US20090000185A1 - Aviation-grade kerosene from independently produced blendstocks - Google Patents

Aviation-grade kerosene from independently produced blendstocks Download PDF

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US20090000185A1
US20090000185A1 US12/147,783 US14778308A US2009000185A1 US 20090000185 A1 US20090000185 A1 US 20090000185A1 US 14778308 A US14778308 A US 14778308A US 2009000185 A1 US2009000185 A1 US 2009000185A1
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blendstock
vol
kerosene
derived
aviation
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Ted R. Aulich
Ron C. Timpe
Chad A. Wocken
Carsten Heide
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Energy and Environmental Research Center Foundation
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Priority to US12/147,783 priority Critical patent/US20090000185A1/en
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Assigned to ENERGY & ENVIRONMENTAL RESEARCH CENTER FOUNDATION reassignment ENERGY & ENVIRONMENTAL RESEARCH CENTER FOUNDATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HEIDE, CARSTEN, AULICH, TED R., TIMPE, RONALD C., WOCKEN, CHAD A.
Priority to US12/950,795 priority patent/US20110061290A1/en
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1025—Natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates generally to aviation-grade high-cetane kerosene fuel. More particularly, herein disclosed is an aviation-grade kerosene fuel produced in part or fully from non-petroleum feedstocks. Specifically, the disclosed kerosene fuel comprises at least two independently produced blendstocks, with the first blendstock comprising primarily isoparaffins and normal paraffins (I/N) derived from non-petroleum feedstocks and the second blendstock comprising primarily cycloalkanes and aromatics (C/A) derived from petroleum or non-petroleum feedstocks.
  • I/N isoparaffins and normal paraffins
  • C/A cycloalkanes and aromatics
  • a kerosene fuel suitable for use as aviation turbine fuel having drop-in and fit-for-purpose compatibility with conventional petroleum-derived fuels comprises up to 95 volume % (vol. %) I/N blendstock and up to 35 vol. % C/A blendstock.
  • Kerosene is used to describe the fraction of crude petroleum that boils approximately in the range of 293° F. to 572° F. (145° C. to 300° C.) and consists of hydrocarbons primarily in the range of C 8 -C 16 .
  • Kerosenes are the lighter end of a group of petroleum substances known as middle distillates.
  • Jet A and Jet A-1 are kerosene-type fuels.
  • the primary physical difference between Jet A and Jet A-1 is freeze point (the temperature at which wax crystals disappear in a laboratory test). Jet A, which is mainly used in the United States, must have a freeze point of ⁇ 40° C or below, while Jet A-1 must have a freeze point of ⁇ 47° C. or below. Jet A does not normally contain a static dissipater additive, while Jet A-1 often requires this additive.
  • ASTM D1655 and Def Stan 91-91/5 standards are additional differences between the two fuels, and full specifications are outlined under the ASTM D1655 and Def Stan 91-91/5 standards, respectively.
  • JP-5 and JP-8 are defined by Mil-DTL-5624 and Mil-DTL-83133, respectively. These fuels are kerosene-type fuels made to more exacting specifications than the commercial jet fuels. They also contain unique performance enhancing additives. Throughout the world, many governments have issued a variety of standards such as for TS-1 premium kerosene, TS-1 regular kerosene, and T-1 regular kerosene in Russia. The crude oil fraction for all of these aviation-grade kerosenes is basically limited to the range of 300° F. to 500° F. (149° C. to 260° C.), with additional specifications based on recovery rates at given temperature points. Hydrocarbons are primarily in the range of C 8 -C 16 .
  • U.S. Pat. No. 4,645,585 discloses the production of novel fuel blends from hydroprocessing highly aromatic heavy oils such as those derived from coal pyrolysis and coal hydrogenation.
  • International Patent WO 2005/001002 A2 relates to a distillate fuel comprising a stable, low-sulfur, highly paraffinic, moderately unsaturated distillate fuel blendstock.
  • the highly paraffinic, moderately unsaturated distillate fuel blendstock is prepared from a Fischer-Tropsch-derived product that is hydroprocessed under conditions during which a moderate amount of unsaturates are formed or retained to improve stability of the product.
