten Verfahrensschritt des erfindungsgemäßen Verfahrens kann der oxidationsstabilisierte Biodiesel in einer Menge von 0,1 bis 99,9 Vol.-%, insbesondere von 1 bis 20 Vol.-%, bevorzugt von 2 bis 10 Vol.-% und besonders bevorzugt von 3 bis 5 Vol.-% einem flüssigen Energieträger, insbesondere Dieselkraftstoff oder Heizöl, zugegeben werden.In a particular embodiment of the method according to the invention can be used as biodiesel mixtures of saturated and / or unsaturated fatty acid alkyl esters with liquid fuels, such as diesel fuel, fuel oil. Particular preference is given to using a mixture of diesel fuel and from 0.1 to 99.9% by volume, in particular from 2 to 10% by volume and preferably from 3 to 5% by volume, of saturated and / or unsaturated fatty acid alkyl esters. In a downstream process step of the process according to the invention, the oxidation-stabilized biodiesel can be present in an amount of from 0.1 to 99.9% by volume, in particular from 1 to 20% by volume, preferably from 2 to 10% by volume and more preferably from 3 to 5 vol .-% of a liquid energy carrier, in particular diesel fuel or fuel oil, are added.

Das primäre Antioxidants wird in dem erfindungsgemäßen Verfahren bevorzugt direkt zugegeben, insbesondere in einer Menge von 10 bis 20000 ppm (w/w), vorzugsweise von 50 bis 12000 ppm (w/w) und bevorzugt von 100 bis 8000 ppm (w/w), wobei unter einer direkten Zugabe verstanden wird, dass keine Herstellung einer Lösung oder eines Masterbatches der primären Antioxidants in einem vorangegangenen Verfahrensschritt erfolgt ist. In diesem Verfahrensschritt können dem Biodiesel auch sekundäre Antioxidantien in einer Menge von 10 bis 20000 ppm (w/w), vorzugsweise von 50 bis 12000 ppm (w/w) und bevorzugt von 100 bis 8000 ppm (w/w), zugegeben werden.The primary antioxidant is preferably directly in the process of the invention added, in particular in an amount of 10 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), wherein a direct addition is understood to mean no preparation of a solution or a masterbatch of the primary antioxidants was carried out in a preceding process step. In this process step, secondary antioxidants may also be added to the biodiesel in an amount of from 10 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).

Vorzugsweise wird das primäre Antioxidants unter Rühren bei einer Temperatur von 18°C bis 60°C, bevorzugt bei 20°C bis 40°C, in dem Biodiesel gelöst.Preferably, the primary antioxidant is dissolved with stirring at a temperature of 18 ° C to 60 ° C, preferably at 20 ° C to 40 ° C, in the biodiesel.

Weiterhin ist Gegenstand der Erfmdung die Verwendung eines primären Antioxidants, das einen Schmelzpunkt kleiner gleich 40°C und zumindest eine Verbindung gemäß der Struktur I zur Erhöhung der Oxidationsstabilität von Biodiesel aufweist.Furthermore, the subject matter of the invention is the use of a primary antioxidant which has a melting point of less than or equal to 40 ° C. and at least one compound according to the structure I for increasing the oxidation stability of biodiesel.

Besonders bevorzugt wird eine Mischung als primäres Antioxidants verwendet, die ausschließlich Verbindungen gemäß der Struktur I aufweist. Diese Mischung hat den Vorteil, dass sie ausschließlich Verbindungen gemäß der Struktur I aufweist, die alle eine oxidationsstabilisierende Wirkung gegenüber Biodiesel aufweisen. Vorzugsweise wird ein primäres Antioxidants eingesetzt, das zumindest eine Verbindung gemäß der Struktur II aufweist, verwendet. Bevorzugt wird jedoch ein primäres Antioxidants verwendet, das zumindest eine Verbindung gemäß der Struktur III aufweist. Besonders bevorzugt wird ein primäres Antioxidants verwendet, das zumindest eine Verbindung gemäß der Struktur IV aufweist.It is particularly preferred to use a mixture as the primary antioxidant which comprises exclusively compounds according to structure I. This mixture has the advantage of having only compounds according to structure I , all of which have an oxidation-stabilizing effect on biodiesel. Preferably, a primary antioxidant is used which has at least one compound according to structure II . Preferably, however, a primary antioxidant is used which comprises at least one compound according to structure III . Particularly preferably, a primary antioxidant is used which has at least one compound according to structure IV .

