CN104066818B - The hydro-conversion of renewable raw materials - Google Patents

The hydro-conversion of renewable raw materials Download PDF

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Publication number
CN104066818B
CN104066818B CN201280067929.5A CN201280067929A CN104066818B CN 104066818 B CN104066818 B CN 104066818B CN 201280067929 A CN201280067929 A CN 201280067929A CN 104066818 B CN104066818 B CN 104066818B
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catalyst
raw material
liquid effluent
weight
product
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CN104066818A (en
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陈聪岩
A·E·库珀曼
W·J·卡内拉
T·L·M·梅伊森
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Chevron USA Inc
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Chevron USA Inc
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Priority claimed from US13/315,729 external-priority patent/US9199909B2/en
Priority claimed from US13/315,575 external-priority patent/US8884077B2/en
Priority claimed from US13/315,774 external-priority patent/US8865949B2/en
Priority claimed from US13/315,611 external-priority patent/US8704007B2/en
Priority claimed from US13/315,683 external-priority patent/US20130150641A1/en
Priority claimed from US13/315,650 external-priority patent/US9035115B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/177—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of a carboxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • C10G3/50—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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • 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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/4012—Pressure
    • 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
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  • General Chemical & Material Sciences (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Hydrogenating conversion process includes making to comprise the raw material of the recyclable materials catalyst under hydroprocessing conditions with the promotion selected from self-supported catalyst, loaded catalyst and combinations thereof and contacts, and wherein reaction condition may be tailored to make described renewable raw materials be directly translated into the desired product including fatty alcohol, ester, normal paraffin hydrocarbons or a combination thereof.Described catalyst comprises at least one the group vib metal selected from molybdenum and tungsten, a kind of group VIII metal selected from cobalt and nickel so that described raw material changes into any one in fatty alcohol, ester and normal paraffin hydrocarbons.In some embodiments, described method also includes the other step producing various desired product, described desired product includes alhpa olefin (or PAO, by making described fatty alcohol product be dehydrated), lubricant and bright stock (oligomeric from described PAO) and 3 race's lubricants (common oligomeric from described PAO and some short-chain olefins).

Description

The hydro-conversion of renewable raw materials
Cross-Reference to Related Applications
This application claims U.S. Patent application 13/315,611, No. 13/315,774, No. 13/315,575,13/315, No. 729,13/315, No. 650 and 13/315, the priority of No. 683, the submission date of these patent applications is all in December, 2011 9 days.This application claims that the preferential of above-mentioned patent application benefits from for the time being above-mentioned patent application, the disclosure of these patent applications It is incorporated herein by reference.
Technical field
The application is usually directed to by making renewable raw materials with at least one multimetal reforming catalyst under hydroprocessing conditions The method contacted and make described renewable raw materials change into the such as grease chemical article of fatty alcohol, ester and normal paraffin hydrocarbons.
Background
Fossil fuel is the limited non-renewable resources formed by corrupt plant and animal, and it is exposed to the heat of the earth's crust Crude oil, coal, natural gas or heavy oil is changed into through hundreds of millions of years with pressure.But, because world petroleum resource is along with it Ever-increasing price and dilution, so whole world many industry is look for renewable/endurable raw material (" biological money Source ") substitute the material based on oil in their manufacturing process.
Commercial grease chemicals can be used for manufacturing surfactant, lubricant, fuel, plastics etc..Grease chemical article includes But it is not limited to fatty alcohol, ester and alkane.By being highly desirable to provide, recyclable materials is directly translated into the effective of described product Method.
The living resources of such as lipid (such as, vegetable oil, Animal fat etc.) are changed into such as jet/diesel fuel A kind of art methods of the high value products of (alkane) is to produce such as long-chain via base catalyzed reactions under there is alcohol Arrcostab or the ester of fatty acid methyl ester (FAME).Hydrotreating is the other method that living resources change into useful products.So And, in U.S. Patent application 2009/0166256, disclose and the most typically containing planting of triglyceride and fatty acid In the case of the biological components raw material of thing oil and Animal fat, the big triglyceride in biological components raw material and fatty acid molecule Contestable ground adsorbs on the active site of hydrotreating catalyst and blocks the active site of hydrotreating catalyst.Need Renewable raw materials is made to become the catalysis with suitable form, structure and best catalytic activity of high value products with high yield conversion Agent.
Base oil be commonly used to manufacture in automobile, the commercial Application etc. use process oil, white oil, Metalworking fluid and Lubricant.It is increasingly difficult to be met the lubricant of some standard in the automotive industry by conventional mineral oil manufacture.Need to utilize Renewable raw materials manufactures the ameliorative way of lubricant and bright stock as initial source.
Summary of the invention
On the one hand, it is provided that catalysis conversion method, it include making renewable raw materials under hydroprocessing conditions with at least one Self-supported catalyst or loaded catalyst contact with formed effluent and from described effluent reclaim comprise normal paraffin hydrocarbons Hydrocarbon-fraction, wherein said hydroprocessing condition includes temperature and the 50-3000psig of 446-752 (230 DEG C-400 DEG C) The total reaction pressure of (0.35-20.7MPa gauge pressure).
On the other hand, it is provided that catalysis conversion method, it includes making renewable raw materials under hydroprocessing conditions with at least one Kind of self-supported catalyst or loaded catalyst contact are to form effluent and to reclaim aliphatic mono from described effluent and evaporate Point, wherein said hydroprocessing condition includes temperature and the 50-3000psig (0.35-of 302-554 (150 DEG C-290 DEG C) 20.7MPa gauge pressure) total reaction pressure.
Another aspect, it is provided that hydroconversion process, it include making renewable raw materials under hydroprocessing conditions with at least one Self-supported catalyst or loaded catalyst contact with formation effluent and reclaim fatty alcohol fractions from described effluent, its Described in hydroprocessing condition include temperature and the 50-3000psig (0.35-of 302-554 (150 DEG C-290 DEG C) 20.7MPa gauge pressure) total reaction pressure.In one embodiment, it is processed further forming lattice by described aliphatic alcohol moiety Er Beite (Guerbet) alcohol.
Another aspect, it is provided that catalysis conversion method, wherein make renewable raw materials at least with at least one self-supported catalysis Described fatty alcohol, to form the effluent containing fatty alcohol, is wherein reclaimed and subsequently in dehydration by agent or loaded catalyst contact District is dehydrated under dehydration conditions form alpha-olefin product.
In one embodiment, make formed alpha-olefin product the most oligomeric to be formed in oligomerization zones Oligomer.In yet another embodiment, make formed oligomer in the temperature including 302-752 (150 DEG C-400 DEG C) Oily with hydrogenating under the hydroprocessing condition of the total reaction pressure of 50-3000psig (0.35-20.7MPa gauge pressure) with basis of formation.
In the present invention, the self-supported catalyst of described promotion or the loaded catalyst of described promotion comprise selected from molybdenum With at least one group vib metal of tungsten, selected from least one group VIII metal of cobalt and nickel, accelerator is selected from having steric configuration And there is hydroxyl-(the two)-carboxylic acid of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, aromatics, alcohol, branch or not The alkyl of branch, wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0.
Accompanying drawing is sketched
Fig. 1 be show hydrotreating such as triglyceride renewable raw materials, produce such as long chain n-paraffins, fat The schematic diagram of the various response paths in the various desired products of alcohol, fatty acid and ester.
Fig. 2 is that display is formed such as oligomer, ester, Guerbet alcohol by the upgrading of the renewable raw materials of such as triglyceride The schematic diagram of the formation with the various desired product of EOR (enhancing recovery of oil) surfactant.
Detailed Description Of The Invention
Use following term throughout the specification, and unless otherwise indicated, otherwise following term will have following meaning Think.
" renewable raw materials " refers to be different from that obtain by the fossil resource such as such as crude oil, coal, natural gas, sad oil The raw material of a little raw materials, it refers to be derived in part from such as such as the material based on plant of vegetablefats/oil or include algae Raw material with the Bio Feedstock Component of the Animal fat/oil of fish fats/oil.In one embodiment, described renewable raw materials For the renewable raw materials containing triglyceride.
" grease chemical article " refers to biogenic, the chemicals i.e. obtained by biogenic Renewable resource.This term is public Not think and include Fossil fuel.
" midbarrel " is the hydrocarbon products of the boiling range with 250-1100 (121 DEG C-593 DEG C)." centre evaporates term Point " include jet fuel, kerosene, diesel oil, add deep fat boiling range part.It may also include a part of Petroleum or light oil." jet is fired Material " for having the hydrocarbon products of the boiling range in jet fuel boiling range.Term " jet fuel boiling range " refers to have 280-572 The hydrocarbon of the boiling range of (138 DEG C-300 DEG C).Term " diesel fuel boiling range " refers to have 250-1000 (121 DEG C-538 DEG C) The hydrocarbon of boiling range." boiling range " is 10 volume % boiling points-final boiling point (99.5 volume %), including end points, as by ASTM D2887-08 (" standard test method (the Standard Test Method of the boiling Range Distribution Analysis of the petroleum distillate carried out by gas chromatography for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography) ") measure.
" triglyceride " refers to the molecular classification with formula (1):
Wherein R, R1And R2Independently be and there is 6-22 carbon atom (such as 8-20 carbon atom or 10-16 carbon atom) Aliphatic residue.Term " aliphatic " refers to fully saturated or containing one or more unsaturated units straight chain (that is, non-branch) Or branch, substituted or unsubstituted hydrocarbon chain.
" fatty alcohol " refers to that per molecule is generally of 8-24 carbon atom, the primary aliphatic alcohols of usual 8-18 carbon atom.
" aliphatic mono " refers to the compound with formula (2):
Wherein R3And R4Independently be moieties.In some embodiments, this aliphatic (acid) ester per molecule has 16-40 Carbon atom (such as, 18-36 or 20-34 carbon atom).Described ester can be used as lubricant.
" alkane " refers to any saturated hydrocarbon compound, such as, have formula CnH(2n+2) alkane, wherein n is non-zero Positive integer.
" normal paraffin hydrocarbons " refers to saturated straight chain hydrocarbon.
" isoparaffin " refers to saturated branch chain hydrocarbon.
