EP2683798A1 - Améliorations portant sur les formulations de carburants de type essence - Google Patents

Améliorations portant sur les formulations de carburants de type essence

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Publication number
EP2683798A1
EP2683798A1 EP12707804.6A EP12707804A EP2683798A1 EP 2683798 A1 EP2683798 A1 EP 2683798A1 EP 12707804 A EP12707804 A EP 12707804A EP 2683798 A1 EP2683798 A1 EP 2683798A1
Authority
EP
European Patent Office
Prior art keywords
fuel
formulation
component
monoterpene
camphene
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.)
Granted
Application number
EP12707804.6A
Other languages
German (de)
English (en)
Other versions
EP2683798B1 (fr
Inventor
Richard John Price
Martin Tom CROFT
Renate UITZ
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
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Priority to EP12707804.6A priority Critical patent/EP2683798B1/fr
Publication of EP2683798A1 publication Critical patent/EP2683798A1/fr
Application granted granted Critical
Publication of EP2683798B1 publication Critical patent/EP2683798B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • 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
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark 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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark 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
    • 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
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • 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
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy

Definitions

  • This invention relates to fuel formulations, their preparation and their use, and to the use of certain materials in fuel formulations for new purposes.
  • Bio-derived fuel components are derived from
  • formulations containing high amounts of bio-derived components that could overcome or at least mitigate some of the problems associated with formulations comprising known oxygenates such as ethanol.
  • camphene a monoterpene component
  • the invention encompasses a number of aspects. Where context permits, preferred features of each aspect of the invention may be as described in connection with any of the other aspects.
  • Monoterpenes are a large and varied class of organic compounds, produced primarily by a wide variety of plants, particularly conifers, and also by some insects. Monoterpenes may be synthetic or naturally occurring, and may be bio-derived, particularly from gum turpentine and crude sulphate turpentine (produced by the wood pulping industry) . Structurally, monoterpenes comprise isomers of
  • Monoterpenes may be linear (acyclic) or may contain rings.
  • Acyclic monoterpenes include myrcene and ocimene, and the various stereoisomers thereof.
  • Monocyclic monoterpenes include limonene, ⁇ -terpinene, a- and ⁇ -phellandrene, a- and ⁇ - terpinolene, and the various stereoisomers thereof.
  • Bicyclic monoterpenes include 3-carene, a- and ⁇ -pinene, a-fenchene, and camphene, and the various stereoisomers thereof. Some examples of monoterpene structures are shown in Table 1 below. Table 1
  • WO 01/53437A1 proposes further reduction of vapour pressure of a fuel formulation comprising a C3 to C12 hydrocarbon component, ethanol, and a second oxygenate, by the incorporation of from 0 to 99% by volume of an individual hydrocarbon selected from C6 to C ⁇ 2 aliphatic or alicyclic, saturated or unsaturated hydrocarbons;
  • limonene and myrcene suitable examples include limonene and myrcene .
  • Limonene is also proposed for use in fuel blends in US-A-4 818 250 in an amount up to 20% by volume.
  • Terpenes comprising at least 60%wt pinenes are proposed for use with a gasoline base fuel in EP-A1-2 290 037, in particular as a
  • US-A-3 274 224 proposes the use of a small amount (from 0.33 to about 6% by weight) of terpenes comprising at least 60%wt a-pinene, to provide thermal stability for tetraethyl lead antiknock blends; camphene is mentioned as a minor impurity (4 to 8%) in one of three sources of terpenes. More recently, terpenes have been proposed in WO 2010/017099 for use as an optional component of a modified fuel comprising a base fuel, a lower alcohol and a triglyceride derived from a fatty acid, in an amount of less than 1% by volume; the modified fuel as a whole is said to provide increased horsepower and/or increased octane .
  • RU-2105041 CI appears to disclose a fuel composition
  • a fuel composition comprising a base fuel, a fatty acid-based soluble iron compound and 0.006 to 0.03%wt of a camphene to increase both octane number in gasolines and cetane number in diesel fuels.
  • a base fuel a fatty acid-based soluble iron compound
  • 0.006 to 0.03%wt of a camphene to increase both octane number in gasolines and cetane number in diesel fuels.
  • DE 3031158 Al proposes the use of from 0.1 to 1% of bicyclic monoterpene hydrocarbons, amongst other options, in a mixture also containing 70 to 85% vol of water and ethanol; the mixture is used with gasoline, naphtha, gas oil or fuel oil to increase acceleration and octane number with reduced NOx in exhaust gases.
  • the monoterpene component used according to the invention comprises or consists of camphene . Camphene
  • CAS no. 79-92-5 is a monoterpene with a bicyclic structure, as shown in Table 1. It is a white crystalline solid with a boiling point of 159 °C, i.e. within the normal gasoline boiling range.
  • the monoterpene component may comprise at least 70% or at least 80% or at least 90% or even at least 95% v/v of camphene, based on the total volume of the component.
