WO2012087505A2 - Production d'un biocarburant faisant intervenir l'introduction simultanée, dans une installation de valorisation, de cire de fischer-tropsch et d'huile dérivée de la biomasse - Google Patents

Production d'un biocarburant faisant intervenir l'introduction simultanée, dans une installation de valorisation, de cire de fischer-tropsch et d'huile dérivée de la biomasse Download PDF

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Publication number
WO2012087505A2
WO2012087505A2 PCT/US2011/062426 US2011062426W WO2012087505A2 WO 2012087505 A2 WO2012087505 A2 WO 2012087505A2 US 2011062426 W US2011062426 W US 2011062426W WO 2012087505 A2 WO2012087505 A2 WO 2012087505A2
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component
biomass
catalyst
hydrocarbons
synthesis gas
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PCT/US2011/062426
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English (en)
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WO2012087505A3 (fr
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Belma Demirel
Harold Wright
Robert Freerks
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Rentech, Inc.
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Publication of WO2012087505A2 publication Critical patent/WO2012087505A2/fr
Publication of WO2012087505A3 publication Critical patent/WO2012087505A3/fr

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    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1252—Cyclic or aromatic 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • 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
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    • C10G2300/1018—Biomass of animal origin
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    • 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
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    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203—Naphthenic acids, TAN
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/307—Cetane number, cetane index
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2400/04—Diesel oil
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • 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

  • This invention relates generally to the field of synthetic liquid hydrocarbons. More particularly, the invention relates to the conversion of triglycerides and synthesis gas to chemicals and/or fuel range hydrocarbons. Still more specifically, the invention relates to the production of fuels and/or chemicals via upgrading of Fischer-Tropsch hydrocarbons and biomass.
  • An alternative non-petroleum source of hydrocarbons for producing fuels and chemicals is the natural carbon found in plants and animals.
  • Such sources include, for example, oils and fats as well as pyrolyis oils.
  • Such natural carbon resources, or renewable hydrocarbons are widely available and have thus been targeted for the production of hydrocarbons.
  • oils and fats such as those in vegetable oil
  • One such product is biodiesel, which may be produced by subjecting a base vegetable oil to a transesterification process using methanol to convert the base oil to desired methyl esters, according to reaction (1) below.
  • Glycerol is produced as a by-product of the transesterification process.
  • C16-C18 range to diesel fuel, provided that other properties of the additive paraffin(s), such as, for example, cloud point, pour point, viscosity, etc., are congruent with those of the diesel fuel.
  • Processes for converting vegetable oil into hydrocarbons are known. However, in order to achieve the conversion, harsh reaction conditions are often employed, some of the reaction products may be undesirable, and/or the product may not exhibit acceptable physical properties (e.g., pour point and/or cloud point) for use in diesel fuel. Furthermore, such processes are generally complex and costly.
  • Gasoline, diesel and various chemicals are produced in upgrading processes of petroleum refineries, including, among others, hydrotreating, hydrocracking and catalytic cracking processes. Accordingly, petroleum refineries contain such upgrading units.
  • the introduction of a variety of biomass oils, including vegetable oil and grease, into a hydrocracker with Vacuum Gas Oil (VGO) to produce gasoline, into a diesel hydrotreater with diesel to produce diesel and into a catalytic cracker with VGO to produce chemicals such as olefins and paraffins having less than three carbon atoms have been investigated in the art.
  • VGO Vacuum Gas Oil
  • U.S. Patent App. 2007/0175795 teaches a process for producing, under hydrotreating conditions, hydrocarbons in the diesel fuel boiling range from hydrocarbons boiling in the range of from about 600°F to about 800°F and triglycerides, such as vegetable oils.
  • Suitable hydrocarbons boiling in the range of from about 600°F to about 800°F are taught to be middle distillate fuels, gasoline, naphtha and atmospheric tower bottoms.
  • a preferred middle distillate fuel is taught to be light cycle oil (LCO).
  • LCO light cycle oil
  • the disclosed process yields significant quantities of desirable hydrocarbon products such as n-Ci 7 fractions.
  • the products of the disclosed process are said to exhibit improved physical properties that enhance the cetane rating of diesel fuel when combined therewith.
  • the process is operable to convert triglycerides to diesel range materials having an enhanced cetane number over that of the feedstock.
  • FT production apparatus comprising at least one FT reactor configured for the production of FT hydrocarbons from synthesis gas; and upgrading apparatus fluidly connected with the FT production apparatus and configured to receive, via one or more inlets, a first component comprising FT hydrocarbons and a second component comprising biomass oil and decrease the degree of unsaturation thereof via hydrogenation.
  • the upgrading apparatus comprises at least one unit selected from the group consisting of hydrotreaters, hydrocrackers, hydroisomerizers, desulfurization units, denitrogenation units, and deoxygenation units.
  • the system comprises at least one catalyst selected from the group consisting of cobalt molybdenum sulfide, nickel molybdenum sulfide, platinum on a refractory support, palladium on a refractory support, and mixtures thereof.
  • the system can comprise a hydrotreater operable with a hydrotreating catalyst comprising nickel and molybdenum or cobalt and molybdenum.
  • the system comprises at least one catalytic reactor selected from the group consisting of hydrotreaters, hydrocrackers and hydroisomerizers, the system further comprising at least one unit selected from the group consisting of desulfurization units, deoxygenation units and denitrogenation units.
  • the system comprises a deoxygenation unit upstream of a hydrotreater.
  • the FT production apparatus comprises at least one FT reactor.
  • the at least one FT reactor can comprise an FT catalyst.
  • the FT catalyst is a cobalt catalyst.
  • the FT catalyst is an iron catalyst.
  • the iron catalyst can comprise Fe/K/Cu with or without silica.
  • the system further comprises synthesis gas production apparatus configured for the production of synthesis gas from a feed comprising at least one material selected from the group consisting of coal, natural gas, biomass, municipal solid waste and combinations thereof.
  • the synthesis gas production apparatus comprises at least one unit selected from the group consisting of gasifiers, pyrolizers and reformers.
  • the system further comprising synthesis gas clean-up apparatus configured to remove at least one component from synthesis gas produced via the synthesis gas production apparatus.
  • the synthesis gas clean-up apparatus can comprise at least one clean-up unit selected from the group consisting of acid gas removal units, water gas shift reactors and combinations thereof.
  • the system further comprises biomass supply apparatus configured to separate an undesired component from a biomass feed material, to bring a biomass feed material to desired operating conditions for upgrading, or both.
  • the biomass supply apparatus can comprise at least one unit selected from the group consisting of centrifuges, filters, settlers, and combinations thereof.
  • Also disclosed herein is a method of producing a biofuel or biochemical by introducing a first component comprising FT hydrocarbons and a second component comprising at least one triglyceride into an upgrading apparatus configured to receive, via one or more inlets, the first component and the second component and decrease the degree of unsaturation thereof via hydrogenation, and extracting upgraded product comprising at least one component selected from the group consisting of fuels and chemicals from the upgrading apparatus.
  • the second component comprises at least one material selected from the group consisting of vegetable oils, brown grease, yellow grease, animal fats, pyrolysis oils, and combinations thereof.
  • the upgraded product comprises FT diesel.
  • the upgraded product comprises FT jet.
  • the upgraded product comprises a chemical.
  • the chemical comprises propane.
  • the method further comprises producing FT hydrocarbons by introducing synthesis gas into at least one FT reactor, operating the FT reactor under FT synthesis conditions, and extracting a product comprising FT hydrocarbons from the at least one FT reactor.
  • the at least one FT reactor can contain therein an FT catalyst.
  • the FT catalyst is an iron-based FT catalyst.
  • the FT catalyst is promoted with potassium.
  • the iron-based FT catalyst is a precipitated, unsupported iron catalyst.
  • the iron-based FT catalyst is a precipitated supported iron catalyst.
  • the iron-based catalyst is structurally supported by silica.
  • the upgrading apparatus comprises at least one unit selected from the group consisting of hydrogenation reactors, hydrotreaters, desulfurization units, deoxygenation units, denitrogenation units, hydrocrackers, hydroisomerization units and combinations thereof.
  • the upgraded product comprises a greater amount by weight of Ci7 hydrocarbons than Qg hydrocarbons.
  • hydrogenation is performed at a pressure in the range of from about 100 psig (689 kPa) to about 1000 psig (6895 kPa).
