AU2010200726A1 - Diesel fuel composition, comprising components based on biological raw material, obtained by hydrogenating and decomposition fatty acids - Google Patents

Diesel fuel composition, comprising components based on biological raw material, obtained by hydrogenating and decomposition fatty acids Download PDF

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Publication number
AU2010200726A1
AU2010200726A1 AU2010200726A AU2010200726A AU2010200726A1 AU 2010200726 A1 AU2010200726 A1 AU 2010200726A1 AU 2010200726 A AU2010200726 A AU 2010200726A AU 2010200726 A AU2010200726 A AU 2010200726A AU 2010200726 A1 AU2010200726 A1 AU 2010200726A1
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Prior art keywords
oil
fuel composition
raw material
components
biological raw
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AU2010200726A
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Pekka Aalto
Juha Jakkula
Ulla Kiiski
Seppo Mikkonen
Vesa Niemi
Jouko Nikkonen
Outi Piirainen
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Neste Oyj
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Neste Oyj
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Application filed by Neste Oyj filed Critical Neste Oyj
Priority to AU2010200726A priority Critical patent/AU2010200726A1/en
Publication of AU2010200726A1 publication Critical patent/AU2010200726A1/en
Priority to AU2015205854A priority patent/AU2015205854B2/en
Priority to AU2017279689A priority patent/AU2017279689B2/en
Priority to AU2020203806A priority patent/AU2020203806B2/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/32Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328Oil emulsions containing water or any other hydrophilic phase
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • C10G2300/1014Biomass of vegetal origin
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • C10G2300/1018Biomass of animal origin
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1022Fischer-Tropsch products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1033Oil well production fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1048Middle distillates
    • C10G2300/1055Diesel having a boiling range of about 230 - 330 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04Diesel oil
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/12Inorganic compounds
    • C10L1/1233Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C10L1/125Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1616Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/185Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852Ethers; Acetals; Ketals; Orthoesters
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/19Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Fats And Perfumes (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Description

AUSTRALIA Patents Act 1990 ORIGINAL COMPLETE SPECIFICATION INVENTION TITLE: DIESEL FUEL COMPOSITION, COMPRISING COMPONENTS BASED ON BIOLOGICAL RAW MATERIAL, OBTAINED BY HYDROGENATING AND DECOMPOSING FATTY ACIDS The following statement is a full description of this invention, including the best method of performing it known to us:- -2 DIESEL FUEL COMPOSITION, COMPRISING COMPONENTS BASED ON BIOLOGICAL RAW MATERIAL, OBTAINED BY HYDROGENATING AND DECOMPOSING FATTY ACIDS 5 Technical field This application is a divisional of Australian Application No. 2003258753, the disclosure of which is deemed to be incorporated herein. The present invention relates to a fuel composition for diesel engines, comprising 10 components based on animal fat, diesel components based on crude oil and/or fractions from Fischer-Tropsch process, and optionally components containing oxygen. Prior art 15 Currently used fuels for diesel engines mainly contain components from crude oil. The aim of the climate agreement of Kyoto is to eliminate detrimental influences due to human activities on the atmosphere, and thus on the climate. The EU has agreed on reducing emissions of carbon dioxide, methane and other greenhouse gases by eight per cent until 2010, starting from the levels of 1990. One of the objects of the 20 EU agricultural policy is to find uses for agricultural overproduction, and to increase the self-sufficiency for fuels. Accordingly, an EU directive is being prepared, demanding that at least two per cent of the petrol and diesel fuel consumed in 2005 should be of biological origin. It is anticipated that one of the requirements of this directive is to increase the proportion of biocomponents to about six per cent until 25 2010. The directive will be validated in all EU countries in the near future. At the moment, the most