  • Violi et al. An attempt for better modeling of the variety of different hydrocarbon constituents was made by Violi et al. (Violi, A.; Yan, S.; Eddings, E. G.; Sarofim, A. F.; Granata, S.; Faravelli, T.; Ranzi, E.; Combust. Sci. Technol. 2002, 174 (11-12) 399-417). Violi et al.
  • JP-8 modeled JP-8 as a six-compound blend of well-known hydrocarbons with the following molar composition: 10% iso-octane (C 8 H 18 ), 20% methylcyclohexane (C 7 H 14 ), 15% m-xylene (C 8 H 10 ), 30% normal-dodecane (C 12 H 26 ), 5% tetralin (C 10 H 12 ), and 20% tetradecane (C 14 H 30 ).
  • This surrogate blend simulates the volatility and smoke point of a practical JP-8 fuel.
  • this method of reducing the fuel to a mere six-compound blend does not reproduce all required performance specifications of JP-8.
  • aviation-grade kerosene comprising: a first blendstock derived from non-petroleum feedstock and comprising primarily hydrocarbons selected from the group consisting of isoparaffins and normal paraffins, and a second blendstock comprising primarily hydrocarbons selected from the group consisting of cycloalkanes and aromatics.
  • the second blendstock is derived from feedstock comprising non-petroleum feedstock. It is desirable for the aviation-grade kerosene is capable of being blended with petroleum-derived jet fuel in any proportion such that the resulting blend meets fuel grade specification of the petroleum-derived jet fuel.
  • the aviation-grade kerosene comprises up to 95 vol. % of first blendstock and up to 35 vol. % of second blendstock.
  • the aviation-grade kerosene comprises up to 95 vol. % first blendstock, from about 0 vol. % to about 30 vol. % cycloalkanes, and from about 0 vol. % to about 15 vol. % aromatics.
  • this kerosene comprising up to 95 vol. % first blendstock, from about 0 vol. % to about 30 vol. % cycloalkanes, and from about 0 vol. % to about 15 vol. % aromatics meets fit-for-purpose requirements.
  • at least 50 weight % of the kerosene is derived from coal, natural gas, or a combination thereof.
  • the second blendstock is derived from coal, biomass, oil-shale, tar, oil sands, or a combination thereof.
  • at least 50 weight % of the kerosene is derived from biomass.
  • at least 10 weight % of the kerosene is derived from non-cracked bio-oil.
  • Also disclosed herein is a method for the production of aviation-grade kerosene comprising: producing a first blendstock from at least one non-petroleum feedstock, the first blendstock comprising primarily hydrocarbons selected from the group consisting of isoparaffins and normal paraffins; producing a second blendstock comprising primarily hydrocarbons selected from the group consisting of cycloalkanes and aromatics; and blending at least a portion of the first blendstock with at least a portion of the second blendstock to produce aviation-grade kerosene.
  • first and second blendstocks are independently-produced.
  • the non-petroleum feedstock is selected from the group consisting of coal, natural gas, biomass, vegetable oils, biomass pyrolysis bio-oils, biologically-derived oils and combinations thereof.
  • first blendstock is produced via indirect liquefaction.
  • Indirect liquefaction may comprise Fischer-Tropsch processing of a feedstock selected from the group consisting of natural gas, coal, biomass, and combinations thereof.
  • the kerosene may comprise up to about 90 vol. % first blendstock produced via indirect liquefaction.
  • the at least one non-petroleum feedstock comprises triglyceride and/or fatty acid feedstock.
  • the kerosene may comprise from about 65 vol. % to about 75 vol. % of first blendstock, the at least one non-petroleum feedstock for which comprises triglyceride and/or fatty acid feedstock.
  • second blendstock is produced by catalytic cyclization and/or reforming of a portion of first blendstock, the at least one non-petroleum feedstock for which comprises triglyceride and/or fatty acid feedstock.
  • the kerosene may comprise about 65 vol.
  • first blendstock the at least one non-petroleum feedstock for which comprises triglyceride and/or fatty acid feedstock; and about 35 vol. % second blendstock produced by catalytic cyclization and/or reforming of a portion of first blendstock.
  • the kerosene comprises about 70 vol. % first blendstock produced via catalytic processing of triglyceride and/or fatty acid feedstock and about 30 vol. % second blendstock produced via pyrolysis processing of high cycloalkane-content material.
