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US20130338414A1 - Hydrodesulfurization, deoxygenation and dewaxing processes with water stable catalysts for biomass-containing hydrocarbon feedstocks - Google Patents

Hydrodesulfurization, deoxygenation and dewaxing processes with water stable catalysts for biomass-containing hydrocarbon feedstocks Download PDF

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US20130338414A1
US20130338414A1 US13/906,907 US201313906907A US2013338414A1 US 20130338414 A1 US20130338414 A1 US 20130338414A1 US 201313906907 A US201313906907 A US 201313906907A US 2013338414 A1 US2013338414 A1 US 2013338414A1
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reaction zone
zsm
hydrocarbon feedstock
product
binder
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Bradley R. Fingland
Joseph E. Gatt
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Priority to US13/906,907 priority Critical patent/US20130338414A1/en
Priority to JP2015516085A priority patent/JP6173446B2/ja
Priority to CN201380029116.1A priority patent/CN104508090B/zh
Priority to AU2013271891A priority patent/AU2013271891B2/en
Priority to SG11201406795TA priority patent/SG11201406795TA/en
Priority to PCT/US2013/043826 priority patent/WO2013184545A1/fr
Priority to EP13728301.6A priority patent/EP2855635B1/fr
Priority to CA2872826A priority patent/CA2872826C/fr
Assigned to EXXONMOBIL RESEARCH AND ENGINEERING COMPANY reassignment EXXONMOBIL RESEARCH AND ENGINEERING COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GATT, JOSEPH E., FINGLAND, BRADLEY R.
Publication of US20130338414A1 publication Critical patent/US20130338414A1/en
Abandoned legal-status Critical Current

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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
    • 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
    • C10G45/10—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 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • 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
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • 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
    • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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 to a method for processing feedstreams containing both sulfur-containing mineral oils and biomass-derived feedstocks in a single reactor configuration.
  • the process produces a desulfurized, deoxygenated and dewaxed hydrocarbon product having reduced oxygen content, increased iso-paraffin content, low n-paraffin content, and good cold flow properties.
  • Biomass feedstocks present an enormous potential in this respect, as they are renewable and can be CO 2 neutral.
  • crude oil upon which “mineral oils” may be derived
  • biomass and biomass-derived materials typically contain large concentrations of oxygenates.
  • the oxygen atoms are removed as water during deoxygenation processing, and, in some cases such as pyrolysis oil, the feed already contains large amounts of water.
  • a problem that exists is that most existing refinery processes and associated equipment are designed to process only crude oils or “mineral oil” based feedstocks. Processing of biomass derived feedstocks often requires separate processing steps, equipment and catalysts for converting these feedstocks into motor fuels and chemical feedstocks and such process may not be compatible with co-processing of these conventional (mineral oil) feedstocks.
  • the existing refinery systems designed for processing strictly mineral based feedstocks are not designed with dedicated processes to handle both the biomass derived feedstocks and the conventional feedstocks separately. Costs to do so would be prohibited.
  • the article by J. Hancsok et al. ( Microporous and Mesoporous Materials, 101 (2007), 148-152) describes a metal/zeolite catalyst used for isomerizing oxygenate-containing feedstocks.
  • the catalyst is bound with alumina, and it is noted that oxygenate contents of just over 1% in the feedstock cause a 50% acidity loss, indicating a reduced conversion activity.
  • the article by O. V. Kikhtyanin et al. Fuel, 89 (2010), 3085-3092
  • catalysts containing alumina can be among the most effective catalysts for many necessary processes, such as heteroatom removal (e.g., deoxygenation) and isomerization.
  • Water-induced deactivation of such catalysts can occur via numerous mechanisms (e.g., sintering, titration of acid sites, competitive adsorption, zeolite support dealumination, and reduction of mechanical stability, inter alia), and such deactivation should be an increasingly important issue, due to the increasing demand for biofuels and other biomass-derived products.
  • achieving both of these simultaneously in a given refinery process and catalyst system has resulted in less than adequate results mainly due to catalyst instability and/or significant losses in hydrodesulfurization efficiencies in the catalyst system.
  • the embodiments of the invention herein are process & catalyst solutions to enable existing mineral oil refineries to co-process feedstocks containing a mixture of both mineral oils and biomass to achieve fuel products that meet refinery specifications such as biomass content, oxygen content, sulfur content, and cloud point while maximizing the use of existing refinery equipment.
  • a hydrocarbon feedstock comprised of a mineral oil component and a biomass oil component to form at least one liquid motor fuel product, such method comprising:
  • the dewaxing catalyst comprises a zeolitic support, at least one active metal compound comprising one or more of Group VIB metals and Group VIII metals deposited thereon, and a hydrophilic, hydrothermally-stable binder comprising one or more of: (A) an oxide, carbide, nitride, phosphide, sulfide, or combination thereof of one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium, (B) activated carbon, and (C) carbon on which is deposited one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium.
  • A an oxide, carbide, nitride, phosphide, sulfide, or combination thereof of one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium
  • B activated carbon
  • C carbon on which is deposited
  • the binder of the dewaxing catalyst comprises zirconia, vanadia, titania, molybdenum oxide, manganese oxide, cerium oxide, carbon, or a combination thereof.
  • the binder of the dewaxing catalyst comprises one or metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium. While in most preferred embodiments, the binder of the dewaxing catalyst comprises titanium.
  • the zeolitic support of the dewaxing catalyst comprises ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, zeolite Beta, zeolite Y, USY, mordenite, ferrierite, or a combination thereof.
  • the hydrodesulfurization/deoxygenation catalyst comprises at least one Group VIII metal oxide selected from Fe, Co and Ni, and at least one Group VI metal oxide selected from Mo and W and a support selected from alumina, silica, and silica-alumina.
  • At least one liquid motor fuel product is produced from a diesel boiling range fraction of the reactor effluent product wherein the cloud point of the diesel boiling range fraction is less than 0° C.
  • the hydrocarbon feedstock contains from 80 wt % to about 98 wt % of the mineral oil component and from 2 wt % to about 20 wt % of the biomass oil component, the mineral oil component contains at least 500 ppmw sulfur, and the reactor effluent product contains less than 100 ppmw sulfur.
  • the second hydroprocessing conditions include a water partial pressure of greater than 2 psia, greater than 5 psia, or even greater than 10 psia.
  • FIG. 1 illustrates a simplified of a process schematic of a first embodiment of the hydroprocessing reactor system and associated product separation systems of invention.
  • FIG. 2 illustrates a simplified process schematic of a second embodiment of the hydroprocessing reactor system and associated product separation systems of invention.
  • FIG. 3 shows comparative GC-MS spectra of a stearic acid feed converted using two different catalyst compositions having identical metal and support components but differing in the binder component.
  • the present invention relates to processes and catalysts for producing a desulfurized, deoxygenated, and dewaxed hydrocarbon motor fuel product stream from a hydrocarbon feedstock comprised of a mineral oil component and a biomass oil component utilizing a two-part catalyst system in a single hydroprocessing reactor.
