CN102625822A - Fuel production from feedstock containing lipidic material - Google Patents

Fuel production from feedstock containing lipidic material Download PDF

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Publication number
CN102625822A
CN102625822A CN2010800503462A CN201080050346A CN102625822A CN 102625822 A CN102625822 A CN 102625822A CN 2010800503462 A CN2010800503462 A CN 2010800503462A CN 201080050346 A CN201080050346 A CN 201080050346A CN 102625822 A CN102625822 A CN 102625822A
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CN
China
Prior art keywords
fuel
hydroisomerization
dewaxing
raw material
lipid
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Pending
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CN2010800503462A
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Chinese (zh)
Inventor
W·J·诺瓦克
P·L·汉克斯
T·L·希尔伯特
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Publication of CN102625822A publication Critical patent/CN102625822A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G45/58—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
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
    • 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
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

This invention relates to the production of dewaxed and/or hydroisomerized fuel composition that includes a step of hydrotreating a feedstock containing the lipidic material. The fuel compositions are high quality fuel compositions in which the fuel can be ultimately tailored for a variety of end uses such as jet fuel or diesel fuel.

Description

From containing the feedstock production fuel of lipid material
Technical field
The present invention relates to from containing the raw material production fuel composition of lipid material.More particularly, the production of fuel composition that the present invention relates to dewax and/or hydroisomerization, it comprises that hydrogen treatment contains the step of the raw material of lipid material.
Background technology
The cost that raises threatens with shortage and supply failure make recently more significantly need be based on the alternative fuel source of the product of oil.Biofuel becomes the focus of alternative fuel especially.
The open No.2009/0158637 of USP discloses a kind of method of producing aviation fuel from renewable raw materials.This raw material comprises vegetables oil and animal tallow and oil.This method relates to through hydrogenation and deoxidation treatment renewable raw materials and has about 8 n-paraffin to about 24 carbon atoms to provide.At least some n-paraffin by isomerizing to improve cold flow properties.At least the cracking of being selected property of part paraffinic hydrocarbons is to provide the paraffinic hydrocarbons of the specification that satisfies different aviation fuel such as JP-8.
The open No.2009/0088351 of USP discloses a kind of processing and has contained tri-glyceride, biologically-derived oil to produce the method for lubricant and transport fuel.This method comprises tri-glyceride is converted into free fatty acids and through saturated type separation of fatty acids.Should make through the type separation and possibly prepare lubricant and transport fuel.
The open No.2008/0244962 of USP discloses a kind of method that can be used as the different alkane product of jet fuel from renewable raw materials production.This method also comprises from renewable raw materials co-production jet fuel and LPG liquefied petroleum gas (LPG) level and dividing.This method comprises that the hydrogen treatment renewable raw materials divides to produce hydroisomerization unit weighs quality and grade branch (comprising isoparaffin) with production hydrogen treatment unit weighs quality and grade branch (comprising n-paraffin) and this hydrogen treatment unit weighs quality and grade of hydroisomerization.This method comprises also that through hydroisomerization unit recycling hydroisomerization unit weighs quality and grade branch to produce different alkane product, said different alkane product can be classified to jet fuel and LPG level branch.The product of this production is the jet fuel with specific cold flow properties from renewable raw materials production.
Exist with from the relevant specific question of any multiple renewable raw materials production fuel.Particularly, aspect the multiple desired characteristic of making and reclaim jet fuel and diesel-fuel, fuel.Aspect jet fuel, the desired characteristic of these zero pour and smoke point is especially unapproachable.Therefore, need wherein can effectively utilize the method that renewable raw material is made high quality fuel.
The invention summary
The present invention produces high quality fuel from the source that is considered to renewable raw materials.Method of the present invention is intended to produce fuel composition from the lipid biomass especially.
According to an aspect of the present invention, a kind of method of producing fuel composition dewaxing and/or hydroisomerization is provided.The preparation or supply raw materials (wherein this raw material contains the lipid biomass).Preferably, said raw material further comprises MO.Can be with the raw material hydrogen treatment to produce through hydrotreated material.Can be then with at least partly should only dewaxing to produce the fuel composition of dewaxing through hydrotreated material; Only hydroisomerization to be producing the fuel composition of hydroisomerization, or not only dewaxed but also hydroisomerization to produce dewaxing and fuel composition hydroisomerization.
In one embodiment, can part fuel composition this dewaxing and/or hydroisomerization at least be recovered as jet fuel or diesel-fuel, for example after distilling.In specific implementations, the fuel composition of recovery can show one or more in the property: the smoke point of 25.0mm at least; Be not higher than-35 ℃ zero pour; ASTMD8690% distillation point in 250 ℃ to 290 ℃ scopes; ASTM D8690% distillation point in 200 ℃ to 240 ℃ scopes; ASTM D8690% distillation point in 260 ℃ to 350 ℃ scopes.
Detailed description of the present invention
The present invention provides a kind of method from the high-quality fuel composition of raw material production that contains the lipid material.Method of the present invention can be through adjusting suitable type feedstock composition advantageously obtain high-quality fuel with the suitable procedure of processing of type.Customizable multiple end-use such as jet fuel or the diesel-fuel of being used for of fuel is especially suitable for use as jet fuel.
The raw material that uses in the present invention comprises the lipid biomass.In one embodiment, raw material comprises lipid biomass and MO.When raw material not only comprised the lipid biomass but also comprises MO, in one embodiment, the lipid biomass can account for the 5wt% to 50wt% of raw material; 5wt% to 35wt% for example, 5wt% to 25wt%, 10wt% to 40wt%; 10wt% to 30wt%, 20wt% to 40wt%, 25wt% to 50wt%; 25wt% to 40wt%, or 35wt% to 50wt%.When raw material not only comprised the lipid biomass but also comprises MO, in another embodiment, the lipid biomass can account for the 50wt% to 95wt% of raw material; 50wt% to 85wt% for example, 50wt% to 75wt%, 55wt% to 85wt%; 60wt% to 90wt%, 60wt% to 75wt%, 70wt% to 90wt%; 75wt% to 95wt%, or 80wt% to 95wt%.
