EP1481042A1 - Low emissions fuel emulsion comprising fischer-tropsch derived hydrocarbon - Google Patents

Low emissions fuel emulsion comprising fischer-tropsch derived hydrocarbon

Info

Publication number
EP1481042A1
EP1481042A1 EP03709019A EP03709019A EP1481042A1 EP 1481042 A1 EP1481042 A1 EP 1481042A1 EP 03709019 A EP03709019 A EP 03709019A EP 03709019 A EP03709019 A EP 03709019A EP 1481042 A1 EP1481042 A1 EP 1481042A1
Authority
EP
European Patent Office
Prior art keywords
fuel
emulsion
hydrocarbon
water
range
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
EP03709019A
Other languages
German (de)
French (fr)
Other versions
EP1481042B1 (en
Inventor
Paul Joseph Berlowitz
Robert Jay Wittenbrink
Tapan Chakrabarty
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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 ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP1481042A1 publication Critical patent/EP1481042A1/en
Application granted granted Critical
Publication of EP1481042B1 publication Critical patent/EP1481042B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

  • the present invention relates to an improved fuel which has reduced paiticulate matter emission characteristics. More particularly the invention is directed to fuels that are in the form of hydrocarbon-in- water emulsions.
  • Hydrocarbon-in-water emulsions have many potential uses, such as in internal combustion engines and as a fuel for heating purposes. Indeed, various studies have suggested that burning hydrocarbon-in-water emulsions has the advantage of lowering the nitrogen oxide emissions normally associated witli burning hydrocarbons. Emulsions are believed to reduce nitrogen oxide (NO ⁇ ) emissions by lowering the peak flame temperature during their combustion. A lower flame temperature, however, often is associated with an increase in the emission of paiticulate matter (Pm). This phenomenon, known as the Pm-NO x trade off, is believed to limit the improvements one can make to diesel emissions.
  • NO ⁇ nitrogen oxide
  • Pm paiticulate matter
  • an object of the present invention is to develop a method of more effectively controlling paiticulate emissions without adversely impacting presently achievable reduced nitrogen oxide emission levels demonstrated for emulsified fuels.
  • reduced paiticulate matter emissions are achieved with an emulsion of a hydiocaibon and water in which the hydrocarbon is a Fischer-Tropsch (FT) derived hydiocaibon fuel or a mixture of a FT fuel and a conventional hydiocaibon fuel and in which emulsion a major poition of the hydrocarbon has particle sizes of 1 micron or less.
  • the emulsion is a hydrocarbon-in-water emulsion.
  • the hydiocaibon is a FT derived hydiocaibon boiling in the diesel fuel range.
  • Figure 1 is a diagiammatic iUustiation of one aiiangement of multiple static mixers used to prepare an emulsion according to the invention.
  • Figures 2 and 3 graphically compare the performance of an emulsion of the invention with two non-emulsified fuels in a diesel engine without timing adjustments.
  • FIGS 4 and 5 graphically compare the performance of the fuels of Figures 2 and 3 with timing adjustment. DETAILED DESCRIPTION OF THE INVENTION
  • the emulsions of the present invention contain as the hydiocaibon, a Fischer-Tropsch derived hydrocarbon fuel or a mixture of a FT fuel and a conventional hydrocarbon fuel.
  • the hydrocarbon is a FT derived fuel.
  • the hydiocaibon fuels produced in the Fischer-Tropsch process may be separated from the product cmde by standard distillation techniques. Additionally, however, the waxy component of the cmde may be converted into fuels by known teclmiques such as hydrotreating, hydroisomerization and hydrocrack- ing. An example of one such process can be found in U.S. 5,378,348, which is incorporated herein by reference.
  • the Fischer-Tropsch derived hydrocarbon fuel may comprise either the direct liquid product (C5+) from the Fischer-Tropsch process, a converted Fischer-Tropsch product, or a blend of the foregoing.
  • Fischer-Tropsch products boiling in the range of from about 25 °C to about 450°C are suitable.
  • Such fuels include that disclosed in U.S. 5,807,413 which patent is incorporated herein by reference.
  • Fischer-Tropsch products such as those boiling, in the range of about 140°C to about 370°C and preferably in the range of about 160°C to about 350°C.
  • the water of the emulsion of the invention may be that typically used in foiming fuel emulsions such as tap water, distilled or deionized water.