  • the monoterpene component is
  • substantially free may refer to a
  • the monoterpene component may exclude tricyclene.
  • the monoterpene component may be obtained by any suitable method.
  • the monoterpene component may be synthetic or naturally occurring.
  • the monoterpene component may be synthetic or naturally occurring.
  • the monoterpene component is bio-derived, by which is meant that it has been obtained - either
  • bio- derived as used herein may be defined as “comprising at least about 0.1 dpm/gC of carbon-14".
  • the monoterpene component is used in the fuel formulation at a concentration, based on the total volume of the fuel formulation, of from 2 to 15 % v/v.
  • This concentration is of the pure monoterpene component in the formulation.
  • the concentration is 2, 4 or 5% v/v or greater.
  • it is up to 10% v/v.
  • the concentration of pure monoterpene component in the fuel formulation may be in the range of from 4 to 10% v/v.
  • the monoterpene component is used in the fuel formulation in an amount in the range of from 5 to 10 % v/v of which at least 90% by volume, more preferably at least 95% by volume, is camphene .
  • the monoterpene component should ideally be
  • a carrier fluid for example a solvent selected from alkanes (for example n- heptane or other n-alkanes, or iso-octane) ; alcohols (for example ethanol or butanol); ethers (for example methyl t-butyl ether or ethyl t-butyl ether) ; alkenes such as diisobutylene ; fuel components such as alkylates,
  • alkanes for example n- heptane or other n-alkanes, or iso-octane
  • alcohols for example ethanol or butanol
  • ethers for example methyl t-butyl ether or ethyl t-butyl ether
  • alkenes such as diisobutylene
  • fuel components such as alkylates
  • the monoterpene component may be used, in accordance with the invention, in any suitable fuel formulation, especially a gasoline fuel formulation (e.g. automotive) .
  • a gasoline fuel formulation e.g. automotive
  • it may be used in a gasoline fuel formulation comprising a base fuel, preferably as defined below.
  • the monoterpene component may be used in a gasoline fuel formulation comprising a base fuel and one or more additional components, such as, for example, a bio-derived component or an oxygenate (e.g. ethanol) .
  • additional components such as, for example, a bio-derived component or an oxygenate (e.g. ethanol) .
  • Preferred additional components, in particular bio-derived components and oxygenates are described below .
  • an individual bio- derived component e.g. ethanol
  • the natures and concentrations of the components of such a combination can be chosen so as to achieve desired properties for the overall fuel formulation which contains it, and thus to increase the total bio-derived content of the formulation without unduly impairing its performance. This in turn can assist the fuel formulator in meeting increasingly stringent fuel specifications.
  • vapour pressure as used herein may refer to the dry vapour pressure equivalent (DVPE) and should be construed as such unless context requires otherwise.
  • the DVPE of a formulation is the vapour pressure of that formulation at 37.8 °C. DVPE values may be measured using the standard test method EN
  • Blending rules allow for calculation of the DVPE of a blend of components from the blending DVPE values of its individual components.
  • the blending DVPE of a fuel formulation component is a measure of how the DVPE of the fuel formulation may change with the addition of that component.
  • bDVPE blending DVPE
  • DVPEbase is the dry vapour pressure equivalent of the base fuel
  • DVPE baS e+n is the dry vapour pressure equivalent of the blend
  • v n is the volume fraction of n in the blend.
  • the DVPE of a blend of fuel components (for example monoterpene, ethanol and an additional bio-derived fuel component) in a base fuel may also be calculated from the relevant blending DVPE (bDVPE) values using the Chevron blend rule, which provides that:
  • DVPE 1 ' 25 DVPE base 1 " 25 v base + ⁇ bDVPEn 1 " 25 v n (2)
  • bDVPE n and v n are the blending DVPE and volume fraction of component n
  • DVPEbase and Vb ase are the DVPE and volume fraction of the base fuel.
  • the monoterpene component may be used, for example, in fuel formulations having a DVPE of 100 kPa or less.
  • the DVPE of such fuel formulations may be 90 or 95 or 80 or - in particular where it is intended for use as a summer grade fuel - 70 or 60 kPa or less.
  • the use of a monoterpene component according to the invention has been found to be particularly beneficial in fuel formulations having a DVPE of 45 kPa or more, such as, for example 50 or 55 or 60 kPa or more.
  • fuel formulations typically comprise a base fuel and may also contain additional components such as bio-derived or oxygenate components.
  • the monoterpene component may be used, according to the invention, for the purpose of reducing the vapour pressure of a fuel formulation to a level below the vapour pressure of a bio-derived or oxygenate component comprised in the fuel formulation.
  • the monoterpene component may be used for the purpose of reducing the vapour pressure of the formulation to a level below the vapour pressure of a mixture of a base fuel and a bio-derived or oxygenate component comprised in the fuel formulation.
  • the monoterpene component may even be used for the purpose of reducing the vapour pressure of the formulation to a level below the vapour pressure of a base fuel comprised in the fuel formulation.