Term used according to the invention " lipid biomass " is the compsn of being made up of biomaterial.Usually, these biomaterials comprise the component of vegetation fat/oil, animal tallow/oil, fish oil, pyrolysis oil and algae lipid/oil and these materials.More particularly, these lipid biomass comprise one or more lipid compounds.Lipid compounds is normally water insoluble but be dissolved in the biological compound of nonpolar (or fat) solvent.The non-limitative example of these solvents comprises alcohol, ether, chloroform, alkyl acetate, benzene and combination thereof.
The main type of lipid comprises; But must not be limited to lipid acid, glycerine deutero-lipid (comprising fat, oil and and phosphatide), sphingosine-deutero-lipid (comprising ceramide, cerebroside, Sphingolipids,sialo and sphingophospholipid), steroide and verivate, terpenes and verivate thereof, liposoluble vitamin, some aromatic substance and long-chain alcohol and wax.
In the organism that lives, lipid is usually as the basis of cytolemma and the form of fuel storage.Also can find lipid and protein or glucide conjugation, like form with lipoprotein and LPS.
The example of available vegetables oil includes but not limited to vegetable seed (rape) oil, VT 18, Oleum Cocois, sunflower oil, plam oil, palm-kernel oil, peanut oil, linseed oil, Yatall MA, Semen Maydis oil, Viscotrol C, curcas oil, Jojoba oil, sweet oil, flax-seed oil, false flax oil, Thistle oil, babassu oil, tallow oil and Rice pollard oil according to the present invention.In the method for the invention, preferred Oleum Cocois, plam oil, palm-kernel oil and babassu oil.
Preferred plants oil also can comprise the vegetables oil material through processing here.The non-limitative example of the vegetables oil material of warp processing comprises lipid acid and fatty acid alkyl ester.Alkyl ester generally includes C 1-C 5Alkyl ester.Preferred one or more methyl ester, ethyl ester and propyl diester.
The example of available animal tallow includes but not limited to according to the present invention, beef fat (butter), pork fat (lard), turkey fatty ester, fish fats/oil and chicken fat.Animal tallow can obtain from the source of any appropriate, and said source comprises dining room and meat production factory.
Preferred animal fat also comprises the animal tallow material through processing among this paper.The non-limitative example of the animal tallow material of warp processing comprises lipid acid and fatty acid alkyl ester.Alkyl ester generally includes C 1-C 5Alkyl ester.Preferred one or more methyl ester, ethyl ester and propyl diester.
Algae oil or lipid are contained in the algae with the form of membrane component, storage product and metabolite usually.Some algae strain, particularly microalgae such as diatom and cyanobacteria contain a high proportion of lipid.Preferably, be the basis with the gross weight of biomass itself, the lipid of 2wt% to 40wt% is contained in the algae source that is used for algae oil.
The algae source that is used for algae oil includes but not limited to, unicellular and many cells algae.The example of these algae comprises red algae (rhodophyte), green alga (chlorophyte), length haematococcus (heterokontophyte), three ripple algaes (tribophyte), grey born of the same parents algae door (glaucophyte), filopodium worm door (chlorarachniophyte), euglena (euglenoid), chrysophyceae (haptophyte), latent algae (cryptomonad), dinoflagellate (dinoflagellum), plant plankton (phytoplankton) and analogue, with and combination.The preferably Chlorophyceae and/or the algae of deciding whip algae door (Haptophyta).Concrete kind includes but not limited to, the new green alga of rich oil (Neochloris oleoabundans), dimorphism grid algae (Scenedesmus dimorphus), very thin Euglena (Euglena gracilis), Phaeodactylum tricornutum (Phaeodactylum tricornutum), cocolith (Pleurochrysis carterae), decides whip chrysophyceae (Prymnesium parvum) and Zhou Shi flat algae (Tetraselmis chui), Chlamydomonas reinhardtii (Chlanydomonas reinhardtii) for a short time.
In one embodiment, raw material is made up of the lipid biomass, wherein is the basis with the gross weight that is included in the lipid biomass in the raw material, and the lipid biomass have total triglyceride content of 2wt% at least.Preferably, raw material is made up of the lipid biomass, wherein is the basis with the gross weight that is included in the lipid biomass in the raw material, and the lipid biomass have 10wt% at least, for example 40wt% or total triglyceride content of 60wt% at least at least.
The type of tri-glyceride can be confirmed according to fatty acid component.Fatty acid component can easily use gc (GC) assay determination.This analysis relates to extracts fat or oily, said fat of saponification (hydrolysis) or oil, prepare said through saponified fat or oily alkyl (for example methyl) ester, and the type of use GC assay determination (methyl) ester.
In an embodiment of the invention, be the basis, be present in most of tri-glyceride in the lipid biomass by C with the gross weight that is present in the tri-glyceride in the lipid biomass 8To C 18Lipid acid is formed.For the sake of clarity, be indicated as being " C when lipid acid or fatty ester molecule Xx" lipid acid or fatty ester, mean " xx " carbonatoms for the carbon side of carboxylicesters bonding, that is, comprise carboxylicesters carbon, and in fatty ester, ester carbon is not included in " C Xx" in, and be the carbon on the oxygen side of carboxylicesters bonding, that is, terminate in carboxylicesters oxygen.In addition, tri-glyceride is the molecule with structure identical with the reaction product of glycerine and three lipid acid.Therefore, though describe tri-glyceride in this article, be to be understood that fatty acid component must not contain carboxylic acid hydrogen for to form by lipid acid.In the method for the invention, be the basis, be present in most of tri-glyceride in the lipid biomass preferably by C with the gross weight that is present in the tri-glyceride in the lipid biomass 10To C 16, C for example 12To C 14Lipid acid is formed.