  • an existing refinery hydroprocessing reactor can be utilized in the processes herein to economically retrofit an existing conventional (mineral oil) refining process into a process for refining the hydrocarbon feedstock comprised both the mineral oil and biomass oil components.
  • the processes and catalysts of invention herein are designed to process mixed hydrocarbon feedstock comprised of both a mineral oil (or “conventional oil”) component and a biomass oil (or “biomass” or “biomass-derived” or “biofeed”) component.
  • the hydrocarbon feedstock can have an initial boiling point of at least about 200° F. (93° C.), or at least about 250° F. (121° C.), or at least about 300° F. (149° C.), or at least about 350° F. (177° C.), or at least about 400° F. (204° C.), or at least about 450° F. (232° C.).
  • the initial boiling can vary widely, depending on how much kerosene or other lighter distillate components are included in a feedstock.
  • the hydrocarbon feedstock can have a final boiling point of about 800° F. (427° C.) or less, or about 750° F. (399° C.) or less, or about 700° F. (371° C.) or less.
  • the final boiling point can be about 1100° F. (593° C.) or less, or about 1000° F. (538° C.) or less, or about 900° F. (482° C.) or less.
  • Another way of characterizing a feedstock is based on the boiling point required to boil a specified percentage of the feed. For example, the temperature required to boil at least 5 wt % of a feed is referred to as a “T5” boiling point.
  • the feedstock can have a T5 boiling point at least about 200° F. (93° C.), or at least about 250° F.
  • the feed can have a T95 boiling point of about 800° F. (427° C.) or less, or about 750° F. (399° C.) or less, or about 700° F. (371° C.) or less.
  • suitable feeds include various atmospheric and/or vacuum gas oil feeds, diesel boiling range feeds, and feeds corresponding to mixtures thereof.
  • the hydrocarbon feedstock can include at least 0.5 wt % biomass, based on total weight of the hydrocarbon feedstock provided, more preferably at least 1 wt %; for example at least 2 wt %, at least 3 wt %, at least 4 wt %, at least 5 wt %, at least 10 wt %, at least 20 wt %, at least 30 wt %, at least 40 wt %, at least 50 wt %, at least 60 wt %, at least 70 wt %, at least 80 wt %, at least 90 wt %, at least 95 wt %, or at least 99 wt %.
  • the biomass component is from about 2 wt % to about 20 wt %, or more preferably from about 5 wt % to about 15 wt %, of the hydrocarbon feedstock.
  • the mineral oil component is from about 80 wt % to about 98 wt %, or more preferably from about 85 wt % to about 95 wt %, of the hydrocarbon feedstock.
  • the processes and catalysts of invention herein are designed to process mixed hydrocarbon feedstock comprised of both a mineral oil (or “conventional oil”) component and a biomass (or “biomass-derived”) component.
  • the mineral oil component is the component that is derived from “non-renewable” fossil/mineral oil reserves such as crude oils, tar sands bitumens, as well as liquid hydrocarbon streams derived from tar sands bitumen, coal, or oil shale. These are considered as “non-renewable” resources as the time frame required for production and replacement of these supplies of mineral oils is at least several thousands of years.
  • mineral oils can include, but are not limited to, straight run (atmospheric) gas oils, vacuum gas oils, demetallized oils, coker distillates, cat cracker distillates, heavy naphthas, diesel boiling range distillate fraction, jet fuel boiling range distillate fraction, kerosene boiling range distillate fraction, and coal liquids.
  • the mineral oil portion of the feedstocks herein can comprise any one of these example streams or any combination thereof.
  • the mineral oil component contains at least 250 ppmw of sulfur. More preferably in the processes herein, the mineral oil component contains, at least 500 ppmw, or at least 1,000 ppmw, or at least 5,000 ppmw, or even at least 10,000 ppmw sulfur. The majority of the sulfur present in the mineral oil component will be organically bound sulfur.
  • the biological materials that make up the biomass component can include vegetable fats/oils, animal fats/oils, fish oils, pyrolysis oils, and algae lipids/oils, as well as components of such materials.
  • the biomass can include one or more type of lipid compounds, which are typically biological compounds that are insoluble in water, but soluble in nonpolar (or fat) solvents.
  • Non-limiting examples of such solvents include alcohols, ethers, chloroform, alkyl acetates, benzene, and combinations thereof.
  • lipids include, but are not necessarily limited to, fatty acids, glycerol-derived lipids (including fats, oils and phospholipids), sphingosine-derived lipids (including ceramides, cerebrosides, gangliosides, and sphingomyelins), steroids and their derivatives, terpenes and their derivatives, fat-soluble vitamins, certain aromatic compounds, and long-chain alcohols and waxes.
  • lipids In living organisms, lipids generally serve as the basis for cell membranes and as a form of fuel storage. Lipids can also be found conjugated with proteins or carbohydrates, such as in the form of lipoproteins and lipopolysaccharides.
  • vegetable oils examples include, but are not limited to rapeseed (canola) oil, soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil, linseed oil, tall oil, corn oil, castor oil, jatropha oil, jojoba oil, olive oil, flaxseed oil, camelina oil, safflower oil, babassu oil, tallow oil and rice bran oil.
  • rapeseed canola
  • soybean oil coconut oil
  • sunflower oil palm oil
  • palm kernel oil peanut oil
  • linseed oil tall oil
  • corn oil castor oil
  • jatropha oil jatropha oil
  • jojoba oil olive oil
  • flaxseed oil camelina oil
  • safflower oil camelina oil
  • babassu oil babassu oil
  • tallow oil examples of vegetable oils that can be used in accordance with this invention.
  • Vegetable oils as referred to herein can also include processed vegetable oil material.
  • processed vegetable oil material include fatty acids and fatty acid alkyl esters.
  • Alkyl esters typically include C 1 -C 5 alkyl esters. One or more of methyl, ethyl, and propyl esters are preferred.
  • animal fats examples include, but are not limited to, beef fat (tallow), hog fat (lard), turkey fat, fish fat/oil, and chicken fat.
  • the animal fats can be obtained from any suitable source including restaurants and meat production facilities.
  • Animal fats as referred to herein also include processed animal fat material.
  • processed animal fat material include fatty acids and fatty acid alkyl esters.
  • Alkyl esters typically include C 1 -C 5 alkyl esters. One or more of methyl, ethyl, and propyl esters are preferred.
  • Algae oils or lipids are typically contained in algae in the form of membrane components, storage products, and metabolites. Certain algal strains, particularly microalgae such as diatoms and cyanobacteria, contain proportionally high levels of lipids. Algal sources for the algae oils can contain varying amounts, e.g., from 2 wt % to 40 wt % of lipids, based on total weight of the biomass itself. Additionally or alternately, algae can be genetically modified to produce oils that are not lipids, e.g., that contain oxygenated hydrocarbons, such as wax esters, fatty ketones, fatty aldehydes, fatty alcohols, and the like.
