EP2342311B1 - Verfahren zur verbesserung der oxidationsstabilität von biodiesel gemäss dem rancimat-test - Google Patents

Verfahren zur verbesserung der oxidationsstabilität von biodiesel gemäss dem rancimat-test Download PDF

Info

Publication number
EP2342311B1
EP2342311B1 EP09814893.5A EP09814893A EP2342311B1 EP 2342311 B1 EP2342311 B1 EP 2342311B1 EP 09814893 A EP09814893 A EP 09814893A EP 2342311 B1 EP2342311 B1 EP 2342311B1
Authority
EP
European Patent Office
Prior art keywords
fuel
biodiesel
stability
mixture
biodiesel fuel
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
EP09814893.5A
Other languages
English (en)
French (fr)
Other versions
EP2342311A1 (de
EP2342311A4 (de
Inventor
Marc-Andre Poirier
Alex S. Lang
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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 ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP2342311A1 publication Critical patent/EP2342311A1/de
Publication of EP2342311A4 publication Critical patent/EP2342311A4/de
Application granted granted Critical
Publication of EP2342311B1 publication Critical patent/EP2342311B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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

Definitions

  • the present invention relates to biodiesel fuels or mixtures of biodiesel fuel and conventional diesel fuel and to the improvement of the oxidation stability of such fuels by the use of additives.
  • Biodiesel fuels which constitute the short chain alkyl esters of vegetable or animal oils or fats, while having been identified in the art as useful for combustion in diesel engines or as blending stock for mixtures with conventional diesel fuels are characterized as being less stable than conventional diesel fuels.
  • Biodiesel fuels are mixtures of short chain alkyl esters of saturated and unsaturated vegetable oils or animal oils or fats and as such contain olefinic double bonds as well as the ester moiety. Such functionalities are susceptible to oxidative degradation leading to the degradation of the biodiesel and its consequential unsuitability for use due to its lack of long-term stability caused by the presence therein of acids, alcohols, aldehydes, ketones, etc.
  • WO 2008/056203 teaches stabilizer compositions for blends of petroleum and renewable fuels.
  • Mixtures of renewable fuels such as biodiesel, ethanol and biomass mixed with conventional petroleum fuel are stabilized by the addition thereto of a multifunctional additive package which is a combination of one or more additives selected from the group consisting of a free radical chain terminating agent, a peroxide decomposition agent, an acid scavenger, a photochemical stabilizer, a gum dispersant and a metal sequestering agent.
  • Peroxide decomposition agents are selected from the group containing sulfur, nitrogen and phosphorus compounds.
  • Suitable nitrogen-containing compounds are of the general formula: wherein R, R' and R" can be alkyl linear, branched, saturated or unsaturated C 1 -C 30 , aromatic, cyclic, poly alkoxy, polycyclic.
  • R, R' and R" can be alkyl linear, branched, saturated or unsaturated C 1 -C 30 , aromatic, cyclic, poly alkoxy, polycyclic.
  • Identified as a useful nitrogen containing compound is N,N-dimethylcyclohexylamine. While N,N-dimethylcyclohexylamine is taught as a useful peroxide decomposition agent, in the examples it is never employed by itself but always in combination with a phenolic anti-oxidant.
  • US2004/0152930 teaches stable blended diesel fuel comprising an olefinic diesel fuel blending stock containing olefins in an amount of 2 to 80 wt%, non-olefins in an amount of 20 to 98 wt% wherein the non-olefins are substantially comprised of paraffins, oxygenates in an amount of at least 0.012 wt% and sulfur in an amount of less than 1 ppm, the blend diesel being stabilized by an effective amount of a sulfur-free antioxidant.
  • An effective amount of sulfur-free antioxidant is identified as 5 to 500 ppm, preferably 8 to 200 ppm of additive.
  • the sulfur-free antioxidant is selected from the group consisting of phenols, cyclic amines and combinations thereof.
  • the phenols contain one hydroxyl group and are hindered phenols.
  • the cyclic amine antioxidants are amines of the formula: wherein A is a six-membered cycloalkyl or aryl ring, R 1 , R 2 , R 3 and R 4 are independently H or alkyl and X is 1 or 2.
  • An example of a sulfur-free antioxidant is given as di-methylcyclohexylamine. See also U.S. Patent 7,179,311 .
  • U.S. 2008/0127550 discloses stabilized biodiesel fuel composition wherein the stabilizing agent is a combination of: i) one or more compounds selected from the group consisting of sterically-hindered phenolic anti-oxidants; and ii) one or more compounds selected from the group consisting of triazole metal deactivators.
  • U.S. 2007/0289203 discloses a stabilized biodiesel wherein the stabilizing additive is a mixture of at least one aromatic diamine and at least one sterically-hindered phenol.
  • U.S. 2007/0151143 discloses a stabilized biodiesel wherein the stabilizing additive is selected from one or more of the group consisting of the 3-arylbenzofuranones and the hindered amine light stabilizers and, optionally, one or more hindered phenolic anti-oxidants.
  • U.S. 2007/0248740 discloses an additive composition comprising 2,5-di-tert-butyl hydroquinone (BHQ), N,N'-disalicylidenepropylenediamine.
  • BHQ 2,5-di-tert-butyl hydroquinone
  • N,N'-disalicylidenepropylenediamine The additive is used to stabilize fuel containing at least 2% by weight of an oil derived from plant or animal material.
  • U.S. 2007/0113467 discloses a biodiesel fuel composition having improved oxidation stability.
  • the fuel contains at least one anti-oxidant that increases the oxidative stability of the fuel selected from the group recited in paragraphs [0006] to [0012] of said published application.
  • U.S. Patent 3,336,124 discloses stabilized distillate fuel oils and additive compositions for such fuel oils.
  • One additive composition comprises a mixture of: (a) an oil soluble dispersant terpolymer of a particular type; (b) from 0.2 to about 3 parts by weight per part of said oil soluble dispersant tripolymer of N,N-dimethylcyclohexylamine; and (c) a normally liquid inert hydrocarbon carrier solvent in an amount to constitute from about 20% to 80% by weight of the additive composition. See also GB 1,036,384 .
