EP2892985A1 - Kraftstoffzusammensetzung - Google Patents

Kraftstoffzusammensetzung

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Publication number
EP2892985A1
EP2892985A1 EP13758863.8A EP13758863A EP2892985A1 EP 2892985 A1 EP2892985 A1 EP 2892985A1 EP 13758863 A EP13758863 A EP 13758863A EP 2892985 A1 EP2892985 A1 EP 2892985A1
Authority
EP
European Patent Office
Prior art keywords
ether
component
fuel
composition
ether component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13758863.8A
Other languages
English (en)
French (fr)
Inventor
Aldo Caiazzo
Lionel Clarke
Tor Kit Goh
George Robert Lee
David Alexander PARKER
Richard John Price
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.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP13758863.8A priority Critical patent/EP2892985A1/de
Publication of EP2892985A1 publication Critical patent/EP2892985A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C10L1/18Organic compounds containing oxygen
    • C10L1/185Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852Ethers; Acetals; Ketals; Orthoesters
    • 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
    • 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/12Use of additives to fuels or fires for particular purposes for improving the cetane number
    • 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
    • C10L2200/00Components of fuel compositions
    • C10L2200/04Organic 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
    • C10L2200/00Components of fuel compositions
    • C10L2200/04Organic compounds
    • C10L2200/0407Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446Diesel
    • 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
    • C10L2200/00Components of fuel compositions
    • C10L2200/04Organic compounds
    • C10L2200/0461Fractions defined by their origin
    • C10L2200/0469Renewables or materials of biological origin
    • C10L2200/0476Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • 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

Definitions

  • This invention relates to diesel fuel compositions comprising certain ethers, their preparation and their use, as well as to the use of certain ethers in fuel compositions for new purposes.
  • diesel fuel compositions contain cetane boost components, also known as ignition improvers.
  • the cetane number of a fuel or fuel composition/formulation is a measure of its ease of ignition. With a lower cetane number fuel a compression ignition (diesel) engine tends to be more difficult to start and may run more noisily when cold. There is a general preference therefore for a diesel fuel composition to have a high cetane number, and as such automotive diesel specifications generally stipulate a minimum cetane number.
  • Biofuels are combustible fuels, derived from biological sources, which result in a reduction in "well-to-wheels" (ie from source to combustion) greenhouse gas emissions.
  • fatty acid alkyl esters FAMEs
  • FAMEs fatty acid methyl esters
  • FAMEs in particular FAMEs
  • FAMEs can be used in low concentrations as cetane boost components in diesel fuels.
  • cetane boosting effect of FAMEs diminishes as the blend ratio of FAME to base fuel is increased.
  • the potential of FAMEs as cetane boost components is thus limited for more than one reason, necessitating additional cetane boost additives, at least in some applications.
  • cetane boost components for use in diesel fuel compositions, which suffer from fewer of the drawbacks and limitations associated with FAAEs.
  • such components should be biologically derivable, ie biofuels, and also have minimal transfer into the engine sump and cause minimal dilution of lubricant as a result.
  • Flash point in particular can be a handling issue for diesel fuels, and in an overall fuel composition must be above a specified limit to ensure that flammable mixtures of fuel and air do not form within the fuel supply and distribution system.
  • the melting point of a molecule meanwhile, will directly affect the cloud point and cold filter plugging point of a fuel composition into which it is blended, and these properties must also be controlled in order to allow satisfactory vehicle operability during winter months .
  • an alternative cetane boost component particularly if it is a biofuel oxygenate component, will have properties - in particular a flash point and melting point - which allow it to be blended into diesel fuel compositions at concentrations above the current 7% v/v limit for FAMES.
  • diisopropylether and are utilised in bulk quantities;
  • the second oxygenate proposed is selected from diglyme, triglyme and dipentylether and is proposed for use in quantities of 10% v/v or less.
