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WO2013034617A1 - Compositions de carburant liquide - Google Patents

Compositions de carburant liquide Download PDF

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Publication number
WO2013034617A1
WO2013034617A1 PCT/EP2012/067362 EP2012067362W WO2013034617A1 WO 2013034617 A1 WO2013034617 A1 WO 2013034617A1 EP 2012067362 W EP2012067362 W EP 2012067362W WO 2013034617 A1 WO2013034617 A1 WO 2013034617A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel composition
diesel fuel
diesel
fuel
cycle oil
Prior art date
Application number
PCT/EP2012/067362
Other languages
English (en)
Inventor
Felix Johannes BALTHASAR
Ingo Torsen MAHLKE
Original Assignee
Shell Internationale Research Maatschappij B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP12753744.7A priority Critical patent/EP2748290A1/fr
Publication of WO2013034617A1 publication Critical patent/WO2013034617A1/fr

Links

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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

  • the present invention relates to a liquid fuel composition.
  • the present invention relates to a liquid diesel fuel composition comprising Heavy Cycle Oil for providing reduced power loss, e.g. due to injector fouling, in a diesel engine.
  • a known problem that affects high performance diesel engines is deposit formation. Particularly stubborn deposits form at and around the injector valve seat and nozzle. This phenomenon, also referred to as injector fouling, often results in injector drift, power loss and an increase in smoke emissions.
  • Diesel fuel injectors have always been prone to injector fouling, however improvements in the design of fuel injection equipment to meet increasing regulatory and consumer demands may mean that the fuel injection equipment is more sensitive to fouling.
  • New injection systems are being designed to run at higher pressures with smaller fuel injector nozzle sizes and multiple injections, to allow for smoother running, better combustion and to enable sophisticated after treatment devices such as diesel particulate filters.
  • Tighter tolerances and nozzle hole sizes in the order of 100 microns mean that fouling can have a more significant impact on power, emissions and fuel economy.
  • Fischer-Tropsch gas oil leads to markedly lower engine deposits compared to petroleum derived fuels, and may be used to x clean-up' fouled injectors to remove deposits built up through use of another fuel (Examples 1 and 2) .
  • Heavy Cycle Oil is a petroleum-derived
  • the present invention provides the use of Heavy Cycle Oil in a diesel fuel composition for reducing injector fouling or reducing power loss in a compression ignition (diesel) engine to which the diesel fuel composition is introduced.
  • the present invention further provides a method for reducing injector fouling or reducing power loss of an engine, the method comprising introducing into a
  • composition comprising Heavy Cycle Oil.
  • the present invention also provides a diesel fuel composition which comprises a diesel base fuel and in the range of from 0.05 wt% to 5 wt% of Heavy Cycle Oil, by weight of the diesel fuel composition, and a process for its preparation by the addition of Heavy Cycle Oil to a diesel base fuel in the appropriate amount.
  • reducing power loss or “reduced power loss” means the reduction of loss of power in an engine. This is directly proportional to a decrease in torque for the engine run at constant engine speed or at fixed throttle conditions.
  • reducing injector fouling or “reduced injector fouling” means a reduction of deposits formed at and around the injector valve seat and/or nozzle.
  • the liquid diesel fuel composition of the present invention comprises a base fuel suitable for use in a compression ignition engine and a Heavy Cycle Oil.
  • Heavy Cycle Oil is well known to those skilled in the art. Heavy Cycle Oil is a petroleum- derived hydrocarbaceous fraction obtained from an FCC
  • the product from the FCC unit contains fractions of light olefins, gasoline, Light Cycle Oil (LCO) and a heavy hydrocarbon fraction, such as slurry oil or Heavy Cycle Oil (HCO) .
  • LCO Light Cycle Oil
  • HCO Heavy Cycle Oil
  • the heavy hydrocarbon fraction remaining in the bottoms of the FCC unit is removed.
  • the resulting energy density of this heavy hydrocarbon fraction can be affected by the operation of the FCC unit. Operation of the FCC unit at relatively high severity, for example, higher temperatures with a higher catalyst to hydrocarbon ratio, will yield products with higher energy densities and higher carbon to hydrogen ratios.
  • US -A-6,039,771 discloses the use of a hydrocarbon component, which is the distillate from the distillation of Heavy Cycle Oil to remove, inter alia, contaminants, as an additive blend component to combine with a diesel fuel component to form an energy fortified diesel fuel for off-highway compression ignition engines.
  • a hydrocarbon component which is the distillate from the distillation of Heavy Cycle Oil to remove, inter alia, contaminants
  • distillate is used in quantities from about 10% to about 90% of said diesel fuel.
  • US-A-6, 039, 771 reports attempts to use LCO-diesel fuel blends in on-highway compression ignition engines, which were unsuccessful even when using stabilizers; Column 3, lines 26 to 31, note that the findings using LCO-diesel blends cause the industry to expect that HCO-diesel blends would be even less stable.
  • the diesel fuel compositions used herein comprise from 0.05 wt% to 5 wt%, preferably 0.1 wt% to 1 wt ⁇ 6 , more preferably 0.2 wt% to 0.7 wt%, of HCO, by weight of the diesel fuel composition.
  • the base fuel used is a diesel fuel, and includes diesel fuels for use in automotive compression ignition engines, as well as in other types of engine such as for example off road, marine, railroad and stationary engines.
  • the diesel fuel used as the base fuel in the diesel fuel composition of the present invention may conveniently also be referred to as iesel base fuel' .
  • the diesel 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 one or more base fuels which may typically comprise liquid hydrocarbon middle distillate gas oil (s) , for instance petroleum derived gas oils.
  • base fuels 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°C, depending on grade and use. They will typically have a density from 750 to 1000 kg/m 3 , preferably from 780 to
  • 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 amount of Fischer-Tropsch derived fuel used in the diesel fuel may be from 0% to 100%v of the overall diesel fuel, preferably from 5% to 100%v, more preferably from 5% to 75%v. It may be desirable for such a diesel fuel to contain 10%v or greater, more preferably 20 ⁇ or greater, still more preferably 30%v or greater, of the Fischer-Tropsch derived fuel. It is particularly
