EP2334767B1 - Compositions d'esters gras dotées d'une stabilité améliorée à l'oxydation - Google Patents

Compositions d'esters gras dotées d'une stabilité améliorée à l'oxydation Download PDF

Info

Publication number
EP2334767B1
EP2334767B1 EP09782335.5A EP09782335A EP2334767B1 EP 2334767 B1 EP2334767 B1 EP 2334767B1 EP 09782335 A EP09782335 A EP 09782335A EP 2334767 B1 EP2334767 B1 EP 2334767B1
Authority
EP
European Patent Office
Prior art keywords
composition
nitroxide
ppm
alkylalkanolamine
fatty ester
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.)
Not-in-force
Application number
EP09782335.5A
Other languages
German (de)
English (en)
Other versions
EP2334767A1 (fr
Inventor
Nicholas M. Martyak
Daniel Alford
Conor M. Dowling
Michael D. Gernon
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.)
Taminco BV
Original Assignee
Taminco BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Taminco BV filed Critical Taminco BV
Publication of EP2334767A1 publication Critical patent/EP2334767A1/fr
Application granted granted Critical
Publication of EP2334767B1 publication Critical patent/EP2334767B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0042—Preserving by using additives, e.g. anti-oxidants containing nitrogen
    • C11B5/005—Amines or imines
    • 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
    • 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
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • 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
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
    • C10L1/2412—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides sulfur bond to an aromatic radical
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2425—Thiocarbonic acids and derivatives thereof, e.g. xanthates; Thiocarbamic acids or derivatives thereof, e.g. dithio-carbamates; Thiurams