  • a fuel composition comprising: a diesel base fuel; from 1 to 10% v/v of a fatty acid alkyl ester; and more than 10% v/v of an ether component, the ether component comprising or consisting of one or more ether compounds having in the range of from 8 to 12 carbon atoms and selected from compounds of formula I
  • R1-O-R2 (I) wherein R x and R 2 are independently C 2 to Ci 0 primary or secondary alkyl.
  • ether compounds are meant compounds that contain only one ether group.
  • C8+ ethers can function highly effectively as cetane boost additives in diesel fuel at high concentrations in excess of 10% v/v e.g. up to 50% v/v.
  • the ether component may be a biofuel and generally does not suffer from the drawbacks associated with FAAEs in the context of lubricant dilution. For example, the ether component is less prone to
  • the ether component can thus be incorporated into diesel fuel compositions at concentrations significantly higher than the current 7% v/v FAME limit, without build-up of biofuel components in engine oil and whilst maintaining a positive effect on cetane numbers of the overall compositions.
  • the ether component is to be understood herein as an added component.
  • the ether component may be, or be taken to be, the sole source of the ether compound (s) that it consists of in the composition, but this is not essential.
  • the ether component is defined herein as comprising or consisting of one or more ether compounds having at least 8 carbon atoms (C8+ ether), or at least 9 carbon atoms (C9+ ether), or most preferably at least 10 carbon atoms (C10+ ether) .
  • the ether component may comprise, or be, C8+ ether, C9+ ether, or C10+ ether. Higher molecular weight ethers tend to have particularly advantageous volatility and cetane properties.
  • the ether compounds of the ether component may comprise at most 12 carbon atoms, or most preferably at most 10 carbon atoms.
  • Ether compounds with a relatively low number of carbon atoms may be preferred for their ease of biological synthesis.
  • CIO ethers are particularly preferred.
  • the ether compound (s) of the ether component may be symmetrical or asymmetrical; dialkyl, dicycloalkyl, or alkylcycloalkyl . Symmetrical compounds are preferred. A particularly preferred ether is dipentyl ether (DPE).
  • DPE dipentyl ether
  • the ether compound (s) may be selected from compounds of formula I
  • R1-O-R2 (I) wherein R x and R 2 are independently C 2 to C 24 primary or secondary alkyl, provided that the total number of carbon atoms in formula (I) is as required, e.g. at least 8, 9 or 10, or as defined anywhere hereinabove.
  • Ri and/or R 2 may be C 3 to Ci 5 alkyl, more preferably C 4 to C 7 .
  • Ri and/or R 2 may be C 3 to Ci 5 alkyl, more preferably C 4 to C 7 .
  • Ri and/or R 2 may be C 3 to Ci 5 alkyl, more preferably C 4 to C 7 .
  • Ri and/or R 2 may be C 5 alkyl. Since the ether component may preferably comprise or consist of symmetrical compounds, Ri and R 2 may be C 5 alkyl. Since the ether component may preferably comprise or consist of symmetrical compounds, Ri and R 2 may
  • the ether component may comprise or consist of one or more of the ether compounds or ether compound mixtures described hereinabove. Most preferably, the ether component may comprise or consist of dipentyl ether.
  • the ether component may comprise a mixture of two or more ether compounds as defined hereinabove .
  • the ether component may comprise at least 50% v/v, or 70% v/v or 90% v/v, or even 95% v/v of any one of the ether compounds or ether compound mixtures described hereinabove .
  • the ether component may be accompanied by a small amount of impurities, for example by-products of ether synthesis that have no substantive effect on the overall properties of the ether component.
  • impurities may, for example, be present in an amount of at most about 3%, e.g. as measured by gas chromatography (GC) commonly employed by suppliers such as Sigma Aldrich.
  • GC gas chromatography
  • impurities up to 3% as measured by GC may be considered part of the ether component, in which case the component consists substantially of the ether compounds .
  • the cetane number of the ether component will typically be higher than the cetane number of the diesel base fuel.
  • the cetane number of the ether component may be at least 90, preferably at least 100, or at least 102, most preferably at least 104.
