US20090300971A1 - Biorenewable naphtha - Google Patents

Biorenewable naphtha Download PDF

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US20090300971A1
US20090300971A1 US12/132,915 US13291508A US2009300971A1 US 20090300971 A1 US20090300971 A1 US 20090300971A1 US 13291508 A US13291508 A US 13291508A US 2009300971 A1 US2009300971 A1 US 2009300971A1
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naphtha
composition
biorenewable
oils
fraction
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US12/132,915
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Ramin Abhari
H. Lynn Tomlinson
Gary Roth
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REG Synthetic Fuels LLC
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Individual
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Priority to US12/132,915 priority Critical patent/US20090300971A1/en
Application filed by Individual filed Critical Individual
Assigned to SYNTROLEUM CORPORATION, A DELAWARE CORPORATION reassignment SYNTROLEUM CORPORATION, A DELAWARE CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ABHARI, RAMIN, ROTH, GARY, TOMLINSON, H. LYNN
Priority to SG2013043062A priority patent/SG192401A1/en
Priority to EP09759070A priority patent/EP2300563A4/en
Priority to PCT/US2009/045404 priority patent/WO2009148909A2/en
Publication of US20090300971A1 publication Critical patent/US20090300971A1/en
Priority to US13/196,768 priority patent/US8581013B2/en
Priority to US13/197,542 priority patent/US20110308142A1/en
Priority to US13/742,255 priority patent/US8558042B2/en
Priority to US14/050,559 priority patent/US9061951B2/en
Assigned to REG SYNTHETIC FUELS, LLC reassignment REG SYNTHETIC FUELS, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SYNTROLEUM CORPORATION
Priority to US14/458,119 priority patent/US9133080B2/en
Abandoned legal-status Critical Current