" hydro-conversion " can exchange with term " hydrotreating " and to use and to refer to carry out under there is hydrogen and catalyst Any method.Described method includes but not limited to methanation, water gas shift, hydrogenation, hydrotreating, hydrodesulfurization, hydrogenation Denitrogenation, hydrogenation deoxidation, HDM, hydrogenation aromatics-removing, hydroisomerization, Hydrodewaxing and include selective hydrogenation cracking It is hydrocracked.
" isomerization " refers to that its paraffin is converted at least partly into its isomer containing more multiple-limb or phase counter-example As normal paraffin hydrocarbons changes into the catalysis process of isoparaffin.Described isomerization is generally carried out by catalytic pathway.
" loaded catalyst " refers to that the active component of the most such as VIII and group vib metal or its compound is deposited on Supported catalyst.
" self-supported catalyst " can exchange with " unsupported catalyst " or " body catalyst " and use, and refers to do not have The carbon monoxide-olefin polymeric of conventional catalyst form, described conventional catalyst form has prefabricated preformed catalyst carrier, subsequently Via dipping or deposition to carrier to load metal compound.In one embodiment, described self-supported catalyst via Precipitation is formed.In another embodiment, described self-supported catalyst has the bonding being incorporated in described carbon monoxide-olefin polymeric Agent.In yet another embodiment, described self-supported catalyst is by metallic compound and in the case of not having any binding agent Formed.
In one embodiment, " catalyst precarsor " refers to the compound containing following material: selected from Group IIA, IIB Race, IVA race, group VIII metal and combinations thereof (such as, one or more Group IIA metal, one or more Group IIB metal, one or more IVA race metal, one or more group VIII metal and combinations thereof) at least one metal；At least one group vib metal；Optionally One or more organic oxygen-containing accelerator, and this compound can directly use (as catalyst) after renewable raw materials is upgraded Maybe can vulcanize so that the hydrotreating catalyst as sulfuration uses.
" Group IIA " or " Group IIA metal " refers to the beryllium of any one (Be) in element, compound or ionic species, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra) and combinations thereof.
" Group IIB " or " Group IIB metal " refers to the zinc of any one (Zn) in element, compound or ionic species, cadmium (Cd), hydrargyrum (Hg) and combinations thereof.
" IVA race " or " IVA race metal " refers to the germanium of any one (Ge) in element, compound or ionic species, stannum Or lead (Pb) and combinations thereof (Sn).
" group vib " or " group vib metal " refers to the chromium of any one (Cr) in element, compound or ionic species, molybdenum (Mo), tungsten (W) and combinations thereof.
" VIII " or " group VIII metal " refer to the ferrum of any one (Fe) in element, compound or ionic species, Cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Ro), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt) and combinations thereof.
The periodic table of elements refer to chemistry and medical science CRC handbook in the version published by CRC Press, the 88th edition (2007-2008).The name of the element family in periodic chart is given with Chemical Abstracts Service (CAS) notation at this.
" conversion ratio " refers to triglyceride amount in the charging of the compound changed in addition to triglyceride.Conversion ratio It is expressed as based on the percetage by weight of triglyceride meter in charging." selectivity " is expressed as based on the triglyceride meter converted Percentage by weight.
" noble metal " refers to the metal selected from ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.
" accelerator " refer to strongly to interact with inorganic reagent in the reaction (chemically or physically) with formed catalyst or Catalyst precarsor, causes structure, configuration of surface and composition to change, and produces again the organic reagent of the catalysis activity strengthened.
Such as H is there is in " presulfurization " or " presulfurization " before referring to contact with raw material in escalation process2S or diformazan The sulfuration of catalyst precarsor under conditions of vulcanization under the vulcanizing agent of base sulfur (DMDS).
Raw material:Raw material is substantially made up of renewable raw materials (more than 99 weight %), and in one embodiment, it has Less than the petroleum feeding of 1 weight %, in this second embodiment, it has the petroleum feeding less than 2 weight %, and real the 3rd Executing in scheme, it has the petroleum feeding less than 5 weight %.In another embodiment, described raw material be renewable source with The mixture of petroleum feeding, wherein petroleum is up to 50 weight %.In one embodiment, the amount of petroleum is 1-99 Weight %, remainder is renewable raw materials；In this second embodiment, the amount of petroleum is 10-90 weight %, and In three embodiments, the amount of petroleum is 20-80 weight %.In another embodiment, described raw material be purely can be again Raw feedstock (it is only made up of renewable raw materials), does not comprise petroleum feeding.
Spendable described renewable raw materials includes any one in those raw materials comprising triglyceride.Described raw material leads to Often derive from the biomass sources selected from crops, plant, microalgae, Animal fat and combinations thereof.Described raw material generally comprises at least The triglyceride (such as, at least 50 weight %, 75 weight %, 90 weight % or the triglyceride of 95 weight %) of 25 weight %. Generally, any biogenetic derivation of lipid all may act as can by its obtain described raw material biomass.Exemplary raw material include but not It is limited to low erucic acid rapeseed oil, Oleum Cocois, Petiolus Trachycarpi oil, palm-kernel oil, Oleum Arachidis hypogaeae semen, Oleum Brassicae campestris, soybean oil etc..
Reaction path:In the conversion of the renewable raw materials of such as triglyceride, in one embodiment, reaction path As shown in FIG. 1, various product, such as long chain n-paraffins (jet and diesel range material), Long-chain primary alcohols are wherein formed And fatty acid.According to reaction condition, also can form ester, as Long-chain primary alcohols and the product of fatty acids products.
In one embodiment, the present invention relates to customize described reaction condition to optimize such as alkane, alcohol and/or ester The formation (that is, maximize) of concrete product, use with selected from there is steric configuration, there is hydroxyl-(the two)-carboxylic of following structure The hydrotreating catalyst that the accelerator of acid promotes:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, aromatics, alcohol, branch or not The alkyl of branch, wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0." hydroxyl-(two)-carboxylic acid " refers to hydroxyl Yl carboxylic acid or hydroxydicarboxylic acid.Example includes but not limited to (R, S)-malic acid HOOC-CH2-CHOH-COOH or maleic acid HOOC-CH=CH-COOH.In one embodiment, described accelerator is with group vib metal and at least another metal such as VIII The amount of at least 0.05 mol times of the total mole number of race's metal exists.In one embodiment, described accelerator is with metal Total mole number 0.05-about 1000 mol times amount exist.
Form being formed of alkane (hydrocarbon of jet/diesel range) about by triglyceride, there are three kinds of basic reactions Approach:
Hydrogenation decarboxylation:
(RCOO)3C3H5+3H2→3RH+C3H8+3CO2 (A)
Hydrogenation decarbonylation base:
(RCOO)3C3H5+6H2→3RH+C3H8+3CO+3H2O (B)
Hydrogenation deoxidation:
(RCOO)3C3H5+12H2→3RCH3+C3H8+6H2O. (C)
As indicated, hydrogen consumption changes according to differential responses approach.Along with hydrotreating harsh carry out, i.e. from hydrogenation decarboxylation Hydrogenated decarbonylation base increases to hydrogenation deoxidation, hydrogen consumption.The invention still further relates to the economy customizing reaction condition to optimize hydrogen consumption.
Catalyst-self-supported the catalyst promoted:In one embodiment, for described in renewable raw materials upgrading Catalyst is the self-supported catalyst of the promotion derived from catalyst precarsor.Described catalyst precarsor can be by least one Group vib metal precursor feeds the hydroxide with at least another metal precursor feed preparation or oxide material.Described the most another One metal precursor can be with MPExchange and use, refer to that the activity strengthening catalyst is (with the catalyst phase not having this at least another metal Relatively, such as compared with the catalyst only with group vib metal) material, wherein accelerator is with group vib metal and the most another The amount of at least 0.05-about 5 mol times of the total mole number of one metal such as group VIII metal exists.An embodiment In, described accelerator exists with up to 1000 mol times of the total mole number of described metal.
Obtained self-supported or unsupported catalyst precursor can change into hydrogenation conversion catalyst when sulfuration and (become Must have catalysis activity).But, described self-supported catalyst precarsor itself is used in the conversion of renewable raw materials (as urging Agent), or it can vulcanize or the most In-situ sulphiding under there is vulcanizing agent before the use.An embodiment In, described self-supported catalyst precarsor uses in the case of unvulcanized, is being with or without vulcanizing agent (such as, H2S) to instead Use in the case of answering any interpolation of device system or intrinsic for charging, even for basic by recyclable materials form former The hydro-conversion of material (there is not any sulfur in charging as vulcanizing agent).
In one embodiment, it is possible to use self-supported poly-metal deoxide.Described self-supported multi-metal oxygen Thing comprises at least one group VIII metal and at least two group vib metal.In one embodiment, VIB in described precursor Race's metal is about 10:1-about 1:10 with the ratio of group VIII metal.In another embodiment, described oxide catalyst precursor By formula: (X)b(Mo)c(W)dOfRepresent, wherein X is Ni or Co, and Mo is molybdenum, and W is tungsten, b:(c+d) mol ratio be 0.5:1-3:1 (such as, 0.75:1-1.5:1, or 0.75:1-1.25:1), the mol ratio of c:d > 0.01:1 is (such as, more than 0.1:1,1:10- 10:1, or 1:3-3:1), and f=[2b+6 (c+d)]/2.Described oxide catalyst precursor also comprises one or more accelerator L. In one embodiment, described self-supported catalyst precarsor has formula (NiL)x(MoyW1-y)O(x+3), wherein L refer to one or Multiple accelerator；And wherein x:(1-y) it is 1.7-2.4；And y is 0.25-0.67.Described oxide precursor is by combination group vib Metal and group VIII metal, form product, calcines its product formed subsequently and produces.
In another embodiment, described catalyst precarsor is to comprise at least one group VIII metal and at least two VIB The form of the hydroxide compound of race's metal.In one embodiment, described hydroxide catalyst precursor is by formula: Av [(MP)(OH)x(L)n y]z(MVIBO4) represent, wherein A is one or more univalent cation material；MPAccording to the metal used There are+2 or+4 oxidation state (P)；L is one or more oxygen containing accelerator, and L has neutrality or negative charge n≤0；MVIBFor having At least one group vib metal of the oxidation state of+6；MP:MVIBThere is the atomic ratio between 100:1 and 1:100；v-2+P*z-x* Z+n*y*z=0；And 0 < v≤2；0<x≤P；0<y≤-P/n；0<z.In one embodiment, described catalyst precarsor is not Electroneutral with clean plus or minus electric charge.