Definitions

  • the invention relates to fatty ester compositions. More particularly, it relates to fatty ester compositions that contain at least 50 wt% of a fatty ester component which comprises an unsaturated fatty ester and that contain moreover additives, including at least one alkylalkanolamine, that reduce their oxidative degradation.
  • Fatty esters are widely used commercially in a variety of applications. Commonly used esters include natural fats and oils, especially triglyceride oils. Well known examples include soybean oil, rapeseed oil, jathropa oil, palm oil, canola oil, olive oil, linseed oil, and tung oil.
  • Biodiesel a clean-burning alternative fuel produced from domestic, renewable resources.
  • Biodiesel contains no petroleum, but it can be blended at any level with petroleum diesel to create a fuel blend. It can be used in compression-ignition (diesel) engines with little or no modification.
  • Biodiesel is biodegradable, essentially nontoxic, and essentially free of sulfur and aromatic compounds, and thus can provide certain environmental advantages.
  • Biodiesel is more particularly an alkyl ester fuel that meets the specifications of ASTM D 6751, which is incorporated herein by reference.
  • Biodiesel is essentially a mixture of methyl, ethyl, and/or isopropyl esters of fatty acids, made through transesterification of fatty acid triglycerides (oils) with the respective alcohols.
  • the most commonly used raw material oils are seed oils such as soybean oil, palm oil, and rapeseed oil.
  • oils contain a component, sometimes a major one, of unsaturated fatty acids (mainly in the form of esters). These include such acids as oleic, linoleic, linolenic, and others bearing one or more olefinic moieties. Accordingly, biodiesel fuels made from these oils also typically contain unsaturated acids and/or esters thereof. In both natural oils and biodiesel, the unsaturation makes the materials susceptible to oxidation by atmospheric oxygen and perhaps other oxidants. Such oxidation, for example during processing or storage, may result in an increase in rancidity, viscosity and/or pour point temperature, which in many cases is undesirable. Therefore, ways of reducing or eliminating oxidative degradation of fatty esters are sought in the various industries in which these materials are used.
  • WO 2007/146567 discloses an alkyl ester fuel, in particular a biodiesel, the oxidative stability of which is improved by adding a combination of an alkylalkanolamine and an alkylhydroxylamine. Both additives, and the combination thereof, were found to increase the oxidative stability. In the examples relatively high amounts of both additives were used, namely 500 ppm of DEHA (diethylhydroxylamine) and 1000 ppm of ODEA (octydiethanolamine).
  • an alkylhydroxylamine in particular DEHA
  • the alkylhydroxylamine is more particularly used in combination with a phenolic antioxidant. This combination appeared to have synergetic effects on the oxidative stability of the fatty ester composition.
  • the phenolic antioxidant is in particular a hydroquinone which is commonly used in biodiesel compositions.
  • the hydroquinone phenolic antioxidant
  • the DEHA alkylhydroxylamine
  • the oxidative stability of biodiesel is an important property thereof and is subjected to criteria which may differ from country to country.
  • oxidative testing of biodiesel is done according to ASTM 6751-08 whereby the B100 (100% biodiesel) must pass a minimum of three hours oxidative stability as done by the Rancimat test.
  • the European oxidation criteria is a minimum of six hours as per EN 14112.
  • a problem with the biodiesel compositions disclosed in WO 2007/146567 and in US 2007/0137098 is that their long term oxidative stability depends to a large extent on the conditions wherein the biodiesel is handled and stored.
  • the antioxidants used therein are indeed oxygen scavengers which decompose or are converted to their oxidized form by reaction with oxygen. They react with the oxygen dissolved in the biodiesel and, when they are rather volatile like DEHA, they may even react with the oxygen present in the headspace above the biodiesel.
  • the storage tank is kept closed, the biodiesel can be stored for a long period of time. However, with continued ingress of oxygen into the biodiesel (from opening and closing the storage tank), the antioxidants can be quickly consumed.
  • An object of the present invention is therefore to provide a new fatty ester composition, which comprises at least one alkylalkanolamine and the oxidative stability of which is less dependent on the amount of oxygen which comes into contact with the composition.
  • composition according to the invention further comprises at least one nitroxide free-radical scavenger.
  • Oxidation of the fatty ester component follows three steps: initiation, propagation and termination.
  • initiation step free radicals are produced by reaction with initiator molecules. These free radicals can then react with dissolved oxygen producing peroxide molecules and subsequently new free radicals.
  • Continuation of this propagation stage is a chain reaction resulting in numerous hydroperoxides and fatty ester radicals leading to accelerated oxidative instability until the dissolved oxygen is consumed.
  • nitroxide free-radical scavenger used in the composition of the present invention is that it stops the oxidation process already during the initiation stage so that smaller amounts thereof are required and so that the consumption of this free radical scavenger is not, or at least much less, affected by the amount of oxygen which is supplied to the fatty ester composition.