  • the monoterpene component is used in such a fuel
  • ADVPE is the difference between the DVPE of the overall fuel formulation and that of the base fuel.
  • the ADVPE may also be the difference between the DVPE of the overall fuel formulation and that of the same formulation in the absence of a monoterpene component and any additional bio-derived or oxygenate component (s) .
  • the monoterpene component may advantageously be used for the purpose of adjusting or reducing the vapour pressure of the fuel formulation to be neutral or close to neutral with respect to the vapour pressure of the base fuel.
  • neutral or close to neutral is meant that the vapour pressure of the formulation is adjusted to lie within plus or minus 15%, preferably plus or minus 10% of the vapour pressure of the base fuel.
  • Vapour pressure (DVPE) is an indicator of
  • vapour pressure Reducing the vapour pressure of a fuel
  • formulation may hence comprise influencing or adjusting any fuel property dependent on vapour pressure.
  • the distillation properties of a fuel formulation may be expressed in terms of E-values and T-values.
  • E70 value for a formulation is the volume percentage of the formulation that has been distilled at 70 ° C
  • E100 value is the volume percentage of the formulation that has been distilled at 100 ° C. Both E70 and E100 values, as well as other E-values, can be measured using the standard test method EN ISO 3405.
  • T70 value for a formulation is the temperature on its distillation curve at which 70% of its volume has evaporated at standard atmospheric pressure
  • T100 value for a formulation is the T100 value for a formulation
  • T70 and T100 values can be measured using the standard test method EN ISO 3405.
  • blending E-values can be calculated using the following equation: (3) where bE70 n is the blending E70 value for component n in the relevant blend, v n is the volume fraction of the component n in the blend; E70 base is the E70 value of the base fuel; and E70bi e nd is the E70 value of the blend containing the base fuel and component n.
  • the distillation properties, for example E70 or E100, of a fuel formulation may be calculated from the blending E70 (bE70) values for a fuel formulation using linear blending rules, which provide for example that:
  • E70 blend E70 base v base + ⁇ bE70 n v n (4)
  • bE70 n and v n are the blending E70 and volume fraction of component n
  • E70 baS e fuel and v base f ue i are the E70 and volume fraction of the base fuel.
  • the monoterpene component according to the first aspect of the invention may preferably be for the purpose of influencing or adjusting the E70 and E100 values of the fuel formulation.
  • the monoterpene component, or particularly the combination or use of the monoterpene component with any additional bio- derived components or oxygenates in the fuel formulation does not significantly alter the E70 and E100 values for the fuel formulation as a whole compared to the values for a base fuel of the formulation alone.
  • both the E70 value and the E100 value of the fuel formulation are maintained within 25%, or within 20%, or within 15%, of both the E70 value and the E100 value of the base fuel, and/or that the value of (E70 + E100) for the fuel formulation is maintained within 15%, or within 10%, or within 5% of the value of (E70 + E100) for the base fuel.
  • ⁇ 70 is the difference between the E70 of the overall fuel formulation and that of the same formulation in the absence of the monoterpene component and any additional bio-derived component (s) or oxygenate ( s )
  • ⁇ 100 is the difference between the E100 of the overall fuel formulation and that of the same formulation in the absence of any monoterpene component and the additional bio-derived component (s) or oxygenate ( s )
  • ⁇ 70 may be seen as the difference between the E70 of the overall fuel formulation and that of the base fuel alone, and ⁇ 100 as the difference between the E100 of the overall fuel formulation and that of the base fuel alone.
  • Vfn bE70 n - E70 base E100 base - ⁇ v fc bE100 n (5) wherein :
  • Vf n is the volume fraction of the component represented by n in the ternary mixture of a monoterpene, ethanol and X,
  • bE70 n is the blending E70 value of the component
  • bE100 n is the blending E100 value of the component represented by n
  • E70base is the E70 value of the base fuel
  • ElOObase is the E100 value of the base fuel.
  • component can be tailored to have acceptable distillation properties, as can a blend containing one or more
  • bio-derived components or oxygenates with a monoterpene component, a base fuel and optionally
  • the invention resides in the use of a monoterpene component which comprises camphene in a fuel formulation, for the purpose of improving or maintaining one or more properties of the fuel formulation selected from: lubricity, oxidative stability, deposit-forming tendency, elastomer
  • Use according to the second aspect of the invention may in particular be for the purpose of achieving a desired target property, particularly by mitigating a detrimental effect on the property of other bio-derived or oxygenate components, such as ethanol, within the formulation .
  • the lubricity of a fuel formulation can be assessed by any suitable method.
  • One such method involves
  • “improvement” in the lubricity of a formulation may be manifested for example by a lower degree of wear scar, or of other friction-induced damage, in two relatively- moving components which are exposed to the formulation.
  • the oxidative stability of a fuel formulation can be assessed by any suitable method.
  • One such method involves measuring the concentration of peroxides in the fuel formulation before storage and upon storage of the fuel formulation at various temperatures and time intervals. For example, peroxide concentration may be measured initially, and may then be measured again after a three- month storage of the fuel formulation at 0-2 °C. A similar experiment may be performed with the storage occurring at 40 °C.
