Classifications

• • 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
  • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
  • C10J3/60—Processes
  • C10J3/64—Processes with decomposition of the distillation products
  • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
• • 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
  • C07C29/15—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 oxides of carbon exclusively
  • C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
  • C07C29/1516—Multisteps
• • 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
  • C10L9/00—Treating solid fuels to improve their combustion
  • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
  • C10L9/083—Torrefaction
• • 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
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0916—Biomass
• • 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
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0916—Biomass
  • C10J2300/092—Wood, cellulose
• • 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
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
• • 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
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1656—Conversion of synthesis gas to chemicals
  • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
• • 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
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1656—Conversion of synthesis gas to chemicals
  • C10J2300/1668—Conversion of synthesis gas to chemicals to urea; to ammonia
• • 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

Definitions

• This invention relates to flexible, efficient, and scalable methods and systems to convert carbonaceous materials (such as biomass) into synthesis gas and other downstream products (such as alcohols).
• Synthesis gas (hereinafter referred to as "syngas”) is a mixture of gas comprising predominantly hydrogen (H 2 ) and carbon monoxide (CO). Syngas is essentially a gaseous mixture of stable molecules that contain the elements carbon (C), hydrogen (H), and oxygen (O). Syngas is a platform intermediate in the chemical and biorefming industries and has a vast number of uses, as is well- known in the art. Syngas can be converted into alkanes, olefins, oxygenates, and alcohols. Some of these chemicals can be blended into, or used directly as, diesel fuel, gasoline, and other liquid fuels. Syngas can also be directly combusted to produce heat and power.
• Syngas can be produced, in principle, from virtually any material containing C, H, and O.
• materials commonly include fossil resources such as natural gas, petroleum, coal, and lignite; and renewable resources such as lignocellulosic biomass and various carbon-rich waste materials. It is preferable to utilize a renewable resource to produce syngas because of the rising economic, environmental, and social costs associated with fossil resources.
• the present invention provides a method of forming syngas, the method comprising the steps of: (a) pyrolyzing or torrefying a carbon-containing first feed material to form a pyrolyzed or torrefied first feed material; and (b) converting the pyrolyzed or torrefied first feed material into syngas.
• Step (a) can be conducted in the presence of a catalyst.
• the method can further include converting into syngas a second feed material that has not been pyrolyzed or torrefied.
• the method can further include combining the pyrolyzed or torrefied first feed material with a second feed material that has not been pyrolyzed or torrefied such that both the pyrolyzed or torrefied first feed material and the second feed material are converted into syngas.
• the method includes pyrolyzing a carbon- containing first feed material to form a pyrolyzed first feed material, torrefying a carbon-containing feed second material to form a torrefied second feed material, and converting the pyrolyzed first feed material and the torrefied second feed material into syngas.
• the method includes introducing the torrefied first feed material into a pyrolysis reactor to form a pyrolyzed first feed material. The method can be conducted, at least in part, in the presence of a catalyst.
• the pyrolyzed or torrefied first feed material can be converted into syngas by passing the pyrolyzed or torrefied first feed material through a heated reaction vessel, such as a steam reformer or partial-oxidation reactor, to form syngas.
• conversion to syngas comprises the substeps of: (i) devolatilizing the pyrolyzed or torrefied first feed material to form a gas phase and/or solid phase in a devolatilization unit; and (ii) passing the gas phase and/or solid phase through a heated reaction vessel to form syngas.
• Certain embodiments provide for converting into syngas a pyrolyzed or torrefied first feed material and a second carbon-containing feed material that has not been pyrolyzed or torrefied. Certain embodiments include pyrolyzing a carbon-containing first feed material to form the pyrolyzed first feed material, torrefying a carbon-containing third feed material to form a torrefied third feed material, and converting the pyrolyzed first feed material, the second feed material, and the torrefied third feed material into syngas. Other embodiments combine, prior to converting the material into syngas, the pyrolyzed or torrefied first feed material and the second feed material.
• methods include converting the pyrolyzed or torrefied first feed material and the second feed material into syngas.
• This particular method comprises the steps of: (i) devolatilizing the pyrolyzed or torrefied first feed material and the second feed material to form a gas phase and/or solid phase in a devolatilization unit; and (ii) passing the gas phase and/or solid phase through a heated reaction vessel to form syngas.
