Classifications

• • 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
  • C10G3/50—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
• • 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
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
• • 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
  • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
  • C10G2300/1014—Biomass of vegetal origin
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
• • 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
• • 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
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • 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
  • C10G2300/304—Pour point, cloud point, cold flow 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/04—Diesel oil
• • 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

• This invention relates generally to diesel fuels, and specifically to methods and systems for efficiently making low-sulfur hybrid diesel biofuels by co-processing blends of petroleum diesel and vegetable or crop oils.
• Biofuels are of increasing interest for a number of reasons including: (1) they are a renewable resource, (2) their production is less dependent on geopolitical considerations, (3) they provide the possibility of a direct replacement of petroleum- based fuels in existing vehicles, and (4) the net greenhouse gas emissions can be substantially reduced by virtue of CO 2 uptake by biofuel precursors — particularly in the case of cellulosic feedstocks. See Pearce, "Fuels Gold,” New Scientist, 23 September, pp. 36-41, 2006.
• An easily-obtainable biofuel is vegetable oil, which largely comprises triglycerides and some free fatty acids.
• the properties of vegetable oil make it generally inappropriate for use as a direct replacement for petroleum diesel in vehicle engines, as the vegetable oils' viscosities are generally too high and do not burn cleanly enough, thereby leaving damaging carbon deposits on the engine. Additionally, vegetable oils tend to gel at lower temperatures, thereby hindering their use in colder climates. These problems are mitigated when the vegetable oils are blended with petroleum fuels, but still remain an impediment for long-term use in diesel engines. See Pearce, 2006; Huber et al, "Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering," Chem. Rev., vol. 106, pp. 4044-4098, 2006.
• An alternative to the above-described transesterif ⁇ cation, and as described herein, is to mix a vegetable oil (e.g., canola oil) with conventional diesel to form a mixture, and to then hydrotreat the mixture to yield a hybrid diesel biofuel.
• a vegetable oil e.g., canola oil
• conventional diesel e.g., canola oil
• the vegetable oil is present in the mixture in an amount that is less than that of the conventional diesel.
• the vegetable oil typically comprises less than about 10 weight percent of the mixture.
• the present invention is directed to methods (i.e., processes) and systems for co-processing vegetable oil and petroleum diesel to yield a hybrid diesel product comprising a biomass-derived component.
• methods and systems work to provide a hybrid diesel product that benefits from a (partial) biomass-derived component, but without the poor low-temperature properties of conventional ester-based biodiesel.
• the present invention is directed to methods by which a mixture of vegetable oil and petroleum diesel is first hydrotreated to yield a reduced-sulfur hybrid intermediate, and then the hybrid intermediate is processed in an isomerization unit to yield a low cloud point hybrid (bio)diesel product that is partially derived from biomass.
• the low cloud point hybrid diesel product ideally possesses a cloud point within (or at least close to) the standard diesel range.
• such embodiments utilize a sulfur- and/or nitrogen-tolerant isomerization catalyst such that H 2 S and NH 3 are generally not removed from the hybrid intermediate stream prior to isomerization.
• Such sulfur- and/or nitrogen-tolerant isomerization catalysts can enable the favorable economics of such methods/systems.
• Such isomerization catalysts are described in Miller, United States Patent Application Serial No. 12/181,652, filed July 29, 2008, and incorporated by reference herein.
• the present invention is directed to one or more methods for producing a hybrid diesel (bio)fuel product, such methods comprising the steps of: (a) combining vegetable oil with diesel fuel to form a first mixture, wherein the vegetable oil comprises not more than 10 weight percent of said first mixture; (b) hydrotreating the first mixture to yield a second mixture, wherein triglyceride components of the first mixture are deoxygenated, and wherein at least 95 atomic percent of the sulfur present in the first mixture is converted to H 2 S in the second mixture; (c) isomerizing the second mixture in the presence of an isomerization catalyst to yield a third mixture comprising hybrid diesel fuel having a cloud point that is lower than that of the second mixture, wherein H 2 S in the second mixture has not been removed prior to isomerizing; and (d) isolating the hybrid diesel fuel of the third mixture to yield a hybrid diesel fuel product.
