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
  • C10L1/10—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
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
• • 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
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
• • 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
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • 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
  • C10L1/1985—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 polyethers, e.g. di- polygylcols and derivatives; ethers - 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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • 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
  • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/307—Cetane number, cetane index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/80—Additives
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the present invention relates to a biodiesel fuel mixture comprising polyoxymethylene dialkyl ether.
• oils i.e. fatty acid esters, typically triglycerides, which can generally be classified as biodegradable and harmless to the environment.
• Rapeseed oil can be regarded as a prototype of such vegetable oils.
• oils comprise the glycerides of a number of acids, the acids being variable with the type and origin of the vegetable oil, and additionally phosphoglycides if appropriate.
• Such oils may be obtained by known processes.
• the vegetable oils can be transesterified to obtain the alkyl esters, for example the methyl esters, of the fatty acids bonded in the glycerides.
• FR-A 2 492 402 describes a fuel composition comprising one or more fatty acid esters of animal or vegetable origin of the general formula R 1 —COOR 2 , in which R 1 is a substantially linear saturated or unsaturated aliphatic radical having from 5 to 23 carbon atoms and R 2 is a linear or branched, saturated or unsaturated aliphatic radical having 1 to 12 carbon atoms.
• R 1 is a substantially linear saturated or unsaturated aliphatic radical having from 5 to 23 carbon atoms
• R 2 is a linear or branched, saturated or unsaturated aliphatic radical having 1 to 12 carbon atoms.
• Such fuel compositions are described as being suitable for use in diesel engines since they have a cetane number which corresponds approximately to the cetane number of conventional diesel fuels which are obtained from mineral oils.
• biodiesel as a renewable fuel is the reduction in the net CO 2 emission. Moreover, the exhaust emissions of sulfur oxides, particles and carbon monoxide are reduced. In contrast, the nitrogen oxide emissions can be slightly increased. Thus, it can be assumed that the amount of CO 2 released when biodiesel is combusted (approx. 2.4 t/t of biodiesel) can be assimilated again by growing plants from which vegetable oils for biodiesel are obtained in turn, so that the net CO 2 output is close to 0. Biodiesel is also virtually sulfur-free (sulfur content between 0 and 0.0024 ppm, compared to up to 350 ppm of sulfur in conventional fossil diesel fuel).
• biodiesel The energy content of biodiesel is still 92% of that of fossil diesel, so that approx. 1.1 l of biodiesel replace 1 l of fossil diesel fuel.
• cetane number of diesel fuels can be increased by admixing linear ethers.
• the cold properties of the fuel are improved and the dilution reduces the contents of aromatic hydrocarbons and sulfur.
• the ethers also have a positive effect on the emissions.
• the high cetane number leads to lower emission of hydrocarbons and carbon monoxide.
• the high oxygen content in the ether additionally leads to a reduction of soot particles in the exhaust gas.
• EP-A 1 070 755 discloses a diesel fuel mixture with a cetane number >40 composed of a typical diesel oil cut and from 1 to 20% by volume of polyoxymethylene dialkyl ethers. The addition of the polyoxymethylene dialkyl ethers raises the cetane number from 48 to a value between 63 and 100.
• biodiesel fuel mixture having a cetane number of >40, comprising
• the inventive biodiesel fuel mixture comprises from 1 to 100% by weight, generally from 5 to 90% by weight, preferably from 5 to 50% by weight and more preferably from 10 to 50% by weight, of biodiesel.
• Biodiesel generally has a viscosity at 40° C. of from 1.9 to 6.5 cSt, preferably from 3.5 to 5.0 cSt, a sulfur content of not more than 0.05% by weight, preferably 0.01% by weight, a cetane number of at least 40, preferably at least 49, and an acid number of up to 0.80 mg KOH/g, preferably of up to 0.50 mg KOH/g.
• Biodiesel consists generally of fatty acid esters of the general formula R 1 —COOR 2 in which R 1 is a substantially linear saturated or unsaturated aliphatic radical having from 5 to 23 carbon atoms and R 2 is a linear or branched, saturated or unsaturated aliphatic radical having from 1 to 12 carbon atoms.
