WO2014040031A1 - Génération de vapeurs de pyrolyse désoxygénées - Google Patents

Génération de vapeurs de pyrolyse désoxygénées Download PDF

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Publication number
WO2014040031A1
WO2014040031A1 PCT/US2013/058956 US2013058956W WO2014040031A1 WO 2014040031 A1 WO2014040031 A1 WO 2014040031A1 US 2013058956 W US2013058956 W US 2013058956W WO 2014040031 A1 WO2014040031 A1 WO 2014040031A1
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Prior art keywords
upgrading
reactor
gaseous product
pyrolysis
primary gaseous
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PCT/US2013/058956
Other languages
English (en)
Inventor
Mark A. Hughes
Johnathan T. Gorke
Samuel T. Jones
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Phillips 66 Company
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Application filed by Phillips 66 Company filed Critical Phillips 66 Company
Priority to EP13765894.4A priority Critical patent/EP2892978A1/fr
Priority to CA2884469A priority patent/CA2884469A1/fr
Publication of WO2014040031A1 publication Critical patent/WO2014040031A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/52—Ash-removing devices
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/30—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses with moving purifying masses
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • 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
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This invention relates to pyrolysis of organic matter into useful chemical or fuel products.
  • catalysts may be employed during the pyrolysis process.
  • Catalysts such as zeolites can deoxygenate the primary products from pyrolysis to create an intermediate liquid that can be upgraded to a fuel using conventional refining methodology.
  • Hydrogen may also be added to perform hydro-catalytic pyrolysis, which improves the quality of the product by significantly lowering the oxygen content, the acid content, etc.
  • the use of hydrogen increases the yield of pyrolysis oil by hydrogenating the primary pyrolysis products, which removes oxygen as water instead of carbon oxides.
  • the relatively low oxygen content intermediate produced is easily upgradable to bio-derived fuels.
  • a process comprising a process for the production and upgrading of a pyrolysis product, including the steps of: (a) pyrolyzing a biomass feedstock in a first reactor comprising at least one auger that conveys the feedstock through the reactor from a first end towards a second end , wherein said pyrolyzing forms primary pyrolysis products comprising a primary gaseous product and char; (b) passing the primary gaseous product through a first outlet at or near the top of the first reactor and to an upgrading reactor; (c) contacting the primary gaseous product with an upgrading catalyst in the upgrading reactor that is isolated from contact with the char, wherein the primary gaseous product does not condense prior to the contacting and comprises compounds containing less than 16 carbon atoms.
  • the total metal content entrained in the primary gaseous product in the upgrading reactor is less than 250 ppm, or less than 100 ppm. In certain embodiments of the process, greater than 99.5 wt. % of char, optionally, greater than 99.9 wt. % of char is prevented from leaving the first reactor via the first outlet, thereby extending the activity of the upgrading catalyst. In certain embodiments of the process, the elapsed time prior to the contacting is less than the time required for the primary gaseous product to oligomerize to form a secondary product comprising compounds containing more than 15 carbon atoms. In certain embodiments of the process, the elapsed time is less than three seconds, optionally less than one second, and optionally less than 0.25 seconds.
  • the upgrading catalyst may optionally comprises two or more upgrading catalysts that may be arranged to contact the primary gaseous product in parallel, in series or as mixtures of the two or more catalysts.
  • the two or more upgrading catalysts may contact the primary gaseous product under different conditions that comprise at least one of temperature, pressure, and humidity.
  • the primary gaseous product flows through two or more upgrading reactors, wherein each upgrading reactor is maintained at a temperature and pressure that optimize the upgrading reactions taking place therein.
  • the secondary product (that comprises greater than 15 carbons) in turn comprises phenolic dimers, phenolic oligomers, cross-linked lignin, char or combinations of these.
  • the primary product comprises one or more of: aromatic monomers, furan monomers, anhydrosugar monomers, olefins, alcohols, aldehydes, carboxylic acids, ketones, ethers, esters and hydrocarbons.
  • FIG. 1 is a simplified diagram of the inventive process depicting a pyrolysis reactor with a catalyst vessel to receive and upgrade the vapors from the pyrolysis reactor.
  • FIG. 2 is a simplified diagram of the inventive process depicting a pyrolysis reactor with a catalyst vessel to receive and upgrade the vapors from the pyrolysis reactor.
