WO2019084657A1 - Procédé de production de biocarburants hydrocarbonés - Google Patents

Procédé de production de biocarburants hydrocarbonés Download PDF

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Publication number
WO2019084657A1
WO2019084657A1 PCT/CA2017/051317 CA2017051317W WO2019084657A1 WO 2019084657 A1 WO2019084657 A1 WO 2019084657A1 CA 2017051317 W CA2017051317 W CA 2017051317W WO 2019084657 A1 WO2019084657 A1 WO 2019084657A1
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Prior art keywords
catalyst
fatty acid
hydrogen
oil
organic compound
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PCT/CA2017/051317
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English (en)
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Sundaramurthy VEDACHALAM
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The Saskatchewan Research Council
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Publication of WO2019084657A1 publication Critical patent/WO2019084657A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
    • 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
    • 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
    • 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
    • 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 disclosure relates to methods, compositions, and uses of decarbonylation and decarboxylation catalysts to produce renewable hydrocarbons.
  • Biofuels are fuels produced from biomass - organic matter derived from living, or recently living organisms. Biofuels, as opposed to fossils fuels, are renewable resources and can provide a sustainable supply of fuel. However, compared to fossil fuels, biomass is more functionalized and requires defunctionalization in order to make it readily usable with existing fuel consumption technologies 1 .
  • Biodiesel a first generation biofuel
  • a transesterifi cation process resulting in a fuel that is chemically different from petrodiesel, because it contains oxygen atoms in the form of a fatty acid methyl ester.
  • the presence of oxygen in biodiesel reduces energy density.
  • Biodiesel also has issues of reduced fluidity at low temperature and difficulties in long term storage due to oxidative degradation of its unsaturated components. Thus, biodiesel is not typically used as a complete replacement for petrodiesel fuel, but is rather blended with petrodiesel.
  • Biodiesel is a first generation biofuel, meaning that only a portion of the energy potentially available in the biomass is used.
  • renewable diesel also called green diesel, second generation diesel, and drop-in diesel
  • green diesel is a second generation biofuel that overcomes the drawbacks of biodiesel. This is because renewable diesel is functionally similar and as oxygen-free as petrodiesel. Renewable diesel can be simply "dropped-in" in place of petrodiesel.
  • hydrodeoxygenation reaction is the most commonly used pathway for deoxygenating oils and fats ⁇ e.g. triglycerides) and their derivatives such as fatty acids and fatty acid esters to hydrocarbons. Hydrodeoxygenation of a fatty acid is shown below:
  • noble metal based catalysts especially pailadium and platinum, have been used in decarboxylation/decarbonylation reactions 2 34 . These noble metal based catalysts generally result in excellent yields of hydrocarbons from free fatty acids.
  • palladium and platinum are expensive and can rapidly deactivate. Therefore finding an inexpensive or less expensive catalyst showing similar performance and greater durability is of great interest for use in an industrial setting.
  • the present invention relates to catalysts for use in deoxygenation reactions, wherein the catalyst is a mixed metal oxide.
  • the present invention provides a method of deoxygenating a feedstock, said feedstock comprising at least one oxygenated organic compound, to form a hydrocarbon product, comprising the steps of contacting the feedstock with a mixed metal oxide catalyst under conditions to promote deoxygenation of the at least one oxygenated compound.
  • the catalyst comprises a mixed metal oxide of the empirical formula:
  • M 1 is a metal selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Mo, Ni, Os, Pd, Pt, Rh, Ru, and W
  • 2 is a metal selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Mo, Ni, Os,Pd, Pt, Rh, Ru, and W, but is not the same as M 1
  • x is 0 or 1
  • y is 0 or 1 .
  • 2 is selected from the group consisting of Ag, Au, Co, Ir, Ni, Os, Pd, Pt, Rh, and Ru.
  • M 1 is selected from the group consisting of Co and Ni.
  • the catalyst comprises a mixed metal oxide of the formula: MO-
  • Advantages of the present invention may include low cost of the catalyst since it uses mostly non-noble metals, and long life of the catalyst compared with Pd only catalysts.
  • Advantages of the present invention when using, in particular the two-step process (i.e. triglycerides are first converted into free fatty acids (FFA) or fatty acid methyl esters (FAME) and then deoxygenated with the present catalyst into hydrocarbons), may include: deoxygenation of FFA and FAME with the present catalyst can occur at near atmospheric pressure (e.g. 0.5 MPa), hydrogen consumption due to the methanation side reaction is minimal, and hydrogen is principally consumed simply to saturate the olefin bonds.