Ferner kann ein primäres Antioxidants verwendet werden, das ausschließlich Verbindungen, ausgewählt aus

  • Tri-tert.-butylphenolen, insbesondere 2,4,6 Tri-tert.-butylphenol,
  • Di-tert.-butylphenolen, insbesondere 2,4-Di-tert.-butylphenol, 2,5-Di-tert.-butylphenol, 2,6-Di-tert.-butylphenol,
  • Di-tert.-butylmethylphenole, insbesondere 2,5-Di-tert.-butyl-4-methylphenol, 2,6-Di-tert.-butyl-4-methylphenol, 4,6-Di-tert.-butyl-2-methylphenol, Di-tert.-butyl-3-methylphenol,
  • tert.-Butylmethylphenole, insbesondere 2-tert.-Butyl-4-methylphenol, 6-tert.-Butyl-2-methylphenol, 4-tert.-Butyl-2-methylphenol, 6-tert.-Butyl-3-methylphenol,
  • tert.-Butyldimethylphenole, insbesondere 4-tert.-Butyl-2,6-dimethylphenol, 6-tert.-Butyl-2,4-dimethylphenol, tert.-Butyl-2,5-dimethylphenol,
  • tert.-Butylphenolen, insbesondere 2-tert.-Butylphenol, 4-tert.-Butylphenol,
  • Di-sec.-butylphenole,
  • sec.-Butylphenole, insbesondere 2-sec.-Butylphenol, 2-sec.-Butyl-4-tert.-butylphenol, 4-sec.-Butyl-2,6-di-tert.-butylphenol,
  • tert.-Amylphenole, insbesondere 2-tert.-Amylphenol,
  • Di-tert.-Amylphenole, insbesondere 2,4-Di-tert.-amylphenol,
  • 2-Isopropylphenol, 4-Octylphenol, 4-Nonylphenole, 2,6-Di-tert.-butyl-4-nonylphenol, 4-Dodecylphenol und/oder Octadecylphenol
    oder eine Mischung dieser Verbindungen aufweist, wobei dieses primäre Antioxidants einen Schmelzpunkt von kleiner gleich 40°C aufweist.
Furthermore, a primary antioxidant may be used which exclusively comprises compounds selected from
  • Tri-tert-butylphenols, in particular 2,4,6-tri-tert-butylphenol,
  • Di-tert-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol,
  • Di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2 methylphenol, di-tert-butyl-3-methylphenol,
  • tert-butylmethylphenols, in particular 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol,
  • tert-butyldimethylphenols, in particular 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol,
  • tert-butylphenols, in particular 2-tert-butylphenol, 4-tert-butylphenol,
  • Di-sec-butyl phenols,
  • sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol,
  • tert-amylphenols, in particular 2-tert-amylphenol,
  • Di-tert-amylphenols, in particular 2,4-di-tert-amylphenol,
  • 2-isopropylphenol, 4-octylphenol, 4-nonylphenols, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol and / or octadecylphenol
    or a mixture of these compounds, said primary antioxidant having a melting point of less than or equal to 40 ° C.

Reinsubstanzen oder Mischungen, die Verbindungen gemäß den Strukturen I bis IV sind oder aufweisen und einen Schmelzpunkt von größer 40°C aufweisen, sind von dieser Erfindung ausgenommen.Pure substances or mixtures which are or have compounds according to structures I to IV and have a melting point greater than 40 ° C. are excluded from this invention.

Der erfindungsgemäße oxidationsstabilisierter Biodiesel zeichnet sich dadurch aus, dass dieser Biodiesel von 10 bis 20000 ppm (w/w), vorzugsweise von 50 bis 12000 ppm (w/w) und bevorzugt von 100 bis 8000 ppm (w/w) eines primären Antioxidants aufweist, das einen Schmelzpunkt kleiner gleich 40°C und zumindest eine Verbindung gemäß der Struktur I aufweist.The oxidation-stabilized biodiesel according to the invention is characterized in that this biodiesel has from 10 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) of a primary antioxidant which has a melting point less than or equal to 40 ° C and at least one compound according to structure I.

