WO1983000638A1 - Procede et systeme de production d'hydrogene au moyen d'un lit fluidifie rotatif - Google Patents

Procede et systeme de production d'hydrogene au moyen d'un lit fluidifie rotatif Download PDF

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Publication number
WO1983000638A1
WO1983000638A1 PCT/US1979/001089 US7901089W WO8300638A1 WO 1983000638 A1 WO1983000638 A1 WO 1983000638A1 US 7901089 W US7901089 W US 7901089W WO 8300638 A1 WO8300638 A1 WO 8300638A1
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Prior art keywords
chamber
particles
steam
bed
perforated wall
Prior art date
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PCT/US1979/001089
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English (en)
Inventor
William H Belke
George B Grim
Original Assignee
Belke, William, H.
Grim, George, B.
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Filing date
Publication date
Application filed by Belke, William, H., Grim, George, B. filed Critical Belke, William, H.
Priority to PCT/US1979/001089 priority Critical patent/WO1983000638A1/fr
Publication of WO1983000638A1 publication Critical patent/WO1983000638A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/725—Redox processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
    • B01J8/382—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it with a rotatable device only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
    • C01B3/105—Cyclic methods
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • 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
    • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
    • 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
    • C10J2300/093—Coal
    • 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
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • 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
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • 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
    • C10J2300/12—Heating the gasifier
    • C10J2300/1253—Heating the gasifier by injecting hot gas
    • 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
    • C10J2300/1869—Heat exchange between at least two process streams with one stream being air, oxygen or ozone
    • 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
    • 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
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates generally to the production of hydrogen and, more particularly, to a method and rotating fluidized bed apparatus for the production of hydrogen by the iron-steam process.
  • fluidized beds have found many diverse uses in power generating systems and chemical processes. They have served as chemical reactors, particularly for finely divided materials; as incin ⁇ erators for liquid, solid or gaseous substances; as pressurized' or atmospheric, coal-, lignite-, petroleum-, peat-, wood- and/or paper-fired boiler or combustor units for power generation; and, as sites for various process treatments such as drying, baking, coating, oxidizing, etc.
  • fluidized beds which are in use today are static beds established when air or other fluidiz- ing gas is introduced into a plenum chamber under pressure and forced upwardly through a diffusing medium (e.g., membrane, grate) to a superimposed chamber containing a particulate bed, of inert or reactive, finely divided, pulverulent solid material.
  • a diffusing medium e.g., membrane, grate
  • Gas forced upwardly through the diffusing medium into the fluidizing chamber under a sufficient pre ⁇ determined pressure, fluidizes the particulates.
  • the gas pressure required to accomplish this is de ⁇ termined, in part, by the nature and degree of fine ⁇ ness of the particulates to be fluidized.
  • Other diffusing medium e.g., membrane, grate
  • O ..T1 influencing factors are the depth of the bed and the size, number and design of the plenum chamber com ⁇ partments and passages into the superimposed fluidiz- ing chamber.
  • the rate at which a chemical reaction takes place in a fluidized bed between a solid material and a gaseous agent depends to a major extent on the rate at which the reactants are brought together, the rate at which the heat of reaction is furnished or removed and the rate at which the reaction products are re ⁇ moved.
  • the rate at which the fluidizing gaseous agent, which by and large also serves as the fluidizing agent, can be blown through the bed is limited by the fact that the fluidizing currents within the fluidized zone are vertical, i.e., only the gravity force on the bed particles opposes the balancing gaseous agent force needed to maintain fluidization. If the force opposing the balancing fluidizing force could be increased, then the fluidizing agent flow rate through the bed and the reaction rate of the system would be increased.
  • the extent of the centrifugal force and, thus, of the opposing fluidizing gaseous agent rate can be controlled by controlling the speed of bed rotation.
  • the Swithen ⁇ bank system includes a vertical shaft around which rotates a generally cylindrical combustor using natural gas as the fuel.
  • the gas is introduced at the center of the combustor, i.e., along the axis of rotation, and is mixed with fluidizing air forced through the bed particles from the bed periphery toward the cen ⁇ ter.
  • the bed which is heated by the combustion heat generated and the mixing action accompanying rotation, preheats the ' entering fluidizing air.
