US20100275514A1 - Biomass gasification/pyrolysis system and process - Google Patents
Biomass gasification/pyrolysis system and process Download PDFInfo
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- US20100275514A1 US20100275514A1 US12/831,601 US83160110A US2010275514A1 US 20100275514 A1 US20100275514 A1 US 20100275514A1 US 83160110 A US83160110 A US 83160110A US 2010275514 A1 US2010275514 A1 US 2010275514A1
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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
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
- C10J3/34—Grates; Mechanical ash-removing devices
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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
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
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- 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
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- 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
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/16—Features of high-temperature carbonising processes
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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
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/06—Continuous processes
- C10J3/08—Continuous processes with ash-removal in liquid state
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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
- C10J3/72—Other features
- C10J3/723—Controlling or regulating the gasification process
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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
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
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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
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
- C10J2200/158—Screws
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- 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
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- 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
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
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- 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
- C10J2300/12—Heating the gasifier
- C10J2300/1269—Heating the gasifier by radiating device, e.g. radiant tubes
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- 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
- C10J2300/12—Heating the gasifier
- C10J2300/1269—Heating the gasifier by radiating device, e.g. radiant tubes
- C10J2300/1276—Heating the gasifier by radiating device, e.g. radiant tubes by electricity, e.g. resistor heating
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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
- 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
- C10J2300/1643—Conversion of synthesis gas to energy
- C10J2300/1646—Conversion of synthesis gas to energy integrated with a fuel cell
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- 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
- C10J2300/1693—Integration of gasification processes with another plant or parts within the plant with storage facilities for intermediate, feed and/or product
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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
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1853—Steam reforming, i.e. injection of steam only
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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
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1861—Heat exchange between at least two process streams
- C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
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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
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1861—Heat exchange between at least two process streams
- C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam
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- 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
- C10K1/02—Dust removal
- C10K1/024—Dust removal by filtration
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- 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
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- 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
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- 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
- the present invention generally relates to the conversion of organic lignocellulosic materials (biomass) into useful fuels (biofuels), and more particularly to a system and process capable of continuous conversion of biomass into synthesis gas (syngas).
- Syngas is a gas mixture containing carbon monoxide (CO) and hydrogen gas (H 2 ) produced by the conversion of carbonaceous materials, such as coal, petroleum, and biomass materials. Though having a lower energy density than natural gas, syngas is suitable for use as a fuel source for a variety of applications, including but not limited to gas turbines and automotive internal combustion engines. Syngas can also be used to produce methanol and hydrogen, or converted via the Fischer-Tropsch process to produce a synthetic petroleum substitute.
- CO carbon monoxide
- H 2 hydrogen gas
- syngas as a fuel is more efficient than direct combustion of the original biomass because more of the energy contained in the biomass is extracted by the conversion process, known as gasification.
- gasification a carbonaceous material is combusted in an atmosphere where the oxygen content is below the stoichiometric limit at which complete combustion can occur. This oxygen-starved combustion of carbonaceous material releases volatiles, in the case of dry feedstock, produces a carbon-rich char, and releases heat.
- This heat raises the temperature of non-combusted carbonaceous material, causing it to pyrolyze, releasing flammable volatiles such as carbon monoxide (CO), hydrogen (H 2 ) and, depending on the temperatures used, may also produce methane (CH 4 ) and hydrocarbon molecules having a greater number of carbon atoms.
- flammable volatiles such as carbon monoxide (CO), hydrogen (H 2 ) and, depending on the temperatures used, may also produce methane (CH 4 ) and hydrocarbon molecules having a greater number of carbon atoms.
- This blend of flammable volatiles is termed synthesis gas, or syngas, for short.
- the biomass gasification process employs sub-stoichiometric quantities of oxygen or air to combust a portion of the biomass and through pyrolysis, and the optional injection of steam, produce syngas and heat (energy).
- Pyrolysis is an endothermic process, and various heating techniques have been proposed for use in the production of syngas, including but not limited to partial combustion of the biomass products through air injection, direct heat transfer by mixing with a hot gas, indirect heat transfer with exchange surfaces (for example, walls or tubes), and direct heat transfer with circulating solids.
- Each of these heating techniques has significant technical shortcomings.
- partial combustion results in poor-quality products, for example, a syngas having an energy content of 150 BTU/ft 3 or less, because of the dilution of the fuel gasses by the nitrogen in the injected air and the gaseous products of the combustion.
- gasifier designs including counter-current fixed bed (up-draft) gasifiers, con-current fixed bed (down-draft) gasifiers, fluidized bed gasifiers, and entrained flow gasifiers.
- up-draft counter-current fixed bed
- down-draft con-current fixed bed
- fluidized bed gasifiers fluidized bed gasifiers
- entrained flow gasifiers entrained flow gasifiers.
