Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine

Definitions

• the present invention relates to fuel compositions comprising a gas oil base fuel, particularly to such compositions containing a levulinate ester, and to their preparation and use.
• diesel fuel components include the so-called “biofuels” which derive from biological materials. Examples include levulinate esters.
• Levulinate esters esters of lev ⁇ linic acid
• their preparation by reaction of the appropriate alcohol with furfuryl acetate are described in Zh. Prikl. Khim. (Leningrad) (1969) 42(4), 958-9, and in particular the methyl, ethyl, propyl, butyl, pentyl and hexyl esters.
• WO-A-94/21753 discloses fuels for internal combustion engines, including both gasoline and diesel fuel, containing proportions (e.g. 1 to 90%v, 1 to 50%v, preferably 1 to 20%v) of esters of 04.-5 keto-carbonic acids, preferably levulinic acid, with C ⁇ -22 alcohols.
• Esters with C]__8 alcohols are described as being particularly suitable for inclusion in gasolines, and esters with C9-.22 alcohols are described as being particularly suitable for inclusion in diesel fuels.
• WO-A-03/002696 discloses a fuel composition incorporating levulinic acid, or a functional derivative thereof, with the object of providing more oxygen by volume than ethanol or traditional oxygenates such as MTBE or ETBE, giving little or no increase in fuel Reid vapour pressure and little or no effect on the flash point of the base fuel.
• the functional derivative is preferably an alkyl derivative, more preferably a C ] __ ] _g alkyl derivative.
• Ethyl levulinate is said to be preferred, with methyl levulinate a preferred alternative.
• the levulinic acid or functional derivative is preferably used to form 0.1 to 5%v of the fuel.
• the temperature at which this occurs is termed the "Phase separation temperature”.
• Diesel fuel specifications such as ASTM D975-02 (USA) and EN590 (Europe) include limits on Cloud Point temperature in order to ensure that diesel fuel remains fluid at the lowest anticipated service temperature and that blocking of fuel filters by wax is prevented.
• any separated liquid layers may be unsuitable as a fuel for the engine.
• the blending of a Standard commercial diesel base fuel with other fuel components, to modify the overall fuel properties and/or performance, can therefore have an adverse impact on the performance of the blend in the engines for which it is intended.
• any diesel fuel blend it is desirable for any diesel fuel blend to have an overall specification as close as possible to that of the standard commercially available diesel base fuels for which engines tend to be optimised.
• the phase separation temperature of the fuel composition is dependent upon the level of aromatic constituents in the base fuel.
• the phase separation temperature is lowered when the level of aromatic constituents is increased.
• the amount of alkyl levulinate that can be incorporated in a homogeneous mixture is increased.
• a fuel composition comprising a gas oil base fuel, an alkyl levulinate and one or more additional components, each of which components contains one or more aromatic constituents.
• a method of reducing the phase separation temperature of a fuel composition comprising a gas oil base fuel and an alkyl levulinate, which method comprises increasing the level of aromatic constituents in the fuel composition, preferably by incorporating in the fuel composition one or more additional components, each of which components contains one or more aromatic constituents .
• a fuel composition comprising a gas oil base fuel and an alkyl levulinate of one or more additional components, each of which components contains one or more aromatic constituents, for the purpose of reducing the phase separation temperature of the fuel composition
• a method of operating a heating appliance provided with a burner comprises supplying to said burner a fuel composition according to the present invention.
• a process for the preparation of a fuel composition which process involves blending a gas oil base fuel, an alkyl levulinate and one or more additional components, each of which components contains one or more aromatic constituents.
• said alkyl levulinate is selected from C2-8 alkyl levulinates, more preferably ethyl levulinate, n-propyl levulinate, n-butyl levulinate, n-pentyl levulinate, 2-hexyl levulinate and 2-ethyl hexyl levulinate, still more preferably ethyl levulinate, n-butyl levulinate or n-pentyl levulinate, most preferably ethyl levulinate.
• said additional components are selected from materials which are suitable to be blended with fuel compositions, such as for example (i) a refinery product stream with an aromatic content higher than that of the base fuel, or (ii) an aromatic solvent, e.g. SHELLSOL AB (available ex. Shell companies) , boiling in the normal temperature range of gas oil.