  • second blendstock is produced via pyrolysis of a feedstock selected from the group consisting of coal, oil shale, oil sands, tar, biomass, and combinations thereof.
  • the kerosene may comprise about 80 vol. % first blendstock produced via Fischer-Tropsch processing of natural gas, coal, and/or biomass and about 20 vol. % second blendstock produced via pyrolysis processing of coal tar fraction.
  • the second blendstock is produced via direct liquefaction.
  • the kerosene comprises about 25 vol. % second blendstock produced via direct liquefaction.
  • the kerosene further comprises about 75 vol. % first blendstock derived from Fischer-Tropsch processing of natural gas, coal, and/or biomass.
  • second blendstock is produced from a biomass-derived lignin feedstock.
  • the kerosene may comprise from about 25 vol. % to about 30 vol. % second blendstock produced from a biomass-derived lignin feedstock.
  • the kerosene comprises about 30 vol. % second blendstock produced via pyrolysis processing of biomass-derived lignin and about 70 vol. % first blendstock produced via Fischer-Tropsch processing of natural gas, coal, and/or biomass.
  • the kerosene comprises about 25 vol. % second blendstock produced from a biomass-derived lignin feedstock and about 75 vol. % first blendstock derived from catalytic processing of triglyceride feedstock.
  • the method further comprises testing the aviation grade kerosene for at least one requirement selected from the group consisting of fit-for-purpose requirements, ASTM requirements, and combinations thereof.
  • the method further comprises adjusting the ratio of first blendstock and second blendstock in the kerosene to meet at least one requirement selected from the group consisting of fit-for-purpose requirements, ASTM requirements, and combinations thereof.
  • the method further comprises adjusting the amount of cycloalkanes and aromatics in the second blendstock to meet at least one requirement selected from the group consisting of fit-for-purpose requirements, ASTM requirements, and combinations thereof.
  • FIG. 1 is a schematic of an indirect liquefaction process suitable for producing isoparaffin/n-paraffin (I/N) blendstock according to an embodiment of the present disclosure.
  • FIG. 2 is a schematic of a pyrolysis process suitable for producing cycloalkane/aromatic (C/A) blendstock according to an embodiment of the present disclosure.
  • FIG. 3 is a schematic of a direct liquefaction process suitable for producing cycloalkane/aromatic (C/A) blendstock according to an embodiment of the present disclosure.
  • FIG. 4 is a comparison of gas chromatography data from FT (FT derived liquid fuel from natural gas—bottom) and Fuel Sample A (top) produced from two discrete blendstocks and technological process: (1) an isoparaffinic kerosene (IPK) produced from FT technology and natural gas feedstock and (2) an aromatic/cycloparaffinic blendstock produced from petroleum feedstock.
  • IPK isoparaffinic kerosene
  • FIG. 5 is a comparison of gas chromatography data from typical JP-8 (bottom) and Fuel Sample C (top) produced from two discrete blendstocks and technological process: (1) an isoparaffinic kerosene (IPK) produced from a crop oil feedstock and (2) an aromatic/cycloparaffinic blendstock produced from a crop oil feedstock.
  • IPK isoparaffinic kerosene
  • I/N blendstock refers to a material that comprises at least 95 weight % of isoparaffins, normal paraffins, or a mixture thereof.
  • C/A blendstock refers to a material that comprises at least 95 weight % of cycloalkanes, aromatics, or a mixture thereof.
  • kerosene-type fuels that are specified by military turbine fuel grades such as JP-5 and JP-8 and defined by Mil-DTL-5624 and Mil-DTL-83133, respectively, or civilian aviation jet fuels such as Jet A or Jet A-1 with full specifications outlined under the ASTM D1655 and Def Stan 91-91/5 standards, respectively.
  • military turbine fuel grades such as JP-5 and JP-8 and defined by Mil-DTL-5624 and Mil-DTL-83133, respectively
  • civilian aviation jet fuels such as Jet A or Jet A-1 with full specifications outlined under the ASTM D1655 and Def Stan 91-91/5 standards, respectively.
  • fit-for-purpose requirements refers to fuel property requirements that are not necessarily addressed by military or ASTM standards, but are still important to fuel performance and stability in jet engines and during fuel handling, distribution, and storage.