  • Peroxide concentrations which provide a suitable metric for the oxidative stability of a fuel formulation, can be measured using the standard test method SMS 359 or an analogous method.
  • the oxidative stability of a fuel formulation can also be assessed using the induction period after a period of storage at a specified temperature (e.g. 3 months at 0-2 °C or 40 °C) .
  • the induction period which provides a suitable metric for the oxidative stability of a fuel formulation, can be measured using the standard test method EN ISO 7536 or an analogous method.
  • inclusion of a monoterpene in a fuel formulation can improve or maintain deposit-forming tendencies of the fuel formulation.
  • 'improve or maintain deposit-forming tendencies' is meant that there is a decreased or equal tendency of the monoterpene-containing fuel formulation to form deposits, particularly gum deposits, relative to the relevant reference point.
  • the deposit-forming tendencies of a fuel formulation can be assessed by any suitable method.
  • One such method is the MIHPT (multiple inclined hot plate rig test) method. This method uses an intake valve deposit
  • compatibility is a measure of a fuel formulation's tendency to cause elastomer-damaging effects, ie effects that reduce the ability of an elastomeric material to function correctly in a fuel-consuming system and/or in the presence of the fuel formulation.
  • An example of an elastomer damaging effect is swelling of the elastomer when in contact with the fuel formulation. Elastomer damage also includes a change (typically a reduction) in the hardness and/or flexibility of the elastomer when in contact with the fuel formulation.
  • Elastomer swell measurements in particular provide a measure of the compatibility of elastomeric materials, such as are used in fuel pump seals and other engine components, with a fuel component or formulation.
  • this compatibility is evaluated by assessing changes in the properties of an elastomer due to its immersion in a test fluid.
  • the elastomer swelling effects of a fuel formulation may for instance be assessed by measuring the increase or percentage increase in volume or mass of an elastomeric material on immersion in the formulation for a predetermined period of time. A smaller volume or mass increase indicates a reduction in
  • elastomer swelling effects This assessment may for example be carried out for nitrile and/or fluorocarbon elastomers.
  • a standard test method such as DIN 51605-1 or ISO 1817:1998 may be used to measure elastomer swell effects. Changes in the hardness and/or flexibility of an elastomeric material may be assessed using standard test methods such as the Shore hardness test or TMS 556.
  • a monoterpene component especially one which comprises camphene
  • a fuel formulation can improve or maintain an octane number of the formulation.
  • the research octane number (RON) may be measured by any suitable method. It can be measured using the standard test methods ASTM D2699 or EN 25164 or analogous methods such as PrEN ISO 5164.
  • the motor octane number (MON) may be measured by any suitable method. It can be measured using the standard test methods ASTM D2700 or EN 25163 or analogous methods such as PrEN ISO 5163.
  • the effectiveness of the monoterpene component in improving or maintaining octane number depends on the one hand on the octane number of the fuel formulation to which it is added and on the other hand on the structure of the monoterpene ( s ) present in the monoterpene
  • the monoterpene component may be used to maintain or improve the octane number of a fuel formulation having a RON of 100 or less or 99 or 98 or 95 or less and/or a MON of 95 or less, or 90 or 88 or less.
  • camphene is
  • the invention resides in use of camphene in a fuel
  • the third aspect embraces use of camphene in a fuel formulation to achieve:
  • ARON is the difference between the RON of the camphene-containing fuel formulation and that of the base fuel alone.
  • the ARON may also be the difference between the RON of the overall fuel formulation and that of the same formulation in the absence of camphene and any additional bio-derived or oxygenate component (s) .
  • Blending RON and MON values may be calculated in an analogous fashion to blending E-values, as discussed above :
  • MON values can be calculated from the respective blending values in a similar manner.
  • purposive uses of the invention may alternatively be expressed as methods of achieving one or more target properties in a fuel formulation by blending an effective amount of a monoterpene, especially camphene, component with the fuel formulation.
  • the invention resides in a method of achieving a target vapour pressure in a fuel formulation, the method
  • invention resides in a method of achieving a target lubricity, oxidative stability, deposit-forming tendency, elastomer compatibility or octane number in a fuel formulation, the method comprising blending an effective amount of a monoterpene component which comprises
  • camphene with the fuel formulation.
  • a sixth aspect of the invention provides a method of achieving a target octane number in a fuel formulation, the method comprising blending an effective amount of camphene with the fuel formulation.
  • a seventh aspect provides the use of a bio- derived monoterpene component which comprises camphene, in a fuel formulation, particularly a fuel formulation comprising another bio-derived component or oxygenate, for the purpose of increasing the bio-derived content of the formulation without, or without unduly, increasing the vapour pressure of the formulation.
  • a fuel formulation comprising another bio- derived component or oxygenate, for the purpose of increasing the bio-derived content of the formulation without, or without unduly, reducing an octane number of the formulation.