  • the ether component may offer a good property fit with the diesel base fuel, particularly with a view to the composition meeting EN590 or another specification .
  • the ether component may preferably have a density, measured according to ASTM D 4052, of at least 0.750 g/cm 3 , more preferably at least 0.770 g/cm 3 .
  • the density of the ether component may, for example, be at most 0.830 g/cm 3 .
  • the ether component may preferably have a flash point, measured according to ASTM D 93, of at least 20°C, more preferably at least 50°C.
  • the ether component may preferably have a vapour pressure, measured at 25°C, of at most 500 Torr (66661.2 Pa), preferably at most 50 Torr (6666.1 Pa), or even at most 5 Torr (666.6 Pa) .
  • the vapour pressure of the ether component may, for example, be at least 0.5 Torr (66.6
  • the ether component may preferably have a boiling point, measured according to ASTM D 86, of at least 40°C, more preferably at least 100°C.
  • the boiling point of the ether component may, for example, be at most 480 °C.
  • the ether component may be prepared by any suitable process known in the art.
  • One well known synthesis is the Williamson ether synthesis, which involves treatment of a parent alcohol with a strong base to form an alkoxide, followed by addition of an appropriate aliphatic compound bearing a leaving group such as halide or sulfonate. This synthesis works particularly well for acyclic,
  • symmetrical ethers are typically prepared by the dehydration of a parent alcohol.
  • Dipentyl ether for example, may be prepared by dehydrating 1-pentanol in the presence of sulphuric acid.
  • the alcohols or other starting materials for the synthesis of ethers may be obtained from any available source.
  • parent alcohols such as amyl alcohol
  • olefins which may in turn be petroleum derived (see e.g. K Weissermel and H-J Arpe, Industrial Organic Chemistry,
  • the ether component may be a biofuel component, ie derived from a biological source.
  • the ether component may comprise or consist of ether compounds derived from parent molecules, e.g. alcohols, which are in turn obtained from a renewable carbonaceous feedstock. For example, it is known to obtain alcohols by
  • alcohols can be any biological routes to alcohols, such as pentanol, via fermentation of renewable feedstocks (organic carbon sources) using microorganisms, fungi (such as members of the genus Saccharomyces ) , protists, algae, bacteria (including cyanobacteria) and archaea are increasingly being proposed.
  • alcohols can be any biological routes to alcohols, such as pentanol, via fermentation of renewable feedstocks (organic carbon sources) using microorganisms, fungi (such as members of the genus Saccharomyces ) , protists, algae, bacteria (including cyanobacteria) and archaea.
  • alcohols can be any biological routes to alcohols, such as pentanol, via fermentation of renewable feedstocks (organic carbon sources) using microorganisms, fungi (such as members of the genus Saccharomyces ) , protists, algae, bacteria (including cyanobacteria) and archa
  • the ether component may comprise at least about 0.1 dpm/gC of carbon-14. It is known in the art that carbon-14, which has a half-life of about 5700 years, is found in
  • Carbon-14 levels can be determined by measuring its decay process (disintegrations per minute per gram carbon or dpm/gC) through liquid scintillation counting.
  • the concentration of the ether component in the overall fuel composition is preferably 90 % v/v or less, more preferably 80 % v/v or less, yet more preferably 70 or 60 or 50 % v/v or less, based on the total
  • composition/mixture As a minimum it is more than 10 % v/v, or 12 % v/v or greater, such as 15 % or 25 % v/v or greater, or even 30 or 40 % v/v or greater, based on the total composition/mixture.
  • the amount of the ether component may represent a balance of the fuel
  • the ether component after inclusion of the base fuel component, and any further (optional) components and additives, the ether component may therefore be present in an amount to represent the balance to 100% v/v in the composition.
  • the diesel base fuel may be any fuel component, or mixture thereof, which is suitable and/or adapted for use in a diesel fuel composition and therefore for combustion within a compression ignition (diesel) engine. It will typically be a liquid hydrocarbon middle distillate fuel, more typically a gas oil. It may be or contain a kerosene fuel component.