  • FFA free fatty acids
  • FAME fatty acid methyl esters
  • Figure 1 shows a scheme for the production of renewable diesel from triglycerides.
  • Figure 2 shows a co-precipitation method of catalyst synthesis.
  • Figure 3 shows results of a catalyst screening test.
  • Figure 4 shows the composition of FAME obtained from canola, palm and carinata oils.
  • the first bar represents canola FA E
  • the second bar represents palm FAME
  • the third bar represents carinata FAME.
  • the present invention provides a method of deoxygenating a feedstock, comprising at least one oxygenated organic compound, to form a hydrocarbon product, comprising the steps of contacting the feedstock with a catalyst under conditions to promote deoxygenation of the at least one oxygenated compound.
  • the catalyst comprises a mixed metal oxide of the empirical formula:
  • M 1 is a metal selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Mo, Ni, Os, Pd, Pt, Rh, Ru, and W
  • M 2 is a metal selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Mo, Ni, Os, Pd, Pt, Rh, Ru, and W, but is not the same as M 1
  • x is 0 or 1
  • y is 0 or 1 .
  • 1 is selected from the group consisting of Co and Ni.
  • M 2 is selected from the group consisting of Ag, Au, Co, Ir, Ni, Os, Pd, Pt, Rh. and Ru.
  • the catalyst comprises a mixed metal oxide of the formula MO- ZnO-(AI 2 0 3 ) >; , wherein M is Co, Ni, or CoNi , and x is 0 or 1. Definitions
  • biomass refers to a renewable resource of biological origin, such as plants or animals, such resources generally being exclusive of fossil fuels.
  • Bioly-derived oil or fat refers to oil or fat that is, at least partially, derived from a biomass such as, but not limited to, craps, vegetables, microalgae, and the like.
  • Renewable Fuel refers to a hydrocarbon-based fuel, derived from biomass, suitable for consumption by vehicles. Such fuels include, but are not limited to, diesel, gasoline, jet fuel and the like. "Renewable diesel” refers to herein as green diesel, second generation diesel, or drop-in diesel.
  • Renewable Jet Fuel refers to herein as biojet fuel, aviation fuel, or drop-in jet fuel.
  • Triglyceride refers to class of molecules having the following general formula:
  • R 1 , R 2 , and R 3 are molecular chains comprising carbon and hydrogen, and can be the same or different, and wherein one or more of the branches defined by R 1 , R 2 , and R 3 can have unsaturated regions.
  • a "fatty acid,” or “free fatty acid” (FFA) as defined herein, is a class of organic acids having the general formula R— COOH, where R is generally a molecular chain comprising carbon and hydrogen, which can have unsaturated regions, i.e. R is a saturated (alkyl) hydrocarbon chain or a mono- or polyunsaturated (alkenyl) hydrocarbon chain.
  • a "fatty acid methyl ester” as defined herein, is a class of organic esters have the general formula R— COOCH 3 , where R is generally a molecular chain comprising carbon and hydrogen, which can have unsaturated regions, i.e. R is a saturated (alkyl) hydrocarbon chain or a mono- or polyunsaturated (alkenyl) hydrocarbon chain. They are generally derived from vegetable oils by transesterification of fats with methanol.
  • An “oxygenated organic compound”, as defined herein, is any oxygen containing organic compound, in particular, a carboxylic acid, a carboxylic ester, a ketone, an aldehyde, or a mixture thereof.
  • the oxygenated organic compound may be a triglyceride, a free fatty acid, a fatty acid alkyl ester, a fatty aldehyde, or a combination thereof.
  • the oxygenated organic compound is an FFA or a FAM E.
  • Deoxygenation refers to the removal of oxygen from organic molecules, such as fatty acid derivatives, alcohols, ketones, aldehydes or ethers.
  • Decarboxylation refers to the removal of the carboxyl oxygen from acid and ester molecules as carbon dioxide.
  • Decarbonylation refers to the removal of carbonyl oxygen from organic molecules with carbonyl functional groups.
  • “Lower alkyl” or “lower aliphatic” refers to an alkyl or aliphatic group, respectively, having 1 to 6 carbon atoms.
  • the feedstock used in the embodiments described herein originates from renewable sources, such as fats and oils from plants, animals, and/or algae, biocrudes from wood, and compounds derived therefrom.
  • suitable materials are wood-based, plant-based, or vegetable-based fats and oils.
  • Suitable materials also include micro and macro algae sources.