  • this is accomplished by providing a multi stage hydrogen generator and method for generating hydrogen wherein a first stage produces a relatively low BTU gas, a second stage utilizes the gas in an exothermic re ⁇ action to reduce ferric oxide to iron and to generate
  • At least one of the stages utilizes a rotating fluidized bed system to provide enhanced reaction efficiency and economy of operation.
  • the multi ⁇ stage hydrogen generator includes a condenser to cool the hydrogen rich gas stream generated in the third stage.
  • the steam portion of the gas stream is condensed and the condensate utilized in second stage steam generation.
  • a rotating fluidized bed is used in each of the stages to accelerate the chemical reactions, and a rotating fluidized bed heat exchanger is used as the condenser.
  • the hydrogen produced by the multi ⁇ stage generator of the present invention exceeds 99% in purity and can usefully serve as the fuel in * a gas turbine or other combustion engine.
  • Figure 1 is a block diagram of a three stage preferred hydrogen generator system of the present invention.
  • Figures 2A and 2B are composite drawings,com- prising two sheets assembled along lines 2A and 2B, illustrating a side elevational schematic view of one embodiment of a three stage hydrogen generator of the present invention showing the use of rotating fluidized beds in each of the three stages and in the condenser.
  • FIG 3 shows the manner in which Figures 2A and 2B are assembled.
  • the multi stage hydrogen generator system of the present invention utilizing a rotating fluidized bed in at least one of its stages for enhanced effi ⁇ ciency, economy and compactness, has wide utility whereever hydrogen generators may be used but, due to its outstanding compactness and high capacity, is particularly adaptable for fueling gas turbine engines in plants located on small sites and in rela ⁇ tively congested areas.
  • FIG 1 the general outline of the preferred three stage hydrogen generator system 10 of the present invention is more clearly depicted. As can be seen, the system 10 in ⁇ cludes a first stage 12 in which a low BTU gas compris ⁇ ing at least hydrogen and carbon monoxide is produced for use in the second stage of the generator system.
  • the first stage comprises a combustor- gasifier arrangement in which powdered coal is em ⁇ ployed as the solid fuel.
  • the coal exothermically reacts with oxygen (air) to produce carbon dioxide and approximately" 174,000 BTU/mole of carbon combusted.
  • Water fed to the combustor generally in the form of steam, reacts endothermically with the carbon in the combustor at the high temperatures generated by the carbon-oxygen combustion reaction to produce carbon monoxide, carbon dioxide and hydrogen.
  • the combustion and reaction product gases generated in the first stage 12 provide a low BTU gas (about 150-
  • BTU gas from first stage 12 is reacted with ferric oxide (Fe ⁇ O.) to reduce the oxide to nearly pure iron
  • the heat evolved from the reaction is extracted by steam generation means, such as a steam generator coil communicating with a source of water, to pro ⁇ cute steam, preferably superheated steam, used in the third stage 16 of the system.
  • steam generation means such as a steam generator coil communicating with a source of water
  • pro ⁇ preferably superheated steam
  • the unreacted and reaction product gases leaving the second stage 14 are relatively lean and may be used for power gen ⁇ eration or for other useful purposes in other portions of the system.
  • the relatively pure iron powder and the steam generated in second stage 14 are directed into third stage 16 wherein the steam and iron react to produce a relatively hot, hydrogen rich gas stream according to the following reaction:
  • any heat required by this reaction may be derived from the superheat of the reactant steam.
  • the iron oxide produced is returned to the second stage 14 for use in the iron oxide reduction reac ⁇ tion taking place therein.
  • the gas stream produced in the third --itage comprises a mixture of reaction product hydrogen and unreacted steam.
  • the hydrogen and steam are readily separated in condenser 18 where ⁇ in the relatively hot gas stream (at least about 212°F.) gives up thermal energy to air or water passed in heat exchange relationship thereto.
  • the steam in the gas stream is caused to condense and may be directed, via condensate return line 20, into the second stage 14 of the generator system as the water source for the production of superheated steam.
  • the exiting heated air may be di ⁇ rected via air return line 22 back to the first stage 12 of the generator system as the combustion air source for reaction with the solid fuel therein.
  • at least one of stages 12, 14, 16 utilizes a rotating fluidized bed, for example, as the combustor-gasifier in first stage 12 and/or as a reaction chamber in second and/or third stages 14, 16.
  • condenser 18 desirably comprises a rotating fluidized bed heat exchanger.