• the present invention is directed to one or more systems for generating a hybrid diesel fuel product, such systems generally comprising: (a) a mixing unit for combining vegetable oil with diesel fuel so as to form a first mixture, wherein the vegetable oil comprises not more than 10 weight percent of said first mixture; (b) a hydrotreating unit for hydrotreating the first mixture to yield a second mixture, wherein said unit is operable for deoxygenating triglyceride components of the first mixture, and wherein at least 95 atomic percent of the sulfur present in the first mixture is converted to H 2 S in the second mixture; and (c) an isomerization unit for isomerizing the second mixture in the presence of an isomerization catalyst to yield a third mixture comprising hybrid diesel fuel having a cloud point that is lower than that of the second mixture, wherein H 2 S in the second mixture has not been removed prior to isomer
• FIG. 1 illustrates, in flow diagram form, methods for producing hybrid diesel bio fuel compositions, in accordance with some embodiments of the present invention.
• FIG. 2 depicts, schematically, systems for implementing methods such as illustrated in FIG. 1, in accordance with some embodiments of the present invention.
• Embodiments of the present invention are directed to methods (processes) and systems for co-processing vegetable oil and petroleum diesel to yield a hybrid diesel (bio)fuel composition.
• the present invention is directed to methods (and systems for implementing such methods) by which a mixture of vegetable oil and petroleum diesel is co-processed in two stages: the mixture is first hydrotreated to yield a reduced-sulfur hybrid intermediate, and then the hybrid intermediate is processed in an isomerization unit to yield a low cloud point hybrid diesel product that is partially derived from biomass.
• the low cloud point hybrid diesel product generally possesses a cloud point within (or at least close to) the standard diesel range.
• a unique aspect of at least some such above-described embodiments of the present invention is that between the steps/stages of hydrotreating and isomerizing, there is no interstage removal of H 2 S and NH3.
• this elimination of H 2 S/NH 3 interstage removal is enabled via use of sulfur- and nitrogen- tolerant/resistant isomerization catalysts, such as those described in Miller, United States Patent Application Serial No. 12/181,652, filed July 29, 2008, and incorporated by reference herein.
• the efficiency of such large-scale co-processing can be greatly increased, thereby reducing overall production costs.
• bio refers to an association with a renewable resource of biological origin, such resources generally being exclusive of fossil fuels.
• a “biologically-derived oil,” as defined herein, refers to any triglyceride- containing oil that is at least partially derived from a biological source such as, but not limited to, crops, vegetables, microalgae, and the like. Such oils may further comprise free fatty acids.
• the biological source is henceforth referred to as "biomass.”
• biomass For more on the advantages of using microalgae as a source of triglycerides, see R. Baum, "Microalgae are Possible Source of Biodiesel Fuel,” Chem. & Eng. News, vol. 72(14), pp. 28-29, 1994.
• the terms “vegetable oil,” “crop oil,” and “biologically-derived oil” will generally be used interchangeably.
• Triglyceride refers to a class of molecules having the following molecular structure:
• x, y, and z can be the same or different, and wherein one or more of the branches defined by x, y, and z can have unsaturated regions.
• a “carboxylic acid” or “fatty acid,” as defined herein, is a class of organic acids having the general formula:
• R is generally a saturated (alkyl) hydrocarbon chain or a mono- or polyunsaturated (alkenyl) hydrocarbon chain.
• Lipids as defined herein, broadly refers to the class of molecules comprising fatty acids, and tri-, di-, and monoglycerides.
• Hydrolysis of triglycerides yields free fatty acids and glycerol, such fatty acid species also commonly referred to as carboxylic acids (see above).
• Transesterif ⁇ cation or simply “esterification,” refers to the reaction between a fatty acid and an alcohol to yield an ester species.
• Hydroprocessing or “hydrotreating” refers to processes or treatments that react a hydrocarbon-based material with hydrogen, typically under pressure and with a catalyst (hydroprocessing can be non-catalytic). Such processes include, but are not limited to, hydrodeoxygenation (of oxygenated species), hydrotreating, hydrocracking, hydroisomerization, and hydrodewaxing. For examples of such processes, see Cash et al, United States Patent No. 6,630,066; and Elomari, United States Patent No. 6,841,063. Embodiments of the present invention utilize such hydroprocessing to convert triglycerides to paraffins.