Das primäre Antioxidants des erfindungsgemäßen oxidationsstabilisierten Biodiesels weist daher vorzugsweise ausschließlich Alkyphenole und/oder substituierte Alkylphenole auf. Insbesondere weist der erfindungsgemäße oxidationsstabilisierte Biodiesel eine Mischung als primäres Antioxidants auf, wobei diese Mischung verschiedene substituierte und/oder unsubstituierte Alkylphenole aufweist. Vorzugsweise weist der erfindungsgemäße Biodiesel ein primäres Antioxidants auf, das von 0,1 bis 99,9 Gew.-%, bevorzugt von 50 bis 99 Gew.% und besonders bevorzugt von 55 bis 99 Gew.% einer oder mehreren Verbindungen gemäß Struktur I aufweist. Besonders bevorzugt weist der erfindungsgemäße Biodiesel eine Mischung als primäres Antioxidants auf, das ausschließlich Verbindungen gemäß der Struktur I aufweist.The primary antioxidant of the oxidation-stabilized biodiesel according to the invention therefore preferably comprises exclusively alkyphenols and / or substituted alkylphenols. In particular, the oxidation-stabilized biodiesel according to the invention has a mixture as the primary antioxidant, this mixture having various substituted and / or unsubstituted alkylphenols. The biodiesel according to the invention preferably has a primary antioxidant which contains from 0.1 to 99.9% by weight, preferably from 50 to 99% by weight and more preferably from 55 to 99% by weight, of one or more compounds according to Structure I has. The biodiesel according to the invention particularly preferably has a mixture as the primary antioxidant, which comprises exclusively compounds according to structure I.

Der erfindungsgemäße Biodiesel weist vorzugsweise ein primäres Antioxidants auf, das zumindest eine Verbindung gemäß der Struktur II aufweist. Bevorzugt weist der erfindungsgemäße Biodiesel ein primäres Antioxidants auf, das zumindest eine Verbindung gemäß der Struktur III aufweist. Besonders bevorzugt weist der erfindungsgemäße Biodiesel ein primäres Antioxidants auf, das zumindest eine Verbindung gemäß der Struktur IV aufweist.The biodiesel according to the invention preferably has a primary antioxidant which has at least one compound according to structure II . The biodiesel according to the invention preferably has a primary antioxidant which has at least one compound according to structure III . The biodiesel according to the invention particularly preferably has a primary antioxidant which has at least one compound according to structure IV .

Ferner kann der erfindungsgemäße Biodiesel ein primäres Antioxidants aufweisen, das ausschließlich Verbindungen, ausgewählt aus

  • Tri-tert.-butylphenolen, insbesondere 2,4,6 Tri-tert.-butylphenol,
  • Di-tert.-butylphenolen, insbesondere 2,4-Di-tert.-butylphenol, 2,5-Di-tert.-butylphenol, 2,6-Di-tert.-butylphenol,
  • Di-tert.-butylmethylphenole, insbesondere 2,5-Di-tert.-butyl-4-methylphenol, 2,6-Di-tert.-butyl-4-methylphenol, 4,6-Di-tert.-butyl-2-methylphenol, Di-tert.-butyl-3-methylphenol,
  • tert.-Butylmethylphenole, insbesondere 2-tert.-Butyl-4-methylphenol, 6-tert.-Butyl-2-methylphenol, 4-tert.-Butyl-2-methylphenol, 6-tert.-Butyl-3-methylphenol,
  • tert.-Butyldimethylphenole, insbesondere 4-tert.-Butyl-2,6-dimethylphenol, 6-tert.-Butyl-2,4-dimethylphenol, tert.-Butyl-2,5-dimethylphenol,
  • tert.-Butylphenolen, insbesondere 2-tert.-Butylphenol, 4-tert.-Butylphenol,
  • Di-sec.-butylphenole,
  • sec.-Butylphenole, insbesondere 2-sec.-Butylphenol, 2-sec.-Butyl-4-tert.-butylphenol, 4-sec.-Butyl-2,6-di-tert.-butylphenol,
  • tert.-Amylphenole, insbesondere 2-tert.-Amylphenol,
  • Di-tert.-Amylphenole, insbesondere 2,4-Di-tert.-amylphenol,
  • 2-Isopropylphenol, 4-Octylphenol, 4-Nonylphenole, 2,6-Di-tert.-butyl-4-nonylphenol, 4-Dodecylphenol und/oder Octadecylphenol
oder eine Mischung dieser Verbindungen aufweist.Furthermore, the biodiesel according to the invention may comprise a primary antioxidant which exclusively comprises compounds selected from
  • Tri-tert-butylphenols, in particular 2,4,6-tri-tert-butylphenol,
  • Di-tert-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol,
  • Di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2 methylphenol, di-tert-butyl-3-methylphenol,
  • tert-butylmethylphenols, in particular 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol,
  • tert-butyldimethylphenols, in particular 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol,
  • tert-butylphenols, in particular 2-tert-butylphenol, 4-tert-butylphenol,
  • Di-sec-butyl phenols,
  • sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol,
  • tert-amylphenols, in particular 2-tert-amylphenol,
  • Di-tert-amylphenols, in particular 2,4-di-tert-amylphenol,
  • 2-isopropylphenol, 4-octylphenol, 4-nonylphenols, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol and / or octadecylphenol
or a mixture of these compounds.