In another embodiment of the present invention, be the basis with the gross weight that is present in the tri-glyceride in the lipid biomass, the 60wt% at least that is present in the tri-glyceride in the lipid biomass is by C 8To C 18Lipid acid is formed.Preferably, be the basis with the gross weight that is present in the tri-glyceride in the lipid biomass, the 60wt% at least that is present in the tri-glyceride in the lipid biomass is by C 10To C 16Form, for example, the 60wt% at least that is present in the tri-glyceride in the lipid biomass is by C 12To C 14Lipid acid is formed.
In another embodiment of the present invention, be the basis with the gross weight that is present in the tri-glyceride in the lipid biomass, the 80wt% at least that is present in the tri-glyceride in the lipid biomass is by C 8To C 18Lipid acid is formed.Preferably, be the basis with the gross weight that is present in the tri-glyceride in the lipid biomass, the 80wt% at least that is present in the tri-glyceride in the lipid biomass is by C 10To C 16Form, for example, the 80wt% at least that is present in the tri-glyceride in the lipid biomass is by C 12To C 14Lipid acid is formed.
In specific implementations, raw material comprises tri-glyceride, and wherein tri-glyceride comprises LAURIC ACID 99 MIN (C12:0).Use mark " Cxx:yy " to be illustrated on the main chain (that is) and have " xx " individual carbon atom, and on main chain, have the compound of " yy " individual unsaturated (two key) in the carboxylate group's who comprises carboxylicesters carbon carbon side.Preferably, this tri-glyceride is made up of 40% to 60% LAURIC ACID 99 MIN component, for example is made up of 42% to 58% or 44% to 55% LAURIC ACID 99 MIN component.Only if specify the free burial ground for the destitute undoubtedly separately, the percentage ratio of explaining among this paper is the percentage ratio based on element or component sum.
In another embodiment, raw material comprises tri-glyceride, and wherein tri-glyceride comprises tetradecanoic acid (C14:0).Preferably, this tri-glyceride is made up of 10% to 28% tetradecanoic acid component, for example is made up of tetradecanoic acid component 12% to 26% or 14% to 24%.
In another embodiment of the invention, be present in lipid biomass in the raw material and form by the fatty acid alkyl ester of 20wt% at least that (for example, methyl or ethyl correspond respectively to FAME or FAEE, are the basis with the gross weight of lipid biomass.Preferably, fatty acid alkyl ester is a compsn, and it comprises at least a fatty acid alkyl ester, and wherein this fatty acid component is selected from capric acid (C10:0), LAURIC ACID 99 MIN (C12:0), tetradecanoic acid (C14:0), palmitinic acid (C16:0) and Triple Pressed Stearic Acid (C18:0)).More preferably, be the basis with the gross weight of lipid biomass, be present in lipid biomass in the raw material by 30wt% at least, for example the fatty acid alkyl ester of 40wt% (like FAME) is formed at least.
The lipid biomass part of the raw material that uses among the present invention can comprise at least a terpenes.Terpenes is considered to one type and comprises that a plurality of is the unitary biosynthetic hydrocarbon of isoprene (2-methyl isophthalic acid, 3-divinyl) of five-carbon hydrocarbon.Said isoprene unit can be joined together to form non-annularity (comprising branching or linearly aligned carbon atom) or cyclic skeleton.
Terpenic non-limitative example comprises hemiterpene, and it forms (for example, isoprene) by an isoprene unit; Monoterpene, it forms (for example ， limonene and myrcene) by two isoprene residues; Sesquiterpene, it is made up of three isoprene residues, includes but not limited to acyclic sesquiterpene (for example, farnesene) and cyclic sesquiterpene (for example, cuparene, curcumene, zingiberene and limene); Diterpene, it forms (for example, cembrene and Japanese yew diene) by four isoprene residues; Triterpene, it forms (for example, Supraene) by six isoprene residues; Tetraterpene, it forms (for example, the α of Serlabo, acyclic Lyeopene, single cyclic gamma carotene and double-ring-and β-Hu Luobusu) by eight isoprene residues.The terpenes that is especially suitable for use as raw material or feed composition comprises at least a compound that is selected from isoprene, myrcene, ocimene, limonene, terpinolene, phellandrene, farnesene, cuparene, cuprenene (cuprenene), different crust bundle alkene (isobazzanene), sesquiphellandrene, A Basa alkene (abisabolene), curcumene, zingiberene and Ba Ba alkene (barbatene).
In an embodiment of the invention, be the basis with the gross weight of lipid biomass, raw material can comprise the terpenes of 5wt% at least.For example, be the basis with the gross weight of lipid biomass, raw material can comprise 10wt% at least, for example, and 20wt% or 30wt% terpenes at least at least.
In one embodiment, raw material comprises the lipid biomass with the saponification value that is particularly suitable for forming jet fuel.The saponification value of lipid biomass (like oil or fat) is defined as the milligram number of the required Pottasium Hydroxide of lipid acid that neutralization obtains by complete hydrolysis 1 gram lipid biomass samples.In one embodiment, raw material comprises the lipid biomass, and wherein said lipid biomass have 180mgKOH/g oil to 300mg KOH/g oil, and for example 200mg KOH/g oil to 280mg KOH/g oil or 215mg KOH/g oil are to 270mg KOH/g oil saponification value.