• fuel compositions such as for example (i) a refinery product stream with an aromatic content higher than that of the base fuel, or (ii) an aromatic solvent, e.g. SHELLSOL AB (available ex. Shell companies) , boiling in the normal temperature range of gas oil.
• the concentration of said additional component (s) in the fuel composition accords with one or more of the following parameters :-
• the concentration of aromatic constituents in the fuel composition containing said additional component (s) accords with one or more of the following parameters :-
• phase separation temperature of said fuel composition is reduced by at least 3°C, more preferably by at least 5°C, still more preferably by at least 1O 0 C, and most preferably by at least 2O 0 C.
• said phase separation temperature of said fuel composition is below -5 0 C, more preferably below -10 0 C, still more preferably below -20°C, and most preferably below -30 0 C.
• blends of two or more of the alkyl levulinates may be included in the fuel composition.
• selection of the particular components of said blends and their proportions is dependent upon one or more desired characteristics of the fuel composition.
• the present invention may be used tc formulate fuel blends which are expected to be of particular use in modern commercially available diesel engines as alternatives to the standard diesel base fuels, for instance as commercial and legislative pressures favour the use of increasing quantities of organically derived "biofuels".
• a fuel component in a fuel composition means incorporating the component into the composition, typically as a blend (i.e. a physical mixture) with one or more other fuel components, conveniently before the composition is introduced into an engine.
• the fuel composition will typically contain a major proportion of the base fuel, such as from 50 to 99%v, preferably from 50 to 98%v, more preferably from 80 to 98%v, most preferably from 90 to 98%v.
• the proportions of the alkyl levulinates will be chosen to achieve the desired degree of miscibility, i.e. phase separation temperature, and may also be influenced by other properties required of the overall composition.
• the fuel compositions to which the present invention relates include diesel fuels for use in automotive compression ignition engines, as well as in other types of engine such as for example marine, railroad and stationary engines, and industrial gas oils for use in heating applications (e.g. boilers).
• the base fuel may itself comprise a mixture of two or more different diesel fuel components, and/or be additivated as described below.
• Such diesel fuels will contain a base fuel which may typically comprise liquid hydrocarbon middle distillate gas oil(s), for instance petroleum derived gas oils.
• a base fuel which may typically comprise liquid hydrocarbon middle distillate gas oil(s), for instance petroleum derived gas oils.
• Such fuels will typically have boiling points within the usual diesel range of 150 to 400 0 C, depending on grade and use. They will typically have a density from 750 to
• 900 kg/m 3 preferably from 800 to 860 kg/m 3 , at 15 0 C (e.g. ASTM D4502 or IP 365) and a cetane number (ASTM D613) of from 35 to 80, more preferably from 40 to 75. They will typically have an initial boiling point in the range 150 to 23O 0 C and a final boiling pc:.nt in the range 290 to 400 0 C. Their kinematic viscosity at 40°C (ASTM
• D445) might suitably be from 1.5 to 4.5 rrm2/s.
• Such industrial gas oils will contain a base fuel which may comprise fuel fractions such as the kerosene or gas oil fractions obtained in traditional refinery processes, which upgrade crude petroleum feedstock to useful products.
• a base fuel which may comprise fuel fractions such as the kerosene or gas oil fractions obtained in traditional refinery processes, which upgrade crude petroleum feedstock to useful products.
• fuel fractions such as the kerosene or gas oil fractions obtained in traditional refinery processes, which upgrade crude petroleum feedstock to useful products.
• such fractions contain components having carbon numbers in the range 5 to 40, more preferably 5 to 31, yet more preferably 6 to 25, most preferably 9 to 25, and such fractions have a density at 15°C of 650 to 1000 kg/m 3 , a kinematic viscosity at 20 0 C of 1 to 80 mm 2 /s, and a boiling range of 150 to 400 0 C.
• non-mineral oil based fuels such as bio-fuels or Fischer-Tropsch derived fuels
• Fischer-Tropsch fuels may for example be derived from natural gas, natural gas liquids, petroleum or shale oil, petroleum or shale oil processing residues, coal or biomass .