  • It may be petroleum derived. Alternatively it may be synthetic: for instance it may be the product of a
  • Fischer-Tropsch condensation It may be derived from a biological source.
  • a diesel base fuel will typically boil in the range from 150 or 180 to 370°C (ASTM D86 or EN ISO 3405) . It will suitably have a measured cetane number (ASTM D613) of from 40 to 70 or from 40 to 65 or from 51 to 65 or to 70.
  • a fuel composition according to the invention may include (or may include a greater proportion of) a base fuel which has a relatively low cetane number. This can increase the options available to the fuel formulator .
  • the ether component may therefore be used for the purpose of allowing the inclusion, in a diesel fuel composition, of one or more lower cetane number fuel components (for example diesel base fuels), or of a higher concentration of one or more such fuel components, without, or without undue, detriment to the cetane number of the overall composition.
  • a "lower cetane number" fuel component may for example have a measured cetane number of less than 50, or of less than 45 or 40 or in cases of less than 35.
  • “Without undue detriment to the cetane number” may for example mean without reducing the cetane number by more than 30%, or in cases by more than 20 or 10 or 5 or 1%, of its value if a higher cetane number fuel component (for example, with a measured cetane number of 40 or greater, or of 45 or 50 or greater) were to be used in the fuel
  • composition at the same concentration, in place of the lower cetane number fuel component. It may entail the overall fuel composition meeting a desired target specification, for example the European diesel fuel specification EN 590.
  • the diesel base fuel may suitably be present in the composition in an amount of 10 % v/v or greater, or 20 or 30 or 40% or 50% v/v or greater, based on the total composition. It may be present in an amount of less than 90 % v/v, or up to 85 or up to 80 or 75% v/v, or up to 70 or 65 or 60% v/v, based on the total composition.
  • the amount of the base fuel may represent a balance of the fuel composition: after inclusion of the ether component, the fatty acid alkyl ester, and any further (optional) components and additives, the diesel base fuel may therefore represent the balance to 100% v/v in the composition .
  • the fuel composition may be prepared by simple blending of its components in any suitable order, and such methods of blending any of the fuel compositions herein are embraced by the invention.
  • the fuel composition may comprise, in addition to the diesel base fuel, the fatty acid alkyl ester, and the ether component, one or more fuel or refinery additives, in particular additives which are suitable for use in automotive diesel fuels. Many such additives are known and commercially available.
  • the composition may for example comprise one or more additives selected from cetane boost additives, antistatic additives, lubricity additives, cold flow additives, and combinations thereof. Such additives may be included at a concentration of up to 300 ppmw (parts per million by weight), for example of from 50 to 300 ppmw. Due to the inclusion of the ether component, however, it may, as described below, be possible for the composition to contain lower levels of cetane boost additive, or in cases for the composition not to contain such type of additive.
  • the fuel composition should be suitable and/or adapted for use in a compression ignition (diesel) internal combustion engine. It may in particular be an automotive fuel composition. In further embodiments it may be suitable and/or adapted for use as an industrial gas oil, or as a domestic heating oil.
  • the fuel composition may suitably comply with applicable current standard diesel fuel specification ( s ) such as for example EN 590 (for Europe) or ASTM D975 (for the USA) .
  • the overall composition may have a density from 820 to 845 kg/m 3 at 15°C (ASTM D4052 or EN ISO 3675); a T95 boiling point (ASTM D86 or EN ISO 3405) of 360°C or less; a measured cetane number (ASTM D613) of 40 or greater, ideally of 51 or greater; a kinematic viscosity at 40°C (VK40) (ASTM D445 or EN ISO
  • PAH PAH content
  • EN 12916 EN 12916
  • a lubricity measured using a high frequency reciprocating rig for example according to ISO 12156 and expressed as a "HFRR wear scar", of 460 ⁇ or less.