  • oxygenated hydrocarbons such as wax esters, fatty ketones, fatty aldehydes, fatty alcohols, and the like.
  • algae can be genetically modified to produce non-oxygenated hydrocarbons.
  • the algae may indeed exhibit an increased content of oil material and/or such oil material may advantageously have reduced oxygen content, compared to contents observable and/or attainable in conventional biomass.
  • Algal sources for algae oils include, but are not limited to, unicellular and multicellular algae.
  • Examples of such algae can include a rhodophyte, chlorophyte, heteronochphyte, tribophyte, glaucophyte, chlorarachniophyte, euglenoid, haptophyte, cryptomonad, dinoflagellum, phytoplankton, and the like, and combinations thereof.
  • algae can be of the classes Chlorophyceae and/or Haptophyta.
  • Neochloris oleoabundans Scenedesmus dimorphus, Euglena gracilis, Phaeodactylum tricornutum, Pleurochrysis carterae, Prymnesium parvum, Tetraselmis chui , and Chlamydomonas reinhardtii .
  • algae can include, but are not limited to, Achnanthes, Amphiprora, Amphora, Ankistrodesmus, Asteromonas, Boekelovia, Borodinella, Botryococcus, Bracteococcus, Chaetoceros, Carteria, Chlamydomonas, Chlorococcum, Chlorogonium, Chlorella, Chroomonas, Chrysosphaera, Cricosphaera, Crypthecodinium, Cryptomonas, Cyclotella, Dunaliella, Ellipsoidon, Emiliania, Eremosphaera, Ernodesmius, Euglena, Franceia, Fragilaria, Gloeothamnion, Haematococcus, Halocafeteria, Hymenomonas, Isochrysis, Lepocinclis, Micractinium, Monoraphidium, Nannochloris, Nannochloropsis, Navicul
  • prokaryotic organisms which include cyanobacterial species, from which oils qualifying as algae oils herein can be isolated/derived can include, but are not limited to, one or more of the following species: Agmenellum, Anabaena, Anabaenopsis, Anacystis, Aphanizomenon, Arthrospira, Asterocapsa, Borzia, Calothrix, Chamaesiphon, Chlorogloeopsis, Chroococcidiopsis, Chroococcus, Crinalium, Cyano bacterium, Cyanobium, Cyanocystis, Cyanospira, Cyanothece, Cylindrospermopsis, Cylindrospermum, Dactylococcopsis, Dermocarpella, Fischerella, Fremyella, Geitleria, Geitlerinema, Gloeobacter, Gloeocapsa, Gloeothece, Halospirulina, Iyengariella,
  • the biomass component can comprise a fatty acid alkyl ester.
  • the fatty acid alkyl ester can preferably comprise fatty acid methyl esters (FAME), fatty acid ethyl esters (FAEE), and/or fatty acid propyl esters.
  • the biomass component can include at least about 1 wt % oxygen, for example at least about 2 wt %, at least about 3 wt %, at least about 4 wt %, at least about 5 wt %, at least about 6 wt %, or at least about 8 wt %.
  • the majority of the oxygen present in the biomass component will be organically bound oxygen.
  • the processes of the present invention preferably utilize a single reactor comprised of at least two catalyst beds with processes and catalysts for producing a desulfurized, deoxygenated, and dewaxed hydrocarbon motor fuel product stream from a hydrocarbon feedstock comprised of a mineral oil component and a biomass oil component.
  • a hydrocarbon feedstock comprised of a mineral oil component and a biomass oil component.
  • an existing refinery hydroprocessing reactor can be utilized to economically retrofit an existing conventional (mineral oil) refining process into a process for refining the hydrocarbon feedstocks herein which are comprised both the sulfur-containing mineral oil and oxygen-containing biomass oil components.
  • the first reaction zone contains a catalyst operated under first hydroprocessing conditions suitable for both hydrodesulfurizing and deoxygenating the combined hydrocarbon feedstock comprising both a mineral oil component and a biomass oil component.
  • This first reaction zone may contain multiple catalyst beds. However, in this zone, at least one of these catalysts beds is to be comprised of the “hydrodesulfurization/deoxygenation catalyst”, or as may be alternately referred to herein as the “first catalyst”, as further described herein.
  • This first catalyst is preferably comprised of at least one Group VIII metal oxide, preferably an oxide of a metal selected from Fe, Co and Ni, more preferably selected from Co and/or Ni, and most preferably Co; and at least one Group VI metal oxide, preferably an oxide of a metal selected from Mo and W, more preferably Mo, on a high surface area support material, preferably comprising alumina, silica, or silica-alumina.
  • Group VIII metal oxide preferably an oxide of a metal selected from Fe, Co and Ni, more preferably selected from Co and/or Ni, and most preferably Co
  • at least one Group VI metal oxide preferably an oxide of a metal selected from Mo and W, more preferably Mo, on a high surface area support material, preferably comprising alumina, silica, or silica-alumina.
  • Other suitable hydrodesulfurization/deoxygenation catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from Pd and Pt.
  • the Group VIII metal oxide of the hydrodesulfurization/deoxygenation catalyst is present in an amount ranging from about 0.1 to about 20 wt %, preferably from about 1 to about 12 wt %, based on the weight of the catalyst.
  • the Group VI metal oxide is preferably present in an amount ranging from about 1 to about 50 wt %, preferably from about 2 to about 20 wt %, based on the weight of the catalyst.
  • the hydrodesulfurization/deoxygenation catalysts used in the practice of the present invention are preferably supported catalysts. Any suitable refractory catalyst support material, preferably inorganic oxide support materials, can be used as supports for the hydrodesulfurization/deoxygenation catalyst utilized in the present invention.
  • Non-limiting examples of suitable support materials include: zeolites, alumina, silica, titania, calcium oxide, strontium oxide, barium oxide, carbons, zirconia, diatomaceous earth, lanthanide oxides including cerium oxide, lanthanum oxide, neodynium oxide, yttrium oxide, and praesodymium oxide; chromia, thorium oxide, urania, niobia, tantala, tin oxide, zinc oxide, and aluminum phosphate.
  • Preferred are alumina, silica, and silica-alumina. More preferred is alumina.
  • Preferred conditions in this first reaction zone of the hydroprocessing reactor include contacting the hydrocarbon feedstock and a first hydrogen treat gas stream with the hydrodesulfurization/deoxygenation catalyst under first hydroprocessing conditions sufficient to produce a first reaction zone effluent which contains less organically bound sulfur than the feedstock and less organically bound oxygen than the hydrocarbon feedstock.
  • These first hydroprocessing conditions can comprise one or more of: a weight average bed temperature (WABT) from about 500° F. (about 260° C.) to about 800° F. (about 427° C.), for example from about 550° F. (about 288° C.) to about 700° F.