• hydroprocessing and “hydrotreating” are used interchangeably herein.
• Isomerizing refers to catalytic processes that typically convert n-alkanes to branched isomers.
• ISODEWAXING Trademark of CHEVRON U.S.A. INC.
• catalysts are representative catalysts used in such processes. See, e.g., Zones et al., United States Patent No. 5,300,210; Miller, United States Patent No. 5,158,665; and Miller, United States Patent No. 4,859,312.
• Transportation fuels refer to hydrocarbon-based fuels suitable for consumption by vehicles. Such fuels include, but are not limited to, diesel, gasoline, jet fuel and the like.
• Diesel fuel is a material suitable for use in diesel engines and conforming to the current version at least one of the following specifications: ASTM D 975 - "Standard Specification for Diesel Fuel Oils”; European Grade CEN 90; Japanese Fuel Standards JIS K 2204; The United States National Conference on Weights and Measures (NCWM) 1997 guidelines for premium diesel fuel; and The United States Engine Manufacturers Association recommended guideline for premium diesel fuel (FQP-IA).
• biodiesel refers to diesel fuel that is at least significantly derived from a biological source, and which is generally consistent with ASTM International Standard Test Method D-6751. Often, biodiesel is blended with conventional petroleum diesel. B20 is a blend of 20 percent biodiesel with 80 percent conventional diesel. BlOO denotes pure biodiesel.
• Conventional biodiesel refers to ester-based biodiesel produced via a transesterification of triglyceride-containing vegetable oils.
• hybrid diesel biofuel specifically refers to diesel produced via the co-processing (hydrotreating + isomerizing) of vegetable oil and conventional (petroleum) diesel, in accordance with methods and system of the present invention.
• Pul point represents the lowest temperature at which a fluid will pour or flow. See, e.g., ASTM International Standard Test Methods D 5950-96, D 6892-03, and D 97.
• Cloud point represents the temperature at which a fluid begins to phase separate due to crystal formation. See, e.g., ASTM Standard Test Methods D 5773-95, D 2500, D 5551, and D 5771.
• C n As defined herein, "C n ,” where “n” is an integer, describes a hydrocarbon or hydrocarbon-containing molecule or fragment (e.g., an alkyl or alkenyl group) wherein “n” denotes the number of carbon atoms in the fragment or molecule — irrespective of linearity or branching.
• the present invention is directed to one or more methods for co-processing vegetable oil with conventional diesel to yield a hybrid (bio)diesel fuel product, said methods generally comprising the steps of: (Step 101) combining vegetable oil with diesel fuel to form a first mixture, wherein the vegetable oil comprises not more than 10 weight percent of said first mixture; (Step 102) hydrotreating the first mixture to yield a second mixture, wherein triglyceride components of the first mixture are deoxygenated, and wherein at least 95 atomic percent of the sulfur present in the first mixture is converted to H 2 S in the second mixture; (Step 103) isomerizing the second mixture in the presence of an isomerization catalyst to yield a third mixture comprising hybrid diesel fuel having a cloud point that is lower than that of the second mixture, wherein H 2 S in the second mixture has not been removed prior to isomerizing; and (Step 104) isolating the hybrid diesel fuel of the third mixture to yield a hybrid diesel
• the isomerization catalyst is sufficiently-tolerant of sulfur so as to make it unnecessary to remove the H 2 S (from the second mixture) prior to isomerizing.
• the first mixture comprises a nitrogen content greater than 50 ppm. In some or other such embodiments, the first mixture comprises a nitrogen content of up to about 500 ppm.
• the step of isomerizing results in superior fuel properties relative to those of the non-isomerized paraffmic (i.e., n- paraffm or n-alkane) product — although the n-paraff ⁇ nic product itself could find use as a fuel or other commodity.
• One such fuel property that can be improved by isomerization is cloud point, i.e., isomerization can lower the cloud point of a mixture.
• isomerization is carried out using an isomerization catalyst.
• isomerization catalysts have traditionally comprised Pt or Pd on a support such as SAPO-I l, SM-3, SSZ-32, ZSM-23, ZSM-22, and similar such supports; and/or on an acidic support material such as beta or zeolite Y molecular sieves, SiO 2 , Al 2 ⁇ 3, SiO2- Al 2 O 3 , and combinations thereof.