common component of biological origin in fuels is rapeseed oil methyl ester, referred to as RME. RME is either used as such or as a mixture with fuels. Drawbacks of RME are its poor miscibility with diesel fuels, and, in 30 comparison to a conventional diesel fuel (EN 590), particularly under low temperature conditions, its poor storage stability and poor performance at low 26/02/10,ckl8173specification&claims.doc.2 -3 temperatures. Moreover, it causes engine fouling and increases emissions of nitrogen oxides (NO,). A by-product of the production process of RME is glycerol, which may become a problem when high amounts of the product are produced. Esters of other vegetable oils may be produced in similar manner, and methyl esters of fatty 5 acids are generally known as FAMEs (fatty acid methyl ester). These FAMEs may be used in similar applications as the rapeseed oil methyl ester, but they also have a negative effect on the quality of the diesel fuel, particularly with respect to the performance thereof at low temperatures, and in addition, the use thereof in fuels increases the emissions of nitrogen oxides. In some cases FAME and RME cause 10 higher particle emissions and smoke development of the cold driven engine. Vegetable oils and animal fats may be processed to decompose the ester and/or fatty acid structure and to saturate the double bonds of the hydrocarbon chains, thus obtaining about 80 to 85 % of n-paraffin product relative to the mass of the starting 15 material. This product may be directly mixed with a diesel fuel, but a problem with the fuel so produced is its poor performance at low temperatures. In addition, n paraffins having a carbon number of fatty acids are waxy with a high solidification point, typically above +10 *C, thus limiting the use of these compounds in diesel fuels at least at low temperatures. 20 WO 2001049812 discloses a method for producing a diesel fuel with a molar ratio of iso-paraffins to n-paraffins of at least 21:1. In the method, a feedstock containing at least 50 % of CIo-paraffins is contacted with a catalyst in the isomerisation reaction zone. 25 WO 2001012581 discloses a method for producing methyl esters useful as biological diesel fuel, wherein mixtures of fatty acids and triglycerides are esterified in one phase. In this method, a solution is formed from fatty acids, triglycerides, alcohol, acid catalyst and co-solvents at a temperature below the boiling point of the solution. 30 A co-solvent is used in amounts to provide a single phase then the solution is maintained for a period of time sufficient for the acid catalyzed esterification of the fatty acids to take place. Thereafter, the acid catalyst is neutralised, a base catalyst is 26/02/IOckl8173specification&caims.doc.3 -4 added to transesterify the triglycerides, and finally, the esters are separated from the solution. Thus a biofuel containing esters is obtained, having a glycerol content of less than 0.4 % by weight. 5 US 6,174,501 presents a method for producing oxidized diesel fuel of biological origin. This oxidized biological diesel fuel comprises a mixture of transesterified triglycerides. FI 100248 describes a two-step process for producing middle distillate from 10 vegetable oil by hydrogenating fatty acids of the vegetable oil, or triglycerides, to give n-paraffins, and then by isomerising the n-paraffins to give branched-chain paraffins. A published foreign counterpart of this patent is patent application SE 9700149, which has matured into patent SE 520633. 15 Any gases, liquid droplets and solid particles present in the atmosphere in amounts being hazardous to human health and/or having a detrimental effect on animals, plants and different materials, are considered as air pollutants. Air pollution mainly originates from three main emission sources, i.e. the industry, energy production, and traffic. 20 The harmfulness of particle emissions is caused by the substances and compounds they carry, such as heavy metals and other carcinogenic and mutagenic compounds. Particles present in exhaust gases are small and thus hazardous to health. 25 Greenhouse gases allow for the penetration of the radiation from the sun to reach the earth, preventing, however, the thermal radiation from escaping from the earth back to space. They thus contribute to the warming of the earth. One of the most significant greenhouse gases is carbon dioxide released, for instance, during the combustion of fossil fuels. 