  • the hydrogen generator system 10 benefits from improved heat transfer rates, enhanced mixing of reactants and accelerated chemical reaction rates, all contributing to increasing the compactness and capacity of the system.
  • the over-all compactness and efficiency of the sys- tern suffers.
  • system 10 is superior to exist ⁇ ing hydrogen gas generation systems as long as at least one of the stages 12,14, 16 utilizes a rotating fluidized bed.
  • First stage 12 is desirably a rotating fluidized bed combustor-gasifier unit 100 capable of compactly generating a low BTU gas com ⁇ prising carbon monoxide and hydrogen for use in the second stage 14 of the system.
  • Combustor-gasifier unit 100 includes a housing 101 through which com ⁇ pressed air is ducted into inlet plenum chamber 102.
  • the compressed air is desirably preheated air.
  • a co pressor means 50 shown in phantom, may be employed to draw cool or preheated air into housing 101 and to compress the air.
  • an external source of compressed air can be fed directly into inlet plenum chamber 102.
  • Fuel fed through entry port 104 is mixed with the compressed air prior to entering the inlet plenum chamber 102 and is conveyed by the air to the rotating fluidized bed portion 106 of the combustor-gasifier.
  • the fuel is powdered coal, desirably solvent refined coal, to minimize ash removal problems.
  • the rotating fluidized bed portion 106 comprises an outer perforated cylindrical wall 108, an inner perforated cylindrical wall 110 and appropriate en- closing walls 109 defining therebetween an annular fluidizing chamber 112 in which pulverulent solid particles 114 are disposed.
  • the perforations in walls 108 and 110 are small enough to contain par ⁇ ticles 114 within chamber 112 and to control the exhaust of solid combustion and reaction products
  • the fluidized bed portion 106 rotates on horizontal, vertical or other appropriate axis, preferably about a longitudi ⁇ nal axis 119 which corresponds to the axis of coaxial cylindrical walls 108, 110. Rotation is motivated by available rotational means 111, such as appropriate gearing to drives for conventional engine functions, and is controlled to a speed sufficient to impart a centrifugal force to the particles 114 within the bed.
  • the centrifugal force causes the particles 114 to gravitate away from axis 119 toward outer perforated wall 108.
  • the flow of air and steam from inlet plenum chamber 102 through perforated outer wall 108 opposes the centrifugally induced movement of the particles 114 and, in so doing, fluidizes the bed.
  • Combustion occurs within the fluidizing chamber 112 between the fluidizing air and the fuel, e.g., powdered coal, to produce hot combustion gases and release a large amount of thermal energy within the bed. Combustion may also occur outside the fluid- izing chamber 112, for example within elongated cylin ⁇ drical core chamber 118.
  • reaction occurs within the. fluidizing chamber 112 between the fluidizing steam and the carbon par ⁇ ticles, e.g., powdered coal, in the bed to produce hot reaction product gases within the bed.
  • These hot reaction product gases and hot combustion gases are swept out of the bed through inner perforated wall 110 by the continuing flow of air and steam through the bed.
  • the unreacted air and steam and the hot combustion and reaction product gases pass from outlet plenum chamber 116 into core 118 where they mix with any combustion gases which may have formed as a result of combustion within core 118.
  • core 118 is an elongated cylindrical chamber which directs the flow of unre ⁇ acted air and steam and combustion and reaction pro- duct gases to the second stage 14 of system 10.
  • the bed particles 114 are preferably an admix ⁇ ture of inert materials, e.g., sand, dolomite, other sulfur absorbers, or any other inert material gener ⁇ ally found suitable for use in fluidized beds, and a carbonaceous fuel, such as powdered coal.
  • inert materials e.g., sand, dolomite, other sulfur absorbers, or any other inert material gener ⁇ ally found suitable for use in fluidized beds
  • a carbonaceous fuel such as powdered coal.
  • a suitable combination of materials com ⁇ prises a particulate mixture of coal, dolomite, sand and coal ash.
  • a generally useful proportion of bed particles is 95% inert materials, 5%fuel.
  • coal ash is formed and becomes a part of the inert particulate portion of the bed.
  • Spent bed material is removed from the bed through bed reclaiming outlet conduit 130.
  • Any ash and sulfur in the spent bed material may be separated and removed by separation means 134 and the reclaimed bed material returned to the bed through bed reclaiming return conduit 132. If solvent refined coal is used, ash and sulfur removal is generally not a significant problem since this type coal permits operation for lengthy periods with ⁇ out any interruption.