  • nitroxide free-radical scavengers used in accordance with the present invention, are on the contrary stable compounds which remain in the composition until they react with any free radical produced during the initiation stage.
  • An important advantage of the nitroxide free-radical scavengers is further that, in contrast to the alkylhydroxylamines used in the prior art, they are also much less volatile so that they remain in the composition.
  • the nitroxide free-radical scavenger is combined with an alkanolamine.
  • a first advantage of this combination is that the nitroxide can easily be dissolved into the alkylalkanolamine whereas it is difficult to be dissolved in the fatty ester component itself.
  • a further advantage of this combination is that the antioxidant effects of the nitroxide are improved by the presence of the alkylalkanolamine, i.e. this combination has a synergetic effect on the oxidative stability of the composition.
  • the nitroxide free-radical scavenger has preferably the formula (I): wherein each of R 1 , R 2 and R 3 and R 4 is an alkyl group or heteroatom substituted alkyl group having 1 to 15 carbon atoms, and wherein R 5 and R 6 (a) each being an alkyl group having 1 to 15 carbon atoms, or a substituted alkyl group having 1 to 15 carbon atoms wherein the substituent is halogen, cyano, -CONH 2 , -SC 6 H 5 , -S-COCH 3 , -OCOCH 3 , -OCOC 2 H 5 , carbonyl, alkenyl wherein the double bond is not conjugated with the nitroxide moiety, or -COOR wherein R of the -COOR group is alkyl or aryl, or (b) together forming part of a ring that contains 4 or 5 carbon atoms and up to two heteratoms of O, N or S.
  • the nitroxide is selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethylpiperidino-1-oxy (4-hydroxy TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidino-1-oxy and 2,2,6,6-tetramethylpiperidino-1-oxy (TEMPO), the nitroxide comprising preferably 4-hydroxy-2,2,6,6-tetramethylpiperidino-1-oxy.
  • composition according to the invention comprises at least one alkylalkanolamine selected from the group consisting of N-alkylalkanolamines, N-alkyldialkanolamines and N-dialkylalkanolamines, the alkylalkanolamine having preferably the the formula (II): R 1 R 2 NCH 2 CH 2 OH wherein R 1 is an alkyl group or an isoalkyl group of 3 to 24 carbon atoms and R 2 is -H, -CH 3 , -CH 2 CH 2 OH or -R 1 .
  • composition according to the invention comprises at least one hydroxylamine which has the formula (III): R 1 R 2 NOH wherein R 1 and R 2 are each independently hydrogen, a linear or branched, saturated or unsaturated C1-C20 aliphatic moiety, or a C6-C12 aryl moiety, a C7-C14 araliphatic moiety or a C5-C7 cycloaliphatic moiety.
  • composition according to the invention may comprises other additives, in particular:
  • the present invention also relates to a method of making a stabilized composition
  • a fatty ester component comprising an unsaturated fatty ester, at least one nitroxide free-radical scavenger and at least one alkylalkanolamine.
  • said nitroxide free-radical scavenger is dissolved in said alkylalkanolamine or in a hydroxylamine or in a mixture of a hydroxylamine with the alkylalkanolamine before being blended with said fatty ester component.
  • nitroxide free-radical scavengers described hereabove dissolve only slowly in the fatty ester composition so that this composition should be heated. It has been found that the nitroxide free-radical scavenger can however be dissolved easily in the alkylalkanolamine or in a hydroxylamine (or in a mixture thereof) so that heating and subsequently cooling of the fatty ester composition can be avoided.
  • compositions comprising fatty esters may be treated by the addition of an antioxidant package that slows or prevents oxidative instability such as an increase in rancidity as reflected in an increase in viscosity of the composition and/or increases in the pour point temperature.
  • an antioxidant package that slows or prevents oxidative instability such as an increase in rancidity as reflected in an increase in viscosity of the composition and/or increases in the pour point temperature.
  • the composition includes at least the following:
  • compositions to be treated with the antioxidant package include those containing at least 50 wt% of a fatty ester component comprising unsaturated fatty esters.
  • a fatty ester component comprising unsaturated fatty esters.
  • the fatty ester component will constitute at least 80 wt% of the composition, more typically at least 90 wt% and most typically at least 95 wt%.
  • the fatty ester may be natural or synthetic.
  • the fatty ester component contains at least 10 wt%, in particular at least 25 wt% and more particularly at least 40 wt% of unsaturated fatty esters.
  • Nonlimiting examples of natural esters include soybean oil, japtropha oil, canola oil, corn oil, olive oil, linseed oil, palm oil, rapeseed oil, safflower oil, sunflower oil, algae and tung oil.
  • the ester may be a biodiesel, by which is meant a natural oil that has been transesterified with a lower alcohol, typically methanol, ethanol, and/or isopropanol. Biodiesel derived from any natural or synthetic fat or oil is suitable for treatment according to the invention, for example algae.
  • the composition may also contain a petroleum distillate, or it may be essentially free of distillates.