  • WABT weight average bed temperature
  • a total pressure from about 300 psig (about 2.1 MPag) to about 3000 psig (about 20.7 MPag), for example from about 700 psig (about 4.8 MPag) to about 2000 psig (about 13.8 MPag); an LHSV from about 0.1 hr ⁇ 1 to about 20 hr ⁇ 1 , for example from about 0.2 hr ⁇ 1 to about 10 hr ⁇ 1 ; and a hydrogen treat gas rate from about 500 scf/bbl (about 89 m 3 /m 3 ) to about 10000 scf/bbl (about 1781 m 3 /m 3 ), for example from about 750 scf/bbl (about 134 m 3 /m 3 ) to about 7000 scf/bbl (about 1247 m 3 /m 3 ) or from about 1000 scf/bbl (about 178 m 3 /m 3 ) to about
  • treat gas hydrogen treat gas
  • hydrogen treat gas stream a gas stream which can be either pure hydrogen or a hydrogen-containing gas, which contains hydrogen in an amount at least sufficient for the intended reaction purpose(s), optionally in addition to one or more other gases (e.g., nitrogen, light hydrocarbons such as methane, and the like, and combinations thereof) that generally do not adversely interfere with or affect either the reactions or the products.
  • gases e.g., nitrogen, light hydrocarbons such as methane, and the like, and combinations thereof
  • Impurities such as H 2 S, NH 3 , CO, and CO 2 are typically undesirable and would typically be removed from, or reduced to desirably low levels in, the hydrogen treat gas before it is conducted to the reactor bed/zones(s).
  • the treat gas stream introduced into the hydroprocessing reactor can preferably contains at least about 50 vol % hydrogen. However, the treat gas streams utilized herein more preferably contains at least 75 vol % hydrogen, more preferably at least 85 vol % hydrogen, or even at least 95 vol % hydrogen.
  • the first reaction zone effluent preferably contains less than 25 wt %, more preferably less than 10 wt % and most preferably less than 5 wt % of organically bound sulfur than exists in the hydrocarbon feedstock. In preferred embodiments, first reaction zone effluent contains less than 250 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm and most preferably less than 30 ppm of organically bound sulfur. The majority of the organic sulfur content of the hydrocarbon feedstream is converted into H 2 S in this first reactor bed.
  • the first reaction zone effluent also preferably contains less than 50 wt %, more preferably, less than 25 wt % and most preferably less than 10 wt % of organically bound oxygen that exists in the hydrocarbon feedstock.
  • first reaction zone effluent contains less than less than 10,000 ppm, more preferably less than 5,000 ppm, even more preferably less than 1,000 ppm and most preferably less than 500 ppm of organically bound oxygen.
  • the majority of the organic oxygen content is converted into H 2 O (or “water”, which also may be in the form of steam) in this first reaction zone.
  • the water partial pressure in the first reaction zone effluent will be greater than 2 psia, or greater than 5 psia, or in some instances, even greater than 10 psia under these hydroprocessing conditions and these conditions will be experienced in the second reaction zone of the hydroprocessing reactor in the processes herein.
  • the first reaction zone effluent is passed to the second reaction zone without separation of the reaction components within the first reaction zone effluent stream.
  • Additional streams such as a second hydrogen treat gas stream, may be added to the first reaction zone effluent prior to, or simultaneous with, contact of the first reaction zone effluent with the catalyst(s) located in the second reaction zone of the hydroprocessing reactor.
  • the second reaction zone contains a catalyst operated under process conditions suitable for catalytic hydrodewaxing the first reaction zone effluent, which has been derived from a combined hydrocarbon feedstock comprising both a mineral oil component and a biomass oil component.
  • catalytic hydrodewaxing (or conversely “dewaxing”) as utilized herein, it is meant process where a hydrocarbon containing waxy molecules, including n-paraffins which contain at least 12 or more carbon atoms (i.e. “C 12 +” hydrocarbons), are at least partially converted into isomers (i.e., “isomerized”) in the presence of a catalyst and excess hydrogen.
  • This second reaction zone may contain multiple catalysts beds. In this second reaction zone, at least one of these catalyst beds is to be comprised of the “dewaxing catalyst”, or as may be alternatively referred to herein as the “second catalyst”, as further described herein.
  • a particular problem in dewaxing the resulting first reaction zone effluent is the high content of water reactant products present in the resultant effluent from the first reaction zone.
  • conventional dewaxing catalysts in particular alumina supported dewaxing catalysts, can be physically unstable, resulting in catalyst loss as well as a corresponding decrease in hydroconversion efficiencies.
  • dewaxing catalyst compositions utilized in the second reaction zone should be capable of hydroisomerization/dewaxing while minimizing physical catalyst loss and maximizing/maintaining high conversion efficiencies.
  • the dewaxing catalyst compositions utilized according to the invention may additionally be capable of at least partially hydrocracking the first reactor bed effluent.
  • the water-resistant dewaxing catalyst compositions utilized herein comprise a hydrophilic, hydrothermally-stable support such as a zeolitic support, at least one active metal compound comprising one or more of Group VIB metals and Group VIII metals deposited thereon, and a hydrophilic, hydrothermally-stable binder.
  • Zeolitic supports according to use in the dewaxing catalysts of the present invention can include, but are not limited to crystalline aluminosilicates molecular sieves and/or 1-D or 3-D molecular sieve (for example, 10-member ring 1-D molecular sieves).
  • suitable dewaxing catalyst supports can include, but are not limited to, ferrierite, mordenite, ZSM-5, ZSM-22 (also known as theta one or TON), ZSM-23, ZSM-35, ZSM-48, zeolite Beta, zeolite Y, USY, other Group IIA, IVB, VB, and/or VIB oxides, and combinations thereof (for example, molecular sieves such as ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, and combinations thereof, particularly molecular sieves such as ZSM-5, ZSM-48, and/or ZSM-23).
  • the at least one active metal compound which typically includes a metal hydrogenation component, can comprise a Group VIII metal.
  • Suitable Group VIII metals can include Pt, Pd, Ni, Co, or combinations thereof.
  • the dewaxing catalyst composition can include at least 0.1 wt % of the Group VIII metal(s), for example at least about 0.3 wt %, at least about 0.5 wt %, at least about 1.0 wt %, at least about 2.5 wt %, or at least about 5.0 wt %.
  • the catalyst composition can include about 10.0 wt % or less of the Group VIII metal(s), for example about 5.0 wt % or less, about 2.5 wt % or less, about 1.5 wt % or less, or about 1.0 wt % or less.
  • the dewaxing catalyst composition can include as an additional hydrogenation component a Group VIB metal, such as W and/or Mo.
  • a Group VIB metal such as W and/or Mo.
  • the Group VIB metal(s) can be present when the Group VIII metal(s) comprise(s) a non-noble metal (such as Ni and/or Co).
  • An example of such an embodiment could be a dewaxing catalyst composition that includes the following metals: NiW, NiMo, or NiMoW.
  • the dewaxing catalyst composition can include at least about 0.5 wt % of the Group VIB metal(s), for example at least about 1.0 wt %, at least about 2.5 wt %, or at least about 5.0 wt %.