- the most common type of gasifier used in biomass gasification is believed to be the up-draft design, in which a gasification agent (air, oxygen and/or steam) flows upward through a permeable bed of biomass and counter-currently to the flow of ash and other byproducts of the reaction.
- gasifier designs have significant technical shortcomings, particularly if the intent is to produce a syngas having a higher energy content, for example, about 300 BTU/ft 3 or more, from cellulosic agricultural residue.
- the present invention provides a system and process capable of efficient production of syngas from biomass materials in a manner capable of yielding energy contents of as much as 300 BTU/ft 3 and higher.
- the system includes a reactor containing a reactor tube having an internal passage, an entrance to the internal passage, and an exit to the internal passage, means for compacting a loose biomass material and simultaneously introducing the compacted biomass material into the entrance of the reactor tube, means for heating the compacted biomass material within the reactor tube to a temperature at which organic molecules within the compacted biomass material break down to form ash and a fuel gas mixture comprising predominantly carbon monoxide and hydrogen gases, means for withdrawing the fuel gas mixture from the reactor tube, means for removing the ash from the reactor tube through the exit thereof, and means comprising the entrance and the exit of the reactor tube, the compacting means, and the removing means for inhibiting ingress of air into the reactor tube by sufficiently compacting the biomass material at the entrance of the reactor tube to form a plug of the compacted biomass material at the entrance and compacting the ash at the exit of the reactor tube to form a plug of the ash at the exit.
- the process includes compacting a loose biomass material and simultaneously introducing the compacted biomass material into an entrance of a reactor tube, heating the compacted biomass material within the reactor tube to a temperature at which organic molecules within the compacted biomass material break down to form ash and a fuel gas mixture, withdrawing the fuel gas mixture from the reactor tube, removing the ash from the reactor tube through an exit thereof, and inhibiting ingress of air into the reactor tube by sufficiently compacting the biomass material at the entrance of the reactor tube to form a plug of the compacted biomass material at the entrance and compacting the ash at the exit of the reactor tube to form a plug of the ash at the exit.
- the system and process are capable of producing a syngas having an energy content higher than otherwise possible.
- FIG. 1 is a schematic of a biomass gasifier system incorporating a neutral atmospheric pressure capability in accordance with a preferred aspect of this invention.
- FIG. 1 schematically represents a biomass gasifier system 10 in accordance with an embodiment of the invention.
- the system 10 is configured to have a neutral atmospheric pressure reactor 12 , whose configuration is capable of minimizing energy input and equipment complexity of the system 10 .
- FIG. 1 represents a biomass material as being delivered to the reactor 12 from a bulk hopper 16 via a feeder device 18 , represented in FIG. 1 as an auger powered by a motor (M), though other methods of delivery are also within the scope of the invention, such as through the use of a ram or by gravity feed only.
- M motor
- the biomass material enters a reactor tube 14 within the reactor 12 through an entrance or throat 20 at an upper end of the tube 14 .
- the tube 14 serves as the containment vessel and defines an internal passage within which the gasification process occurs, producing syngas as a desired product and dry ash as a byproduct.
- the reactor 12 is configured such that syngas flows out, as does the ash. These characteristics distinguish the present invention from typical gasifiers.
- the reactor 12 is represented as comprising a single reactor tube 14 , though the reactor 12 could comprise an array of parallel tubes (linear, planar, or convex surface) in accordance with co-pending U.S. patent application Ser. No. 12/760,241.
- the tubes 14 are preferably arranged so that their throats 20 lie on a common two-dimensional (2-D) surface (either Euclidian or Riemann), such as on a rectilinear grid or other geometric arrangement for coupling with the biomass hopper 16 .
- 2-D two-dimensional
- the reactor 12 and its tube 14 are represented in FIG. 1 as vertically oriented, the tube 14 can be oriented horizontally or at various angles with respect to each other and with respect to gravity (vertical).
- the biomass conveyed from the hopper 16 into the open throat 20 of the reactor tube 14 is preferably size-reduced, as is typically the case for corn stover, wood chips, gin trash, dry distillers grain solids, and mess hall organic waste.
- the particle size of the biomass material is preferably limited to about one-sixth of the diameter of the reactor tube 14 . For reasons discussed in more detail below, it is advantageous that the amount of biomass material in the hopper 16 be maintained at a sufficient level to ensure that there is always biomass available to every tube 14 within the reactor 12 , such that backflow of syngas is minimized.
- the biomass within the hopper 16 may be stirred to maintain the material at a uniform height within the hopper 16 , especially if the plane in which the tube throat 20 lies is substantially normal to the earth's surface.
- the vertical orientation of the reactor tube 14 results in the biomass material being conveyed downward by gravity and/or other conveying means to the tube 14 .
- the exterior of the reactor 12 is represented in FIG. 1 as provided with heating elements 22 for heating the biomass within the tube 14 .