  • a ninth aspect of the invention provides the use of a monoterpene which comprises camphene in a gasoline fuel formulation, for the purpose of replacing, at least partially, a bio-derived component and/or an oxygenate in the formulation.
  • the monoterpene component is biologically derived.
  • the monoterpene component may thus be used as a substitute for at least some of the bio-derived component or oxygenate which would otherwise have been included in the formulation, for example so as to achieve a desired target
  • a quantity of biologically derived monoterpene component may be included in a fuel formulation in place of the same or a similar quantity of ethanol, allowing a target minimum bio-derived content to be achieved but without, or with fewer of, the drawbacks associated with the use of ethanol alone.
  • the invention resides in a fuel formulation obtainable by or resulting from the use or method of any of the first to ninth aspects of the invention .
  • the base fuel component of a fuel formulation in the context of the invention is typically a liquid
  • hydrocarbon distillate gasoline fuel component or mixture of such components, containing hydrocarbons that boil in the range from 0 to 250°C (ASTM D86 or EN ISO 3405) or from 20 or 25 to 200 or 230°C.
  • ASTM D86 or EN ISO 3405 The optimal boiling ranges and distillation curves for such base fuels will typically vary according to the conditions of their intended use, for example the climate, the season and any applicable local regulatory standards or consumer preferences .
  • the hydrocarbon fuel component (s) in the base fuel may be obtained from any suitable source. They may for example be derived from petroleum, coal tar, natural gas or wood, in particular petroleum.
  • they may be synthetic products such as from a Fischer-Tropsch synthesis. Conveniently they may be derived in any known manner from straight-run
  • base fuels comprise components selected from one or more of the following groups: saturated hydrocarbons, olefinic hydrocarbons, and aromatic
  • the olefinic hydrocarbon content of a base fuel is in the range from 0 to 40% v/v; it may for instance be in the range from 0 to 30% v/v.
  • the aromatic hydrocarbon content of a base fuel is from 0 to 70% v/v; it may for instance be from 10 to 60% v/v.
  • the benzene content of a base fuel is typically at most 10% v/v, or at most 5% v/v, or at most 1% v/v.
  • the saturated hydrocarbon content of a base fuel is at least 40% v/v; it may for instance be from 40 to 80% v/v.
  • the base fuel suitably has a low or ultra low sulphur content, for instance at most 1000 ppmw (parts per million by weight) of sulphur, or no more than
  • a base fuel will typically have a research octane number (RON) (ASTM D2699 or EN 25164) of 80 or greater, or of 85 or 90 or 93 or 94 or 95 or 98 or greater, for example from 80 to 110 or from 85 to 115 or from 90 to 105 or from 93 to 102 or from 94 to 100.
  • RON research octane number
  • a monoterpene component may advantageously be used in a fuel formulation comprising a base fuel having a RON of 115 or less, or of 105 or 102 or 100 or 99 or even 98 or less.
  • a base fuel will typically have a motor octane number (MON) (ASTM D2700 or EN 25163) of 70 or greater, or of 75 or 80 or 84 or 85 or greater, for example from 70 to 110 or from 75 to 105 or from 84 to
  • MON motor octane number
  • formulation comprising a base fuel having a MON of 110 or less, or of 105 or 100 or 95 or 90 or even 88 or less.
  • a base fuel will typically have an E70 value of 10% v/v or greater, or of 14 or 15 or 20 or 22% v/v or greater. Its E70 value might typically be up to 55% v/v, or up to 51 or 50 or 48% v/v. Its E70 value might for example be from 10 to 55% v/v, or from 14 to 51% v/v, or from 14 to 50% v/v, or from 20 to 50% v/v. In an
  • it has an E70 value of from 20 to 48% v/v. In an alternative embodiment, it has an E70 value of from 22 to 50% v/v.
  • the base fuel will typically have an E100 value of 35% v/v or greater, or of 40 or 45 or 46% v/v or greater.
  • E100 value might typically be up to 75% v/v, or up to 72 or 71% v/v. Its E100 value might for example be from 35 to 75% v/v, or from 40 to 72% v/v, or from 40 to 71% v/v, or from 46 to 71% v/v.
  • the base fuel may be a reformulated base fuel, for example one which has been reformulated so as to
  • composition, RON and MON of the base fuel are not however critical for the purposes of its use in the present invention .
  • a base fuel might typically have a density from
  • a base fuel might typically have a vapour pressure at
  • DVPE 37.8°C
  • DVPE 37.8°C
  • Suitable base fuels include those having an olefinic hydrocarbon content of from 0 to 20% v/v
  • the base fuel complies with the current European gasoline fuel standard EN 228. In an embodiment, it complies with the current US gasoline fuel standard ASTM D4814-08b.
  • the concentration of the base fuel may be up to 99.99% v/v, or up to 99.95% v/v, or up to 99.9 or 99.5% v/v based on the total volume of the fuel formulation. It may be up to 99% v/v, for example up to 98 or 95 or 90% v/v, or in cases up to 85 or 80 or 75 or 70 or 65 or 60% v/v based on the total volume of the fuel formulation.