  • hydrogenation is effected by introducing a hydrogen-containing gas into the upgrading apparatus, and wherein the hydrogen-containing gas is present therein in amount in the range of from about 300 standard cubic feet per barrel of the first and second components to about 4000 standard cubic feet per barrel of the first and second components.
  • the upgrading apparatus is operated at a liquid hourly space velocity in the range of from about 0.1 hr "1 to about 4 hr "1 .
  • the second component is present in an amount in the range of from about 0.01 to about 49.9 weight percent, based on the combined weight of the first and the second components. In embodiments, the second component is present in an amount in the range of from about 2 to about 40 weight percent, based on the combined weight of the first component and the second component.
  • the first component can comprise at least one component selected from the group consisting of FT wax, FT liquid hydrocarbons and combinations thereof. In embodiments, the second component is selected from the group consisting of vegetable oil, brown grease, yellow grease, animal fats and mixtures thereof.
  • the upgraded product can comprise from about 0.5 weight percent to about 90 weight percent of hydrocarbons with between 5 and 20 carbon atoms per molecule, based on the total weight of the upgraded product.
  • the upgraded product has a total acidity number (TAN) of less than about 1.
  • Also disclosed herein is a method comprising contacting an FT component comprising at least one hydrocarbon produced via FT conversion and a biomass component comprising at least one triglyceride with hydrogen under conditions sufficient to produce a reaction product comprising primarily paraffins, wherein the reaction product is suitable for use as a fuel, as a fuel additive or both.
  • Sufficient conditions can include a pressure of less than about 1200 psig (8274 kPa) and a temperature in the range of from about 600°F (316°C) to about 800°F (427°C).
  • the reaction product has a cetane number that is greater than the cetane number of the FT component.
  • the reaction product comprises a greater weight percent of C17 hydrocarbon products than Ci 8 hydrocarbon products.
  • the FT component has a boiling point in the range of from about 150°F (66°C) to about 1500°F (816°C).
  • the biomass component can be present in the range of from about 1 to about 100 weight percent, based on the combined weight of the FT component and the biomass component.
  • the at least one triglyceride is present in the range of from about 2 to about 80 weight percent, based on the combined weight of the FT component and the biomass component.
  • contacting an FT component comprising at least one hydrocarbon produced via FT synthesis and a biomass component comprising at least one triglyceride with hydrogen comprises contacting with a hydrogen-containing gas in an amount in the range of from about 300 standard cubic feet per barrel of combined FT component and biomass component to about 4000 standard cubic feet per barrel combined FT component and biomass component.
  • the FT component can comprise FT wax having a melt point above 100°F (38°C), an average carbon number of greater than about 20, or both.
  • the biomass component can comprise at least one triglyceride source selected from the group consisting of vegetable oil, brown grease, yellow grease, animal fats and mixtures thereof.
  • FIGURE 1 is a schematic of a system suitable for the production of biofuels and/or biochemicals from Fischer-Tropsch hydrocarbons and biomass oil according to an embodiment of this disclosure
  • FIGURE 2 is a schematic of a method for the production of biofuels and/or biochemicals from Fischer-Tropsch hydrocarbons and biomass oil according to an embodiment of this disclosure
  • FIGURE 3 is a schematic of a method for providing a first component comprising Fischer-Tropsch hydrocarbon(s) according to an embodiment of this disclosure
  • FIGURE 4 is a schematic of a method for providing a second component comprising biomass according to an embodiment of this disclosure.
  • FIGURE 5 is a schematic of a method for upgrading first and second components to produce product, according to an embodiment of this disclosure.
  • 'triglyceride is used herein to refer generally to any naturally occurring ester of a fatty acid and/or glycerol having the general formula CH 2 (OCORi)CH(OCOR2)CH 2 (OCOR3), where Rj, R 2 , and R3 are the same or different, and may vary in chain length and, unless otherwise noted, the term 'triglyceride' refers to both triglycerides and triglyceride-containing compounds.
  • the term 'biofueP is used to refer to any fuel product (e.g. diesel fuel, jet fuel) at least a fraction of which was derived from a non-petroleum carbon source (e.g. biomass).
  • fuel product e.g. diesel fuel, jet fuel
  • non-petroleum carbon source e.g. biomass
  • biochemical is meant to refer to any chemical product (e.g. propane) at least a fraction of which was derived from a non-petroleum carbon source (e.g. biomass).
  • a non-petroleum carbon source e.g. biomass
  • the term 'bioproduct' is meant to refer to any chemical product or fuel at least a fraction of which was derived from a non-petroleum carbon source.
  • biomass oil' is meant to refer to any biomass comprising triglycerides which may be converted (i.e. 'upgraded') to hydrocarbons (e.g. paraffins) via saturation (i.e. hydrogenation).
  • hydrocarbons e.g. paraffins
  • saturation i.e. hydrogenation
  • 'biomass oil' refers to both primarily solid and primarily liquid materials, including greases, fats and oils.
  • biomass oil including, but not limited to, vegetable oil, yellow grease, such as used in restaurant oil and those from cooking oil, animal fats, pyrolysis oil and mixtures thereof, are introduced into an upgrader along with Fischer-Tropsch hydrocarbons (e.g. FT wax). Upgrading is operated to produce FT jet, FT diesel and/or FT chemical from the biomass oil and FT hydrocarbons.
  • this disclosure provides a system and method for the conversion (e.g. hydrotreating) of hydrocarbons from FT conversion of synthesis gas along with triglycerides from biomass (e.g. vegetable oil) to diesel boiling range hydrocarbons suitable for use as or production of diesel fuel.
  • this disclosure provides a system and method for upgrading hydrocarbons from FT conversion of synthesis gas along with triglycerides from biomass to hydrocarbons suitable for use as or for the production of jet fuel. In embodiments, this disclosure provides a system and method for upgrading hydrocarbons from FT conversion of synthesis gas along with triglycerides from biomass to FT chemical(s).
  • the system and method enable conversion of triglycerides and/or triglyceride-containing compounds to diesel boiling range hydrocarbons via upgrading in an upgrader of a Fischer-Tropsch plant along with FT hydrocarbons.
  • the system and method enable improved yields of reaction products including diesel boiling range hydrocarbons, such as, for example, C17-C1 fractions relative to systems and methods absent the biomass components.
  • the system and method may allow production of a product comprising hydrocarbons having suitable or improved (i.e. increased) cetane number, suitable or improved (i.e. decreased) cloud point, suitable or improved (i.e. decreased) pour point, suitable or improved (i.e.
  • the disclosed system and method enable production of a biofuel having an increase in cetane number relative to diesel produced from a feed comprising FT hydrocarbons alone.
  • the disclosed system and method enable production of a reaction product containing an increased amount of hydrocarbon products containing 17 carbon atoms (i.e. C17 hydrocarbon products) than hydrocarbon products containing 18 carbon atoms (Ci 8 hydrocarbon products).
  • FIG. 1 is a schematic of a system I for the production of biofuels and/or biochemicals from FT hydrocarbons and biomass oil.
  • System I comprises upgrading apparatus 40.
  • the system of this disclosure may further comprise synthesis gas production apparatus 10, synthesis gas cleanup apparatus 20, FT conversion apparatus 30, biomass supply apparatus 50, or any combination thereof.
  • system I comprises upgrading apparatus 40 alone; upgrading apparatus 40 and FT conversion apparatus 30; upgrading apparatus 40, FT conversion apparatus 30 and synthesis gas cleanup apparatus 20; upgrading apparatus 40, FT conversion apparatus 30, synthesis gas cleanup apparatus 20 and synthesis gas production apparatus 10; upgrading apparatus 40 and biomass supply apparatus 50; or some other permutation of units 10-50 containing upgrading apparatus 40.
  • Apparatus 50 can be either a remote unit such as, but not limited to, a remote pyrolysis unit from which the oil is transported or it can be an on site unit for generating oils including, but not limited to, pyrolysis oil.
  • Upgrading Apparatus 40 comprises upgrading apparatus 40.
  • Upgrading apparatus 40 comprises one or more units configured for the removal of one or more undesirable compound(s) from and/or modification of the characteristic (e.g. via conversion, such as hydrogenation, of at least a portion thereof) of a first component comprising FT hydrocarbon product (also referred to herein as FT wax, FT hydrocarbons and FT liquids), a second component comprising biomass oil, or both first and second components separately or together (e.g. upgrading a feed mixture comprising both first and second components or upgrading a first component and a second component and combining at least a portion of the products of the upgrading to provide a fuel or chemical).