- the heating elements 22 can be of a variety of types, including but not limited to resistance heaters, radiant heaters including heat lamps, plasma heaters and electromagnetic heaters.
- the heating elements 22 are preferably arranged so that the tube 14 , and particularly multiple axially-spaced regions (Zones # 1 , # 2 and # 3 ) of the tube 14 , capture substantially all of the heat energy generated by the elements 22 and, if multiple tubes 14 are present, the temperature within a given zone within a tube 14 is as similar as possible to the same zone within other tubes.
- the diameter of the reactor tube 14 is preferably selected such that the heating elements 22 are as nearly as possible able to uniformly heat the biomass material across the cross-section of the tube 14 and within the time period required for the biomass material to travel through the tube 14 and become pyrolized.
- the length and diameter of the reactor tube 14 are interdependent based on this common concept.
- FIG. 1 further shows the reactor 12 fitted with a gas line 24 that withdraws syngas from the tube 14 as it is produced.
- the entrance to the gas line 24 is preferably oriented and located outside the heated zones to reduce the likelihood that biomass material will enter the gas line 24 .
- syngas produced by the pyrolysis and gasification process is drawn through the gas line 24 with a blower 26 (or other suitable device, such as a compressor).
- the blower 26 draws the syngas through a series of heat exchangers (HX) and particulate filters 30 before being delivered to a prime mover (as indicated in FIG. 1 ), a holding tank, downstream process, fuel cell, or any other suitable destination.
- HX heat exchangers
- particulate filters 30 particulate filters
- a gasification agent may be employed to assist in the conversion of char to syngas via the known water-gas shift reaction.
- the gasification agent may be steam and the source of the steam may be water that is drawn from a water source by a pump 42 and then heated by a heat exchanger 28 through which the syngas passes, such that the syngas serves as the heat source for generating the steam introduced into the tube 14 through the line 36 .
- the reactor 12 and its tube 14 are configured to promote compaction of the biomass within the throat 20 of the tube 14 , such that backflow of syngas through the tube 14 is inhibited.
- the biomass is preferably continuously supplied to the tube 14 to form a moving “plug” of biomass material within the tube throat 20 .
- the throat 20 may be configured to have a flared shape (not shown) that promotes compaction of the biomass as it enters the tube 14 .
- the tube 14 may be optionally sealed to prevent backflow of syngases toward the tube throat 20 , as well as to allow for maintenance.
- the continuous supply of biomass to the tube 14 also serves to push the dry ash byproduct of the reaction through the tube 14 and into a manifold 32 , which can employ gravity and/or another ash removal system 34 (such as the auger represented in FIG. 1 ) to remove the ash from the system 10 .
- a manifold 32 which can employ gravity and/or another ash removal system 34 (such as the auger represented in FIG. 1 ) to remove the ash from the system 10 .
- the biomass is continuously supplied to the reactor tube 14 to promote the formation of an ash plug within the ash removal system 34 located downstream of the manifold 32 , effectively forming a seal within the manifold 32 .
- the formation of an ash plug within the manifold 32 can be promoted by tapering the manifold 32 as shown in FIG.
- plugging the ends of the tube 14 with biomass and ash also serves to better contain the heat within the reactor tube 14 to promote the gasification reaction and reduce the risk of a fire in the hopper 16 .
- the degree to which the tube throat 20 is tapered, the degree to which the feeder device 16 is capable of packing the biomass material into the throat 20 , and the distance of the feeder device 16 from the opening of the throat 20 will all affect the axial length and density of the biomass plug within the tube 14 . It can be appreciated that there may be more than one combination of these three factors which provide the desired or optimal performance in a given configuration.
- the tube 14 may be equipped with means (not shown) for closing its throat 22 .
- closing means may include, but is not limited to, driving the corresponding feeder device 16 further into the throat 20 of the starved tube 14 and providing with a flat plate to promote a better seal, provide a knife valve at or near the throat 20 to seal a starved tube 14 , and/or closing a valve (not shown) through which syngas is drawn from the starved tube 14 .
- Each of these closing means individually or in combination, may be employed to minimize the risk of fire, minimize back-diffusion of the desired syngas product, and minimize heat loss to promote process efficiency and reduced hazard risks.
- the temperature of pyrolysis employed by this invention can vary, but preferably ranges from about 800 to about 1100° C.
- a temperature profile which most effectively converts the solid biomass into syngas. This profile may prompt the use of the three-zone heater arrangement shown in FIG. 1 where, for example, biomass encounters the first heating zone (Zone # 1 ) after it enters the tube 14 where the biomass is heated to nearly its volatilization temperature (typically around 350° C.), then enters a second heating zone (Zone # 2 ) where its temperature is increased to the full pyrolysis temperature, such that molecules are rapidly cracked before they can form heavy or toxic compounds. If a third heating zone (Zone # 3 ) is used as shown in FIG. 1 , the temperature within the third zone is maintained so that mineral ash remaining after pyrolysis will not form low-melting point glasses that may not flow readily through the reactor tube 14 .