  • water from the Fischer-Tropsch process constitutes the continuous phase of the emulsion.
  • Fischer-Tropsch process water typically contains about ⁇ 2 wt% of oxygenates.
  • Table 1 A typical composition is shown in Table 1 below:
  • the amount of water used in fomiing the emulsion may be vaiied over a wide range.
  • the volume ratio of Fischer-Tropsch hydrocarbon fuel to water may range from about 95:5 to about 60:40.
  • the emulsions of the present invention also include a nonionic surfactant or mixture of nonionic surfactants.
  • the type of nonionic surfactants suitable include ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated carboxylic esters, glycerol esters, sorbital esters and the like.
  • the nonionic surfactant will have an HLB in the range of 5 to 30 and preferably 8 to 15.
  • suitable surfactants ethoxylated alkyl phenols having from about 5 to about 30 and preferably 10 to 15 mole of ethylene oxide groups deserve special mention.
  • the amount of surfactant or mixtures thereof in the emulsion will range from about 0.05 wt% to about 5.0 wt% based on the total weight of hydrocarbons and water with 0.05 wt% to about 2 wt% being typical.
  • the emulsion compositions of the invention may include minor but effective amounts of conventional additives such as emulsions stabilizers, antioxidants and the like. In the case where the fuel is diesel fuel the fuel may also contain conventional quantities of diesel fuel additives such as cetane improvers, detergents, heat stabilizers and the like.
  • emulsions can be formed by any number of procedures. Central to all of these is providing sufficient shearing of the components to cause emulsification.
  • the fuel is added to a mixture of water and surfactant and sheared under conditions sufficient to produce hydiocaibon paiticles of predominantly 1 micron in size or less.
  • the particles are substantially uniform in size, i.e., greater than 50% are in the range of about 0.1 to about 1.0 microns in size.
  • extensive shearing results in the formation of a "gel” and consequently the shearing will be less than that which would produce a gel.
  • FIG. 1 A diagiammatic illustration of one arrangement of static mixers suitable for carrying out the emulsification of this invention is shown in the accompanying Figure. As shown, each of the six mixers have different dimen- sions. Obviously, different members and sizes of mixers may be used so long as the requisite shearing is achieved. The dimensions of tlie illustrated mixers are given in Table 2 below.
  • a water and surfactant solution is fed to the mixer 1 via line 7 and tlie Fischer-Tropsch derived hydrocarbon fuel via line 8.
  • the product of each mixer is sequentially fed to tlie next mixer in the series, e.g., the product of mixer 1 is fed to mixer 2; tlie product of mixer 2 is fed to mixer 3 and so on.
  • the emulsion exiting mixer 6 via line 9 has a particle size predominantly less than 1 micron.
  • the emulsion in the instance where the Fisher-Tropsch fuel is a diesel fuel has a viscosity in the range of about 50 to 200 mm2/sec at 20°C.
  • a non-ionic surfactant an ethoxylated nonyl phenol having 10 mols of ethylene oxide groups
  • a Fischer-Tropsch diesel fuel (boiling range ⁇ 40°C to 300°C) comprising 90 + % of C to C linear paraffins was also fed with tl e water and surfactant through tlie four mixers.
  • the volume ratio of fuel to water was 70:30.
  • the hydrocarbon flow rate was 2650 ml/min. and the water surfactant solution flow rate was 1380 ml/min.
  • the temperature was 24°C.
  • the product of mixer 4 was not a hydrocarbon-in-water emulsion.
  • Swedish Class 1 Diesel fuel also called Urban Diesel ECI
  • Urban Diesel ECI is a standard low emissions reference diesel fuel that produces about 10% to 20% lower NO x and 40% to 50% lower paiticulate matter (Pm) than conventional diesel fuel.
  • Pm paiticulate matter
  • Figures 2 and 3 show the relative emissions performance of the Fischer-Tropsch fuel and an emulsion of the invention (Example 1) vs. Swedish Class I Diesel fuel at low and medium load.
  • tl e FTF exhibits similar behavior to Swedish Class I Diesel Fuel whereas the a fuel emulsion of tlie invention shows NO x emissions 22% below Swedish Class 1 and Pm 53% below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Emulsions of a hydrocarbon and water in which the hydrocarbon preferably is a Fischer-Tropsch derived hydrocarbon fuel and in which emulsion a major portion of the hydrocarbon has particle sizes of 1 micron or less produce reduced particulate matter emissions upon combustion.