• the isomerization is carried out at a temperature between about 500 0 F and about 750 0 F.
• the operating pressure is typically 200 to 2000 pounds-force per square inch gauge (psig), and more typically 200 psig to 1000 psig.
• Hydrogen flow rate is typically 50 to 5000 standard cubic feet/barrel (SCF/barrel).
• SCF/barrel standard cubic feet/barrel
• an important advantage of the present invention is the ability to eliminate interstage removal of H 2 S/NH 3 between hydrotreating and isomerization, this ability provided by an isomerization catalyst that is sulfur- and nitrogen-tolerant.
• the isomerization catalyst comprises an active metal catalyst (e.g., Pt) on a support such as any of those described in Miller, United States Patent Application Serial No. 12/181,652, filed July 29, 2008, and incorporated by reference herein.
• the silicoaluminophosphate support described in Miller is designated as SM-7, this support being isostructural with conventional SAPO-I l.
• the isomerization catalyst comprises Pt (and/or other active metal, such as Pd) on an SAPO-I l support. Reaction conditions for such isomerizing are typically within the parameters of traditional isomerization methods (see above).
• the methods described herein may be conducted by contacting the n-paraff ⁇ nic product with a fixed stationary bed of catalyst, with a fixed fluidized bed, or with a transport bed.
• a trickle-bed operation is employed, wherein such feed is allowed to trickle through a stationary fixed bed, typically in the presence of hydrogen.
• a stationary fixed bed typically in the presence of hydrogen.
• the vegetable oil originates from a biomass source selected from the group consisting of crops, vegetables, microalgae, and combinations thereof. Accordingly, the term "vegetable oil” is actually quite broad and can generally be extended to include any biologically- derived oil (see above definitions).
• a biologically-derived oil e.g., vegetable oil
• triglycerides e.g., triglycerides
• exemplary vegetable oils/oil sources include, but are not limited to, canola, soy, rapeseed, palm, peanut, jatropha, yellow grease, algae, and the like.
• the step of hydrotreating involves a hydroprocessing/hydrotreating catalyst and a hydrogen-containing environment.
• hydroprocessing/hydrotreating see, e.g., Rana et al., "A Review of Recent Advances on Process Technologies for Upgrading of Heavy Oils and Residua," Fuel, vol. 86, pp. 1216-1231, 2007.
• triglycerides can be hydroprocessed to yield a paraffmic product, see Craig et al., United States Patent No. 4,992,605.
• the step of hydrotreating involves or otherwise utilizes a hydrotreating catalyst comprising an active metal or metal-alloy hydrotreating catalyst component that is operationally integrated with a refractory support material.
• active metal catalyst component is selected from the group consisting of cobalt-molybdenum (Co-Mo) catalyst, nickel-molybdenum (Ni-Mo) catalyst, noble metal catalyst, and combinations thereof.
• the refractory support material typically comprises a refractory oxide support such as, but not limited to, AI2O3, SiO 2 - AI2O3, and combinations thereof.
• the hydrotreating step makes use of an alumina-supported nickel-molybdenum catalyst.
• the hydrotreating is carried out at a temperature between 550 0 F and 800 0 F. In some such embodiments, the hydrotreating is carried out under a H 2 partial pressure of between 400 psig and 2000 psig. In some or other such embodiments, the hydrotreating is carried out under a H 2 partial pressure of between 500 psig and 1500 psig.
• the second mixture has, exclusive of H 2 S, a reduced sulfur content of typically not more than 20 ppm, and of preferably not more than 10 ppm. Note that hydrotreating also permits the removal of oxygen (in the form of H 2 O).
• Hydrotreating can also affect the cloud point, typically lowering the cloud point of the second mixture relative to that of the first mixture.
• the second mixture has cloud point of -6 0 C or less, while in some or other embodiments, the second mixture has a cloud point of -8 0 C or less.
• Isolation of the hybrid diesel (bio)fuel from the third mixture is achieved simply by removing any H 2 S present, where H 2 S removal at this stage is typically easier than its removal between the hydrotreating and isomerizing steps.
• isolation of the hybrid diesel fuel is at least partly achieved by stripping the third mixture OfH 2 S.
• the method embodiments of the present invention produce a hybrid diesel (bio)fuel that is low in sulfur content.