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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06Catalytic processes
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2078Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • C10G3/44Catalytic treatment characterised by the catalyst used
    • C10G3/45Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/064Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • C07C2529/072Iron group metals or copper
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • C10G2300/1014Biomass of vegetal origin
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • C10G2300/1018Biomass of animal origin
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/301Boiling range
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/308Gravity, density, e.g. API
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081Recycling aspects
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02Gasoline
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/18Solvents
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention generally relates to a method for producing hydrocarbons from biomass. Specifically, the present invention relates to converting naturally occurring triglycerides and fatty acids to a composition including naphtha boiling range hydrocarbons. The present invention also relates to the resultant biorenewable naphtha product, whereby the naphtha is used as chemical feed stock, fuel, fuel blend stock, or solvent.
  • the term “green chemistry” has been used to describe synthesis of chemicals from biorenewable feed stocks. It is considered a sustainable alternative to petroleum-based chemistry, and may mitigate the effect of high oil prices.
  • One of the challenges facing transition to a green chemical industry is that the existing production facilities and infrastructure are designed around hydrocarbon feed stocks.
  • the building blocks of the chemical industry olefins and BTX aromatics (benzene, toluene, and xylene) are produced in steam crackers (also referred to as ethylene crackers) and catalytic reformers that run on light hydrocarbons.
  • Synthesis gas, or syngas for short is another chemical building block. Syngas is a mixture of carbon monoxide and hydrogen and can be produced by steam reforming of light hydrocarbons.
  • Naphtha is a C 5 -C 9 hydrocarbon cut that is commonly used as the feedstock for both catalytic reformers and steam crackers. It may also be used as feed for steam reforming units for production of syngas.
  • paraffinic naphtha is considered a highly desired feed for steam crackers due to its high ethylene and propylene yields.
  • Production of naphtha from biorenewable sources would enable transition to a green chemical industry without the need to develop new chemistries and build new production facilities.
  • renewable energy has been used to refer to renewable sources of energy.
  • Biorenewable fuels are a key component of sustainable energy initiatives. Naphtha may be used directly as fuel in industrial furnaces or turbines. It may also be used in small industrial engines such as lawn mowers and chain saws.
  • naphtha hydrocarbons are in the motor gasoline boiling range, they may be used as a gasoline blend stock.
  • Gasoline blends need to meet vapor pressure and octane rating requirements.
  • One method of producing naphtha hydrocarbons from biomass is by the Fischer-Tropsch (F-T) process.
  • F-T Fischer-Tropsch
  • U.S. Pat. No. 7,214,720 to Bayle and co-inventors describes a process involving the steps of (a) gasification, (b) syngas purification, (c) F-T conversion, (d) separation, and (e) recycle of at least a portion of the naphtha to gasifier.
  • gasifiers suffer from a low reliability record.
  • the capital costs associated with gasification and F-T conversion are known to be very high. This is in part due to solids handling requirements for the gasifier and heat removal provisions for the highly exothermic F-T reaction.
  • the need to recycle part of the naphtha to the gasifier further reduces the efficiency of this process as a source of bio-renewable naphtha.
  • U.S. Pat. No. 5,186,722 to Cantrell and Chong describes a catalytic process to convert biomass feeds such as limonene to a composition of cyclic and aromatic compounds in the naphtha boiling range. Although these products are reported to have high octane rating and hence good gasoline blend stocks, they lack the desired properties as a chemical feed stock. As feeds for steam crackers, aromatic compounds give low ethylene and propylene yields. More importantly, the terpene feeds used in the process are among the only biomass sources that to begin with are hydrocarbons. Virtually all other sources of biomass have high oxygen content, typically greater than 10 wt %.
  • Deoxygenation of biomass feeds such as triglycerides and fatty acids are disclosed in U.S. Pat. No. 7,232,935 to Jakkula and co-inventors.
  • a two step process is disclosed which includes hydrodeoxygenation of triglycerides/fatty acids followed by hydroisomerization. The process produces diesel boiling-range isoparaffins.
  • the present invention is a method process for converting high oxygen content biomass, such as sources of triglycerides and/or fatty acids, into naphtha boiling-range hydrocarbons using standard refining processes.
  • the present invention relates to a method for producing from a biorenewable feed stock a hydrocarbon naphtha composition useful for producing olefins, BTX aromatics, hydrogen, and also for direct use as gasoline blend stock and solvent.
  • the biorenewable feed stock includes sources of glycerides (i.e. monoglycerides, diglycerides, triglycerides, etc.) and/or fatty acids and combinations thereof, such as animal fats, animal oils, poultry fat, poultry oils, vegetable oils, vegetable fats, plant fats and oils, rendered fats, rendered oils, restaurant grease, brown grease, waste industrial frying oils, fish oils, tall oil, and the like and any combinations thereof.
  • the method for producing hydrocarbon naphtha includes hydrotreating a renewable feedstock to produce a heavy hydrocarbon fraction. This is followed by hydrocracking of the hydrotreated heavy fraction to produce a distribution of hydrocarbon components, typically C 3 -C 18 , which is fractionated to recover the naphtha product.
  • the heavy fraction is optionally recycled to the hydrocracker.
  • hydrotreating of triglycerides and fatty acids involves olefin hydrogenation and deoxygenation. Hydrotreating thus converts fatty acids into long chain paraffins as illustrated in Equations 1 and 2 for conversion of oleic acid to n-octadecane and n-heptadecane.
  • the hydrotreating reactions of Equations 1 and 2 produce propane as well as the long chain, heavy hydrocarbon fraction.
  • the heavy hydrocarbon fraction is predominantly in the C 12 to C 22 range.