  • FIG. 3 is a simplified diagram of the inventive process depicting a pyrolysis reactor with a catalyst vessel to receive and upgrade the vapors from the pyrolysis reactor.
  • FIG. 4 is a graph illustrating the relationship between residence time and the pyrolysis products formed.
  • a biomass feedstock is fed to a pyrolysis reactor for conversion into a mixture comprising hydrocarbons that are fungible with petroleum-derived fuels that may include, but are not limited to, gasoline, jet-fuel, diesel and gasoil.
  • the methods and systems described herein protect and extend the lifespan of the downstream upgrading catalyst(s) by preventing contact between the catalyst(s) and the char generated during pyrolysis of the biomass feedstock, while simultaneously minimizing the time between production of the pyrolysis vapors and subsequent upgrading, thereby maximizing upgradability of the vapors to fuels that are fungible with petroleum-derived transportation fuels.
  • the pyrolysis reactor preferably comprises at least one auger that assists in rapidly and evenly distributing heat to the feedstock, as well as helping to convey the feedstock through the pyrolysis reactor.
  • Oxygenated hydrocarbon vapors are produced in the pyrolysis reactor, and these vapors are gravitationally separated from char, heat carrier, and metals in a disengagement zone while avoiding vapor condensation.
  • the vapors are then rapidly contacted with an upgrading catalyst in at least one upgrading reactor comprising at least one upgrading catalyst for conversion of the vapors into a hydrocarbon mixture fungible with current petroleum-derived fuels.
  • Residence time between production of pyrolysis vapors (i.e., the primary gaseous product) and contact with the one or more upgrading catalysts is minimized to prevent secondary pyrolysis reactions that decrease upgradability of the compounds that comprise the primary gaseous product.
  • the char created by the process described herein is conveyed through the reactor along with heat carrier by the at least one auger, then falls by force of gravity into a sealed char catch and is eliminated from the reactor.
  • the pyrolysis vapors are swept through the pyrolysis reactor, out an outlet near the top of the reactor and immediately into an upgrading vessel containing at least one upgrading catalyst, which may hydrogenate and deoxygenate the pyrolysis products.
  • the vessel may be operated as a fixed bed, fluid bed, or moving bed. Removing the char prior to contacting pyrolysis products with catalyst prevents catalyst fouling/poisoning.
  • the products from the upgrading vessel are condensed or further upgraded, thereby generating a viable transportation fuel or refinable intermediate.
  • biomass feedstock used in the present invention examples include, but are not limited to, oil-containing biomass, such as jatropha plant, macroalgae or microalgae.
  • Carbohydrate-based biomass may also be used as feedstock, where carbohydrate-based refers to biomass where at least a fraction of its composition is made of carbohydrates.
  • Carbohydrate-based biomasses are available from a variety of sources including cellulosic biomass and algal biomass.
  • feedstock useful in the current invention include, but are not limited to: sugars, carbohydrates, fatty acids, proteins, oils, eucalyptus oil, forest residues, dead trees, branches, leaves, tree stumps, yard clippings, wood chips, wood fiber, sugar beets, miscanthus, switchgrass, hemp, corn, corn fiber, poplar, willow, sorghum, sugarcane, palm oil, corn syrup, algal cultures, bacterial cultures, fermentation cultures, paper manufacturing waste, agricultural residues (e.g., corn stover, wheat straw and sugarcane bagasse), dedicated energy crops (e.g., poplar trees, switchgrass, and miscanthus giganteus sugarcane) sawmill and paper mill discards, food manufacturing waste, meat processing waste, animal waste, biological waste and/or municipal sewage.
  • sugars carbohydrates, fatty acids, proteins, oils, eucalyptus oil, forest residues, dead trees, branches, leaves, tree stumps, yard clippings, wood chips, wood fiber, sugar beets
  • FIG. 1 depicts an exemplary embodiment for a system for conducting pyrolysis of organic material or biomass to useful chemical products or fuel products.
  • a pyrolysis reactor 20 comprises an external housing 21, a heat carrier inlet 17 for a heat carrier 15, an feedstock inlet 10 for a biomass feedstock 12 and one or more helical augers 22 that when driven by a motor 25 to rotate about a longitudinal axis convey the biomass feedstock 12 along the length of the housing 21 from an inlet end 18 towards an outlet end 28. Near the outlet end 28, the char falls into a char catch 31 by gravitational force.