  • the combustion temperature within the combustor- gasifier bed is controlled in part by the ratio of air to fuel fed into the bed.
  • bed temp- erature may be controlled by controlling the amount of heat transferred to or from the bed tubes (or coils) 120 which pass substantially longitudinally through the bed.
  • the tubes 120 may, if desired, be used to generate steam from water supplied thereto from steam/water supply source 122. Alternatively, tubes 120 may be used to superheat steam furnished by source 122.
  • the resulting steam exiting tubes 120 may be collected or recovered in steam collection chamber 124 and optionally directed into inlet plenum chamber 102 to comprise all or a part of the steam supply to the combustor-gasifier.
  • the carbon monoxide and hydrogen containing low BTU gas from combustor-gasifier 100 is directed to the second stage 14 of system 10 which is a rotat ⁇ ing fluidized bed reactor 200 wherein ferric oxide (Fe 3 0.) is reduced to nearly pure iron (Fe) .
  • Reactor 200 includes a housing 201 through which the low BTU gas from first stage 12 is ducted into inlet plenum chamber 202.
  • the low BTU gas acts as the fluidizing medium for the solid particles in the rotating fluid ⁇ ized bed portion 206 of reactor 200 and reacts ex- othermically with the ferric oxide particles in bed portion 206 to produce iron (Fe) and a gas stream comprising carbon dioxide and steam.
  • the rotating fluidized bed portion 206 comprises an outer perforated cylindrical wall 208, an inner perforated cylindrical wall 210 and appropriate en- closing walls 209 defining therebetween an annular
  • OM fluidizing chamber 212 in which pulverulent solid particles 214 are disposed.
  • the perforations in walls 208 and 210 are small enough to contain particles 214 within chamber 212 and to control the exhaust of solid reaction products but large enough to sustain the free flow of fluidizing gas from the inlet plenum chamber 202 through wall 208, into and through chamber 212, through wall 210 and into outlet plenum chamber 216.
  • the fluidized bed portion 206 rotates on hori- zontal, vertical or other appropriate axis, preferably about a longitudinal axis 119 which corresponds to the axis of coaxial cylindrical walls 208, 210 and to the axis of combustor-gasifier 100.
  • Rotation is motivated by available rotational means 111, such as appropriate gearing to drives for conventional engine functions, and is controlled to a speed suf ⁇ ficient to impart a centrifugal force to the particles 214 within the bed.
  • the centrifugal force causes the particles 214 to gravitate away from axis 119, toward outer perforated wall 208.
  • the flow of low BTU gas from inlet plenum chamber 202 through per ⁇ forated outer wall 208 opposes the centrifugally induced movement of the particles 214 and, in so doing, fluidizes the bed. Reaction occurs within the fluidizing chamber 212 between the fluidizing gas and the ferric oxide to produce nearly pure iron and reaction product gases and releases a large amount of thermal energy within the bed.
  • reaction product gases are swept out of the bed through inner perforated wall 210 by the continuing flow of low BTU gas through the bed.
  • the unreacted low BTU gas and the hot reaction product gases pass from outlet plenum chamber 216 into core 218 of reactor 200.
  • core 218 is an elongated cylindrical chamber which directs the flow of unre- acted and reaction product gases, which at this point is a lean gas stream at high temperature to other portions of the system 10 for power generation or other uses.
  • the bed particles 114 are an admixture of ferric oxide and nearly pure iron.
  • the ferric oxide concentration is greatest adjacent inner per ⁇ forated wall 210 and the iron concentration in greatest adjacent outer perforated wall 208. This facilitates the continuous cycling of Fe and Fe 3 0.
  • the reaction temperature within the fluidized bed portion 206 of reactor 200 is controlled in part by the rate at which first stage low BTU gas is fed into bed portion 206.
  • bed temperature may be controlled by controlling the amount of heat transferred to the bed tubes (or coils) 220 which pass substantially longitudinally through the bed.
  • the tubes 220 may, if desired, be used to generate steam from water supplied thereto from a readily available water supply source 222.
  • a preferred water supply source is the condensate resulting from cooling third stage reaction product gas in condenser 18.