  • the base fuel will typically represent the major proportion, i.e. more than 50% v/v, of a fuel formulation according to the invention.
  • a fuel formulation may also contain one or more additional fuel components.
  • the fuel formulation may comprise at least one additional fuel component which causes an increase in vapour pressure relative to the vapour pressure of the base fuel.
  • the fuel formulation may include one or more
  • gasoline fuel additives of the type well known in the art .
  • the fuel formulation may contain one or more
  • additional bio-derived components may have boiling points within the normal gasoline boiling range, and in the case of bio-derived components will have been derived - whether directly or indirectly - from biological sources.
  • The, or each, additional bio-derived fuel component may comprise at least about 0.1 dpm/gC of carbon-14.
  • the formulation may contain one or more oxygenates, which may for example be selected from alcohols, ethers (including cyclic ethers), esters, carboxylic acids and their derivatives, aldehydes, ketones, and mixtures thereof.
  • the formulation contains one or more oxygenates selected from alcohols, ethers, esters and mixtures thereof.
  • it contains one or more oxygenates selected from alcohols, ethers and mixtures thereof.
  • oxygenates are suitably bio- derived components.
  • Alcohols suitable for inclusion in a fuel are alcohols suitable for inclusion in a fuel
  • formulation in the context of the invention include CI to C5 saturated or unsaturated alcohols, in particular CI to C4 aliphatic alcohols such as ethanol and butanol.
  • a formulation may include ethanol. It may include ethanol and one or more - for example one - additional bio-derived components. It may include ethanol and one or more - for example one - additional
  • Ethers suitable for inclusion in a fuel formulation include dialkyl ethers, in particular alkyl t-butyl ethers, more particularly (CI to C3 alkyl) t-butyl ethers such as methyl t-butyl ether and ethyl t-butyl ether.
  • Other suitable ethers include furans; C5 and C5+ ethers having boiling points below 210°C; and C7 ethers - in particular ethyl ethers - such as 2-ethoxy-2-methylbutane and l-ethoxy-3-methylbutane .
  • a formulation may include ethanol together with one or more ethers selected from (CI to C3 alkyl) t-butyl ethers and
  • a fuel formulation contains a bio-derived or oxygenate component, especially ethanol
  • the bio- derived/oxygenate or ethanol concentration may for example be 1 or 2 or 5% v/v or greater, or 8 or 10 or 15 or 20 or 25 or 30% v/v or greater, based on the total volume of the formulation.
  • the ethanol or bio- derived/oxygenate concentration may be up to 50% v/v, or up to 45 or 40 or 35% v/v. In cases it may be up to 30 or 25 or 20 or 15 or 10% v/v.
  • the amount of oxygenate is usefully such as to provide a fuel formulation having an oxygen content of from 0 to 5% w/w (EN 1601) .
  • the volume ratio of the monoterpene component to the ethanol or bio-derived/oxygenate component may be for example 1:100 or greater, or 1:50 or 1:10 or greater, for example 1:5 or 1:2 or greater, or 1:1 or 1.5:1 or greater. It may be up to 5:1, or up to 4:1 or 3:1 or 2:1 or 1:1.
  • the volume ratio of the monoterpene component to ethanol may be 1:1 or greater, or 1.2:1 or greater, or 1.5:1 or greater, or 1.8:1 or greater; in this case the ratio may for example be up to 5:1, or up to 4:1 or 3:1 or 2.5:1, for example from 1.5:1 to 3:1.
  • the concentration of the combination in the formulation may be 3 or 4 or 5% v/v or greater.
  • the concentration of the combination may be up to 50% v/v, or up to 40 or 30% v/v, or up to 25 or
  • the formulation resulting from uses and methods according to the invention should be suitable for use in a spark ignition (petrol) internal combustion engine. It may in particular be suitable for use as an automotive fuel.
  • the RON of a formulation resulting from the uses and methods of the invention is suitably 80 or greater. It may be 85 or 90 or 93 or 94 or 95 or 98 or 98.4 or greater. The RON may for example be from 80 to 110 or from 85 to 115 or from 90 to 105 or from 93 to 102 or from 94 to 100.
  • the MON of a fuel formulation resulting from the uses and methods of the invention is suitably 70 or greater, or 75 or 80 or greater. It may be 84 or 85 or greater. The MON may for example be from 70 to 110 or from 75 to 105 or from 84 to 95.
  • any feature disclosed herein may be replaced by an alternative feature serving the same or a similar
  • a monoterpene component may be used to produce a fuel formulation that has an octane number above a desired target value, or a vapour pressure below a desired target value .
  • use of a monoterpene component in a fuel formulation means incorporating a monoterpene component into the
  • formulation typically as a blend (i.e. a physical mixture) with one or more other fuel components such as a base fuel and optionally one or more additional bio- derived components or oxygenates.
