WO2007039459A1 - Compositions de combustible - Google Patents

Compositions de combustible Download PDF

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Publication number
WO2007039459A1
WO2007039459A1 PCT/EP2006/066531 EP2006066531W WO2007039459A1 WO 2007039459 A1 WO2007039459 A1 WO 2007039459A1 EP 2006066531 W EP2006066531 W EP 2006066531W WO 2007039459 A1 WO2007039459 A1 WO 2007039459A1
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Prior art keywords
fuel
dendrimer
heating
composition according
fuel composition
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PCT/EP2006/066531
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English (en)
Inventor
Ingrid Maja Guenther
Frank Haase
Kay Krueger
George Robert Lee
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Shell Internationale Research Maatschappij B.V.
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Publication of WO2007039459A1 publication Critical patent/WO2007039459A1/fr

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    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular 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
    • C10L1/18—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
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2381—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds polyamides; polyamide-esters; polyurethane, polyureas
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides

Definitions

  • the present invention relates to fuel compositions for heating and/or lighting applications.
  • the present invention relates to the use of such fuel compositions in heating and/or lighting appliances which contain burners.
  • Such heating appliances include boilers, for example standard boilers, low temperature boilers and condensing boilers .
  • Such lighting appliances include, for example, lamps provided with wick burners, such as those that are fuelled by kerosene.
  • Such boilers are typically used for heating water for commercial or domestic applications such as space heating and water heating. In standard and low temperature boilers, it is ensured that flue gas leaves the boiler as gas.
  • Condensing boilers are described for example in EP-A-0789203, in particular a gas-fired condensing boiler. These boilers are called condensing boilers because the gases produced by combustion are cooled inside the apparatus until the water vapour contained therein condenses, so as to recover the latent condensation heat and transfer it to the water to be heated, which flows through said boilers. This latent heat is sometimes also used to pre-heat the combustion air .
  • Natural gas is used as fuel in boilers.
  • the Netherlands which is equipped with a widespread natural gas grid, many households use a boiler for domestic heating in combination with warm water supply.
  • the wide application of these boilers is due to their attractive energy efficiency and the presence of the natural gas supply grid.
  • a disadvantage of all boilers that use natural gas is that they cannot be easily applied in regions where no natural gas grid is present.
  • a solution to this problem is to use a liquid fuel.
  • Liquid fuels can be easily transported to and stored by the end user, for example in a storage tank connected to the boiler by copper lines. Such tanks may, for example, be underground or in basements .
  • the general pattern of the flame of such an oil burner assembly is one of heterogeneity in terms of fuel concentrations; the pockets of fuel-lean mixture give rise to high nitric oxide concentrations from both the fuel nitrogen and the atmospheric nitrogen, while the pockets of fuel-rich mixture give rise to soot.
  • the visible flame from such a system is yellow.
  • the yellow colour is the visible radiation from the high temperature soot particles and this completely masks other visible radiations as far as the human eye is concerned. These soot particles result from unburnt carbon.
  • Yellow flame burners operate on the principle that a pump delivers the fuel through an electrical pre-heater which raises the fuel temperature to approximately 70 0 C. The pressurised fuel is then delivered through a nozzle and forms a spray. Oxygen-containing air for combustion is introduced and distributed via a so-called swirl plate to mix vigorously with the fuel spray. At the initial system start, the spray is ignited by an ignition electrode. In yellow flame systems, only an insufficient evaporation of the fuel is achieved before the combustion takes place. For complete combustion of the carbon, that is, soot-free combustion, the step-wise combustion of carbon to carbon dioxide via the intermediate carbon monoxide stage gives rise to a visible radiation in the blue region of the light spectrum. When this occurs the blue radiation becomes visible in a soot-free or low-luminosity flame, and oil burners for such soot-free flames are known as blue flame burners .
  • Blue flame burners are characterised in that the combustion of the hydrocarbon fuel to carbon dioxide is performed such that part of the flue gas is recycled to the flame and more suitably to the nozzle of the burner. Recycling part of the flue gas externally of the burner may effect such recirculation of the flue gas.
  • This is enabled by a flame tube, which is attached to the burner. This tube is provided with recirculation holes or slits through which the recirculated gases enter the front part of the flame tube.
  • recycling may be achieved by swirling the combustible mixture of fuel and oxygen-containing gas, wherein at the axis of the swirling flame some recirculation of the flue gas takes place .