In an embodiment of the invention, raw material comprises the lipid biomass, and said lipid biomass have the iodine number that is particularly suitable for forming jet fuel.The iodine number of lipid biomass (like oil or fat) is defined as, by the gram number of the iodine of 100 gram lipid biomass samples absorptions.Iodine number is preferably according to standard method EN 14111 (2003): 1 measures.In one embodiment, raw material comprises the lipid biomass, and wherein the lipid biomass have and are no more than 130, preferably are no more than 120, for example is no more than 110 or be no more than 100 iodine number.In specific implementations, raw material comprises the lipid biomass, and wherein the lipid biomass have 1 to 130, and is preferred 1 to 120, for example 1 to 100 iodine number.
Can transform any a large amount of lipid and advantageously carry out method of the present invention through pre-treatment before hydrogen treatment.For example, present method is favourable, is the ester (like FAME) that it needn't be converted into tri-glyceride free lipid acid or finally be converted into free lipid acid through those technology (like transesterify).The special benefit of this embodiment is that raw material can comprise the glycerine of limited amount, and it can be considered to the not required by product from ester exchange method.
In one embodiment, be the basis with the gross weight of raw material, raw material of the present invention comprises the glycerine that is no more than 10wt%.In preferred embodiment, be the basis with the gross weight of raw material, raw material of the present invention comprises and is no more than 5wt%, for example is no more than 3wt% or is no more than the glycerine of 2wt%.
In one embodiment, be the basis with the gross weight of raw material, raw material can comprise the lipid biomass of 0.05wt% at least.In preferred embodiment, be the basis with the gross weight of raw material, raw material comprises 0.5wt% at least, 1wt% at least for example, 2wt% at least, or the lipid biomass of 4wt% at least.
In addition or replacedly, be the basis with the gross weight of raw material, raw material can comprise the lipid biomass that are no more than 90wt%.In preferred embodiment, be the basis with the gross weight of raw material, raw material comprises and is no more than 60wt%, for example is no more than 40wt% or is no more than the lipid biomass of 20wt%.
The raw material that uses among the present invention can further comprise MO.The example of MO includes but not limited to, straight run (atmosphere) gas oil, vacuum gas oil, demetallated oil, coking overhead product, catalytic pyrolysis overhead product, heavy naphtha (choosing wantonly but preferably denitrogenation and/or desulfurization at least in part at least in part), diesel oil range of boiling overhead product level branch (choosing wantonly but preferably denitrogenation and/or desulfurization at least in part at least in part), jet fuel range of boiling overhead product level branch (choosing wantonly but preferably denitrogenation and/or desulfurization at least in part at least in part), kerosene range of boiling overhead product level branch (choosing wantonly but preferably denitrogenation and/or desulfurization at least in part at least in part) and coal liquid.Preferably, raw material does not contain considerable bituminous matter arbitrarily.In one embodiment, MO can mix then hydrogen treatment with the lipid biomass to form hydrotreated material.In another embodiment, with before the lipid biomass are mixed, MO can be hydrogenated processing to reduce nitrogen and/or sulphur content.
The MO component can contain nitrogenous compound (being abbreviated as " nitrogen ").This nitrogen can exist with the organic nitrogen compound form usually, and is that the amount of 1wppm to 1.0wt% exists with the gross weight based on the MO component usually.
MO contains sulfocompound (being abbreviated as " sulphur ") usually.This sulphur can be present in the MO with the organosulfur compound form usually, and in untreated MO, is the basis with the gross weight of MO, usually to exist from the amount greater than 0.15wt%.
In one embodiment, be the basis with the gross weight of raw material, raw material can comprise the MO that is no more than 99wt%.Preferably, be the basis with the gross weight of raw material, raw material can comprise and is no more than 98wt%, for example is no more than 95wt%, is no more than 90wt%, or is no more than the MO of 80wt%.
In addition or replacedly, be the basis with the gross weight of raw material, raw material can comprise the MO of 5wt% at least.In one embodiment, be the basis with the gross weight of raw material, raw material can comprise 10wt% at least, 20wt% at least for example, 30wt% at least, or the MO of 40wt% at least.
According to an aspect of the present invention, the range of boiling of raw material can be narrower than the range of boiling of common vacuum gas oil.Measure the basic test method of the range of boiling of such raw material and fuel composition produced according to the invention; Can be through according to ASTM D86-09e1, Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure carries out batch distillation.
In one embodiment, raw material can have at least 100 ° of C, preferably at least 150 ° of C, the for example initial boiling point of at least 180 ° of C or at least 200 ° of C.
In addition or replacedly, raw material can have and is no more than 500 ° of C, preferably is no more than 450 ° of C, for example is no more than the full boiling point of 400 ° of C.
Method of the present invention comprises that the hydrogen treatment raw material is to produce the step through hydrotreated material.Hydrogen treatment refers to wherein to treat that hydrotreated charging is optional with hydrogen-containing treat gas but the process that preferably in the presence of one or more hydrogen treatment catalyzer, contacts.
In one embodiment, the hydrogen treatment catalyzer can comprise the hydrogen treatment catalyzer that can effectively remove multiple metal pollutant (like arsenic, nickel and vanadium).In another embodiment, the hydrogen treatment catalyzer also can effectively be removed heteroatoms, like sulphur and nitrogen.In an embodiment again, the hydrogen treatment catalyzer is also saturated effectively to make aromatic substance and other unsaturatess with hydrogen.Usually, in hydrogen treatment operation, minimize the cracking (that is, will bigger hydrocarbon molecule be broken for less hydrocarbon molecule) of the hydrocarbon molecule in the raw material, fully or partly hydrogenation with unsaturated hydrocarbons.