Description

OW EMISSIONS FUEL EMULSION COMPRISING FISCHER- ROPSCH DERIVED HYDROCARBON
FIELD OF INVENTION
[0001] The present invention relates to an improved fuel which has reduced paiticulate matter emission characteristics. More particularly the invention is directed to fuels that are in the form of hydrocarbon-in- water emulsions.
BACKGROUND OF The INVENTION
[0002] Hydrocarbon-in-water emulsions have many potential uses, such as in internal combustion engines and as a fuel for heating purposes. Indeed, various studies have suggested that burning hydrocarbon-in-water emulsions has the advantage of lowering the nitrogen oxide emissions normally associated witli burning hydrocarbons. Emulsions are believed to reduce nitrogen oxide (NOχ) emissions by lowering the peak flame temperature during their combustion. A lower flame temperature, however, often is associated with an increase in the emission of paiticulate matter (Pm). This phenomenon, known as the Pm-NOx trade off, is believed to limit the improvements one can make to diesel emissions.
[0003] In recent years there has been a tendency for more stringent emission regulations, including paiticulate emissions. Therefore, an object of the present invention is to develop a method of more effectively controlling paiticulate emissions without adversely impacting presently achievable reduced nitrogen oxide emission levels demonstrated for emulsified fuels.
[0004] In the instance of diesel fueled engines, the reduction of paiticulate emissions is particularly important. Consequently, another object of the inven- tion is to provide an improved diesel fuel having reduced paiticulate matter emission characteristics.
SUMMARY OF INVENTION
[0005] In accordance with the invention reduced paiticulate matter emissions are achieved with an emulsion of a hydiocaibon and water in which the hydrocarbon is a Fischer-Tropsch (FT) derived hydiocaibon fuel or a mixture of a FT fuel and a conventional hydiocaibon fuel and in which emulsion a major poition of the hydrocarbon has particle sizes of 1 micron or less. Preferably, the emulsion is a hydrocarbon-in-water emulsion.
[0006] In a particularly preferred embodiment of the invention the hydiocaibon is a FT derived hydiocaibon boiling in the diesel fuel range.
[0007] These and otlier embodiments will become appaient upon a reading of the detailed description of the invention which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Figure 1 is a diagiammatic iUustiation of one aiiangement of multiple static mixers used to prepare an emulsion according to the invention.
[0009] Figures 2 and 3 graphically compare the performance of an emulsion of the invention with two non-emulsified fuels in a diesel engine without timing adjustments.
[0010] Figures 4 and 5 graphically compare the performance of the fuels of Figures 2 and 3 with timing adjustment. DETAILED DESCRIPTION OF THE INVENTION
[0011] The emulsions of the present invention contain as the hydiocaibon, a Fischer-Tropsch derived hydrocarbon fuel or a mixture of a FT fuel and a conventional hydrocarbon fuel. Preferably, the hydrocarbon is a FT derived fuel.
[0012] As is well known in the ait the Fischer-Tropsch process involves the reaction of a hydrogen and carbon monoxide containing feed in the presence of a suitable catalyst to produce a largely normal paraffin synthetic crude. The process is described, for example, in U.S. Patents 5,348,982 and 5,545,674, and suitable catalysts in U.S. Patent 4,568,663, each of which is incorporated herein by reference.
[0013] The hydiocaibon fuels produced in the Fischer-Tropsch process may be separated from the product cmde by standard distillation techniques. Additionally, however, the waxy component of the cmde may be converted into fuels by known teclmiques such as hydrotreating, hydroisomerization and hydrocrack- ing. An example of one such process can be found in U.S. 5,378,348, which is incorporated herein by reference.