  • Petroleum distillates suitable for admixture with biodiesel fuels for use according to the invention include any of a variety of petroleum-based fuels, including but not limited to those normally referred to as "diesel.” Exemplary distillates may also include gasoline, gas-oil, and bunker fuel. Petroleum middle distillates will be used in many applications, and such middle distillates include mineral oils boiling in a range from 120 to 450°C obtained by distillation of crude oil, for example standard kerosene, low-sulfur kerosene, jet fuel, diesel and heating oil such as No. 2 fuel oil.
  • Exemplary distillates that may be blended with biodiesel for treatment with an antioxidant package of this invention are those which contain not more than 500 ppm, in particular less than 200 ppm, of sulfur and in specific cases less than 50 ppm of sulfur or even less than 5 ppm.
  • Useful distillates, especially middle distillates are generally those which were subjected to refinement under hydrogenating conditions and which therefore contain only small amounts of polyaromatic and polar compounds that impart natural lubricating activity to them.
  • Distillates that have 95% distillation points of less than 370°C, in particular less than 350°C, and in special cases less than 330°C, may also be used.
  • Biodiesel is susceptible to oxidative instability due to unsaturation within the methyl esters. Oxidation of B100 follows three steps: initiation, propagation and termination. During the initiation or induction stage, a hydrogen atom is extracted from the methyl ester backbone (by an initiator molecule, ⁇ I) producing a free radical, R ⁇ . In the presence of oxygen, a diradical itself, a radical peroxide molecule forms, ROO ⁇ . It is possible to form a hydroperoxide molecule, ROOH, if another hydrogen atom is extracted from an adjacent methyl ester again forming and additional methyl ester radical. Continuation of this propagation stage results in numerous hydroperoxides and methyl ester radicals leading to accelerated oxidative instability. This will continue until the dissolved oxygen is consumed. Termination follows with the formation of a simple hydrocarbon, R-R:
  • DEHA is oxidized in the process going through a series of sequential steps and in the process DO is reduced to water.
  • the driving force for the decomposition of the hydroxylamine to the nitrone is the reduction of dissolved oxygen to water.
  • the nitrone can then hydrolyze forming ethyhydroxylamine and acetaldehyde.
  • Step 1 initiation, is allowed to progress resulting in a large number of free methyl ester radicals, R ⁇ .
  • TEAO triethylamine N-oxide
  • ethylene is a by-product of TEAO decomposition and as such, its concentration may build is a closed storage container possible leading to an unwanted, hazardous and explosive condition.
  • compositions according to the invention comprise at least one nitroxide free-radical scavenger. Moreover, they comprise at least one alkylalkanolamine.
  • oxidative instability is slowed or halted in Step 1 vs. Step 2.
  • a nitroxide is already a free radical, R-O ⁇ , and as soon as the methyl ester radicals form in Step 1, they are capped or stabilized by the nitroxide.
  • the difference between using a hydroxylamine which produces an intermediate nitroxide and a molecule such as TEMPO is that the TEMPO is a stable nitroxide whereas the nitroxide produced from DEHA decomposition is unstable.
  • DEHA may be too volatile being rapidly lost from continued opening and closing of the storage vessel.
  • TEMPO or other nitroxides are not nearly as volatile and therefore are not lost leading to a more stabilized fuel.
  • the nitroxide free-radical scavenger is a stable free radical having preferably the formula (I): wherein R 1 , R 2 , R 3 and R 4 are alkyl groups or heteroatom substituted alkyl groups and no hydrogen is bound to the remaining valences on the carbon atoms bound to the nitrogen.
  • the alkyl (or heteroatom substituted) groups R 1 -R 4 may be the same or different, and preferably contain 1 to 15 carbon atoms.
  • R 1 -R 4 are methyl, ethyl, or propyl groups.
  • the heteroatom substituents may include, halogen, oxygen, sulfur, nitrogen and the like.
  • R 5 and R 6 may be satisfied by any atom or group except hydrogen which can bond covalently to carbon, although some groups may reduce the stabilizing power of the nitroxide structure and are undesirable.
  • R 5 and R 6 are halogen, cyano, -COOR wherein R is alkyl or aryl, -CONH 2 , -S-C 6 H 5 , -S-COCH 3 , -OCOC 2 H 5 , carbonyl, alkenyl where the double bond is not conjugated with the nitroxide moiety or alkyl of 1 to 15 carbon atoms, R 5 and R 6 may also form a ring of 4 or 5 carbon atoms and up to two heteroatoms, such as O, N or S by R 5 and R 6 together.
  • R 5 and R 6 examples of suitable compounds having the structure above and in which R 5 and R 6 form part of the ring are pyrrolidin-1-oxys, piperidinyl-1-oxys, the morpholines and pierazines.
  • Particular examples wherein the R 5 and R 6 above form part of a ring are 4-hydroxy-2,2,6,6-tetramethyl-piperidino-1-oxy (4-hydroxy TEMPO), 2,2,6,6-tetramethyl-piperidino-1-oxy (TEMPO), 4-oxo-2,2,6,6-tetramethyl-piperidino-1-oxy and pyrrolin-1-oxyl.
  • Suitable R 5 and R 6 groups are methyl, ethyl, and propyl groups.
  • R 1 -R 6 are alkyl groups
  • the preferred carbonyl containing nitroxides are those wherein the R 5 and R 6 form a ring structure with the nitrogen, preferably a six number ring, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidino-1-oxy, which is the preferred nitroxide for use in the present invention.
  • the composition contains preferably at least 1 ppm, more preferably at least 5 ppm and most preferably at least 10 ppm of said nitroxide or nitroxides.
  • it contains less than 200 ppm, preferably less than 100 ppm and more preferably less than 50 ppm of said nitroxide or nitroxides.