  • compositions may contain individual fuel components with properties outside of these ranges, since the properties of an overall blend may differ, often significantly, from those of its individual constituents.
  • the fuel composition comprises, in addition to the diesel base fuel and the ether component, a fatty acid alkyl ester, in particular a fatty acid methyl ester (FAME) such as rapeseed methyl ester or palm oil methyl ester. It is further possible for one or more further biofuel components, particularly other than ether or
  • the biofuel component may suitably comprise an alcohol, for example ethanol, and/or a fatty alcohol ester, and/or a hydrogenated vegetable oil.
  • the fatty acid alkyl ester may be present in an amount of at least 1% v/v, or 2 or 3 or 4 or 5% v/v, and up to 10 or 7 or 5 % v/v, based on the total composition.
  • the amount of further biofuel component may be at least 1% v/v, or 2 or 3 or 4 or 5% v/v, and up to 30% v/v, or up to 20 or 10 or 7 or 5 % v/v, based on the total composition. Due to the inclusion of the ether component, it may, as described below, be possible for the
  • composition to contain lower levels of biofuel composition to contain lower levels of biofuel
  • compositions or in cases for the composition not to contain additional biofuel components.
  • composition also comprises a a fatty acid alkyl ester.
  • a fatty acid alkyl ester there is provided the use of an ether component as defined above, in a diesel fuel composition containing a fatty acid alkyl ester, for the purpose of increasing the cetane number of the composition.
  • the present invention can provide for a further cetane boost.
  • the ether component may be used to replace all or part of a fatty acid ester or fatty alcohol ester which was previously, or was intended to be, or would otherwise have been, included in the diesel fuel
  • the ether component may be used to achieve any degree of increase in the cetane number of the diesel fuel composition, and/or for the purpose of achieving a desired target cetane number, for example a target set by an applicable regulatory standard such as EN 590, or a target set by a user (which includes a handler, keeper or distributor) or potential user of the composition. It may be used to achieve a cetane number increase which is greater than that which would be possible using the same concentration of another biofuel component, in particular of a fatty alcohol ester such as an alkyl acetate, or of a fatty acid alkyl ester such as a FAME.
  • the increase in cetane number will typically be as compared to the cetane number of the composition prior to adding ether component to it .
  • the ether component may be used to produce a diesel fuel composition which has a cetane number higher than a desired target standard.
  • the cetane number of a fuel composition may be determined using any suitable method, for instance using the standard test procedure ASTM D613 (ISO 5165, IP 41) which provides a so-called “measured” cetane number obtained under engine running conditions .
  • ASTM D613 ISO 5165, IP 41
  • the cetane number may be determined using the more recent
  • IQT ignition quality test
  • cetane number may be measured by near infrared spectroscopy (NIR) , as for example described in US-A-5, 349, 188. This method may be preferred in a refinery environment as it can be less cumbersome than for instance ASTM D613. NIR measurements make use of a correlation between the measured spectrum and the actual cetane number of a sample. An underlying model is prepared by correlating the known cetane numbers of a variety of fuel samples with their near infrared spectral data .
  • NIR near infrared spectroscopy
  • the present invention preferably results in a diesel fuel composition which has a measured cetane number (ASTM D613) of 40 or greater, or of 45 or 50 or 51 or greater, for example of 55 or 60 or 65 or greater, in cases of 70 or 75 or greater .
  • ASTM D613 measured cetane number
  • the invention may additionally or alternatively be used to adjust any property of the diesel fuel composition which is equivalent to or associated with cetane number, for example to improve the combustion performance of the composition (eg to shorten ignition delays, to facilitate cold starting and/or to reduce incomplete combustion and/or associated emissions in a fuel-consuming system running on the fuel composition) and/or to improve fuel economy.