  • the biomass feedstock 12 is heated in the pyrolysis reactor 20 by at least one heating method that may include a heating jacket 21, a heated auger 22, or via introduction of a heat carrier 15 via a heat carrier inlet 17 proximal the inlet end 18 of the auger reactor 20.
  • the pyrolysis reactor 20 is operated to exclude most oxygen or air by the introduction of a sweep gas.
  • the sweep gas 19 enters through sweep gas inlet 16, although the sweep gas may alternatively enter the system via other points of entry, such as the biomass feedstock inlet 10 or heat carrier inlet 17.
  • primary gaseous product 37 rise to the upper portion of the pyrolysis reactor 20 and are swept toward the second reactor end 28, exiting through a first outlet 32.
  • an upgrading reactor 40 Arranged within close proximity of the pyrolysis reactor first outlet 28 is an upgrading reactor 40 containing at least one bed of an active upgrading catalyst 42.
  • the pyrolysis reactor 20 is in direct contact with the upgrading reactor 40 with minimal distance between the pyrolysis reactor 20 and the upgrading catalyst 42.
  • a distributor plate 52 is placed above the outlet 32 to assist in retaining within the reactor 20 any residual particulates that may be entrained in the primary gaseous product (pyrolysis vapors) 37 leaving the reactor 20 through outlet 32.
  • Distributor plate 52 may also serve to evenly distribute gases within the upgrading reactor 40, such as when the upgrading catalyst 42 contained within comprises, for example, a fluidized bed (not depicted).
  • the reactor described herein comprises an auger
  • the reactor is more efficient in char removal than a conventional fluidized bed reactor, which produces char fines by attrition that elutriate into the vapor product stream.
  • the majority of char formed during pyrolysis is conveyed by the auger 22 along with heat carrier 15 towards the outlet end 28 of the pyrolysis reactor 20.
  • the majority of char and/or ash produced during pyrolysis of the feedstock exits the pyrolysis reactor 20 by force of gravity into char catch 31.
  • the char is diverted from entering the upgrading reactor 40 and coming in contact with the upgrading catalyst bed 42, which dramatically enhances the longevity of the upgrading catalyst(s) 42.
  • the biomass feedstock 12 it is common for the biomass feedstock 12 to include measurable amounts of metals that act as poisons to desirable upgrading catalysts, and we have found that this metal content becomes concentrated in the char produced during pyrolysis.
  • catalyst that are more susceptible to poisoning by metals may be used to upgrade the pyrolysis vapors, since the impact of metal poisoning and coke formation is dramatically reduced.
  • the product leaving the upgrading bed is free of solids and metals, thereby removing the need for subsequent particle removal
  • the pyrolysis reactor preferably comprises at least one auger and may take many forms.
  • a single rotating auger transports sand, biomass and solid pyrolysis products through an elongated, cylindrical reactor.
  • two rotating augers 22 operate in parallel.
  • the first pyrolysis product exits through a first outlet 32 located on the upper side of the auger pyrolyzer 20, preferably near the top of the reactor to prevent solids from leaving the reactor via this outlet.
  • the outlet 32 conveys the primary gaseous product 37 immediately to contact an upgrading catalyst 42, which is optionally contained within an upgrading reactor 40.
  • the temperature within the pyrolysis reactor may be maintained via one or more of several mechanisms, such as heating of the reactor walls, heating of the at least one auger, microwave or inductive heating, addition of a heated sweep gas, and addition a of a solid particulate that has been pre-heated to a temperature of at least 900 °F (482 °C). Regardless of the heating mechanism utilized, preferably the pyrolysis reactor is maintained at a temperature of at least 600 °F (315 °C).
  • the median heat carrier particle size is greater than about 100 microns, and preferably greater than about 250 microns.
  • the bulk density of the heat carrier particles is at least 500 kg/m 3 , and preferably greater than about 1,000 kg/m 3 .