  • FT hydrocarbon product also referred to herein as FT wax, FT hydrocarbons and FT liquids
  • second component comprising biomass oil
  • both first and second components separately or together e.g. upgrading a feed mixture comprising both first and second components or upgrading a first component and a second component and combining at least a portion of the
  • upgrading apparatus 40 comprises one or more units operable to produce diesel fuel (i.e. also sometimes referred to herein as FT diesel or biodiesel) from FT hydrocarbons and biomass oil.
  • upgrading apparatus 40 comprises one or more units operable to produce jet fuel (also referred to herein as FT jet or biojet) from FT hydrocarbons and biomass oil.
  • an inlet line 36 is utilized to introduce a first component comprising FT hydrocarbons, into upgrading apparatus 40.
  • another inlet line 57 is configured to introduce, into upgrading apparatus 40, a second component comprising biomass oil that may include, but is not limited to, pyrolysis oil produced in close proximity to the facility and or produced at a remote site and transported to the central facility.
  • a line 58 is configured to combine biomass oil with FT hydrocarbon in inlet line 36 prior to introduction into upgrading apparatus 40, as indicated in Figure 1.
  • upgrading apparatus 40 comprises one or more units configured for the removal of an undesirable compound from the first component, the second component, or a feed mixture thereof.
  • the undesirable compound may be selected from compounds that are corrosive and/or harmful to the environment and compounds that are undesirable for use as or in a biochemical and/or biofuel.
  • upgrading apparatus 40 can comprise one or more units configured for the removal of sulfur, sulfur-containing compounds (such as, but not limited to, hydrogen sulfide, carbonyl sulfide, mercaptans, thiophenes, carbon disulfide), oxygen, oxygen-containing compounds (such as, but not limited to, alcohols and esters), nitrogen, nitrogen-containing compounds (such as, but not limited to, ammonia, HCN, CH 3 CN), carbon oxides (such as carbon monoxide and carbon dioxide).
  • sulfur-containing compounds such as, but not limited to, hydrogen sulfide, carbonyl sulfide, mercaptans, thiophenes, carbon disulfide
  • oxygen-containing compounds such as, but not limited to, alcohols and esters
  • nitrogen, nitrogen-containing compounds such as, but not limited to, ammonia, HCN, CH 3 CN
  • carbon oxides such as carbon monoxide and carbon dioxide
  • upgrading apparatus 40 comprises a desulfurization unit configured for the removal of sulfur and/or sulfur containing compounds from the first component, from the second component, from a feed mixture thereof.
  • upgrading apparatus 40 comprises one desulfurization apparatus for desulfurization of the first component comprising FT hydrocarbons and another desulfurization apparatus configured for desulfurization of the second component comprising biomass.
  • the desulfurization unit(s) may be hydrodesulfurization unit(s).
  • System I may comprise one or more desulfurization units known in the art for removal of sulfur and/or sulfur-containing compounds from hydrocarbons.
  • System I comprises one or more desulfurization unit(s) selected from ZnO beds, carbon beds, RECTISOL®, or SELEXOLTM type units or other solvent wash type systems.
  • the one or more desulfurization units of upgrading apparatus 40 may be operable, for example, to remove compounds selected from, but are not limited to, hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS) mercaptans (RSH), organic sulfides (R--S--R), organic disulfides (R--S--S--R), thiophene, substituted thiophenes, organic trisulfides, organic tetrasulfides, benzothiophene, alkyl thiophenes, dibenzothiophene, alkyl benzothiophenes, alkyl dibenzothiophenes, and the like, and mixtures thereof as well as heavier molecular weights of the same, wherein each R can be an alkyl, cycloalkyl, or aryl group containing 1 to about 10 carbon atoms.
  • upgrading apparatus 40 may comprise a desulfurization unit configured for removal of sulfur from the diesel product.
  • the diesel desulfurization unit may be configured for operation in the presence of hydrogen at about 370°C and a pressure of 60 bars.
  • the sulfur atoms leave the hydrocarbons and bond with hydrogen to produce hydrogen sulfide, H 2 S.
  • upgrading apparatus 40 may further comprise sulfur isolation apparatus downstream of the desulfurization unit(s), such sulfur isolation apparatus configured for isolation of elemental sulfur (in molten or solid form) from desulfurization product gas comprising H 2 S.
  • upgrading apparatus 40 comprises one or more unit(s) configured for removal of nitrogen and/or nitrogen-containing compounds from the first (FT) component, the second (biomass) component or a feed comprising both first and second components.
  • upgrading apparatus 40 comprises at least one deoxygenation unit configured for removal of nitrogen (and/or nitrogen-containing compounds) from the first (FT) component and at least one other denitrogenation unit configured for removal of nitrogen (and/or nitrogen-containing compounds) from the second (biomass) component.
  • the denitrogenation unit(s) may be hydrodenitrogenation unit(s).
  • System I may comprise one or more denitrogenation units known in the art for the removal of nitrogen and/or nitrogen-containing compounds from hydrocarbons.
  • system I comprises one ore more denitrogenation unit(s) selected from carbon beds, water wash units, solvent wash units, RECTISOL®, or SELEXOLTM type units.
  • upgrading apparatus 40 comprises one or more deoxygenation units (e.g. hydrodeoxygenation units) configured for the removal of oxygen from the first component, the second component or a feed comprising both first and second components.
  • upgrading apparatus 40 comprises at least one deoxygenation unit configured for removal of oxygen (and/or oxygen-containing compounds) from the first (FT) component and at least one other deoxygenation unit configured for removal of oxygen (and/or oxygen-containing compounds) from the second (biomass) component.
  • the deoxygenation unit(s) may be hydrodeoxygenation unit(s).
  • System I may comprise one or more deoxygenation units known in the art for the removal of oxygen and/or oxygen-containing compounds from hydrocarbons.
  • System I comprises one or more deoxygenation units known in the art, such as those selected from selective catalytic reaction systems, absorbent beds using materials such as carbon, cerium oxides, ZnO, etc.
  • upgrading apparatus 40 comprises one or more unit(s) configured for modification of at least one characteristic of a first component comprising FT hydrocarbon product and/or a second component comprising biomass oil, or a feed mixture comprising both first and second components.
  • Modification at least one characteristic of a feed component may be effected by converting at least a portion of the feed to different compounds.
  • modification of the characteristic may comprise saturating (e.g. by hydrogenating) at least a portion of the compounds in the feed component, increasing or decreasing the average chain lengths of the compounds in the feed component (e.g. by hydrocracking), increasing or decreasing the degree of chain branching (e.g. by isomerizing) of a compound.
  • upgrading apparatus 40 comprises one or more unit selected from hydrotreaters, catalytic crackers (e.g. hydrocrackers) and isomerization units (e.g. hydroisomerization units).
  • the octane rating is a measure of the resistance of petrol and other fuels to autoignition in spark-ignition internal combustion engines.
  • the octane rating measures the tendency of petrol to avoid self-ignition.
  • the cetane number is measurement of the combustion quality of diesel fuel during compression ignition.
  • Upgrading apparatus 40 can comprise one or more units configured to increase the octane number of the first component, the second component or a feed comprising both first and second components and/or one or more units configured to increase the cetane number of the first component and one or more units configured to increase the octane number of the second component.
  • Such upgrading units are known in the art.
  • System I can comprise one or more hydroprocessing units operable to reduce heavy hydrocarbons into lighter fractions through catalytic addition of hydrogen.
  • hydroprocessing units may be selected from the group consisting of hydrotreaters, hydrogenation units, and hydrocrackers and combinations thereof.
  • upgrading apparatus 40 comprises at least one catalytic reformer configured for increasing the octane or cetane number of a feed comprising a mixture of a first component comprising FT hydrocarbons and a second component comprising biomass.
  • upgrading apparatus 40 comprises one or more catalytic reformers.
  • Such reformers may be operable at about 500°C and 10 bars of pressure, with platinum as a catalyst.
  • System I may comprise other units suitable for increasing the octane rating, for example alkylation units and units configured for the production of MTBE (methyl tertiary butyl ether) and/or ETBE (ethyl tertiary butyl ether), which have excellent anti-self-ignition properties.
  • Upgrading apparatus 40 comprises at least one apparatus configured for catalytic saturation of the triglycerides of the second component and the FT hydrocarbons of the first component.
  • Such an apparatus may be referred to herein as a hydrotreatment reactor.
  • suitable catalysts include hydrotreating catalysts.
  • the term 'hydrotreating catalyst' as used herein, generally describes a catalyst that is capable of utilizing hydrogen to accomplish saturation of unsaturated materials, such as aromatic compounds.