30 Nitrogen oxides are acidifying compounds. This acidification may, for instance, lead to plant damages and species changes in surface waters. Nitrogen oxides may also 26/02/1 Ock I8173specification&claims.doc.4 - 5 react with oxygen to give ozone. This phenomenon contributes particularly to air quality in cities. As the above teachings indicate, there is a need for a high quality fuel composition 5 for diesel engines containing components of biological origin and also meeting the quality requirements for diesel fuels under low temperature operation conditions. Moreover, the fuel should be more environmentally friendly than prior art solutions. It would be advantageous to a more environmentally friendly fuel composition for 10 diesel engines containing components of biological origin, and also meeting the quality requirements for diesel fuels under low temperature conditions. General description of the invention The fuel composition for diesel engines of the invention, containing components of 15 biological origin, comprises at least one component produced from a biological starting material obtained from animals, diesel components based on crude oil and/or fractions from Fischer-Tropsch process, and optionally components containing oxygen. 20 The characteristic features of the fuel composition for diesel engines containing components of biological origin are presented in the appended claims. In an embodiment of the invention there is provided a fuel composition for diesel engines, wherein the fuel composition comprises: a) 0.1-99% by volume of a 25 component or a mixture of components produced from biological raw material originating from animals by hydrogenating and decomposing fatty acids and/or fatty acid esters to give hydrocarbons and isomerising the hydrocarbons to give iso paraffins; b) 0-20% by volume of components containing oxygen selected from the group consisting of aliphatic alcohols, ethers, fatty acid esters, water and mixtures 30 containing the same; both components a) and b) being mixed as an emulsion with or dissolved in diesel components based on crude oil and/or fractions from Fischer Tropsch process. 26/02/1Ock18 173specification&claims.doc,5 -6 Detailed description of the invention It was surprisingly found that the diesel fuel composition of the invention, containing components of biological origin, also meets the quality requirements for diesel fuels under low temperature conditions. The composition of the diesel fuel of the invention 5 comprises: a) 0.1-99% by volume of a component or a mixture of components produced from biological raw material originating from animals, or both animals and plants, or originating from animals, plants and/or fish, by hydrogenating and decomposing fatty acids and/or fatty acid esters to give hydrocarbons and isomerising the hydrocarbons to give iso-paraffins; b) 0-20% by volume of 10 components containing oxygen selected from the group consisting of aliphatic alcohols, ethers, fatty acid esters, water and mixtures containing the same; both components a) and b) being mixed as an emulsion with or dissolved in diesel components based on crude oil and/or fractions from Fischer-Tropsch process. Said components a) and b) are mixed in diesel components based on crude oil and/or in 15 fractions from Fischer-Tropsch process by forming an emulsion with or by dissolving said components in diesel components based on crude oil and/or fractions from Fischer-Tropsch process. Preferably the composition of the invention comprises: a) 5-80% by volume of a 20 component or a mixture of components produced from biological raw material originating from animals, or both animals and plants, by hydrogenating and decomposing fatty acids and/or fatty acid esters to give hydrocarbons and isomerising the hydrocarbons to give iso-paraffins; b) 0-20% by volume of components containing oxygen selected from the group consisting of aliphatic 25 alcohols, ethers, fatty acid esters, water and mixtures containing the same; both components a) and b) being mixed as an emulsion with or dissolved in diesel components based on crude oil and/or fractions from Fischer-Tropsch process. More preferably the composition of the invention comprises: a) 10-80% by volume 30 of a component or a mixture of components produced from biological raw material originating from animals, or both animals and plants, by hydrogenating and decomposing fatty acids and/or fatty acid esters to give hydrocarbons and 26/02/1 Ock 8 173specification&claims.doc.6 -7 isomerising the hydrocarbons to give iso-paraffins; b) 0-20% by volume of components containing oxygen selected from the group consisting of aliphatic alcohols, ethers, fatty acid esters, water and mixtures containing the same; both components a) and b) being mixed as an emulsion with or dissolved in diesel 5 components based on crude