  • US-A-6127481 discloses a branched polyolefin additive for use in fuel and/or lubricating oil in the form of a comb, star, nanogel and structural combinations thereof in which a plurity of polyolefin arms are attached to a backbone having repeating units containing aliphatic groups, aromatic groups, heteroatom-containing groups and combinations thereof, to provide a branched polymeric additive in which the properties of the additive can be conveniently tailored to a single or multi-functional performance criteria of a fuel and/or lubricating oil composition.
  • dendrimers are used as the backbone, and the reactive terminal groups of the dendrimer are reacted with polyolefin prearms to provide a polymeric product in which the terminal groups are polyolefinic groups.
  • the examples wherein dendrimers are used as the backbone are Examples 15, 17, 21 and 22 in US-A-6127481.
  • ethylene- propylene polymer arms are functionalised with an end group which will react with a reactive terminal group on a dendrimer, and the resulting polyolefin prearms are reacted with dendrimer such that each reactive terminal group reacts with a polyolefin prearm to form an ester, imide, amine, ether or urea linkage, thereby leaving no terminal amino, hydroxyl or carboxylate groups.
  • WO-A-96/12755 discloses an oil soluble dendrimer-based cold flow improver comprising a central core linked through a plurality of polar groups to a dendritic body which is linked through a plurality of polar groups to a hydrocarbyl periphery, the periphery consisting of n-alkyl groups which contain from 8 to 1000 carbon atoms.
  • dendrimer-based cold flow improvers are used in crude oil, lubricating oil or fuel oil (e.g. kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils).
  • fuel oils e.g. kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils.
  • concentration (w/w) is 0.0001 to 1% (1 to 10,000 ppmw), preferably 0.1 to 0.2% (1000 to 2000 ppmw) (page 7, lines 5 to 17, of WO-A-96/12755, although the examples employ 100 to 200 ppmw (0.01 to 0.02 %w/w) .
  • WO-A-02/102928 discloses a method for solubilising asphaltenes in an asphaltenes-containing hydrocarbon mixture by adding thereto an effective amount of a dendrimeric compound; and a hydrocarbon mixture comprising (in addition to hydrocarbons), asphaltenes and at least one dendrimeric compound.
  • Asphaltenes are aromatic hydrocarbons which are insoluble in n-heptane, and are generally determined in accordance with ASTM D 6560. Asphaltenes cause problems in oil recovery and oil refining processes, by forming solid desposits or dark sludge, e.g. in oil formations, in oil-well equipment or in oil pipelines.
  • the Examples in WO-A-02/102928 demonstrate solubilising of asphaltenes in crude oil, and show improved performance for dendrimers in which a proportion of terminal hydroxyl groups have been modified by reaction with poly (isobutenyl) succinic anhydride in which the poly (isobutenyl) chain contained about 22 isobutylene units .
  • WO-A-97/41092 discloses alkoxy acetic acid derivatives of general formula
  • R is the residue of an amine, an aminoalcohol or a polyol linked to the or each -CHR ' -CO- moiety via an amide or ester linkage :
  • R' is hydrogen or C ⁇ _ 4 alkyl;
  • R 1 is an optionally substituted hydrocarbyl group of 1 to
  • R 2 and R ⁇ are independently selected from hydrogen and optionally substituted hydrocarbyl of 1 to 10 carbon atoms, the other of R 2 and R ⁇ being independently selected from optionally substituted hydrocarbyl of 1 to
  • “Starburst” (trade mark) dendrimers may be used, e.g. the compound of formula [CH 2 N ( (CH 2 ) 2CONH (CH 2 ) 2 NH 2 ) 2 ] 2 .
  • This latter compound, “Starburst” (PAMAM, generation O) dendrimer is used in Example 25 resulting in a compound of formula I wherein R is a dendrimer backbone having 3 remaining terminal amino groups .
  • R(H)p is selected from the group consisting of pentaerythritol, triethylenetetramine and tris (2-aminoethyl ) amine. It can be noted (Table 1 in WO-A-97/41092) that the product of Example 25 is not among the most active of the materials tested, and the person skilled in the art would not have been encouraged to pursue further derivatives of dendrimers instead of polyalkylene glycol derivatives of pentaerythritol, triethylenetetramine and tris (2-aminoethyl) amine, in the quest for advantageous gasoline additives .
  • a fuel composition for heating and/or lighting applications comprising a major amount of a base fuel and a minor amount of a fuel-compatible dendrimer having a plurality of terminal functional groups independently selected from amino, hydroxyl and carboxylate groups.
  • Said heating and/or lighting applications preferably comprise use in heating and/or lighting appliances which contain burners.
  • dendrimers as three-dimensional highly-ordered oligomers or polymers. They are obtainable by reiterative reaction sequences starting from an initiator core having one or more reactive sites. To each reactive site is attached one functional group only of a polyfunctional reactant. The reactant is then caused to react through its remaining functional group or groups with additional molecules either the same as the original core if it is polyfunctional or a different, polyfunctional, molecule or molecules, and so on, in each case under reaction conditions such that unwanted side reactions, for example, crosslinking, are avoided.
  • steps A and B produce higher generations which after Generation 4 result in concentric spheres of cells, the outermost sphere carrying external reactive groups.
  • Other dendrimers described by Tomalia et al . include polyethylenimine, hydrocarbon, polyether, polythioether, polyamide, polyamido-alcohol and polyarylamine dendrimers. Syntheses of such dendrimers are variously described, for example, in US-A-4435548, US-A-4507466 , US-A-4558120 and US-A-4568737.
  • Polyamide- and ester-based dendrimers are also described by Newkome et al . , J. Am. Chem. Soc, 112 (1990) 8458.