  • Examples of hydrotreating catalysts useful in the present system and methods include, but are not limited to, materials containing compounds selected from Group VI and Group VIII metals, and their oxides and sulfides.
  • hydrotreating catalysts include, but are not limited to, alumina supported cobalt-molybdenum, nickel sulfide, nickel-tungsten, cobalt-tungsten and nickel-molybdenum (such as for example, commercially available under the trade designation TK-573 from Haldor Topsoe).
  • suitable hydrotreating catalysts may also be promoted with a halogen, such as, but not limited to, fluorine.
  • the metal of a catalyst useful for upgrading in upgrading apparatus 40 may be distributed over the surface of a support in a manner than maximizes the surface area of the metal.
  • Suitable support materials for the hydrogenation catalysts include, but are not limited to, silica, silica- alumina, aluminum oxide (AI2O3), silica-magnesia, silica-titania and acidic zeolites of natural or synthetic origin.
  • the metal catalyst may be prepared by any method known in the art, including combining the metal with the support using conventional means including but not limited to impregnation, ion exchange and vapor deposition.
  • the catalyst contains molybdenum and cobalt supported on alumina or molybdenum and nickel supported on alumina.
  • fluorine can be incorporated into or onto a nickel-molybdenum or cobalt-molybdenum catalyst by impregnating said catalyst with ammonium bifluoride.
  • Suitable catalysts are sorbent compositions.
  • Suitable sorbent compositions include any sorbent composition useful in converting triglyceride-containing materials or a mixture of triglyceride-containing material and a FT product into hydrocarbons.
  • the sorbent compositions can be used in either fixed-bed reactor or fluidized bed reactor upgrading units.
  • a useful sorbent composition can be any sufficiently fluidizable, circulatable, and regenerable zinc oxide-based composition. Descriptions of such sorbent compositions are provided in U.S. Pat. No. 6,429,170, U.S. Pat. No. 6,864,215 and U.S. Pat. App. No. 2007/0175795, the disclosures of each of which are incorporated herein by reference for all content not contrary to this disclosure.
  • the sorbent composition comprises zinc oxide and a reduced-valence promoter metal component.
  • the promoter metal is generally present as a substitutional solid metal solution with zinc.
  • the reduced-valence promoter metal component of the reduced sorbent preferably comprises a promoter metal selected from a group consisting of nickel, cobalt, iron, manganese, tungsten, silver, gold, copper, platinum, zinc, tin, ruthenium, molybdenum, antimony, vanadium, iridium, chromium, palladium.
  • the reduced-valence promoter metal component comprises nickel as the promoter metal.
  • the term 'reduced-valence' when describing the promoter metal component shall denote a promoter metal component having a valence which is less than the valence of the promoter metal component in its common oxidized state.
  • the solid sorbent employed in the method should include a promoter metal component having a valence which is less than the valence of the promoter metal component of the sorbent composition before it is reduced. Most preferably, substantially the entire promoter metal component of the reduced solid sorbent has a valence of zero.
  • the sorbent employed in upgrading apparatus 40 may further comprise a porosity enhancer and an aluminate.
  • the aluminate is preferably a promoter metal-zinc aluminate substitutional solid solution.
  • the porosity enhancer when employed, can be any compound which ultimately increases the macroporosity of the solid sorbent particles.
  • the porosity enhancer is perlite.
  • the zinc oxide is present in the sorbent composition in an amount in the range of from about 10 to about 90 weight percent, based on the total weight of the sorbent composition.
  • the substitutional solid metal solution is generally present in an amount in the range of from about 5 to about 70 weight percent based on the total weight of the sorbent composition and the promoter metal-zinc aluminate substitutional solid solution is present in an amount in the range of from about 2 to about 50 weight percent, based on the total weight of the sorbent composition.
  • Upgrading apparatus 40 may comprise one or more hydrotreaters that enable intimate contact of the reactants and control of the operating conditions under a set of reaction conditions that include total pressure, temperature, liquid hourly space velocity, and hydrogen flow rate.
  • the reactants may be added to the reaction chamber in any suitable manner or in any suitable order.
  • the catalyst can be added first to the reactants and thereafter, fed with hydrogen. According to this disclosure, either fixed bed reactors or fluidized bed reactors can be used.
  • the term 'fluidized bed reactor' denotes a reactor wherein a fluid feed can be contacted with solid particles in a manner such that the solid particles are at least partly suspended within the reaction zone by the flow of the fluid feed through the reaction zone and the solid particles are substantially free to move about within the reaction zone as driven by the flow of the fluid feed through the reaction zone.
  • the term 'fluid' denotes gas, liquid, vapor and combinations thereof.
  • Upgrading apparatus 40 may further comprise one or more separation units configured to separate a diesel product, a jet fuel product, a naphtha product, a gasoline product or a combination thereof from an upstream unit (as described hereinabove) within upgrading apparatus 40.
  • upgrading apparatus 40 comprises one or more separation units downstream of one or more units (as described hereinabove) configured for the removal of one or more undesirable compound(s) from a first component comprising FT hydrocarbon product, a second component comprising biomass oil, or a feed mixture comprising both first and second components, one or more separation units downstream of one or more units (as described hereinabove) configured for modification of at least one characteristic of a first component comprising FT hydrocarbon product, a second component comprising biomass oil, or a feed mixture comprising both first and second components, or one or more separation units downstream of one or more units selected from the group consisting of units (as described hereinabove) configured for the removal of one or more undesirable compound(s) from a first component comprising FT hydrocarbon product, a second component comprising biomass oil, or a feed mixture comprising both first and second components and downstream of one or more units (as described hereinabove) configured for modification of at least one characteristic of a first component comprising FT hydrocarbon product,
  • upgrading apparatus 40 is configured to produce at least one product selected from diesel meeting ASTM D975 specifications; jet fuel meeting commercial ASTM specifications or military specifications such as JP-8; naphtha fuel comprising at least some C5 to C12 paraffins, and/or one or more chemicals selected from the group consisting of propane, butane, solvents, drilling fluids, and combinations thereof.
  • System I of this disclosure further comprises FT conversion apparatus (also referred to herein as FT production apparatus) 30 for the production of a first component comprising FT hydrocarbons, said component suitable for upgrading in upgrading apparatus 40.
  • FT conversion apparatus 30 is positioned upstream upgrading apparatus 40 and is operable to produce FT hydrocarbons from synthesis gas.
  • FT conversion apparatus 30 can be any apparatus known in the art for the production of FT hydrocarbons from synthesis gas.
  • Fischer-Tropsch (FT) synthesis represents a catalytic method for the creation of synthetic liquid fuels.
  • the reaction occurs by the metal catalysis of an exothermic reaction between carbon monoxide and hydrogen gas mixtures, called synthesis gas, or syngas.
  • the liquid product of the reaction is refined to produce a range of synthetic fuels, lubricants and waxes.
  • the primary metals utilized as catalysts are cobalt and iron.
  • FT production apparatus 40 comprises one or more FT reactors configured for the production of FT hydrocarbons.
  • the one or more FT reactor(s) can contain suitable FT catalyst.
  • FT production apparatus 30 comprises one or more FT reactor(s) containing an iron FT catalyst.
  • FT production apparatus 30 comprises one or more FT reactor(s) containing a copper FT catalyst.
  • FT production apparatus 30 is operable with an iron catalyst as described in U.S. Patent No. 5,504,118, the disclosure of which is hereby incorporated herein in its entirety for all purposes not contrary to this disclosure.
  • FT production apparatus 30 is operable with an iron catalyst as described in U.S. Patent Apps. No. 12/207,859 and/or 12/198,459, the disclosures of each of which are hereby incorporated herein in its entirety for all purposes not contrary to this disclosure.
  • FT production apparatus comprises a structurally promoted catalyst comprising crystalline silica; at least one basic chemical promoter; and iron; wherein the catalyst comprises Si0 2 :Fe in a ratio of from about 2: 100 to about 24: 100.
  • the chemical promoter comprises an alkali hydroxide.
  • the alkali hydroxide may comprise potassium hydroxide.
  • the structurally promoted catalyst further comprises copper.
  • the ratio of K:Fe in the catalyst is from about 1 :100 to about 10: 100.
  • catalyst comprises copper, and the Cu: Fe ratio comprises Cu: Fe in the range of from 1 : 100 to about 10:100.
  • the structurally promoted catalyst may have an ASTM air jet attrition resistance such that less than about 5 wt% fines are produced within a testing duration of 5 hours. In embodiments, the catalyst will produce less than about lwt% fines during ASTM air jet testing for at least 5 hours.