[0014] In the context of the embodiments of the present invention the Fischer-Tropsch derived hydrocarbon fuel may comprise either the direct liquid product (C5+) from the Fischer-Tropsch process, a converted Fischer-Tropsch product, or a blend of the foregoing. Thus, Fischer-Tropsch products boiling in the range of from about 25 °C to about 450°C are suitable. Such fuels include that disclosed in U.S. 5,807,413 which patent is incorporated herein by reference. Also included are more convention Fischer-Tropsch products such as those boiling, in the range of about 140°C to about 370°C and preferably in the range of about 160°C to about 350°C. [0015] The water of the emulsion of the invention may be that typically used in foiming fuel emulsions such as tap water, distilled or deionized water. In one embodiment, water from the Fischer-Tropsch process constitutes the continuous phase of the emulsion. Fischer-Tropsch process water typically contains about < 2 wt% of oxygenates. A typical composition is shown in Table 1 below:
TABLE 1 Oxygenates Amount
C1-C12 alcohols 0.05 - 2 wt%
C2-C6 acids 0 - 50 wppm
C2-C6 ketones- aldehydes, acetates 0 - 50 wppm other 0 - 500 wppm
[0016] The amount of water used in fomiing the emulsion may be vaiied over a wide range. For example, the volume ratio of Fischer-Tropsch hydrocarbon fuel to water may range from about 95:5 to about 60:40.
[0017] The emulsions of the present invention also include a nonionic surfactant or mixture of nonionic surfactants. The type of nonionic surfactants suitable include ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated carboxylic esters, glycerol esters, sorbital esters and the like. In general, the nonionic surfactant will have an HLB in the range of 5 to 30 and preferably 8 to 15. Among suitable surfactants ethoxylated alkyl phenols having from about 5 to about 30 and preferably 10 to 15 mole of ethylene oxide groups deserve special mention.
[0018] The amount of surfactant or mixtures thereof in the emulsion will range from about 0.05 wt% to about 5.0 wt% based on the total weight of hydrocarbons and water with 0.05 wt% to about 2 wt% being typical. [0019] The emulsion compositions of the invention may include minor but effective amounts of conventional additives such as emulsions stabilizers, antioxidants and the like. In the case where the fuel is diesel fuel the fuel may also contain conventional quantities of diesel fuel additives such as cetane improvers, detergents, heat stabilizers and the like.
[0020] As is known in the ait emulsions can be formed by any number of procedures. Central to all of these is providing sufficient shearing of the components to cause emulsification. In the practice of the present invention the fuel is added to a mixture of water and surfactant and sheared under conditions sufficient to produce hydiocaibon paiticles of predominantly 1 micron in size or less. Stated differently, the particles are substantially uniform in size, i.e., greater than 50% are in the range of about 0.1 to about 1.0 microns in size. Experience has shown that extensive shearing results in the formation of a "gel" and consequently the shearing will be less than that which would produce a gel.
[0021] To achieve the requisite shearing it is particularly prefened to employ one or more static mixtures such as those described in U.S. Patents 5,405,439; 5,236,624; and 4,832,747. In general more than one mixer will be used and the mixers will not be of the same size (length, diameter, number of internal elements). Rather the number, size and elements are selected to adjust mixing efficiency and emulsion particle size. In the practice of the present invention a combination of static mixtures is selected to provide sufficient shearing of the hydrocarbon and water to produce an emulsion having particle sizes predominantly 1 micron or less and less shearing than that which would produce a "gel".