  • the present invention relates to a method for improving the oxidation stability of biodiesel fuel(s) or mixtures or biodiesel fuel(s) and conventional diesel fuel(s) by the addition thereto of stability additive selected from the group consisting of one or a mixture of N,N-di(C 1 -C 5 -alkyl)cyclohexylamine, preferably one or a mixture of N,N-di(C 1 -C 2 -alkyl)cyclohexylamine, most preferably N,N-dimethylcyclohexylamine so as to increase the oxidation stability of said additized fuel as measured by the Rancimat Test by at least about 50%, preferably by at least about 60%, more preferably by at least about 65%, most preferably by 100% or more as compared to the oxidation stability of the fuel without the stability additive, said method comprising adding to the biodiesel fuel or mixture of biodiesel fuel and conventional diesel fuel at least 250 mg, preferably at least 500 mg, more preferably
  • the stability additive is employed in the absence of any phenolic and/or aminic anti-oxidant.
  • the addition to such fuels of the above-described stability additive in the amounts indicated above can increase the oxidation stability time to at least the six hour minimum induction time necessary to satisfy the EN 14214 specification for stability of biodiesel fuels as measured by the Rancimat Test.
  • Biodiesel fuels are mixtures of lower, short chain esters of fixed saturated and unsaturated straight chain fatty acids derived from vegetable and/or animal fats and oils.
  • the straight chain fatty acids are, typically, C 10 to C 26 fatty acids, preferably C 12 to C 22 fatty acids.
  • the fatty acids are made into biodiesel by transesterification using short chain alcohols; e.g., C 1 to C 5 alcohols, in the presence of a catalyst such as a strong base.
  • Vegetable and/or animal oils and fats are natural triglycerides and are renewable sources of starting material.
  • Typical vegetable oils are soybean oil, rapeseed oil, corn oil, jojoba oil, safflower oil, sunflower seed oil, hemp oil, coconut oil, cottonseed oil, sunflower oil, palm oil, canola oil, peanut oil, mustard seed oil, olive oil, spent cooking oil, etc., without limitation.
  • Animal fats and oils include beef, pork, chicken fat, fish oil and oil recovered by the rendering of animal tissue.
  • the biodiesel is made by esterifying one or a mixture of such oils and fats using one or a mixture of short chain; e.g., C 1 to C 5 , alcohols, preferably methanol.
  • Transesterification is effected by the base catalyzed reaction of the fat and/or oil with the alcohol, direct acid catalyzed esterification of the oil and/or fat with the alcohol, conversion of the oil and/or fat to fatty acids and then to alkyl esters with as acid catalyst.
  • base catalyzed transesterification the oil and/or fat is reacted with a short chain (such as methanol or ethanol) alcohol in the presence of a catalyst such as sodium hydroxide or potassium hydroxide to produce glycerin and short chain alkyl esters.
  • the glycerin is separated from the product mixture and biodiesel is recovered. Any unreacted alcohol is removed by distillation. The recovered biodiesel is washed to remove residual catalyst or soap and dried.
  • the fuel is either 100% biodiesel, typically identified in the art as B100, or it is a mixture of biodiesel with conventional diesel fuel; i.e., X% conventional diesel fuel and Y% biodiesel which would be identified as BY; for example, 80% conventional diesel and 20% biodiesel fuel would be described as B20.
  • the biodiesel fuel has its stability against oxidation increased by at least 50%, preferably by at least 60%, more preferably by at least 65%, most preferably by 100% or more, as measured by the Rancimat Test by the addition thereto of the above-described stability additive in the amount indicated.
  • Biodiesel fuels or mixtures of biodiesel fuel and conventional fuels exhibiting oxidation stabilities of less than six hours can have their oxidation stabilities increased to an extent sufficient to meet the six hour induction time specification established in EN 14214 for biodiesel fuels as measured by the Rancimat Test (ISO 6886).
  • the biodiesel can be combined with N,N-dimethylcyclohexylamine (DMCHA) in an amount of at least 250 mg, preferably at least 500 mg, more preferably at least 1000 mg of DMCHA per liter of biodiesel fuel (B100) or per liter of the biodiesel fuel component in the mixture of biodiesel fuel and conventional diesel fuel.
  • DMCHA N,N-dimethylcyclohexylamine
  • the determination whether the fuel when additized has its oxidation stability increased by at least 50%, preferably by at least 60%, more preferably by at least 65%, most preferably by 100% or more as compared to the fuel without the additive, or, alternatively, meets the minimum six hours induction time is made by subjecting the fuel to the Rancimat Test (ISO 6886, per EN 14112).
  • Rancimat Test samples of liquid are aged at a constant temperature (110°C) while air is passed through the liquid at a rate of 10 liters/hour.
  • the exhaust airflow passes through a measuring cell filled with distilled water. The conductivity of the measuring cell is determined continuously and recorded automatically.
  • the biodiesel fuels can contain other performance additives commonly used in conventional diesel fuels such as dispersants, detergents, cetane improvers (such as 2-ethyl hexyl nitrate), demulsifiers, biocides, antifoaming agents, lubricity additives, dyes.
  • performance additives commonly used in conventional diesel fuels such as dispersants, detergents, cetane improvers (such as 2-ethyl hexyl nitrate), demulsifiers, biocides, antifoaming agents, lubricity additives, dyes.
  • any supplemental anti-oxidant e.g., phenolic and/or aromatic amine
  • supplemental phenol preferably hindered phenol and/or amine, preferably aromatic amine (e.g., diphenyl amines or phenylnaphthyl amines) anti-oxidant is not employed in the stabilization process of the present invention.
  • the Rancimat oxidation tests were run according to EN 14112.
  • B100 canola methyl ester an unsaturated fatty acid methyl ester
  • the N,N-dimethylcyclohexylamine was acquired from Innospec.
  • Dicyclocarbodiimide acid scavenger Additin RC 8500 was acquired from Akzo Nobel.
  • the 2-ethylhexyl-3,4-epoxycyclohexane carboxylate acid scavenger was acquired from ATOFINA.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (7)