  • the heavy hydrocarbons may be hydrocracked into shorter chain hydrocarbons to produce biorenewable naphtha.
  • n-octadecane is hydrocracked into naphtha-range hydrocarbons, nonanes, hexanes, pentanes, and propane/butanes byproducts.
  • FIG. 1 is a schematic diagram of an operation for producing biorenewable naphtha according to the present invention.
  • FIG. 2 is a schematic diagram of another embodiment of a method for producing biorenewable naphtha in accordance with the present invention.
  • FIG. 3 is a gas chromatogram showing product from an example.
  • the present invention relates to a method for producing from a biorenewable feedstock a hydrocarbon product of naphtha boiling point range that can be used as feedstock for olefins, BTX aromatics, and hydrogen plants.
  • the biorenewable naphtha of the present invention may also be used directly as a fuel, a fuel blend stock, or a solvent.
  • a biorenewable feed 101 is transferred to a hydrotreater 102 where it reacts with hydrogen under pressure of from about 300 psig to about 3,000 psig, preferably from about 1,000 psig to about 2,000 psig. Feed 101 may optionally be pretreated to remove contaminants.
  • the hydrotreater 102 is preferably a packed bed of sulfided bimetallic catalyst, preferably nickel-molybdenum (NiMo), nickel-tungsten (NiW), or cobalt-molybdenum (CoMo) on alumina support. It should be understood by one of ordinary skill in the art that any catalyst may be used in the present invention so long as the catalyst functions in accordance with the present invention as described herein.
  • feed 101 may be supplemented with a sulfur composed that decomposes to hydrogen sulfide when heated and/or contacted with a catalyst.
  • a sulfur composed that decomposes to hydrogen sulfide when heated and/or contacted with a catalyst.
  • Two preferred sulfur compounds are dimethyl disulfide and carbon disulfide. Preferred concentration of these in the feed 101 is from about 100 to about 2,000 ppm by weight sulfur.
  • feed 101 may include a biorenewable component and a petroleum fraction wherein the petroleum-fraction provides the sulfur.
  • Feed 101 may be preheated before entering the hydrotreater 102 .
  • the hydrotreater 102 operates from about 300° F. to about 900° F., preferably from about 550° F. to about 650° F., and from about 250 psig to about 3,000 psig.
  • a number of methods known in the art may be used. These methods include, but are not limited to, feed dilution with a solvent or other diluent, liquid product or solvent recycle, and use of quench zones within the fixed-bed reactor wherein hydrogen is introduced.
  • the biorenewable feed 101 liquid hourly space velocity through the hydrotreater 102 is from about 0.2 h ⁇ 1 to about 10 h ⁇ 1 , preferably from about 0.5 h ⁇ 1 to about 5.0 h ⁇ 1 .
  • the ratio of hydrogen-rich treat gas 110 to biorenewable feed 101 is preferably in the about 2,000 to about 15,000 SCF/bbl range.
  • the hydrogen-rich treat gas 110 may contain from about 70 mol % to about 100 mol % hydrogen.
  • a hydrotreater effluent 103 includes a deoxygenated heavy hydrotreater fraction and unreacted hydrogen.
  • the hydrotreater effluent 103 may also include water, carbon oxides, ammonia, and hydrogen sulfide.
  • the long chain, heavy hydrocarbon fraction in the liquid phase is separated from the gas phase components in a separation unit 104 .
  • the separation unit 104 includes a high pressure drum (not shown) operated at hydrotreater discharge pressure (about 1,000 psig to about 2,000 psig in the preferred embodiment), wherein long chain, heavy hydrocarbon liquids are separated from hydrogen and gas phase hydrotreater byproducts. It should be understood that the hydrotreater discharge pressure may be operated from about 200 psig to about 3,000 psig. Depending on the temperature of the separation unit 104 , water may be in vapor or liquid phase. In a preferred embodiment, the separation unit 104 has a temperature in the about 350° F. to about 500° F. range whereby water, carbon oxides, ammonia, hydrogen sulfide, and propane are removed with hydrogen in a separator drum vapor phase. To enhance removal of the components from the heavy hydrocarbon fraction, the separation unit 104 optionally includes a stripping section (not shown). Water 111 may be condensed, separated, and the hydrogen-rich gas phase 105 recycled to the hydrotreater 102 .
  • a long chain hydrocarbon product stream 112 from the separation unit 104 is then cracked in a hydrocracker 114 .
  • Product stream 112 is optionally combined with unconverted heavies from the hydrocracker 114 , and recycled stream 125 , to form a hydrocracker feed 113 .
  • the heavy hydrocarbon feed 113 cracks in the hydrocracker 114 to form naphtha-range hydrocarbons.
  • the hydrocracker 114 operates from about 250 psig to about 3,000 psig, more preferably from about 1,000 psig to about 2,000 psig.
  • Hydrocracker 114 temperatures are from about 400° F. to about 900° F., preferably from about 580° F. to about 750° F.
  • Suitable catalysts for hydrocracking according to the present invention as described herein are bi-functional catalysts with hydrogenation and acidic functionalities. Such catalysts include Group VIII metals on amorphous (e.g. silica-alumina) or crystalline (e.g. zeolite) supports.
  • Preferred hydrocracking catalysts are platinum, palladium or combinations of same on an amorphous silica-alumina support. However, it should be understood that any catalyst may be used in accordance with the present invention as long as it functions as described herein.
  • Preferred ratios of the hydrogen-rich gas to liquid feed for hydrocracking are in the about 1,000 to about 10,000 SCF/bbl range, and liquid hourly space velocity in the about 0.1 h ⁇ 1 to about 8 h ⁇ 1 range, preferably from about 0.2 h ⁇ 1 to about 4 h ⁇ .
  • Stream 1115 is an effluent of the hydrocracker 114 wherein un-reacted hydrogen includes a gas phase. Hydrogen-rich gas is separated from the hydrocarbon product in a separation unit 116 .
  • the separation unit 116 includes a high pressure separation drum (not shown), operating at hydrocracker discharge pressure, about 1,000 psig to about 2,000 psig in the preferred embodiment, where hydrocarbon liquids are separated from hydrogen, hydrocarbon vapors, and any other gas phase cracked products. It should be understood that the hydrocracker discharge pressure may be operated from about 200 psig to about 3,000 psig.
  • a hydrogen-rich gas 117 from the separation unit 116 is combined with a hydrogen-rich gas 105 from the separation unit 104 and optionally processed through an absorption column or scrubber 108 to remove ammonia, carbon oxides, and/or hydrogen sulfide, before recompression for recycle to the hydrotreater 102 and/or hydrocracker 114 .