  • the fatty ester compositions of the present invention contain at least one alkylalkanolamine.
  • This alkylalkanolamine may comprise at least one alkylalkanolamine selected from the group consisting of N-alkylalkanolamines, N-alkyldialkanolamines and N-dialkylalkanolamines.
  • the alkylalkanolamine may thus have the formula (II): R 1 R 2 NCH 2 CH 2 OH wherein R 1 is an alkyl group or an isoalkyl group of 3 to 24 carbon atoms and R 2 is -H, -CH 3 , -CH 2 CH 2 OH or -R 1 .
  • the alkylalkanolamine is preferably selected from the group comprising butyldiethanolamine (BDEA), butylaminoethanol (BAE), dibutylaminoethanol (DBAE), diisopropylaminoethanol (DIPAE), octylaminoethanol (OAE) and octyldiethanolamine (ODEA).
  • BDEA butyldiethanolamine
  • BAE butylaminoethanol
  • DBAE dibutylaminoethanol
  • DIPAE diisopropylaminoethanol
  • OAE octylaminoethanol
  • ODEA octyldiethanolamine
  • the composition contains preferably at least 50 ppm, more preferably at least 100 ppm and most preferably at least 200 ppm of said alkylalkanolamine or alkylalkanolamines.
  • the total alkylalkanolamine content is however preferably less than 10 000 ppm.
  • an alkylalkanolamine cannot only be used to improve the oxidative stability of the composition, but also to assist in dissolving the nitroxide free-radical scavenger.
  • This nitroxide is soluble in the fatty ester composition but doesn't dissolve easily therein. It takes indeed a long time to dissolve the nitroxide therein or the fatty ester composition has first to be heated. It has however now been found that the nitroxide dissolves easily in the alkylalkanolamine so that it can first dissolved therein and the obtained solution can then be added easily to the fatty ester component. The nitroxide remains dissolved therein and no heating of the fatty ester component is required.
  • the composition may, aside from the nitroxide and the alkylalkanolamine, consist essentially of the biodiesel (and optionally the petroleum distillates), or it may also contain other optional additives such as those detailed below. It should be noted that certain additives, when included in the compositions of this invention, may have a substantial effect on important properties of the treated composition. The effects of such changes may or may not be desirable in a given situation, and therefore some embodiments of the invention preclude the use of certain additives in an amount that materially affects one or more of these properties.
  • additives examples include compounds known to accelerate atmospheric oxidation of unsaturated fatty acids and their esters, including for example cobalt and manganese driers such as are used for curing alkyds and drying oils.
  • cobalt and manganese driers such as are used for curing alkyds and drying oils.
  • oxidizing agents should be avoided.
  • Such materials might include hydrogen peroxide or organic peroxides.
  • certain other additives may typically be included in the treated composition in an amount sufficient to achieve certain performance advantages.
  • the composition comprises a biodiesel
  • conventional diesel additives may be included.
  • surfactants may be included to help reduce the build-up of deposits.
  • Other ingredients might also include octane boosters, cetane enhancers, pour point or cloud point depressants, and explosion suppressors (e.g., tetraethyllead), and fatty acids for use as friction modifiers. Water may also be present in the treated fuel.
  • water may in some embodiments be included in only small amounts, i.e., at less than 2 wt% or even less than 0.5 wt%, most typically less than 500 ppm, as measured by ASTM 6751. It may however be present in larger amounts, for example from 2 to 25 wt% based on the total weight of the resulting mixture, more commonly 10 to 15 wt%, in the form of a solution, stabilized emulsion, or other dispersion.
  • the nonphenolic oxygen scavenger may be a hydroxylamine.
  • hydroxylamines are oxygen scavengers which can assist in improving the oxidative stability of the fatty ester composition.
  • Nonlimiting examples of suitable hydroxylamines are according to the formula R 1 R 2 NOH, wherein R 1 and R 2 are each independently hydrogen, a linear or branched, saturated or unsaturated C1-C20 aliphatic moiety, which can optionally be mono- or polysubstituted, or a C6-C12 aryl moiety, a C7-C14 araliphatic moiety or a C5-C7 cycloaliphatic moiety.
  • hydroxylamines include but are not limited to: hydroxylamine, methylhydroxylamine, dimethylhydroxylamine, methylethylhydroxylamine, ethylhydroxylamine, diethylhydroxylamine (DEHA), dibutylhydroxylamine, dibenzyl-hydroxylamine, monoisopropylhydroxylamine and mixtures thereof.
  • the composition contains preferably at least 50 ppm, more preferably at least 100 ppm and most preferably at least 200 ppm of said hydroxylamine or hydroxylamines.
  • the total hydroxylamine content is however preferably less than 10 000 ppm.
  • the hydroxylamine can also be used to dissolve the nitroxide free-radical scavenger into the fatty ester component. It has indeed been found that the nitroxide dissolves easily in the hydroxylamine so that it can first be dissolved therein and the obtained solution can then be added easily to the fatty ester component. The nitroxide remains dissolved therein and no heating of the fatty ester component is required. Instead of dissolving the nitroxide into the alkylalkanolamine or into the hydroxylamine, it can also be dissolved in a mixture thereof.
  • oximes derived from aldehydes or ketones examples include 2-butanone oxime, acetone oxime, cyclohexanone oxime, benzoin oxime, propanal oxime, butanal oxime, and isobutanal oxime.