  1. Verfahren zur Verbesserung der Oxidationsstabilität von Biodieselkraftstoff (en) oder Mischungen von Biodieselkraftstoff(en) und konventionellen Dieselkraftstoff(en), das die Zugabe eines Stabilitätsadditivs, ausgewählt aus der Gruppe bestehend aus einem N,N-Di(C1-C5-alkyl)cyclohexylamin oder einer Mischung von N,N-Di(C1-C5-alkyl)cyclohexylaminen, in einer Menge von mindestens 250 mg des einen N,N-Di(C1-C5-alkyl)cyclohexylamins oder einer Mischung von N,N-Di(C1-C5-alkyl)cyclohexylaminen pro Liter des Biodieselkraftstoffs oder pro Liter der Biodieselkraftstoffkomponenten in der Mischung von Biodieselkraftstoff und konventionellem Dieselkraftstoff zu Biodieselkraftstoff(en) oder Mischungen von Biodieselkraftstoff(en) und konventionellen Dieselkraftstoff(en), umfasst, wobei die Oxidationsstabilität des additivierten Kraftstoffs, gemessen nach dem Rancimat-Test, um mindestens etwa 50 % erhöht wird, verglichen mit der Oxidationsstabilität des Kraftstoffs ohne das Stabilitätsadditiv, und wobei das Stabilitätsadditiv in Abwesenheit von jeglichem phenolischem und/oder aromatischem Amin-Antioxidans verwendet wird.
  2. Verfahren nach Anspruch 1, bei dem das Stabilitätsadditiv ein N,N-Di(C1-C2-alkyl)cyclohexylamin oder eine Mischung von N,N-Di(C1-C2-alkyl)cyclohexylaminen ist.
  3. Verfahren nach Anspruch 1, bei dem das Stabilitätsadditiv N,N-Dimethylcyclohexylamin ist.
  4. Verfahren nach Anspruch 1, 2 oder 3, bei dem das Stabilitätsadditiv dem Biodieselkraftstoff/den Biodieselkraftstoffen oder der Mischung von Biodieselkraftstoff(en) und konventionellen Dieselkraftstoff(en) in einer Menge von mindestens 500 mg des Stabilitätsadditivs pro Liter des Biodieselkraftstoffs oder pro Liter der Biodieselkraftstoffkomponente in der Mischung von Biodieselkraftstoff(en) und konventionellen Dieselkraftstoff(en) zugefügt wird.
  5. Verfahren nach Anspruch 1, 2 oder 3, bei dem das Stabilitätsadditiv dem Biodieselkraftstoff/den Biodieselkraftstoffen oder der Mischung von Biodieselkraftstoff(en) und konventionellen Dieselkraftstoff(en) in einer Menge von mindestens 1000 mg des Stabilitätsadditivs pro Liter des Biodieselkraftstoffs/der Biodieselkraftstoffe oder pro Liter der Biodieselkraftstoffkomponente(n) in der Mischung von Biodieselkraftstoff(en) und konventionellen Dieselkraftstoff(en) zugefügt wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem die Oxidationsstabilität um mindestens etwa 65 % erhöht wird.
  7. Verfahren nach einem der Ansprüche 1 bis 5, bei dem die Oxidationsstabilität um 100 % oder mehr erhöht wird.
EP09814893.5A 2008-09-17 2009-09-17 Verfahren zur verbesserung der oxidationsstabilität von biodiesel gemäss dem rancimat-test Not-in-force EP2342311B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19232908P 2008-09-17 2008-09-17
PCT/US2009/005185 WO2010033201A1 (en) 2008-09-17 2009-09-17 Method for improving the oxidation stability of biodiesel as measured by the rancimat test