  • the scrubber 108 may use various solvents such as amine and caustic solutions. It is clear to those skilled in the art that other gas cleanup technologies may be used instead of or in addition to the scrubber 108 to remove contaminants that affect the hydrotreater 102 and hydrocracker 114 catalyst activity and selectivity. Examples of alternative gas cleanup technologies include membrane systems and adsorbent beds.
  • a purge stream 107 may be removed from a recycle gas 106 to prevent buildup of contaminants that are not effectively removed in the scrubber 108 .
  • the cleaned hydrogen-rich gas 108 a from the scrubber 108 may be combined with makeup hydrogen 109 to form a hydrogen-rich gas stream 110 for the hydrotreater 102 and hydrocracker 114 .
  • Stream 123 is the liquid hydrocarbon phase from the separation unit 116 .
  • Stream 123 is processed through fractionator unit 124 to fraction the hydrocracker products into a hydrocarbon vapors product 127 , the desired naphtha product 126 , and a heavies fraction 125 which is optionally recycled to extinction through the hydrocracker 114 .
  • the fractionator unit 124 is operated to recover biorenewable naphtha, typically with a C 4 -C 9 hydrocarbon distribution.
  • a biorenewable feed enters a hydrotreater reactor (not shown).
  • Stream 212 is the heavy hydrocarbon product of the hydrotreating reaction in the hydrotreater.
  • Stream 212 is optionally combined with an unconverted heavy fraction 225 to form a hydrocracker feed 213 .
  • Hydrocracker feed 213 a C 15 -C 22 hydrocarbon distribution for most common triglycerides and fatty acids, is converted to a C 3 -C 18 distribution in a hydrocracker 214 .
  • An effluent 215 from the hydrocracker 214 is separated into a hydrogen-rich gas stream 217 and a cracked liquids stream 223 in a separation unit 216 . Operating conditions are the same as for FIG. 1 .
  • a fraction of the hydrogen-rich gas 217 is purged as stream 207 and the remaining fraction of the hydrogen-rich gas 217 is cleaned up in scrubber 208 .
  • the cleaned hydrogen-rich gas 208 a is then combined with makeup hydrogen 209 to form a recycle hydrogen-rich gas as hydrocracker stream 210 .
  • Stream 223 cracked liquids from the separation unit 216 , is transferred to a product fractionators unit 224 .
  • the illustrative C 3 -C 18 hydrocracked product is fractioned into a C 3 /C 4 gas stream 227 , a naphtha product stream 226 , a middle distillate stream 228 suitable for use as jet kerosene or diesel, and a heavies recycle stream 225 .
  • the resultant biorenewable naphtha has a boiling point range from about 70° F. to about 400° F. and a specific gravity at 20° C. of from about 0.680 to about 0.740.
  • the naphtha product includes C 4 -C 10 paraffins that are considered superior feed components for steam crackers, and is also an appropriate feed for conversion to BTX aromatics, and hydrogen production.
  • the naphtha composition is also useful as a solvent in applications where low flash point is not a limitation.
  • the renewable naphtha provides some benefit as a bio-renewable addition to ethanol in that ethanol typically suffers from low vapor pressures and low energy density.
  • the biorenewable naphtha typically has a Reid Vapor Pressure (RVP)>10 psi and may be blended with ethanol in concentrations of 1-30% to make an entirely renewable gasoline replacement for automobiles that has an improved energy density.
  • RVP Reid Vapor Pressure
  • the bio-renewable naphtha has low octane ratings (typically less than 40 RON) which is offset by the higher octane of the ethanol fuel which is reported to be in the 129 RON range.
  • the resulting blend easily meets U.S. performance requirements for vapor pressure and octane rating by utilizing the benefits of both fuels.
  • An alternate approach for using the biorenewable naphtha of the present invention as described herein as a renewable blend stock for motor gasoline is by isomerization of the C 5 /C 6 fraction, which is a standard refinery unit process.
  • the C 5 /C 6 fraction of the biorenewable naphtha composition may be isomerized to raise RON and make it suitable for blending with gasoline stocks.
  • Typical isomerized products include 2-methylbutane and 2,3-dimethylbutane, with RON values of 93.5 and 105 respectively.
  • the biorenewable naphtha is used as fuel for industrial burners, boilers, and turbines as an industrial solvent.
  • the bio-renewable naphtha may also be used as a hydrogen source or as a fuel cell fuel.
  • the present example demonstrates how naphtha was made from a renewable feedstock.
  • a 100 cc isothermal tubular reactor was filled with 80 cc of a commercial NiMo catalyst and +70-100 mesh glass beads.
  • the catalyst was sulfided with dimethyl disulfide.
  • the sulfiding procedure included step-wise temperature increase to 650° F. After sulfiding, the reactor was cooled to 400° F.
  • a triglyceride/fatty acid feed was introduced to the isothermal reactor.
  • the reactor was slowly heated to 650° F. to achieve full conversion of the triglyceride/fatty acid feed to n-paraffins.
  • the reactor temperature was further increased to 700° F. to maintain good catalyst activity at 80 cc/hr feed rate (1 LHSV).
  • the hydrotreater performance with beef tallow as the triglyceride/fatty acid feed is summarized in Table 1.
  • the yield of total products on feed basis exceeds 100% in part due to addition of hydrogen and also due to measurement errors associated with gas phase analysis.
  • FIG. 3 is the chromatogram of the product, showing areas where cracked products and unconverted feed would appear.
  • the mainly C15-C18 n-paraffin composition obtained from hydrotreating bio-renewable feed stocks was used as feed for a hydrocracking pilot plant.
  • These long chain hydrocarbons were derived via hydrotreating a biorenewable feed in a procedure similar to Example 1.
  • the bio-renewable feed was a blend of chicken fat (45%), brown grease (19%), yellow grease (18%), floatation grease (9%), and miscellaneous waste animal fats from industrial food processing operations (9%).
  • the hydrocracking pilot plant was a prototype of the embodiment of the present invention represented by FIG. 2 .
  • the hydrocracker reactor system was loaded with 4.8 liters of a commercial hydrocracking catalyst.
  • the catalyst was platinum-palladium on amorphous alumina/silica
  • the reactor was pressurized to 1,000 psig. After catalyst preconditioning, the temperature was increased again to achieve the desired level of hydrocracking to produce the biorenewable naphtha product.
  • the ratio of hydrogen-rich gas (recycle and makeup) to feed was 3,800 SCF/bbl.
  • the pilot plant fractionation system included three distillation columns in series.
  • Table 2 provides the composition and properties of the hydrotreated hydrocarbon fraction and Table 3 summarizes the operating conditions of the hydrocracker, conversion performance thereof, and product properties therefrom.