  • the FT production apparatus comprises a structurally promoted precipitated iron catalyst comprising Si(3 ⁇ 4:Fe in a ratio of from about 2: 100 to about 24:100. In embodiments, the catalyst also comprises K:Fe in a ratio of from about 1 : 100 to about 10: 100.
  • FT conversion apparatus 30 can be connected with upgrading apparatus 40 via a line 36.
  • FT conversion apparatus 30 can further comprise one or more outlets 35 for the removal of components from FT product hydrocarbons to be utilized as the first component in upgrading apparatus 40.
  • a line 35 may be configured to remove tailgas comprise unreacted synthesis gas and gaseous FT products from FT production apparatus 30. All or a portion of the tailgas (i.e. synthesis gas) may be recycled to FT production apparatus 30.
  • One or more component e.g. carbon dioxide and/or gaseous FT products may be removed from the tailgas prior to recycle.
  • line 36 is configured to introduce a first component comprising FT hydrocarbons (either from a pipeline or from an FT production apparatus 30) into upgrading apparatus 40.
  • the FT hydrocarbons of the first component may be selected from FT wax, FT liquids and a combination thereof.
  • an inlet line 26 is configured to introduce synthesis gas into FT conversion apparatus 30.
  • FT conversion apparatus 30 is operable to convert an FT feed gas comprising synthesis gas into FT hydrocarbons.
  • the FT feed gas can comprise hydrogen and carbon monoxide at a molar ratio of from about 0.7: 1 to about 2: 1.
  • FT conversion apparatus 30 is operable to convert an FT feed gas comprising a molar ratio of H 2 :CO in the range of from about 1 : 1 to about 2: 1.
  • FT conversion apparatus 30 is configured to convert an FT feed gas comprising a molar ratio of H 2 :CO of about 0.5: 1, about 1 : 1, about 1.7:1 or about 2: 1.
  • system I comprises at least one FT conversion reactor operable ,to produce long chain hydrocarbons from synthesis gas at a temperature in the range of from about 200°C to about 300°C, from about 220°C to about 270°C or from about 240°C to about 260°C.
  • system I comprises at least one FT conversion reactor operable to produce hydrocarbons from synthesis gas at a pressure in the range of from about 100 psig (689 kPa) to about 600 psig (4137 kPa), from about 200 psig (1379 kPa) to about 500 psig (3447 kPa) or from about 300 psig (2068 kPa) to about 400 psig (2758 kPa).
  • Synthesis Gas Production Apparatus 10 can further comprise synthesis gas production apparatus 10 upstream of FT Production Apparatus 30.
  • Synthesis gas production apparatus 10 can be any apparatus known in the art for the production of a gas comprising synthesis gas.
  • Synthesis gas production apparatus 10 can comprise one or more units selected from reformers configured for steam reforming of natural gas or liquid hydrocarbons to syngas and gasifiers and pyrolizers configured for the production of synthesis gas by gasification of a feed material.
  • the feed material gasified may be selected from coal, waste (e.g. municipal solid waste, MSW), biomass, and combinations thereof.
  • synthesis gas production apparatus 10 comprises a coal gasifier configured for the production of syngas from coal.
  • Synthesis gas production apparatus 10 may comprise one or more inlet lines 15. Such lines may be configured for the introduction of reactants to synthesis gas production apparatus 10.
  • synthesis gas production apparatus 10 may comprise an inlet for a material (e.g. coal) to be gasified, an inlet for steam, an inlet for air, an inlet for substantially pure oxygen, an inlet for oxygen-enriched air or a combination thereof.
  • system I comprises a gasifier configured to produce synthesis gas having a molar ratio of carbon monoxide to hydrogen in the range of from about 0.2 to about2.0, from about 0.3 to about 1.6, or from about 0.3 to about 1.2.
  • the gasifier may be operable to produce synthesis gas at a temperature in the range of from about 1300°F (704°C) to about 2500°F (1371 °C), from about 1400°F (760°C) to about 2200°F (1204°C), or from about 1500°F (816°C) to about 2000°F (1093°C).
  • the gasifier may be operable to produce synthesis gas at a pressure in the range of from about 0 psig (0 kPa) to about 1000 psig (6895 kPa), from about 5 psig (34 kPa) to about 60 psig (414 kPa), or from about 10 psig (69 kPa) to about 50 psig (345 kPa).
  • the feed may comprise coal selected from lignite, anthracite, bituminous coal, biomass, wood chips, bagasse, municipal solid waste and combinations thereof.
  • Synthesis Gas Clean-up/Conditioning Apparatus 20 can further comprise synthesis gas clean-up and/or conditioning apparatus 20.
  • Synthesis gas clean-up/conditioning apparatus 20 can be any apparatus known in the art for the removal of one or more undesirable components from synthesis gas, for example, from synthesis gas produced in synthesis gas •production apparatus 10 or obtained from a pipeline 16.
  • synthesis gas clean-up/conditioning apparatus 20 is fluidly connected with FT production apparatus 30 via FT production apparatus inlet line 26.
  • One or more undesired components is removed, via one or more contaminant outlet lines 25, from a synthesis gas introduced into synthesis gas cleanup/conditioning apparatus 20 via inlet line 16.
  • synthesis gas clean-up/conditioning apparatus 20 is configured for removal of at least component selected from the group consisting of hydrogen, carbon dioxide, hydrogen sulfide and combinations thereof.
  • synthesis gas cleanup/conditioning apparatus 20 comprises one or more units selected from the group consisting of acid gas removal units (AGRU), water gas shift reactors, partial oxidation units for tar destruction, catalytic reactor systems for tar reforming, aromatics and other contaminant removal systems like tri-ethylene glycol units, carbon beds, zinc oxide for sulfur removal, absorbent systems like amine units for C0 2 and other contaminant removal, absorber towers, hydrogen membrane units to remove excess hydrogen, water gas shift reactor systems to adjust the molar ratio of H 2 :CO, RECTISOL® units, SELEXOLTM units, other lean gas absorbers, and other removal units and combinations thereof.
  • AGU acid gas removal units
  • water gas shift reactors partial oxidation units for tar destruction
  • catalytic reactor systems for tar reforming aromatics and other contaminant removal systems like tri-ethylene glyco
  • Synthesis gas clean-up/conditioning apparatus 20 may be configured to produce an FT feed stream comprising less than about 30%, 20% or 10% carbon dioxide from a crude synthesis gas.
  • Synthesis gas clean-up/conditioning apparatus 20 may be configured to produce a synthesis gas product comprising a molar ratio of H 2 :CO in the range of from about 0.3 to about 2.2, from about 0.8 to about 1.6 or from about 0.9 to about 1.1 from a crude synthesis gas comprising a molar ratio of H 2 :CO in the range of from about 0.3 to about 2.1, from about 0.8 to about 1.6 or from about 0.9 to about 1.1.
  • synthesis gas clean-up/conditioning apparatus 20 comprises a water gas shift reactor.
  • synthesis gas clean-up/conditioning apparatus 20 is fluidly connected with synthesis gas production apparatus 10 via line 16. In embodiments, synthesis gas clean-up/conditioning apparatus 20 is fluidly connected with a synthesis gas pipeline 16 (i.e. in embodiments, system I does not comprise a synthesis gas production apparatus 10).
  • Biomass Supply Apparatus 50 further comprises biomass supply apparatus 50.
  • Biomass supply apparatus 50 can comprise one or more units configured for preparation of a second component comprising biomass for introduction into upgrading apparatus 40.
  • biomass supply apparatus 50 can comprise one or more separators configured for the removal of components from a biomass feed.
  • biomass supply apparatus 50 can comprise a filter for removal of solids from a biomass material.
  • biomass supply apparatus 50 comprises a biomass supply line.
  • biomass supply apparatus 50 comprises a unit configured to heat a biomass feed oil to a desired operating temperature for introduction into upgrading apparatus 40 and/or to pressurize a biomass feed material to a desired operating pressure for introduction into upgrading apparatus 40.
  • FIG. 1 is a schematic of a method II for the production of biofuels and/or biochemicals according to an embodiment of this disclosure.
  • Method II comprises providing a first component comprising one or more Fischer- Tropsch hydrocarbon at 100, providing a second component comprising biomass at 200 and upgrading the first and second components to produce a product selected from biofuels and chemicals.
  • providing a first component comprising one or more Fischer-Tropsch hydrocarbons 100 can comprise providing at least a fraction of an FT Product as the first component 140.