Der erfindungsgemäße Biodiesel weist insbesondere C12-C24-Fettsäurealkylester, bevorzugt C12-C24-Fettsäuremethylester oder C12-C24-Fettsäureethylester, auf, die rein oder auch als Gemisch vorliegen können. Darüber hinaus kann der erfindungsgemäße Biodiesel alle üblichen Zusatzstoffe, wie beispielsweise sekundäre Antioxidantien, Entschäumer, enthalten. Bevorzugt weist der erfindungsgemäße Biodiesel Umesterungsprodukte von Rapsöl, Sojaöl, Sonnenblumenöl, Palmkernöl, Kokosöl, Jatrophaöl und/oder Altspeiseölen auf. Besonders bevorzugt weist der erfmdungsgemäße Biodiesel Umesterungsprodukte auf, die durch die Umesterung aus Rapsöl, Sonnenblumenöl oder Sojaöl gewonnen werden. Der erfindungsgemäße Biodiesel kann auch Mischungen der Umesterungsprodukte von verschiedenen pflanzlichen und/oder tierischen Ölen aufweisen.The biodiesel according to the invention has, in particular, C 12 -C 24 fatty acid alkyl esters, preferably C 12 -C 24 fatty acid methyl esters or C 12 -C 24 fatty acid ethyl esters, which may be present in pure form or as a mixture. In addition, the biodiesel according to the invention may contain all customary additives, such as, for example, secondary antioxidants, defoamers. The biodiesel according to the invention preferably comprises transesterification products of rapeseed oil, soybean oil, sunflower oil, palm kernel oil, coconut oil, jatropha oil and / or used cooking oils. Particularly preferably, the inventive biodiesel on transesterification products, which are obtained by the transesterification of rapeseed 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.

Darüber hinaus kann der erfmdungsgemäße Biodiesel alle üblichen Zusatzstoffe, wie beispielsweise sekundäre Antioxidantien, Entschäumer, Kältefließverbesserer, enthalten. Als sekundäre Antioxidantien kann der erfindungsgemäße Biodiesel Alkylthiomethylphenole, vorzugsweise ausgewählt aus

  • 2,4-Di-((octylthio)methyl)-6-tert.-butylphenol,
  • 2,4-Di-((octylthio)methyl)-6-methylphenol,
  • 2,4-Di-((octylthio)methyl))-6-ethylphenol oder
  • 2,6-Di-((dodecylthio)methyl)-4-nonylphenol, hydroxylierte Thiodiphenylether, vorzugsweise ausgewählt aus
  • 2,2'-Thiobis[6-tert.-butyl-4-methylphenol],
  • 2,2'-Thiobis[4-octylphenol],
  • 4,4'-Thiobis[6-tert.-butyl-3-methylphenol],
  • 4,4'-Thiobis[6-tert.-butyl-2-methylphenol],
  • 4,4'-Thiobis[3,6-di-sec.-amylphenol] oder
  • 4,4'-Bis[2,6-dimethyl-4-hydroxyphenyl]disulfid,
In addition, the biodiesel according to the invention may contain all customary additives, such as, for example, secondary antioxidants, defoamers, cold flow improvers. As secondary antioxidants, the biodiesel according to the invention may be alkylthiomethylphenols, preferably selected from
  • 2,4-Di - ((octylthio) methyl) -6-tert-butylphenol,
  • 2,4-Di - ((octylthio) methyl) -6-methylphenol,
  • 2,4-di - ((octylthio) methyl)) - 6-ethylphenol or
  • 2,6-di - ((dodecylthio) methyl) -4-nonylphenol, hydroxylated thiodiphenyl ethers, preferably selected from
  • 2,2'-thiobis [6-tert-butyl-4-methyl phenol],
  • 2,2'-thiobis [4-octylphenol]
  • 4,4'-thiobis [6-tert-butyl-3-methyl phenol],
  • 4,4'-thiobis [6-tert-butyl-2-methyl phenol],
  • 4,4'-thiobis [3,6-di-sec-amylphenol] or
  • 4,4'-bis [2,6-dimethyl-4-hydroxyphenyl] disulfide,