In one embodiment, A is selected from alkali metal cation, ammonium cation, organoammonium cations and phosphorus cation.
In one embodiment, MPThere is the oxidation state of+2 or+4.MPFor Group IIA metal, Group IIB metal, IVA race gold At least one in genus, group VIII metal and combinations thereof.In one embodiment, MPFor at least one group VIII metal, its Middle MPThere is oxidation state P of+2.In another embodiment, MPSelected from Group IIB metal, IVA race metal and combinations thereof.At one In embodiment, MPSelected from the Group IIB metal of their element, compound or ionic species and Group VIA metal, such as zinc, Cadmium, hydrargyrum, germanium, stannum or lead and combinations thereof.In another embodiment, MPFor the Group IIA gold selected from magnesium, calcium, strontium and barium compound Belong to compound.MPCan be in the solution or partly with solid-state, such as water soluble compound, such as carbonate, hydroxide, rich horse Their mixture of hydrochlorate, phosphate, phosphite, sulfide, molybdate, tungstates, oxide.
In one embodiment, described accelerator L has neutrality or negative charge n≤0.The example of accelerator L include but It is not limited to carboxylate, carboxylic acid, aldehyde, ketone, the enolate-forms of aldehyde, the enolate-forms of ketone and hemiacetal；Organic acid addition Salt, such as formic acid, acetic acid, propanoic acid, maleic acid, malic acid, cluconic acid, fumaric acid, succinic acid, tartaric acid, citric acid, second Diacid, glyoxalic acid, aspartic acid, alkane sulfonic acid such as methanesulfonic acid and ethyl sulfonic acid, aryl sulfonic acid such as benzenesulfonic acid and p-methyl benzenesulfonic acid And aryl carboxylic acid；The compound of carboxylate-containing, such as maleic anhydride, formates, acetate, propionate, butyrate, valerate, Caproate, dicarboxylate, and combinations thereof.
In one embodiment, MVIBAt least one group vib metal of oxidation state for having+6.Another embodiment party In case, MVIBMixture at least two group vib metal such as molybdenum and tungsten.MVIBCan be in the solution or partly with solid-state.One In individual embodiment, MP:MVIBThere is the mol ratio of 10:1-1:10.
In one embodiment, described self-supported catalyst is by hybrid metal sulfide (" MMS ") catalyst precarsor Preparation, it is characterised in that it has the Ni:Mo:W composition of optimization, and wherein the mol ratio of Ni/W is 1.62≤Ni/W≤2.5, W/Mo Mol ratio in the range of 0.5≤W/Mo≤6.0, and the mol ratio of Ni/ (Mo+W) is at 0.57 < Ni/ (Mo+W) < in the range of 2.1. In another embodiment, described MMS catalyst precarsor comprises the group having being limited by four some ABCD in ternary phase diagrams Proportional amount of nickel, molybdenum and tungsten in the range of one-tenth, wherein the molar fraction of these 4 ABCD is by defined below: A (Nix=0.36, Mox=0.41, Wx=0.22)；B(Niy=0.45, Moy=0.36, Wy=0.18)；C(Niz=0.58, Moz=0.06, Wz= 0.36) and D (Niw=0.68, Mow=0.05, Ww=0.27).Described MMS catalyst precarsor can be in presulfurization or not presulfurization In the case of or in the case of being with or without any vulcanizing agent that is existing or that be added in raw material, be directly used in renewable raw materials Upgrading.
About the more details of catalyst precarsor and the description of the self-supported catalyst of formation thereof in many patents and specially Described in profit application, these patents and patent applicationss include United States Patent (USP) 6,156, No. 695,6,162, No. 350,6,274,530 Number, No. 6,299,760, No. 6,566,296, No. 6,620,313, No. 6,635,599, No. 6,652,738, No. 6,758,963,6, No. 783,663, No. 6,860,987, No. 7,179,366, No. 7,229,548, No. 7,232,515, No. 7,288,182,7,544, No. 285, No. 7,615,196, No. 7,803,735, No. 7,807,599, No. 7,816,298, No. 7,838,696,7,910,761 Number, No. 7,931,799, No. 7,964,524, No. 7,964,525, No. 7,964,526, No. 8,058,203 and U.S. Patent application Announce No. 2007/0090024, No. 2009/0107886, No. 2009/0107883, No. 2009/0107889 and 2009/0111683 Number, relevant disclosure is included herein by reference.
Manufacture the embodiment of method of self-supported catalyst precarsor as described at list of references indicated above and It is incorporated herein by reference.In one embodiment, described first step is blend step, wherein by least one The charging of group vib metal precursor and at least one another metal precursor feed in settling step (also referred to as cogelledization or co-precipitation) In combine, wherein catalyst precarsor is as gel formation.This precipitation (or " cogelledization ") is at group vib metallic compound At least another metallic compound is carried out at the temperature and pH of its lower precipitation (such as, forming gel).An embodiment In, described temperature is 25 DEG C-350 DEG C and described pressure is 0-3000psig (0-20.7MPa gauge pressure).Described reactant mixture It is (cogelled that pH can be increased or decreased settling velocity according to the desired characteristics of the catalyst precarsor product of such as acidic catalyst precursor Change).In one embodiment, described mixture keeps being under its natural pH during reactions steps.An embodiment party In case, describedpH maintains in the range of 3-9；And in this second embodiment, described pH maintains in the range of 5-8.
Catalyst-self-supported the catalyst promoted:In another embodiment, described hydrotreating catalyst is selected from suitable Close the loaded catalyst of the hydro-conversion of renewable raw materials.Described catalyst comprises at least one gold selected from group VIII metal Belong to component and/or at least one metal component selected from group vib metal.Group VIII metal includes ferrum (Fe), cobalt (Co) and nickel (Ni).Such as the noble metal of palladium (Pd) and/or platinum (Pt) may be included in described hydrotreating catalyst.Group vib metal includes Chromium (Cr), molybdenum (Mo) and tungsten (W).Group VIII metal can be with 0.5-25 weight % (such as, 2-20 weight %, 3-10 weight %, 5- 10 weight % or 5-8 weight %) amount be present in described catalyst and group vib metal can be with 0.5-25 weight % (such as 5- 20 weight % or 10-15 weight %) amount be present in described catalyst, this tittle is by every 100 parts by weight of total catalyst Metallic compound calculates, wherein percetage by weight weight based on the procatalyst in sulfuration meter.In one embodiment, exist The total weight percent of the metal used in described hydrotreating catalyst is at least 5 weight %.The remainder of described catalyst Divide and can be made up of supported materials, although optionally can there are other components (such as, filler, molecular sieve etc., or a combination thereof).
Metal component in described loaded catalyst can be with oxide and/or sulphided form.If at least one The combination of group VIII metal component and group vib metal component exists as (mixing) oxide, then suitable in hydrotreating It can be carried out presulfurization process before use.Suitably, described catalyst generally comprises one or more component of Ni and/or Co One or more component with Mo and/or W.But, described supported catalyst precursor can be with or without to reactor assembly Any vulcanizing agent (such as, H2S) add in the case of or in the case of being with or without the vulcanizing agent that charging is intrinsic individually Convert renewable raw materials (unvulcanized or as catalyst), or it can presulfurization before use or in the reactor or in charging In exist under vulcanizing agent In-situ sulphiding.
Described loaded catalyst can be prepared with binding agent by being blended or be co-mulled and made into the activated source of above-mentioned metal.Bonding The example of agent includes silicon oxide, carborundum, amorphous and crystalline silica-aluminium oxide, silica-magnesias, aluminum phosphate, oxygen Change boron, titanium oxide, zirconium oxide etc. and its mixture and cogelled.Preferably carrier include silicon oxide, aluminium oxide, aluminium oxide- Silicon oxide and crystalline silica-aluminium oxide, particularly classify as those materials of clay or zeolitic material.Particularly preferred load Body material includes aluminium oxide, silicon oxide and aluminium oxide-silicon oxide, particularly aluminium oxide or silicon oxide.Other components of such as phosphorus Can add as desired with for wanted applied customization catalyst particle.The component being blended therefore can be such as by extruding, doing Dry and at a temperature of up to 1200 (649 DEG C) calcining come molding to manufacture finished catalyst.Or, prepare described amorphous The additive method of catalyst include such as by extrusion, be dried and calcining prepare oxide adhesive particle, be then used by such as The method of dipping deposits above-mentioned metal on oxide particle.Loaded catalyst containing above-mentioned metal therefore can be as adding Hydrogen processes before catalyst uses and is further dried and calcines.
In one embodiment, described loaded catalyst is to prepare as disclosed in US20090298677A1 Hydrotreating catalyst, relevant disclosure is incorporated herein by reference, and it comprises at least one element by deposition The group vib metal of periodic chart and the compositions of at least one group VIII metal, the most phosphorous acidic components and at least one rush Enter agent to the supporting body with water voids volume, deposit to have on the supporting body of water voids volume, and subsequently more than 200 DEG C and prepare less than calcining the supporting body of dipping at a temperature of the decomposition temperature of this accelerator.In one embodiment, institute State group vib metal selected from molybdenum Mo and tungsten W.Described group VIII metal is selected from cobalt Co and nickel.Described accelerator with described group vib and The amount of the 0.05-of the total mole number of group VIII metal about 5 mol times exists.In one embodiment, described VIII gold Belong to the mol ratio with described group vib metal and be about 0.05-about 0.75.
In one embodiment, described accelerator selected from hydroxy carboxylic acid, ethylene glycol, glycerol, ethanolamine, Polyethylene Glycol, Hydroquinone, ethylenediamine, ethylenediamino tetraacetic acid, cysteine, alanine, methionine, gluconic acid, pyridine-2,3-dicarboxylic acids, thiophene- 2-carboxylic acid, mercapto succinic acid, nicotinic acid, breast SA-1,3-dicarboxylic acids.In another embodiment, described accelerator is selected from Hydroxy carboxylic acid, such as tartaric acid, malic acid, glyceric acid, citric acid and gluconic acid.In yet another embodiment, described accelerator For citric acid.
In one embodiment, described loaded catalyst have 1-10nm (such as, 5-10nm) average pore size and 20-400m2/ g (such as, 100-300m2/ g) surface area.