  • fit-for-purpose requirements include fuel compatibility with aircraft fuel and engine system materials of construction, adequate fuel performance in compression ignition (versus turbine) engines in a wide variety of ground environments, and possible fuel performance requirements related to swelling of elastomeric seals in, for example, turbine engines.
  • drop-in compatibility refers to aviation-grade kerosene capable of being blended with petroleum-derived jet fuel in any proportion (i.e. from 0% to 100%) such that the resulting blend meets fuel grade specification and fit-for-purpose requirements of the equivalent petroleum-based jet fuel.
  • I/N-C/A fuel refers to aviation-grade kerosene derived from at least two independently produced blendstocks, with a first I/N blendstock derived from non-petroleum feedstocks and a second C/A blendstock derived from petroleum or non-petroleum feedstocks.
  • the disclosed I/N-C/A fuel comprises a blend of fuel components, namely straight-chain (normal) and branched (iso-) paraffins, cycloalkanes, and/or aromatics.
  • the aviation-grade kerosene herein disclosed is produced from at least two independently-produced blendstocks, with a first blendstock comprising primarily hydrocarbons selected from the group consisting of isoparaffins and normal paraffins (I/N) and derived from non-petroleum feedstocks and a second blendstock comprising primarily hydrocarbons selected from the group consisting of cycloalkanes and aromatics (C/A) and derived from petroleum or non-petroleum feedstocks.
  • the finished I/N-C/A jet fuel comprises up to 95 volume % (vol. %) I/N blendstock and up to 35 (vol. %) C/A blendstock.
  • Petroleum-based kerosene may be obtained either from the atmospheric distillation of crude oil (“straight-run” kerosene) or from cracking of heavier petroleum streams (“cracked” kerosene).
  • the kerosene is further treated by a variety of processes to remove or reduce the level of undesirable components, e.g., aromatic hydrocarbons, sulfur, nitrogen, or olefinic materials. This additional processing also reduces compositional variation and enriches components that improve performance (cycloalkanes and isoparaffins, for example).
  • hydrodesulfurization treatment with hydrogen to remove sulfur components
  • washing with caustic soda solution to remove sulfur components
  • hydrogenation to remove, for example, olefins, sulfur, metals, and/or nitrogen components.
  • Aromatics that may have formed during the cracking process are removed via solvent extraction.
  • hydrodesulfurized kerosene is obtained by treating a kerosene-range petroleum stock with hydrogen to convert organic sulfur to hydrogen sulfide, which is then removed. These subsequent treatments may blur the distinction between straight-run and cracked kerosenes.
  • kerosenes While kerosenes are essentially similar in composition, the precise composition of a specific kerosene-range refinery stream depends on the crude oil from which the kerosene was derived and on the refinery processes used for its production. Because they are complex hydrocarbon mixtures, materials in this category are typically not defined by detailed compositional data but instead by process history, physical properties, and product-use ASTM and similar specifications.
  • compositional information for the streams in this category is limited.
  • major components of kerosenes comprise branched and straight-chain paraffins (iso- and normal or n-alkanes) and naphthenes (cycloparaffins or cycloalkanes), which normally account for at least 75 vol. % of a finished fuel.
  • Aromatic hydrocarbons in this boiling range such as alkylbenzenes (single ring) and alkylnaphthalenes (double ring) do not normally exceed 25 vol.
  • % of a kerosene product Olefins are usually not present at more than 5% by volume.
  • the distillation range of kerosenes is such that benzene (80° C. boiling point) and normal-hexane (69° C. boiling point) concentrations are generally less than 0.01% by mass.
  • the boiling points of the 3-7 fused-ring polycyclic aromatic compounds (PACs) are well above the boiling range of straight-run kerosene streams. Consequently, the concentrations of PACs found in kerosenes are very low, if not below the limits of detection of the available analytical methods.
  • a detailed analysis of a hydrodesulfurized kerosene illustrates this and is presented as Table 2.
  • the herein disclosed I/N-C/A blend fuel comprises at least one I/N blendstock comprising primarily hydrocarbons selected from the group consisting of isoparaffins and normal paraffins, the hydrocarbons derived from non-petroleum feedstock.
  • the finished I/N-C/A jet fuel comprises up to 95 vol. % of I/N blendstock.