Publications (3)

Publication Number Publication Date
EP2342311A1 EP2342311A1 (de) 2011-07-13
EP2342311A4 EP2342311A4 (de) 2012-04-18
EP2342311B1 true EP2342311B1 (de) 2016-03-09

Family

ID=42039792

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09814893.5A Not-in-force EP2342311B1 (de) 2008-09-17 2009-09-17 Verfahren zur verbesserung der oxidationsstabilität von biodiesel gemäss dem rancimat-test

Country Status (6)

Country Link
US (1) US20110146139A1 (de)
EP (1) EP2342311B1 (de)
JP (1) JP2012503040A (de)
AU (1) AU2009292637A1 (de)
CA (1) CA2734958A1 (de)
WO (1) WO2010033201A1 (de)

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1036384A (en) 1964-03-24 1966-07-20 Du Pont Stabilized petroleum distillate fuels boiling in the fuel oil range and additive compositions therefor
US3336124A (en) * 1964-08-25 1967-08-15 Du Pont Stabilized distillate fuel oils and additive compositions therefor
US3490882A (en) * 1966-08-11 1970-01-20 Du Pont Stabilized distillate fuel oils and additive compositions therefor
US3640692A (en) * 1969-10-29 1972-02-08 Cities Service Oil Co Stabilized distillate hydrocarbon fuel oil compositions and additives therefor
CA2010183A1 (en) * 1989-03-02 1990-09-02 John G. Bostick Middle distillate fuel having improved storage stability
DE69004692T2 (de) * 1990-09-20 1994-03-10 Ethyl Petroleum Additives Ltd Kohlenwasserstoffzusammensetzungen und Zusätze dafür.
US6143702A (en) * 1998-10-09 2000-11-07 Exxon Research And Engineering Company Lubricating oils of enhanced oxidation stability containing n-phenyl-naphthyl amines, or substituted derivatives of n-phenyl naphthyl amine and carbodiimide acid scavengers
US20060201056A1 (en) * 2000-04-14 2006-09-14 Oryxe Energy International, Inc. Biodiesel fuel additive
US7179311B2 (en) * 2003-01-31 2007-02-20 Chevron U.S.A. Inc. Stable olefinic, low sulfur diesel fuels
AU2004200235B2 (en) * 2003-01-31 2009-12-03 Chevron U.S.A. Inc. Stable olefinic, low sulfur diesel fuels
US7479168B2 (en) * 2003-01-31 2009-01-20 Chevron U.S.A. Inc. Stable low-sulfur diesel blend of an olefinic blend component, a low-sulfur blend component, and a sulfur-free antioxidant
DE102005015474A1 (de) * 2005-04-04 2006-10-05 Degussa Ag Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel
US8287608B2 (en) * 2005-06-27 2012-10-16 Afton Chemical Corporation Lubricity additive for fuels
WO2007062304A2 (en) * 2005-11-23 2007-05-31 Novus International, Inc. Biodiesel fuel compositions having increased oxidative stability
JP2009522421A (ja) * 2006-01-04 2009-06-11 チバ ホールディング インコーポレーテッド 安定化されたバイオディーゼル燃料組成物
EP1847584A3 (de) * 2006-04-21 2008-10-22 Infineum International Limited Verbesserungen bei Biokraftstoffen
US7964002B2 (en) * 2006-06-14 2011-06-21 Chemtura Corporation Antioxidant additive for biodiesel fuels
AU2006350703B2 (en) * 2006-07-11 2011-09-22 Innospec Fuel Specialties Llc Stabilizer compositions for blends of petroleum and renewable fuels
CN101541928A (zh) * 2006-11-27 2009-09-23 西巴控股有限公司 稳定化的生物柴油燃料组合物