Phosphite oder Phosphonite, vorzugsweise ausgewählt aus

  • Triphenylphosphit,
  • Diphenylalkylphosphite,
  • Phenyldialkylphosphite,
  • Tris[nonylphenyl]phosphit,
  • Trilaurylphosphit,
  • Trioctadecylphosphit,
  • Distearyl-pentaerythritdiphosphit,
  • Tris[2,4-di-tert.-butylphenyl]phosphit,
  • Düsodecylpentaerythrit-diphosphit,
  • Bis[2,4-di-tert.-butylphenyl]pentaerythritdiphosphit,
  • Bis[2,6-di-tert.-butyl-4-methylphenyl]pentaerythritdiphosphit,
  • Bis[isodecyloxy]pentaerythritdiphosphit,
  • Bis[2,4-di-tert.-butyl-6-methylphenyl]pentaerythritdiphosphit,
  • Bis[2,4,6-tri-tert.-butylphenyl]pentaerythritdiphosphit,
  • Tristearyl-sorbit-triphosphit,
  • Tetrakis[2,4-di-tert.-butylphenyl]-4,4'-biphenylen-diphosphonit,
  • 6-Isooctyloxy-2,4,8,10-tetra-tert.-butyl-12H -dibenz[d,g]-1,3,2-dioxaphosphocin,
  • 6-Fluor-2,4,8, 10-tetra-tert.-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,
  • Bis[2,4-di-tert.-butyl-6-methylphenyl]methylphosphit oder
  • Bis[2,4-di-tert.-butyl-6-methylphenyl]ethylphosphit, oder peroxidzerstörende Verbindungen, vorzugsweise ausgewählt aus
  • Ester der β-Thio-dipropionsäure, bevorzugt der Lauryl-, Stearyl-, Myristyl- oder Tridecylester,
  • Mercaptobenzimidazol,
  • Zinksalz des 2-Mercaptobenzimidazols,
  • Zink-dibutyl-dithiocarbamat,
  • Dioctadecyldisulfid oder
  • Pentaerythrit-tetrakis[β-dodecylmercapto]propionat,
    oder Mischungen dieser Verbindungen aufweisen.
Phosphites or phosphonites, preferably selected from
  • triphenylphosphite,
  • diphenyl,
  • phenyldialkylphosphites,
  • Tris [nonylphenyl] phosphite,
  • trilaurylphosphite,
  • trioctadecyl,
  • Distearyl pentaerythritol,
  • Tris [2,4-di-tert-butylphenyl] phosphite,
  • Düsodecylpentaerythrit diphosphite,
  • Bis [2,4-di-tert-butyl-phenyl] pentaerythritol,
  • Bis [2,6-di-tert-butyl-4-methyl-phenyl] pentaerythritol,
  • Bis [isodecyloxy] pentaerythritol,
  • Bis [2,4-di-tert-butyl-6-methylphenyl] pentaerythritol diphosphite,
  • Bis [2,4,6-tri-tert-butyl-phenyl] pentaerythritol,
  • Tristearyl sorbitol triphosphite,
  • Tetrakis [2,4-di-tert-butylphenyl] -4,4'-biphenylene diphosphonite,
  • 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphocine,
  • 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocine,
  • Bis [2,4-di-tert-butyl-6-methylphenyl] methyl phosphite or
  • Bis [2,4-di-tert-butyl-6-methylphenyl] ethyl phosphite, or peroxide-destroying compounds, preferably selected from
  • Esters of β-thio-dipropionic acid, preferably the lauryl, stearyl, myristyl or tridecyl ester,
  • mercaptobenzimidazole,
  • Zinc salt of 2-mercaptobenzimidazole,
  • Zinc dibutyldithiocarbamate,
  • Dioctadecyl disulfide or
  • Pentaerythritol tetrakis [β-dodecylmercapto] propionate,
    or mixtures of these compounds.