Abstract

The present invention generally relates to a method for producing a naphtha product from a renewable feedstock. The method includes hydrotreating the renewable feedstock to produce a hydrotreating unit heavy fraction that includes n-paraffins, and hydrocracking the hydrotreating unit heavy fraction to produce a hydrocracking unit product that includes the naphtha product. The method also includes separating the naphtha fraction and optionally recycling the hydrocracking unit heavy fraction through the hydrocracking unit. The present invention also relates to a biorenewable naphtha product suitable for use as feed stock for steam crackers and catalytic reforming units, and for use as fuel, or fuel blend stock.

Description

    STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
  • Not applicable.
  • CROSS-REFERENCE TO RELATED APPLICATIONS
  • Not applicable.
  • FIELD OF THE INVENTION
  • The present invention generally relates to a method for producing hydrocarbons from biomass. Specifically, the present invention relates to converting naturally occurring triglycerides and fatty acids to a composition including naphtha boiling range hydrocarbons. The present invention also relates to the resultant biorenewable naphtha product, whereby the naphtha is used as chemical feed stock, fuel, fuel blend stock, or solvent.
  • BACKGROUND OF THE INVENTION
  • The term “green chemistry” has been used to describe synthesis of chemicals from biorenewable feed stocks. It is considered a sustainable alternative to petroleum-based chemistry, and may mitigate the effect of high oil prices. One of the challenges facing transition to a green chemical industry is that the existing production facilities and infrastructure are designed around hydrocarbon feed stocks. For example, the building blocks of the chemical industry, olefins and BTX aromatics (benzene, toluene, and xylene), are produced in steam crackers (also referred to as ethylene crackers) and catalytic reformers that run on light hydrocarbons. Synthesis gas, or syngas for short, is another chemical building block. Syngas is a mixture of carbon monoxide and hydrogen and can be produced by steam reforming of light hydrocarbons. Naphtha is a C5-C9 hydrocarbon cut that is commonly used as the feedstock for both catalytic reformers and steam crackers. It may also be used as feed for steam reforming units for production of syngas.
  • In particular, paraffinic naphtha is considered a highly desired feed for steam crackers due to its high ethylene and propylene yields. Production of naphtha from biorenewable sources would enable transition to a green chemical industry without the need to develop new chemistries and build new production facilities.
  • Similarly, the term “sustainable energy” has been used to refer to renewable sources of energy. Biorenewable fuels are a key component of sustainable energy initiatives. Naphtha may be used directly as fuel in industrial furnaces or turbines. It may also be used in small industrial engines such as lawn mowers and chain saws.
  • Furthermore, since naphtha hydrocarbons are in the motor gasoline boiling range, they may be used as a gasoline blend stock. Gasoline blends need to meet vapor pressure and octane rating requirements.
  • One method of producing naphtha hydrocarbons from biomass is by the Fischer-Tropsch (F-T) process. U.S. Pat. No. 7,214,720 to Bayle and co-inventors describes a process involving the steps of (a) gasification, (b) syngas purification, (c) F-T conversion, (d) separation, and (e) recycle of at least a portion of the naphtha to gasifier. Although the process produces the desired hydrocarbon naphtha from a bio-renewable source, gasifiers suffer from a low reliability record. Additionally, the capital costs associated with gasification and F-T conversion are known to be very high. This is in part due to solids handling requirements for the gasifier and heat removal provisions for the highly exothermic F-T reaction. Furthermore, the need to recycle part of the naphtha to the gasifier further reduces the efficiency of this process as a source of bio-renewable naphtha.
  • U.S. Pat. No. 5,186,722 to Cantrell and Chong describes a catalytic process to convert biomass feeds such as limonene to a composition of cyclic and aromatic compounds in the naphtha boiling range. Although these products are reported to have high octane rating and hence good gasoline blend stocks, they lack the desired properties as a chemical feed stock. As feeds for steam crackers, aromatic compounds give low ethylene and propylene yields. More importantly, the terpene feeds used in the process are among the only biomass sources that to begin with are hydrocarbons. Virtually all other sources of biomass have high oxygen content, typically greater than 10 wt %.
  • Deoxygenation of biomass feeds such as triglycerides and fatty acids are disclosed in U.S. Pat. No. 7,232,935 to Jakkula and co-inventors. A two step process is disclosed which includes hydrodeoxygenation of triglycerides/fatty acids followed by hydroisomerization. The process produces diesel boiling-range isoparaffins.
  • To this end, there is a need for biorenewable naphtha that can be used as feed stock for existing petrochemical and refining facilities. In particular, the present invention is a method process for converting high oxygen content biomass, such as sources of triglycerides and/or fatty acids, into naphtha boiling-range hydrocarbons using standard refining processes.
  • SUMMARY OF THE INVENTION
  • The present invention relates to a method for producing from a biorenewable feed stock a hydrocarbon naphtha composition useful for producing olefins, BTX aromatics, hydrogen, and also for direct use as gasoline blend stock and solvent. The biorenewable feed stock includes sources of glycerides (i.e. monoglycerides, diglycerides, triglycerides, etc.) and/or fatty acids and combinations thereof, such as animal fats, animal oils, poultry fat, poultry oils, vegetable oils, vegetable fats, plant fats and oils, rendered fats, rendered oils, restaurant grease, brown grease, waste industrial frying oils, fish oils, tall oil, and the like and any combinations thereof.
  • The method for producing hydrocarbon naphtha includes hydrotreating a renewable feedstock to produce a heavy hydrocarbon fraction. This is followed by hydrocracking of the hydrotreated heavy fraction to produce a distribution of hydrocarbon components, typically C3-C18, which is fractionated to recover the naphtha product. The heavy fraction is optionally recycled to the hydrocracker.
  • The hydrotreating of triglycerides and fatty acids involves olefin hydrogenation and deoxygenation. Hydrotreating thus converts fatty acids into long chain paraffins as illustrated in Equations 1 and 2 for conversion of oleic acid to n-octadecane and n-heptadecane.