• the fatty acid esters present in the biodiesel preferably derive from linear, saturated or unsaturated fatty acids R 1 COOH with from 11 to 23 carbon atoms in the R 1 radical, in particular from saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid and lignoceric acid, monoethylenically unsaturated fatty acids such as lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid and erucic acid, and also di- or polyethylenically unsaturated fatty acids such as linoleic acid and linolenic acid.
• saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid and lignoceric acid
• monoethylenically unsaturated fatty acids such as lauroleic acid
• the fatty acids of the fatty acid esters present in the biodiesel are obtained from vegetable or animal fats.
• Vegetable fats are, for example, rapeseed oil, sunflower oil, copra oil, corn oil, cottonseed oil, soya oil and peanut oil.
• Suitable fats of animal origin are, for example, pork fat or beef tallow.
• the alcohol component of the ester present in biodiesel is preferably selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylhexanol or dodecanol.
• the fatty acid esters are preferably obtained from the glycerides present in the natural fats of vegetable or animal origin by transesterification with the alcohol R 2 OH.
• the inventive biodiesel fuel mixture comprises conventional diesel oil of fossil origin.
• Diesel represents the high boiler fraction of the middle distillates of mineral oil.
• Typical diesel oil cuts have a boiling point in the range from 150 to 380° C., preferably from 200 to 350° C., and a density of from 0.76 to 0.935 g/ml at 15° C.
• the inventive biodiesel fuel mixture comprises from 0.1 to 20% by weight, generally from 1 to 20% by weight, preferably from 3 to 11% by weight, more preferably from 4 to 11% by weight, of polyoxymethylene dialkyl ether.
• preference is given to the dimethyl ether and diethyl ether.
• Particular preference is given to polyoxymethylene dimethyl ethers with 3, 4 or 5 oxymethylene units and mixtures thereof.
• the invention also provides for the use of the polyoxymethylene dialkyl ethers as additives for biodiesel fuel mixtures which comprise at least 1% by weight of biodiesel for increasing the cetane number.
• the polyoxymethylene dialkyl ethers c) may, as described in EP-A 1 070 755 be prepared by reacting the appropriate alcohol, preferably methanol, with formaldehyde in the presence of acidic catalysts.
• methylal In the reaction of methylal with trioxane to give the polyoxymethylene dimethyl ethers, no water is formed as a by-product.
• the reaction is carried out generally at a temperature of from 50 to 200° C., preferably from 90 to 150° C., and a pressure of from 1 to 20 bar, preferably from 2 to 10 bar.
• the molar methylal:trioxane ratio is generally from 0.1 to 10, preferably from 0.5 to 5.
• the acidic catalyst may be a homogeneous or heterogeneous acidic catalyst.
• Suitable acidic catalysts are mineral acids such as substantially anhydrous sulfuric acid, sulfonic acids such as trifluoromethanesulfonic acid and para-toluenesulfonic acid, heteropolyacids, acid ion exchange resins, zeolites, aluminosilicates, silicon dioxide, aluminum oxide, titanium dioxide and zirconium dioxide.
• Oxidic catalysts may, in order to increase their acid strength, be doped with sulfate or phosphate groups, generally in amounts of from 0.05 to 10% by weight.
• the reaction may be carried out in a stirred tank reactor (CSTR) or a tubular reactor.
• CSTR stirred tank reactor
• a heterogeneous catalyst preference is given to a fixed bed reactor.
• the product mixture can subsequently be contacted with an anion exchange resin in order to obtain a substantially acid-free product mixture.
• the amount of water introduced by methylal and trioxane and by the catalyst is in total ⁇ 1% by weight, preferably ⁇ 0.5% by weight, more preferably ⁇ 0.2% by weight and in particular ⁇ 0.1% by weight, based on the reaction mixture composed of methylal, trioxane and the catalyst.
• a reaction mixture composed of methylal, trioxane and the catalyst preferably ⁇ 0.5% by weight, more preferably ⁇ 0.2% by weight and in particular ⁇ 0.1% by weight.