  • providing a first component comprising one or more Fischer-Tropsch hydrocarbons can further comprise producing synthesis gas 1 10, removing one or more components from synthesis gas, subjecting synthesis gas to FT synthesis to produce an FT liquid product or a combination thereof.
  • providing a first component comprising one or more FT hydrocarbons 100 may comprise obtaining an FT liquid product and providing at least a fraction of the FT product hydrocarbons as the first component.
  • the FT liquid product of step 140 is obtained by subjecting synthesis gas to FT synthesis to produce the FT liquid product at 130.
  • the synthesis gas for use at 130 (or 120) is obtained via, for example a syngas pipeline.
  • the syngas utilized at 130 (and/or 120) is obtained by producing synthesis gas at 1 10.
  • the synthesis gas produced at 1 10 may be further treated at 120 for removal of at least one component therefrom.
  • providing a first component comprising FT hydrocarbon(s) at 100 comprises producing synthesis gas 1 10.
  • Producing synthesis gas 1 10 can comprise introducing a feed material into a synthesis gas production apparatus 10 and operating synthesis gas production apparatus 10 at syngas producing conditions to provide synthesis gas.
  • Synthesis gas may be produced by gasification of coal at a temperature in the range of from about 1500°F (816°C) to about 2500°F (1371 °C), from about 1600°F (871 °C) to about 2300°F (1260°C) or from about 1800°F (982°C) to about 2100°F (1 149°C).
  • Synthesis gas may be produced by gasification of coal at a pressure in the range of from about 50 psig (345 kPa) to about 500 psig (3447 kPa), from about 100 psig (689 kPa) to about 450 psig (3102 kPa) or from about 300 psig (2068 kPa) to about 450 psig (3103 kPa).
  • Feed material is introduced into syngas production apparatus 10 via one or more inlet lines 15.
  • feed material comprising biomass, coal, natural gas, waste material or a combination thereof is converted to synthesis gas within synthesis gas production apparatus 10.
  • synthesis gas production apparatus 10 comprises a gasifier and synthesis gas is produced via gasification. Gasification of a feed material comprising coal, waste material, biomass, or a combination thereof may be carried out to produce synthesis gas at 1 10. Steam may also be introduced into syngas production apparatus 10.
  • producing synthesis gas at 1 10 comprises steam reforming of natural gas or liquids by introduction thereof along with steam (via one or more inlet lines 15) into a steam reformer 10.
  • the synthesis gas produced in synthesis gas production apparatus 20 may comprise one or more undesirable components or may have an undesirable molar ratio of synthesis gas components (i.e. hydrogen and carbon monoxide).
  • method II may further comprise removing one or more components from the synthesis gas prior to FT conversion at 130.
  • the crude synthesis gas produced at 1 10 or a synthesis gas obtained via a pipeline is introduced into synthesis gas clean-up/conditioning apparatus 20 to remove at least one undesirable component therefrom and/or to increase the amount of a desired component therein (e.g. increase H 2 and decrease CO via the water gas shift reaction, WGSR).
  • synthesis gas clean-up/conditioning apparatus is operated to increase the molar ratio of H :CO from a crude synthesis gas having a molar ratio in the range of from about H 2 :CO in the range of from about 0.3 to about 2.2, from about 0.8 to about 1.6 or from about 0.9 to about 1.1 from a crude synthesis gas comprising a molar ratio of H 2 :CO in the range of from about 0.3 to about 2.1, from about 0.8 to about 1.6 or from about 0.9 to about 1.1.
  • providing first component comprising FT hydrocarbons 100 further comprises subjecting synthesis gas to FT synthesis to produce FT product 130.
  • cleaned-up and/or conditioned synthesis gas from 120 and/or synthesis gas obtained via a pipeline is subjected at 130 to FT synthesis to produce FT product comprising hydrocarbons.
  • the first component of step 100 is a fraction of an FT product comprising FT liquids. In embodiments, the first component of step 100 is a fraction of an FT product comprising FT wax. In embodiments, the first component of step 100 is a fraction of an FT product comprising light products; the light products may be in the range of from about C3- C20.
  • the first step in some embodiments is to hydrotreat the light FT liquids (which are vapors at reaction conditions with a boiling range of C3-C20 typically. The light liquids can be hydrotreated over a standard petroleum refining catalyst system comprising cobalt and/or molybdenum sulfide on a support.
  • Hydrocracking can also use cobalt and molybdenum sulfide catalyst and/or precious metal containing catalysts. This typically occurs at pressures from 600 - 2500 psig (4137 - 17,237 kPa) at temperatures from 400°F (204°C) to 800°F (427°C) and typically higher temperature than the hydrotreating step.
  • the first component comprises one or more FT hydrocarbons boiling at a temperature in the range of from about 80°F (27°C) to about 1000°F (538 °C).
  • suitable FT hydrocarbons include middle distillate fuels.
  • Middle distillate fuels generally contain hydrocarbons that boil in the middle distillate boiling range in the range from about 300°F (149°C) to about 750°F (399°C).
  • Typical middle distillates may include for example, jet fuel, kerosene, diesel fuel, light cycle oil, atmospheric gas oil, and vacuum gas oil.
  • the feed generally may contain a mixture of hydrocarbons having a boiling range (ASTM D86) of from about 300°F (149°C) to about 750°F (399°C).
  • the middle distillate feed has a boiling range of from about 350°F (177°C) to about 725°F (385°C).
  • the middle distillate feed may have a mid-boiling point (ASTM D86) of greater than about 350°F (149°C).
  • the middle distillate feed has a mid-boiling point of greater than about 400°F (204°C).
  • the middle distillate feed has a mid-boiling point of greater than about 450°F (232°C).
  • the middle distillate feed has an API gravity (ASTM D287) of from about 20 to about 50.
  • suitable middle distillate feeds generally have a minimum flash point (ASTM D93) of greater than about 80°F (27°C).
  • the middle distillate feed has a minimum flash point of greater than about 90°F (32°C).
  • a suitable middle distillate feed is light cycle oil (LCO).
  • one or more triglycerides can mix with a middle distillate feed.
  • hydrocarbons include, but are not limited to, gasoline, naphtha, and atmospheric tower bottom.
  • FT hydrocarbons useful as first component generally may contain a quantity of aromatics, olefins, and sulfur, as well as paraffins and naphthenes.
  • the amount of aromatics in the FT hydrocarbon generally may be in an amount in the range of from about 10 to about 90 weight percent aromatics based on the total weight of the hydrocarbon. In an embodiment, aromatics are present in an amount in the range of from about 20 to about 80 weight percent, based on the total weight of the first component.
  • the amount of olefins in the FT hydrocarbon generally may be in an amount of less than about 10 weight percent olefins based on the total weight the first component. In an embodiment, olefins are present in an amount of less than about 5 weight percent olefins. In another embodiment, olefins are present in an amount of less than about 2 weight percent olefins.
  • the amount of sulfur in the first (FT hydrocarbon) component will generally be less than about 10 parts per million by weight (ppmw) sulfur.
  • sulfur is present in the first component is in the range of from about 25 ppmw to about 50 ppmw sulfur.
  • sulfur is present in the first component in the range of from about 150 ppmw to 4,000 ppmw.
  • the term 'sulfur' denotes elemental sulfur, and also any sulfur compounds normally present in a hydrocarbon stream, such as diesel fuel.
  • Product upgrading apparatus 40 may thus comprise desulfurization apparatus, as described hereinabove.
  • product upgrading at 300 can comprise removing one or more sulfur compounds from the first component, from the second component, from both the first component and the second component separately, or from a mixture of the first and second components.
  • method II further comprises providing a second component comprising biomass at 200.
  • Figure 4 is a schematic of a method 200 of providing a second component comprising biomass 200 according to an embodiment of this disclosure.
  • providing a second component comprising biomass comprises obtaining biomass 210.
  • Obtaining biomass 210 comprises obtaining a biomass containing one or more triglycerides or fatty acids of triglycerides, or mixtures thereof. According to this disclosure, such triglycerides, fatty acids of triglycerides, or mixtures thereof can be converted, to form a hydrocarbon mixture useful for liquid fuels and chemicals.
  • 'triglyceride refers to any naturally occurring ester of a fatty acid and/or glycerol having the general formula CH 2 (OCORi)CH(OCOR 2 )CH 2 (OCOR 3 ), where Ri, R 2 , and R3 are the same or different, and may vary in chain length.