  • I/N blendstock comprises isoparaffin and/or normal paraffin compounds containing primarily from eight to sixteen carbon atoms per molecule (C8 to C16 compounds). In embodiments, these compounds are produced directly via a chemical process such as, but not limited to, Fischer-Tropsch condensation of syngas, thermocatalytic processing of vegetable oils, pyrolysis, liquefaction, and gas-to-liquids processing.
  • I/N blendstock is derived from one or a combination of the following feedstocks: natural gas, coal, biomass, vegetable oils, biomass pyrolysis bio-oils, and other biologically-derived oils.
  • I/N blendstock can be produced by several routes.
  • indirect liquefaction is used to produce I/N blendstock.
  • Indirect liquefaction feedstock, such as coal or biomass, 10 is gasified in gasifier 40 with steam 20 and/or oil 30 .
  • Gasifier effluent 50 may comprise carbon monoxide, hydrogen, carbon dioxide, hydrogen sulfide, and/or ammonia.
  • Gasifier effluent 50 is purified and upgraded in step 60 , whereby a contaminant stream(s) 70 comprising, for example, hydrogen sulfide, ammonia, and/or carbon dioxide is removed.
  • Syngas stream 80 comprising primarily CO and H 2 , undergoes liquefaction 90 to yield liquid products 100 .
  • liquid products 100 are synthesized from syngas 80 by catalytic Fischer-Tropsch (F-T) processing.
  • F-T catalytic Fischer-Tropsch
  • the Fischer-Tropsch reactions produce a wide spectrum of oxygenated compounds, in particular, alcohols and paraffins ranging in carbon numbers from C 1 -C 3 (gases) to C 35+ (solid waxes).
  • Fischer-Tropsch products yield distillate fuels that comprise C 8 -C 16 paraffins and, through isomerization, C8-C 16 isoparaffins that have excellent cetane numbers and very low sulfur and aromatic content. These properties make F-T products suitable for use as I/N blendstock.
  • Fischer-Tropsch distillate fuels are typically unable to meet all military and ASTM specifications and fit-for-purpose requirements. Therefore, as described further hereinbelow, I/N blendstock is blended with C/A blendstock to obtain aviation-grade I/N-C/A fuel.
  • I/N-C/A fuel comprises up to 95 vol. % I/N blendstock, alternatively about 90 vol.
  • I/N-C/A fuel comprises about 80 vol. % I/N blendstock derived from Fischer-Tropsch processing of natural gas, coal, and/or biomass. In alternative embodiments, I/N-C/A fuel comprises about 70 vol. % I/N blendstock derived from Fischer-Tropsch processing of natural gas, coal, and/or biomass.
  • I/N blendstock is produced from triglyceride and/or fatty acid feedstocks.
  • I/N blendstock n-paraffins may be produced, for example, via: (1) catalytic triglyceride dissociation into fatty acids and glycerol, (2) glycerol removal, and (3) oxygen removal from fatty acids (e.g., via catalytic decarboxylation and/or reduction) to yield normal paraffins.
  • I/N blendstock isoparaffins may be produced via (4) catalytic isomerization of a portion of these normal paraffins to yield isoparaffins.
  • I/N-C/A fuel comprises from about 65 vol. % to about 95 vol. % I/N blendstock derived from catalytic processing of triglyceride feedstock. In specific embodiments, I/N-C/A fuel comprises about 75 vol. % I/N blendstock derived from catalytic processing of triglyceride feedstock. In alternative embodiments, I/N-C/A fuel comprises about 80 vol. % I/N blendstock derived from catalytic processing of triglyceride feedstock. In alternative embodiments, I/N-C/A fuel comprises about 80 to 90 vol. % I/N blendstock derived from catalytic processing of triglyceride feedstock.
  • I/N blendstock typically has a density below minimum requirements.
  • the I/N blendstock typically has a density below the MIL-DTL-83133-specified minimum requirement of 0.775 kg/L and may be very near to exceeding or may exceed the freeze point maximum requirement of less than ⁇ 47° C.
  • the disclosed I/N-C/A fuel further comprises at least one independently-produced C/A blendstock to obtain required density and cold-flow performance.
  • the C/A blendstock comprises primarily hydrocarbons selected from the group consisting of cycloalkanes and aromatics.