  • concentration of a biofuel component than would have been predicted to be possible - whilst still achieving a desired target cetane number - based on the properties of the fatty acid/alcohol esters. It can be desirable to increase biofuel concentrations for a number of reasons, for instance to meet regulatory requirements or consumer expectations or more generally to reduce the "well-to- wheels" carbon dioxide emissions associated with the production and use of the fuel. It can also be desirable to increase the concentration of fatty alcohol esters, not only as biofuel components but also, for example, in order to improve the lubricity of a fuel composition containing an acid-based lubricity additive, as described in US-A-2011/0154728. However it would have been thought necessary, in the past, to balance such benefits against the potential reduction in cetane number which would be expected to result from increasing the concentration of a fatty alcohol ester, particularly for those esters having shorter (for example CIO or less) carbon chains.
  • an ether component as defined above in a diesel fuel composition, for the purpose of increasing the concentration of a biofuel component in the composition, without undue detriment to: the cetane number of the composition; and/or lubricant dilution under engine operating conditions.
  • the biofuel component may, for example, comprise a fatty alcohol ester: the ether component may therefore be used to increase the concentration of fatty alcohol esters in the diesel fuel composition, without or without undue detriment to its cetane number and/or lubricant dilution properties under engine operating conditions .
  • the biofuel component may be taken as including all biologically derived fuel components in the composition.
  • the invention may be used to increase the options available, to the fuel formulator, for increasing the biofuel content of a diesel fuel composition whilst still meeting relevant fuel
  • cetane number may for example mean without reducing the cetane number by more than 30%, or in cases by more than 20 or 10 or 5 or 1%, of its original value.
  • Lubricant dilution may be measured in any suitable manner, e.g. based on gas chromatography (GC) analysis of lubricant sump samples.
  • GC gas chromatography
  • the ether component may be used to enhance or maintain lubricant lifetime during use of the composition, or to maintain or increase the oil drain interval.
  • the ether component may be used to achieve any degree of increase in the concentration of the relevant biofuel component.
  • the ether component is used to increase the concentration of the biofuel component whilst at the same time increasing (which again embraces any degree of increase) the cetane number of the diesel fuel composition.
  • a further aspect of the invention provides the use of an ether component as defined above in a diesel fuel composition, for the purpose of reducing the
  • the term "reducing" embraces any degree of reduction, including reduction to zero.
  • the reduction may for instance be 10% or more of the original concentration of the cetane boost additive, or 25 or 50 or 75 or 90% or more.
  • the reduction may be as compared to the
  • composition in order to achieve the properties and performance required and/or desired of it in the context of its intended use.
  • This may for instance be the concentration of the additive which was present in the composition prior to the realisation that the ether component could be used in the way provided by the present invention, and/or which was present in an otherwise analogous fuel composition intended (eg marketed) for use in an analogous context, prior to adding the ether component to it in accordance with the invention .
  • the reduction in concentration of the cetane boost additive may be as compared to the concentration of the additive which would be predicted to be necessary to achieve a desired cetane number for the composition in the absence of the ether component.
  • a cetane boost additive may be any additive which is capable of increasing, or intended to increase, the cetane number of a diesel fuel composition to which it is added, and/or to improve the ignition properties of such a composition when it is used in an engine or other fuel- consuming system.
  • a cetane boost additive may also be known as a cetane improver, a cetane number improver or an ignition improver. Many such additives are known and commercially available; they typically function by increasing the concentration of free radicals when a fuel begins to react in a combustion chamber of a fuel- consuming system.
  • Examples include organic nitrates and nitrites, in particular (cyclo)alkyl nitrates such as isopropyl nitrate, 2-ethylhexyl nitrate (2-EHN) and cyclohexyl nitrate, and ethyl nitrates such as
  • cetane boosting diesel fuel additives are commercially available for instance as HITECTM 4103 (ex Afton Chemical) and as CI-0801 and CI- 0806 (ex Innospec Inc) .