[0022] A diagiammatic illustration of one arrangement of static mixers suitable for carrying out the emulsification of this invention is shown in the accompanying Figure. As shown, each of the six mixers have different dimen- sions. Obviously, different members and sizes of mixers may be used so long as the requisite shearing is achieved. The dimensions of tlie illustrated mixers are given in Table 2 below.
TABLE 2
Mixer Length, inches Diameter, inches
1 12 1/2
2 6 1/2
3 4 1/4
4 4 1/4
5 6 3/16
6 4 3/16
[0023] In the arrangement shown in tl e Figure, a water and surfactant solution is fed to the mixer 1 via line 7 and tlie Fischer-Tropsch derived hydrocarbon fuel via line 8. The product of each mixer is sequentially fed to tlie next mixer in the series, e.g., the product of mixer 1 is fed to mixer 2; tlie product of mixer 2 is fed to mixer 3 and so on. The emulsion exiting mixer 6 via line 9 has a particle size predominantly less than 1 micron. The emulsion in the instance where the Fisher-Tropsch fuel is a diesel fuel, has a viscosity in the range of about 50 to 200 mm2/sec at 20°C.
EXAMPLES
COMPARATIVE EXAMPLE I
[0024] 3000 gms of a non-ionic surfactant (an ethoxylated nonyl phenol having 10 mols of ethylene oxide groups) was added to 9700 gms of water and fed through mixers 1 to 4 shown in tl e Figure. A Fischer-Tropsch diesel fuel (boiling range ~40°C to 300°C) comprising 90+% of C to C linear paraffins was also fed with tl e water and surfactant through tlie four mixers. The volume ratio of fuel to water was 70:30. The hydrocarbon flow rate was 2650 ml/min. and the water surfactant solution flow rate was 1380 ml/min. The temperature was 24°C. The product of mixer 4 was not a hydrocarbon-in-water emulsion.
EXAMPLE 1
[0025] The same ingredients and amounts described in Comparative Example 1 were fed throug mixers 1 to 6 shown in the Figure. The flow rate and temperature was the same as in Comparative Example 1. In this instance the product of mixer 6 was hydrocarbon-in-water emulsion having a density of
0.82 gm/cc and a viscosity of 150 mm^/sec at 20°C. The hydrocarbon paiticles averaged 0.7 microns with 95% below 1 micron in size. This emulsion was shelf stable for more than 6 months.
EXAMPLE 2
[0026] The perfomiance of tl e emulsified Fischer-Tropsch fuel of Example 1 was compared to tl e same but not emulsified Fischer-Tropsch diesel fuel and to Swedish Class 1 Diesel fuel using a Catapillar 1 Y 540 single cylinder heavy duty Research engine. Two conditions were measured, low load (1500 lpm, 60 Nn torque and 3.0 bar BMEP and medium load (1500 lpm, 110 Nm torques and 5.5 bar BMEP.
[0027] As is known Swedish Class 1 Diesel fuel (also called Urban Diesel ECI) is a standard low emissions reference diesel fuel that produces about 10% to 20% lower NOx and 40% to 50% lower paiticulate matter (Pm) than conventional diesel fuel. The specification for Swedish Class 1 diesel fuel are given in Table 3. TABLE 3
Cetane > 50 Cloud Point
Summer 0°C
Winter - 16°C Density, kg/m" 800 - 820 IBP, °C 180 T95, °C 285 maximum
Viscosity at 40°C, mm2/second 1.2 to 4.0 Sulfur, ppm 10 maximum AiOmatics, vol% 5 maximum Poly aromatics not detectable
[0028] The unemulsified Fischer-Tropsch fuel (FTF) has been shown to have excellent emissions performance (see U.S. 5,807,413) with NOx reductions of
10-25%) and Pm reductions of 40-60% compared with conventional diesel fuels. Figures 2 and 3 show the relative emissions performance of the Fischer-Tropsch fuel and an emulsion of the invention (Example 1) vs. Swedish Class I Diesel fuel at low and medium load.
[0029] As can be seen in Figure 2, tl e FTF exhibits similar behavior to Swedish Class I Diesel Fuel whereas the a fuel emulsion of tlie invention shows NOx emissions 22% below Swedish Class 1 and Pm 53% below.
[0030] In Figure 3 a fuel emulsion of tl e invention shows even larger PM reduction (91.5%) than Swedish Class 1 fuel.
[0031] In Figures 4 and 5 tl e Pm/NOx performance of the fuels is plotted against change in spark timing. As can be seen in the case of the FTF and Swedish claim 1 fuels one can retard the timing to lower the NOx emissions.