  • Nitrones are also suitable for use as nonphenolic oxygen scavengers. Any nitrone may be used. Suitable classes of nitrones may be described according to the formula wherein R 1 and R 2 may be the same or different and are each selected from the group consisting of hydrogen and hydrocarbon radicals having between one and ten carbon atoms. R 3 is a hydrocarbon radical having between one and ten carbon atoms. R 1 , R 2 , and R 3 may all be selected from alkyl groups (saturated or unsaturated), cycloalkyl groups, aryl groups, or aralkyl groups.
  • alkyl groups examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the various n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl and n-decenyl radicals.
  • cycloalkyl, aryl, and aralkyl groups respectively, include cyclohexyl, phenyl, and tolyl radicals.
  • hydrocarbon radicals are groups having from one to seven carbons.
  • suitable nitrones include formaldehyde isopropylnitrone; formaldehyde ethylnitrone, formaldehyde methylnitrone, acetaldehyde isopropylnitrone, acetaldehyde propylnitrone, acetaldehyde ethylnitrone, acetaldehyde methylnitrone, acetone isopropylnitrone, acetone propylnitrone, acetone ethylnitrone, acetone methylnitrone, acetone n-butylnitrone, acetone benzylnitrone, formaldehyde n-hexylnitrone, methyl ethyl ketone ethylnitrone, formaldehyde cyclohexylnitrone, isobutyraldehyde isopropyl
  • the oxygen scavenger comprises a compound having a vapor pressure greater than 10 Torr at 25°C, preferably greater than 20 Torr, and more preferably greater than 30 Torr. Diethylhydroxylamine is an example of such a compound, having a vapor pressure of 32 Torr.
  • the use of a sufficiently volatile scavenger may improve the efficacy of the antioxidant package by capturing oxygen in the headspace above the composition, thereby preventing at least some of the oxygen from reacting with unsaturated fatty esters. A drawback of such antioxidants is however that they may be more quickly lost.
  • the nonphenolic oxygen scavenger (and/or precursor thereof) may be incorporated in the treated composition in any amount. Typically, it will be present in an amount equal to from 0.001 to 5 wt% relative to the fatty ester component, more typically from 0.01 to 2 wt%, and most typically from 0.01 to 1 wt%.
  • Precursors to certain non-phenolic oxygen scavengers may be used in place of or in addition to the non-phenolic oxygen scavengers themselves.
  • the term "precursor” means a compound that liberates, or is converted to, the desired compound in the composition in an amount sufficient to provide resistance to oxidative degradation.
  • one type of precursor is a salt thereof with an organic or inorganic acid.
  • acids may include as nonlimiting examples hydrochloric acid, sulfuric acid, sulfonic acids, phosphonic acids, and carboxylic acids.
  • amine N-oxides Another type of precursor for hydroxylamines is amine N-oxides.
  • triethylamine N-oxide decomposes slowly under typical ambient conditions to form ethylene and diethylhydroxylamine.
  • Any N-oxide is suitable for use.
  • amine N-oxide types that show little surfactancy include those of the formula R 3 R 4 R 5 N ⁇ O, in which R 3 , R 4 , and R 5 are each individually selected from C1-C8 linear or branched alkyl groups, provided that at least one of R 3 , R 4 , and R 5 has a primary, secondary, or tertiary carbon atom at the 2 position relative to N, so that the group may split out to form an olefin and thereby produce a hydroxylamine.
  • Suitable phenolic antioxidants may be selected from a wide variety of materials known in the art. For example they may be substituted or unsubstituted hydroquinones. Nonlimiting examples include hydroquinones substituted in the ortho or meta positions (or both) with moieties including but not limited to C-1 to C-6 alkyl or aryl moieties. Two suitable examples are methylhydroquinone and tert-butylhydroquinone. In general, suitable phenolic antioxidants include any known dihydroxybenzene or aminohydroxybenzene compound or a lower alkyl, e.g., 1 to 8 carbon atoms, substituted derivative thereof.
  • Specific suitable compounds include 2,4-diaminophenol; 5-methyl-o-aminophenol; o-aminophenol; p-aminophenol; 3-methyl-p-aminophenol; 4,6-diamino-2-methylphenol; p-methylaminophenol; m-aminophenol; p-(N-methyl-amino)phenol; o-(N-butylamino)phenol; 3,4-dihydroxybenzaldehyde; and 2,5-dihydroxybenzaldehyde.
  • Other examples include catechols and substituted catechols, especially tertiary alkyl substituted ones.
  • phenolic antioxidants include benzoquinone and naphthoquinone, which may be converted to the corresponding phenolic compounds by contact with a reducing agent such as the nonphenolic oxygen scavenger.
  • the phenolic antioxidant (and/or precursor thereof) may be incorporated in the treated composition in any amount.
  • the effective amount of phenolic antioxidant may in some cases be as low as 0.01 ppm by weight, relative to the fatty ester component. Typically, it will be present in an amount equal to from 1 to 500 ppm, more typically from 2 to 200 ppm, and most typically from 4 to 100 ppm.
  • Treated compositions according to the invention generally provide low rates of oxidative degradation, making them suitable for use in a number of applications. They may for example be particularly suitable as biodiesel fuels for use in cold climates, where the negative effects of oxidative degradation are may be particularly troublesome due to the resulting increase in pour point temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Claims (18)