Reactor assembly:Hydrotreating method for described renewable raw materials of upgrading can be single-stage or multistage reactor system System.In one embodiment, described method utilizes single level system.Described reactor assembly can be any type of reactor.? In one embodiment, described raw material is processed in fixed bed reactors.In one embodiment, unreacted glycerol can be made Three esters are recycled to the reactor of described single-stage reactor system (only having a reactor) or in described multistage reactor system To be processed further so that the maximum production of desired product in one of reactor of system (there is multiple reactor).
In one embodiment, described reactor assembly includes the different reactor string using identical or different catalyst At least two reactor of connection.In another embodiment, described reactor includes having the single of at least two catalyst zone Reactor, wherein said different catalysts district uses identical or different catalyst.In the 3rd embodiment, described system is Single reactor containing single catalyst type, self-supported catalyst or loaded catalyst.
In using an embodiment of reactor assembly of different catalysts, described different catalysts is at stratiform or heap Folded bed reactor system uses." stratiform " or " stacked bed " refers to that the first catalyst is at single catalyst layer, bed, reactor Or occur in reaction zone, and the second catalyst is about the independent catalyst in the downstream of described first catalyst that flows of charging Layer, bed, reactor or reaction zone occur.In an embodiment of stacked bed system, described system comprises about 5-95 body Described first catalyst of long-pending %, described second catalyst constitutes remainder.In this second embodiment, described first catalysis The volume ratio of agent is about 30-60 volume %.In the 3rd embodiment, the volume ratio of described first catalyst is 5-about 50 body Long-pending %.In an embodiment of stacked bed system, described first catalyst is loaded catalyst, and described second catalysis Agent is self-supported catalyst.
Hydroprocessing condition:May select described hydroprocessing condition so that the total of triglyceride converts in described raw material Rate is at least 20 weight % (such as, at least 50 weight %, 60 weight %, 70 weight %, 80 weight %, 90 weight % or 95 weights Amount %).Suitably hydroprocessing condition can include 302-752 (150 DEG C-400 DEG C), such as 383-464 (195 DEG C- 240 DEG C), 491-662 (255 DEG C-350 DEG C) or the temperature of 491-563 (255 DEG C-295 DEG C)；50-3000psig (0.35-20.7MPa gauge pressure), such as 800-2000psig (5.5-13.8MPa gauge pressure) or 1600-2000psig (11.0- 13.8MPa gauge pressure) total reaction pressure；0.1-5h-1, such as 0.5-2h-1Liquid hourly space velocity (LHSV) (LHSV)；And 0.1-20MSCF/ Bbl (MSCF/bucket), the hydrogen gas feed rate of such as 1-10MSCF/bbl.It should be noted that the charging of 10MSCF/bbl Speed is equivalent to 1781L H2/ L feeds.
In one embodiment, described hydroprocessing condition includes reaction temperature and the 50-of at least 446 (230 DEG C) The reaction pressure of 3000psig (0.35-20.7MPa gauge pressure), thus described liquid effluent has the normal chain of at least 90 weight % Alkane concentration.In another embodiment, described hydroprocessing condition includes the reaction of 302-554 (150 DEG C-290 DEG C) Temperature and the total reaction pressure of 50-3000psig (0.35-20.7MPa gauge pressure), thus described liquid effluent has at least 5 weights The fatty alcohol concentration of amount %.In another 3rd embodiment, described hydroprocessing condition include 302-554 (150 DEG C- 290 DEG C) temperature and the total reaction pressure of 50-3000psig (0.35-20.7MPa gauge pressure), thus described liquid effluent tool There is the aliphatic mono concentration of at least 5 weight %.
Except reaction condition being customized/optimizes so that reaction path optionally occurs, produces desired product in addition to, urge The type of agent is elected single variable as or is incorporated into reaction condition selection.The self-supported catalyst promoted is than promotion Loaded catalyst has more activity.There is two kinds of different catalysts types, the self-supported catalyst i.e. promoted and promotion Loaded catalyst combination layered catalyst system an embodiment in, the self-supported catalyst of promotion and rush The volume ratio of the loaded catalyst entered changes according to desired product.Such as, in hydrogenation decarboxylation/hydrogenation de-carbonyl reaction, Compared with the loaded catalyst promoted, select the self-supported catalyst promoted more, wherein with reaction path (C) phase Ratio, the self-supported catalyst of promotion is more beneficial for reaction path (A) and (B), and it consumes or needs less hydrogen.
Hydrogenation decarboxylation:
(RCOO)3C3H5+3H2→3RH+C3H8+3CO2 (A)
Hydrogenation decarbonylation base:
(RCOO)3C3H5+6H2→3RH+C3H8+3CO+3H2O (B)
Hydrogenation deoxidation:
(RCOO)3C3H5+12H2→3RCH3+C3H8+6H2O (C)。
In using an embodiment of self-supported antigravity system of described promotion, even for single reactor System, also obtains the triglyceride conversion ratio more than 90%.Even if it addition, using unvulcanized rush in single reactor assembly The catalyst precarsor that enters and not in the case of any vulcanizing agent of interpolation of described reactor assembly, also obtains more than 90% Conversion ratio.
Temperature of reactor is optionally to affect reaction path and therefore affect another variable of end product.Reactor temperature Spend the highest (such as, 500 or higher), be more conducive to reaction path (A) and (B).Comprising the raw material of triglyceride, such as Main by C18Fatty acid and C16It is during upgrading that the soybean oil of fatty acid composition feeds, and higher temperature of reactor causes via instead Answer approach (A) and (B) to be formed and compare n-C18Alkane (and n-C16Alkane) how n-C17Alkane (and n-C15Alkane), its In its dependent variable keep constant, temperature of reactor often increases by 50 (such as, increasing to 550 from 500) and causes n-C17Alkane Hydrocarbon increase at least 10%.On the contrary, relatively low temperature of reactor is conducive to the C=O bond fission in triglyceride, produce more N-C18(and n-C16) paraffin product.In 550 or higher temperature of reactor and the overall reaction pressure of 1000psig or lower Under power, formed and compare n-C18The n-C that alkane is many17Alkane.
Another variable of the formation optionally affecting end product is total reaction pressure, such as, again for mainly by C18Fatty acid and C16The soybean oil charging of fatty acid composition, relatively low total reaction pressure is conducive to reaction path (A) and (B), draws Play formation and compare n-C18Alkane (and n-C16Alkane) how n-C17Alkane (and n-C15Alkane), with 1500psi or higher Total reaction pressure compare, its dependent variable keep constant, the total reaction pressure of 1000psi or lower causes n-C17Alkane increases Add at least 10%.
Main by C such as using18Fatty acid and C16The soybean oil charging of fatty acid composition forms Major long chain normal paraffin hydrocarbons Optimization system in, described reaction temperature is at least 450, thus triglyceride conversion ratio is at least 85% (that is, unconverted Triglyceride is less than 15%)；In one embodiment, described reaction temperature is at least 500 (260 DEG C), thus glycerol three Ester conversion rate is at least 90%；In this second embodiment, triglyceride conversion ratio is at least 95%, and in the 3rd embodiment In, triglyceride conversion ratio is at least 99%.
As indicated, scalable reaction temperature with adapt to such as can H2The facility process conditions of charging.Forming long-chain In the reaction path of normal paraffin hydrocarbons, the H that the reaction of described hydrogenation deoxidation consumes2Amount is for being hydrogenated with the H required for decarboxylic reaction2Amount Four times.The H available in order to adapt to described reaction2The minimizing of raw material, still obtains desired jet/diesel oil simultaneously and finally produces Thing, in one embodiment, maintains described reaction temperature at a temperature of at least 550, and in this second embodiment, Described reaction temperature is maintained at a temperature of at least 600.In yet another embodiment and except the increase of temperature of reactor Outside, for excellent conversion yield and optimization jet/diesel product (such as, effluent comprising normal paraffin hydrocarbons of at least 90% Product) the combination of production, total reaction pressure is maintained under 1200psi or lower pressure.
In one embodiment, for the H of optimization and upgrading system2Consume and/or utilization rate, the most still obtain and wanted The distribution of jet/diesel oil end product, described hydroprocessing condition can in the following manner in any one regulation: increase at least The temperature of reactor of 50, the reaction pressure reducing at least 500psi and combinations thereof, so that the available H of described method2For Described system reduces 10% every time, minimal amount of H2For the mol ratio of triglyceride in the feed at least 4 times.Temperature of reactor Often increase at least 50 or total reaction pressure be often reduced at least 100psi and cause hydrogen in the process in one embodiment Depletion the most at least 10SCF/ bucket raw material and in this second embodiment hydrogen consumption at least reduce at least 20SCF/ bucket raw material.
As shown in FIG. 1, in reactor assembly, for renewable raw materials, (such as, wherein most fatty acid is sweet Oil three esters vegetable oil) conversion can there is multiple reaction path: a) triglyceride changes into normal paraffin hydrocarbons；B) triglyceride turns Chemical conversion compound fat acid (it gathers described triglyceride)；C) manufacturing fatty alcohol, described fatty acid has and these in the molecule The carbon number that fatty acid is identical；And d) manufacture ester via the ester exchange of gained alcohol with fatty acid.All these reactions can be instead Answer in device system and occur simultaneously.
In one embodiment, at least one during the product liquid of described reaction comprises following thing: alkane, Alcohol, acid, ester (being formed by gained alcohol and acid), unconverted triglyceride (if any) and combinations thereof.Described composition depends on In selected catalyst and hydroprocessing condition.Under some reaction condition, such as such as 450 or lower relatively low temperature Under degree (it is less favorable for the formation of normal paraffin hydrocarbons), along with temperature reduces, compared with normal paraffin hydrocarbons, more triglyceride turns Chemical conversion alcohol and fatty acid, forms less normal paraffin hydrocarbons, as with main by C18Fatty acid and C16The soybean oil of fatty acid composition enters Material is illustrated.It addition, temperature is the lowest, along with the ester exchange of gained alcohol Yu fatty acid, form the most esters.On the contrary, it is warm Spend the highest, form more alcohol along with temperature increases by 50 (such as, increase to 450 from 400), cause the formation amount of alcohol to increase Add at least 10%.
As discussed, described hydroprocessing condition is selected from impact from desired product in the effluent of described reactor Any parameter of level subsequently.On the one hand, described hydrotreating parameter is a kind of following parameter: it obtains in described reaction mixing The productivity of the product in thing, increases the productivity of product, optimizes the selectivity of product in described reactor or it effectively converts in institute State the triglyceride in reactor.In one embodiment, described hydrotreating parameter is selected from temperature of reactor, overall reaction pressure Power and combinations thereof.