  • the biomass comprises one or more vegetable oil, such as for example, canola and soybean oils containing triglycerides with three fatty acid chains.
  • Suitable triglycerides include triglycerides that can be converted to hydrocarbons when contacted under suitable reaction conditions.
  • suitable triglycerides include, but are not limited to, vegetable oils including soybean and corn oil, peanut oil, sunflower seed oil, coconut oil, babassu oil, grape seed oil, poppy seed oil, almond oil, hazelnut oil, walnut oil, olive oil, avocado oil, sesame, oil, tall oil, cottonseed oil, palm oil, ricebran oil, canola oil, cocoa butter, shea butter, butyrospermum, wheat germ oil, illipse butter, meadowfoam, seed oil, rapeseed oil, borange seed oil, linseed oil, castor oil, vernoia oil, tung oil, jojoba oil, ongokea oil, yellow grease (for example, as those derived from used cooking oils), and animal fats, such as tallow animal fat, beef fat, and milk fat, and the like and mixtures and combinations thereof.
  • vegetable oils including soybean and corn oil, peanut oil, sunflower seed oil, coconut oil, babassu oil, grape seed oil, poppy seed oil, almond oil,
  • brown greases which include waste vegetable oils, animal fats, grease, etc. that are recovered from a waste water component called a grease trap.
  • Brown grease is generally the grease that is removed from wastewater sent down a restaurant's sink drain. As brown grease is contaminated and generally considered unsuitable for re-use in most applications, it may be particularly desirable as a second component herein for economic reasons.
  • yellow grease is also suitable for use as second component according to this disclosure. Yellow grease is distinct from brown grease, and is typically used-frying oils from deep fryers, whereas brown grease is sourced from grease interceptors. Yellow grease can also refer to lower-quality grades of tallow from rendering plants.
  • yellow grease is recovered, traded as a marginally valuable commodity, and has traditionally been used to spray on roads as dust control, or as animal feed additive, but has also become a feedstock for biodiesel production.
  • the utilization of yellow grease may be particularly attractive for use as at least a fraction of the second biomass component because it is an inexpensive waste and can be converted via the disclosed system and method into valuable product(s) (i.e. into fuel and/or biochemical). This makes it particularly desirable for utilization in method II disclosed herein.
  • any suitable triglyceride can be used as or as a component of the second component in combination with the one or more FT hydrocarbons of the first component.
  • at least a portion of the second component comprises one or more triglycerides selected from the group consisting of vegetable oil, yellow grease (used restaurant oil), brown grease, animal fats, and combinations of any two or more thereof.
  • providing second component 200 can further comprise removing one or more undesirable component from biomass to provide a purified biomass 220.
  • one or more components may be removed from the biomass obtained at 210 by any method known in the art.
  • removing one or more component from the biomass at 220 may comprise removing solids via centrifugation, filtration, settling or a combination thereof.
  • providing second component 200 can further comprise bringing the biomass from 210 or 220 to desired operating conditions upgrading.
  • the biomass or biomass derived oil is heated and/or maintained at a temperature in the range of from about 50°F (10°C) to about 300°F (149°C), from about 100°F (38°C) to about 300°F (149°C), or from about 100°F (38°C) to about 250°F (121°C) prior to upgrading.
  • the biomass is pressurized and/or maintained at a pressure in the range of from about 0 psig (0 kPa) to about 500 psig (3447 kPa), from about 50 psig (35 kPa) to about 200 psig (1379 kPa), or from about 75 psig (517 kPa) to about 150 psig (1034 kPa) prior to upgrading.
  • the amount of sulfur in the second (biomass) component will generally be less than about 50 parts per million by weight (ppmw) sulfur.
  • sulfur is present in the second component in the range of from about 100 ppmw to about 50,000 ppmw sulfur.
  • sulfur is present in the second component in the range of from about 150 ppmw to 4,000 ppmw.
  • Product upgrading apparatus 40 may thus comprise desulfurization apparatus, as described hereinabove.
  • product upgrading at 300 can comprise removing one or more sulfur compounds from the first component, from the second component, from both the first component and the second component separately, or -from a mixture of the first and second components.
  • method II further comprises upgrading first and second components at 300 to produce product selected from biofuels and chemicals.
  • Figure 5 is a schematic of a method 500 of upgrading first and second components 300 to produce desirable product according to an embodiment of this disclosure.
  • upgrading first and second components at 300 comprises converting at least a fraction of the first and second components to bioproduct.
  • Upgrading first and second components at 300 may further comprise removing at least one undesirable compound from the first and/or the second components 320 or from the product of 310.
  • First component obtained at 100 and second component obtained at 200 are upgraded at 300 to produce a desired product selected from biofuels and biochemicals.
  • first and second components are combined, for example via lines 36 and 58 to form a feed mixture that is subsequently introduced into upgrading apparatus 40.
  • lines 57 and/or 58 can be used to feed pyrolysis oil produced either at a remote pyrolysis unit and transported to the site or produced via an on-site pyrolysis oil generator.
  • the first component and the second component are introduced separately, for example via lines 36 and 57, into upgrading apparatus 40.
  • the first component is introduced into a different unit of product upgrading apparatus 40 from the unit into which the second component is introduced.
  • the second (biomass) component may be introduced into a unit of product upgrading apparatus 40 configured for saturation and removal of the high level of oxygen that could be present in fats, vegetable oils, and pyrolysis oils there from in the presence of an oxygen-resistant catalyst. Subsequent saturation and removal of oxygen, the first component and the saturated second component may be introduced into another unit within product upgrading apparatus 40. In this manner, catalyst utilization may be reduced.
  • a separate unit may be desirable because a FT LFTL HT may not be designed for the higher O in these feedstocks.
  • the amount of triglyceride used as the starting material for upgrading apparatus 40 will generally depend on the size of the commercial process and the suitability of the mixing reaction vessel.
  • the second (biomass) component is present in an amount in the range of from about 0.1 to about 100 percent by weight, based on the total weight percent of first and second components.
  • the triglyceride-containing material is present in an amount of from about 2 weight percent to about 80 weight percent, based on the total weight first and second components.
  • the triglyceride-containing material is present in an amount of less than 50 weight percent, based on the total weight of the first and second components.
  • the first component i.e. the FT hydrocarbon
  • the first component is present in an amount in the range of from about 0.1 to about 99.9 percent, based on the total weight percent the first and second components.
  • the FT hydrocarbon is present in an amount in the range of from about 50 weight percent to about 99.9 weight percent based on the total weight of the first and second components.
  • upgrading first and second components comprises contacting the first component comprising FT hydrocarbon(s) and the second component comprising triglycerides or mixtures thereof with a catalyst composition under a condition sufficient to produce a reaction product containing diesel, jet or a combination thereof.
  • Useful catalyst compositions for use in upgrading at 300 include catalysts effective in the conversion of triglycerides to hydrocarbons when contacted under suitable reaction conditions, as disclosed hereinabove.
  • upgrading at 300 comprises hydrotreating the first component, the second component or both (separately, concomitantly or as a mixture).
  • the reaction conditions for hydrotreating can comprise an operating temperature in the range of from about 600°F (316°C) to about 800°F (427°C), or in the range of from about 700°F (371 °C) to about 800°F (427°C).
  • the pressure is generally in the range of from about 100 pounds per square inch gauge (psig; 689 kPa) to about 750 psig (5171 kPa), in the range of from about 100 psig (689 kPa) to about 350 psig (2413 kPa) or about 150 psig (1034 kPa).
  • the pressure may be in the range of from about 400 psig (2757 kPa) to about 750 psig (5171 kPa) or may be about 500 psig (3447 kPa).
  • 'liquid hourly space velocity' or 'LHSV is defined as the numerical ratio of the rate at which the reactants are charged to the reaction zone in barrels per hour at standard conditions of temperature and pressure (STP) divided by the barrels of catalyst contained in the reaction zone to which the reactants are charged.
  • the LHSV for hydrotreating is generally in the range of from about 0.2 h "1 to about 10 h "1 , from about 0.5 h "1 to about 5 h " ', from about 1.0 h '1 to about 4.0 h 'or from about 1.5 h "1 to 3.0 h "1 .
  • Upgrading at 300 comprises contacting a first FT liquid product, a second biomass component comprising a triglyceride-containing material and/or both (separately or as a mixture) with a hydrogen-containing gas.
  • hydrogen-containing gas is introduced into upgrading apparatus 40 via hydrogen supply line 37.
  • the hydrogen- containing gas contains more than about 25 volume percent hydrogen based on the total volume of the hydrogen-containing gas.