- Waste heat generated from the heating elements 22 and lost from the tube 14 may be harvested and used for a variety of purposes.
- the gas effluent may also be run through a heat exchanger, heat pipe, or other means of heat transfer to provide heat which can be used to advantage in the overall method.
- the waste heat can be conveyed in many ways, including but not limited to a working fluid, a heat pipe (single-phase or two-phase), a conductive media such as metal or diamond, by radiation, or by convection of a suitable working fluid.
- the harvested waste heat may be used, as nonlimiting examples, to dry incoming biomass, heat the reactor tube 14 (such as at Zone # 1 ), and heat devices used to remove liquid and/or solid residues from the system.
- Waste heat may also be harvested in more useful forms, such as for the purpose of running a Stirling engine for mechanical work, operating a thermoelectric cooler (Peltier effect) for electrical power, or used outside the system 10 for essentially any desired purpose.
- Waste heat including exhaust gasses from a prime mover or SOFC, can be particularly useful for drying a biomass material that has a high moisture content. Injection of hot, dry air into the hopper 16 could be used for this purpose to obtain several benefits, including driving-off excess moisture in the biomass material and separating or fluffing the biomass material to avoid bridging or rat-holing.
- the primary axis of the reactor tube 14 is horizontal, it may be advantageous for the axis to tilt downward toward the end of the tube 14 opposite its throat 20 . The purpose of this slope is to encourage any gasses, rolling debris, or packed ash to be conveyed to the ash manifold 32 coupled to the end of the tube 14 .
- the primary axis of the reactor tube 14 is essentially vertical, it may be advantageous to provide the tube 14 with one or more spikes (not shown) that project into the interior of the tube 14 so that biomass material falling into the tube 14 impinges the spikes to break up any large biomass chunks as well as restrict the flow of biomass material through the tube 14 and thereby increase the residence time of the biomass material within the hottest zones of the tube 14 .
- a grate can be located at or near the base of each spike to assure that little or no biomass material falls entirely through the reactor tube 14 without becoming gasified.
- the system 10 of this invention is configured to have a neutral atmospheric pressure achieved by plugging the entrance (throat 20 ) and exit (manifold 32 ) of the tube 14 with biomass and ash, respectively.
- a neutral atmospheric pressure achieved by plugging the entrance (throat 20 ) and exit (manifold 32 ) of the tube 14 with biomass and ash, respectively.
- Such a capability can be promoted by utilizing highly sensitive differential pressure sensors 38 at the tube entrance and/or the ash removal section of the system 10 and a closed-loop control system 40 to monitor and adjust the volumetric rate of gaseous discharge via the blower 26 used to draw the syngas through the gas line 24 .
- the integrity of the biomass and ash seals at a given pressure is a function of leakage rate due to the porosity/composition of the biomass or ash plug.
- the porosity of the plugs can be adjusted by the degree of compaction of the biomass material being transported. This capability is particularly desirable from the stand point of eliminating the need for a lock hopper system to prevent the ingress of air into the reactor tube 14 or unwanted leakage of syngas from the ash removal section 34 by ensuring that the system 10 operates with inlet and outlet pressures within certain limits.
- the closed-loop control system 40 can also be used to introduce a controlled amount of water or water vapor (including steam) based on properties of the syngas. These properties may include, but are not limited to, the moisture content of the syngas, the moisture content of the incoming carbonaceous feedstock material, the amount of liquid condensed out in a condenser, the conductivity of the gas, or other means known to those skilled in the art. There are also means by which the output gas properties, such as pressure or temperature, can be used in a chemical and/or mechanical system to regulate the amount of water introduced. Introduction of the water may be accomplished in many ways, including but not limited to injection, osmosis, control valve, diffusion, or wicking/capillary action.
Abstract
Description
- This application claims the benefit of U.S. Provisional Application No. 61/270,393, filed Jul. 8, 2009, and is a continuation-in-part patent application of co-pending U.S. patent application Ser. No. 12/760,241, filed Apr. 14, 2010, which claims the benefit of U.S. Provisional Application No. 61/212,624, filed Apr. 14, 2009. The contents of these prior patent applications are incorporated herein by reference.
- The present invention generally relates to the conversion of organic lignocellulosic materials (biomass) into useful fuels (biofuels), and more particularly to a system and process capable of continuous conversion of biomass into synthesis gas (syngas).