• the torrefied first feed material can be introduced into a pyrolysis reactor to form a pyrolyzed first feed material.
• Some embodiments provide a method of forming syngas, the method comprising the steps of: (a) devolatilizing a pyrolyzed or torrefied first feed material to form a gas phase and solid phase in a devolatilization unit; and (b) passing the gas phase and solid phase through a heated reaction vessel to form syngas.
• Pyrolysis of a carbon-containing feed material can form the first feed material.
• torrefaction of a carbon-containing feed material can form the first feed material.
• a second feed material that has not been pyrolyzed or torrefied can be mixed with the first feed material and converted into syngas.
• both the pyrolyzed or torrefied first feed material and the second feed material are converted into syngas.
• Certain embodiments include pyrolyzing a carbon-containing first feed material to form the pyrolyzed first feed material, torrefying a carbon-containing third feed material to form a torrefied third feed material, and converting the pyrolyzed first feed material, the second feed material, and the torrefied third feed material into syngas.
• the pyrolyzed or torrefied first feed material and the second feed material can be combined prior to converting the pyrolyzed or torrefied first feed material and the second feed material into syngas.
• the torrefied first feed material can be used to form a pyrolyzed first feed material.
• Some embodiments employ modular units for at least some steps of the methods previously described.
• Some embodiments further include the step of converting the syngas to a product, such as a product selected from the group consisting of an alcohol, an olefin, an aldehyde, a hydrocarbon, an ether, hydrogen, ammonia, and/or acetic acid.
• a product such as a product selected from the group consisting of an alcohol, an olefin, an aldehyde, a hydrocarbon, an ether, hydrogen, ammonia, and/or acetic acid.
• the hydrocarbon can be a linear or branched C 5 -C 15 hydrocarbon.
• the alcohol can be methanol and/or ethanol.
• a second aspect relates to apparatus for practicing some embodiments of the invention.
• an apparatus for producing syngas comprising a pyrolysis and/or torrefaction reactor in communication with a devolatilization unit that is in communication with a heated reaction vessel.
• the pyrolysis reactor, torrefaction reactor, or both of these reactors is suitable for containing one or more catalysts for pyrolysis or torrefaction.
• the apparatus further includes a device for combining pyrolyzed feed material with feed material that has not been pyrolyzed. In some embodiments, the apparatus further includes a device for combining torrefied feed material with feed material that has not been torrefied.
• Some embodiments of this aspect provide an apparatus for producing syngas comprising a pyrolysis and/or torrefaction reactor (which can be catalytic) in communication with a device for combining a pyrolyzed or torrefied first feed material with a second feed material that has not been pyrolyzed or torrefied, wherein the device is in communication with a syngas reactor for converting the first feed material and the second feed material into syngas.
• a pyrolysis and/or torrefaction reactor which can be catalytic
• Certain apparatus include a device for combining pyrolyzed feed material with torrefied feed material, wherein the device is in communication with: (i) the pyrolysis reactor and/or the torrefaction reactor, and (ii) the syngas reactor.
• the syngas reactor can comprise a devolatilization unit that is in communication with a heated reaction vessel.
• Some apparatus of the invention further include a product reactor for converting syngas into a product, such as C1-C4 alcohols (e.g., methanol and/or ethanol), wherein the product reactor is in communication with the syngas reactor.
• a product reactor for converting syngas into a product, such as C1-C4 alcohols (e.g., methanol and/or ethanol), wherein the product reactor is in communication with the syngas reactor.
• the present invention features methods and apparatus for the pyrolysis or torrefaction of a feedstock before it is converted to syngas. Pyrolysis and torrefaction produce a relatively energy-dense feedstock (e.g., by the removal of water and/or the densification of the feedstock), thereby reducing the transportation costs of the resulting feedstocks.
• a pyrolyzed feedstock and a torrefied feedstock are converted to syngas.
• a pyrolyzed feedstock and a feedstock that has not undergone pyrolysis or torrefaction are converted to syngas.
• Some embodiments convert a torrefied feedstock and a feedstock that has not undergone pyrolysis or torrefaction to syngas.
• a torrefied feedstock, a pyrolyzed feed stock, and a feedstock that has not undergone pyrolysis or torrefaction are converted to syngas.