• the amount of Fischer-Tropsch derived fuel used in a diesel fuel composition may be from 0.5 to 100%v of the overall diesel fuel composition, preferably from 5 to 75%v. It may be desirable for the composition to contain 10%v or greater, more preferably 20%v or ⁇ rreater, still more preferably 30%v or greater, of the Fischer-Tropsch derived fuel. It is particularly preferred for the composition to contain 30 to 75%v, and particularly 30 or 70%v, of the Fischer-Tropsch derived fuel. The balance of the fuel composition is made up of one or more other fuels .
• An industrial gas oil composition will preferably comprise more than 50 wt%, more preferably more than 70 wt%, of a Fischer-Tropsch derived fuel component.
• Such a Fischer-Tropsch derived fuel component is any fraction of the middle distillate fuel range, which can be isolated from the (hydrocracked) Fischer-Tropsch synthesis product. Typical fractions will boil in the naphtha, kerosene or gas oil range. Preferably, a Fischer-Tropsch product boiling in the kerosene or gas oil range is used because these products are easier to handle in for example domestic environments. Such products will suitably comprise a fraction larger than 90 wt% which boils between 160 and 400 0 C, preferably to about 37O 0 C.
• Fischer-Tropsch derived kerosene and gas oils are described in EP-A-0583836, WO-A-97/14768, WO-A-97/14769, WO-A-00/11116, WO-A-00/11117, WO-A-01/83406, WO-A-01/83648 , WO-A-01/83647, WO-A-01/83641, WO-A-00/20535, WO-A-00/20534, EP-A-1101813, US-A-5766274 , US-A-5378348 , US-A-5888376 and US-A-6204426.
• the Fischer-Tropsch product will suitably contain more than 80 wt% and more suitably more than 95 wt% iso and normal paraffins and less than 1 wt% aromatics, the balance being naphthenics compounds.
• the content of sulphur and nitrogen will be very low and normally below the detection limits for such compounds. For this reason the sulphur content of a fuel composition containing a Fischer-Tropsch product may be very low.
• the fuel composition preferably contains no more than 5000ppmw sulphur, more preferably no more than 500ppmw, or no more than 350ppmw, or no more than 150ppmw, or no more than lOOppmw, or no more than 50ppmw, or most preferably no more than lOppmw sulphur.
• the fuel composition of the present invention may, if required, contain one or more additives as described below.
• the base fuel may itself be additivated (additive- containing) or unadditivated (additive-free) . If additivated, e.g. at the refinery, it will contain minor amounts of one or more additives selected for example from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers) , lubricity- additives, antioxidants and wax anti-settling agents.
• additives selected for example from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers) , lubricity- additives, antioxidants and wax anti-settling agents.
• Detergent-containing diesel fuel additives are known and commercially available. Such additives may be added to diesel fuels at levels intended to reduce, remove, or slow the build up of engine deposits.
• detergents suitable for use in fuel additives for the present purpose include polyolefin substituted succinimides or succinamides of polyamines, for instance polyisobutylene succinimides or polyisobutylene amine succinamides, aliphatic amines, Mannich bases or amines and polyolefin (e.g. polyisobutylene) maleic anhydrides.
• Succinimide dispersant additives are described for example in GB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 and WO-A-98/42808.
• Particularly preferred are polyolefin substituted succinimides such as polyisobutylene succinimides.
• the additive may contain other components in addition to the detergent.
• lubricity enhancers e.g. alkoxylated phenol formaldehyde polymers
• anti-foaming agents e.g. polyether-modified polysiloxanes
• ignition improvers cetan ⁇ improvers
• anti-rust agents e.g. 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate, di-tert-butyl peroxide and those disclosed in US-A-4208190 at column 2, line 27 to column 3, line 21
• anti-rust agents e.g.
• succinic acid derivative having on at least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group containing from 20 to 500 carbon atoms, e.g. the pentaerythritol diester of polyisobutylene-substituted succinic acid) ; corrosion inhibitors; reodorants; anti-wear additives; anti-oxidants (e.g. phenolics such as
• the additive include a lubricity enhancer, especially when the fuel composition has a low (e.g. 500 ppmw or less) sulphur content.