  • the monoterpene may conveniently be incorporated before the formulation is introduced into an engine or other system that is to be run on the formulation.
  • the monoterpene component together with instructions for its use in a fuel formulation to achieve the purpose (s) of any of the aspects of the invention.
  • the monoterpene 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 monoterpene component may be included in such a composition for the purpose of influencing its relevant effects on a fuel formulation.
  • a fuel formulation according to the invention, or a formulation 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 monoterpene component.
  • the marketing of such a formulation may include an activity selected from (a) enclosing the formulation in a container that comprises the relevant indication; (b) supplying the formulation 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 formulation or product; 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 monoterpene component.
  • the invention may involve
  • assessing the relevant property of the formulation during or after its preparation may involve assessing the relevant property both before and after incorporation of the monoterpene component, for example so as to confirm that the monoterpene component contributes to the
  • Example 1 The present invention will now be further described with reference to the following non-limiting examples.
  • Example 1 The present invention will now be further described with reference to the following non-limiting examples.
  • GBF2 The properties of GBF2 are summarised in Table 2 below .
  • myrcene (95% purity), S(-) limonene (96% purity), and camphene (95% purity) were sourced from Sigma-Aldrich; ocimene (90% purity), -pinene (98% purity) and ⁇ -pinene (99% purity) from Aldrich; and R(+) limonene (97% purity) from Sigma.
  • Myrcene and ocimene are acyclic monoterpenes.
  • Limonene is a monocyclic monoterpene.
  • Pinene and camphene are acyclic monoterpenes.
  • Table 3 illustrates that all monoterpenes tested reduce the DVPE in the 10% v/v blend, relative to base fuel alone and relative to the ethanol 10 % v/v blend, reflecting the relatively high boiling point of these molecules.
  • the high reduction of 6 kPa (from 63.3 kPa for the base fuel to 56.2 kPa for the base fuel + 10% v/v camphene) for the camphene blend in particular was unexpected .
  • Blending DVPE values obtained for each of the monoterpene components when blended with GBF2 were calculated according to Equation 1 above and are shown in Table 4 below. Table 4
  • a number of monoterpene components were blended with GBF2.
  • the monoterpene components and base fuel were the same as those detailed in Example 1 above.
  • Tables 5 and 6 illustrate the superior octane properties of camphene compared to the other monoterpenes tested. Its blending RON is significantly higher than those of the other monoterpenes. Since its blending RON is >98.2 at 10% v/v there is no RON penalty when camphene is blended with a base fuel such as GBF2. By contrast, there is a small RON penalty and larger MON penalty when adding the other monoterpenes to the base fuel. Thus, camphene can be seen to be superior to the other
  • the elastomer swell caused by the eight formulations prepared in Example 2 was assessed using the standard test method DIN 51605-1 (measurements taken in triplicate and averaged) .
  • the elastomer tested was the nitrile elastomer SRE-NBR 34. The results are shown in Table 7 below .
  • Camphene 10 29.8 19.1 These data show that each of the monoterpenes and especially camphene causes significantly less elastomer swell than ethanol, and indeed that each has an elastomer compatibility similar to that of the base fuel alone. Thus, each of the monoterpenes and especially camphene could be substituted for at least a proportion of the ethanol in an ethanol/base fuel blend, in order to mitigate the elastomer damaging effects caused by the ethanol .
  • Gasoline fuel formulations were prepared by blending the base fuel GBF2 with 10% v/v of each of the
  • a sample of the fuel or blend under test was placed in a test reservoir which was maintained at a specified test temperature.
  • a fixed steel ball was held in a vertically mounted chuck and forced against a horizontally mounted stationary steel plate with an applied load.
  • the test ball was oscillated at a fixed frequency and stroke length while the interface with the plate was fully immersed in the fluid reservoir.
  • the metallurgies of the ball and plate, and the temperature, load, frequency, and stroke length were as specified in ISO 12156.
  • the ambient conditions during the test were then used to correct the size of the wear scar generated on the test ball to a standard set of ambient conditions, again as per ISO
  • the corrected wear scar diameter provides a measure of the test fluid lubricity: the lower the wear scar diameter, the higher the lubricity improvement.
  • Table 8 The results are shown in Table 8 below.
  • a gasoline fuel formulation for use according to the invention was prepared by dissolving 10 % v/v camphene in a commercially available unleaded gasoline base fuel from Germany, GBF2 (see Example 1) .
  • camphene was sourced from Sigma-Aldrich . It had a purity of 95%.
  • Another gasoline fuel formulation was prepared by dissolving 10 % v/v camphene in a commercially available unleaded gasoline base fuel GBF1.
  • GBF1 had an octane (RON) rating of 95.
  • MIHPT multiple inclined hot plate rig test
  • test rig utilised four inclined plates in parallel.
  • the plates were strips of sandblasted
  • aluminium each 50 cm long and 2.5 cm wide, each having a 3 mm wide, 1 mm deep central groove along its length.