  • the resulting steam exiting tubes 220 may most use ⁇ fully be directed via tubes 221 into inlet plenum chamber 302 of third stage reactor 300 to comprise all or a part of the fluidizing steam supply thereto.
  • the third stage 14 of system 10 comprises a rotating fluidized bed iron-steam reactor 300 wherein nearly pure iron is reacted with steam to produce a relatively hot gas stream which is relatively rich in hydrogen and contains unreacted steam.
  • the re- actant steam preferably superheated, is furnished to inlet plenum chamber 302 of reactor 300 via tubes 221.
  • the steam acts as the fluidizing medium for the solid particles in the rotating fluidized bed portion 306 of reactor 300 and provides whatever thermal energy may be necessary to react with the iron in bed portion 306 to produce ferric oxide and the hydrogen rich hot gas stream.
  • the rotating fluidized bed portion 306 comprises an outer perforated cylindrical wall 308, an inner perforated cylindrical wall 310 and appropriate en- closing walls 309 defining therebetween an annular fluidizing chamber 312 in which pulverulent solid particles 314 are disposed.
  • the perforations in walls 308 and 310 are small enough to contain particles 314 within chamber 312 and to control the exhaust of solid reaction products but large enough to sustain the free flow of fluidizing steam from the inlet plenum chamber 302 through wall 308, into and through chamber 312, through wall 310 and into outlet plenum chamber 316.
  • the fluidized bed portion 306 rotates on horizontal, vertical or other appropriate axis, preferably about a longitudinal axis 119 which cor ⁇ responds to the axis of coaxial cylindrical walls 308, 310 and to the axis of combustor-gasifier 100 and reactor 200.
  • Rotation is motivated by available rotational means 111, such as appropriate gearing to drives for conventional engine functions, and is controlled to a speed sufficient to impart a centri ⁇ fugal force to the particles 314 within the bed.
  • the centrifugal force causes the particles 314 to gravitate away from axis 119 toward outer perforated wall 308.
  • core 318 is an elongated cylindrical chamber which directs the flow of unreacted steam and reaction product hydrogen gas to a condenser 18 to separate the hydrogen gas from the steam.
  • the bed particles 314 are an admixture of ferric oxide and nearly pure iron.
  • the ferric oxide concentration is greatest adjacent inner per ⁇ forated wall 310 and the iron concentration is great ⁇ est adjacent outer perforated wall 308. This faci ⁇ litates the continuous cycling of Fe and e ⁇ O. between second stage 14 and third stage 16. It will be ap- predated that as the reaction between the fluidizing steam from second stage 14 and iron proceeds, the iron particles in the bed are oxidized and the con ⁇ centration of ferric oxide increases.
  • the ferric oxide formed by the reaction in third stage 16 is transferred, preferably continuously, via ferric oxide feed conduit 232 to the rotating fluidized bed por ⁇ tion 206 of second stage reactor 200.
  • the iron con ⁇ tent of bed portion 306 is replenished, preferably continuously, by transferring the iron formed in reactor 200 to bed portion 306 via iron return conduit 230.
  • the hydrogen content of the hydrogen rich gas stream exiting the third stage reactor 300 via core chamber 318 is readily recoverable in a condenser unit 18 wherein the relatively pure (99+%) hydrogen may be separated from the steam content of the stream.
  • a preferred condenser unit is a rotating fluidized bed heat exchanger 400 wherein the hydrogen-steam hot gas stream is passed in heat transfer relation- ship with a relatively cool heat exchange fluid, preferably cooling air. Thermal energy from the hot gas stream is transferred to the cooling air to cause the steam in the hot gas stream to condense and the cooling air to become heated to about 212 C F.
  • the condensate is desirably returned via condensate return line 20 to water source 222 feeding tubes 220 of reactor 200 for the production of superheated steam.
  • the heated air is usefully compressed, as necessary, and utilized as the compressed air ducted via heated air return line 22 into housing 101 and inlet plenum 102 of combustor-gasifier 100.
  • the rotating fluidized bed heat exchanger 400 used as condenser 18 comprises a housing 401 which includes an inlet plenum chamber 402 into which the relatively hot, hydrogen rich gas stream passes and is directed through the rotating fluidized bed of the heat exchanger as the heating and fluidizing medium therefor.
  • the relatively hot gas stream gives up a portion of its thermal energy in passing through the heat exchanger 400 and exits as condensed steam and hydrogen.