  • the aviation-grade I/N-C/A fuel comprises an appropriate blend of aromatics and cycloalkanes whereby requisite density and freeze point specifications of the resulting high cetane kerosene fuel are met.
  • the hydrocarbons of the C/A blendstock are derived from petroleum feedstocks.
  • the hydrocarbons of the C/A blendstock are derived from non-petroleum feedstocks.
  • the hydrocarbons of the C/A blendstock are derived from a combination of petroleum and non-petroleum feedstocks.
  • the I/N-C/A fuel comprises up to 35 vol. % C/A blendstock.
  • the C/A blendstock comprises aromatics.
  • the C/A blendstock comprises aromatics selected primarily from the group consisting of C9 to C15 aromatics which provide the requisite density.
  • the aromatics are primarily alkylated benzene compounds.
  • aromatics may also contribute to beneficial seal swelling and may provide needed lubricity and viscosity.
  • the C/A blendstock comprises less than about 15 vol. % aromatics. In embodiments, the C/A blendstock comprises from about 0 vol. % to about 15 vol. % aromatics.
  • C/A blendstock comprises cycloalkanes.
  • the C/A blendstock comprises cycloalkanes primarily selected from the group consisting of C9 to C15 cycloalkanes which reduce freeze point (to counteract the freeze point increase resulting from aromatic addition) without adversely decreasing flash point.
  • C/A blendstock comprises less than about 30 vol. % cycloalkane.
  • suitable freezepoint are obtained in the I/N-C/A fuel by selection of aromatics (i.e. having high density and low freezepoint) for the C/A blendstock such that the C/A blendstock comprises 0% cycloalkanes.
  • C/A blendstock comprises from about 0 vol.
  • jet-fuel compliant I/N-C/A fuel comprises up to 95 vol. % of paraffins selected from isoparaffins and normal paraffins, from about 0 vol. % to about 30 vol. % cycloalkanes, and from about 0 vol. % to about 15 vol. % aromatics.
  • I/N-C/A fuel comprises about 95 vol. % I/N blendstock and about 5% high density low freezepoint aromatic.
  • C/A blendstock may be derived from one or a combination of the following feedstocks: petroleum, oil shale, oil sands, natural gas, coal, biomass, vegetable oil, biomass pyrolysis bio-oil, and other biologically-derived oils.
  • aviation-grade I/N-C/A kerosene comprises at least 50 weight % of hydrocarbons selected from cycloalkanes and aromatics, said hydrocarbons derived from coal, biomass, or a combination thereof.
  • FIG. 2 shows an embodiment for the production of C/A blendstock via pyrolysis (heating in a deficiency of oxygen). Pyrolysis may be performed by any method known to one of skill in the art.
  • pyrolysis feedstock 110 undergoes pyrolysis 120 .
  • Suitable pyrolysis feedstock 110 includes, without limitation, coal, oil shale, oil sands, biomass, and combinations thereof. Gases 140 and char/ash/minerals 130 are removed. Pyrolysis oil vapors are condensed, the resulting pyrolysis oil 150 is hydrotreated as is known to those of skill in the art.
  • catalytic hydrotreating is used to reduce the level of at least one contaminant selected from the group consisting of nitrogen, sulfur, oxygen, and metals.
  • pyrolysis oil 150 is treated with hydrogen 180 and the level of sulfur and/or nitrogen in pyrolysis oil 150 is reduced via elimination of gas stream(s) 170 comprising, for example, hydrogen sulfide and/or ammonia.
  • gas stream(s) 170 comprising, for example, hydrogen sulfide and/or ammonia.
  • contaminant-reduced liquid products 190 are obtained. This procedure is similar to the procedure used in upgrading crude oil in a refinery to produce a variety of liquid fuels, as known to those of skill in the art.
  • Table 3 presents a comparison of pyrolyzed coal tar fractions based on typical boiling range and major hydrocarbon constituents.
  • low-temperature tar and light oils formed from sub-bituminous and bituminous coals at temperatures below about 700° C. as relatively fluid, dark brown oils that comprise phenols, pyridines, paraffins, and/or olefins.
  • the oils are heterogeneous, with any one component constituting only a fraction of a percent of the total mass.
  • the lignite tars may also contain up to 10% of paraffin waxes, so the product has a “butter-like consistency” and solidifies at temperatures as high as 6° C. to 8° C.