  • This zone is designed to provide a space where the upward local velocity of the primary gaseous product product 37 prior to passing through the first outlet 32 is sufficient to entrain less than 0.5 % (by wt.) of the char produced by the pyrolysis of the biomass feedstock. In certain embodiments, the upward local velocity of the primary gaseous product 37 prior to passing through the first outlet 32 is sufficient to entrain less than 0.1 % (by wt.) of the char produced by the pyrolysis of the biomass feedstock. Achieving this low percentage of char carryover requires designing the height and diameter of the disengagement zone 45 to allow the terminal falling velocity of the char and heat carrier particles to exceed the upward local velocity of the primary gaseous product 37 exiting the first outlet 32. This results in nearly all char particles being retained in the pyrolysis reactor, thereby preventing these particles from contacting the upgrading catalyst.
  • Figure 2 depicts an alternative embodiment, wherein the disengagement zone 45 may be smaller (or not present) and residual char particles may be instead be removed by passing the primary gaseous product 37 through an upgrading reactor 40 comprising a fluidized bed 42.
  • the primary gaseous product 37 may rise through a reactor 55 comprising a granular moving bed filter that additionally comprises an initial upgrading catalyst 60.
  • the catalyst may migrate downward in counter-current flow against the rising gases, and char 31 and spent catalyst 62 would leave out the bottom of the reactor 20.
  • a sweep gas may comprise one or more of many gases that are either inert or reactive.
  • the sweep gas may comprise gases such as nitrogen, helium, argon, hydrogen, methane and mixtures thereof.
  • the reactive gas may optionally react with the biomass during pyrolysis, may serve as a reactant when the pyrolysis products are upgraded by contacting the upgrading catalyst(s), or both.
  • the sweep gas may be injected into the system at more than one point, or injected simultaneously at multiple points.
  • One point may comprise combining the sweep gas with the feedstock prior to entering the pyrolysis reactor, while another may comprise injecting sweep gas directly into the pyrolysis reactor proximal to the biomass feedstock inlet.
  • a third point may comprise injecting the sweep gas proximal to the first outlet of the pyrolysis reactor. This may be preferable if the sweep gas is to be used as a reactant during upgrading of the primary gaseous product.
  • a gas may be injected just upstream of the pyrolysis reactor first outlet in order to 1) assist in preventing entrained char and heat carrier particles from leaving the pyrolysis reactor, 2) quench the primary gaseous product to a lower temperature, 3) heat the primary gaseous product to a higher temperature, or combinations thereof.
  • the sweep gas serves to quench the primary gaseous product
  • such quenching may prevent coking.
  • the sweep gas serves to heat the primary gaseous product may prevent formation of char and secondary pyrolysis reactions that may reduce the subsequent upgradability of the primary gaseous product to a bio-derived fuel.
  • quenching is limited such that the quenched primary gaseous product does not condense prior to contacting the upgrading catalyst(s). Typically, this requires that the quenched primary gaseous product still maintains a temperature of at least 250 °C to prevent condensation.
  • volumetric flow rate or "standard gas hourly space velocity" (SGHSV) of the sweep gas is adjusted to minimize the time between pyrolysis and catalytic upgrading, such that the upgrading catalyst (or optionally, catalysts) contacts primary products of pyrolysis and not secondary pyrolysis products that comprise 16 or more carbons and are more difficult to upgrade to a bio-derived fuel.
  • Volumetric flow rate for a given embodiment depends upon factors including, but not limited to, the volume of the pyrolysis reactor, the temperature and pressure at which the pyrolysis reactor is maintained, the feed rate of the biomass feedstock to the pyrolysis reactor, and the type of feedstock utilized.
  • a paper by J.N. Brown, et al. provides one example of how these variables can be adjusted to determine an optimal volumetric flow rate for a desired pyrolysis outcome, including, for example, the pyrolysis liquid to pygas ratio, and the relative percentage of the feedstock converted to char.
  • the pressure maintained within the pyrolysis reactor is generally within a range of about 0 psig to 3000 psig.
  • the pyrolysis reactor is maintained at a pressure in the range of 100 psig to 500 psig to increase throughput of biomass feedstock, and in certain embodiments, facilitate catalytic upgrading of the primary gaseous product.
  • the primary gaseous product is driven by the sweep gas (or optionally, a pressure differential) from the pyrolysis reactor via the first outlet and enters an upgrading reactor and contacts an upgrading catalyst.
  • Minimizing residence time of the primary gaseous product in the pyrolysis reactor is important for maximizing the percentage of primary gaseous product that is successfully upgraded to a bio-derived fuel.