Claims

CLAIMS:
1. A method for reducing paiticulate emissions during combustion of a hydrocarbon fuel which comprises combusting an emulsion of a hydiOcarbon fuel and water wherein the fuel is a Fischer-Tropsch (FT) derived hydiocaibon as a mixture of a FT fuel and a conventional fuel, and in which emulsion, a major poition of tl e hydiocaibon has particle sizes of 1 micron or less.
2. The method of claim 1 wherein the emulsion is a hydrocarbon- in-water emulsion.
3. The method of claim 2 wherein the fuel is a FT derived fuel.
4. The method of claim 3 wherein greater than 50% of the hydrocarbon paiticles are in tl e range of about 0.1 to about 1.0 microns in size.
5. The method of claim 4 wherein tl e volume ratio of hydrocarbon to water is in the range of 95:5 to 60:40.
6. The method of claim 5 wherein greater than 80% of tlie hydrocarbon paiticles are in tlie range of about 0.1 to about 1.0 microns in size.
7. The method of claim 6 wherein the Fischer-Tropsch derived hydrocarbon boils in the diesel fuel range.
8. The method of claim 7 wherein tl e emulsion has a viscosity in the range of about 50 to 200 mm2/sec.
9. A method for forming a fuel in water emulsion which when combusted has reduced paiticulate matter emissions compared with Swedish Class I Diesel Fuel comprising sheaiing a Fischer-Tropsch derived hydiocai'bon boiling in the diesel fuel range and water in the volume ratio of hydrocarbon to water of 95:5 to 40:60 and about 0.05 to about 5.0 wt% based on the weight of hydrocarbon and water with a non-ionic surfactant or mixtures thereof having a HLB of about 5 to about 30 under sheaiing conditions sufficient to produce a liquid emulsion in which a major poition of the hydiocaibon has paiticle sizes of 1 micron or less.
10. A liquid fuel composition comprising an emulsion of FT derived fuel in water wherein the fuel in the emulsion has fuel paiticle sizes predominately of 1 micron or less and tlie emulsion has a viscosity of above about 50 mm2/sec at 20°C.
11. The composition of claim 10 wherein greater than 50%) of the fuel paiticles has paiticle sizes in the range of about 0.1 to about 1.0 microns.
12. The composition of claim 11 wherein the Fischer-Tropsch derived fuel boils in the diesel fuel range.
EP03709019A 2002-03-01 2003-02-07 Low emissions fuel emulsion comprising fischer-tropsch derived hydrocarbon Expired - Lifetime EP1481042B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US86775 1979-10-22
US10/086,775 US20030163946A1 (en) 2002-03-01 2002-03-01 Low emissions fuel emulsion
PCT/US2003/003850 WO2003074638A1 (en) 2002-03-01 2003-02-07 Low emissions fuel emulsion comprising fischer-tropsch derived hydrocarbon

Publications (2)

Publication Number Publication Date
EP1481042A1 true EP1481042A1 (en) 2004-12-01
EP1481042B1 EP1481042B1 (en) 2012-01-18

Family

ID=27787511

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03709019A Expired - Lifetime EP1481042B1 (en) 2002-03-01 2003-02-07 Low emissions fuel emulsion comprising fischer-tropsch derived hydrocarbon

Country Status (13)

Country Link
US (1) US20030163946A1 (en)
EP (1) EP1481042B1 (en)
JP (1) JP4518798B2 (en)
KR (1) KR20040106282A (en)
CN (1) CN100526441C (en)
AT (1) ATE541916T1 (en)
AU (1) AU2003212975B2 (en)
BR (1) BR0307567A (en)
CA (3) CA2702107A1 (en)
MY (1) MY142387A (en)
TW (1) TWI282816B (en)
WO (1) WO2003074638A1 (en)
ZA (1) ZA200406035B (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR043292A1 (en) * 2002-04-25 2005-07-27 Shell Int Research USE OF FISCHER-TROPSCH GASOIL AND A COMBUSTIBLE COMPOSITION CONTAINING IT
CN1856562B (en) * 2003-09-03 2010-06-23 国际壳牌研究有限公司 Fuel composition, method for producing same and use thereof
WO2005021688A1 (en) * 2003-09-03 2005-03-10 Shell Internationale Research Maatschappij B.V. Fuel compositions comprising fischer-tropsch derived fuel
US20060156620A1 (en) * 2004-12-23 2006-07-20 Clayton Christopher W Fuels for compression-ignition engines
CA2650333A1 (en) * 2006-04-27 2007-11-08 New Generation Biofuels, Inc. Biofuel composition and method of producing a biofuel
NL1033989C2 (en) * 2007-06-14 2008-12-16 Hendrik Loggers Engine fuel, comprises emulsified mixture of mineral fuels, optional plant oil and emulsifier
NL1035106C2 (en) 2008-02-29 2009-09-01 Hendrik Loggers Water applying method for replacing part of e.g. normal fuel, involves feeding water into cylinder of engine, and injecting fuel into cylinder, where water is heated due to combustion of fuel to produce water vapor
JP5095517B2 (en) * 2008-06-19 2012-12-12 独立行政法人科学技術振興機構 Aluminum-containing zinc oxide n-type thermoelectric conversion material
WO2020159350A2 (en) * 2019-02-01 2020-08-06 Treviño Quintanilla Sergio Antonio Process for the production of an improved diesel fuel