  • Algae oils or lipids can typically be contained in algae in the form of membrane components, storage products, and/or metabolites.
  • Certain algal strains, particularly microalgae such as diatoms and cyanobacteria, can contain proportionally high levels of lipids.
  • Suitable oils include algae oil, babassu oil, camelina oil, carinata oil (from Brassica carinata), castor oil, coconut oil, colza oil, corn oil, flaxseed (linseed) oil, hempseed oil, jatropha oil, jojoba oil, lard, mustard oil, olive oil, palm oil, palm kernel oil, peanut oil, pennycress oil, pongamia oil, rapeseed (canola) oil, rice bran oil, safflower oil, soybean oil, sunflower oil, tall oil, tallow oil, or any combination thereof.
  • the feedstock is an industrial oilseed crop.
  • Suitable material also includes feedstocks from an industrial or other non-biological source, such as, for example industrial waste oils, recycled lipids, yellow and brown greases, and waxes.
  • Suitable feedstocks comprise an oxygenated organic compound .
  • Such oxygenated organic compound is preferably a carboxylic acid, a carboxylic ester, an aldehyde, a ketone or a mixture thereof.
  • the oxygenated organic compound may be a triglyceride, a free fatty acid, a fatty acid alkyl ester (wherein the alkyl groups typically contain one to five carbon atoms), a fatty aldehyde and ketone, or a combination thereof.
  • the oxygenated organic compound is a triglyceride, a free fatty acid (FFA), a fatty acid methyl ester (FAME) a fatty acid ethyl ester (FAEE), or a combination thereof.
  • the suitable materials comprise C e -C 2 4 fatty acids, or derivatives thereof, or triglycerides thereof.
  • Suitable feedstocks usable in the present invention can include any of those which comprise triglycerides, free fatty acids (FFAs), or fatty acid alkyl esters (e.g. FAMEs and/or FAEEs), or a mixture thereof.
  • the triglycerides, FFAs, and FAMEs typically contain aliphatic hydrocarbon chains in their structure having from 6 to 36 carbons, preferably from 10 to 26 carbons, for example from 12 to 24 carbons.
  • Types of triglycerides can be determined according to their fatty acid constituents. The fatty acid constituents can be readily determined using Gas Chromatography (GC) analysis.
  • GC Gas Chromatography
  • This analysis involves extracting the fat or oil, saponifying (hydrolyzing) the fat or oil, preparing an alkyl (e.g., methyl) ester of the saponified fat or oil, and determining the type of (methyl) ester using GC analysis.
  • a majority (i.e., greater than 50%) of the triglyceride present in the lipid material can be comprised of C a to C 3 ⁇ 4 fatty acid constituents, based on total triglyceride present in the lipid material.
  • a triglyceride is a molecule having a structure identical to the reaction product of glycerol and three fatty acids.
  • a triglyceride is described herein as being comprised of fatty acids, it should be understood that the fatty acid component does not necessarily contain a carboxylic acid hydrogen. If triglycerides are present, a majority of triglycerides present in the bio mass feed can preferably be comprised of C 12 to C 2 4 fatty acid constituents, based on total triglyceride content. Other types of feed that are derived from biological raw material components can include fatty acid alkyl esters, such FAME and/or FAEE, as well as fatty aldehydes and ketones.
  • the feedstock can include at least 0.1 wt % of feedstock based on a biomass source, or at least 20 wt%, or at least 50 wt%, or at least 70 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at least 95 wt%, or at least 97 wt%, or at least 98 wt%, or at least 99 wt%, or 100 wt%.
  • the feedstock can include at least about 1 % by weight of glycerides, lipids, fatty acids, fatty aldehydes, fatty acid esters (such as fatty acid alkyl esters), fatty aldehyde ketones or a combination thereof.
  • the glycerides can include monoglycerides, diglycerides, or triglycerides.
  • the feedstock can include at least about 50 wt%, at least about 70 wt%, at least about 75 wt%, at least about 80 wt %, at least about 85 wt%, at least about 90 wt%, at least about 95 wt%, at least about 97 wt%, or about 100 wt% of glycerides, lipids, fatty acids, fatty aldehydes, fatty acid esters, fatty acid alkyl esters, ketones or a combination thereof.
  • the glycerides, FFAs, and fatty acid alkyl esters of the typical vegetable oil or animal fat contain aliphatic hydrocarbon chains in their structure which have about 6 to about 24 carbon atoms.