  • the dewaxing catalyst composition can include about 20.0 wt % or less of the Group VIB metal(s), for example about 15.0 wt % or less, about 10.0 wt % or less, about 5.0 wt % or less, or about 1.0 wt % or less.
  • the dewaxing catalyst composition contains only Group VIII metals, however, noble Group VIII metals (such as Pt and/or Pd) are the preferred Group VIII metals.
  • the binder of the dewaxing catalyst composition which can advantageously be hydrophilic and/or hydrothermally-stable, is comprised of one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium, activated carbon, and/or carbon on which is deposited one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium. More preferably, the binder of the dewaxing catalyst is comprised of one or metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium. Even more preferably, the binder of the dewaxing catalyst is comprised of one or metals selected from titanium, zirconium, and cerium. Most preferably, the binder comprises titanium.
  • the binder of the dewaxing catalyst consists essentially of one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium, activated carbon, and/or carbon on which is deposited one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium.
  • the binder of the dewaxing catalyst consists essentially of one or metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium.
  • the binder of the dewaxing catalyst consists essentially of one or metals selected from titanium, zirconium, and cerium.
  • the binder consists essentially of titanium.
  • the form of the one or more metals may be metallic but typically comprises an oxide, carbide, nitride, phosphide, sulfide, or combination thereof (e.g., a combination of a carbide and nitride could be a nitrile; a combination of a phosphide and an oxide could be a phosphate, a phosphite, a hypophosphite, or the like).
  • the binder comprises titania (aka titanium dioxide).
  • the dewaxing catalyst compositions according to the present invention may consist essentially of the aforementioned components or may optionally contain additional components, such as sources of other transition metals (e.g., Group V metals such as niobium), sources of rare earth metals, organic ligands (e.g., as added or as precursors left over from oxidation and/or sulfidization steps), phosphorus compounds, boron compounds, fluorine-containing compounds, silicon-containing compounds, promoters, additional binders, fillers, or like agents, or combinations thereof.
  • the Groups referred to herein refer to Groups of the CAS Version as found in the Periodic Table of the Elements in Hawley's Condensed Chemical Dictionary, 13 th Edition.
  • Preferred conditions in the second reaction zone of the hydroprocessing reactor include contacting the hydrocarbon feedstock and a first hydrogen treat gas stream with the dewaxing catalyst under second hydroprocessing conditions sufficient to produce a second reaction zone effluent with improved cold flow properties, such as, but not limited to improved cloud point properties.
  • These second hydroprocessing conditions can comprise one or more of: a weight average bed temperature (WABT) from about 500° F. (about 260° C.) to about 800° F. (about 427° C.), for example from about 550° F. (about 288° C.) to about 700° F.
  • WABT weight average bed temperature
  • a second hydrogen treat gas may be added to the first reaction zone effluent prior to, or simultaneously with the contacting of the first reaction zone effluent with the dewaxing catalyst located in the second reaction zone.
  • a second hydrogen treat gas rate from about 200 scf/bbl (about 36 m 3 /m 3 ) to about 5000 scf/bbl (about 890 m 3 /m 3 ) is preferred.
  • the product of this second reaction zone processing is the “second reaction zone effluent”.
  • This effluent may be further processed by additional catalyst beds and/or reaction zones in the hydroprocessing reactor, but not to be limiting and simply for the sake of simplicity, we will continue to describe the processes herein in terms of an embodiment wherein only the first reaction zone and second reaction zones and associated catalysts beds are present in the hydroprocessing reactor.
  • the second reaction zone effluent is withdrawn from the hydroprocessing reactor.
  • Preferably at least a portion of the second reaction zone effluent is separated to form a gas phase product and a reactor effluent product.
  • reaction zone effluent is withdrawn from the hydroprocessing reactor and sent to a fractionator tower wherein the gas phase product is removed from the reactor effluent product and the reactor effluent product is simultaneously fractionated into two or more different boiling range liquid product streams.
  • reactor effluent product is considered to be the combination of the liquid product streams fractionated unless otherwise designated as, or referred to as, a particular fraction of the overall reactor effluent product herein.
  • liquid product or “liquid product stream” as utilized in the context herein it is meant the reactor product components of the present processes which are a liquid at standard (atmospheric) pressure and temperature.
  • FIG. 1 shows a simplified schematic of an embodiment of the process configuration herein wherein a single reactor is utilized with only two (2) reaction zones as have been described herein.
  • FIG. 1 also shows the optional use of a flash drum to separate the gas phase products from the second reaction zone effluent in order to form a reactor effluent product which can be further separated for motor fuel use.
  • a mineral oil component 1 and a biomass oil component 5 are combined to form a combined hydrocarbon feedstock 10 .
  • the two component streams will be mixed in a portion of the process significantly prior to introduction into the hydroprocessing reactor 20 .
  • the combined streams may additional undergo pre-processing prior to the step of the processes as illustrated in FIG. 1 .
  • the combined hydrocarbon feedstock 10 enters the hydroprocessing reactor 20 .
  • a first hydrogen treat gas stream 15 is combined with the hydrocarbon feedstock. In FIG. 1 , this combining is shown as mixing with the hydrocarbon feedstock stream 10 prior to entry into the reactor. However, the first hydrogen treat gas stream 15 may be introduced into the processes herein optionally, or additionally, directly into the hydroprocessing reactor 20 .
  • the hydrogen feedstock 10 and first hydrogen treat gas 15 contact the catalyst(s) in the first reactor zone 25 under first hydroprocessing conditions as have been described herein.
  • the first reaction zone 25 contains a hydrodesulfurization/deoxygenation catalyst as has been described in the details of the invention herein.
  • the combined stream components pass through the catalyst(s) in the first reaction zone 25 where the components are catalytically converted into different molecular products and emerge from the first reaction zone as a first reaction zone effluent (not separately designated in the figure) which then passes to the second reaction zone 30 under second hydroprocessing conditions as have been described herein.
  • a second hydrogen treat gas stream 35 can be added to the process prior to the second reaction zone 30 as shown.
  • the first reaction zone effluent is catalytically converted in the second reaction zone 30 to produce the product properties as described in the detailed description herein and can be withdrawn from the hydroprocessing reactor 20 as a second reaction zone effluent 40 as shown.
  • a flash drum 50 is utilized to separate the second reaction zone effluent 40 into gas phase products 55 and a reactor effluent product 60 .
  • the second reaction zone effluent 40 may undergo additional cooling prior to entering the flash drum 50 .
  • the reactor effluent product 60 can then be further processed and/or separated into fractions for use in diesel, kerosene, jet, heating oil, marine, bunker fuels, and/or lubes.
  • FIG. 2 illustrates another optional embodiment of the processes herein.
  • elements/processes 1 through 40 as were described in FIG. 1 are essentially the same as shown in FIG. 2 .
  • a preferred use of the processes herein are to produce at least on motor fuel product stream, such as a naphtha stream (for gasoline blending) or distillate (for diesel blending) which meet motor fuel specifications while co-processing a combined mineral oil/biomass component stream, a fractionator tower 70 is utilized to directly separate the second reaction zone effluent 40 into useable motor fuel fractions.