• a fossil fuel e.g., crude oil, coal, and/or petroleum
• one or more of the following are converted to syngas: a pyrolyzed feedstock, a torrefied feedstock, and a feedstock that has not undergone pyrolysis or torrefaction.
• the invention features methods and systems that use modular units for the pyrolysis or torrefaction of a feedstock.
• a feedstock can be reacted in a modular pyrolysis or torrefaction reactor and then transported to a plant for further processing, such as the conversion of the reacted feedstock to syngas or other downstream products.
• modular units are also used to devolatilize and/or stream reform the pyrolyzed or torrefied feedstock.
• a pyrolyzed or torrefied feedstock can be introduced into a modular unit for devolatilizing the feedstock.
• the modular devolatilization unit is in communication with (such as operably linked to) a modular unit for steam reforming the product of the devolatilization unit, thereby forming syngas.
• the product from the modular devolatilization unit is transported to a plant for further processing, such as the conversion to syngas or other downstream products.
• Biomass for the purposes of the present invention, is any material not derived from fossil resources and comprising at least carbon, hydrogen, and oxygen. Biomass includes, for example, plant and plant-derived material, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal- derived waste, poultry-derived waste, and municipal solid waste. Other exemplary feedstocks include cellulose, hydrocarbons, carbohydrates or derivates thereof, charcoal, and renewable feedstocks. The present invention can also be used for carbon-containing feedstocks other than biomass, such as a fossil fuel (e.g., coal or petroleum). Thus, any method, apparatus, or system described herein in reference to biomass can alternatively be used with any other feedstock.
• a fossil fuel e.g., coal or petroleum
• the biomass feedstock can include one or more materials selected from: timber harvesting residues, softwood chips, hardwood chips, tree branches, tree stumps, leaves, bark, sawdust, off-spec paper pulp, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, miscanthus, animal manure, municipal garbage, municipal sewage, commercial waste, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, plastic, and cloth.
• the feedstock options are virtually unlimited.
• selection of a particular feedstock or feedstocks is not regarded as technically critical, but is carried out in a manner that tends to favor an economical process.
• the feedstock can optionally be dried prior to processing.
• reforming or “steam reforming” refers to the production of syngas when steam is the reactant.
• Partial oxidation refers to the production of syngas when oxygen is the reactant.
• Gasification generally refers to the production of a mixture of at least CO, CO 2 , and H 2 , and can include one or more of devolatilization, reforming, or partial oxidation, as well as some amount of pyro lysis, combustion, water-gas shift, and other chemical reactions.
• Some exemplary variations provide a process for synthesizing syngas from biomass or other carbon-containing material.
• a feedstock reactor such as a pyrolysis reactor or torrefaction reactor.
• the product from the feedstock reactor is then introduced into a syngas reactor.
• a portion of the feedstock is not introduced into the feedstock reactor. Instead, this portion is added directly to a syngas reactor.
• the syngas reactor includes a devolatilization unit and/or reformer reactor.
• the syngas produced in the syngas reactor can be cooled and compressed.
• the syngas is filtered, purified, or otherwise conditioned prior to being converted to another product.
• syngas may be introduced to a syngas conditioning section, where benzene, toluene, ethyl benzene, xylene, sulfur compounds, nitrogen, metals, and/or other impurities or potential catalyst poisons are optionally removed from the syngas.
• the syngas is introduced into one or more product reactors for the conversion of syngas into another product, such as methanol and/or ethanol.
• Exemplary feedstock reactors include one or more standard pyrolysis reactors and/or torrefaction reactors.
• a pyrolysis reactor is used to pyrolyze a portion of or the entire feedstock using standard methods (see, for example, Czernik and Bridgwater, Energy & Fuels, 18:590-598, 2004, and Mohan et al, Energy & Fuels, 20:848-889, 2006, which are each hereby incorporated by reference in their entireties, particularly with respect to pyrolysis reactors and methods).
• Pyrolysis is the thermal decomposition of a feed stock.
• less oxygen is present than required for complete combustion of the feedstock (such as about or less than 40, 30, 20, 10, 5, 1, 0.5, or 0.01% of the oxygen that is required for complete combustion of the feedstock).
• pyrolysis is performed in the absence of oxygen.
• Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from a heat source increases the temperature inside the feedstock; (ii) the initiation of primary pyrolysis reactions at this higher temperature releases volatiles and forms a char; (iii) the flow of hot volatiles toward cooler solids results in heat transfer between hot volatiles and cooler unpyrolyzed feedstock; (iv) condensation of some of the volatiles in the cooler parts of the feedstock, followed by secondary reactions, can produce tar; (v) autocatalytic secondary pyrolysis reactions proceed while primary pyrolytic reactions simultaneously occur in competition; and (vi) further thermal decomposition, reforming, water-gas shift reactions, free-radical recombination, and/or dehydrations can also occur, which are a function of the residence time, temperature, and pressure profile.
• Pyrolysis partially dehydrates the feedstock.
• pyrolysis removes greater than or about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90% or more of the water from the feedstock. It can be beneficial, but not necessary, to remove at least 90% of the water initially present.
• the products from the pyrolysis reactor are typically a gas, an oil (also referred to as "pyrolysis oil” or "bio-oil”), and a char.
• Any standard pyrolysis reactor can be used to pyrolyze the feedstock.
• Exemplary reactor configurations include, but are not limited to, augers, ablative reactors, rotating cones, fluidized-bed reactors (e.g., circulating fluidized-bed reactors), entrained-flow reactors, vacuum moving-bed reactors, transported-bed reactors, fixed-bed reactors, and microwave-assisted pyrolysis reactors.
• the feedstock and sand are fed at one end of a screw.
• the screw mixes the sand and feedstock and conveys them through the reactor.
• the screw can provide good control of the feedstock residence time and does not dilute the pyrolyzed products with a carrier or fluidizing gas.
• the sand is reheated in a separate vessel.
• the feedstock is moved at a high speed against a hot metal surface. Ablation of any char forming at the particle surface maintains a high rate of heat transfer.
• the apparatus utilizes a metal surface spinning at a high speed within a bed of feedstock, which prevents any dilution of the products.
• the feedstock particles may be suspended in a carrier gas and introduced at a high speed through a cyclone whose wall is heated. The products are diluted with the carrier gas.
• preheated hot sand and feedstock are introduced into a rotating cone. Due to the rotation of the cone, the mixture of sand and feedstock is transported across the cone surface by centrifugal force. Like other shallow transported-bed reactors, relatively fine particles are used to obtain a good liquid yield.
• the feedstock is introduced into a bed of hot sand fluidized by a gas, which is usually a recirculated product gas. High heat transfer rates from fluidized sand result in rapid heating of the feedstock. There can be some ablation by attrition with the sand particles. Heat is usually provided by heat-exchanger tubes through which hot combustion gas flows. There is some dilution of the products, which makes it more difficult to condense and then remove the bio-oil mist from the gas exiting the condensers.
• the feedstock is introduced into a circulating fluidized-bed of hot sand.
• Gas, sand, and feedstock move together.
• Exemplary transport gases include recirculated product gases and combustion gases. High heat-transfer rates from the sand ensure rapid heating of the feedstock, and ablation is stronger than with regular fluidized beds.
• a fast separator separates the product gases and vapors from the sand and char particles. The sand particles are reheated in a fluidized burner vessel and recycled to the reactor.
• Any standard reaction conditions can be used to pyrolyze the feedstock in the pyrolysis reactor (see, for example, Czernik and Bridgwater, Energy & Fuels, 18:590-598, 2004; and Mohan et al, Energy & Fuels, 20:848-889, 2006).
• One skilled in the art can select a combination of temperature, pressure, and residence time that produces a liquid as a product of the pyrolysis process (rather than only forming a solid and/or gas). For example, if the reaction temperature, pressure, and/or residence time is too low or too high, the product may be primarily a solid.
• a skilled artisan, by routine experimentation, can adjust the parameters to obtain primarily a liquid as the pyrolyzed product.
• fast pyrolysis is used.
• Fast pyrolysis is a high- temperature process in which feedstock is rapidly heated.
• the feedstock is heated in the absence of oxygen.
• the feedstock decomposes to generate vapors, aerosols, and some charcoal-like char.
• a dark brown mobile liquid is formed that has a heating value that is about half that of conventional fuel oil. Rapid heating and rapid quenching can produce the intermediate pyrolysis liquid products, which condense before further reactions break down higher-molecular- weight species into gaseous products.