  • the oxygen level in the feedstock for natural oils can range from 0.5 to 20 wt% and more typically from 5 to 15 wt%.
  • the feedstocks may contain trace amounts of impurities such as P, Na, Ca, Mg and K originating from the phospholipids, a naturally occurring group of compounds in the oils. These impurities may adversely affect the performance of the deoxygenation process and may need to be removed to ppm levels prior to this step.
  • Typical pretreatment processes employed for this purpose include, but are not limited to, low temperature batch processes using solid adsorbents such as silica gel 10 , ion exchange resins 11 and clays, and the use of guard reactors using hydrotreating type catalysts operating at higher temperatures that are well known in the hydrotreating art.
  • the feedstock can also contain small amounts of nitrogen compounds derived from animal proteins or chlorophyll. The nitrogen content typically ranges from 0.5 ppm to 5000 ppm. Additional optional pretreatment steps may be used.
  • the feedstock can also include biodiesel fuels, which contain oxygenated organic compounds, such as FA Es and fatty acid ethyl esters (FAEE).
  • the feedstock can also include a wax ester, which is an ester of a fatty acid and a fatty alcohol.
  • Figure 1 shows a scheme for the production of renewable diesel from triglycerides, as well as from derivatives (i.e. FFA and FAME) thereof.
  • Triglycerides can be converted into free fatty acids (FFA) through a hydrolysis reaction:
  • FFAs and their derivatives can then be deoxygenated through decarbonylation or decarboxylation reactions to form hydrocarbons, in the presence of a deoxygenation catalyst.
  • Deoxygenation reactions are discussed in detail below.
  • the present application relates to the conversion of the triglycerides, FFAs and/or derivatives to hydrocarbons. These can be further upgraded ⁇ e.g. isomerized) to a drop-in fuel product, such as renewable diesel, renewable gasoline or jet fuel.
  • a drop-in fuel product such as renewable diesel, renewable gasoline or jet fuel.
  • the feedstock used in the present invention can be any organic hydrocarbon source containing an oxygenated hydrocarbon.
  • the feedstock can contain, for example, triglycerides, and/or it may contain FAMEs and/or FFAs, for example.
  • Triglycerides can be converted into hydrocarbons by either in a single step process or a two-step process.
  • the single-step process involves the direct deoxygenation of triglycerides into hydrocarbons.
  • triglycerides smoke, and thus deactivate catalysts.
  • deoxygenation is generally carried out at a hydrogen pressure of 8 MPa and above.
  • the deoxygenation reaction consumes hydrogen due to a side reaction, namely methanation of CO and C0 2 .
  • the presently described catalyst can be used in a single step deoxygenation process to produce hydrocarbons, it may, in some embodiments, be advantageous to use a two-step process due to lower hydrogen consumption.
  • the triglycerides are first converted into FAMEs or FFAs.
  • the FAMEs or FFAs are then deoxygenated with deoxygenation catalyst as described herein to form the alkanes.
  • the n-alkanes can then be further upgraded into drop-in fuels by methods known in the art.
  • the catalyst comprises a mixed metal oxide of the empirical formula:
  • M 1 is a metal selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Mo, Ni, Os, Pd, Pt, Rh, Ru, and W
  • M 2 is a metal selected from the group consisting o ⁇ Ag, Au, Co, Cr, Cu, Fe, Ir, Mo, Ni, Os, Pd, Pt, Rh, Ru, and W, but is not the same as M 1
  • x is 0 or 1
  • y is 0 or 1 .
  • 1 is selected from the group consisting of Co and Ni.
  • M 2 is selected from the group consisting of Ag, Au, Co, Ir, Ni, Os, Pd, Pt, Rh, and Ru.
  • the catalyst comprises a mixed metal oxide of the formula MO- ZnO-(AI 2 0 3 )>;, wherein M is Co, Ni or CoNi , and x is 0 or 1.
  • the catalyst can be or can comprise CoO-ZnO, CoO-ZnO-AI 2 0 3 , NiO-ZnO-AI 2 0 3 , NiO-ZnO, CoO-NiO-ZnO or CoO- iO-ZnO-AI 2 0 3 .
  • the weight ratio of MO to ZnO (or 1 M 2 0 to ZnO) is from 0.01 to 4.0, or more particularly from 0.25 to 1 .5.
  • the atomic ratio of M to Zn can be from about 0.01 :1 ,2 to about 1 :0,25, or more particularly from 0.25:1 to 0.8:0.5.
  • the amount of Al 2 0 3 in the catalyst varies from 0.1 % to 60 %, or more particularly from 1 % to 40%.