  • diesel fuels preferred for such diesel fuels to contain 30 to 75%v, and particularly 30 to 70%v, of the Fischer-Tropsch derived fuel.
  • the balance of the diesel fuel is made up of one or more other diesel fuel components.
  • Such a Fischer-Tropsch derived fuel component is any fraction of the middle distillate fuel range, which can be isolated from the (optionally hydrocracked)
  • Fischer-Tropsch synthesis product Typical fractions will boil in the naphtha, kerosene or gas oil range.
  • 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
  • Such products will suitably comprise a fraction larger than 90 wt% which boils between 160 and 400°C, preferably to about 370°C.
  • Fischer- Tropsch derived kerosene and gas oils are described in EP-A-0583836, WO-A- 97 / 14768 , WO-A- 97 / 14769 ,
  • 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 diesel fuel composition
  • containing a Fischer-Tropsch product may be very low.
  • the diesel fuel composition preferably contains no more than 5000ppmw sulphur, more preferably no more than 500ppmw, or no more than 350ppmw, or no more than
  • the composition may contain no more than 70 ppmw, or no more than 50ppmw, or no more than 30ppmw, or no more than 20ppmw, or no more than lOppmw sulphur.
  • diesel fuel components which may be used herein include the so-called “biofuels” which derive from biological materials.
  • biofuels include fatty acid alkyl esters (FAAE) , such as fatty acid methyl esters (FAME) .
  • FAME fatty acid methyl esters
  • the diesel 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 selected for example from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers) , lubricity
  • 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 diesel 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.
  • the diesel fuel additive mixture may contain other components in addition to the detergent.
  • lubricity enhancers e.g. alkoxylated phenol formaldehyde polymers
  • anti-foaming agents e.g.
  • cetane improvers 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. a propane-1 , 2-diol semi-ester of tetrapropenyl succinic acid, or polyhydric alcohol esters of a succinic acid derivative
  • 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 polyisobutylene-substituted succinic acid
  • corrosion inhibitors corrosion inhibitors
  • reodorants anti-wear additives
  • anti-oxidants e.g. phenolics such as phenolics
  • deactivators combustion improvers; static dissipator additives; cold flow improvers; and wax anti-settling agents.
  • the diesel fuel additive mixture may contain a lubricity enhancer, especially when the diesel fuel composition has a low (e.g. 500 ppmw or less) sulphur content.
  • the lubricity enhancer is conveniently present at a low (e.g. 500 ppmw or less) sulphur content.
  • 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:
  • composition to contain an anti-foaming agent, more preferably in combination with an anti-rust agent and/or a corrosion inhibitor and/or a lubricity enhancing additive.
  • concentration of each such optional additive component in the additivated diesel 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 diesel 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, and especially from 1 to 5 ppmw.
  • concentration of any ignition improver present will preferably be 2600 ppmw or less, more preferably 2000 ppmw or less, even more preferably 300 to 1500 ppmw.
  • concentration of any detergent in the diesel fuel composition will preferably be in the range from 5 to 1500 ppmw, more preferably from 10 to 750 ppmw, most preferably from 20 to 500 ppmw.
  • the fuel additive mixture will typically contain a detergent, optionally together with other components as described above, and a diesel fuel-compatible diluent, which may be a mineral oil, a solvent such as 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,
  • a detergent optionally together with other components as described above
  • a diesel fuel-compatible diluent which may be a mineral oil, a solvent such as 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 07-9 primary alcohols, or a C]_2-14 alcohol mixture which is commercially available.
  • the total content of the additives in the diesel fuel composition may be suitably between 0 and 10000 ppmw and preferably below 5000 ppmw.
  • amounts (concentrations, % vol, ppmw, % wt) of components are of active matter, i.e. exclusive of volatile solvents/diluent materials.
  • the diesel fuel composition of the present invention is produced by admixing the Heavy Cycle Oil with a diesel base fuel suitable for use in an internal combustion engine .
  • the present invention therefore provides a method of reducing injector fouling or reducing power loss of a diesel engine, the method comprising introducing into a combustion chamber of the diesel engine a diesel fuel composition comprising Heavy Cycle Oil.
  • the engine used for this test was a VW Euro 4 Engine.
  • the engine used a PD (Pumpe-Duse) electronic unit injector direct Injection system.
  • the Euro 4 engine uses HHE (High-Hydraulic- Efficiency) Siemens VDO (now part of Continental AG) injectors. Table 1 below shows the details of the VW engine used in this test.
  • test procedure is based on measurements of torque loss (in Nm) that can be due to injector fouling.
  • the test procedure entails alternating the candidate and reference fuels in 10 hour fixed throttle, high part load
  • Figure 1 shows the Fouling Cycle Power Loss for Fuel A and Fuel B in Example 1.
  • FIG. 1 shows the Fouling Cycle Power Loss for Fuel
  • Example 1 used Fuel A and Fuel B in the procedure above.
  • Fuel A was an EN 590 diesel fuels which promoted deposit formation and served as a reference fuel.
  • Key properties of the EN 590 diesel fuel (Reference Fuel A) are shown in Table 2 below.
  • Fuel B was identical to Fuel A.
  • the results of Example 1 are shown in Table 3 and in Figure 1.
  • Example 2 used Fuel C and Fuel A in the procedure above.
  • Fuel C consisted of Fuel A with the addition of 0.6% Heavy Cycle Oil by vol.
  • the Heavy Cycle Oil used was obtained from an FCC unit and had the following
  • Example 2 Vapour pressure: ⁇ 0.1 kPa @ 40°C; Initial boiling point: approximately 150°C; Final boiling point: >600°C; Density: 1010 kg/m3 - 1060 kg/m3; Flash point:> 60C; Kinematic Viscosity: approximately 700 cSt; Sulphur content: 10000 mg/kg.
  • Table 4 The results of Example 2 are shown in Table 4 and in Figure 2.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