- Syngas is a gas mixture containing carbon monoxide (CO) and hydrogen gas (H2) produced by the conversion of carbonaceous materials, such as coal, petroleum, and biomass materials. Though having a lower energy density than natural gas, syngas is suitable for use as a fuel source for a variety of applications, including but not limited to gas turbines and automotive internal combustion engines. Syngas can also be used to produce methanol and hydrogen, or converted via the Fischer-Tropsch process to produce a synthetic petroleum substitute.
- The use of syngas as a fuel is more efficient than direct combustion of the original biomass because more of the energy contained in the biomass is extracted by the conversion process, known as gasification. Within a typical biomass gasifier, a carbonaceous material is combusted in an atmosphere where the oxygen content is below the stoichiometric limit at which complete combustion can occur. This oxygen-starved combustion of carbonaceous material releases volatiles, in the case of dry feedstock, produces a carbon-rich char, and releases heat. This heat raises the temperature of non-combusted carbonaceous material, causing it to pyrolyze, releasing flammable volatiles such as carbon monoxide (CO), hydrogen (H2) and, depending on the temperatures used, may also produce methane (CH4) and hydrocarbon molecules having a greater number of carbon atoms. This blend of flammable volatiles is termed synthesis gas, or syngas, for short.
- In the case of dry feedstock material, it is possible to convert the char into flammable volatiles. One such method is the injection of steam (H2O), which reacts with the char to produce more CO and H2, according to the reaction
-
C+H2O→H2+CO - Consequently, the biomass gasification process employs sub-stoichiometric quantities of oxygen or air to combust a portion of the biomass and through pyrolysis, and the optional injection of steam, produce syngas and heat (energy).
- Pyrolysis is an endothermic process, and various heating techniques have been proposed for use in the production of syngas, including but not limited to partial combustion of the biomass products through air injection, direct heat transfer by mixing with a hot gas, indirect heat transfer with exchange surfaces (for example, walls or tubes), and direct heat transfer with circulating solids. Each of these heating techniques has significant technical shortcomings. For example, partial combustion results in poor-quality products, for example, a syngas having an energy content of 150 BTU/ft3 or less, because of the dilution of the fuel gasses by the nitrogen in the injected air and the gaseous products of the combustion. With direct heat transfer, typically with a product gas that is reheated and recycled, a shortcoming is that a very large ratio of recycle gas to feed gas is required to provide sufficient heat with reasonable gas flowrates. For indirect heat transfer, it can be difficult to maintain desired heat transfer rates because the process deposits coatings on the heat transfer surfaces that act as insulating materials. Finally, direct heat transfer with circulating solids is effective but requires complex technology because the circulating solids, which typically transfer heat between a burner and a pyrolysis reactor, involve a moving bed that requires a significant investment in equipment and energy management to be effective in a continuous process.
- Various types of gasifier designs are known, including counter-current fixed bed (up-draft) gasifiers, con-current fixed bed (down-draft) gasifiers, fluidized bed gasifiers, and entrained flow gasifiers. The most common type of gasifier used in biomass gasification is believed to be the up-draft design, in which a gasification agent (air, oxygen and/or steam) flows upward through a permeable bed of biomass and counter-currently to the flow of ash and other byproducts of the reaction. These gasifier designs have significant technical shortcomings, particularly if the intent is to produce a syngas having a higher energy content, for example, about 300 BTU/ft3 or more, from cellulosic agricultural residue. Most current available technologies, including up-draft and down-draft fixed beds, fluidized beds, or entrained flow gasifiers, can be either pressurized or non-pressurized (atmospheric) design. As previously noted, the use of air for partial combustion to provide the energy for pyrolysis and gasification introduces a large volume of inert diluting gas (nitrogen), which is the major contributing factor to the production of low BTU syngas. Because biomass is a low-energy content fuel and is dispersed geographically, low-BTU syngas negatively affects the economic payback for the gasifier system. The use of an external heat source and/or pure oxygen would overcome the diluent effect of air to allow for the production of a medium BTU syngas (about 300 BTU/ft3 or more). However, a major problem remains as to how to prevent the ingress of air while allowing the egress of syngas from the feed material ingress and the egress of ash from the spent material outlet.
- The present invention provides a system and process capable of efficient production of syngas from biomass materials in a manner capable of yielding energy contents of as much as 300 BTU/ft3 and higher.
- According to a first aspect of the invention, the system includes a reactor containing a reactor tube having an internal passage, an entrance to the internal passage, and an exit to the internal passage, means for compacting a loose biomass material and simultaneously introducing the compacted biomass material into the entrance of the reactor tube, means for heating the compacted biomass material within the reactor tube to a temperature at which organic molecules within the compacted biomass material break down to form ash and a fuel gas mixture comprising predominantly carbon monoxide and hydrogen gases, means for withdrawing the fuel gas mixture from the reactor tube, means for removing the ash from the reactor tube through the exit thereof, and means comprising the entrance and the exit of the reactor tube, the compacting means, and the removing means for inhibiting ingress of air into the reactor tube by sufficiently compacting the biomass material at the entrance of the reactor tube to form a plug of the compacted biomass material at the entrance and compacting the ash at the exit of the reactor tube to form a plug of the ash at the exit.