  • the catalyst is used in a reduced form, having the formula (M 2 )y(M 1 )-ZnO-(AI 2 0 3 )x , wherein M 1 is a reduced metal selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Mo, Ni, Os, Pd, Pt, Rh, Ru, and W; M 2 is a reduced metal selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Mo, Ni, Os, Pd, Pt, Rh, Ru, and W, but is not the same as M1 ; x is 0 or 1 ; and y is 0 or 1.
  • the oxide form of the catalyst is typically reduced prior to deoxygenation reaction using reducing agents known in the art, such as hydrogen.
  • the reduced from of the catalyst can be or can comprise Co- ZnO, Co-ZnO-AI 2 0 3 , Ni-ZnO-AI 2 0 3 , Ni-ZnO, Co-Ni-ZnO or Co-Ni-ZnO-AI 2 0 3 .
  • the reduced form of catalyst may contain some intermetallic particles of Zn. 12
  • Suitable mixed metal oxide compositions can advantageously exhibit a specific surface area (as measured via the nitrogen Brunauer-Emmett-Teller (BET) method using a Micromehtics ASAP 2010 instrument) of at least about 15 m 2 /g.
  • BET Brunauer-Emmett-Teller
  • the bulk metal oxide catalyst compositions can exhibit, in some embodiments, a specific surface area of not more than about 600 m 2 /g.
  • the catalyst is a heterogeneous catalyst and may be used as a bulk unsupported catalyst or as a supported catalyst.
  • the catalyst used in the present invention is a bulk catalyst.
  • the term "bulk”, when describing a mixed metal catalyst composition, indicates that the catalyst composition is self- supporting in that it does not require a carrier or support.
  • bulk catalysts may have some minor amount of carrier or support material in their compositions (e.g., about 15 wt % or less, about 10 wt % or less, about 5 wt % or less, or substantially no carrier or support, based on the total weight of the catalyst composition); for instance, bulk catalysts may contain an amount of a binder, e.g., to improve the physical and/or thermal properties of the catalyst.
  • the bulk metal catalyst comprises at least 90 wt %, more preferably at least 95 wt %, active metals.
  • the remainder of these bulk metal catalysts may be comprised of a suitable carrier or support, or in some embodiments, may contain additional organic compounds.
  • the mixed metal oxide catalyst may also be a supported catalyst.
  • Supported catalysts contain the mixed metal oxides on a high surface area material ⁇ i.e. su port).
  • the support may be, for example, alumina, silica-alumina, zeolites, mesoporous aluminosilicates, activated carbon, clay, hydrotalcite, or a metal oxide.
  • methods known in the art such as wet impregnation, may be used.
  • the bulk catalysts of the present invention may be converted to supported catalysts by dispersing the active mixed metal oxide or metal oxide precursors on the support, such as on an activated carbon support.
  • the mixed metal oxide catalyst is supported on an activated carbon support having a BET surface area of between 500 and 1500 m 2 /g.
  • the catalyst is deposited on a support selected from silica, alumina, silica-alumina, titania, zirconia, clay, zeolites, mesoporous aluminosilicates and mixtures thereof, and the support has a BET surface area of between 100 and 1000 m 2 /g.
  • the supported catalyst may contain least 1 %, by weight of the mixed metal oxide, based on the total weight of the catalyst, including any other desirable active components as well as an optional support material.
  • the amount of the mixed metal oxide will vary depending on how the catalyst is dispersed on the support.
  • the bulk catalyst can be prepared by methods know in the art. For instance, it can be prepared by co-precipitating metals with a carbonate solution followed by calcination to form an oxide form of catalyst, as shown in Figure 2.
  • MO-ZnO can be prepared by impregnating a metal salt solution onto ZnO. Examples of methods for making suitable CoO-ZnO and NiO-ZnO catalysts are known. 13 14
  • the prepared catalyst is generally in oxide form. In use, it is generally activated by in-situ or ex-situ reduction with hydrogen at 400-550 D C, 425-525 D C, or about 500°C.
  • the feedstock is contacted with the deoxygenation catalyst in a suitable reactor.
  • a single or multiple catalyst beds may be used.
  • the feed is passed over the catalyst in a fixed bed reactor operating in continuous mode.
  • the feed contacts the catalyst in a slurry bed reactor in continuous mode.
  • Either an upflow or downflow type reactor can be used. Multiple reactors may be used in parallel.
  • the feedstock can also be contacted with the catalyst in a batch reactor.