Der erfindungsgemäße Biodiesel kann diese sekundären Antioxidantien in einer Menge von 10 bis 20000 ppm (w/w), vorzugsweise von 50 bis 12000 ppm (w/w) und bevorzugt von 100 bis 8000 ppm (w/w) aufweisen.The biodiesel of the present invention may have these secondary antioxidants in an amount of 10 to 20,000 ppm (w / w), preferably 50 to 12,000 ppm (w / w), and preferably 100 to 8,000 ppm (w / w).

Hergestellt wird der erfindungsgemäße Biodiesel bevorzugt gemäß dem erfindungsgemäßen Verfahren.The biodiesel according to the invention is preferably prepared according to the process of the invention.

Die nachfolgenden Beispiele sollen das erfindungsgemäße Verfahren näher erläutern, ohne dass die Erfindung auf diese Ausführungsform beschränkt sein soll.The following examples are intended to explain the process according to the invention in more detail, without the invention being restricted to this embodiment.

Beispiel 1 - Herstellung der Proben Example 1 - Preparation of the samples

In einem Becherglas wird bei 20°C unter Rühren das primäre Antioxidants in Biodiesel gelöst,
wobei so lange gerührt wird, bis eine klare Lösung des primären Antioxidants im Biodiesel erhalten wird. Die eingesetzten primären Antioxidantien als auch der eingesetzte Biodiesel, sowie die Mengenverhältnisse sind der Tabelle 1 zu entnehmen.In a beaker, the primary antioxidant is dissolved in biodiesel at 20 ° C with stirring,
stirring is continued until a clear solution of the primary antioxidant in the biodiesel is obtained. The primary antioxidants used as well as the biodiesel used, as well as the proportions are shown in Table 1.

Beispiel 2 - Zusammensetzungen der eingesetzten primären Antioxidantien Example 2 - Compositions of the Primary Antioxidants Used

Primäres Antioxidants 1
(bezogen von der Degussa AG unter dem Handelsnamen IONOL 99): > 99,0 Gew.-% 2,6-Di-tert.-butylphenol < 0,5 Gew.-% 2-tert.-Butylphenol <0,5 Gew.-% 2,4-Di-tert.-butylphenol Primary Antioxidants 1
(obtained from Degussa AG under the trade name IONOL 99): > 99.0% by weight 2,6-di-tert-butyl phenol <0.5% by weight 2-tert-butylphenol <0.5% by weight 2,4-di-tert-butylphenol

Primäres Antioxidants 2
(bezogen von der Degussa AG unter dem Handelsnamen IONOL K98): > 98,5 Gew.-% 6-tert.-Butyl-2,4-dimethylphenol < 1,5 Gew.-% 4-tert.-Butyl-2,6-dimethylphenol und Di-tert.-butylmethylphenole Primary antioxidant 2
(obtained from Degussa AG under the trade name IONOL K98): > 98.5% by weight 6-tert-butyl-2,4-dimethylphenol <1.5% by weight 4-tert-butyl-2,6-dimethylphenol and di-tert-butylmethylphenols

Primäre Antioxidants 3
(bezogen von der Degussa AG unter dem Handelsnamen IONOL K65): > 55 Gew.-% 6-tert.-Butyl-2,4-dimethylphenol > 15 Gew.-% 2,6-Di-tert.-butyl-4-methylphenol 18-22 Gew.-% tert.-Butyl-2,5-dimethylphenol < 1 Gew.-% 4,6-Di-tert.-butyl-2-methylphenol < 3,5 Gew.-% Di-tert.-butyl-3-methylphenol < 3,5 Gew.-% 2,5-Di-tert.-butyl-4-methylphenol Primary Antioxidants 3
(obtained from Degussa AG under the trade name IONOL K65): > 55% by weight 6-tert-butyl-2,4-dimethylphenol > 15% by weight 2,6-di-tert-butyl-4-methylphenol 18-22% by weight tert-butyl-2,5-dimethylphenol <1% by weight 4,6-di-tert-butyl-2-methylphenol <3.5% by weight Di-tert-butyl-3-methylphenol <3.5% by weight 2,5-di-tert-butyl-4-methylphenol