- According to a second aspect of the invention, the process includes compacting a loose biomass material and simultaneously introducing the compacted biomass material into an entrance of a reactor tube, heating the compacted biomass material within the reactor tube to a temperature at which organic molecules within the compacted biomass material break down to form ash and a fuel gas mixture, withdrawing the fuel gas mixture from the reactor tube, removing the ash from the reactor tube through an exit thereof, and inhibiting ingress of air into the reactor tube by sufficiently compacting the biomass material at the entrance of the reactor tube to form a plug of the compacted biomass material at the entrance and compacting the ash at the exit of the reactor tube to form a plug of the ash at the exit.
- By preventing the ingress of air with the biomass and ash plugs at the entrance and exit, respectively, of the reactor tube, the system and process are capable of producing a syngas having an energy content higher than otherwise possible. Other aspects and advantages of this invention will be better appreciated from the following detailed description.
-
FIG. 1 is a schematic of a biomass gasifier system incorporating a neutral atmospheric pressure capability in accordance with a preferred aspect of this invention. -
FIG. 1 schematically represents abiomass gasifier system 10 in accordance with an embodiment of the invention. Thesystem 10 is configured to have a neutralatmospheric pressure reactor 12, whose configuration is capable of minimizing energy input and equipment complexity of thesystem 10.FIG. 1 represents a biomass material as being delivered to thereactor 12 from abulk hopper 16 via afeeder device 18, represented inFIG. 1 as an auger powered by a motor (M), though other methods of delivery are also within the scope of the invention, such as through the use of a ram or by gravity feed only. The biomass material enters areactor tube 14 within thereactor 12 through an entrance orthroat 20 at an upper end of thetube 14. Thetube 14 serves as the containment vessel and defines an internal passage within which the gasification process occurs, producing syngas as a desired product and dry ash as a byproduct. Thereactor 12 is configured such that syngas flows out, as does the ash. These characteristics distinguish the present invention from typical gasifiers. Thereactor 12 is represented as comprising asingle reactor tube 14, though thereactor 12 could comprise an array of parallel tubes (linear, planar, or convex surface) in accordance with co-pending U.S. patent application Ser. No. 12/760,241. If an array ofreactor tubes 14 is employed, thetubes 14 are preferably arranged so that theirthroats 20 lie on a common two-dimensional (2-D) surface (either Euclidian or Riemann), such as on a rectilinear grid or other geometric arrangement for coupling with the biomass hopper 16. Though thereactor 12 and itstube 14 are represented inFIG. 1 as vertically oriented, thetube 14 can be oriented horizontally or at various angles with respect to each other and with respect to gravity (vertical). - The biomass conveyed from the
hopper 16 into theopen throat 20 of thereactor tube 14 is preferably size-reduced, as is typically the case for corn stover, wood chips, gin trash, dry distillers grain solids, and mess hall organic waste. The particle size of the biomass material is preferably limited to about one-sixth of the diameter of thereactor tube 14. For reasons discussed in more detail below, it is advantageous that the amount of biomass material in thehopper 16 be maintained at a sufficient level to ensure that there is always biomass available to everytube 14 within thereactor 12, such that backflow of syngas is minimized. The biomass within thehopper 16 may be stirred to maintain the material at a uniform height within thehopper 16, especially if the plane in which thetube throat 20 lies is substantially normal to the earth's surface. InFIG. 1 , the vertical orientation of thereactor tube 14 results in the biomass material being conveyed downward by gravity and/or other conveying means to thetube 14. - The exterior of the
reactor 12 is represented inFIG. 1 as provided withheating elements 22 for heating the biomass within thetube 14. Theheating elements 22 can be of a variety of types, including but not limited to resistance heaters, radiant heaters including heat lamps, plasma heaters and electromagnetic heaters. Theheating elements 22 are preferably arranged so that thetube 14, and particularly multiple axially-spaced regions (Zones # 1, #2 and #3) of thetube 14, capture substantially all of the heat energy generated by theelements 22 and, ifmultiple tubes 14 are present, the temperature within a given zone within atube 14 is as similar as possible to the same zone within other tubes. The diameter of thereactor tube 14 is preferably selected such that theheating elements 22 are as nearly as possible able to uniformly heat the biomass material across the cross-section of thetube 14 and within the time period required for the biomass material to travel through thetube 14 and become pyrolized. Thus, the length and diameter of thereactor tube 14 are interdependent based on this common concept. -