  • the hydrogen containing gas contains more than about 50 volume percent hydrogen.
  • the hydrogen containing gas contains more than about 75 volume percent hydrogen.
  • the rate at which the hydrogen-containing gas is introduced to the reaction zone of a hydrotreater of product upgrading apparatus 40 is in the range of from about 300 standard cubic feet per barrel (SCFB) of reactants (first and/or second components) to about 10,000 SCFB.
  • the hydrogen-containing gas is introduced to the reaction zone of a hydrotreater of product upgrading apparatus 40 at a rate in the range of from about 1,200 SCFB to about 8,000 SCFB, from about 2,500 SCFB to about 6,000 SCFB, or from about 3,000 SCFB to 5,000 SCFB.
  • the triglyceride-containing second component and/or FT hydrocarbon-containing first component are introduced into one or more hydrotreaters concomitantly with hydrogen- containing gas.
  • a common inlet port may be utilized in embodiments.
  • the FT hydrocarbon-containing first component, the triglyceride-containing second component and hydrogen-containing gas are combined prior to introduction into product upgrading apparatus (e.g. a hydrotreater thereof), and are thereafter co-fed into the reaction zone.
  • the hydrogen consumption rate under reaction conditions is proportional to the pressure of the reaction conditions employed.
  • hydrogen may be consumed in an amount up to the amount of hydrogen initially charged to the reaction zone of upgrading apparatus 40.
  • the amount of hydrogen consumed in the reaction at a pressure of less than about 500 psig (3447 kPa) is less than the amount of hydrogen consumed in the reaction at a pressure of about 500 psig (3447 kPa).
  • sulfur compounds present in the first and/or second components are removed via upgrading at 300, especially in embodiments employing a sorbent composition.
  • the initial amount of sulfur present in the feed to the upgrading apparatus is greater than about 500 ppm.
  • hydrocarbon products obtained via upgrading at 300 have a sulfur content that is less than the sulfur content present in the reaction feed.
  • the sulfur content of the product is at least 5, 10, 15 or 25% less than the sulfur content of the upgrading apparatus feed.
  • upgrading at 300 comprises removing sulfur and/or sulfur compounds from the first component, the second component, or both (together of separately) by subjecting the first component and/or the second component or a mixture of the first and second components to desulfurization.
  • upgrading apparatus 40 comprises desulfurization apparatus configured for removal of sulfur compounds including, but not limited to, hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS) mercaptans (RSH), organic sulfides (R--S--R), organic disulfides (R--S--S--R), thiophene, substituted thiophenes, organic trisulfides, organic tetrasulfides, benzothiophene, alkyl thiophenes, dibenzothiophene, alkyl benzothiophenes, alkyl dibenzothiophenes, and the like, and mixtures thereof as well as heavier molecular weights
  • upgrading at 300 comprises removing nitrogen and/or nitrogen compounds from the first component, the second component, or both (together of separately) by subjecting the first component and/or the second component or a mixture of the first and second components to denitrogenation.
  • upgrading apparatus 40 comprises denitrogenation apparatus configured for removal of nitrogen compounds including, but not limited to, nitrogen, ammonia and cyanide compounds.
  • upgrading at 300 comprises removing oxygen and or oxygen-containing compounds from the first component, the second component, or both (together of separately) by subjecting the first component and/or the second component or a mixture of the first and second components to deoxygenation.
  • upgrading apparatus 40 comprises deoxygenation apparatus configured for removal of oxygen compounds including, but not limited to, olefins and alcohols.
  • upgrading 300 comprises olefin saturation, aromatic saturation, and/or decarboxylation to remove carboxylic acids followed by hydroisomerization to convert some normal paraffins to iso-paraffins.
  • the reaction product in accordance with the present invention, generally comprises gas and liquid fractions containing hydrocarbon products, which include, but are not limited to, diesel boiling-range hydrocarbons, hydrocarbons suitable for use as or in jet fuel, and valuable biochemicals, such as propane.
  • the reaction product generally comprises long chain carbon compounds having 13-20 or more carbon atoms per molecule.
  • the reaction product comprises carbon compounds having 15 to 18 or more carbon atoms per molecule.
  • the reaction product can further comprise propane and by-products of carbon monoxide and carbon dioxide (CO x ).
  • the upgraded product comprises primarily (i.e. greater than 75, 80, 85, 90 or 95 weight percent) straight chain hydrocarbons.
  • the upgraded product comprises.
  • the reaction product comprises diesel meeting ASTM D975 specifications.
  • the reaction product comprises jet fuel meeting commercial jet fuel specifications incorporated in ASTM D1655.
  • the reaction product comprises diesel and or jet fuel comprising less than about 50 ppm sulfur.
  • the hydrocarbon reaction product contains a greater amount of Ci 7 fractions than Ci 8 fractions.
  • the Ci 7 /Ci 8 fraction is greater than about 1.
  • the Q 7 /Ci 8 fraction is greater than about 1.2.
  • the Ci /Ci 8 fraction may be increased by utilizing reaction conditions including pressures generally in the range of from about 100 psig (689 kPa) to about 200 psig (1,379 kPa). Lower reaction pressures may result in the greater production of Ci 7 , less hydrogen consumption, and lower product cloud and pour points. A reduction in pressure may also promote decarboxylation (i.e., removal of C0 2 ) over dehydration to give a higher ratio of Ci 7 /Ci 8 and a lower consumption of hydrogen.
  • the acid content of the hydrocarbon product is measured by the total acid number or 'TAN.'
  • the total acid number (TAN) is defined as milligrams of potassium hydroxide (KOH) necessary to neutralize the acid in 1 gram of oil and is determined using ASTM test method D 644-95 (Test Method for Neutralization Number by Potentiometric Titration).
  • KOH potassium hydroxide
  • ASTM test method D 644-95 Test Method for Neutralization Number by Potentiometric Titration
  • the cetane number of the hydrocarbon product is determined using ASTM test method D 613.65.
  • the cetane number of the hydrocarbon product produced according to this disclosure has a cetane number greater than that of the feed material (i.e. the first and second components).
  • the pour point is the lowest temperature at which a hydrocarbon product will begin to flow and is measured at intervals of 5°F ( ⁇ 2.5°C). This interval gives a range in which to account for error inherent in the measuring procedure. For example, a sample with a pour point of 10.5°F (- 1 1.9°C) and a sample with a pour point of 14.5°F (-9.7°C) would be labeled as having a pour point of 15°F (-9.4°C).
  • the pour point of the hydrocarbon product produced in accordance with the present invention can be determined using ASTM test method D 97.
  • FT fuels produced via this disclosure have a pour point of less than 20°F (-6.7°C), less than 10°F (-12.2°C) or less than 5°F (-15°C).
  • the cloud point of the hydrocarbon product can be determined using ASTM test method D 2500.
  • the cloud point is the temperature at which dissolved solids, such as wax crystals, begin to form in a hydrocarbon product as it is cooled.
  • the FT fuels produced via this disclosure exhibit a cloud point of less than 25°F (-3.9°C), less than 20°F (-6.7°C), or less than 10°F (-12.2°C).

Abstract

La présente invention concerne un système de production d'au moins un biocarburant, un additif pour biocarburant ou un produit biochimique, comprenant un appareil de production FT comportant au moins un réacteur FT assurant la production d'hydrocarbures FT à partir de gaz de synthèse, et un appareil de valorisation en connexion fluidique avec l'appareil de production FT et conçu pour accueillir, par l'intermédiaire d'un ou plusieurs orifices d'entrée, un premier composant contenant des hydrocarbures FT et un second composant contenant de l'huile issue de la biomasse, cela étant suivi de la réduction du degré d'insaturation desdits composants par hydrogénation. L'invention concerne également un procédé de production d'un biocarburant ou d'un produit biochimique, comprenant les étapes consistant à introduire un premier composant contenant des hydrocarbures FT et un second composant contenant au moins un triglycéride dans un appareil de valorisation conçu pour accueillir le premier composant et le second composant, à réduire le degré d'insaturation de ceux-ci par hydrogénation, et à extraire, dudit appareil de valorisation, le produit valorisé contenant au moins un composant choisi dans le groupe constitué des carburants et des produits chimiques.
PCT/US2011/062426 2010-12-21 2011-11-29 Production d'un biocarburant faisant intervenir l'introduction simultanée, dans une installation de valorisation, de cire de fischer-tropsch et d'huile dérivée de la biomasse WO2012087505A2 (fr)

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