  • HOOC—C17H33+2H2 →n-C18H38+2H2O  (1)

  • HOOC—C17H33+H2 →n-C17H36+CO2  (2)
  • When the fatty acids are supported on a glycerol backbone, for example as triglycerides or diglycerides, the hydrotreating reactions of Equations 1 and 2 produce propane as well as the long chain, heavy hydrocarbon fraction. Depending on the source of the fatty acid/triglyceride, the heavy hydrocarbon fraction is predominantly in the C12 to C22 range.
  • The heavy hydrocarbons may be hydrocracked into shorter chain hydrocarbons to produce biorenewable naphtha. In the illustrative hydrocracking reactions of Equations 3-5, n-octadecane is hydrocracked into naphtha-range hydrocarbons, nonanes, hexanes, pentanes, and propane/butanes byproducts.

  • C18H38+H2 →n-C9H20 +i-C9H20  (3)

  • i-C9H20+H2 →i-C5H12 +i-C4H10  (4)

  • n-C9H20+H2 →i-C6H14+C3H8  (5)
  • BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
  • FIG. 1 is a schematic diagram of an operation for producing biorenewable naphtha according to the present invention.
  • FIG. 2 is a schematic diagram of another embodiment of a method for producing biorenewable naphtha in accordance with the present invention.
  • FIG. 3 is a gas chromatogram showing product from an example.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention relates to a method for producing from a biorenewable feedstock a hydrocarbon product of naphtha boiling point range that can be used as feedstock for olefins, BTX aromatics, and hydrogen plants. The biorenewable naphtha of the present invention may also be used directly as a fuel, a fuel blend stock, or a solvent.
  • Referring to the process embodiment of FIG. 1, a biorenewable feed 101 is transferred to a hydrotreater 102 where it reacts with hydrogen under pressure of from about 300 psig to about 3,000 psig, preferably from about 1,000 psig to about 2,000 psig. Feed 101 may optionally be pretreated to remove contaminants. The hydrotreater 102 is preferably a packed bed of sulfided bimetallic catalyst, preferably nickel-molybdenum (NiMo), nickel-tungsten (NiW), or cobalt-molybdenum (CoMo) on alumina support. It should be understood by one of ordinary skill in the art that any catalyst may be used in the present invention so long as the catalyst functions in accordance with the present invention as described herein.
  • To maintain the active metal sulfide functionality of the catalyst despite absence of organic sulfur in most bio-renewable feeds, feed 101 may be supplemented with a sulfur composed that decomposes to hydrogen sulfide when heated and/or contacted with a catalyst. Two preferred sulfur compounds are dimethyl disulfide and carbon disulfide. Preferred concentration of these in the feed 101 is from about 100 to about 2,000 ppm by weight sulfur. Alternatively, feed 101 may include a biorenewable component and a petroleum fraction wherein the petroleum-fraction provides the sulfur.
  • Feed 101 may be preheated before entering the hydrotreater 102. The hydrotreater 102 operates from about 300° F. to about 900° F., preferably from about 550° F. to about 650° F., and from about 250 psig to about 3,000 psig. In order to reduce the adiabatic temperature rise from the exothermic hydrotreating reactions and to maintain the hydrotreater 102 in the preferred operating range, a number of methods known in the art may be used. These methods include, but are not limited to, feed dilution with a solvent or other diluent, liquid product or solvent recycle, and use of quench zones within the fixed-bed reactor wherein hydrogen is introduced.
  • The biorenewable feed 101 liquid hourly space velocity through the hydrotreater 102 is from about 0.2 h−1 to about 10 h−1, preferably from about 0.5 h−1 to about 5.0 h−1. The ratio of hydrogen-rich treat gas 110 to biorenewable feed 101 is preferably in the about 2,000 to about 15,000 SCF/bbl range. The hydrogen-rich treat gas 110 may contain from about 70 mol % to about 100 mol % hydrogen.
  • A hydrotreater effluent 103 includes a deoxygenated heavy hydrotreater fraction and unreacted hydrogen. The hydrotreater effluent 103 may also include water, carbon oxides, ammonia, and hydrogen sulfide. The long chain, heavy hydrocarbon fraction in the liquid phase is separated from the gas phase components in a separation unit 104.
  • The separation unit 104 includes a high pressure drum (not shown) operated at hydrotreater discharge pressure (about 1,000 psig to about 2,000 psig in the preferred embodiment), wherein long chain, heavy hydrocarbon liquids are separated from hydrogen and gas phase hydrotreater byproducts. It should be understood that the hydrotreater discharge pressure may be operated from about 200 psig to about 3,000 psig. Depending on the temperature of the separation unit 104, water may be in vapor or liquid phase. In a preferred embodiment, the separation unit 104 has a temperature in the about 350° F. to about 500° F. range whereby water, carbon oxides, ammonia, hydrogen sulfide, and propane are removed with hydrogen in a separator drum vapor phase. To enhance removal of the components from the heavy hydrocarbon fraction, the separation unit 104 optionally includes a stripping section (not shown). Water 111 may be condensed, separated, and the hydrogen-rich gas phase 105 recycled to the hydrotreater 102.
  • A long chain hydrocarbon product stream 112 from the separation unit 104 is then cracked in a hydrocracker 114. Product stream 112 is optionally combined with unconverted heavies from the hydrocracker 114, and recycled stream 125, to form a hydrocracker feed 113.
  • The heavy hydrocarbon feed 113 cracks in the hydrocracker 114 to form naphtha-range hydrocarbons. Preferably, the hydrocracker 114 operates from about 250 psig to about 3,000 psig, more preferably from about 1,000 psig to about 2,000 psig. Hydrocracker 114 temperatures are from about 400° F. to about 900° F., preferably from about 580° F. to about 750° F. Suitable catalysts for hydrocracking according to the present invention as described herein are bi-functional catalysts with hydrogenation and acidic functionalities. Such catalysts include Group VIII metals on amorphous (e.g. silica-alumina) or crystalline (e.g. zeolite) supports. Preferred hydrocracking catalysts are platinum, palladium or combinations of same on an amorphous silica-alumina support. However, it should be understood that any catalyst may be used in accordance with the present invention as long as it functions as described herein. Preferred ratios of the hydrogen-rich gas to liquid feed for hydrocracking are in the about 1,000 to about 10,000 SCF/bbl range, and liquid hourly space velocity in the about 0.1 h−1 to about 8 h−1 range, preferably from about 0.2 h−1 to about 4 h. Stream 1115 is an effluent of the hydrocracker 114 wherein un-reacted hydrogen includes a gas phase. Hydrogen-rich gas is separated from the hydrocarbon product in a separation unit 116.
  • The separation unit 116 includes a high pressure separation drum (not shown), operating at hydrocracker discharge pressure, about 1,000 psig to about 2,000 psig in the preferred embodiment, where hydrocarbon liquids are separated from hydrogen, hydrocarbon vapors, and any other gas phase cracked products. It should be understood that the hydrocracker discharge pressure may be operated from about 200 psig to about 3,000 psig.
  • A hydrogen-rich gas 117 from the separation unit 116 is combined with a hydrogen-rich gas 105 from the separation unit 104 and optionally processed through an absorption column or scrubber 108 to remove ammonia, carbon oxides, and/or hydrogen sulfide, before recompression for recycle to the hydrotreater 102 and/or hydrocracker 114. Depending on the contaminant to be removed, the scrubber 108 may use various solvents such as amine and caustic solutions. It is clear to those skilled in the art that other gas cleanup technologies may be used instead of or in addition to the scrubber 108 to remove contaminants that affect the hydrotreater 102 and hydrocracker 114 catalyst activity and selectivity. Examples of alternative gas cleanup technologies include membrane systems and adsorbent beds.
  • A purge stream 107 may be removed from a recycle gas 106 to prevent buildup of contaminants that are not effectively removed in the scrubber 108. The cleaned hydrogen-rich gas 108 a from the scrubber 108 may be combined with makeup hydrogen 109 to form a hydrogen-rich gas stream 110 for the hydrotreater 102 and hydrocracker 114.
  • Stream 123 is the liquid hydrocarbon phase from the separation unit 116. Stream 123 is processed through fractionator unit 124 to fraction the hydrocracker products into a hydrocarbon vapors product 127, the desired naphtha product 126, and a heavies fraction 125 which is optionally recycled to extinction through the hydrocracker 114.
  • The fractionator unit 124 is operated to recover biorenewable naphtha, typically with a C4-C9 hydrocarbon distribution.
  • Referring now to FIG. 2, another embodiment of the present invention is illustrated. A biorenewable feed enters a hydrotreater reactor (not shown). Stream 212 is the heavy hydrocarbon product of the hydrotreating reaction in the hydrotreater. Stream 212 is optionally combined with an unconverted heavy fraction 225 to form a hydrocracker feed 213. Hydrocracker feed 213, a C15-C22 hydrocarbon distribution for most common triglycerides and fatty acids, is converted to a C3-C18 distribution in a hydrocracker 214. An effluent 215 from the hydrocracker 214, is separated into a hydrogen-rich gas stream 217 and a cracked liquids stream 223 in a separation unit 216. Operating conditions are the same as for FIG. 1.