  • the primary high-temperature tar vapors formed above 700° C. are more homogeneous.
  • the light oils are predominantly benzene, toluene, and xylenes (BTX) and the tars are bitumen-like viscous mixtures that contain high proportions of polycondensed aromatics.
  • BTX xylenes
  • the pyrolysis tars and oils are not suitable final fuel products. Often they are unstable, and when warmed, they polymerize and become more viscous.
  • Ash and mineral matter 130 is removed in pyrolysis 120 , which increases the heating value, but sulfur and nitrogen are not completely removed in pyrolysis 120 .
  • a more stable and useful product is obtained by hydrogenating 160 and removing the sulfur and/or nitrogen from the fuel as hydrogen sulfide and/or ammonia in stream(s) 170 .
  • hydrotreated liquid products 190 may be further refined and upgraded, by any methods known to one of skill in the art, to yield a mix of cycloalkanes and aromatics of which the C/A blendstock is comprised.
  • the I/N-C/A fuel comprises about 20 vol. % C/A blendstock derived from pyrolysis processing of a coal tar fraction. In embodiments, the I/N-C/A fuel comprises about 80 vol. % I/N blendstock derived from Fischer-Tropsch processing of natural gas, coal, and/or biomass, and about 20 vol. % C/A blendstock derived from pyrolysis processing of coal tar fraction. In embodiments, I/N-C/A fuel comprises about 30 vol. % C/A blendstock derived from pyrolysis processing of a high cycloparaffin-content material derived from oil shale or oil sand feedstock. In embodiments, I/N-C/A fuel comprises about 70 vol.
  • % I/N blendstock derived from catalytic processing of triglyceride feedstock and about 30 vol. % C/A blendstock derived from pyrolysis processing of a high cycloparaffin-content material derived from an oil shale or oil sand feedstock.
  • direct liquefaction 220 of liquefaction feedstock 210 is used to produce C/A blendstock.
  • Liquefaction feedstock 210 may comprise, for example, coal and/or biomass.
  • hydroliquefaction coal 210 is mixed with recycled coal oil 230 and, together with hydrogen 240 , fed to high-pressure catalytic reactor 220 where hydrogenation of coal 210 takes place.
  • solvent extraction also termed “solvent refining,” coal 210 and hydrogen 240 are dissolved at high pressure in a recycled coal-derived solvent 230 which transfers hydrogen 240 to coal 210 .
  • phase separation 260 wherein gases 270 and ash 280 may be removed from coal liquid 250 which may be further cleaned and upgraded by refinery procedures to produce liquid fuels 290 .
  • solvent refining with a low level of hydrogen transfer, a solid, relatively clean fuel termed “solvent refined coal” 290 is obtained.
  • solvent refined coal As in pyrolysis, the compounds are similar to the coal tars and highly aromatic in nature. Hydrogenation and selective catalytic processing, as known to one of skill in the art, may be performed to yield a mix of cycloalkanes and aromatics that provide the C/A blendstock.
  • the I/N-C/A fuel comprises about 20 vol. % C/A blendstock derived from direct liquefaction of a coal feedstock. In embodiments, the I/N-C/A fuel comprises about 80 vol. % I/N blendstock derived from Fischer-Tropsch processing of natural gas, coal, and/or biomass, and about 20 vol. % C/A blendstock derived from direct liquefaction of a coal feedstock.
  • C/A blendstock comprises cycloalkanes obtained by separation (e.g., via distillation or extraction) of cycloalkanes selected from the group consisting of C9-C15 cycloalkanes from petroleum feedstocks.
  • C/A blendstock comprises aromatic compounds obtained by separation (e.g., via distillation or extraction) of aromatic compounds selected from the group consisting of C9-C15 single-ring aromatic compounds from petroleum feedstocks.
  • Suitable petroleum feedstocks comprise oil sand- and/or oil shale-derived products that are inherently rich in cycloalkanes.
  • C/A blendstock is produced by catalytic cyclization and/or reforming of I/N blendstock prepared from triglyceride and/or fatty acid feedstocks as disclosed hereinabove.
  • I/N blendstock may be produced via: (1) catalytic triglyceride dissociation into fatty acids and glycerol, (2) glycerol removal, (3) oxygen removal from fatty acids (via catalytic decarboxylation and/or reduction) to yield normal paraffins, and, to the extent desired, (4) catalytic isomerization of a portion of these normal paraffins to yield isoparaffins.