• Fast pyrolysis processes typically produce 60-75 wt% of liquid bio-oil, 15-25 wt% of solid char, and 10-20 wt% of noncondensable gases, for example, depending on the feedstock used.
• Pyrolysis can be performed in the presence of a catalyst.
• exemplary catalysts include heterogeneous catalysts (such as SiO 2 -Al 2 Os, Pt/SiO 2 -Al 2 ⁇ 3, WO x /ZrO 2 , SO x /ZrO 2 ), zeolites (such as HY-zeolite, ⁇ -zeolite, HZSM-5, ZSM-5, or klinoptilolite), acid catalysts, clay catalysts (e.g., acidified or activated clay catalysts), Al-MCM-41 type mesoporous catalysts, activated alumina, Co-Mo catalysts (such as Criterion-534), and Ni/ Al co-precipitated catalysts.
• a cation such as K + , Li + , or Ca 2+ can be used to increase the selectivity and yield of char and/or to lower the selectivity and yield of tar during pyrolysis.
• the feedstock is finely ground before it is added to the pyrolysis reactor to facilitate high heating rates and fast heat transfer.
• the reaction temperature is between about 300-600 0 C, such as about 45O 0 C, when a pyrolysis catalyst is used.
• the temperature is between about 300-400 0 C, about 400-500 0 C, or about 500-600 0 C.
• use of a pyrolysis catalyst allows a lower temperature to be used, such as about 250-450 0 C. High reaction rates minimize char formation. Under some conditions, no char is formed.
• the pressure is between about 0 to about 2,000 psi, such as between about 0 to about 50 psi.
• the residence time is between about 0.1 seconds to about 10 seconds, such as about 1-5 seconds.
• the pyrolysis vapors and aerosols are rapidly cooled to generate pyrolysis oil.
• Slow pyrolysis can also used.
• the feedstock is heated to about 500 0 C.
• the vapor residence time varies from about 5 minutes to about 30 minutes. Vapors do not escape as rapidly in slow pyrolysis as they do in fast pyrolysis. Thus, components in the vapor phase continue to react with each other as the solid char and any liquid are being formed.
• the heating rate in slow pyrolysis is typically much slower than that used in fast pyrolysis.
• a feedstock can be held at constant temperature or slowly heated. Vapors can be continuously removed as they are formed.
• vacuum pyrolysis is used.
• the feedstock is heated in a vacuum to decrease the boiling point and/or avoid adverse chemical reactions.
• Slow or fast heating rates can be used.
• Some embodiments employ a temperature of about 45O 0 C and a pressure of between about 1-5 psi.
• the pyrolysis oil may contain water, such as about 10 to about 25% water (weight %). If desired, part or the entire water layer of the pyrolysis oil can be removed before it is added to a devolatilization unit and/or reformer reactor using standard methods, such as phase separation or separation based on differences in volatility. Exemplary methods include phase separation by decanting, distillation, and separation using membranes. In some embodiments, none of the water is removed from the pyrolysis oil before it is added to the devolatilization unit and/or reformer reactor.
• the water in the pyrolysis oil can provide a source of steam, which can be used to increase the hydrogen content of the syngas through the water-gas shift reaction, if desired.
• Torrefaction can improve the properties of a carbon-containing feedstock (e.g., biomass). Torrefaction consists of a slow heating of feedstock in an inert atmosphere to a maximum temperature of about 300 0 C. The treatment yields a solid uniform product with a lower moisture content and a higher energy content compared to the initial feedstock. The process may be called mild pyro lysis, with removal of smoke-producing compounds and formation of a solid product, retaining (in some embodiments) about 70% of the initial weight and about 90% of the original energy content.
• Torrefied material typically has the following properties: (i) hydrophobic nature (e.g., the material does not regain humidity in storage and therefore, unlike wood and charcoal, is stable with a well-defined composition); (ii) lower moisture content and higher calorific values compared to the initial feedstock; (iii) formation of less smoke when burned; and (iv) higher density and similar mechanical strength compared to the initial feedstock.