  • A fraction of the hydrogen-rich gas 217 is purged as stream 207 and the remaining fraction of the hydrogen-rich gas 217 is cleaned up in scrubber 208. The cleaned hydrogen-rich gas 208 a is then combined with makeup hydrogen 209 to form a recycle hydrogen-rich gas as hydrocracker stream 210.
  • Stream 223, cracked liquids from the separation unit 216, is transferred to a product fractionators unit 224. The illustrative C3-C18 hydrocracked product is fractioned into a C3/C4 gas stream 227, a naphtha product stream 226, a middle distillate stream 228 suitable for use as jet kerosene or diesel, and a heavies recycle stream 225.
  • The resultant biorenewable naphtha has a boiling point range from about 70° F. to about 400° F. and a specific gravity at 20° C. of from about 0.680 to about 0.740. The naphtha product includes C4-C10 paraffins that are considered superior feed components for steam crackers, and is also an appropriate feed for conversion to BTX aromatics, and hydrogen production. The naphtha composition is also useful as a solvent in applications where low flash point is not a limitation.
  • As a fuel or fuel additive, the renewable naphtha provides some benefit as a bio-renewable addition to ethanol in that ethanol typically suffers from low vapor pressures and low energy density. The biorenewable naphtha typically has a Reid Vapor Pressure (RVP)>10 psi and may be blended with ethanol in concentrations of 1-30% to make an entirely renewable gasoline replacement for automobiles that has an improved energy density. The bio-renewable naphtha has low octane ratings (typically less than 40 RON) which is offset by the higher octane of the ethanol fuel which is reported to be in the 129 RON range. Thus, the resulting blend easily meets U.S. performance requirements for vapor pressure and octane rating by utilizing the benefits of both fuels.
  • An alternate approach for using the biorenewable naphtha of the present invention as described herein as a renewable blend stock for motor gasoline is by isomerization of the C5/C6 fraction, which is a standard refinery unit process. The C5/C6 fraction of the biorenewable naphtha composition may be isomerized to raise RON and make it suitable for blending with gasoline stocks. Typical isomerized products include 2-methylbutane and 2,3-dimethylbutane, with RON values of 93.5 and 105 respectively.
  • The biorenewable naphtha is used as fuel for industrial burners, boilers, and turbines as an industrial solvent.
  • Due to its paraffinic nature and its high hydrogen-to-carbon ratio, the bio-renewable naphtha may also be used as a hydrogen source or as a fuel cell fuel.
  • In order to further illustrate the present invention, the following examples are given. However, it is to be understood that the examples are for illustrative purposes only and are not to be construed as limiting the scope of the subject invention.
  • EXAMPLES Example 1 Hydrotreating of a Biorenewable Feed Stock
  • The present example demonstrates how naphtha was made from a renewable feedstock. A 100 cc isothermal tubular reactor was filled with 80 cc of a commercial NiMo catalyst and +70-100 mesh glass beads. The catalyst was sulfided with dimethyl disulfide. The sulfiding procedure included step-wise temperature increase to 650° F. After sulfiding, the reactor was cooled to 400° F.
  • Next a triglyceride/fatty acid feed was introduced to the isothermal reactor. The reactor was slowly heated to 650° F. to achieve full conversion of the triglyceride/fatty acid feed to n-paraffins. The reactor temperature was further increased to 700° F. to maintain good catalyst activity at 80 cc/hr feed rate (1 LHSV).
  • The hydrotreater performance with beef tallow as the triglyceride/fatty acid feed is summarized in Table 1. The yield of total products on feed basis exceeds 100% in part due to addition of hydrogen and also due to measurement errors associated with gas phase analysis.
  • TABLE 1
    Hydrotreater Conditions and Conversion Performance.
    Catalyst
    Active Metals Sulfided NiMo
    Support Alumina
    Reactor Conditions
    Feed Inedible tallow
    Temperature (F.) 700
    Pressure (psig) 1,200
    Gas/Oil Ratio (scf/bbl) 14,000
    LHSV
    Products (wt % feed basis)
    C1 + C2 1.5
    Propane 6.1
    Water 5.3
    Total Liquid Hydrocarbons 88.2
  • The gas chromatogram of the liquid hydrocarbon product confirmed that under the hydrotreater conditions of Table 1 the tallow feed was converted C15-C18 n-paraffins with no detectable oxygenates remaining. No cracked products (C12—) were detected. FIG. 3 is the chromatogram of the product, showing areas where cracked products and unconverted feed would appear.
  • Example 2 Hydrocracking of Bio-Derived Heavy Hydrocarbons
  • The mainly C15-C18 n-paraffin composition obtained from hydrotreating bio-renewable feed stocks was used as feed for a hydrocracking pilot plant. These long chain hydrocarbons were derived via hydrotreating a biorenewable feed in a procedure similar to Example 1. The bio-renewable feed was a blend of chicken fat (45%), brown grease (19%), yellow grease (18%), floatation grease (9%), and miscellaneous waste animal fats from industrial food processing operations (9%). The hydrocracking pilot plant was a prototype of the embodiment of the present invention represented by FIG. 2.
  • The hydrocracker reactor system was loaded with 4.8 liters of a commercial hydrocracking catalyst. The catalyst was platinum-palladium on amorphous alumina/silica
  • The reactor was pressurized to 1,000 psig. After catalyst preconditioning, the temperature was increased again to achieve the desired level of hydrocracking to produce the biorenewable naphtha product. The ratio of hydrogen-rich gas (recycle and makeup) to feed was 3,800 SCF/bbl.
  • The pilot plant fractionation system included three distillation columns in series. The first stripped off the light hydrocarbons (“debutanizer”) from the hydrocracker effluent, the second (“naphtha tower”) separated the naphtha overhead, and the third (“recycle tower”) separated a middle distillate cut overhead from the heavy bottoms that were combined with the fresh feed and recycled to the hydrocracker.
  • Table 2 provides the composition and properties of the hydrotreated hydrocarbon fraction and Table 3 summarizes the operating conditions of the hydrocracker, conversion performance thereof, and product properties therefrom.
  • TABLE 2
    Composition and properties of hydrocracker feed of Example 2a
    Normal
    Boiling Example 2 ASTM
    Component Pt. (° F.) Feed D2887SimDist (° F.)
    C10 345 ND IBP 345
    C11 385 ND  5% 516
    C12 421 ND 10% 543
    C13 455 ND 20% 549
    C14 489 1.55 30% 550
    C15 520 1.93 40% 576
    C16 549 26.03 50% 599
    C17 576 4.86 60% 599
    C18 601 64.36 70% 601
    C19 626 0.00 80% 601
    C20 651 1.27 90% 603
    C22 696 ND 95% 604
    total paraffins 100.0 FBP 671
    aND = not detectable
  • TABLE 3
    Hydrocracker Run Conditions, Conversion Performance,
    and Product Propertiesa
    Reactor Conditions
    Reactor 1 Temp (° F.) 726
    Reactor 2 Temp (° F.) 721
    Pressure (psig) 1002
    Feed Rates
    Fresh Feed Wt (g/hr) 2241.0
    Fresh Feed Vol (cc/hr) 2817.5
    Recycle Feed Wt (g/hr) 807.6
    Recycle Feed Vol (cc/hr) 1026
    Total Feed Vol (cc/hr) 3843
    LHSV 0.794
    Gas Rates
    H2 Makeup (scf/hr) 24.5
    Inlet Gas (scf/hr) 102.2
    Bleed Gas (scf/hr) 15.5
    Product Rates
    C3/C4 (g/hr)
    Non-condensed C5-C6 + (g/hr)
    Naphtha (g/hr) 561.3
    Middle Distillate Ovhd (g/hr) 1538.5
    Naphtha Yields
    Non-condensed C5-C6 (wt %) 3.3%
    Condensed naphtha (wt %) 25.0%
    Total naphtha (wt %) 28.3%
    Material Balance Closure 100.1%
    Naphtha Tower Temps
    Reboiler Liquid 336
    Column Skin 409
    Column Top 293
    Preheater 303
    Recycle Tower Temps
    Reboiler Liquid 564
    Column Skin 534
    Column Top 492
    Preheater 499
    Recycle heavies spec. grav. 0.787
    Naphtha Properties
    Specific Gravity 0.705
    D2887 SimDist (° F.)
    IBP 70
     5 91
    10 135
    20 159
    30 194
    40 211
    50 244
    60 260
    70 290
    80 318
    90 358
    95 387
    FBP 432
    Middle Distillate Properties
    API 51.5
    Specific Gravity 0.773
    Freeze Point (° C.) −39.5
    Cloud Point (° C.) −43.0
    Flash Point (° F.) 126
    D2887 SimDist (° F.)
    IBP 226
     5 291
    10 330
    20 374
    30 412
    40 446
    50 479
    60 510
    70 526
    80 544
    90 565
    95 575
    FBP 593
    aNM = not measured
  • Thus there has been shown and described a method for producing a biorenewable naphtha product that fulfills all objectives and advantages sought therefore. While presently preferred embodiments of the invention have been described for purposes of this disclosure, it will be understood that numerous changes may be made which will readily suggest themselves to those skilled in the art and which are accomplished within the spirit of the invention disclosed and claimed herein. From the above description, it is clear that the present invention is well adapted to carry out the objects and to obtain the advantages mentioned herein as well as those inherent in the invention. While presently preferred embodiments of the invention have been described for purposes of this disclosure, it will be understood that numerous changes may be made which will readily suggest themselves to those skilled in the art and which are accomplished within the spirit of the invention disclosed and claimed.