oil and/or fractions from Fischer-Tropsch process. Most preferably the composition of the invention comprises: a) 10-80% by volume of a component or a mixture of components produced from biological raw material originating from animals, or both animals and plants, by hydrogenating and 10 decomposing fatty acids and/or fatty acid esters to give hydrocarbons and isomerising the hydrocarbons to give iso-paraffins; b) 1-20% by volume of components containing oxygen selected from the group consisting of aliphatic alcohols, ethers, fatty acid esters, water and mixtures containing the same; both components a) and b) being mixed as an emulsion with or dissolved in diesel 15 components based on crude oil and/or fractions from Fischer-Tropsch process. It was generally thought that products based on animal origin, as well as products based on recycled fats, could not be used in diesel fuels. These products were expected to contain high amounts of sulphur-, nitrogen- and metal-containing 20 impurities, which would weaken the quality of the composition and make their processing very difficult. This, however, turns out not to be true. The biological based fuel compositions of the current invention have remarkably lower "green house emissions" than the corresponding crude oil based products. The 25 animal- and fish-based fuel compositions of the current invention also have significantly improved performance ability under cold conditions. These compositions may have a turbidity point of lower than 0 0 C, preferably lower than 10*C and more preferably lower than -20*C. These compositions may have a turbidity point of even -30*C or lower while simultaneously having a cetane number 30 of 60 or higher. This differs markedly from the turbidity points presented in SE 9700149, which are considerably higher. 26/02/1 Ock 81 73spccification&claims.doc.7 -8 The biological raw material originating from animals, containing fatty acids and/or fatty acid esters, is processed to yield the biological component of the present application. Said biological component is obtained by hydrogenating and decomposing fatty acids and/or fatty acid esters to give hydrocarbons having carbon 5 number of 6-24, typically n-paraffins as the product having a carbon number of 12 24, and isomerising the hydrocarbons, typically n-paraffins thus obtained to give iso paraffins. Typically, after the isomerisation, the iso-paraffin content is more than 20 wt-%, preferably more than 30 wt-% and more preferably more than 50 wt-%. In one embodiment of the invention the iso-paraffin content may be more than 60 wt-% or 10 even more than 70 wt-% in said biological component. Examples of suitable biological raw materials are animal-based fats such as lard, tallow, train oil, and fats contained in milk, as well as recycled animal fats of the food industry and mixtures of the above. 15 The fuel composition can optionally further comprise a component or mixture of components produced from biological raw material originating from plants. The biological raw material originating from plants can be selected from various vegetable oils, and mixtures thereof containing fatty acids and/or fatty acid esters. 20 Examples of suitable materials are wood-based and other plant-based fats and oils such as rapeseed oil, colza oil, canola oil, tall oil, sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, as well as fats contained in plants bred by means of gene manipulation, and recycled plant sourced fats of the food industry. 25 The basic component of a typical vegetable or animal fat is triglyceride i.e. a triester of glycerol and three fatty acid molecules having the structure presented in the following formula I: 26/02/1Ock 8 1 73specification&claims.doc.8 -9 0 00 where R 1 , R 2 , and R 3 are hydrocarbon chains, and R 1 , R 2 , and R 3 may be saturated or unsaturated C 6 - C 24 alkyl groups. The fatty acid composition may vary considerably 5 in biological raw materials of different origin. n-paraffins, iso-paraffins or mixtures thereof produced from the biological raw material may be used as a diesel fuel component in accordance with the properties desired for the diesel fuel. Fractions from Fischer-Tropsch-process typically contain 10 high levels of n-paraffins and, optionally, they may be isomerised either simultaneously during the processing of the component of biological origin or separately therefrom, or they may be used as such. The biological component may be produced, for instance, with a process comprising 15 at least two steps and optionally utilizing the counter-current operation principle. Before the first step the feedstock may optionally be