  1. Composition comprenant :
    - un composant ester gras constituant au moins 50 % en poids de la composition et comprenant des esters gras insaturés ; et
    - au moins une alkylalkanolamine,
    caractérisée en ce que
    la composition comprend en outre au moins un intercepteur de radicaux libres nitroxyde.
  2. Composition telle que revendiquée dans la revendication 1, qui comprend au moins une alkylakanolamine sélectionnée dans le groupe consistant en N-alkylalkanolamines, N-alkyldialkanolamines et N-dialkylalkanolamines.
  3. Composition telle que revendiquée dans la revendication 2, dans laquelle ladite alkylalkanolamine a la formule (iI) :

            R1R2NCH2CH2OH

    dans laquelle R1 est un groupe alkyle ou un groupe isoalkyle de 3 à 4 atomes de carbone et R2 est -H, -CH3, -CH2CH2OH ou -R1.
  4. Composition telle que revendiquée dans la revendication 2, dans laquelle ladite alkylalkanolamine est sélectionnée dans le groupe consistant en butyldiéthanolamine (BDEA), butylaminoéthanol (BAE), dibutylaminoéthanol (DBAE), diisopropylaminoéthanol (DIPAE), octylaminoéthanol (OAE) et octyldiéthanolamine (ODEA).
  5. Composition telle que revendiquée dans l'une quelconque des revendications 1 à 4, dans laquelle l'intercepteur de radicaux libres nitroxyde a la formule (I);
    Figure imgb0006
     dans laquelle chacun de R1, R2 et R3 et R4 est un groupe alkyle ou un groupe alkyle substitué par un hétéroatome, ayant de 1 à 15 atomes de carbone, et dans laquelle
    R5 et R6 (a) sont chacun un groupe alkyle ayant de 1 à 15 atomes de carbone ou un groupe alkyle substitué ayant de 1 à 15 atomes de carbone dans lequel le substituant est halogène, cyano, -CONH2, -SC6H5, -S-COCH3, -OCOCH3, -OCOC2H5, carbonyle, alcényle dans lequel la double liaison n'est pas conjuguée avec le groupe caractéristique nitroxyde, ou -COOR dans lequel R du groupe -COOR est alkyle ou aryle, ou (b) font ensemble partie d'un cycle qui contient 4 ou 5 atomes de carbone et jusqu'à deux hétéroatomes de O, N ou S.
  6. Composition telle que revendiquée dans la revendication 5, dans laquelle les groupes R1, R2, R3 et R4 dans la formule (I) sont chacun des groupes méthyle, éthyle ou propyle.
  7. Composition telle que revendiquée dans la revendication 5 ou 6, dans laquelle R5 et R6 dans la formule (I) sont chacun des groupes méthyle, éthyle ou propyle.
  8. Composition telle que revendiquée dans l'une quelconque des revendications 1 à 7, dans laquelle le nitroxyde est un pipéridino-1-oxyle, un pyrrolidino-1-oxyle ou un pyrrolin-1-oxyle.
  9. Composition telle que revendiquée dans la revendication 8, dans laquelle le nitroxyde est sélectionné dans le groupe consistant en 4-hydroxy-2,2,6,6-tétraméthylpipéridino-1-oxy (4-hydroxy TEMPO), 4-oxo-2,2,6,6-tétraméthylpipéridino-1-oxy et 2,2,6,6-tétraméthylpipéridino-1-oxy (TEMPO), le nitroxyde comprenant de préférence 4-hydroxy-2,2,6,6-tétraméthylpirpéridino-1-oxy.
  10. Composition telle que revendiquée dans l'une quelconque des revendications 1 à 7, dans laquelle le nitroxyde est di-tert-butyl-nitroxyde.
  11. Composition telle que revendiquée dans l'une quelconque des revendications 1 à 10, qui contient au moins 1 ppm, de préférence au moins 5 ppm et mieux encore au moins 10 ppm dudit nitroxyde.
  12. Composition telle que revendiquée dans l'une quelconque des revendications 1 à 11, qui contient moins de 200 ppm, de préférence moins de 100 ppm et mieux encore moins de 50 ppm dudit nitroxyde.
  13. Composition telle que revendiquée dans l'une quelconque des revendications 1 à 12, qui contient au moins 50 ppm, de préférence au moins 100 ppm et mieux encore au moins 200 ppm de ladite alkylalkanolamine, mais de préférence moins de 10 000 ppm de celle-ci.
  14. Composition telle que revendiquée dans l'une quelconque des revendications 1 à 13, dans laquelle le composant ester gras comprend un biodiesel.
  15. Composition telle que revendiquée dans l'une quelconque des revendications 1 à 14, dans laquelle le composant ester gras contient au moins 10 % en poids, de préférence au moins 25 % en poids et mieux encore au moins 40 % en poids desdits esters gras insaturés.
  16. Procédé de production d'une composition stabilisée telle que revendiquée dans l'une quelconque des revendications 1 à 15, consistant à mélanger ensemble :
    - un composant ester gras comprenant un ester gras insaturé ;
    - au moins une alkylalkanolamine, et
    - un intercepteur de radicaux libres nitroxyde.
  17. Procédé tel que revendiqué dans la revendication 16, dans lequel ledit intercepteur de radicaux libres nitroxyde est dissous dans ladite alkylalkanolamine avant d'être mélangé avec ledit composant ester gras.
  18. Procédé tel que revendiqué dans la revendication 16, dans lequel ledit intercepteur de radicaux libres nitroxyde est dissous dans une hydroxyalamine, ou dans un mélange d'une hydroxylamine et de ladite alkylalkanolamine, avant d'être mélangé avec ledit composant ester gras.
EP09782335.5A 2008-08-28 2009-08-28 Compositions d'esters gras dotées d'une stabilité améliorée à l'oxydation Not-in-force EP2334767B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9261708P 2008-08-28 2008-08-28
PCT/EP2009/061136 WO2010023277A1 (fr) 2008-08-28 2009-08-28 Compositions d'esters gras dotées d'une stabilité améliorée à l'oxydation

Publications (2)

Publication Number Publication Date
EP2334767A1 EP2334767A1 (fr) 2011-06-22
EP2334767B1 true EP2334767B1 (fr) 2013-05-29

Family

ID=41319631

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09782335.5A Not-in-force EP2334767B1 (fr) 2008-08-28 2009-08-28 Compositions d'esters gras dotées d'une stabilité améliorée à l'oxydation

Country Status (7)