The product of liter order reaction:Effluent from described hydrotreating district will comprise liquid part and gaseous parts.Institute State effluent and can lead to one or more separator/dephlegmator to remove gas-phase product (such as, CO, CO2、H2O, methane and third Alkane) and separate from described liquid part one or more completely and/or part deoxidation product section (such as, normal paraffin hydrocarbons, Fatty alcohol and/or aliphatic mono).Different raw materials will produce the different carbon distribution of liquid product.In some embodiments, exist Remove after product gas, described liquid effluent at least partially can be with the adding of the different material from such as petroleum The liquid effluent combination that hydrogen processes.Additionally or for the election, after isolating lightweight end product, the product of recyclable recirculation Logistics is for use as the inlet flow of upgrading reactor assembly.
In one embodiment, described effluent is substantially made up of normal paraffin hydrocarbons.In some embodiments, described Effluent comprises the normal paraffin hydrocarbons (such as, the normal paraffin hydrocarbons of at least 80 weight %) of at least 75 weight %.In some embodiments In, described normal paraffin hydrocarbons has 8-24 carbon atom (such as, 12-18 carbon atom).It should be noted that described normal paraffin hydrocarbons can be used as Midbarrel fuel.But, described normal paraffin hydrocarbons can provide to the isomerization subsequently of isoparaffin has such as freezing point and pour point The product of wider range of cryogenic properties of improvement so that described method is more general and more flexible.
In another embodiment, described liquid product comprises fatty alcohol, aliphatic mono and normal paraffin hydrocarbons.Implement at another In scheme, described product is fatty alcohol, aliphatic mono or a combination thereof.
In some embodiments, described effluent comprises fatty alcohol fractions.In one embodiment, described fatty alcohol There is 8-24 carbon atom, and in this second embodiment, described fatty alcohol has 8-18 carbon atom.In some embodiments In, described effluent comprises the fatty alcohol (such as, the fatty alcohol of at least 10 weight %) of at least 5 weight %.Some embodiment party In case, described effluent has the fatty alcohol of at least 10 weight % (such as, at least 15 weight %, 20 weight % or 25 weight %) Selectivity.
In some embodiments, described effluent comprises aliphatic mono part.In one embodiment, described aliphatic series Monoesters has 18-36 carbon atom.In some embodiments, described effluent comprises the aliphatic mono (example of at least 4 weight % As, at least 7 weight %, 10 weight % or 13 weight %).In some embodiments, described effluent has at least 10 weights The aliphatic mono selectivity of amount % (such as, at least 12 weight %, 15 weight % or 18 weight %).
Product upgrading further:In one embodiment, as shown in FIG. 2, can be processed further by separating/returning The product that the hydrotreating of the renewable raw materials after receipts produces to produce various desired product, including PAO (poly alpha olefin) or Alpha-olefin (by making fatty alcohol product be dehydrated), lubricant and bright stock (oligomeric from PAO) and 3 race's lubricants are (from PAO Common oligomeric with some short-chain olefins).Described alcohol product can be processed to form drilling fluid, EOR (enhancing recovery of oil) surfactant Deng.
Product upgrading-isoversion further:In some embodiments, the normal paraffin as end product is being reclaimed After hydrocarbon, described upgrade method farther includes at least some isoversion making described normal paraffin hydrocarbons and comprises different chain to be formed The step of isomerization of paraffins product.In some embodiments, described isoversion step is relative to the chain of non-isomerization Alkane products produces superior fuel performance (such as, cloud point, pour point etc.).
In some embodiments, described isomerization steps uses isomerization catalyst to carry out.Suitable described isomerization Catalyst can include, but is not limited to Pt and/or Pd on carrier.Suitably carrier includes but not limited to zeolite CIT-1, IM- 5、SSZ-20、SSZ-23、SSZ-24、SSZ-25、SSZ-26、SSZ-31、SSZ-32、SSZ-32、SSZ-33、SSZ-35、SSZ- 36、SSZ-37、SSZ-41、SSZ-42、SSZ-43、SSZ-44、SSZ-46、SSZ-47、SSZ-48、SSZ-51、SSZ-56、SSZ- 57、SSZ-58、SSZ-59、SSZ-60、SSZ-61、SSZ-63、SSZ-64、SSZ-65、SSZ-67、SSZ-68、SSZ-69、SSZ- 70、SSZ-71、SSZ-74、SSZ-75、SSZ-76、SSZ-78、SSZ-81、SSZ-82、SSZ-83、SSZ-86、SUZ-4、TNU- 9, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, EMT-type zeolite, FAU-type zeolite, FER-type zeolite, MEL-type zeolite, MFI-type zeolite, MTT-type zeolite, MTW-type zeolite, MWW-type zeolite, TON-type zeolite, based on crystallization phosphorus Other molecular screen materials of acid aluminum, such as SM-3, SM-7, SAPO-11, SAPO-31, SAPO-41, MAPO-11 and MAPO-31. In some embodiments, described isomerization steps include being supported on selected from β or zeolite Y type of molecular sieve, silicon oxide, aluminium oxide, Pt and/or Pd catalyst on the acidic support material of silica-alumina and combinations thereof.Other suitable isomerization are urged Agent, see for example United States Patent (USP) 4,859, No. 312,5,158, No. 665 and 5,300, No. 210.
Isomerisation conditions can include 200-900 (93 DEG C-482 DEG C), such as 300-800 (149 DEG C-427 DEG C) Or the temperature of 400-800 (204 DEG C-427 DEG C)；15-3000psig (0.1-20.7MPa gauge pressure), such as 50-2500psig The total reaction pressure of (0.3-17.2MPa gauge pressure)；0.1-10h-1, such as 0.25-5h-1LHSV；With 0.1-30MSCF/bbl, The hydrogen treat rate of such as 0.2-20MSCF/bbl or 0.4-10MSCF/bbl.
About above-mentioned isoversion step, in some embodiments, method described herein can by make described just The fixing fixed bed (fixed stationary bed) of alkane and catalyst, fixed fluidized bed or transmission bed contact into OK.In one embodiment, use trickle bed operation, wherein make described charging typically deposit under hydrogen drip through solid Fixed fixed bed.For the explanation of the operation of described catalyst, see United States Patent (USP) 6,204, No. 426 and 6,723, No. 889, phase Pass disclosure is incorporated herein by reference.
In some embodiments, described isomerization product comprises at least 10 weight % isoparaffin (such as, at least 30 weights Amount %, 50 weight % or 70 weight % isoparaffins).In some embodiments, described isomerization product has at least 5:1 The isoparaffin of (such as, at least 10:1,15:1 or 20:1) and normal paraffin hydrocarbons mol ratio.
In some embodiments, described isomerization product have 250-1100 (121 DEG C-593 DEG C), such as 280 -572 (138 DEG C-300 DEG C) or the boiling range of 250-1000 (121 DEG C-538 DEG C).
In some embodiments, described isomerization product is suitable for (or being best suitable for) and is used as transport fuel.At some so Embodiment in, described isomerization product mixes with existing transport fuel or mixes to produce fresh fuel or improve existing fuel Character.Isomerization and blended can be used for regulate and maintain fuel or the pour point of other products and cloud point to be in suitably value.? In some embodiments, before carrying out catalytic hydrogenation, described normal paraffin hydrocarbons is blended with other materials.In some embodiments In, described normal paraffin hydrocarbons is blended with described isomerization product.
Product upgrading further-dehydration:In one embodiment, separating after described effluent, produce as The fatty alcohol of end-product, such as 1-hexanol and/or long-chain biological alcohol, including Cetyl OH etc..Described alcohol product is in dehydration conditions Lower dehydration, forms alpha-olefin product, such as biology-1-alkene, such as biology-1-hexene or biology-cetene.Can be by Thing-olefin product is processed further with prepared biological lubricants throughout one's life.
US20120238788A1 and US20110288352A1 discloses biological-ol is changed into alpha-olefin product Dewatering, relevant disclosure is incorporated herein by reference.In an embodiment of dewatering, by described Fatty alcohol exists under wanted catalyst and is adding at sufficient temp and optionally having in the case of at least one purges gas The heat sufficiently long time.In embodiments, described optional purging gas is nitrogen, argon or the mixing of both gas Thing.In one embodiment, described reaction condition includes atmospheric pressure, the temperature of 250-420 DEG C and 1-5h-1LHSV.? In embodiment, the heating-up temperature for described dehydration is about 300-420 DEG C or about 360-385 DEG C.
In one embodiment, described catalyst is activated alumina.In another embodiment, described catalyst is The equimolar of zinc oxide and aluminium oxide combines, and it has anticipated the time of 24-48 hour at a temperature of 800-1000 DEG C, Process with alkali subsequently, washing, air-dry and process with the chlorosilane in hydrocarbon solvent of 0.1-20 weight % subsequently.
In some embodiments, in dehydration before producing alpha-olefin product, can be by by the liter of renewable raw materials The fatty alcohol that level produces is blended with other fatty alcohol of the fatty alcohol of such as petroleum derivation or the fatty alcohol deriving from Fischer-Tropsch process.
Product upgrading further-oligomeric:In one embodiment, after described dehydration, produced α-alkene Hydrocarbon products can by oligomeric be processed further with formed optionally have other preferable higher oligomers a certain amount of dimer, The mixture of trimer, tetramer and pentamer.Subsequently can be by the hydrogenation of described oligomer product to improve their heat and antioxygen Change stability.In some embodiments, dehydration, oligomeric and hydrogenation each there is dehydration catalyst, oligomerisation catalyst respectively Carry out with under hydrogenation catalyst.In some embodiments, dehydration, oligomeric and hydrogenation can carry out in different reaction zones.? In some embodiment, dehydration, oligomeric and in hydrogenation two or more can be carried out in identical reaction zone.Convert described α- The oligomerization process of olefin product is disclosed in US20110288352A1, and relevant disclosure is incorporated herein by reference.