  • ether component in a diesel fuel composition means incorporating the ether component into the composition, typically as a blend (ie a physical mixture) with one or more other diesel fuel components, for example a diesel base fuel and optionally one or more diesel fuel
  • the ether component will conveniently be incorporated before the composition is introduced into an engine or other system which is to be run on the
  • the use of the ether component may involve running a fuel-consuming system, typically an internal combustion engine, on a diesel fuel composition containing the ether component, typically by introducing the composition into a combustion chamber of an engine. It may involve running a vehicle which is driven by a fuel-consuming system, on a diesel fuel composition containing the ether component. In such cases the engine is suitably a compression ignition (diesel) engine .
  • a fuel-consuming system typically an internal combustion engine
  • diesel fuel composition containing the ether component typically by introducing the composition into a combustion chamber of an engine.
  • the engine is suitably a compression ignition (diesel) engine .
  • "Use” of the ether component in the ways described above may also embrace supplying the ether component together with instructions for its use in a diesel fuel composition in order to increase the cetane number of the composition.
  • the ether component may itself be supplied as part of a composition which is suitable for and/or intended for use as a fuel additive, in which case the ether component may be included in such a composition for the purpose of influencing its effects on the cetane number of a diesel fuel composition.
  • references to "adding" a component to, or “incorporating” a component in, a fuel composition may be taken to embrace addition or incorporation at any point during the production of the composition or at any time prior to its use.
  • the present invention may be used to produce at least 1,000 litres of the ether component- containing fuel composition, or at least 5,000 or 10,000 or 20,000 or 50,000 litres.
  • a fuel composition prepared or used according to the invention may be marketed with an indication that it benefits from an improvement due to the inclusion of the ether component, in particular a higher cetane number.
  • the marketing of such a composition may comprise an activity selected from (a) providing the composition in a container that comprises the relevant indication; (b) supplying the composition with product literature that comprises the indication; (c) providing the indication in a publication or sign (for example at the point of sale) that describes the composition; and (d) providing the indication in a commercial which is aired for instance on the radio, television or internet.
  • the improvement may be attributed, in such an indication, at least partly to the presence of the ether component.
  • the invention may involve assessing the relevant property (in particular the cetane number) of the composition during or after its preparation. It may involve assessing the relevant property both before and after incorporation of the ether component, for example so as to confirm that the ether component contributes to the relevant improvement in the composition .
  • any feature disclosed herein may be replaced by an alternative feature serving the same or a similar purpose.
  • references to fuel and fuel component properties are - unless stated otherwise - to properties measured under ambient conditions, ie at atmospheric pressure and at a temperature from 16 to 22 or 25°C, or from 18 to 22 or 25°C, for example about 20°C.
  • Diesel fuel compositions were prepared by blending a diesel base fuel with an ether component consisting of dipentyl ether (DPE) .
  • DPE dipentyl ether
  • the base fuel was a zero sulphur diesel fuel (ex Shell), which conformed to the European diesel fuel specification EN 590. It did not contain any detergent or lubricity additives, or any oxygenates such as FAMEs. Its properties are summarised in Table 1 below.
  • the ether component was blended with the base fuel at 2, 5, 10, 15, 30 and 50% v/v.
  • the resultant blends were tested for cetane number using the IQT method specified in Table 1. The results are shown in Table 2.
  • - blending CN DPE is the blending cetane number of the ether component when used at volume fraction x;
  • CN comp is the measured cetane number of the base fuel/ether component blend;
  • CN d iesei is the measured cetane number of the diesel base fuel .
  • the blending cetane number of the ether component is a measure of the contribution of the ether component to the measured cetane number of the fuel composition. It can be seen that the blending cetane number of the ether component increases from 91.4 at 10% v/v to 99 at 50% v/v. The effectiveness of the ether component in boosting cetane is thus increased at higher concentrations.
  • Diesel fuel compositions were prepared, for
  • the diesel base fuel was as in Example 1.
  • the FAME component consisted of 100% refinery grade palm oil methyl esters (POME) .
  • the FAME component was blended with the base fuel at 2, 5, 10, 15, 30 and 50% v/v.