  • Conditions of temperature and pressure, as well as reactor dimensions are chosen to assure a residence time of the primary gaseous product in the pyrolysis reactor that is less than 5 seconds, preferably less than 3 seconds, more preferably less than 1 second, even more preferably less than 0.3 second and most preferably less than 0.1 second.
  • Minimizing residence time of the primary gaseous product in the pyrolysis reactor prevents the occurrence of secondary pyrolysis reactions that form larger oxygenated species comprising 16 or more carbon atoms. These larger oxygenated species are likely to form coke, which is extremely detrimental to the process by fouling process equipment and heat carrier. Additionally, diversion of the primary gaseous product into secondary pyrolysis reactions decreases the conversion efficiency of the feedstock into smaller species that are more easily upgraded into a bio-derived fuel.
  • the physical distance between the pyrolyzer and the upgrading catalyst(s) contained within the upgrading reactor may vary, but is preferably minimized, taking into consideration the space velocity of the primary gaseous product (optionally in a mixture with a sweep gas) out of the pyrolysis reactor. Minimizing this distance assists in decreasing the time between production of the primary gaseous product and subsequent contacting with one or more upgrading catalyst(s).
  • the current invention assures that the upgrading catalyst sees primary products from pyrolysis and not secondary products created by reactions occurring after pyrolysis.
  • the distance between the pyrolyzer and the upgrading catalyst(s) is less than 4 ft. More preferably, this distance is less than 1 ft., and most preferably, less than 6 inches.
  • the disengagement zone between the pyrolyzer and the upgrading catalyst may include additional features to limit reactivity of the primary gaseous product prior to contact with the upgrading catalyst(s). These may include (but are not limited to) temperature control, introduction of a gas or fluid to quench the primary gaseous product (as mentioned previously), flow control through judicious choices in geometry (preferably, a geometry minimizing bends and small orifices to decrease the potential for vapor condensation, the presence of a pre-catalyst (such as zeolite monolith, or any of the above- mentioned upgrading catalysts) at the interface between reactors.
  • additional features to limit reactivity of the primary gaseous product prior to contact with the upgrading catalyst(s) may include (but are not limited to) temperature control, introduction of a gas or fluid to quench the primary gaseous product (as mentioned previously), flow control through judicious choices in geometry (preferably, a geometry minimizing bends and small orifices to decrease the potential for vapor condensation, the presence of a pre-cat
  • a catalyst monolith may be utilized as a pre-catalyst bed, or guard bed, while in other embodiments, the pre-catalyst may comprise a fluidized bed of catalyst integrated with the distributor assembly to control reactivity in this region.
  • the fluidized bed of catalyst may additionally function as a moving bed filter to remove residual particulates.
  • the at least one upgrading bed may utilize any type of reactor configuration including, but not limited to, a fixed bed, a bubbling bed, a circulating bed, a moving bed, a counter current reactor or combinations of one or more of these configurations.
  • the catalyst may be periodically removed from the upgrading reactor and passed through a regenerator for de-coking as needed, then returned to the pyrolysis reactor.
  • fresh catalyst may be added on a periodic or continuous basis to the pyrolysis reactor to account for catalyst attrition. In certain embodiments, there may be no means of introducing fresh catalyst.
  • the catalyst may include, but is not limited to zeolites, metal modified zeolites, and other modified zeolites.
  • Other catalysts may include forms of alumina, silica-alumina, and silica, unmodified or modified with various metals, not limited but including, Nickel, Cobalt, Molybdenum, Tungsten, Cerium, Praseodymium, Iron, Platinum, Palladium, Ruthenium and Copper or mixtures thereof.
  • Still other catalysts may include unsupported metals, supported or unsupported metal oxides or metal phosphides, and mixtures thereof.
  • Catalyst types include deoxygenation catalysts, hydrogenation catalysts, hydrotreating catalysts, hydrocracking catalysts, water-gas-shift catalysts, and condensation catalysts. Catalysts may be sulfided or un-sulfided.
  • each catalyst bed may comprise mixtures of one or more catalysts of the types described above.
  • multiple catalyst beds may be placed within a single reactor, or multiple catalyst beds may be placed in different reactors to facilitate different reaction conditions. When multiple reactors are utilized, they may be arranged to either in parallel or series.