Primäre Antioxidants 4
(bezogen von der Degussa AG unter dem Handelsnamen IONOL 75): > 75 Gew.-% 2,6-Di-tert.-butylphenol <5 Gew.-% 2-tert.-Butylphenol <0,5 Gew.-% 4-tert.-Butylphenol <3 Gew.-% 2,4-Di-tert.-butylphenol <1 Gew.-% 2,5-Di-tert.-butylphenol < 15,5 Gew.-% 2,4,6 Tri-tert.-butylphenol Primary antioxidants 4
(obtained from Degussa AG under the trade name IONOL 75): > 75% by weight 2,6-di-tert-butyl phenol <5% by weight 2-tert-butylphenol <0.5% by weight 4-tert-butylphenol <3% by weight 2,4-di-tert-butylphenol <1% by weight 2,5-di-tert-butylphenol <15.5% by weight 2,4,6 tri-tert-butylphenol

Beispiel 3 - Durchführung der Prüfmethode Example 3 - Implementation of the test method

Die gemäß Beispiel 1 hergestellten Proben wurden gemäß der Prüfmethode DIN EN 14112 bzgl. ihrer Oxidationsstabilität bei einer Prüftemperatur von 110°C untersucht.The samples prepared according to Example 1 were tested in accordance with the test method DIN EN 14112 with respect to their oxidation stability at a test temperature of 110 ° C.

Beispiel 4 - Ergebnisse der Prüfmethode Example 4 - Results of the test method

Tabelle 1:Table 1: Antioxidantsantioxidants Menge an flüssiger AntioxidantsAmount of liquid antioxidants [in ppm]in ppm Oxidationsstabilitätoxidation stability [in h bei 110°C][in h at 110 ° C] RapsölmethylesterRapsölmethylester -- -- 5,15.1 11 500500 6,76.7 22 500500 6,56.5 33 500500 6,66.6 44 500500 6,76.7 Baynox *Baynox * 25002500 7,17.1 AltspeisefettemethylesterAltspeisefettemethylester -- -- 4,04.0 11 20002000 9,79.7 22 20002000 9,59.5 33 20002000 9,19.1 44 20002000 9,49.4 Baynox*Baynox * 1000010000 12,012.0 SojaölmethylesterSojaölmethylester -- -- 3,63.6 11 20002000 7,37.3 22 20002000 6,66.6 33 20002000 6,36.3 44 20002000 7,17.1 Baynox*Baynox * 1000010000 8,88.8 SonnenblumenölmethylesterSonnenblumenölmethylester -- -- 1,61.6 11 40004000 8,88.8 22 40004000 7,87.8 33 40004000 6,96.9 44 40004000 8,08.0 Baynox*Baynox * 2000020000 9,09.0 * Baynox ist ein Antioxidants der Fa. Lanxess und ist eine Lösung des destillierten, hochreinen Wirkstoffs in Biodiesel. Der Wirkstoffgehalt ist auf 20% g/l eingestellt. Dabei entsprechen 11 Baynox® 200 g Wirkstoff. Analytische Untersuchen ergaben, dass es sich bei dem Wirkstoff in Baynox® um 2,6-Di-tert.-butyl-4-hydroxytoluol handelt.* Baynox is an antioxidant from Lanxess and is a solution of the distilled, high-purity active ingredient in biodiesel. The active ingredient content is adjusted to 20% g / l. 11 Baynox ® correspond to 200 g of active ingredient. Analysis studies have shown that it is the active ingredient in Baynox ® 2.6-di-tert-butyl-4-hydroxytoluene.

Claims (7)

Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel,
dadurch gekennzeichnet,
dass ein primäres Antioxidants mit einem Schmelzpunkt kleiner gleich 40°C zu dem zu stabilisierenden Biodiesel in einer Menge von 10 bis 20000 ppm (w/w) zugegeben wird,
wobei das primäre Antioxidants zumindest eine Verbindung gemäß der Struktur
Figure imgb0014
 mit:
R1, R2 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20
oder
Figure imgb0015
 wobei * für ein Kohlenstoffatom des aromatischen Ringssystems
steht,
R3, R5 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20,
R4 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 40,
wobei sowohl die Substituenten vom Typ R1 und R2 als auch vom Typ R3 und R5 gleich oder verschieden sind, aufweist.Method for increasing the oxidation stability of biodiesel,
characterized,
that a primary antioxidant having a melting point of less than or equal to 40 ° C is added to the biodiesel to be stabilized in an amount of 10 to 20,000 ppm (w / w),
wherein the primary antioxidant comprises at least one compound according to the structure
Figure imgb0014
 With:
R 1 , R 2 = hydrogen, linear alkyl group having a carbon number of 1 to 20
or
Figure imgb0015
 where * represents a carbon atom of the aromatic ring system
stands,
R 3 , R 5 = hydrogen, linear alkyl group having a carbon number of 1 to 20,
R 4 = hydrogen, linear alkyl group with a carbon number of 1 to 40,
wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different. Verfahren gemäß Anspruch 1,
dadurch gekennzeichnet,
dass eine Mischung als primäres Antioxidants eingesetzt wird, die von 0,1 bis 99,9 Gew.-% einer oder mehrerer Verbindungen gemäß der Struktur I aufweist.Method according to claim 1,
characterized,
that a mixture is used as the primary antioxidant, which has from 0.1 to 99.9 wt .-% of one or more compounds according to the structure I. Verfahren gemäß Anspruch 1,
dadurch gekennzeichnet,
dass eine Mischung als primäre Antioxidants eingesetzt, die ausschließlich Verbindungen gemäß der Struktur I aufweist.Method according to claim 1,
characterized,
in that a mixture is used as the primary antioxidant which comprises exclusively compounds according to structure I. Verfahren gemäß zumindest einem der Ansprüche 1 bis 3,
dadurch gekennzeichnet,
dass das primäre Antioxidants zumindest eine Verbindung gemäß der Struktur
Figure imgb0016
 aufweist.Method according to at least one of claims 1 to 3,
characterized,
that the primary antioxidant at least one compound according to the structure
Figure imgb0016
 having. Verfahren gemäß zumindest einem der Ansprüche 1 bis 3,
dadurch gekennzeichnet,
dass das primäre Antioxidants zumindest eine Verbindung gemäß der Struktur
Figure imgb0017
 aufweist.Method according to at least one of claims 1 to 3,
characterized,
that the primary antioxidant at least one compound according to the structure
Figure imgb0017
 having. Verwendung eines primären Antioxidants, das einen Schmelzpunkt kleiner gleich 40°C und zumindest eine Verbindung gemäß der Struktur
Figure imgb0018
 mit:
R1, R2 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20
oder
Figure imgb0019
 wobei * für ein Kohlenstoffatom des aromatischen Ringssystems
steht,
R3, R5 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20,
R4 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 40,
wobei sowohl die Substituenten vom Typ R1 und R2 als auch vom Typ R3 und R5 gleich oder verschieden sind, aufweist, zur Erhöhung der Oxidationsstabilität von Biodiesel.Use of a primary antioxidant having a melting point less than or equal to 40 ° C and at least one compound according to the structure
Figure imgb0018
 With:
R 1 , R 2 = hydrogen, linear alkyl group having a carbon number of 1 to 20
or
Figure imgb0019
 where * represents a carbon atom of the aromatic ring system
stands,
R 3 , R 5 = hydrogen, linear alkyl group having a carbon number of 1 to 20,
R 4 = hydrogen, linear alkyl group with a carbon number of 1 to 40,
wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different, to increase the oxidation stability of biodiesel. Oxidationsstabilisierter Biodiesel,
dadurch gekennzeichnet,
dass der Biodiesel von 10 bis 20000 ppm (w/w) ein primäres Antioxidants aufweist, wobei das primäre Antioxidants einen Schmelzpunkt kleiner gleich 40°C und zumindest eine Verbindung gemäß der Struktur
Figure imgb0020
 mit:
R1, R2 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20
oder
Figure imgb0021
 wobei * für ein Kohlenstoffatom des aromatischen Ringssystems
steht,
R3, R5 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 20,
R4 = Wasserstoff, lineare Alkylgruppe mit einer Kohlenstoffanzahl von 1 bis 40,
wobei sowohl die Substituenten vom Typ R1 und R2 als auch vom Typ R3 und R5 gleich oder verschieden sind, aufweist.Oxidation-stabilized biodiesel,
characterized,
that has the biodiesel from 10 to 20,000 ppm (w / w) a primary antioxidant, wherein the primary antioxidant has a melting point of less than or equal to 40 ° C and at least one compound according to the structure
Figure imgb0020
 With:
R 1 , R 2 = hydrogen, linear alkyl group having a carbon number of 1 to 20
or
Figure imgb0021
 where * represents a carbon atom of the aromatic ring system
stands,
R 3 , R 5 = hydrogen, linear alkyl group having a carbon number of 1 to 20,
R 4 = hydrogen, linear alkyl group with a carbon number of 1 to 40,
wherein both the substituents of the type R 1 and R 2 and of the type R 3 and R 5 are identical or different.
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