• a torrefaction reactor is used to torrefy a portion of or the entire feedstock using standard methods, such as those described in WO 2007/078199 or in Bergman and Kiel, "Torrefaction for biomass upgrading," 14 th European Biomass Conference & Exhibition, ENC-RX-05-180, Paris, France, 2005, which publications are each hereby incorporated by reference in their entireties, particularly with respect to torrefaction reactors and methods.
• Any standard torrefaction reactor can be used to torrefy the feedstock.
• Exemplary reactor configurations include, but are not limited to, augers, ablative reactors, rotating cones, fluidized-bed reactors (e.g., circulating fluidized-bed reactors), entrained-flow reactors, vacuum moving-bed reactors, transported-bed reactors, and fixed-bed reactors.
• a feedstock is torrefied before it is added to a devolatilization unit or reformer reactor.
• a feedstock is torrefied while it is contained in a devolatilization unit.
• any standard reaction conditions can be used to torrefy the feedstock in the torrefaction reactor.
• One skilled in the art can readily select a combination of temperature, pressure, and residence time that produces a dried solid as a product of the torrefaction process.
• the reaction temperature is between about 150-300 0 C, such as about 200-300 0 C.
• a variety of pressures can be used for torrefaction, such as atmospheric pressure or greater.
• the residence time is between about 10 minutes to about 8 hours. The residence time is preferably adjusted based on the type of feedstock used.
• torrefaction is performed in the absence of oxygen.
• the torrefied feedstock is crushed or densif ⁇ ed (e.g., compressed to form pellets using a pelletizer) using standard methods to form smaller particles that are easier to transport and/or easier to mix with other feedstocks.
• torrefaction is performed in the presence of a catalyst.
• exemplary catalysts for torrefaction include heterogeneous catalysts (such as SiO 2 -Al 2 O 3 , Pt/SiO 2 -Al 2 O 3 , WO x /ZrO 2 , SO x /ZrO 2 ), zeolites (such as HY- zeolite, ⁇ -zeolite, HZSM-5, ZSM-5, or klinoptilolite), acid catalysts, clay catalysts (e.g., acidified or activated clay catalysts), Al-MCM-41 type mesoporous catalysts, activated alumina, Co-Mo catalysts (such as Criterion-534), and Ni/ Al co-precipitated catalysts.
• heterogeneous catalysts such as SiO 2 -Al 2 O 3 , Pt/SiO 2 -Al 2 O 3 , WO x /ZrO 2 , SO x
• a torrefied feedstock (such as a solid product from a torrefaction reactor) can be added to a pyrolysis reactor (such as a pyrolysis reactor described herein) to further process the torrefied feedstock before adding it to a syngas reactor, devolatilization unit, and/or reformer reactor.
• a pyrolyzed product (such as the pyro lysis oil and/or solid product from a pyrolysis reactor) is combined with a torrefied product (such as a solid product from a torrefaction reactor) before they are added to a devolatilization unit and/or reformer reactor. Any standard method can be used for this mixing.
• a screw is used to mix the pyrolyzed products and torrefied products.
• a feed mixer is used, such as a vertical or horizontal mixer.
• a vertical mixer consists, for example, of a vertical screw which takes material to the top where it falls back down again, and repeats that process to mix materials.
• a horizontal mixer includes, for example, paddles or blades attached to a horizontal rotor.
• a mixer with two counter-rotating rotors in a large housing is used to mix the pyrolyzed products and torrefied products.
• a Banbury mixer is used.
• a Banbury mixer includes, for example, two contra-rotating spiral-shaped blades encased in segments of cylindrical housings, intersecting so as to leave a ridge between the blades. The blades may be cored for circulation of heating or cooling media.
• pyrolysis oil is sprayed onto the torrefied product, using, for example, a standard spray pump and nozzle to distribute the pyrolysis oil as a mist over the torrefied product.
• the pyrolyzed products and torrefied products can be further mixed after the pyrolysis oil is sprayed onto the torrefied product.
• a pyrolyzed product such as the pyrolysis oil and/or solid product from a pyrolysis reactor
• a torrefied product such as a solid product from a torrefaction reactor
• another feedstock such as a feedstock that has not undergone pyrolysis or torrefaction
• Any standard method can be used for this mixing, such as any of the methods described above for mixing pyrolyzed products and torrefied products.
• feedstocks When different feedstocks are used, they can be used in any ratio and they can be introduced in the same or different locations of a devolatilization unit or reformer reactor.