L'invention porte sur l'utilisation de gas-oil cyclé lourd (HCO) dans une composition de carburant diesel pour la réduction de la perte de puissance, par exemple due à l'encrassement d'injecteur, dans un moteur dans lequel la composition de carburant est introduite.
PCT/EP2012/067362 2011-09-06 2012-09-06 Compositions de carburant liquide WO2013034617A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12753744.7A EP2748290A1 (fr) 2011-09-06 2012-09-06 Compositions de carburant liquide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11180178.3 2011-09-06
EP11180178 2011-09-06

Publications (1)

Publication Number Publication Date
WO2013034617A1 true WO2013034617A1 (fr) 2013-03-14

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PCT/EP2012/067362 WO2013034617A1 (fr) 2011-09-06 2012-09-06 Compositions de carburant liquide

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EP (1) EP2748290A1 (fr)
WO (1) WO2013034617A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3034383A1 (fr) 2016-08-25 2018-03-01 General Electric Company Reduction de l'encrassement par une huile hydrocarburee

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Publication number Priority date Publication date Assignee Title
GB960493A (en) 1960-12-16 1964-06-10 California Research Corp Motor fuel compositions containing polyolefin substituted succinimides of tetraethylene pentamine
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EP0147240A2 (fr) 1983-12-30 1985-07-03 Ethyl Corporation Compositions de combustibles et des concentrés d'additifs, et leur utilisations pour inhiber la formation de dépôts
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