prehydrogenated to saturate double bonds of the hydrocarbon chain, at a temperature of 1 00-400'C, preferably at 1 50-250'C. In the first hydrodeoxygenation step of the process, carried out at a temperature of 200-400'C, preferably at 250-350'C, optionally running counter 20 current, the structure of the biological raw material is broken, compounds containing oxygen, nitrogen, phosphor and sulphur as welt as light hydrocarbons as gas are removed, and thereafter, olefinic bonds are hydrogenated. In the second, isomerisation step of the process, optionally running counter-current, isomerisation is carried out to give branched hydrocarbon chains, thus improving the low temperature 25 properties of the paraffins. 26/02/ l10A 181 73specification&claimsdo,9 -10 Biological raw material selected from plant oils and fats, animal fats, and mixtures thereof, containing fatty acids and/or fatty acid esters, is used as the feedstock. High quality hydrocarbon component of biological origin, particularly useful as a 5 component of a diesel fuel, as an iso-paraffinic solvent and as a lamp oil, is obtained as the product having a high cetane number that may even be higher than 70. A component with a turbidity point lower than -30 *C and a cetane number higher than 60 can also be achieved. Further, said hydrocarbon component of biological origin is free of aromatics. The content of naphthenes in said hydrocarbon component may be 10 less than 30 wt-%, preferably less than 10 wt-%, more preferably less than 5 wt-% or even less than I wt-%. Both aromatics and naphthenes present in the hydrocarbon product decrease the cetane number and increase cold smoke during start up of the engine. The process can be adjusted according to the desired cetane number and turbidity point. 15 Advantages of the diesel fuel composition of the present invention include superior performance at low temperatures and an excellent cetane number compared to solutions of prior art using FAME-based components like RME. Problems associated with the performance at low temperatures may be avoided by isomerising waxy n 20 paraffins having a carbon number comparable with that of fatty acids to give iso paraffins. The properties of the products thus obtained are excellent, especially with respect to diesel applications, the n-paraffins typically have cetane numbers higher than 70, and iso-paraffins higher than 60, and thus they have an improving effect on the cetane number of the diesel pool, which clearly makes them more valuable as 25 diesel components. Moreover, the turbidity point of the isomerised product may be adjusted to the desired level, for example below -30 *C, whereas the corresponding value is about 0 *C for RME and more than + 15 *C for n-paraffins. Table I below compares the properties of an isomerised biological component, RME, and a commercial diesel fuel. 30 26/02/10,ck I8173specification&claims.doc. 10 - 11 Table 1 Product Density Cetane Turbidity (kg/m 3 ) number point (*C) Isomerised biological component <800 > 60 < -30 RME -880 ~-50 - 0 Diesel fuel EN 590 820-845 > 51 0 to -15 Fouling of engines is considerably diminished and the noise level is clearly lower 5 when using isomerised biological component fuel composition in comparison with similar prior art fuels of biological origin containing FAME components, and further, the density of the composition is lower. The composition does not require any modifications of the automobile technology or logistics. Higher energy content per unit volume may be mentioned as a further advantage compared to RME. 10 The properties of the diesel fuel composition of biological origin according to the invention correspond to those of a high quality diesel fuel based on crude oil. A composition free of aromatics can be obtained and, in contrast to FAME, it leaves no impurity residues. 15 Nitrogen oxide emissions due to the fuel composition of the invention are lower that those from a similar FAME-based product, and further, the particle emissions are clearly lower, and the carbon portion of the particles is smaller. These significant improvements in the emissions of the fuel composition of biological origin are 20 environmentally very important. Table 2 below, compares the cold properties of the animal fat based product of the current invention with those exemplified by the product disclosed in Example 4 from SE 9700149. 