Can use the catalyzer of any raw material of hydrogen treatment effectively.Non-limitative example comprises the catalyzer that comprises group vib metal and/or group VIII metal, randomly is carried on the carrier.Suitable metal can comprise cobalt, nickel, iron, molybdenum, tungsten and combination thereof.Suitable carriers can comprise MOX such as silicon-dioxide, silica-alumina, aluminum oxide and the titanium oxide of relative high-specific surface area.And one preferred embodiment comprise the catalyzer that comprises group vib metal and group VIII metal (for example, with oxide form, or preferably after oxide compound forms, under suitable cure conditions, being vulcanized); Randomly be carried on the carrier; Catalyzer can be in addition or is replacedly contained annexing ingredient, like other transition metal (for example, V family metal such as niobium); Rare earth metal; Organic ligand (for example, former state or remaining from oxidation and/or vulcanisation step) as precursor, phosphorus compound, boron cpd, fluorochemicals, silicon-containing compound, promotor, sticker, filler or similar reagents or its combination.Here the family of indication is meant and is shown in Periodic Table of the Elements in Hawley's Condensed Chemical Dictionary, the CAS Version family in the 13rd edition.As explanation, suitable VIII/VIB family catalyzer has for example been described: United States Patent(USP) No. 6,156,695,6,162,350,6 among one or more in following; 299,760,6,582,590,6,712,955,6; 783,663,6,863,803,6,929,738,7; 229,548,7,288,182,7,410; 924 and 7,544,632, the open No.2005/0277545,2006/0060502,2007/0084754 and 2008/0132407 of U.S. Patent application, and International Publication No.WO 04/007646, WO 2007/084437, WO 2007/084438, WO2007/084439 and WO 2007/084471 and other.
Other suitable hydrogen treatment catalyzer can comprise zeolites catalyzer and noble metal catalyst, and for example, wherein this precious metal is selected from Pd, Pt and combination thereof.In an embodiment of the invention, use more than a kind of hydrogen treatment catalyzer in same step of reaction or Qu Zhongke.In addition or replacedly, can only there be a hydrogen treatment step of reaction or district, maybe can have a plurality of (for example, at least two).
Other hydrogen treatment catalyzer that can use especially are applicable to the hydrogen treatment catalyzer that makes aromatic substance saturated for those.The non-limitative example of these catalyzer comprises nickel, cobalt-molybdenum, nickel-molybdenum, nickel-tungsten and precious metal (for example, platinum and/or palladium) catalyzer, and wherein noble metal catalyst is that sulphur sensitization is perceptual, but removing of aromatic substance had more selectivity.Common base metal hydrogen treatment catalyzer comprises, for example, and the Ni/Mo on the aluminum oxide, the Co/Mo on the aluminum oxide, the Co/Ni/Mo on the aluminum oxide.
Hydrogen treatment is preferably being carried out under the average reactor temperature of at least 40 ° of C.Another preferred embodiment in, hydrogen treatment is carried out under the average reactor temperature that is no more than 440 ° of C.In specific implementations, hydrogen treatment is carried out in the TR of 40 ° of C to 440 ° of C.More preferably, hydrogen treatment can be carried out under the average reactor temperature of 100 ° of C to 425 ° of C (for example 125 ° of C to 400 ° of C).
Also preferably to the average reactor pressure of 204atm (3000psia, or 20.7MPaa), carry out hydrogen treatment at 6.8atm (100psia, or 690kPaa).Another preferred embodiment in, hydrogen treatment can be carried out to the average reactor pressure of 81.7atm (1200psia, or 8.3MPaa) at 13.6atm (200psia, or 1.4MPaa).
Hydrogen treatment also can be carried out under the liquid hourly space velocity (LHSV) of 0.3V/V/Hr to 10V/V/Hr effectively.One preferred embodiment in, hydrogen treatment can be at 1hr -1To 5hr -1LHSV under carry out.
Preferably, can to handle gas velocity at hydrogen be 35.6Nm to hydrogen treatment 3/ m 3To 1780Nm 3/ m 3Carry out in the scope of (200scf/bbl to 10000scf/bbl).Another preferred embodiment in, it is 90Nm that hydrogen treatment can be handled gas velocity at hydrogen 3/ m 3To 890Nm 3/ m 3Carry out in the scope of (500scf/bbl to 5000scf/bbl).
According to an aspect of the present invention, part can be dewaxed through hydrotreated material at least.In the present invention, dewaxing is meant catalytic dewaxing, wherein in heavy hydrocarbon and H-H reaction under reaction conditions in the presence of the dewaxing catalyst.Catalytic dewaxing process is a kind of process for hydrocracking of hydrocarbonaceous in essence.Dewaxing is more specifically based on the selective hydrogenation cracking that is mainly n-paraffin usually.
Process for dewaxing can be introduced the use based on the catalyzer of molecular sieve, and wherein active hydrocracking point can contact with the alkane molecule, the preferred compound of getting rid of bigger aromatics type.Reaction conditions in the dewaxing can preferably be effective in the cold flow properties of further improvement through hydrotreated material, stops up point like zero pour, cloud point, pour point and/or cold filtration.
Can use any with effective catalyzer in the hydrocarbon dewaxing.In one embodiment; The hydrogen treatment catalyst composition can be effective in the dewaxing; Said hydrogen treatment catalyst composition comprises one or more among Co, Ni and the Fe, and comprises among Mo and the W one or more, and loads on Pt and Pd precious metal on the acid carrier.In another embodiment, dewaxing catalyst can comprise (acidity) oxide carrier (support) or loading (carrier).The non-limitative example of this carrier can comprise silicon-dioxide, aluminum oxide, silica-alumina and other shape selective molecular sieves.Preferably; Carrier can make up with at least a catalyst component, said catalyst component such as aluminosilicophosphate (SAPO), titanium oxide, zirconium white, vanadium oxide and other II, IV, V or VI family oxide compound, ferrierite (ferrierite), mordenite, ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-22 (being also referred to as θ 1 or TON), ZSM-48, SAPO-11, SAPO-36, SAPO-37, SAPO-40 and zeolite Y sieve as overstable Y or the like.If, then can use the zeolite that contains the skeleton transition metal (for example, at United States Patent(USP) No. 5 with improved anti-sulphur property if before dewaxing, do not carry out stripping and/or enough high to cause active reduction of dewaxing catalyst or forfeiture through the sulphur content of hydrogen treatment and isolating heavy part; 185; 136,5,185,137 and 5; In 185,138).