Also Published As

Publication number Publication date
JP2012503040A (ja) 2012-02-02
EP2342311A1 (de) 2011-07-13
CA2734958A1 (en) 2010-03-25
US20110146139A1 (en) 2011-06-23
WO2010033201A1 (en) 2010-03-25
AU2009292637A1 (en) 2010-03-25
EP2342311A4 (de) 2012-04-18

Similar Documents

Publication Publication Date Title
US7582126B2 (en) Fatty ester compositions with improved oxidative stability
US7918905B2 (en) Method for improving biodiesel fuel
JP5068523B2 (ja) ディーゼル燃料のセタン価を向上させる組成物及びディーゼル燃料
Agarwal et al. Role of antioxidants in enhancing oxidation stability of biodiesels
KR20100015881A (ko) 지방산 메틸 에스테르(바이오디젤)에 대한 항산화제 배합물
US20100064576A1 (en) Oligo- or polyamines as oxidation stabilizers for biofuel oils
JP2007291390A (ja) バイオ燃料における改善
JP5177478B2 (ja) バイオ燃料における改善
EP2342311B1 (de) Verfahren zur verbesserung der oxidationsstabilität von biodiesel gemäss dem rancimat-test
US8858658B2 (en) Stabilization of fatty oils and esters with alkyl phenol amine aldehyde condensates
EP3320058B1 (de) Dieselzusammensetzungen mit verbesserter cetanzahl und schmierfähigkeitsleistungen
US8709107B2 (en) Biodiesels useful for improving cloud point
US20100088950A1 (en) Oils
EP2771439B1 (de) Verwendung von farbstabile biokraftstoffmischzusammensetzungen
MX2008005934A (en) Biodiesel fuel compositions having increased oxidative stability

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: 20110413

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)
A4 Supplementary search report drawn up and despatched

Effective date: 20120315

RIC1 Information provided on ipc code assigned before grant

Ipc: C10L 1/222 20060101AFI20120309BHEP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602009036709

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C10L0001220000

Ipc: C10L0001040000

RIC1 Information provided on ipc code assigned before grant

Ipc: C10L 1/222 20060101ALI20150610BHEP

Ipc: C10L 1/04 20060101AFI20150610BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150724

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

INTG Intention to grant announced

Effective date: 20160105

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: AT

Ref legal event code: REF

Ref document number: 779535

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160315

Ref country code: CH

Ref legal event code: EP

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: 602009036709

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160309

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

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: 20160609

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: 20160309

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: 20160309

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: 20160610

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: 20160309

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 779535

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160309

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: 20160309

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: 20160309

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: 20160309

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: 20160309

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: 20160309

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

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: 20160309

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: 20160709

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

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: 20160309

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: 20160309

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: 20160309

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: 20160309

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: 20160711

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: 20160309

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009036709

Country of ref document: DE

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: 20160309

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: 20160309

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

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

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: 20160309

26N No opposition filed

Effective date: 20161212

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

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: 20160609

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602009036709

Country of ref document: DE

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: 20160309

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20160917

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

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: 20160309

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: 20170531

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: 20160930

Ref country code: LI

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

Effective date: 20160930

Ref country code: CH

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

Effective date: 20160930

Ref country code: GB

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

Effective date: 20160917

Ref country code: DE

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

Effective date: 20170401

Ref country code: IE

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

Effective date: 20160917

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

Ref country code: LU

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

Effective date: 20160917

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: 20090917

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: 20160309

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: 20160309

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: 20160309

Ref country code: MT

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

Effective date: 20160930