  • the residence time of the pyrolysis vapors in each upgrading reactor generally ranges from 0.01 sec to 1000 sec. Preferably, the residence time is in a range from 0.05 sec to 400 sees. More preferably, the residence time is in a range from 0.1 sec to 200 sec. Most preferably, the residence time is in a range from 0.1 sec to 100 sec.
  • the temperature maintained within each upgrading reactor is generally in the range from 72°F to 1500°F. Preferably, the temperature is in the range from 100 °F to 1000 °F, although if multiple upgrading reactors are used, each may be maintained at a different temperature within this range.
  • Certain upgrading reactions are advantageously conducted at a pressure that is greater than atmospheric pressure.
  • the pressure that is maintained in the one or more upgrading reactors may range from 0-3000 psig, although a preferred pressure range is zero to 1000 psig. In certain embodiments, the pressure may range from 10 to 800 psig, from 20 to 650 psig, from 100 to 500 psig. An exemplary pressure might be 400 psig.
  • each upgrading reactor The flow of gas and vapors within each upgrading reactor is preferably upward, although downward or lateral gas flow may also be utilized.
  • the upgraded gas and/or vapors Upon exiting the final upgrading reactor, the upgraded gas and/or vapors are directed to a condensation system that functions to reduce the temperature of upgraded product vapors to a temperature that is at or below the dew point for at least one component.
  • the conditions utilized do not result in the condensation of methane, but preferably will condense C4+ hydrocarbons.
  • Hydrogen may be separated from the non-condensed gas by a variety of conventional methods and recycled as the sweep gas. In certain embodiments, the recycled hydrogen may be added directly into, or just upstream from, an upgrading reactor to facilitate one or more upgrading reactions.
  • the entirety, or some fraction, of the bulk non-condensable gas is used for the same purpose.
  • the entirety, or some fraction, of the bulk of the non- condensable gas is sent to a combustor or hydrogen generation unit (e.g., a reformer) to generate either heat or hydrogen, respectively.
  • the resulting heat or hydrogen may then be partially or entirely recycled back to the process.
  • Figure 4 demonstrates that at 3 seconds of vapor residence time in a 100 micron capillary maintained at pyrolysis temperatures (610 °F), the proportion of CI 6+ species increased relative to levoglucosan, a key six carbon primary pyrolysis product. Furthermore, the proportion of phenolics, furans, and other carbohydrates/sugars comprising less than 16 carbon atoms decreased at the longer residence times, likely from oligomerization of these primary compounds to heavier compounds of 16 carbons, or greater, which are difficult to upgrade to fuel range hydrocarbons.
  • trainment is defined as transport of a solid particle by a gas stream. Entrainment of a given solid particle typically occurs when the local velocity of a gas stream exceeds the terminal falling velocity of the particle.
  • standard gas hourly space velocity or "SGHSV” refers to the gas hourly space velocity of a gas stream measured at standard conditions.

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Abstract

La présente invention concerne, de manière générale, de nouveaux procédés de pyrolyse de biomasse et des systèmes qui diminuent l'entraînement de résidus carbonés et d'autres contaminants dans les vapeurs de pyrolyse. Le procédé de production et de régénération des produits de pyrolyse comprend les étapes suivantes: (a) pyrolyse d'une charge de biomasse dans un premier réacteur comprenant au moins une vis sans fin qui transporte la charge à travers le réacteur, d'une première extrémité vers une seconde extrémité, ladite pyrolyse générant de produits de pyrolyse primaires comprenant un produit gazeux primaire et des résidus carbonés; (b) passage du produit gazeux primaire par une première sortie située dans le haut ou à proximité du haut du premier réacteur et vers un réacteur de valorisation; (c) mise en contact du produit gazeux primaire avec un catalyseur de valorisation qui est isolé du contact avec les résidus carbonés, le produit gazeux primaire ne subissant pas de condensation avant sa mise en contact avec le catalyseur, et comprenant des composés ayant moins de 16 atomes de carbone.
PCT/US2013/058956 2012-09-10 2013-09-10 Génération de vapeurs de pyrolyse désoxygénées WO2014040031A1 (fr)

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CA2884469A CA2884469A1 (fr) 2012-09-10 2013-09-10 Generation de vapeurs de pyrolyse desoxygenees

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EP2892978A1 (fr) 2015-07-15
CA2884469A1 (fr) 2014-03-13
US20140072480A1 (en) 2014-03-13
WO2014040054A1 (fr) 2014-03-13

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