Country Link
US (1) US20110154724A1 (fr)
EP (1) EP2334767B1 (fr)
CN (1) CN102131902A (fr)
AU (1) AU2009286657A1 (fr)
BR (1) BRPI0917345A2 (fr)
CA (1) CA2734885A1 (fr)
WO (1) WO2010023277A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2197280B1 (fr) 2007-08-27 2013-06-19 Basf Se Composés de pyrazole permettant de lutter contre les nuisibles invertébrés
JP2012503623A (ja) 2008-09-24 2012-02-09 ビーエーエスエフ ソシエタス・ヨーロピア 無脊椎動物系害虫防除用ピラゾール化合物
JP5536073B2 (ja) 2008-09-24 2014-07-02 ビーエーエスエフ ソシエタス・ヨーロピア 無脊椎動物系害虫を防除するためのピラゾール化合物
EP2451804B1 (fr) 2009-07-06 2014-04-30 Basf Se Composés pyridazine destinés à la lutte contre les nuisibles invertébrés
JP2013500246A (ja) 2009-07-24 2013-01-07 ビーエーエスエフ ソシエタス・ヨーロピア 無脊椎動物系害虫防除用ピリジン誘導体化合物
US8343881B2 (en) 2010-06-04 2013-01-01 Applied Materials, Inc. Silicon dioxide layer deposited with BDEAS
US20130104447A1 (en) 2011-10-28 2013-05-02 Exxonmobil Research And Engineering Company Dye-stable biofuel blend compositions
US10597597B1 (en) * 2018-09-12 2020-03-24 Exxonmobil Research And Engineering Company Fuel high temperature antioxidant additive
CN113025399B (zh) * 2021-03-24 2022-12-06 湖北碧美新能源科技有限公司 一种高氧化安定性的生物柴油的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670131A (en) * 1986-01-13 1987-06-02 Exxon Chemical Patents Inc. Method for controlling fouling of hydrocarbon compositions containing olefinic compounds
US5711767A (en) * 1996-07-11 1998-01-27 Ciba Specialty Chemicals Corporation Stabilizers for the prevention of gum formation in gasoline
US7582126B2 (en) 2005-12-20 2009-09-01 Arkema France Fatty ester compositions with improved oxidative stability
US8231694B2 (en) * 2006-06-09 2012-07-31 Arkema France Use of mixtures of alkylalkanolamines and alkylhydroxylamines as stabilizers for alkyl ester fuels
ITRM20060581A1 (it) * 2006-10-26 2008-04-27 Chimec Spa Additivo stabilizzante per olio combustibile

Also Published As

Publication number Publication date
AU2009286657A1 (en) 2010-03-04
WO2010023277A1 (fr) 2010-03-04
US20110154724A1 (en) 2011-06-30
EP2334767A1 (fr) 2011-06-22
CN102131902A (zh) 2011-07-20
CA2734885A1 (fr) 2010-03-04
BRPI0917345A2 (pt) 2015-11-17

Similar Documents

Publication Publication Date Title
EP2334767B1 (fr) Compositions d'esters gras dotées d'une stabilité améliorée à l'oxydation
Kumar Oxidative stability of biodiesel: Causes, effects and prevention
US7582126B2 (en) Fatty ester compositions with improved oxidative stability
Varatharajan et al. Screening of antioxidant additives for biodiesel fuels
AU2006350703B2 (en) Stabilizer compositions for blends of petroleum and renewable fuels
Agarwal et al. Role of antioxidants in enhancing oxidation stability of biodiesels
JP5177478B2 (ja) バイオ燃料における改善
EP2147966B1 (fr) Additif pour combustible liquide, combustible liquide le contenant et son utilisation pour les appareils de production d'énergie et/ou de chauffage et/ou de cuisson
US8858658B2 (en) Stabilization of fatty oils and esters with alkyl phenol amine aldehyde condensates
EP3320058B1 (fr) Compositions de diesel présentant un indice de cétane et des performances de pouvoir lubrifiant améliorés
RU2476585C1 (ru) Композиция антиокислительной присадки, ее раствор и способ повышения стабильности биодизельного топлива при хранении (варианты)
US8231694B2 (en) Use of mixtures of alkylalkanolamines and alkylhydroxylamines as stabilizers for alkyl ester fuels
Kongolo Improvement of the oxidation stability of biodiesel using natural antioxidants
AU2009292637A1 (en) Method for improving the oxidation stability of biodiesel as measured by the Rancimat Test
EP2751236A1 (fr) Composition d'additifs pour combustible liquide de type burning kerosene et ses utilisations

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110325

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

DAX Request for extension of the european patent (deleted)
111Z Information provided on other rights and legal means of execution

Free format text: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

Effective date: 20120620

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 614413

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009016051

Country of ref document: DE

Effective date: 20130801

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 614413

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130529

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130930

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130830

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130929

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130829

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130909

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20130529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130829

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130831

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140301

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130831

26N No opposition filed

Effective date: 20140303

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140430

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602009016051

Country of ref document: DE

Effective date: 20140301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130828

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130902

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20090828

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130529

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130828