  • Use of a long-chain alkylene dibromide as core provided a dendrimer (referred to by Newkome et al . as an arboral) in the form of two spheres linked by an alkylene chain.
  • US-A-5041516 describes molecules similar to those of Tomalia et al . , but made by a "convergent" approach, i.e. starting with the outer surface of the dendrimer, building up a wedge-shaped molecule, and finally reacting a plurality of the "wedges" with a core molecule.
  • GB-A-1575507 describes star-shaped polymers and their use as viscosity improvers, these polymers being based on a cross-linked divinylbenzene core and isoprene branches; in EP-A-0368395 such a hydrocarbon polymer is functionalised through a sulphonamide linkage to provide carboxyl terminal groups .
  • PAMAM dendrimers have a large internal surface area which, in proportion to the external surface area, increases with the number of generations.
  • polyether dendrimers have very little proportional internal surface, which reaches a maximum at Generations 3 to 4.
  • the successive layers of cells may be the same or different, and mixtures of two or more reactants, for example as described by Tomalia et al . , at page 148, may be used.
  • Aldrichimica Acta, Vol. 37, No. 2, 2004 at pages 39 to 57 contains a review by Tomalia of dendrimers and their application as building blocks for nanoscale synthetic organic chemistry. This review is followed by a listing of PAMAM and phosphorous dendrimers available from Aldrich. Aldrich Handbook of Fine Chemicals and Laboratory Equipment 2003-2004 United Kingdom contains listings of dendrimers available from Aldrich, including various DAB-Am dendrimers (page 545), PAMAM dendrimers (pages 1406 to 1408) and PAMAM-OH dendrimers (pages 1408 and 1409) . Other and similar dendrimers are available directly from Dendritech, Inc, Michigan, USA and Dendritic Nano Technologies, Inc. Michigan, USA.
  • the plurality of terminal functional groups are preferably individually selected from NH 2 , -OH and COOX groups, where X represents H, K or Na.
  • the dendrimer is at least one fuel-compatible dendrimer independently selected from DAB-Am, PAMAM, PAMAM-OH and PAMAM-OH/COOH dendrimers.
  • the dendrimer contains from 4 to 64 terminal functional groups, conveniently 4 to 32 terminal functional groups and more conveniently 8 to 16 terminal functional groups, independently selected from amino, hydroxyl and carboxylate groups .
  • the dendrimer is preferably present in the fuel composition in a concentration in the range from 5 ppmw to 500 ppmw, more preferably in the range from 10 ppmw to 200 ppmw, based on total composition.
  • the fuel composition additionally to contain one or more fuel-compatible oxygenate co-solvents selected from C 1 to C 14 alkanols and 2-ethylhexanoic acid.
  • hydrocarbons can be replaced by up to substantial amounts of conventional alcohols or ethers conventionally known for such use, including biofuel components, or of ester biofuel components such as ethyl levulinate.
  • amounts (concentrations) (%v) (ppmw) of components are of active matter, i.e. exclusive of volatile solvents/diluent materials.
  • a process for the preparation of a fuel composition of the present invention which comprises bringing into admixture the base fuel and the fuel-compatible dendrimer, and any other components.
  • the fuel composition of the present invention 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 .
  • 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 ⁇ , a kinematic viscosity at 20 0 C of 1 to 80 mm 2 /s, and a boiling range of 150 to 400 0 C.
  • Preferred fuel fractions are the ultra low sulphur (e.g. less than 50 ppm sulphur) fractions, which are currently on the market.
  • non-mineral oil based fuels such as biofuels 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 proportion of said Fischer-Tropsch derived fuel is preferably more than 50 wt%, more preferably more than 70 wt%.
  • 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 370 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 base fuel of the fuel composition 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.
  • additives selected for example from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copo
  • detergents suitable for use in 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 cetane 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 paper by Danping Wei and H. A. Spikes, "The Lubricity of Diesel Fuels", Wear, III (1986) 217-235;
  • - WO-A-95/33805 cold flow improvers to enhance lubricity of low sulphur fuels
  • - WO-A-94/17160 certain esters of a carboxylic acid and an alcohol wherein the acid has from 2 to 50 carbon atoms and the alcohol has 1 or more carbon atoms, particularly glycerol monooleate and di-isodecyl adipate, as fuel additives for wear reduction in a diesel engine injection system;
  • the additive contain an anti-foaming agent, more preferably in combination with an anti-rust agent and/or a corrosion inhibitor and/or a lubricity additive .
  • 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, still more preferably 5 to 1000 ppmw, and advantageously from 0.1 to 300 ppmw, such as from 0.1 to 150 ppmw, and or from 75 to 300, such as from 95 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, still more preferably 600 ppmw or less, or 500 ppmw or less, conveniently from 300 to 500 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 base 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 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.
  • hexanol, 2-ethylhexanol, decanol, isotridecanol and alcohol mixtures such as those sold by Shell companies under the trade mark "LINEVOL", especially LINEVOL 79 alcohol which is a mixture of C 7 _9 primary alcohols, or a C]_2-14 alcohol mixture which is commercially available.
  • the total content of the additives may be suitably between 0 and 10000 ppmw and preferably below 5000 ppmw.