25 26/02/10,ck18173spccification&claims.doc.1 I - 12 Table 2 Feed Vegetable fat Animal fat Property Method Unit Example 4 from SE9700149 Hydrotreated and Isomerised Density 15'C ENISO kg/m 770 776 12185 Turbidity Point ASTM *C -12 -35 D5771 CFPP EN 116 Ann 0 C -11 -34 Sulphur content ASTM mg/kg 0 <1 D5453 Cetane Number NM 353 >74 78 IQT This Table presents the surprisingly improved results obtained for the instant 5 invention under cold conditions. That is, the animal fat-based fuel composition of the instant invention has excellent cold properties when compared with those compositions presented in SE 9700149. Specifically, the lower turbidity point of the animal fat-based fuel composition of the instant invention affords less fuel filter plugging during cold weather operations. 10 Also, the cold filter plugging point (CFPP) indicates that the animal fat-based fuel composition of the instant invention provides trouble-free flow in fuel systems at ambient temperatures about 20 0 C lower as compared to the cited prior art. Most surprisingly these improved performance qualities are obtained without a decrease in 15 the fuel ignition delay characteristics as evidenced by the instant invention's high cetane number, which is comparable to that of the prior art. It was generally thought that one cannot improve cold flow properties to these low levels without decreasing the fuel ignition delay. 20 The invention will now be illustrated by means of the following examples without intending to limit the scope thereof. 26/02/10ck 8173specification&claims.doc. 12 - 13 EXAMPLES Example 1 Manufacture of animal fat based component 5 The hydrogenation of animal fat was carried out in a fixed bed tube reactor. The hydrogenation reaction was carried out in the presence of NiMo catalyst under a pressure of 50 bars, with WHSV of I - 2 1/h and at a reaction temperature from 250 to 300*C. Hydrogen to oil ratio was 500 - 1500 normal liters H 2 per liter oil fed. 10 The hydrogenated product oil contained no oxygen compounds. Isomerisation of the above-obtained hydrogenated animal fat was carried out in a fixed bed tube reactor in the presence of Pt-SAPO-catalyst under a pressure of 40 bars, with WHSV of 1.5 1/h and at a reaction temperature of 328*C. Hydrogen to oil 15 ratio was 300 normal liters H 2 per liter oil fed. Low temperature properties of the obtained animal fat based component are presented in the Table 3 below. 20 Table 3 Feed Animal fat Property Method Hydrogenated and Isomerised Density / 15'C/ kg/m 3 ENISO 12185 776 Turbidity point /PC ASTM D5771 -35 CFPP / 0 C EN 116 Ann -34 Sulphur / mg/kg ASTM D5453 <1 Cetane Number / IQT NM 353 78 26/02/10.ek 8173specification&claims.doc. 13 - 14 Example 2 Composition containing 20 wt-% of animal fat based component and 80 wt-% crude oil based diesel component 5 The hydrogenated and isomerised animal fat component (biocomponent) produced in example I was blended to crude oil based diesel component (European diesel fuel EN590) in amounts of biocomponent 20 wt-% and EN590 80 wt-%. Table 4 below shows the characteristics of the obtained product and the components. 10 Table 4 Component/Product Animal fat Crude oil Blend Property Method Hydrogenated Diesel fuel 20 wt-% diesel from and isomerised component animal fat and 80 wt % crude oil diesel Density / 15'C / kg/m 3 ENISO 776 829 818 12185 Turbidity point / C ASTM - 35 -29 -31 D5771 CFPP/*C EN 116 -34 -43 -44 Ann Sulphur / mg/kg ASTM < 1 < 5 < 5 D5453 Cetane Number / IQT NM 353 78 51 (engine) 58 26/02/1O.ck 8173specification&claims.doc,14 - 15 Example 3 Composition containing 20 wt-% of animal fat based component and 80 wt-% crude oil based diesel component blended with 5 wt-% of oxygen containing component 5 The hydrogenated and isomerised animal fat component (biocomponent) produced in example I was blended to crude oil based diesel component (European diesel fuel EN590) in amounts of biocomponent 20 wt-% and EN590 80 wt-%. To this blend 5 wt % of oxygen containing component (RME= rapeseed oil fatty acid ester) was 10 blended. The characteristics of the blend and of the obtained product are provided in the Table 5 below: Table 5 Component/Product Property Method Blend Blend + RME 20 wt-% diesel from Blend + 5 wt % RME animal fat and 80 wt-% crude oil diesel Density / 15C /kg/m 3 ENISO 818 821 12185 Turbidity point /*C ASTM -31 -30 D5771 CFPP / *C EN 116 -44 -43 Ann Sulphur / mg/kg ASTM <5 5 D5453 Cetane Number / IQT NM 353 58 58 15 Comparative Example 4 The following Table 6 compares the emission characteristics of a conventional diesel 20 fuel used in Europe in summer, EN 590 (DI), to those of a composition containing 60 26/02/10ckl 8173spccification&cIaims.doc.IS - 16 % by volume of hydrogenated and isomerised tall oil (TOFA), and 40 % by volume of the European summer diesel fuel EN 590. Table 6 5 Characteristic Unit 60 % b.v. TOFA + 40 % b.v. DI DI Turbidity point "C -15 -8 Cetane number - 61.2 55.9 Aromatics % b.w. 8.7 19.2 Total aromatics (IP391) % b.v. 9.1 20.0 Polyaromatics (IP391) % b.v. 0.8 1.6 n-paraffins % b.w. 14.7 24.5 i-paraffins % b.w. 34.2 26.1 Naphtenes % b.w. 42.4 30.2 b.w.