• the hybrid diesel fuel has, exclusive of H 2 S, a sulfur content of not more than 20 ppm, and in some such embodiments of not more than 10 ppm.
• Isomerization of the second mixture can reduce its pour point so as to yield a hybrid diesel biofuel with a pour point that is less than that of the second mixture.
• the hybrid diesel fuel has a cloud point of -10 0 C or less.
• the present invention is directed to one or more systems 200 for co-processing vegetable oil with petroleum diesel so as to afford the production of such above-described hybrid diesel fuel and/or to implement any or all of the aforementioned methods. Accordingly, and still referring to FIG.
• the present invention is generally directed to one or more systems for generating a hybrid diesel fuel product, such systems generally comprising: a mixing unit 201 for combining vegetable oil with diesel fuel so as to form a first mixture, wherein the vegetable oil comprises not more than 10 weight percent of said first mixture; a hydrotreating unit 202 for hydrotreating the first mixture to yield a second mixture, wherein said unit is operable for deoxygenating triglyceride components of the first mixture, and wherein at least 95 atomic percent of the sulfur present in the first mixture is converted to H 2 S in the second mixture; and an isomerization unit 203 for isomerizing the second mixture in the presence of an isomerization catalyst to yield a third mixture comprising hybrid diesel fuel having a cloud point that is lower than that of the second mixture, wherein H 2 S in the second mixture has not been removed prior to isomerizing.
• a mixing unit 201 for combining vegetable oil with diesel fuel so as to form a first mixture, wherein the vegetable oil comprises not more than 10 weight percent of said first
• system 200 further comprises an isolation unit 204 for isolating the hybrid diesel fuel in the third mixture so as to yield a hybrid diesel fuel product.
• the isolation unit comprises an H 2 S stripping unit.
• a preferred isomerization unit is one that utilizes an ISODEWAXING catalyst, preferably containing SM-7 or SSZ-32.
• the isomerization catalyst comprises Pt on an SM-7 support.
• all of the above-described system units are configured for processing a vegetable oil in accordance with the methods described in Section 3. Further, there is typically a proximal relationship between the various units that comprise system 200, but this need not always be the case. Such relationships may be influenced by existing infrastructure and other economic considerations.
• the intermediate (second) mixture is catalytically-isomerized to an isomerized intermediate mixture prior to separation into various components.
• method/system parameters can be configured to produce hybrid (bio)fuels other than diesel. Such variation results in additional method and corresponding system embodiments having alternative step and component sequences, but otherwise generally as described for the embodiments above.
• This Example serves to illustrate an exemplary system for implementing a method embodiment of the present invention, so as to produce a hybrid diesel bio fuel.
• this hybrid diesel intermediate mixture was processed in an isomerization unit employing an ISODEWAXING (IDW) catalyst (Pt on SM-7) to yield a hybrid diesel product having a relatively low cloud point (-13 0 C). This lower cloud point allows the diesel to be used in colder climates. No interstage removal OfH 2 S and NH3 was required, with the total effluent from the first (hydrotreating) stage going to the second (isomerizing) stage.
• IDW ISODEWAXING
• Table 1 below compares yields/properties of products that resulted from diesel and diesel/canola oil feeds having been processed in accordance with some embodiments of the present invention. Processing conditions were as follows: HDS at 0.7 LHSV, ISODEWAXING at 1.8 LHSV, 700 psig total pressure, 525 psig H 2 pressure, and 1300 SCFB H 2 .
• the isomerization catalyst Because of the high activity of the isomerization catalyst, it can be operated at 684°F, not much higher than the 650 0 F of the hydrotreating catalyst. This will extend the run life of the system, and also makes possible the use of the isomerization catalyst downstream of the hydrotreating catalyst in the same reactor (although separate reactors are preferred).
• the present invention is directed to methods/systems by/with which a mixture of vegetable oil and petroleum diesel is co-processed in two stages: the mixture is first hydrotreated to yield a reduced-sulfur hybrid intermediate, and then the hybrid intermediate is processed in an isomerization unit to yield a low cloud point hybrid diesel product that is partially derived from biomass.
• a notable benefit of at least some such methods/systems is that interstage removal of H 2 S and NH 3 is not required between the stages of hydrotreating and isomerizing.

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