Dewaxing can comprise that 300 ° of F (149 ° of C) carry out to the reaction conditions of the average reaction temperature of 900 ° of F (482 ° of C).Preferably, dewaxing can comprise that 550 ° of F (289 ° of C) carry out to the reaction conditions of the average reaction temperature of 800 ° of F (427 ° of C).
Dewaxing also can preferably be carried out to the average response pressure of 136atm (2000psia, or 13.8MPaa) at 27.2atm (400psia, or 2.8MPaa).
Hydrogen-containing treat gas speed in the dewaxing can be 300scf/bbl (53Nm 3/ m 3) to 5000scf/bbl (890Nm 3/ m 3).Preferably, hydrogen-containing treat gas speed can be 2000scf/bbl (356Nm 3/ m 3) to 4000scf/bbl (712Nm 3/ m 3).
Liquid hourly space velocity in the dewaxing in volume/hour (V/V/Hr), can be 0.1 to 10.The preferred liquid hourly space velocity can be 1V/V/Hr to 5V/V/Hr.
According to a further aspect in the invention, can be with at least partly through hydrotreated material hydroisomerization.In preferred embodiment, with part at least through the dewaxing of hydrotreated material to form the fuel composition of dewaxing, then with its hydroisomerization to produce dewaxing and fuel composition hydroisomerization.
Term " hydroisomerization " and " hydroisomerization " used among the present invention refer to catalysis process; Wherein in the presence of hydrogen; Charging contacts with catalyzer; Most wax shape alkanisation compound can be converted into the different alkanisation compound of non-waxy in the charging, and reduces simultaneously and/or minimize the conversion through cracked (just) paraffinic hydrocarbons.The use of hydroisomerization step can increase the volume of the jet engine/diesel-fuel that forms in the whole process effectively.Particularly, use the hydroisomerization step can reduce the heavy part of raw material through the mover/diesel-fuel that this part component is converted into additional volume.
Hydroisomerization can carry out through using catalyzer (like the shape selective sieve catalyst).Especially effectively macropore crystalline molecular sieve or mesoporous molecular sieve.
The macropore crystalline molecular sieve that can be used for hydroisomerization step of the present invention preferably has the restricted index less than 2.The mesopore crystalline molecular sieve that can be used for hydroisomerization step of the present invention preferably has and is at least 2 restricted index.The method of measuring restricted index intactly is described in United States Patent(USP) No. 4,016,218, incorporates this paper into as a reference at this.
In one embodiment, the molecular sieve that is used for isomerization steps of the present invention has the α value less than 100.Said α value is this catalyzer and the standard catalyst active suitable indication of catalytic pyrolysis relatively.It is 1 (rate constant=0.016sec that alpha test provides with respect to be decided to be α -1) standard catalyst, the relative rate constant of detecting catalyst (hexane conversion of every volume of catalyst time per unit).Alpha test is described in United States Patent(USP) No. 3,354, and 078 and J.Catalysis, 4,527 (1965); 6,278 (1966); In 61,395 (1980), the above-mentioned document of the description references of this test.The test experiments condition in order to measure the α value of indication comprises constant temperature and the variable-flow speed of 538 ° of C in this manual, like J.Catalysis, and 61,395 (1980) middle detailed descriptions.
The non-limitative example of large pore molecular sieve catalyzer can include but not limited to, is selected from the molecular sieve of zeolite beta, mordenite, zeolite Y, ZSM-20, ZSM-4 (Ω), zeolite L, VPI-5, SAPO-37, MeAPO-37, AlPO-8, phosphorus gallium molecular sieve (cloverite) and combination thereof.The non-limitative example of mesoporous molecular sieve can include but not limited to, ZSM-22, ZSM-23, ZSM-48, SAPO-11, SAPO-5, MeAPO-11, MeAPO-5 and combination thereof; The example of non-crossing two-dimentional mesoporous molecular sieve is ZSM-35 (a synthetic ferrierite).
The catalyzer that can be used in the hydroisomerization step preferably contains metal hydride, and it can be one or more precious metals, one or more base metals, or its combination.Suitable precious metal comprises group VIII noble metals, like platinum and other platinum metals, like the combination of iridium, palladium and rhodium and these metals.Suitable base metal comprises those of VB, group vib, and (base metal) of the group VIII of periodictable.Preferred base metal includes but not limited to that the combination of chromium, molybdenum, tungsten, cobalt, nickel and these metals comprises cobalt-molybdenum, nickel-tungsten, nickel-molybdenum, cobalt-nickel-molybdenum, nickel-molybdenum-tungsten, cobalt-molybdenum-tungsten and cobalt-nickel-tungsten.Before use can through be exposed at elevated temperatures sulfurous gas (like hydrogen sulfide) with the base metal prevulcanized to influence transformation efficiency (for example, the transformation efficiency of oxide form) to the corresponding sulphided form of metal.
Can metal be added catalyzer through the method for any appropriate or the combination of method, as getting into zeolite through dipping or IX.Metal can add with cationic complexes, anionic complex or neutral compound form.Pt (NH 3) 4 ++The type cationic complexes is used in and exchanges metal on the zeolite.Anionic complex such as molybdate or metatungstate ion also can be used for metal impregnation is gone into catalyzer.