  • These plates were mounted in the rig at an angle of 3 degrees relative to the horizontal. The temperature at the top end of each plate was maintained at 400°C, whilst at the middle of each plate it was maintained at 250°C.
  • test samples each contained 100 ml of the relevant fuel or fuel formulation. They were delivered at a rate of 0.6 ml/minute from glass syringes fitted with 20 gauge steel hypodermic Luer lock needles into the groove at the top end of each plate. Once sample delivery was complete, the plates were allowed to cool to ambient temperature (20°C) and were washed with n-heptane until the run-off liquid was clear. They were then left to dry before assessment of any deposit present.
  • tungsten lamps mounted at a linear distance of 22 cm from the point on the plate upon which the camera was focused and at angles of 33 degrees and 147 degrees relative to the plate.
  • An image was captured of a clear portion of each plate.
  • a second image was then captured of the section of the plate containing deposit.
  • the image analyser divides, pixel by corresponding pixel, the deposit image by the clean image and automatically measures the area and optical density of deposit at the pixels contained within the overall measuring frame, and calculates an integrated optical density for the image, the numerical value of which is recorded as a test rating.
  • a fuel with a high deposit-forming tendency would typically have a MIHPT scan rating of greater than 200.
  • the GBF1 base fuel was determined to have an MIHPT rating of 142, whilst the GBF1 base fuel mixed with 10 %v/v camphene gave a rating of 87. These results reflect the lower deposit-forming tendency of the camphene-containing fuel formulation, further demonstrating the suitability of camphene as a fuel component.
  • the MIHPT rating for GBF2 alone was measured as 71.
  • monoterpenes are suitable for reducing the vapour
  • a blend containing an oxygenate such as ethanol as well as a monoterpene component and base fuel can be tailored to have acceptable properties. Therefore, in accordance with the present invention, a monoterpene component may be used to enhance the overall bio-derived content of fuel formulations.
  • Camphene has been found to be particularly useful in fuel formulations, being capable of lowering DVPE and acting as an octane booster. It is apparent from Examples 1 to 6 that blends of camphene with a gasoline base fuel can have octane numbers, DVPEs and distillation
  • a blend containing ethanol as well as camphene and base fuel can be tailored to have acceptable properties, as can a blend containing one or more additional bio-derived components or
  • camphene also has no negative impact on oxidative stability, whilst the MIHPT results indicate that camphene has a low tendency to form engine inlet valve deposits.

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Abstract

Dans la série des monoterpènes, le camphène est particulièrement utile dans une formulation de carburant de type essence pour améliorer ou maintenir l'indice d'octane moteur (MON) et/ou l'indice d'octane recherche (RON) de la formulation de carburant.
EP12707804.6A 2011-03-10 2012-03-12 Utilisation de camphène en carburants de type essence Not-in-force EP2683798B1 (fr)

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EP11157592 2011-03-10
PCT/EP2012/054247 WO2012120147A1 (fr) 2011-03-10 2012-03-12 Améliorations portant sur les formulations de carburants de type essence
EP12707804.6A EP2683798B1 (fr) 2011-03-10 2012-03-12 Utilisation de camphène en carburants de type essence

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CN104152188B (zh) * 2014-04-16 2015-09-09 肇庆市新迪信生物能源有限公司 一种植物蒎烯燃料油
EP3205701A1 (fr) * 2016-02-11 2017-08-16 Bp Oil International Limited Composition de carburant
EP3205702A1 (fr) 2016-02-11 2017-08-16 Bp Oil International Limited Compositions de carburant avec des additifs
EP3205703A1 (fr) 2016-02-11 2017-08-16 Bp Oil International Limited Additifs de carburant
CN112029547A (zh) * 2020-08-31 2020-12-04 洋浦傲立石化有限公司 一种复合高效汽油抗爆剂及其制备方法

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US3274224A (en) 1963-07-25 1966-09-20 Du Pont Stabilized tetraethyl lead antiknock blends
IT1179351B (it) 1980-07-07 1987-09-16 Mario Scifoni Miscela combustibile
US4818250A (en) 1987-10-21 1989-04-04 Lemco Energy, Inc. Process for producing fuel from plant sources and fuel blends containing same
RU2105041C1 (ru) 1993-08-31 1998-02-20 Александр Петрович Ильин Топливная композиция на основе моторного топлива
DE19544086A1 (de) 1995-11-27 1997-05-28 Hoechst Ag Verfahren zur Herstellung von Camphen durch Umlagerung von alpha-Pinen
WO2001053436A1 (fr) 2000-01-24 2001-07-26 Angelica Golubkov Carburant pour moteurs thermiques à étincelles
CN100386414C (zh) * 2006-08-18 2008-05-07 黄照文 一种汽油添加剂
CA2770134C (fr) 2008-08-05 2018-01-16 Spirit Of The 21St Century Group, Llc Combustibles modifies renfermant de la triglycerine comportant au moins un groupe hydroxyle et methode de fabrication et utilisation associee
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JP2014507542A (ja) 2014-03-27

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