  • gas phase stream 75 is withdrawn from the overhead of the fractionation tower 70 .
  • a flash drum as shown as element 50 in FIG. 1
  • gas phase stream 75 will primarily contain some hydrogen, incondensable products from the reaction process (such as hydrogen sulfide), water, and light petroleum gases or “LPGs” (such as propane and butane).
  • a naphtha range fraction 80 having a boiling range between 80° F. (27° C.) and 450° F. (232° C.) and/or a distillate range fraction 85 having a boiling range between 400° F. (204° C.) and 700° F. (371° C.) are drawn from the fractionator tower 70 .
  • these products will have improved product qualities for use in motor fuels.
  • the naphtha range fraction will have lower sulfur than the hydrocarbon feed introduced to the process and preferably will be low enough in sulfur to meet motor gasoline specifications.
  • the naphtha range fraction should also be improved in isomer content which will improve gasoline octane.
  • the resultant distillate product will have improved product qualities for use in a diesel motor fuel.
  • the distillate range fraction will have lower sulfur than the hydrocarbon feed introduced to the process and preferably will be low enough in sulfur to meet motor diesel specifications.
  • the distillate fraction will also have improved cloud point properties over the unprocessed distillate fraction of the combined hydrocarbon feedstock, and will preferably meet the commercial transportation and use specifications for diesel motor fuels without further conversion processing.
  • a marine/bunker fuel fraction 90 can be withdrawn from the fractionation tower 70 .
  • a lube oil fraction 95 may also be withdrawn from the fractionation tower 70 .
  • the reactor effluent product will have a branched (iso-) paraffin content that is at least 10 wt % higher, and more preferably at least 20 wt % higher, and even more preferably at least 35 wt % higher than the branched (iso-) paraffin content of the combined hydrocarbon feedstock.
  • the reactor effluent product stream after separation of the gas phase stream from the second reaction zone effluent stream, preferably contains less than 25 wt %, more preferably less than 10 wt % and most preferably less than 5 wt % of the sulfur that is present in the hydrocarbon feedstock. In preferred embodiments, the reactor effluent product stream contains less than 250 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm and most preferably less than 30 ppm of sulfur.
  • the reactor effluent product stream after separation of the gas phase stream from the second reaction zone effluent stream, preferably contains less than 50 wt %, more preferably, less than 25 wt % and most preferably less than 10 wt % of the oxygen that is present in the hydrocarbon feedstock.
  • reactor effluent product stream contains less than less than 10,000 ppm, more preferably less than 5,000 ppm, even more preferably less than 1,000 ppm and most preferably less than 500 ppm oxygen.
  • one or more portions of the reactor effluent product (or perhaps even the entire product) of the methods according to the present invention can advantageously be used as one or more transportation fuel compositions and/or may be sent to one or more existing fuel pools.
  • fuel compositions/pools can include, but are not limited to, diesel, kerosene, jet, heating oil, marine, and/or bunker fuels.
  • the distillate portion(s) of the product can be split (e.g., by fractionation or the like) into a kerosene cut having a boiling range between 400° F. (204° C.) and 550° F. (288° C.) and a diesel cut having a boiling range between 550° F. (232° C.) and 700° F. (371° C.).
  • a diesel boiling range fraction of the reactor effluent product is separated/isolated, and the diesel boiling range fraction can exhibit a cloud point that is less than 0° C., preferably less than ⁇ 5° C., or less than ⁇ 10° C., or less than ⁇ 15° C., or less than ⁇ 20° C., or less than ⁇ 25° C., or less than ⁇ 30° C., or less than ⁇ 35° C., or less than ⁇ 40° C.
  • the present invention can include the following embodiments.
  • a method for processing a hydrocarbon feedstock comprised of a mineral oil component and a biomass oil component to form at least one liquid motor fuel product comprising:
  • the dewaxing catalyst comprises a zeolitic support, at least one active metal compound comprising one or more of Group VIB metals and Group VIII metals deposited thereon, and a hydrophilic, hydrothermally-stable binder comprising one or more of: (A) an oxide, carbide, nitride, phosphide, sulfide, or combination thereof of one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium, (B) activated carbon, and (C) carbon on which is deposited one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium.
  • A an oxide, carbide, nitride, phosphide, sulfide, or combination thereof of one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium
  • B activated carbon
  • C carbon on which is deposited
  • the binder of the dewaxing catalyst comprises zirconia, vanadia, titania, molybdenum oxide, manganese oxide, cerium oxide, carbon, or a combination thereof.
  • the binder of the dewaxing catalyst comprises one or metals selected from titanium, zirconium, vanadium, molybdenum, manganese, and cerium.
  • the binder of the dewaxing catalyst comprises one or metals selected from titanium, zirconium, and cerium.
  • the zeolitic support of the dewaxing catalyst comprises ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, zeolite Beta, zeolite Y, USY, mordenite, ferrierite, or a combination thereof.
  • hydrodesulfurization/deoxygenation catalyst comprises at least one Group VIII metal oxide selected from Fe, Co and Ni, and at least one Group VIB metal oxide selected from Mo and W.
  • hydrodesulfurization/deoxygenation catalyst further comprises a support selected from alumina, silica, and silica-alumina.
  • the first hydroprocessing conditions include one or more of: a weight average bed temperature (WABT) from about 500° F. (about 260° C.) to about 800° F. (about 427° C.); a total pressure from about 300 psig (about 2.1 MPag) to about 3000 psig (about 20.7 MPag); an LHSV from about 0.1 hr ⁇ 1 to about 20 hr ⁇ 1 ; and a hydrogen treat gas rate from about 500 scf/bbl (about 89 m 3 /m 3 ) to about 10000 scf/bbl (about 1781 m 3 /m 3 ).
  • WABT weight average bed temperature
  • the second hydroprocessing conditions include one or more of: a weight average bed temperature (WABT) from about 500° F. (about 260° C.) to about 800° F. (about 427° C.); a total pressure from about 300 psig (about 2.1 MPag) to about 3000 psig (about 20.7 MPag); an LHSV from about 0.1 hr ⁇ 1 to about 20 hr ⁇ 1 .
  • WABT weight average bed temperature
  • the second hydroprocessing conditions further include a water partial pressure of greater than 5 psia.
  • the second hydroprocessing conditions include the introduction of a second hydrogen treat gas at a treat gas rate from about 200 scf/bbl (about 36 m 3 /m 3 ) to about 5000 scf/bbl (about 890 m 3 /m 3 ).
  • the hydrocarbon feedstock contains from 80 wt % to about 98 wt % of the mineral oil component and from 2 wt % to about 20 wt % of the biomass oil component, the mineral oil component contains at least 500 ppmw sulfur, and the reactor effluent product contains less than 100 ppmw sulfur.
  • biomass oil component is derived from algae.