FIG. 1 further shows thereactor 12 fitted with agas line 24 that withdraws syngas from thetube 14 as it is produced. The entrance to thegas line 24 is preferably oriented and located outside the heated zones to reduce the likelihood that biomass material will enter thegas line 24. In the embodiment represented inFIG. 1 , syngas produced by the pyrolysis and gasification process is drawn through thegas line 24 with a blower 26 (or other suitable device, such as a compressor). Theblower 26 draws the syngas through a series of heat exchangers (HX) andparticulate filters 30 before being delivered to a prime mover (as indicated inFIG. 1 ), a holding tank, downstream process, fuel cell, or any other suitable destination. A gasification agent may be employed to assist in the conversion of char to syngas via the known water-gas shift reaction. As represented inFIG. 1 , the gasification agent may be steam and the source of the steam may be water that is drawn from a water source by apump 42 and then heated by aheat exchanger 28 through which the syngas passes, such that the syngas serves as the heat source for generating the steam introduced into thetube 14 through the line 36. - According to a preferred aspect of the invention, the
reactor 12 and itstube 14 are configured to promote compaction of the biomass within thethroat 20 of thetube 14, such that backflow of syngas through thetube 14 is inhibited. For this purpose, the biomass is preferably continuously supplied to thetube 14 to form a moving “plug” of biomass material within thetube throat 20. Thethroat 20 may be configured to have a flared shape (not shown) that promotes compaction of the biomass as it enters thetube 14. Thetube 14 may be optionally sealed to prevent backflow of syngases toward thetube throat 20, as well as to allow for maintenance. The continuous supply of biomass to thetube 14 also serves to push the dry ash byproduct of the reaction through thetube 14 and into a manifold 32, which can employ gravity and/or another ash removal system 34 (such as the auger represented inFIG. 1 ) to remove the ash from thesystem 10. In this manner, in addition to forming the aforementioned plug of biomass material to seal thethroat 20 of thetube 14, the biomass is continuously supplied to thereactor tube 14 to promote the formation of an ash plug within theash removal system 34 located downstream of the manifold 32, effectively forming a seal within themanifold 32. The formation of an ash plug within the manifold 32 can be promoted by tapering the manifold 32 as shown inFIG. 1 , which forces or compacts the ash similarly to an extrusion process. An alternative is to have a section of pipe where the transport mechanism (for example, the auger or other device) through the manifold 32 is absent or interrupted and the ash is forced through this portion, thus compacting the ash slightly. - In addition to forming a barrier to the ingress of air into the
tube 14, plugging the ends of thetube 14 with biomass and ash also serves to better contain the heat within thereactor tube 14 to promote the gasification reaction and reduce the risk of a fire in thehopper 16. The degree to which thetube throat 20 is tapered, the degree to which thefeeder device 16 is capable of packing the biomass material into thethroat 20, and the distance of thefeeder device 16 from the opening of thethroat 20 will all affect the axial length and density of the biomass plug within thetube 14. It can be appreciated that there may be more than one combination of these three factors which provide the desired or optimal performance in a given configuration. To address the contingency that thetube 14 becomes starved of biomass material, thetube 14 may be equipped with means (not shown) for closing itsthroat 22. Such closing means may include, but is not limited to, driving thecorresponding feeder device 16 further into thethroat 20 of the starvedtube 14 and providing with a flat plate to promote a better seal, provide a knife valve at or near thethroat 20 to seal astarved tube 14, and/or closing a valve (not shown) through which syngas is drawn from the starvedtube 14. Each of these closing means, individually or in combination, may be employed to minimize the risk of fire, minimize back-diffusion of the desired syngas product, and minimize heat loss to promote process efficiency and reduced hazard risks. - Further features of the
system 10 and of thetube 14 of thesystem 10 are discussed below, some of which are similar to or derived from certain process and design parameters reported in U.S. patent application Ser. No. 12/357,788. - The temperature of pyrolysis employed by this invention can vary, but preferably ranges from about 800 to about 1100° C. Within the
reactor tube 14, there is preferably a temperature profile which most effectively converts the solid biomass into syngas. This profile may prompt the use of the three-zone heater arrangement shown inFIG. 1 where, for example, biomass encounters the first heating zone (Zone #1) after it enters thetube 14 where the biomass is heated to nearly its volatilization temperature (typically around 350° C.), then enters a second heating zone (Zone #2) where its temperature is increased to the full pyrolysis temperature, such that molecules are rapidly cracked before they can form heavy or toxic compounds. If a third heating zone (Zone #3) is used as shown inFIG. 1 , the temperature within the third zone is maintained so that mineral ash remaining after pyrolysis will not form low-melting point glasses that may not flow readily through thereactor tube 14. - Waste heat generated from the