In one embodiment, the hydroisomerization catalyzer can comprise zeolite and metal hydride.One preferred embodiment in, be the basis with the gross weight of catalyzer, catalyzer can comprise 0.01wt% to 20wt%, for example the metal hydride of 0.1wt% to 15wt%.
In one embodiment, molecular sieve can comprise sticker (or matrix) material.Binder material is preferably MOX.The non-limitative example of MOX sticker can include but not limited to; Aluminum oxide, silica-alumina, silica-magnesia, silicon-dioxide-zirconium white (zironcia), silica-thorium oxide, silica-beryllia (berylia), silica-titania; And ternary composition such as silica-alumina-Thorotrast, silica-alumina-zirconium white, silica-alumina-Natural manganese dioxide and silica-magnesia-zirconium white or the like, and combination.In one embodiment, catalyzer is ZSM-23, ZSM-48 or SAPO-11 and zeolite beta, and they combine with aluminum oxide, and forms available form through method (as extruding or compressing tablet).
Hydroisomerization can carry out under the hydroprocessing condition of the temperature and pressure that is raising in the presence of the hydrogen.Whether catalyzer, the catalyzer that the special reaction conditions that is used for hydroisomerization can be depending on the charging of use, use cures, the required character of required productive rate and required product or the like.The condition that can carry out hydroisomerization process of the present invention comprises that temperature is 600 ° of F to 750 ° of F (315 ° of C to 399 ° of C); 600 ° of F to 700 ° of F (315 ° of C to 371 ° of C) for example; With pressure be 1.7atm to 204atm (25psia to 3000psia; Or 170kPaa to 20.7MPaa), 6.8atm to 170atm (100psia to 2500psia, or 1.4MPaa to 17.3MPaa) for example.Hydroisomerization pressure in this context is meant the hydrogen dividing potential drop in the hydroisomerization reactor drum, though when processing gas be 100% or during basic 100% hydrogen, the hydrogen dividing potential drop is identical with stagnation pressure or basic identical.Yet when processing gas contained the gas of hydrogen and other common relative inertness, stagnation pressure will be greater than the hydrogen dividing potential drop.
Liquid hourly space velocity in the contact process can be generally 0.1hr -1To 20hr -1, 0.1hr for example -1To 5hr -1Hydrogen/hydrocarbon ratio can drop on 1.0 moles of H 2To 50 moles of H 2The charging of/mole hydrocarbon, for example 10 moles of H 2To 20 moles of H 2In/mole hydrocarbon charging the scope.
In hydrogen treatment and dewaxing and hydroisomerization, use and handle gas.Term " hydrogen ", " hydrogen processing gas " and " processing gas " use in this article equivalent in meaningly; Can be pure hydrogen or hydrogen-containing treat gas; Hydrogen-containing treat gas is for handling gas streams; This processing gas streams comprises at least the hydrogen to the enough amounts of goal response, and one or more other gases (for example, comprising nitrogen and light hydrocarbon such as methane) of negative interference or influence reaction or product not usually.Impurity such as H 2S and NH 3Normally not required, and will before processing gas is introduced into reactor drum, remove from handling gas usually.The processing gas streams that is introduced into step of reaction can preferably contain at least about 50vol%, more preferably at least about the hydrogen of 75vol%.
Multiple reactor configuration can be used for method of the present invention.But the fixed bed of raw material contact catalyst, thermopnore or liquid bed.A kind of example of configuration is the trickle bed operation, and wherein liquid starting material is through fixed fixed bed drip.Another example of reactor configuration is a counter-current process, that is, wherein the hydrocarbon charging is downward through fixed beds, and H 2Flowing in the other direction.In this configuration, can remove H at the top 2S and/or NH 3
Removable one or more through the lightweight of the material of hydrogen treatment, dewaxing and hydroisomerization or heavy part to produce or to reclaim required fuel composition.In one embodiment, separate through the lightweight of hydrotreated material or heavy component or part and can before dewaxing, carry out.The separation of the lightweight of the material that can dewax in another embodiment, or heavy component or part.In another embodiment, can carry out lightweight or the heavy component or the separation partly of the material of hydroisomerization.In these embodiments, can carry out these and separate to influence fuel mass, at least a jet fuel or diesel-fuel with high quality characteristic particularly is provided.Can use the mode of any appropriate to separate.Preferred classification and/or distillation.Can use the combination of air distillation, vacuum distilling or normal pressure and vacuum distilling.
Can carry out hydrogen treatment, dewaxing, hydroisomerization, the separation of component, or its arbitrary combination is to produce fuel composition, particularly at least a jet fuel or diesel-fuel with highly required fuel characteristic.This method steps is effective especially in producing the jet fuel compsn.
Method steps of the present invention can carry out under predetermined conditions; This predetermined conditions effectively provides at least a jet fuel with one or more predefined characteristics; Said characteristic is smoke point, zero pour or one or more other character (as setting among the ASTM D1655 – 08a Standard Specification for Aviation Turbine Fuels), and its content is incorporated this paper into as a reference.
In one embodiment, can be with raw material hydrogen treatment, dewaxing, hydroisomerization or its combination, be 25.0mm at least thereby form smoke point, preferably 25.5mm, for example 26.0mm or the fuel composition of 26.5mm at least at least at least.Said smoke point is measured according to ASTM D 1322.Fuel is preferably jet fuel.
In another embodiment, can be with raw material hydrogen treatment, dewaxing, hydroisomerization or its combination, be not higher than-35 ° of C thereby form zero pour, preferably be not higher than-45 ° of C, for example be not higher than-50 ° of C or be not higher than the fuel composition of-55 ° of C.Said zero pour is measured according to ASTM D4529.Fuel is preferably jet fuel.