  • the thermal energy transferred from the relatively hot gas stream heats the fluidized bed particles and heats a relatively cool second fluid, for example, compressed inlet air, which is directed through heat exchange tubes disposed within the fluidized bed.
  • the fluidized bed portion 406 of heat exchanger 400 comprises an outer perforated cylindrical wall 408, an inner perforated cylindrical wall 410 and appropriate enclosing walls 409 defining therebetween an annular fluidizing chamber 412 in which pulveru ⁇ lent solid inert particles 414 such as sand, dolo ⁇ mite, coal ash, etc., are disposed.
  • the perfora ⁇ tions in walls 408 and 410 are small enough to con- tain particles 414 within chamber 412 but large enough to sustain the free flow of the relatively hot fluid ⁇ izing gas stream from the inlet plenum chamber 402 through wall 408, into and through chamber 412, through wall 410 and outlet plenum chamber 416 and into outlet core chamber 418.
  • the fluidized bed portion 406 rotates on hori ⁇ zontal, vertical or other appropriate axis, prefer ⁇ ably about a longitudinal axis 119 which corresponds to the axis of coaxial cylindrical walls 408 and 410 and to the axis of combustor-gasifier 100 and reactors 200 and 300.
  • Rotation is motivated by avail ⁇ able rotational means 111, such as appropriate gear ⁇ ing to drives for conventional engine functions, and is controlled to a speed sufficient to impart a centrifugal force to the particles 414 within the bed.
  • the centrifugal force causes the particles 414 to gravitate away from axis 119 toward outer perforated wall 408.
  • core 418 is an elongated cylindrical chamber which directs the flow of cooled hydrogen gas through gas-liquid separa ⁇ tion means (not shown) into appropriate collection means (not shown) .
  • the condensate is ducted via condensate return line 20 to water source 222.
  • the temperature within the bed is controlled in part by the temperature and flow rate of the hot gas stream fed into the bed.
  • bed temp ⁇ erature is controlled by controlling the amount of heat transfer to cooling tubes (or coils) 420 which pass substantially longitudinally through the bed.
  • Tubes 420 generally rotate with the bed although it is not necessary that they do.
  • the tubes 420 direct the flow of compressed air longitudinally within the bed from an air inlet 422 generally adjacent perforated wall 410 to an air outlet 424 generally adjacent perforated wall 408. In this manner, the compressed air flows generally countercurrently to the direction of fluidizing hot gas stream flow through the bed.
  • tubes 420 include an inlet tube 426 extending longitu-
  • OMPI dinally from air inlet 422 along cylindrical wall 410, an outlet tube 428 extending longitudinally along cylindrical wall 408 to air outlet 424 and a plurality of tubes 429 interconnecting the inlet and outlet tubes 426, 428.
  • the interconnecting tubes 429 extend generally radially between the inlet and outlet tubes 426, 428.
  • Compressed air entering tubes 420 through air inlet 422 is directed longitudinally along the length of the fluidized bed portion 406 in inlet tube 426, radially relative to bed axis 119 in intercon ⁇ necting tubes 429 and longitudinally along the length of the fluidized bed portion 406 in outlet tube 428 to air outlet 424.
  • the compressed air is fed to and ducted away from the tubes 420 through a combination of conduits and plenums (not shown) .
  • the compressed air is heated and is directed from air outlets 424 to serve some useful purpose, for example as inlet air via heated air return line 22 to the combustor-gasifier 100.
  • the hot, hydrogen rich gas stream is directed into and through tubes 420 and is cooled by the flow of fluidizing cooling air over the tubes 420.
  • a condensed steam-hydrogen mixture exits tube outlets 424 and is directed through gas-liquid separation means (not shown) into hydrogen gas collection means (not shown) and condensate return line 20.
  • the cooling air is introduced into heat exchanger 400 via inlet plenum chamber 402 through outer perforated wall 408 to oppose the centrifugal movement of and to fluidize particles 414 within chamber 412.
  • the thermal energy of the hot gas stream within tubes 420 heats the bed particles, the tubes 420 and the cooling air flowing through the bed over the tubes.
  • the heated air exits the bed via inner perforated wall 410 and outlet plenum chamber 416 and enters core chamber 418 from which it is directed to serve some useful purpose, such as inlet air via heated air return line 22 to the combustor-gasifier 100.