  • the at least one liquid motor fuel product is produced from a diesel boiling range fraction of the reactor effluent product wherein the cloud point of the diesel boiling range fraction is less than 0° C.
  • the reactor effluent product has a branched (iso-) paraffin content that is at least 20 wt % higher than the branched (iso-) paraffin content of the hydrocarbon feedstock.
  • the dewaxing catalyst is comprised of ZSM-48, and a Group VIII metal selected from palladium and platinum with a metal content from about 0.1 wt % to about 3.0 wt % based on the weight of the ZSM-48, and a titania binder.
  • the dewaxing catalyst is comprised of ZSM-48, a Group VIII non-noble metal selected from nickel, cobalt, and iron with a Group VIII metals content from about 0.5 wt % to about 20 wt % based on the weight of the ZSM-48, a Group VIB metal selected from molybdenum and tungsten with a Group VIB metals content from about 3 wt % to about 25 wt %, based on the weight of the ZSM-48, and a titania binder.
  • Stearic acid feed was converted over a series of different catalyst compositions and at temperatures of about 250° C., about 275° C., about 300° C., and about 325° C.
  • These catalyst compositions included ⁇ 1 wt % Pt on alumina support/binder, ⁇ 1 wt % Pt on ZSM-23 support (total metal on support was about 65% of catalyst weight) with titania binder (about 35% of catalyst weight), ⁇ 1 wt % Pt on ZSM-48 support (total metal on support was about 65% of catalyst weight) with alumina binder (about 35% of catalyst weight), ⁇ 1 wt % Pt on ZSM-48 support with titania binder, ⁇ 1 wt % Pt on ZSM-5 support (total metal on support was about 65% of catalyst weight) with alumina binder (about 35% of catalyst weight), and ZSM-5 with no metal and no binder.
  • titania-containing (or, more broadly, non-alumina-containing) catalyst compositions exhibited higher conversion of the stearic acid feed than alumina-containing catalyst compositions.
  • the titania-(non-alumina-) containing catalysts all exhibited conversion levels of at least 15% (for example from about 20% to about 95%), whereas alumina-containing catalysts exhibited conversion levels below 10%. These conversion levels were based on calculations involving mass balances, which can also be a good indicator for the oxygen content.
  • Example 2 a direct comparison was made between the activity of two catalyst compositions that were identical, except for the binder.
  • the first catalyst composition was ⁇ 1 wt % Pt on ZSM-48 support with an alumina binder, whereas the second catalyst composition was ⁇ 1 wt % Pt on ZSM-48 support with a titania binder.
  • Stearic acid feed was converted over each catalyst at a temperature of about 325° C., with a weight hourly space velocity of about 0.3 hr ⁇ 1 , and under a hydrogen partial pressure of about 400 psig (about 2.8 MPag).
  • the product was analyzed using a gas chromatograph linked to a mass spectrometer (GC-MS). The spectral comparison is shown in FIG.
  • GC-MS mass spectrometer
  • the catalyst composition containing the titania binder showed substantially complete conversion of the feed from paraffin to branched (iso-) paraffin, with substantially complete deoxygenation as well.
  • the pour point of this top sample was determined to be below about ⁇ 50° C., based on analysis via differential scanning calorimetry (DSC), using a temperature rate of change of approximately 10° C./minute.
  • the catalyst composition containing the alumina binder showed large amounts of unconverted stearic acid, with some limited deoxygenation but with only barely detectable (trace) amounts of conversion from paraffin to branched (iso-) paraffin.
  • the pour point of this bottom sample was determined to be about +52° C., based on DSC analysis. For comparison, the pour point (melting point) of the stearic acid feed was about +69° C.

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US13/906,907 2012-06-04 2013-05-31 Hydrodesulfurization, deoxygenation and dewaxing processes with water stable catalysts for biomass-containing hydrocarbon feedstocks Abandoned US20130338414A1 (en)

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US13/906,907 US20130338414A1 (en) 2012-06-04 2013-05-31 Hydrodesulfurization, deoxygenation and dewaxing processes with water stable catalysts for biomass-containing hydrocarbon feedstocks
JP2015516085A JP6173446B2 (ja) 2012-06-04 2013-06-03 バイオマス含有炭化水素原料のための水安定性触媒による水素化脱硫、脱酸素および脱ろうプロセス
CN201380029116.1A CN104508090B (zh) 2012-06-04 2013-06-03 用水稳定性催化剂将包含生物质的烃原料加氢脱硫、脱氧和脱蜡方法
AU2013271891A AU2013271891B2 (en) 2012-06-04 2013-06-03 Hydrodesulfurization, deoxygenation and dewaxing processes with water stable catalysts for biomass-containing hydrocarbon feedstocks
SG11201406795TA SG11201406795TA (en) 2012-06-04 2013-06-03 Hydrodesulfurization, deoxygenation and dewaxing processes with water stable catalysts for biomass-containing hydrocarbon feedstocks
PCT/US2013/043826 WO2013184545A1 (fr) 2012-06-04 2013-06-03 Procédés d'hydrodésulfuration, de désoxygénation et de déparaffinage de charges hydrocarbonées contenant de la biomasse à l'aide de catalyseurs stables dans l'eau
EP13728301.6A EP2855635B1 (fr) 2012-06-04 2013-06-03 Procédés d'hydrodésulfuration, de désoxygénation et de déparaffinage de charges hydrocarbonées contenant de la biomasse à l'aide de catalyseurs stables dans l'eau
CA2872826A CA2872826C (fr) 2012-06-04 2013-06-03 Procedes d'hydrodesulfuration, de desoxygenation et de deparaffinage de charges hydrocarbonees contenant de la biomasse a l'aide de catalyseurs stables dans l'eau

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140274664A1 (en) * 2013-03-14 2014-09-18 Exxonmobil Research And Engineering Company Dewaxing catalysts
WO2015116386A1 (fr) * 2014-01-30 2015-08-06 Kior, Inc. Catalyseur de pyrolyse de biomasse multi-fonctionnel et son procédé d'utilisation
WO2016100395A1 (fr) * 2014-12-18 2016-06-23 Kior, Llc Procédé de thermolyse de biomasse en présence de sulfure d'hydrogène
WO2017093534A1 (fr) * 2015-12-02 2017-06-08 Haldor Topsøe A/S Procédé en une seule étape combinant le chargement de catalyseurs à base de métaux nobles et non nobles