  • amounts (concentrations, %v, ppmw, wt%) of components are of active matter, i.e. exclusive of volatile solvents/diluent materials.
  • the present invention may lead to any of a number of advantageous effects, including reduced levels of soot emissions .
  • the present invention further provides a method of operating a heating and/or lighting appliance provided with one or more burners which comprises supplying to said burner a fuel composition according to the present invention .
  • the present invention also provides use of a fuel composition of the present invention in a heating and/or lighting appliance for the purpose of controlling, preferably reducing, the level of soot emissions.
  • the present invention further provides a method of controlling, preferably reducing, the level of soot emissions from a heating and/or lighting appliance, which comprises replacing the fuel used therein by a fuel composition according to the present invention.
  • Example 1 describes fuel compositions in burners as used in heating appliances such as boilers, whilst Example 2 describes a fuel composition, namely a kerosene fuel, in a wick burning heating and/or lighting appliance .
  • Example 1 describes fuel compositions in burners as used in heating appliances such as boilers, whilst Example 2 describes a fuel composition, namely a kerosene fuel, in a wick burning heating and/or lighting appliance .
  • the solvent used in the Examples was 2-ethyl hexanoic acid, in the ratio 4Og acid to Ig dendrimer.
  • the base fuels that were used in the Examples were Fuel A, which was a standard heating fuel, and Fuel B, which was a low sulphur heating fuel.
  • the properties of said fuels were as set out in Table 1:
  • Burner Bl The equipment used in the tests comprised the following: Burner Bl :
  • Shell 800 ULV S yellow flame burner having a thermal heat output of 13 to 3OkW. As this type of modern burner produces fairly low soot emissions under almost any conditions, it is regarded for present purposes as being a "well-adapted" burner.
  • Burner B2 is regarded for present purposes as being a "well-adapted" burner.
  • a fuel delivery system used in the tests comprised two fuel tanks which were connected by way of respective pipes to a switching valve. Said valve was connected by a further pipe to an oil pump, which fed the burner with fuel. Switching between fuels could therefore be performed whilst the burner was in operation.
  • flue gas emissions were measured directly in the undiluted exhaust gas in an exhaust pipe.
  • the flue gas was continuously led to a measurement system by way of a "TEFLON" probe, at 200°C to prevent condensation of any flue gas components.
  • the flue gas parameters that were measured were CO, CO2, NO x , C x H y (unburned hydrocarbon components) and soot emission (as soot number) .
  • the soot number also known as the Bosch or
  • the measurement system comprised the following: CO and CO ? : Rosemount NGA 2000 GT (IR), having the measurement ranges : for CO, 0 to 3000ppm for CO 2 , 0 to 15.4 %v/v
  • the burner was connected to a standardised "TUV" combustion flame tube (equivalent to a boiler) for testing heating oil burner appliances in accordance with DIN 4787.
  • the burner oil pump was connected to the pipe system and the pressure was set to the typical manufacturers setting (e.g. 10 bar). The pump pressure was kept constant over the entire testing period.
  • the air-fuel ratio (controlled via the different CO2 values in the flue gas) was adapted via the air supply of the burner. After the burner had started with the reference fuel, the combustion air was regulated by a fan controller (or air split range) to a normal CO 2 level defined by the burner manufacturer (for a typical yellow flame burner at 12.5%v/v).
  • the upper operating limits of the burner in these tests was determined by high CO2 levels, where soot emissions or emissions of unburned hydrocarbons started to increase significantly when reaching close to stoichiometric combustion conditions. Typically these high emissions were reached at approximately 14 to 15 %v/v CO 2 in the flue gas. The lower operating limit was reached when the unburned hydrocarbon emissions started to increase when a very high air supply cools the combustion process to an extent where complete combustion becomes impossible. The burner was operated between these two limits and emissions were measured at approximately 1.0 %v/v steps, once steady state at each CO2 level had been reached. In these specific tests, the CO2 level was adjusted via the air supply to the highest possible CO 2 level.
  • Table 2 shows that, under all conditions and for both burners, use of 50ppmw of Dendrimer A in Fuel A led to a reduction in the level of soot emissions.
  • Burner B2 was used, in view of the fact that the percentage reduction in mean soot number was almost identical as between Burners Bl and B2 in the first test cycle.
  • Fuels A and B were used, together with different concentrations of Dendrimer B.
  • the measurement procedure used in the first test cycle was used as appropriate in the second test cycle, in which two sets of runs were performed for each of the Fuels A and B. Emissions at three or four CO2 levels were measured.
  • Tables 3 to 6 show that, under all conditions, use of different concentrations of Dendrimer B in Fuels A and B led to a reduction in the level of soot emissions.
  • Fuels C to F having a wide variety of char points, were used. Duplicate char tests were performed in respect of each of said Fuels on the following fuel compositions: (a) 150OmL of Fuel plus 7mL of ethyl hexanoic acid, and (b) 150OmL of Fuel plus 7mL of ethyl hexanoic acid plus 50 ppmw of Dendrimer B, to determine the effect of polar dendrimers upon combustion charring in wick burners.
  • the properties of said Fuels were as set out in Table 7 :