  • I/N-C/A fuel comprises about 35 vol.
  • I/N-C/A fuel comprises about 65 vol. % I/N blendstock derived from catalytic processing of triglyceride feedstock and about 35 vol. % C/A blendstock derived from catalytic processing of triglyceride feedstock.
  • C/A blendstock is produced from biomass-derived lignin feedstock.
  • C/A blendstock may be produced via catalytic depolymerization of biomass-derived lignin feedstock followed by hydroprocessing as required to yield a desired proportion (for example, JP-8-quality) of cycloalkanes and aromatics.
  • the I/N-C/A fuel comprises about 20 vol. % C/A blendstock derived from pyrolysis of biomass-derived lignin.
  • I/N-C/A fuel comprises about 15 vol. % C/A blendstock derived from catalytic processing of lignin.
  • I/N-C/A fuel comprises about 80 vol.
  • I/N-C/A fuel comprises about 85 vol. % I/N blendstock derived from catalytic processing of triglyceride feedstock and about 15 vol. % C/A blendstock derived from catalytic processing of lignin.
  • a finished I/N-C/A fuel may have “drop-in compatibility” with its petroleum-derived counterpart, i.e. the I/N-C/A fuel may be blended in any proportion, from 0 vol. % to 100 vol. % with a petroleum-derived counterpart.
  • the disclosed I/N-C/A fuel provides for the blending of fuel components (including isoparaffins, normal paraffins, cycloalkanes, and/or aromatics), at least two of which are derived from disparate processes, to create I/N-C/A fuel.
  • at least 50 weight % of an aviation-grade I/N-C/A kerosene fuel is derived from coal, natural gas, or a combination thereof.
  • At least 50 weight % of an I/N-C/A fuel is derived from biomass. In embodiments, at least 10 weight % of an I/N-C/A fuel is derived from non-cracked bio-oil. In embodiments, I/N-C/A fuel has a cetane number of greater than about 70.
  • the I/N-C/A fuel complies with specifications for Jet A and/or another civilian jet fuel. In embodiments, the I/N-C/A fuel complies with a military jet fuel specification selected from JP-8 and other military-grade jet fuel specifications.
  • an I/N-C/A-blended fuel will also meet applicable U.S. military-specified fit-for-purpose requirements that address a variety of fuel performance and materials compatibility issues.
  • fit-for-purpose requirements refers to fuel property requirements that are not necessarily addressed by military or ASTM standards, but are important to fuel performance and stability in jet engines and during fuel handling, distribution, and storage.
  • fit-for-purpose requirements include fuel compatibility with aircraft fuel and engine system materials of construction, adequate fuel performance in compression ignition (versus turbine) engines in a wide variety of ground environments, and possible fuel performance requirements related to swelling of elastomeric seals in, for example, turbine engines.
  • fit for purpose requirements in addition to feedstock properties and ASTM standards are used to determine the optimal ratio of the I/N blendstock to the C/A blendstock.
  • a FT fuel produced from natural gas containing iso-paraffinic and normal paraffin hydrocarbons did not comply with density requirement of the JP-8 military specification (MIL-DTL-83133E).
  • MIL-DTL-83133E a mixture of aromatic hydrocarbon fluid containing aromatic hydrocarbons ranging in carbon chain length from 8-16, was blended to a concentration of 23% by weight with the FT fuel.
  • Table 4 A summary of results from Fuel Sample A compared to specification requirements outlined in MIL-DTL-83133E is provided in Table 4.
  • the resulting fuel had a density of 0.788 g/ml achieving the minimum specification requirement of 0.775 as defined by MIL-DTL-83133E while complying with all of the parameters contained within the specification.
  • Data from gas chromatography of Sample A and a typical FT fuel is provided in FIG. 4 .
  • Example 2 The same FT fuel as used in Example 1 was blended at 82% wt. with 8% wt. of a mixed aromatic fluid and 10% wt. cycloparaffinic fluid.
  • a summary of Fuel Sample B results from key specification parameters is provided in Table 5.
  • the resulting fuel Sample B possessed a MIL-DTL-83133E specification compliant fuel with a density of 0.779 g/ml.

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