In an embodiment of oligomerization step, make the alpha-olefin product of above generation at such as sulfonate resin, solid-state At moderate temperature (such as, 100-300 in phosphoric acid or the heterogeneous acid catalyst of acid zeolite or any other suitable catalyst DEG C) and pressure (such as, 0-1000psig) under be reacted to form the co-oligomer of light olefin of gained alpha-olefin and such as butylene Blend.Can use heterogeneous or homogeneous oligomerisation catalyst, it is described in G.Busca, " Acid Catalysts in Industrial Hydrocarbon Chemistry " in Chem Rev2007 (107) 5366-5410.Other catalyst include Acid solid-phase catalyst, such as aluminium oxide and zeolite (see, e.g. United States Patent (USP) 3,997, No. 621,4,663, No. 406,4, No. 612,406, No. 4,864,068 and No. 5,962,604).In certain embodiments, acid resin catalyst can be used, all Such as Amberlyst-35 catalyst.
Described Oligomerization conditions can optimization as described herein to limit the light or generation of heavy constituent, this is such as by oligomeric step Rapid period suitably selecting catalyst, response time, temperature, pressure etc. simplify downstream fractionation step to meet ideal lubricant and light The real needs of gloss varnish product.It addition, can be more before further processing from the lighter of described oligomerization and/or heavier part Process (by such as distillation etc.) to provide the hydrogenated raw material of such as jet fuel blend raw material.For the election, lighter or heavier Part can separate after hydrogenation/hydrotreating.Can use various method with control gained oligomer molecular weight distribution, described Method includes primarily forming and includes that the dimer of isooctene (see for example United States Patent (USP) 6,689,927), trimer (see example As PCT Patent Application announces WO 2007/091862) and tetramer and pentamer (see for example United States Patent (USP) 6,239,321 Number) method, relevant disclosure is incorporated herein by reference.
Product is upgraded-is total to oligomeric further:In some cases, dehydration the rudimentary branch alkene produced may be little In desired alkene, such as C8 alkene.In one embodiment, less oligomer C4-C8 alkene can be from product mixtures Middle separation, is subsequently introduced oligomerization district with altogether the most oligomeric with other long-chain alpha-olefins, forms 3 race's lubricant product.Real at another Executing in scheme, gained long-chain alpha-olefin alkene can separate from product mixtures, be subsequently introduced oligomerization district with such as fourth Some light olefins of alkene are the most oligomeric, form 3 race's lubricant product.
Embodiment: following illustrative embodiment will be nonrestrictive.
Embodiment 1:The Semen sojae atricolor charging of the api gravity will with 21.6 (0.9223g/ml) is used as raw material.Soybean oil sweet Oil three esters are derived predominantly from five kinds of fatty acids and (see, e.g. D.Firestone, Physical and Chemical Characteristics of Oils, Fats, and Waxes, second edition, 2006, AOCS Press, 149).Table 1 discloses this The a little fatty acid representative scopes in soybean oil.
Table 1:
Fatty acid Carbon atom: double bond Weight %
Palmic acid 16:0 9.7-13.3
Stearic acid 18:0 3.0-5.4
Oleic acid 18:1 17.7-28.5
Linoleic acid 18:2 49.8-57.1
α-linoleic acid 18:3 5.5-9.5
Embodiment 2-8:By from embodiment 1 soybean oil feed under hydroprocessing conditions in single reactor at base In the promotion of Ni-Mo-W-maleic acid catalyst precarsor catalyst (according to the embodiment 1 of United States Patent (USP) 7,807,599) and With the upper test of the catalyst (according to the embodiment 6 of United States Patent (USP) 7,807,599) of the promotion of dimethyl disulfide gas cure.Reaction Device condition includes hydrogen gas rate and the 1.0h of 8.0MSCF/bbl-1LHSV.Other hydroprocessing conditions (temperature of reactor and pressure Power) list in table 2 and table 3.
The composition of overall product is measured by gas chromatogram (GC) and lists with weight % in table 2.As measured by GC, All liquid paraffinic hydrocarbon products are normal paraffin hydrocarbons, have the isoparaffin of the formation of negligible quantity.Methane and propane are substantially Only other Light hydrocarbon products.Water, carbon monoxide (CO) and carbon dioxide (CO2) it is from hydrogenation deoxidation, hydrogenation decarbonylation base And/or the by-product of hydrogenation decarboxylation.
Table 2:
Referring to embodiment, at a temperature of 1900psig and 500 and 550 at (embodiment 4 and embodiment 5) hydrogenation Reason, at 500 times C15/C16Normal paraffin hydrocarbons and C17/C18N-paraffin products weight ratio is all 0.35 (embodiment 4).550 Under (embodiment 5), C15/C16N-paraffin products weight ratio increases to 0.55, and C17/C18N-paraffin products weight ratio increases To 0.59.C15/C16And C17/C18N-paraffin products is pointed out under higher reaction temperatures than increase, relative to hydrogenation deoxidation (system Obtain C16And C18Normal paraffin hydrocarbons and water), this catalyst (prepares C to the Selective long-range DEPT of hydrogenation decarboxylation and/or hydrogenation decarbonylation base15 And C17Normal paraffin hydrocarbons and CO and CO2, additional H2O).Therefore, slightly higher (CO+CO is realized at relatively high temperatures2)/H2O product weight Amount ratio, and reflect, relative to hydrogenation deoxidation, the selectivity for hydrogenation decarboxylation and/or hydrogenation decarbonylation base is a certain degree of Strengthen.
Referring to the embodiment of hydrotreating under 1000psig, at the C of 500 times (embodiments 6)15/C16Normal paraffin hydrocarbons produces Thing weight ratio is 0.56, and C17/C18Normal paraffin hydrocarbons weight ratio is 0.59.At 550 times (embodiment 7), C15/C16Normal paraffin hydrocarbons Products weight ratio increases to 1.02, and C17/C18N-paraffin products weight ratio increases to 1.04.It addition, (implement at 650 times Example 8), C15/C16N-paraffin products weight ratio increases to 1.80, and C17/C18N-paraffin products weight ratio increases to 2.03. C15/C16And C17/C18N-paraffin products is pointed out under higher reaction temperatures than increase, (prepares C relative to hydrogenation deoxidation16With C18Normal paraffin hydrocarbons and water), this catalyst (prepares C to the Selective long-range DEPT of hydrogenation decarboxylation and/or hydrogenation decarbonylation base15And C17Just Alkane and CO and CO2, additional H2O).Therefore, slightly higher (CO+CO is realized at relatively high temperatures2)/H2O products weight ratio, And reflect, relative to hydrogenation deoxidation, for hydrogenation decarboxylation and/or the Selective long-range DEPT of hydrogenation decarbonylation base.
It addition, be respectively compared the result of embodiment 4 and 5 (carrying out under 1900psig) and embodiment 6 and 7 ( Carry out under 1000psig) result, for hydrogenation deoxidation, realize under relatively low reaction pressure for hydrogenation decarboxylation and/ Or the Selective long-range DEPT of hydrogenation decarbonylation base so that hydrogen consumption reduces further.
The conversion ratio of triglyceride and the selectivity of product of hydroprocessing operations are listed in Table 3.
Table 3:
Embodiment 9-12:From embodiment 1 soybean oil feed under hydroprocessing conditions under various temperature in single-stage Reactor kind such as in US20090298677A1 the hydrotreating catalyst of the promotion of disclosed preparation as from Chevron What Lummus Global buied has mean pore sizes and the about 180m of about 8nm2Alumina load type Ni-of the specific surface area of/g Test on Mo catalyst.Reactor condition includes the total reaction pressure of 1900psig (13.1MPa gauge pressure), 8.0MSCF/bbl Hydrogen gas rate and 1.0h–1LHSV.
The composition of overall product is measured by gas chromatogram (GC) and lists with weight % in table 4.As measured by GC, All liquid paraffinic hydrocarbon products are normal paraffin hydrocarbons, have the isoparaffin of the formation of negligible quantity.Methane and propane are substantially Only other hydrocarbon product.Water, carbon monoxide (CO) and carbon dioxide (CO2) be from hydrogenation deoxidation, hydrogenation decarbonylation base and/ Or the by-product of hydrogenation decarboxylation.
Table 4:
The conversion ratio of triglyceride and being listed in Table 5 by the selectivity of product of the hydroprocessing operations of loaded catalyst.
Table 5:
Embodiment 13-14:Soybean oil from embodiment 1 feeds to be used in advance under hydroprocessing conditions in single reactor The self-supported catalyst (as used by embodiment 2-8) of the promotion of sulfuration and the loaded catalyst of the promotion of presulfurization (as used by embodiment 9-12) 550,1000psig, 1.0h-1The H of LHSV and 8000scf/bbl charging2Speed anti- Test under the conditions of Ying.All triglyceride in this charging all convert and alkane is the sole component in liquid product.Table 6 Present the SimDis (simulation carried out by gas chromatogram is distilled) of the diesel product from the two embodiment.De-for hydrogenation Carboxylic-hydrogenation de-carbonyl reaction, the self-supported catalyst of promotion is than the loaded catalyst more selectivity of accelerator.
Table 6
Embodiment 15-16:Soybean oil from embodiment 1 feeds to be used in advance under hydroprocessing conditions in single reactor The self-supported catalyst (as in embodiment 2-8 used by) of the promotion of sulfuration but at 1000psig with 500psig Bu Tong always At temperature, the 0.5h including 600 under reaction pressure-1The H of LHSV and 8000SCF/bbl charging2Other reaction conditions of speed Lower test.All triglyceride in this charging all convert and alkane is the sole component in liquid product.Table 7 presents to come From the SimDis (simulation carried out by gas chromatogram is distilled) of the diesel product of the two embodiment.Relatively low pressure is more favourable In hydrogenation decarboxylation-hydrogenation de-carbonyl reaction.
Table 7
Embodiment 17-18:Soybean oil from embodiment 1 feeds to be used not under hydroprocessing conditions in single reactor Oneself of the self-supported catalyst precarsor (as in embodiment 2-8 used by, but unvulcanized) of the promotion of sulfuration and the promotion that vulcanizes Loaded catalyst (as used by embodiment 2-8), but include 550 temperature, the pressure of 1000psig, 1.0h- 1The H of LHSV and 8000SCF/bbl charging2Test under the same reaction conditions of speed.All triglyceride in this charging are all Convert and alkane is the sole component in liquid product.Table 8 presents the SimDis of the diesel product from the two embodiment (simulation carried out by gas chromatogram is distilled).The self-supported catalyst of the promotion of sulfuration is than unvulcanized pattern activity more Greatly.It is to be noted, however, that i.e. use the catalyst precarsor of unvulcanized promotion, reaction is also carried out.