WO2019212421A1 (fr) * 2018-04-30 2019-11-07 Green Technology Research Co., Ltd Procédé et appareil de traitement de biomatériau
US11078433B2 (en) * 2016-10-14 2021-08-03 Gevo, Inc. Conversion of mixtures of C2—C8 olefins to jet fuel and/or diesel fuel in high yield from bio-based alcohols
CN114929842A (zh) * 2020-01-08 2022-08-19 沙特阿拉伯石油公司 用于改进馏出物的冷流性质的经改性的超稳定y(usy)沸石催化剂
KR20220123553A (ko) * 2018-04-30 2022-09-07 그린 테크놀로지 리서치 씨오., 엘티디 바이오 기반 재료의 처리 방법 및 이를 처리하기 위한 장치
US20220356404A1 (en) * 2014-10-21 2022-11-10 Shell Usa, Inc. Catalyst and process for deoxygenation and conversion of bio-derived feedstocks
US11597889B2 (en) * 2019-12-23 2023-03-07 ExxonMobil Technology and Engineering Company Production of high-value fuel mixtures from synthetic and biologically derived hydrocarbon molecules
WO2023126562A1 (fr) * 2021-12-27 2023-07-06 Neste Oyj Procédé de production de gaz renouvelable, de naphta renouvelable et de carburéacteur renouvelable
US20240034945A1 (en) * 2020-09-25 2024-02-01 Abundia Biomass-to-Liquids Limited Converting biomass to jet-fuel
WO2024082049A1 (fr) * 2022-10-18 2024-04-25 Nanos Technology And Innovations Ltd. Appareil et procédés pour améliorer des hydrocarbures par traitement catalytique à la vapeur d'eau

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3441441A1 (fr) * 2017-08-10 2019-02-13 Total Research & Technology Feluy Utilisation de catalyseur de métal noble pour procédé dco en présence de soufre
WO2020072669A1 (fr) * 2018-10-05 2020-04-09 Reg Synthetic Fuels, Llc Diesel renouvelable
US11566189B2 (en) 2020-05-22 2023-01-31 ExxonMobil Technology and Engineering Company Process to produce high paraffinic diesel
US11597885B2 (en) * 2020-07-21 2023-03-07 ExxonMobil Technology and Engineering Company Methods of whole crude and whole crude wide cut hydrotreating and dewaxing low hetroatom content petroleum
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100317903A1 (en) * 2007-11-09 2010-12-16 Upm-Kymmene Oyj Integrated Process for Producing Diesel Fuel from Biological Material and Products, Uses and Equipment Relating to Said Process
US20110219669A1 (en) * 2010-03-09 2011-09-15 Exxonmobil Research And Engineering Company Hydroprocessing of diesel range biomolecules

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100083563A1 (en) * 2008-10-02 2010-04-08 Chevron U.S.A. Inc. Co-processing diesel fuel with vegetable oil to generate a low cloud point hybrid diesel biofuel
DK2362892T3 (da) * 2008-11-06 2019-07-15 Exxonmobil Res & Eng Co Hydrogenbehandling af biodieselbrændstoffer og blandinger
US8632675B2 (en) * 2008-12-24 2014-01-21 Exxonmobil Research And Engineering Company Co-processing of diesel biofeed and heavy oil
SG183861A1 (en) * 2010-03-09 2012-10-30 Exxonmobil Res & Eng Co Hydroprocessing of diesel range biomolecules
SG183860A1 (en) * 2010-03-09 2012-10-30 Exxonmobil Res & Eng Co Dewaxing of renewable diesel fuel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100317903A1 (en) * 2007-11-09 2010-12-16 Upm-Kymmene Oyj Integrated Process for Producing Diesel Fuel from Biological Material and Products, Uses and Equipment Relating to Said Process
US20110219669A1 (en) * 2010-03-09 2011-09-15 Exxonmobil Research And Engineering Company Hydroprocessing of diesel range biomolecules

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* Cited by examiner, † Cited by third party
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US9433936B2 (en) * 2013-03-14 2016-09-06 Exxonmobil Research And Engineering Company Dewaxing catalysts
US20140274664A1 (en) * 2013-03-14 2014-09-18 Exxonmobil Research And Engineering Company Dewaxing catalysts
WO2015116386A1 (fr) * 2014-01-30 2015-08-06 Kior, Inc. Catalyseur de pyrolyse de biomasse multi-fonctionnel et son procédé d'utilisation
US20220356404A1 (en) * 2014-10-21 2022-11-10 Shell Usa, Inc. Catalyst and process for deoxygenation and conversion of bio-derived feedstocks
WO2016100395A1 (fr) * 2014-12-18 2016-06-23 Kior, Llc Procédé de thermolyse de biomasse en présence de sulfure d'hydrogène
US9644150B2 (en) 2014-12-18 2017-05-09 Inaeris Technologies, Llc Method of thermolyzing biomass in presence of hydrogen sulfide
WO2017093534A1 (fr) * 2015-12-02 2017-06-08 Haldor Topsøe A/S Procédé en une seule étape combinant le chargement de catalyseurs à base de métaux nobles et non nobles
US11078433B2 (en) * 2016-10-14 2021-08-03 Gevo, Inc. Conversion of mixtures of C2—C8 olefins to jet fuel and/or diesel fuel in high yield from bio-based alcohols
US11674096B2 (en) 2018-04-30 2023-06-13 Green Technology Research Co., Ltd. Method of processing a bio-based material and apparatus for processing the same
KR20220123553A (ko) * 2018-04-30 2022-09-07 그린 테크놀로지 리서치 씨오., 엘티디 바이오 기반 재료의 처리 방법 및 이를 처리하기 위한 장치
WO2019212421A1 (fr) * 2018-04-30 2019-11-07 Green Technology Research Co., Ltd Procédé et appareil de traitement de biomatériau
KR102706600B1 (ko) 2018-04-30 2024-09-19 그린 테크놀로지 리서치 씨오., 엘티디 바이오 기반 재료의 처리 방법 및 이를 처리하기 위한 장치
US11597889B2 (en) * 2019-12-23 2023-03-07 ExxonMobil Technology and Engineering Company Production of high-value fuel mixtures from synthetic and biologically derived hydrocarbon molecules
CN114929842A (zh) * 2020-01-08 2022-08-19 沙特阿拉伯石油公司 用于改进馏出物的冷流性质的经改性的超稳定y(usy)沸石催化剂
US20240034945A1 (en) * 2020-09-25 2024-02-01 Abundia Biomass-to-Liquids Limited Converting biomass to jet-fuel
WO2023126562A1 (fr) * 2021-12-27 2023-07-06 Neste Oyj Procédé de production de gaz renouvelable, de naphta renouvelable et de carburéacteur renouvelable
US12529001B2 (en) 2021-12-27 2026-01-20 Neste Oyj Method for producing renewable gas, renewable naphtha, and renewable jet fuel
WO2024082049A1 (fr) * 2022-10-18 2024-04-25 Nanos Technology And Innovations Ltd. Appareil et procédés pour améliorer des hydrocarbures par traitement catalytique à la vapeur d'eau

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JP6173446B2 (ja) 2017-08-02
AU2013271891B2 (en) 2016-03-31
CA2872826A1 (fr) 2013-12-12
WO2013184545A1 (fr) 2013-12-12
CA2872826C (fr) 2020-02-18
EP2855635A1 (fr) 2015-04-08
AU2013271891A1 (en) 2015-01-15
JP2015525271A (ja) 2015-09-03
SG11201406795TA (en) 2014-11-27
EP2855635B1 (fr) 2018-04-25

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