= by weight b.v. = by volume Comparative Example 5 10 Table 7 below compares the emission characteristics of a high quality reformed crude oil based diesel fuel available on the Finnish market (DITC, produced by Fortum Oyj), to those of compositions containing 30 % by volume of hydrogenated and isomerised tall oil (TOFA), and 70 % by volume of DITC, or containing 30 % by 15 volume of tall oil methyl ester (MME), and 70 % by volume of DITC. 26/02/10.ck I 8173specification&claims.doc. 16 - 17 Table 7 Characteristic Unit DITC 30 % b.v. TOFA + 30 % b.v. MME + 70 % b.v. DITC 70 % b.v. DITC Cetane number - 51 57 48 NO, emissions % -I to -4 +3 (compared to DITC) Particles % -3 +22 - carbon % -10 to -30 0 to -10 -PAH % 0 0 Combustion noise - decreases 0 b.v. = by volume 5 Although the fuel composition of Examples 4 and 5 do not directly demonstrate the present invention as the compositions do not contain isomerised animal based biological material, the compositions can be blended with the biocomponent of Example I to provide a useful fuel composition. 10 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. 15 The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form or suggestion that the prior art forms part of the common general knowledge in Australia. 26/02/1 Ock 8173specification&claims.doc. 17

Claims (7)

1. A fuel composition for diesel engines, wherein the fuel composition 5 comprises: a) 0.1-99% by volume of a component or a mixture of components produced from biological raw material originating from animals by hydrogenating and decomposing fatty acids and/or fatty acid esters to give hydrocarbons and isomerising the hydrocarbons to give iso-paraffins; b) 0-20% by volume of components containing oxygen selected from the group consisting of aliphatic 10 alcohols, ethers, fatty acid esters, water and mixtures containing the same; both components a) and b) being mixed as an emulsion with or dissolved in diesel components based on crude oil and/or fractions from Fischer-Tropsch process.
2. The fuel composition of claim 1, wherein the fuel composition 15 comprises 5-80% by volume of a component or a mixture of components produced from biological raw material.
3. The fuel composition according to claim I or 2, wherein the fuel composition further comprises 0.1-99% by volume of a component or mixture of 20 components produced from biological raw material originating from plants by hydrogenating and decomposing fatty acids and/or fatty acid esters to give hydrocarbons and isomerising the hydrocarbons to give iso-paraffins.
4. The fuel composition of claim 3, wherein the plant biological raw 25 material are vegetable oils.
5. The fuel composition according to claim 4, wherein the biological raw material is an animal-based fat, a fat contained in milk, a recycled fat of the food industry or a mixture of the above and the plant biological raw material is selected 30 from the group consisting of a wood-based fat or oil, another plant-based fat or oil, and a fat contained in plants bred by means of gene manipulation. 26/02/1O.ck I 8173specificaion&claims.doc, 18 - 19
6. The fuel composition of claim 5, wherein the animal based fat or the recycled fat of the food industry is lard, tallow or train oil, and that the wood based or other plant-based fat or oil is rapeseed oil, colza oil, canola oil, tall oil, 5 sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil or coconut oil.
7. The fuel composition according to any one of claims 1 to 6, wherein the component or compounds produced from biological raw material is iso 10 paraffin having a carbon number of 12-24. 15 26/02/10ck l8173specification&claims.doc.19
AU2010200726A 2002-09-06 2010-02-26 Diesel fuel composition, comprising components based on biological raw material, obtained by hydrogenating and decomposition fatty acids Abandoned AU2010200726A1 (en)

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AU2003258753A1 (en) 2004-03-29
PL375038A1 (en) 2005-11-14
MY139714A (en) 2009-10-30
EP1546288A1 (en) 2005-06-29
FI20021596A0 (en) 2002-09-06
JP2005538204A (en) 2005-12-15
CA2499489C (en) 2013-04-30
CA2499489A1 (en) 2004-03-18
AU2003258753C1 (en) 2012-06-14
CN1688673A (en) 2005-10-26
BR0314100A (en) 2005-07-19
WO2004022674A1 (en) 2004-03-18
RU2005109935A (en) 2005-08-27
AU2020203806A1 (en) 2020-07-02
AU2020203806B2 (en) 2022-05-26
FI20021596A (en) 2004-03-07
AU2003258753B2 (en) 2008-12-04

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