  • the resultant blends were tested for cetane number using the IQT method specified in Table 1. The results are shown in Table 3.
  • blending CN FAME is the blending cetane number of the FAME component when used at volume fraction x;
  • CN comp is the measured cetane number of the base fuel/ether component blend
  • CiV d i ese j is the measured cetane number of the diesel base fuel .
  • the blending cetane number of the FAME component is a measure of the contribution of the FAME component to the measured cetane number of the fuel composition. It can be seen that the blending cetane number of the FAME component decreases from 75.4 at 10% v/v to 70.4 at 50% v/v. The effectiveness of the FAME component in boosting cetane is thus decreased at higher concentrations.
  • Diesel fuel compositions were prepared, according to the invention, by blending a diesel base fuel with an ether component consisting of dipentyl ether and a fatty acid methyl ester (FAME) component.
  • ether component consisting of dipentyl ether and a fatty acid methyl ester (FAME) component.
  • Example 1 The FAME component was as in Example 2.
  • the ether and FAME components were blended with the base fuel in the amounts shown in Table 4.
  • the resultant blends were tested for cetane number using the IQT method specified in Table 1. The results are shown in Table 4.
  • blending cetane number values were calculated for the combined ether and FAME components as follows .
  • blending CN DPE+FAME ( CN comp - (1-x) * C-Vdi eseI ) / x where :
  • blending CN DPE+FAME is the blending cetane number of the combined ether and FAME components when used at a total volume fraction x;
  • CN comp is the measured cetane number of the base fuel/ether component blend
  • CNd ⁇ esel is the measured cetane number of the diesel base fuel .
  • the blending cetane number of the combined ether and FAME components is a measure of the contribution of these components to the measured cetane number of the fuel composition. It can be seen that, at a consistent concentration of the FAME component, the blending cetane number of the combined components increases from 70.4 at 5% v/v ether component to 94.6 at 45% v/v ether
  • Table 5 shows the properties of composition 3 from Example 1.
  • the diesel fuel used to run the engine did not contain any biofuels (ie. free of FAME and ether) .
  • the components tested were Ether component only, FAME component only, and an equivolume Ether-FAME component mixture.
  • the loss of bio-component was determined from GC analysis of lubricant sump samples.

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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)
EP13758863.8A 2012-09-05 2013-09-05 Kraftstoffzusammensetzung Withdrawn EP2892985A1 (de)

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EP12183067 2012-09-05
PCT/EP2013/068362 WO2014037439A1 (en) 2012-09-05 2013-09-05 Fuel composition
EP13758863.8A EP2892985A1 (de) 2012-09-05 2013-09-05 Kraftstoffzusammensetzung

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FI127887B (en) 2016-12-19 2019-04-30 Neste Oyj Multi-component diesel composition
FI127886B (en) 2016-12-19 2019-04-30 Neste Oyj More Diesel Component Composition
RU2652636C1 (ru) * 2017-03-23 2018-04-28 Общество с ограниченной ответственностью "Малое инновационное предприятие "ФФ-Хим" (ООО "МИП "ФФ-Хим") Топливная композиция для дизельных двигателей

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US2221839A (en) 1936-10-20 1940-11-19 Atlantic Refining Co Fuel for compression ignition engines
US5349188A (en) 1990-04-09 1994-09-20 Ashland Oil, Inc. Near infrared analysis of piano constituents and octane number of hydrocarbons
US5520710A (en) * 1993-09-29 1996-05-28 George A. Olah Cleaner burning and cetane enhancing diesel fuel supplements
US6447558B1 (en) * 1999-12-21 2002-09-10 Exxonmobil Research And Engineering Company Diesel fuel composition
US6758870B2 (en) * 2000-06-14 2004-07-06 Air Products And Chemicals, Inc. Method of producing a diesel fuel blend having a pre-determined flash-point and pre-determined increase in cetane number
US8709111B2 (en) 2009-12-29 2014-04-29 Shell Oil Company Fuel formulations

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