Table 7
Embodiment 19:From embodiment 1 soybean oil feed hydroprocessing condition (500 or 550,1000psig, 1.0h-1The H of LHSV and 8000scf/bbl charging2Speed) under in single reactor with from Chevron Lumnus Noble metal amorphous catalyst under the trade name ICR-419 test of Global.It should be noted that noble metal catalyst seems Effect be there is no for hydrogenation decarboxylation and hydrogenation decarbonylation base, as respectively by 500 times 57 weight % with at 550 times 88 weights Shown by the low triglyceride conversion ratio of amount %, and wherein compared with the formation amount of fatty alcohol and ester, formed relatively little of just Alkane.
For the purpose of this specification and the appended claims book, unless otherwise indicated, otherwise it should be understood that all expressions Other numerical value used in the numeral of quantity, percent or ratio and this specification and the appended claims book are in all cases All modified by term " about ".Therefore, unless pointed out reverse situation, otherwise statement in description below and following claims Numerical parameter is all approximation, its desirable properties can probed into according to the present invention and change.It should be noted that such as this specification Used in following claims, singulative " " and " being somebody's turn to do " include multiple reference substance, unless explicitly and clearly limited It is made as a reference substance.As used herein, term " includes " and grammatical variants is tended to nonrestrictive so that list In every description will not get rid of other similar termses, described similar terms can replace or add in listed item.As herein Used in, term " comprises " element or step referring to determine below at this term, but any described element or step It not the most detailed, and an embodiment can include other elements or step.
Unless otherwise indicated, otherwise can from its select individual components or a dvielement of component mixture, material or other The description of component is intended to include all possible subclass combination of listed component and mixture thereof.
The scope patented of the present invention is defined by the claims, and can include that those skilled in the art can Other embodiments expected.If other embodiments this kind of have the structural elements of the word language being not different from claims Element, if or they include having the word language with claims and there is no an equivalent structural elements of essential difference, then this A little embodiments are intended in the range of claims.For the degree inconsistent with it, draw all of by reference herein With being incorporated herein.

Claims (54)

1. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, described catalyst is selected from self-supported catalyst, loaded catalyst and combinations thereof, and described catalyst comprises selected from molybdenum With at least one group vib metal of tungsten, selected from least one group VIII metal of cobalt and nickel, accelerator is selected from having steric configuration And there is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；With
Reclaim and comprise the described liquid effluent of at least one in normal paraffin hydrocarbons, fatty alcohol, aliphatic mono and combinations thereof,
Wherein said hydroprocessing condition selects essentially according to any one in following condition:
The reaction temperature of at least 230 DEG C, making triglyceride conversion ratio is at least 50%；
The reaction temperature of at least 230 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have to The normal paraffin hydrocarbons concentration of few 30 weight %；
The reaction temperature of 150 DEG C-290 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have The fatty alcohol concentration of at least 5 weight %；
The reaction temperature of 150 DEG C-290 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have The aliphatic mono concentration of at least 5 weight %.
2. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, and described catalyst comprises Selected from least one group vib metal of molybdenum and tungsten, group VIII metal selected from cobalt and nickel, accelerator is selected from having steric configuration And there is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；With
Reclaim the described liquid effluent of the normal paraffin hydrocarbons concentration with at least 30 weight %,
Wherein said hydroprocessing condition includes temperature and the total reaction pressure of 0.35-20.7MPa gauge pressure of 230 DEG C-400 DEG C.
3. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, and described catalyst comprises Selected from least one group vib metal of molybdenum and tungsten, group VIII metal selected from cobalt and nickel, accelerator selected from have steric configuration and There is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；With
Reclaim the described liquid effluent of the fatty alcohol concentration with at least 5 weight %,
Wherein said hydroprocessing condition includes temperature and the total reaction pressure of 0.35-20.7MPa gauge pressure of 150 DEG C-290 DEG C.
4. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, described catalyst bag Containing selected from least one group vib metal of molybdenum and tungsten, group VIII metal selected from cobalt and nickel, described catalyst has sky with being selected from Between configuration and have following structure material accelerator promote:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；With
Reclaim the described liquid effluent of the aliphatic mono concentration with at least 5 weight %,
Wherein said hydroprocessing condition includes temperature and the total reaction pressure of 0.35-20.7MPa gauge pressure of 150 DEG C-290 DEG C.
5. the method according to any one of claim 1-4, wherein said accelerator is total with described group vib and group VIII metal The amount of at least 0.05 mol times of molal quantity exists.
6. the method described in claim 5, wherein said accelerator is with the total mole number of described group vib and group VIII metal The amount of 0.05-1000 mol times exists.
7. the method according to any one of claim 1-4, wherein said raw material is made up of recyclable materials substantially.
8. the method described in claim 7, wherein said recyclable materials is based on vegetable oil and/or Animal fat.
9. the method according to any one of claim 1-4, wherein said raw material comprises the mixed of recyclable materials and petroleum Compound, wherein the amount of petroleum is 1-99 weight %, and remainder is recyclable materials.
10. the method described in claim 9, wherein said raw material comprises the mixture of recyclable materials and petroleum, wherein The amount of petroleum is 20-80 weight %, and remainder is recyclable materials.
Method according to any one of 11. claim 1-4, wherein said catalysis upgrading is carried out in single reactor assembly.
Method according to any one of 12. claim 1-4, wherein said catalysis upgrading uses identical or different rush including The reactor assembly of at least two reactor of the series connection of the catalyst entered is carried out.
Method according to any one of 13. claim 1-4, wherein said catalysis upgrading has containing self-supported catalyst Ground floor and containing loaded catalyst the second layer Layer reaction device system in carry out, the most self-supported catalyst with The volume ratio of loaded catalyst is 5:95-95:5.
Method according to any one of 14. claim 1-4, wherein said catalyst is former with described in the case of non-presulfurization Material contact.
Method according to any one of 15. claim 1-4, wherein said catalyst is pre-sulfur before contacting with described raw material Change.
Method according to any one of 16. claim 1-4, does not wherein add in described raw material or does not also exist any Described catalyst is made to contact with described raw material in the case of vulcanizing agent.
Method according to any one of 17. claim 1-4, wherein with the addition of or also exists the feelings of vulcanizing agent in described raw material Described catalyst is made to contact with described raw material under condition.
Method according to any one of 18. claim 1-4, wherein said catalyst is loaded catalyst.
Method according to any one of 19. claim 1-4, wherein said catalyst is loaded catalyst, and described VIII Race's metal is 0.05-0.75 with the mol ratio of described group vib metal.
Method according to any one of 20. claim 1-4, wherein said catalyst be have 1-10nm average pore size and 20-400m2The loaded catalyst of the surface area of/g.
Method according to any one of 21. claim 1-4, the catalyst of wherein said promotion is self-supported catalyst.
Method described in 22. claim 21, wherein said self-supported catalyst is the catalysis directly contacted with described raw material Agent precursor.
Method described in 23. claim 21, does not wherein add in described raw material or there is not any vulcanizing agent In the case of make described catalyst contact with described raw material.
Method described in 24. claim 21, makes institute in the case of wherein with the addition of in described raw material or there is vulcanizing agent State catalyst to contact with described raw material.
Method described in 25. claim 21, wherein said self-supported catalyst is catalyst precarsor, described catalyst precarsor By presulfurization before contacting described raw material.
Method described in 26. claim 21, the catalyst of wherein said promotion is derived from formula Av[(MP)(OH)x(L)n y]z (MVIBO4) self-supported catalyst precarsor, wherein:
A is selected from alkali metal cation, NH4 +, organoammonium cations and phosphorus cation；
MPFor at least one in Group IIA metal, Group IIB metal, IVA race metal, group VIII metal and combinations thereof, P is oxidation State, wherein MPAccording to MPSelection and there is the oxidation state of+2 or+4；
L is to have neutrality or the accelerator of negative charge n≤0；
MVIBAt least one group vib metal of oxidation state for having+6；
MP:MVIBThere is the atomic ratio between 100:1 and 1:100；
V-2+P*z-x*z+n*y*z=0；And
0<v≤2；0<x≤P；0<y≤-P/n；0<z.
Method described in 27. claim 21, wherein said self-supported catalyst vulcanizes derived from self-supported hybrid metal Thing catalyst precarsor, it has the Ni/W mol ratio of 1.62≤Ni/W≤2.5, the W/Mo in the range of 0.5≤W/Mo≤6.0 rubs You compare and in 0.57 < Ni/ (the Mo+W) < mol ratio of the Ni/ (Mo+W) in the range of 2.1.
Method described in 28. claim 21, wherein said self-supported catalyst is derived from having with by ternary phase diagrams The self-supported hybrid metal sulfuration of the mol ratio of proportional amount of nickel, molybdenum and tungsten in the compositing range of four some ABCD restrictions Thing catalyst precarsor, the molar fraction of wherein said four some ABCD is by defined below: A:Nix=0.36, Mox=0.41, Wx= 0.22；B:Niy=0.45, Moy=0.36, Wy=0.18；C:Niz=0.58, Moz=0.06, Wz=0.36；And D:Niw= 0.68,Mow=0.05, Ww=0.27.
Method described in 29. claim 2, wherein said hydroprocessing condition includes the temperature of at least 288 DEG C so that recovery Liquid effluent has the normal paraffin hydrocarbons concentration of at least 90 weight %.
Method described in 30. claim 2, wherein said hydroprocessing condition includes the total reaction pressure of 1200psi or lower, The liquid effluent reclaimed is made to have the normal paraffin hydrocarbons concentration of at least 90 weight %.
Method described in 31. claim 2, wherein said hydroprocessing condition include the temperature of at least 288 DEG C and 1200psi or Lower total reaction pressure so that the liquid effluent of recovery has and compares n-C18The n-C that alkane is many17Alkane.
Method according to any one of 32. claim 1-2, it also includes that at least some of catalysis making described normal paraffin hydrocarbons is different Structure is to form the isomerization product comprising isoparaffin.
33. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, and described catalyst comprises Selected from least one group vib metal of molybdenum and tungsten, group VIII metal selected from cobalt and nickel, accelerator selected from have steric configuration, There is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；Described hydroprocessing condition includes 230 DEG C-400 DEG C Temperature and the total reaction pressure of 0.35-20.7MPa gauge pressure so that triglyceride conversion ratio is at least 50 weight %；
Reclaim the described liquid effluent of the normal paraffin hydrocarbons concentration with at least 30 weight %, and
Make the isomerization product that at least some of isoversion of described normal paraffin hydrocarbons comprises isoparaffin with formation.
Method according to any one of 34. claim 1-2 and 33, wherein said normal paraffin hydrocarbons has 8-24 carbon atom.
Method described in 35. claim 33, wherein said isoversion step uses and comprises selected from Pt, Pd and combinations thereof The isomerization catalyst of metal.
Method described in 36. claim 33, wherein said isomerization product comprises the isoparaffin of at least 10 weight %.
Method described in 37. claim 33, wherein said isomerization product has isoparaffin and the normal paraffin hydrocarbons of at least 5:1 Mol ratio.
Method described in 38. claim 33, wherein said isomerization product has the boiling range of 121 DEG C-538 DEG C.
Method according to any one of 39. claim 1 and 3, it also includes making described fatty alcohol exist under dehydration conditions Be enough to be formed dehydration at a temperature of alpha-olefin product through the sufficiently long time under at least one catalyst.
40. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, the catalysis of described promotion Agent comprises at least one the group vib metal selected from molybdenum and tungsten, a kind of group VIII metal selected from cobalt and nickel, and accelerator is selected from having Steric configuration, there is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；Described hydroprocessing condition includes 150 DEG C-290 DEG C Temperature and the total reaction pressure of 0.35-20.7MPa gauge pressure so that triglyceride conversion ratio is at least 10 weight %；
Reclaim the described liquid effluent of the fatty alcohol concentration with at least 5 weight %；
Fatty alcohol product is reclaimed from described liquid effluent；With
Described fatty alcohol product is made to be enough to shape through the sufficiently long time under there is at least one catalyst under dehydration conditions Become and be dehydrated at a temperature of alpha-olefin product.
Method described in 41. claim 40, wherein said alpha-olefin product comprises biology-1-alkene.
Method described in 42. claim 40, wherein said catalyst is to use oxygenation pretreatment 1-at a temperature of 100-1000 DEG C 48 hours and the zinc oxide that processes with the chlorosilane in hydrocarbon solvent of 0.1-20 weight % subsequently and the equimolar group of aluminium oxide Close.
Method described in 43. claim 40, it was additionally included in described dehydration before generation alpha-olefin product by other Fatty alcohol is blended in described fatty alcohol product.
Method described in 44. claim 43, other fatty alcohol wherein said include petroleum derivation fatty alcohol, derivative at one's own expense- At least one in fatty alcohol of expelling pathogens by strengthening vital QI and combinations thereof.
45. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, and described catalyst comprises At least one group vib metal selected from molybdenum and tungsten, a kind of group VIII metal selected from cobalt and nickel, accelerator is selected from having space structure Type, there is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；Described hydroprocessing condition includes 150 DEG C-290 DEG C Temperature and the total reaction pressure of 0.35-20.7MPa gauge pressure so that triglyceride conversion ratio is at least 10 weight %；
Reclaim the described liquid effluent of the fatty alcohol concentration with at least 5 weight %；
Fatty alcohol product is reclaimed from described liquid effluent；
Described fatty alcohol product is made to be enough to shape through the sufficiently long time under there is at least one catalyst under dehydration conditions Become and be dehydrated at a temperature of alpha-olefin product；With
Make described alpha-olefin product on heterogeneous acid catalyst at a temperature of 100-300 DEG C and in the pressure of 0-1000psig The blend of oligomer it is reacted to form under power.
Method described in 46. claim 45, wherein said heterogeneous acid catalyst is selected from sulfonate resin, solid-state phosphoric acid, acid Property zeolite, ionic liquid and combinations thereof.
47. methods consumed at the catalysis optimization hydrogen during upgrading of the raw material comprising the recyclable materials being substantially made up of triglyceride, Described method includes:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, and described catalyst comprises At least one group vib metal selected from molybdenum and tungsten, a kind of group VIII metal selected from cobalt and nickel, accelerator is selected from having space structure Type, there is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；Described hydroprocessing condition includes 230 DEG C-400 DEG C Temperature of reactor and the total reaction pressure of 0.35-20.7MPa gauge pressure；With
Reclaim the described liquid effluent of the normal paraffin hydrocarbons concentration with at least 30 weight %,
Wherein said hydroprocessing condition is according to any one regulation in following condition: improve described temperature of reactor at least 50 , reduce described total reaction pressure at least 100psi and combinations thereof so that hydrogen consumption in the process reduces at least 10SCF/ Bucket raw material.
Method described in 48. claim 47, wherein temperature of reactor often improves at least 50 or described total reaction pressure and often drops Low at least 100psi causes the hydrogen consumption in described method to reduce at least 20SCF/ bucket raw material.
49. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, and described catalyst comprises Selected from least one group vib metal of molybdenum and tungsten, group VIII metal selected from cobalt and nickel, accelerator selected from have steric configuration, There is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；With
Reclaim and comprise the described liquid effluent of at least one in normal paraffin hydrocarbons, fatty alcohol, aliphatic mono and combinations thereof,
N-paraffin products is reclaimed from described liquid effluent；
Make the isomerization product that at least some of isoversion of described n-paraffin products comprises isoparaffin with formation；
Wherein said hydroprocessing condition selects essentially according to any one in following condition:
The reaction temperature of at least 230 DEG C so that triglyceride conversion ratio is at least 50 weight %；
The reaction temperature of at least 230 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure so that described liquid effluent has The normal paraffin hydrocarbons concentration of at least 30 weight %；
The reaction temperature of 150 DEG C-290 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have The fatty alcohol concentration of at least 5 weight %；
The reaction temperature of 150 DEG C-290 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have The aliphatic mono concentration of at least 5 weight %.
50. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, the catalyst of described promotion is selected from self-supported catalyst, loaded catalyst and combinations thereof, and described catalyst comprises Selected from least one group vib metal of molybdenum and tungsten, group VIII metal selected from cobalt and nickel, accelerator selected from have steric configuration, There is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；With
Reclaim and comprise the described liquid effluent of at least one in normal paraffin hydrocarbons, fatty alcohol, aliphatic mono and combinations thereof,
Fatty alcohol product is reclaimed from described liquid effluent；
Make described fatty alcohol under dehydration conditions exist under at least one catalyst through the sufficiently long time be enough to be formed α- It is dehydrated at a temperature of olefin product；
Wherein said hydroprocessing condition selects essentially according to any one in following condition:
The reaction temperature of at least 230 DEG C so that triglyceride conversion ratio is at least 50 weight %；
The reaction temperature of at least 230 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure so that described liquid effluent has The normal paraffin hydrocarbons concentration of at least 30 weight %；
The reaction temperature of 150 DEG C-290 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have The fatty alcohol concentration of at least 5 weight %；
The reaction temperature of 150 DEG C-290 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have The aliphatic mono concentration of at least 5 weight %.
51. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, described catalyst is selected from loaded catalyst of the self-supported catalyst of promotion, promotion and combinations thereof, described catalysis Agent comprises at least one the group vib metal selected from molybdenum and tungsten, group VIII metal selected from cobalt and nickel, and accelerator is selected from having space Configuration, there is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；With
Reclaim and comprise the described liquid effluent of at least one in normal paraffin hydrocarbons, fatty alcohol, aliphatic mono and combinations thereof,
Fatty alcohol product is reclaimed from described liquid effluent；
Described fatty alcohol product is made to be enough to shape through the sufficiently long time under there is at least one catalyst under dehydration conditions Become and be dehydrated at a temperature of alpha-olefin product；
Make described alpha-olefin product on heterogeneous acid catalyst at a temperature of 100-300 DEG C and in the pressure of 0-1000psig The blend of oligomer it is reacted to form under power；
Wherein said hydroprocessing condition selects essentially according to any one in following condition:
The reaction temperature of at least 230 DEG C so that triglyceride conversion ratio is at least 50 weight %；
The reaction temperature of at least 230 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure so that described liquid effluent has The normal paraffin hydrocarbons concentration of at least 30 weight %；
The reaction temperature of 150 DEG C-290 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have The fatty alcohol concentration of at least 5 weight %；
The reaction temperature of 150 DEG C-290 DEG C and the total reaction pressure of 0.35-20.7MPa gauge pressure, make described liquid effluent have The aliphatic mono concentration of at least 5 weight %.
52. for being catalyzed the AKU method containing the raw material of the recyclable materials being substantially made up of, described method bag triglyceride Include:
It is gentle that the catalyst making described raw material promote with at least one under hydroprocessing conditions contacts to form liquid effluent State product, described catalyst is selected from loaded catalyst of the self-supported catalyst of promotion, promotion and combinations thereof, described catalysis Agent comprises at least one the group vib metal selected from molybdenum and tungsten, group VIII metal selected from cobalt and nickel, and accelerator is selected from having space Configuration, there is the material of following structure:
Wherein x is 1 or 0, and y is 1 or 0, and R6Or R7For saturated, unsaturated, ring-type, non-annularity, branch or the alkyl of non-branch, Wherein R6Or R7For (CH)2m(CH2)n, wherein m and n is the integer of >=0；Described hydroprocessing condition includes 150 DEG C-290 DEG C Temperature and the total reaction pressure of 0.35-20.7MPa gauge pressure；
Reclaim and comprise the described liquid effluent of at least one in normal paraffin hydrocarbons, fatty alcohol, aliphatic mono and combinations thereof, described Liquid effluent has the fatty alcohol concentration of at least 5 weight %；
Fatty alcohol product is reclaimed from described liquid effluent；
Described fatty alcohol product is made to be enough to shape through the sufficiently long time under there is at least one catalyst under dehydration conditions Become and be dehydrated at a temperature of alpha-olefin product；With
Make described alpha-olefin product and light olefin on heterogeneous acid catalyst at a temperature of 100-300 DEG C and at 0- It is total to the most oligomeric to form 3 race's lubricant product under the pressure of 1000psig.
Method described in 53. claim 52, wherein said light olefin comprises butylene.
Method described in 54. claim 45, wherein said heterogeneous acid catalyst is selected from acid solid-phase catalyst, acid tree Fat catalyst and combinations thereof.
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