  • a continuous downflow fixed-bed reactor system can be used.
  • the reactor system consists of the following sections: (a) Reagent introduction system, (b) reaction chamber, (c) reaction chamber heating system, (d) pressure control system, (e) product collection system and (f) gas analysis system.
  • Reagent gas and liquid can be fed into the reactor via calibrated mass flow controllers and a metering pump.
  • the reaction chamber can consist of a tubular fixed-bed reactor enclosed in a furnace. Reactor products can be quenched in a knock-out pot.
  • the reactor system can be connected with two gas chromatographs equipped with thermal conductivity and flame ionization detectors, respectively, for the on-line analysis of both reagent and product gases.
  • the feed is contacted with the reduced form of catalyst at a temperature of less than 500°C, possibly from 200 to 500°C, possibly from 280 to 400°C.
  • the catalyst bed temperature of the reaction step can be at least about 260° C, for example at least about 300° C. Additionally or alternately, the reaction temperature can be, in one embodiment, not greater than about 450° C, for example not greater than about 400° C.
  • the hydrogen pressure within the reactor is between 101 kPa and 8000 kPa, for example from about 101 kPa to 6000 kPa.
  • feedstocks are diluted in a suitable solvent for deoxygenation.
  • suitable solvents would include hydrocarbons, such as, for example cyclohexane, dodecane or hexadecane.
  • the solvent is recycled hydrocarbons produced by deoxygenation of fatty acids, fatty esters and triglycerides.
  • a mixture of two or more hydrocarbons is used as a solvent, for example petroleum distillates.
  • the solvent is cyclohexane.
  • decarboxylation is carried out without diluting feedstocks with solvents.
  • the LHSV of feedstock is between 0.4-3.0 h "1 .
  • LHSV refers to the volumetric liquid feed rate per total volume of catalyst and is expressed in the inverse of hours (h ⁇ 1 ).
  • the disclosed catalysts are capable of deoxygenating at least 50%, at least 75%, at least 80%, at least 90%, or at least 95% of the fatty acids, fatty alkyl esters and triglycerides feedstocks into hydrocarbons.
  • the disclosed catalysts may deoxygenate 40-80%, 60-95%, or 80-100% of the fatty acids, fatty aldehydes, fatty esters and triglycerides feedstocks into hydrocarbons.
  • the liquid hydrocarbon product is primarily comprised of saturated hydrocarbons (n-alkanes or paraffins) produced by decarboxylation and or decarbonylation in the presence of hydrogen.
  • the liquid product of deoxygenation comprise greater than 70%, greater than 80%, or greater than 90% n-alkanes.
  • the catalyst can be used to deoxygenate the organic oxygenated compound, while producing hydrogen in-situ. This has the benefit that the hydrogen demand in a deoxygenation can be met in-situ. In one aspect, this is carried out by co-feeding a lower aliphatic alcohol with the at least one oxygenated organic compound.
  • the alcohol is methanol or ethanol. In one aspect co-feeding one mole of methanol produces two moles of hydrogen via decomposition.
  • the organic oxygenated compound is a triglyceride, a free fatty acid, a fatty acid alkyl ester, a fatty aldehyde and ketone, or a combination thereof.
  • the catalyst of the invention can thus be active simultaneously for decarbonylation and alcohol decomposition to hydrogen, i.e. catalysts of the invention possesses multiple catalytic functionalities.
  • the present deoxygenation catalyst possess active sites for deoxygenation and also for in-situ hydrogen formation from FAME feedstock or from a lower aliphatic alcohol, such as methanol.
  • the catalysts work not only for the deoxygenation of free fatty acids derived from triglycerides, but also for the deoxygenation of fatty acid methyl esters (FAMEs) and Fatty acid ethyl esters (FAEEs).
  • FAM Es are the principal component of biodiesel.
  • Use of FAMEs as the feedstock has the advantage that (i) the methanol part of the biodiesel reforms into hydrogen, thus reducing the external hydrogen requirements/hydrogen consumption.
  • the hydrocarbon products of deoxygenation of triglycerides, free fatty acids and fatty acid alkyl esters contain straight-chain paraffins (n-paraffins or n-alkanes). These products can be isolated and separated by distillation or other methods known to person of ordinary skill in the art into renewable blending components for gasoline, diesel and jet fuel. Alternatively, the straight chain paraffin product of deoxygenation can be upgraded into a drop-in fuel through a catalytic isomerization method known in the art.