• the lubricity enhancer is conveniently present at a concentration of less than 1000 ppmw, preferably between 50 and 1000 ppmw, more preferably between 100 and 1000 ppmw.
• Suitable commercially available lubricity enhancers include ester- and acid-based additives.
• Other lubricity enhancers are described in the patent literature, in particular in connection with their use in low sulphur content diesel fuels, for example in:
• the (active matter) concentration of each such additional component in the additivated fuel composition is preferably up to 10000 ppmw, more preferably in the range from 0.1 to 1000 ppmw, advantageously from 0.1 to 300 ppmw, such as from 0.1 to 150 ppmw.
• the (active matter) concentration of any dehazer in the fuel composition will preferably be in the range from 0.1 to 20 ppmw, more preferably from 1 to 15 ppmw, still more preferably from 1 to 10 ppmw, advantageously from 1 to 5 ppmw.
• the (active matter) concentration of any ignition improver present will preferably be 2600 ppmw or less, more preferably 2000 ppmw or less, conveniently from 300 to 1500 ppmw.
• the additive components may be co-mixed, preferably together with suitable diluent (s), in an additive concentrate, and the additive concentrate may be dispersed into the fuel, in suitable quantity to result in a composition of the present invention.
• the additive will typically contain a detergent, optionally together with other components as described above, and a diesel fuel-compatible diluent, which may be a carrier oil (e.g. a mineral oil), a polyether, which may be capped or uncapped, a non-polar solvent such as toluene, xylene, white spirits and those sold by Shell companies under the trade mark "SHELLSOL", and/or a polar solvent such as an ester and, in particular, an alcohol, e.g.
• a carrier oil e.g. a mineral oil
• a polyether which may be capped or uncapped
• a non-polar solvent such as toluene, xylene, white spirits and those sold by Shell companies under the trade mark "SHELLSOL”
• a polar solvent such as an ester and, in particular, an alcohol, e.g.
• LINEVOL LINEVOL 79 alcohol which is a mixture of 07-9 primary alcohols, or a
• the alkyl levulinate concentration in the fuel composition accords with one or more of the following parameters :-
• amounts (concentrations, %v, ppmw, wt%) of components are of active matter, i.e. exclusive of volatile solvents/diluent materials.
• the present invention is particularly applicable where the fuel composition is used or intended to be used in a direct injection diesel engine, for example of the rotary pump, in-line pump, unit pump, electronic unit injector or common rail type, or in an indirect injection diesel engine.
• the fuel composition may be suitable for use in heavy and/or light duty diesel engines.
• boilers include standard boilers, low temperature boilers and condensing boilers, and are typically used for heating water for commercial or domestic applications such as space heating and water heating .
• the present invention may lead to any of a number of advantageous effects, including good engine low temperature performance.
• Fuel A was a Dreyfuss ULSD, a hydrotreated AGO having a cloud point of -27 0 C and an aromatics content of 22%m; and (2) Fuel B was a Swedish Class 1 AGO, which is a low density, low aromatics (4%m) diesel fuel with a cloud point of -38 0 C. Both base fuels met the EN590 specification.

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• 2006
  • 2006-07-19 EP EP06792524A patent/EP1907513A1/de not_active Withdrawn
  • 2006-07-19 AU AU2006274057A patent/AU2006274057A1/en not_active Abandoned
  • 2006-07-19 WO PCT/EP2006/064396 patent/WO2007012585A1/en active Application Filing
  • 2006-07-19 JP JP2008523321A patent/JP2009503173A/ja active Pending
  • 2006-07-19 CN CNA2006800273341A patent/CN101233216A/zh active Pending
  • 2006-07-19 CA CA002616080A patent/CA2616080A1/en not_active Abandoned
  • 2006-07-19 BR BRPI0613897A patent/BRPI0613897A2/pt not_active IP Right Cessation
  • 2006-07-21 AR ARP060103170A patent/AR055994A1/es not_active Application Discontinuation
  • 2006-07-25 US US11/492,449 patent/US20070175090A1/en not_active Abandoned
• 2008
  • 2008-01-16 ZA ZA200800473A patent/ZA200800473B/xx unknown
  • 2008-02-22 NO NO20080958A patent/NO20080958L/no not_active Application Discontinuation

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