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6302929B1 (en) * 1994-04-04 2001-10-16 Rudolf W. Gunnerman Aqueous fuel for internal combustion engine and method of preparing
AUPO841197A0 (en) * 1997-08-05 1997-08-28 Apace Research Limited Heat stable emulsions
US6325833B1 (en) * 1997-09-12 2001-12-04 Exxon Research And Engineering Company Emulsion blends
MY118600A (en) * 1997-09-12 2004-12-31 Exxon Research Engineering Co Water emulsions of fischer-tropsch liquids
US7276093B1 (en) * 2000-05-05 2007-10-02 Inievep, S.A. Water in hydrocarbon emulsion useful as low emission fuel and method for forming same
AU2002360596A1 (en) * 2001-12-17 2003-07-24 Exxonmobil Upstream Research Company Solids-stabilized oil-in-water emulsion and a method for preparing same
US7081143B2 (en) * 2002-01-25 2006-07-25 Exxonmobil Research And Engineering Company Alkoxylated triazine emulsion compositions for fuel cell reformer start-up

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03074638A1 *

Also Published As

Publication number Publication date
MY142387A (en) 2010-11-30
JP2005519165A (en) 2005-06-30
JP4518798B2 (en) 2010-08-04
BR0307567A (en) 2005-04-26
CN1639309A (en) 2005-07-13
TW200303917A (en) 2003-09-16
CA2702107A1 (en) 2003-09-12
CA2482339C (en) 2011-01-25
WO2003074638A1 (en) 2003-09-12
CA2702115A1 (en) 2003-09-12
EP1481042B1 (en) 2012-01-18
KR20040106282A (en) 2004-12-17
CN100526441C (en) 2009-08-12
ZA200406035B (en) 2006-05-31
US20030163946A1 (en) 2003-09-04
TWI282816B (en) 2007-06-21
AU2003212975B2 (en) 2008-06-05
CA2482339A1 (en) 2003-09-12
ATE541916T1 (en) 2012-02-15
AU2003212975A1 (en) 2003-09-16

Similar Documents

Publication Publication Date Title
ZA200406036B (en) Catalytic cracking process
CN1745163B (en) watered fuel composition
US8361170B2 (en) Uses of emulsifying agents
UA56158C2 (en) Fuel emulsion, fuel addition, method of the fuel emulsion producing, device for its implementation
US7229481B2 (en) Diesel fuel compositions
CA2708437A1 (en) Emulsification dispersants, a method for emulsification and dispersion using the emulsification dispersants, emulsions, and emulsion fuels
WO1993005127A1 (en) Reducing nitrogen oxides emissions by dual fuel firing of a turbine
AU2003212975B2 (en) Low emissions fuel emulsion comprising Fischer-Tropsch derived hydrocarbon
US20020040546A1 (en) Cloud point depressants for middle distiliate fuels
US5259851A (en) Hybrid liquid fuel composition in aqueous microemulsion form
JP4870905B2 (en) Diesel fuel emulsion
AU2002330733B2 (en) Surfactant composition including ethoxylate of CNSL
CA2120241A1 (en) Emulsification system for light fuel oil emulsions
CA2492968A1 (en) Emulsified water/hydrocarbon fuel, preparation and uses thereof
WO2002092731A1 (en) Compositions for non-polluting fuels, preparation processes and use thereof
EP0194365B1 (en) Emulsions
WO2020124034A1 (en) Fuel compositions
US20030163952A1 (en) Compositions
US20030041507A1 (en) Water-in-oil emulsion fuel
JPH06271874A (en) Diesel light oil composition
CA1275022A (en) Emulsions
EP2145940A1 (en) Use and vehicle
WO2003016439A1 (en) Water-in-oil emulsion fuel
AU5798201A (en) A water-in-oil emulsion fuel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040928

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1072069

Country of ref document: HK

17Q First examination report despatched

Effective date: 20060721

17Q First examination report despatched

Effective date: 20060721

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1072069

Country of ref document: HK

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Ref country code: AT

Ref legal event code: REF

Ref document number: 541916

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60339746

Country of ref document: DE

Effective date: 20120315

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120418

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120518

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120419

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 541916

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120229

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120229

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120229

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20121031

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

26N No opposition filed

Effective date: 20121019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120319

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120207

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60339746

Country of ref document: DE

Effective date: 20121019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030207

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20200115

Year of fee payment: 18

Ref country code: GB

Payment date: 20200130

Year of fee payment: 18

Ref country code: NL

Payment date: 20200130

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60339746

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210207

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20210301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210901

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210207