  • Triglycerides are the ester of one molecule of glycerol and three molecules of fatty acids.
  • Carinata, canola and palm oils contain primarily triglycerides (98 wt% ).
  • Carinata is a member of the mustard family. Its scientific name is Brassica carinata and it produces a non-food oil.
  • the non-food-grade canola oil was derived from damaged canola seeds.
  • Palm oil is derived from the fruit of the oil palms. The amounts of saturated, monounsaturated (one double bond), and polyunsaturated (two or more double bonds) fatty acids in these oils are given below in the Table. Palm oil contains a greater amount of saturated fatty acids than the other two vegetable oils.
  • Carinata oil contains predominantly C ⁇ fatty acids, whereas Cis fatty acids are dominant in canola oil. Palm oil contains an equal amount of C K and C 1 ⁇ fatty acids.
  • a CSTR reactor was charged with 250 g of water and 300 g of canola oil. The reactor was heated to 260 °C. Autogenous pressure was 2.5 to 3 Pa. The reactor further pressurized to 5.5 MPa with inert gas and stirred at 500 rpm. After completion of the reaction, the reaction mixture was transferred into a separatory funnel. The mixture separated into two phases: the water and glycerol heavy phase, and the fatty acid light phase. The fatty acid phase was separated from the glycerol and water; purified to remove any remaining free glycerol; and then dried with anhydrous sodium sulfate (NaS0 4 ). The quality of fatty acid product was analyzed by nuclear magnetic resonance (N R) spectroscopy. The product contains 95 wt% of Cie-Ci 3 fatty acids.
  • reaction mixture was transferred into a separatory funnel and kept for 2 h to get a clear separation between the ester and crude glycerin layers.
  • the top methyl ester layer was separated from the glycerin; purified to remove any remaining KOH, soap and free glycerol; and then dried with anhydrous sodium sulfate (Na 2 SO,i) to remove moisture.
  • Na 2 SO,i anhydrous sodium sulfate
  • the triglycerides employed were canola oil, carinata oil, and palm oil (discussed above).
  • Gas chromatography (GC) and proton magnetic resonance (H-NMR) were used to characterize the product sample.
  • the H-NMR study revealed that the level of glycerides in the product sample was very low, implying the completion of the transesterification reaction.
  • the GC analysis showed a conversion efficiency of 99.5 % with all three vegetable oils:
  • the composition of FAME obtained from canola, palm and carinata oils are shown in Figure 4.
  • NiO-ZnO catalyst was characterized further by X-ray powder diffraction (XRD) and temperature-programmed reduction (TPR).
  • d 0.94A/ cose where 0.89 is Scherrer's constant, ⁇ is the wavelength of X-rays, ⁇ is the Bragg diffraction angle, and ⁇ is the full width at half-maximum (FWHM) of the primary diffraction peak (43.3 for N iO and 36.6 for ZnO).
  • FWHM full width at half-maximum
  • the catalyst was prepared in oxide form. It was activated by in-situ reduction with hydrogen at 500 °C.
  • TPR temperature programmed reduction
  • the hydrogen consumption during reduction of the NiO-ZnO catalyst as a function of time was measured to provide a TPR profile.
  • the TPR profile displayed one major peak at 385°C. This peak corresponds to NiO reduction to metallic Ni (Ni" to Ni°).
  • the experimental weight loss achieved during reduction up to 500°C was compared with the theoretical loss. It showed that nickel oxide is the only component of the catalyst that is reduced at the activation temperature up to 500°C.
  • the TPR profile along with the amount of weight loss confirm that the active form of catalyst contains nickel as metallic nickel and Zn as ZnO. The result was in good agreement with conclusions of the reported studies 17,18 .
  • a gas sample from the reactor was analyzed by an online gas chromatograph (GC) setup equipped with a flame ionization detector (FI D) and thermal conductivity detector (TCD). Reactor liquid products were quenched in a knock-out pot. The liquid product samples were analyzed by GC-FI D and N MR.
  • GC gas chromatograph
  • the amount of liquid and gaseous products formed from carinata FFA over catalyst E is provided in the following reaction stoichiometry, where m denotes the average number of double bonds in the FFA sample.
  • Both catalysts showed a similar selectivity profile to C 15 -C 2 i paraffins, but different selectivity towards gaseous products (C0 2 and CO). Reactants and products were quantified to derive the reaction stoichiometry (see below equation).
  • the Pd/C catalyst consumed 2.8 moles of hydrogen and produced around one mole of CO and one mole of H 2 0 per each mole of free fatty acids reacted.