• virtually anhydrous trioxane and methylal are used, and the amount of water introduced by the catalyst, if appropriate, is correspondingly restricted.
• hemiacetals (monoethers) or polyoxymethylene glycols formed by hydrolysis in the presence of water from already formed polyoxymethylene dimethyl ether have a comparable boiling point to the polyoxymethylene dimethyl ethers, which complicates removal of the polyoxymethylene dimethyl ethers from these by-products.
• a fraction comprising the trimer and tetramer is removed from the product mixture of the reaction of methylal with trioxane, and unconverted methylal, trioxane and polyoxymethylene dimethyl ether where n ⁇ 3 are recycled into the acid-catalyzed reaction.
• the polyoxymethylene dimethyl ethers where n>4 are additionally also recycled into the reaction. As a result of the recycling, a particularly large amount of trimer and tetramer is obtained.
• the first distillation column may be operated, for example, at a pressure of from 0.5 to 1.5 bar
• the second distillation column for example, at a pressure of from 0.05 to 1 bar
• the third distillation column for example, at a pressure of from 0.001 to 0.5 bar.
• a homogeneous catalyst for example a mineral acid or a sulfonic acid
• it remains in the fourth fraction and is recycled with it into the acid-catalyzed reaction.
• Biodiesel has an acid number of generally at least 0.1 mg KOH/g and up to 0.8 mg KOH/g (according to US standard) or of up to 0.5 mg KOH/g (according to DIN 51606).
• the acid number can rise further as a result of the shift in the chemical equilibrium from fatty acid esters to fatty acids.
• the inventive biodiesel fuel mixtures may comprise from 0 to 5% by weight, preferably from 0 to 1% by weight, of further additives.
• Typical further additives are cetane number improvers which may be present in amounts of typically up to 1% by weight.
• the inventive biodiesel fuel mixture has a cetane number of >40, generally of >45, preferably of >50, more preferably of >52.
• a preferred inventive biodiesel mixture comprises
• H 3 CO(CH 2 O) 4 CH 3 150 g of diesel and 20 g of tetraoxymethylene dimethyl ether H 3 CO(CH 2 O) 4 CH 3 were stirred at 25° C. The content of H 3 CO(CH 2 O) 4 CH 3 was determined by gas chromatography at regular intervals. Over the entire experimental duration of 12 days, no decrease in the H 3 CO(CH 2 O) 4 CH 3 content was detected.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Fats And Perfumes (AREA)

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• 2005
  • 2005-06-29 DE DE102005030282A patent/DE102005030282A1/de not_active Withdrawn
• 2006
  • 2006-06-26 EP EP06763872A patent/EP1899438B1/de not_active Not-in-force
  • 2006-06-26 US US11/994,123 patent/US20080216390A1/en not_active Abandoned
  • 2006-06-26 CN CN2006800237044A patent/CN101213274B/zh not_active Expired - Fee Related
  • 2006-06-26 BR BRPI0613571A patent/BRPI0613571A2/pt not_active IP Right Cessation
  • 2006-06-26 NZ NZ564408A patent/NZ564408A/en not_active IP Right Cessation
  • 2006-06-26 MX MX2007015974A patent/MX2007015974A/es unknown
  • 2006-06-26 KR KR1020087001247A patent/KR20080031286A/ko not_active Application Discontinuation
  • 2006-06-26 AT AT06763872T patent/ATE553171T1/de active
  • 2006-06-26 WO PCT/EP2006/063531 patent/WO2007000428A1/de active Application Filing
  • 2006-06-26 AU AU2006263876A patent/AU2006263876B2/en not_active Ceased
  • 2006-06-26 JP JP2008518806A patent/JP4696160B2/ja not_active Expired - Fee Related
  • 2006-06-26 CA CA002613877A patent/CA2613877A1/en not_active Abandoned
• 2007
  • 2007-12-19 NO NO20076505A patent/NO20076505L/no not_active Application Discontinuation

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