In one embodiment, can carry out this method to produce or to reclaim kerosene type or gasoline-type jet fuel.In one embodiment, can carry out this method to produce or to reclaim ASTM D8690% distillation o'clock in 250 ° C to 290 ° C scope, preferably the kerosene type jet fuel in 260 ° C to 280 ° C scope.In another embodiment, can carry out this method to produce or to reclaim ASTM D8690% distillation o'clock in 200 ° C to 240 ° C scope, preferably the gasoline-type jet fuel in 210 ° C to 230 ° C scope.
In one embodiment, can carry out this method to produce or to reclaim ASTM D8610% distillation o'clock in 150 ° C to 200 ° C scope, preferably the kerosene type jet fuel in 160 ° C to 180 ° C scope.In another embodiment, can carry out this method to produce or to reclaim ASTM D8610% distillation o'clock in 110 ° C to 140 ° C scope, preferably the gasoline-type jet fuel in 120 ° C to 130 ° C scope.
In one embodiment, can carry out this method to produce or to reclaim diesel-fuel.In specific implementations, can carry out this method to produce or to reclaim ASTM D8690% distillation o'clock in 260 ° C to 350 ° C scope, preferably the diesel-fuel in 280 ° C to 340 ° C scope.
In another embodiment, can carry out this method to produce or to reclaim ASTM D8610% distillation o'clock in 200 ° C to 240 ° C scope, preferably the diesel-fuel in 210 ° C to 230 ° C scope.
Though these fuel characteristics mention, be to be understood that the fuel of producing or reclaiming can have two or more or even the arbitrary combination of all characteristics/character disclosed herein in each embodiment.
In addition or replacedly, the present invention includes following embodiment.
Embodiment 1.A kind of method that is used to produce the fuel composition of dewaxing comprises: the raw material that contains the lipid biomass is provided; The said raw material of hydrogen treatment is to produce through hydrotreated material; And dewaxing and/or hydroisomerization part should be through hydrotreated material to produce fuel composition dewaxing and/or hydroisomerization at least.
Embodiment 2.Embodiment 1 described method, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as jet fuel or diesel-fuel at least.
Embodiment 3.Embodiment 1 or embodiment 2 described methods, wherein will be at least part fuel composition this dewaxing and/or hydroisomerization be recovered as and have the jet fuel of the smoke point of 25.0mm at least.
Embodiment 4.According to each described method of aforementioned embodiments, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as the jet fuel with the zero pour that is not higher than 35 ℃ at least.
Embodiment 5.According to each described method of aforementioned embodiments, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as the jet fuel that the ASTM D8690% that has in 250 ℃ to 290 ℃ scopes distills point at least.
Embodiment 6.According to each described method of aforementioned embodiments, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as the jet fuel that the ASTM D8690% that has in 200 ℃ to 240 ℃ scopes distills point at least.
Embodiment 7.According to each described method of aforementioned embodiments, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as the diesel-fuel that the ASTM D8690% that has in 260 ℃ to 350 ℃ scopes distills point at least.
Embodiment 8.According to each described method of aforementioned embodiments, wherein part should be distilled by fuel composition dewaxing and/or hydroisomerization at least, and after distillation, reclaims at least a jet fuel or at least a diesel-fuel.
Embodiment 9.According to each described method of aforementioned embodiments, wherein raw material further comprises MO.
Embodiment 10.According to each described method of aforementioned embodiments, wherein will be at least part should be through hydrotreated material dewaxing but hydroisomerization not.
Embodiment 11.According to each described method of aforementioned embodiments, wherein will be at least part should be through hydrotreated material hydroisomerization but do not dewax.
With reference to a plurality of exemplary and preferred embodiment, principle of the present invention and operating method are as stated.It will be apparent to those skilled in the art that the whole invention that limits like claim comprises other and do not enumerate preferred embodiment in this article.

Claims (11)

1. method that is used to produce the fuel composition of dewaxing, it comprises: the raw material that contains the lipid biomass is provided; The said raw material of hydrogen treatment is to produce through hydrotreated material; And dewaxing and/or hydroisomerization part should be through hydrotreated material to produce fuel composition dewaxing and/or hydroisomerization at least.
2. method according to claim 1, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as jet fuel or diesel-fuel at least.
3. according to claim 1 or embodiment 2 described methods, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as and has the jet fuel of the smoke point of 25.0mm at least at least.
4. according to each described method of aforementioned claim, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as the jet fuel with the zero pour that is not higher than 35 ℃ at least.
5. according to each described method of aforementioned claim, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as the jet fuel that the ASTM D8690% that has in 250 ℃ to 290 ℃ scopes distills point at least.
6. according to each described method of aforementioned claim, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as the jet fuel that the ASTM D8690% that has in 200 ℃ to 240 ℃ scopes distills point at least.
7. according to each described method of aforementioned claim, wherein part fuel composition this dewaxing and/or hydroisomerization is recovered as the diesel-fuel that the ASTM D8690% that has in 260 ℃ to 350 ℃ scopes distills point at least.
8. according to each described method of aforementioned claim, wherein part should be distilled by fuel composition dewaxing and/or hydroisomerization at least, and after distillation, reclaims at least a jet fuel or at least a diesel-fuel.
9. according to each described method of aforementioned claim, wherein raw material further comprises MO.
10. according to each described method of aforementioned claim, wherein part should be through hydrotreated material dewaxing but hydroisomerization not at least.
11. according to each described method of aforementioned claim, wherein will be at least part should be through hydrotreated material hydroisomerization but do not dewax.
CN2010800503462A 2009-09-08 2010-09-03 Fuel production from feedstock containing lipidic material Pending CN102625822A (en)

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