• Any ratio of pyrolyzed products to torrefied products can be used, such as a ratio of about 1 :0.01 to about 1 : 100 by weight, such as about 1 :0.1, 1 : 1 , or 1 : 10.
• Any ratio of pyrolyzed products to another feedstock (such as a feedstock that has not undergone pyrolysis or torrefaction) can be used, such as a ratio of about 1 :0.01 to about 1 :100 by weight, such as about 1 :0.1, 1 :1, or 1 :10.
• Any ratio of torrefied products to another feedstock can be used, such as a ratio of about 1 :0.01 to about 1 : 100 by weight. It will be understood that the specific selection of feedstock ratios can be influenced by many factors, including economics (feedstock prices and availability), process optimization (depending on feedstock composition profiles), utility optimization, equipment optimization, and so on.
• Any standard syngas reactor can be used convert a feedstock or a mixture of feedstocks (such as a mixture of two or more of the following: a pyrolyzed feedstock, a torrefied feedstock, and a feedstock that has not been pyrolyzed or torrefied) into syngas.
• feedstock or a mixture of feedstocks such as a mixture of two or more of the following: a pyrolyzed feedstock, a torrefied feedstock, and a feedstock that has not been pyrolyzed or torrefied
• Exemplary reactor configurations include, but are not limited to, fixed-bed reactors (such as countercurrent or co-current fixed- bed reactors), stationary fluidized-bed reactors, circulating fluid-bed reactors (such as those developed by Varnamo, Sweden), oxygen-driven fluid-bed reactors (such as those developed by Biosyn, Canada), bubbling fluid-bed reactors, pressurized fluid-bed reactors (such as pressurized bubbling or circulating fluid- bed reactors), moving-bed gasifiers (such as those developed by BMG, Finland), countercurrent moving-bed reactors, co-current moving-bed reactors, crosscurrent moving-bed reactors, entrained flow reactors (such as slagging or slag bath entrained-flow reactors), oxygen-blown gasifiers, steam gasifiers, and multistage gasifiers (such as those with a unit for combustion and a unit for gasification or those with a devolatilization unit and a reformer reactor).
• fixed-bed reactors such as countercurrent or co-current fixed- bed reactor
• the syngas reactor includes a devolatilization unit and a reformer reactor (see, for example, U.S. Patent. No. 6,863,878 and U.S. Patent. App. Pub. No. 2007/0205092, which are each incorporated herein by reference in their entireties).
• the reactor consists of a fixed bed of a feedstock through which a "gasification agent" (such as steam, oxygen, and/or air) flows in counter-current configuration.
• a "gasification agent” such as steam, oxygen, and/or air
• the ash is either removed dry or as a slag.
• the reactor is similar to the counter-current type, but the gasification agent gas flows in co-current configuration with the feedstock. Heat is added to the upper part of the bed, either by combusting small amounts of the feedstock or from external heat sources. The produced gas leaves the reactor at a high temperature, and much of this heat is transferred to the gasification agent added in the top of the bed, resulting in good energy efficiency. Since tars pass through a hot bed of char in this configuration, tar levels are much lower than the counter-current type.
• the feedstock is fluidized in oxygen and steam or air.
• the ash is removed dry or as heavy agglomerates that defluidize.
• the temperatures are relatively low in dry- ash reactors, so the feedstock is desirably highly reactive.
• the agglomerating reactors have slightly higher temperatures.
• Feedstock throughput is higher than for the fixed bed, but not as high as for the entrained flow reactor. Recycle or subsequent combustion of solids can be used to increase conversion.
• Fluidized- bed reactors are most useful for feedstocks that form highly corrosive ash that would damage the walls of slagging reactors.
• a dry pulverized solid, an atomized liquid feedstock, or a feedstock slurry is gasified with oxygen or air in co-current flow.
• the gasification reactions take place in a dense cloud of very fine particles.
• the high temperatures and pressures also mean that a higher throughput can be achieved; thermal efficiency is somewhat lower, however, as the gas is cooled before it can be cleaned with existing technology.
• the high temperatures also mean that tar and methane are not present in the product gas; the oxygen requirement can be higher than for the other types of reactors.
• Entrained-flow reactors remove the major part of the ash as a slag, as the operating temperature is well above the ash fusion temperature. A smaller fraction of the ash is produced either as a very fine dry fly ash or as a black- colored fly-ash slurry.