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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)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

L’invention concerne une composition de combustible destinée à des applications pour le chauffage et/ou l’éclairage, ladite composition comprenant une quantité majoritaire d’un combustible de base et une quantité minoritaire d’un dendrimère compatible avec le combustible comprenant une pluralité de groupes fonctionnels terminaux choisis indépendamment parmi les groupes amino, hydroxyle et carboxylate ; ainsi que l’utilisation d'une telle composition de combustible en tant que combustible dans des appareils de chauffage et/ou d’éclairage dans le but de contrôler, de préférence de réduire, les niveaux d’émission de suie.
PCT/EP2006/066531 2005-09-20 2006-09-20 Compositions de combustible WO2007039459A1 (fr)

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EP05020450 2005-09-20

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2522014A1 (de) * 1974-05-22 1975-12-04 Autol Ag Zusatzmittel fuer brenn- und treibstoffe
EP0818525A2 (fr) * 1996-07-12 1998-01-14 DSM Copolymer, Inc. Polymères polyoléfiniques ramifiés, comme additifs dans des compositions d'huile lubrifiante et combustible
US5855629A (en) * 1996-04-26 1999-01-05 Shell Oil Company Alkoxy acetic acid derivatives
US5906970A (en) * 1994-10-19 1999-05-25 Exxon Chemical Patents Inc. Additives and oleaginous compositions containing a dendrine coldflow improver additive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2522014A1 (de) * 1974-05-22 1975-12-04 Autol Ag Zusatzmittel fuer brenn- und treibstoffe
US5906970A (en) * 1994-10-19 1999-05-25 Exxon Chemical Patents Inc. Additives and oleaginous compositions containing a dendrine coldflow improver additive
US5855629A (en) * 1996-04-26 1999-01-05 Shell Oil Company Alkoxy acetic acid derivatives
EP0818525A2 (fr) * 1996-07-12 1998-01-14 DSM Copolymer, Inc. Polymères polyoléfiniques ramifiés, comme additifs dans des compositions d'huile lubrifiante et combustible

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