  • Decarboxylation of FAME was carried out in a fixed-bed reactor at temperature, pressure, hydrogen gas/oil ratio, and LHSV of 350°C, 0.5 MPa, 500 (v/v), and 1 h "1 , respectively.
  • the product sample was collected after 48 h of time-on-stream.
  • Catalyst E achieved complete conversion of, canola and carinata FAME feedstocks into paraffinic hydrocarbons, with 100% theoretical yield. Both FAME and free fatty acid feedstocks yielded products with similar hydrocarbon profiles.
  • the NMR and GC studies of product samples of canola and carinata FAMEs confirmed this.
  • the outlet gas stream of canola FAME decarboxylation contained CO as a primary product (see below equation).This indicated that FAME follows the same decarbonylation route as FFA.
  • the quantification of the amount of hydrogen in the inlet and outlet streams showed that catalyst E produced around two moles of in-situ hydrogen from FAME as a by-product. Because of this in-situ hydrogen, only 0.2 moles of external hydrogen per mole of FAME was required for the conversion of canola FAME into paraffinic hydrocarbon product.
  • Catalyst E required only 0.2 moles of H 2 for the conversion of canola FAME into paraffinic hydrocarbons.
  • Methanol co-feeding with FAME was studied as a way to completely eliminate the need for external hydrogen supply.
  • a decarboxylation experiment was conducted by co-feeding of one mole of methanol with canola FAME.
  • the co-fed methanol produced two moles of H 2 ; as a result, the outlet gas stream contained 1.5 more moles H 2 than the inlet gas stream.
  • Palm oil triglycerides contain predominately C16 and C18 fatty acids.

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Abstract

La présente invention concerne un procédé de désoxygénation d'une charge d'alimentation comprenant au moins un composé organique oxygéné, pour former un produit hydrocarboné, qui comprend les étapes consistant à : mettre en contact la charge d'alimentation avec un catalyseur dans des conditions destinées à favoriser la désoxygénation dudit au moins un composé oxygéné, le catalyseur comprenant un oxyde métallique mixte de formule empirique : (M2)y(M1)O-ZnO-(AI2O3)x. L'invention est utile dans la production de carburants renouvelables tels que le diesel renouvelable et le carburéacteur.
PCT/CA2017/051317 2017-11-06 2017-11-06 Procédé de production de biocarburants hydrocarbonés WO2019084657A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114450385A (zh) * 2019-08-14 2022-05-06 内斯特化学股份公司 用于生产生物燃料的通过在高温高压下水解脂肪的进料预处理方法
US20220184581A1 (en) * 2019-02-19 2022-06-16 SBI BioEnergy Catalysts for the deoxygenation of esters of free fatty acids and triglycerides
EP4130202A4 (fr) * 2020-03-25 2024-04-03 Biofuel Technology Research Co., Ltd. Procédé de production d'un carburant biodiesel

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WO2008109877A1 (fr) * 2007-03-08 2008-09-12 Virent Energy Systems, Inc. Synthèse de combustibles et de produits chimiques liquides à partir d'hydrocarbures oxygénés
WO2010028206A1 (fr) * 2008-09-05 2010-03-11 Shell Oil Company Compositions de carburant liquide
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EP3023479A1 (fr) * 2014-11-24 2016-05-25 Centre National De La Recherche Scientifique Procédé de désoxygénation d'alcools et son utilisation

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WO2008109877A1 (fr) * 2007-03-08 2008-09-12 Virent Energy Systems, Inc. Synthèse de combustibles et de produits chimiques liquides à partir d'hydrocarbures oxygénés
AU2013203230A1 (en) * 2007-03-08 2013-05-02 Virent, Inc. Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons
WO2010028206A1 (fr) * 2008-09-05 2010-03-11 Shell Oil Company Compositions de carburant liquide
EP3023479A1 (fr) * 2014-11-24 2016-05-25 Centre National De La Recherche Scientifique Procédé de désoxygénation d'alcools et son utilisation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220184581A1 (en) * 2019-02-19 2022-06-16 SBI BioEnergy Catalysts for the deoxygenation of esters of free fatty acids and triglycerides
CN114450385A (zh) * 2019-08-14 2022-05-06 内斯特化学股份公司 用于生产生物燃料的通过在高温高压下水解脂肪的进料预处理方法
EP4130202A4 (fr) * 2020-03-25 2024-04-03 Biofuel Technology Research Co., Ltd. Procédé de production d'un carburant biodiesel

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