• Some feedstocks in particular certain types of biomass, can form slag that is corrosive for ceramic inner walls that serve to protect the reactor outer wall.
• some entrained-bed reactors do not possess a ceramic inner wall but have an inner water- or steam-cooled wall covered with partially solidified slag. These types of reactors do not suffer from corrosive slags.
• Some feedstocks have ashes with very high ash-fusion temperatures. In this case, limestone can be mixed with the feedstock prior to gasification. Addition of limestone usually can lower the fusion temperatures.
• the feedstock is pulverized, which requires somewhat more energy than for the other types of reactors.
• Torrefied or pyrolyzed biomass can be transported by any known means, such as by truck, train, ship, barge, tractor trailer, or any other vehicle or means of conveyance (e.g., a pipeline).
• a heated truck is used to transport pyrolysis oil or torrefied material to a unit for conversion to products.
• the present invention in certain variations, can utilize modular units for the pyrolysis, torrefaction, devolatilization, reforming, and/or gasification of biomass and other feedstocks to form useful products.
• a “modular unit” means an apparatus that is capable of either operably standing alone or of being operably connected with at least one other modular unit.
• a modular unit for the pyrolysis or torrefaction is in communication with (such as operably linked to) a modular unit for converting the pyrolyzed or torrefied feedstock into syngas.
• a modular unit for the pyrolysis or torrefaction is in communication with (such as operably linked to) a modular unit for devolatizing the feedstock.
• these modular units are also in communication with a modular unit for reforming the product of the devolatilization unit and/or one or more modular units for the conversion of syngas to another product, such as an alcohol.
• Placement of modular units near feedstock sources can minimize transportation energy and thereby increase the yield of syngas (and/or derivatives of syngas) per amount of energy expended.
• the modular unit is a portable unit, such as a unit mounted on skids, a platform, or a conveyer to facilitate the movement of the modular unit between different locations.
• the modular unit can be assembled and/or disassembled in fewer steps or in less time than for a unit that is not capable of being transported.
• a modular unit can be easily dismantled into one or more pieces that can be transported on the back of a tractor trailer.
• the modular unit weights less than or about 80,000, 60,000, or 40,000 lbs.
• the modular unit can be transported in a vehicle that satisfies the specifications for vehicle size and weight established by the U.S. Department of Transportation, which governs the use of the interstate highway system.
• syngas produced as described according to the present invention can be utilized in a number of ways.
• Syngas can generally be chemically converted and/or purified into hydrogen, carbon monoxide, methane, graphite, olefins (such as ethylene), oxygenates (such as dimethyl ether), alcohols (such as methanol and ethanol), paraffins, and other hydrocarbons.
• the syngas produced according to the methods and systems of the invention can further produce: a linear or branched C 5 -C 15 hydrocarbon, diesel fuel, gasoline, waxes, or olefins by Fischer- Tropsch chemistry; methanol, ethanol, and mixed alcohols by a variety of catalysts; isobutane by isosynthesis; ammonia by hydrogen production followed by the Haber process; aldehydes and alcohols by oxosynthesis; and many derivatives of methanol including dimethyl ether, acetic acid, ethylene, propylene, and formaldehyde by various processes.
• the syngas is converted to high yields of alcohols, particularly ethanol.
• Syngas can be selectively converted to ethanol by means of a chemical catalyst, such as described in U.S. Patent App. No. 12/166,203, entitled “METHODS AND APPARATUS FOR PRODUCING ALCOHOLS FROM SYNGAS,” filed July 1, 2008, whose assignee is the same as the assignee of this patent application, and which is hereby incorporated herein by reference.
• syngas can also be fermented to a mixture comprising ethanol using microorganisms.
• syngas produced according to the methods and systems of the invention can also be converted to energy.
• Syngas-based energy-conversion devices include a solid-oxide fuel cell, Stirling engine, micro-turbine, internal combustion engine, thermo-electric generator, scroll expander, gas burner, thermo-photovoltaic device, or gas-to-liquid device.
• the output syngas of two, or more, reactors can be combined to supply syngas to downstream subsystems comprised of syngas coolers, syngas cleaners, and syngas-based energy-conversion devices.

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