heating elements 22 and lost from thetube 14 may be harvested and used for a variety of purposes. The gas effluent may also be run through a heat exchanger, heat pipe, or other means of heat transfer to provide heat which can be used to advantage in the overall method. The waste heat can be conveyed in many ways, including but not limited to a working fluid, a heat pipe (single-phase or two-phase), a conductive media such as metal or diamond, by radiation, or by convection of a suitable working fluid. The harvested waste heat may be used, as nonlimiting examples, to dry incoming biomass, heat the reactor tube 14 (such as at Zone #1), and heat devices used to remove liquid and/or solid residues from the system. Waste heat may also be harvested in more useful forms, such as for the purpose of running a Stirling engine for mechanical work, operating a thermoelectric cooler (Peltier effect) for electrical power, or used outside thesystem 10 for essentially any desired purpose. Waste heat, including exhaust gasses from a prime mover or SOFC, can be particularly useful for drying a biomass material that has a high moisture content. Injection of hot, dry air into thehopper 16 could be used for this purpose to obtain several benefits, including driving-off excess moisture in the biomass material and separating or fluffing the biomass material to avoid bridging or rat-holing. - If the primary axis of the
reactor tube 14 is horizontal, it may be advantageous for the axis to tilt downward toward the end of thetube 14 opposite itsthroat 20. The purpose of this slope is to encourage any gasses, rolling debris, or packed ash to be conveyed to theash manifold 32 coupled to the end of thetube 14. If the primary axis of thereactor tube 14 is essentially vertical, it may be advantageous to provide thetube 14 with one or more spikes (not shown) that project into the interior of thetube 14 so that biomass material falling into thetube 14 impinges the spikes to break up any large biomass chunks as well as restrict the flow of biomass material through thetube 14 and thereby increase the residence time of the biomass material within the hottest zones of thetube 14. In addition, a grate (not shown) can be located at or near the base of each spike to assure that little or no biomass material falls entirely through thereactor tube 14 without becoming gasified. - As previously noted, to minimize energy input and equipment complexity, the
system 10 of this invention is configured to have a neutral atmospheric pressure achieved by plugging the entrance (throat 20) and exit (manifold 32) of thetube 14 with biomass and ash, respectively. Such a capability can be promoted by utilizing highly sensitivedifferential pressure sensors 38 at the tube entrance and/or the ash removal section of thesystem 10 and a closed-loop control system 40 to monitor and adjust the volumetric rate of gaseous discharge via theblower 26 used to draw the syngas through thegas line 24. The integrity of the biomass and ash seals at a given pressure is a function of leakage rate due to the porosity/composition of the biomass or ash plug. The porosity of the plugs can be adjusted by the degree of compaction of the biomass material being transported. This capability is particularly desirable from the stand point of eliminating the need for a lock hopper system to prevent the ingress of air into thereactor tube 14 or unwanted leakage of syngas from theash removal section 34 by ensuring that thesystem 10 operates with inlet and outlet pressures within certain limits. - The closed-
loop control system 40, with suitable parameters (such as a PID controller or other methods known to those skilled in the art), can also be used to introduce a controlled amount of water or water vapor (including steam) based on properties of the syngas. These properties may include, but are not limited to, the moisture content of the syngas, the moisture content of the incoming carbonaceous feedstock material, the amount of liquid condensed out in a condenser, the conductivity of the gas, or other means known to those skilled in the art. There are also means by which the output gas properties, such as pressure or temperature, can be used in a chemical and/or mechanical system to regulate the amount of water introduced. Introduction of the water may be accomplished in many ways, including but not limited to injection, osmosis, control valve, diffusion, or wicking/capillary action. - As should be understood, particularly in view of the foregoing discussion, the ingress of air into the
reactor tube 14 would have an unwanted diluent effect on the syngas produced, thus reducing its heating value and leading to an overall net energy efficiency decrease, while leakage of syngas from thereactor 12 would introduce potentially significant safety issues and have a net overall decrease in energy efficiency, especially if the leakage is such as to reduce the energy production capabilities of thesystem 10. Without the use of biomass and ash plugs within thetube throat 20 andmanifold 32, respectively, direct diffusion of air into thesystem 10 and syngas out of thesystem 10 at balanced is only 4.277×10−6 and 9.427×10−4 mass fraction of syngas production rate, respectively. By utilizing plugs at these locations, the direct diffusion rate is even smaller, resulting in an efficient syngas production process capable of yielding energy contents of as much as 300 BTU/ft3 and higher. - While the invention has been described in terms of a specific embodiment, it is apparent that other forms could be adopted by one skilled in the art. For example, the physical configuration of the
system 10 and its components could differ from that shown, and materials and processes other than those noted could be used. Therefore, the scope of the invention is to be limited only by the following claims.
Claims (20)
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Also Published As
Publication number | Publication date |
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US10093875B2 (en) | 2018-10-09 |
US20160319207A1 (en) | 2016-11-03 |
US20140021028A1 (en) | 2014-01-23 |
US9416326B2 (en) | 2016-08-16 |
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