Claims (21)

1. A method for producing from a renewable feedstock a naphtha boiling-range hydrocarbon, comprising:
a. hydrotreating a renewable feedstock to produce a hydrocarbon fraction;
b. hydrocracking the hydrocarbon fraction of step (a) to produce a distribution of cracked hydrocarbons;
c. separating a naphtha fraction from the distribution of cracked hydrocarbons
2. The method of claim 1 wherein a heavy fraction from the distribution of cracked hydrocarbons is recycled to the hydrocracking step (b)
3. The method as in claim 1 or 2, further comprising the step of recovering from the heavy fraction a middle distillate fraction.
4. The method as in any one of claims 1, 2, and 3, wherein the renewable feedstock comprises monoglycerides, diglycerides, triglycerides, free fatty acids, and combinations thereof.
5. The method of claim 4, wherein the biorenewable feedstock is selected from the group comprising animal fats, animal oils, poultry fat, poultry oil, vegetable fats, vegetable oils, rendered fats, rendered oils, restaurant grease, brown grease, waste industrial frying oils, fish oils, fish fats, and combinations thereof.
6. The method as in any one of claims 1, 2, and 3, wherein the hydrotreating step operating conditions comprise a reaction temperature of from about 300° F. to about 850° F. and a reaction pressure of from about 300 psig to about 3,000 psig.
7. The method as in any one of claims 1, 2, and 3, wherein the hydrocracking step operating conditions comprise a reaction temperature of from about 400° F. to about 900° F. and a reaction pressure of from about 250 psig to about 3,000 psig.
8. The method of claim 1, 2, and 3, wherein the naphtha product has a boiling point range of from about 70° F. to about 400° F.
9. A naphtha composition produced from a renewable feedstock wherein the naphtha has:
a. a boiling range of about 70° F. to about 400° F.; and
c. a specific gravity at 20° C. of from about 0.680 to about 0.740.
10. The composition of claim 9 wherein the naphtha comprises C4, C5, C6, C7, C8, C9, and C10 paraffins.
11. The composition of claim 9, wherein the renewable feedstock comprises monoglycerides, diglycerides, triglycerides, free fatty acids, and combinations thereof.
12. The composition of claim 9, wherein the biorenewable feedstock is selected from the group comprising animal fats, animal oils, poultry fat, poultry oil, vegetable fats, vegetable oils, rendered fats, rendered oils, restaurant grease, brown grease, waste industrial frying oils, fish oils, fish fats, and combinations thereof.
13. The composition of claim 9 wherein the biorenewable naphtha is used as fuel for industrial burners and boilers.
14. The composition of claim 9 wherein the biorenewable naphtha is used for producing hydrogen.
15. The composition of claim 9 wherein the biorenewable naphtha is suitable for use in fuel cell applications.
16. The composition of claim 9 wherein the biorenewable naphtha is used as feedstock for steam crackers.
17. The composition of claim 9 wherein the biorenewable naphtha is used as feedstock for catalytic reforming.
18. The composition of claim 9 wherein the biorenewable naphtha is used as industrial solvent.
19. The composition of claim 9 wherein the biorenewable naphtha is used as an alternative gasoline fuel for combustion engines when blended between 1% and 85% by volume with ethanol.
20. The composition of claim 9 wherein the biorenewable naphtha is used to produce gasoline blend stock via isomerization of the C5/C6 fraction of the composition.
21. The composition of claim 9 wherein the biorenewable naphtha is used as turbine fuel.
US12/132,915 2008-06-04 2008-06-04 Biorenewable naphtha Abandoned US20090300971A1 (en)

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US13/196,768 US8581013B2 (en) 2008-06-04 2011-08-02 Biorenewable naphtha composition and methods of making same
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