  • the multi-stage hydrogen generator system of ' the present invention has broad applicability but is particularly useful in the production of 99+% pure hydrogen for use in fueling combustion engines located on small sites and in relatively congested areas.
  • the system may be usefully employed to produce hydrogen for use as a reagent for chemical processes, including upgrading of hydrocarbon fuels.
  • the system is particularly advantageous when one or more of the stages comprises a rotating fluidized bed since these type fluidized beds contribute en ⁇ hanced efficiency, economy and compactness.
  • a first stage rotating fluidized bed combustor- gasifier 100 upon rotation of fluidized bed portion 106, draws inlet, preferably preheated, compressed air, a solid fuel, such as powdered coal, and steam into its inlet plenum chamber 102, through outer perforated wall 108 into fluidization chamber 112.
  • a solid fuel such as powdered coal
  • steam into its inlet plenum chamber 102
  • the particles 114 within chamber 112 which are an admixture of carbon and inert materials, to gravitate toward outer wall 108
  • the opposing flow of the compressed air stream and steam into the chamber 112 fluidizes the particles.
  • Combustion occurs within fluidizing chamber 112 between the compressed air and the powdered coal fuel to produce hot combustion gases and thermal energy within the bed.
  • the second stage reactor 200 comprises a housing 201 which receives the low BTU gas from the first stage combustor-gasifier 100 and directs it through inlet plenum chamber 202 and outer perforated wall 208 into fluidization chamber 212 to fluidize and react with a bed consisting essentially of ferric oxide and iron particles.
  • the reaction which takes place between the carbon monoxide and hydrogen con ⁇ tent of the low BTU fluidizing gas and the ferric oxide particles in the bed is exothermic and reduces the ferric oxide to iron.
  • the generated heat is transferred to a plurality of tubes 220 which pass substantially longitudinally through the bed.
  • the tubes have water flowing therethrough, preferably condensate from condenser 18, which is converted .
  • the superheated steam serves as the fluidizing medium in rotating fluidized bed reactor 300, passing from second stage 12 via tubes 220 to the inlet plenum chamber 302 of the third stage.
  • the steam fluidizes and reacts in fluidization chamber 312 with the bed particles 314, consisting essentially of iron and ferric oxide, to convert the iron to ferric oxide and to produce hydrogen gas. Any heat required for the reaction is provided by the superheat of the steam.
  • the hydrogen gas and unreacted steam exit fluidization chamber 312 through inner perforated wall 310 via outlet plenum chamber 316 and enter core chamber 318 which directs the hot, hydrogen rich gas stream to condenser 18.
  • Ferric oxide and iron are continuously transferred, via feed conduits 230 and 232, between the fluidization chambers 212, 312 of reactors 200, 300 to replenish the ferric oxide con- sumed in reactor 200 by the iron oxide formed in reactor 300 and to replenish the iron consumed in reactor 300 by the iron formed in reactor 200.
  • condenser 18 is a rotating fluidized bed heat exchanger 400 in which the hydrogen rich gas stream is cooled by heat exchange with a flow of cooling air.
  • Either the hydrogen rich gas stream or the cooling air may serve as the fluidizing medium for the inert particles in fluidization chamber 412.
  • the other passes through chamber 412 in tubes 420 which pass substantially longitudinally through the bed.
  • the fluidizing medium enters heat exchanger 400 via inlet plenum chamber 402, passes through outer wall 408 into fluidization chamber 412 to fluidize the particles therein, passes over tubes 420 and then exits chamber 412 through inner wall 410 and inlet plenum chamber 416 into core chamber 418.
  • the air or hydrogen rich gas stream passing through tubes 420 flows from inlet tube 426 extending longitudinally along wall 408, to outlet tube 428 extending longitudinally along wall 410 through in ⁇ terconnecting tubes 429 extending generally radially between inlet and outlet tubes 426, 428.
  • in ⁇ terconnecting tubes 429 extending generally radially between inlet and outlet tubes 426, 428.
  • its flow is countercurrent or substantially opposite in direction to the flow of fluidizing medium through the bed.
  • the cooling air, heated during passage through rotating fluidized bed heat exchanger 400 is usefully directed back to combustor-gasifier 100 as the inlet air therefor.
  • the steam content of the hydrogen rich gas stream is condensed in heat exchanger 400 and the condensate ducted back to reactor 200 as the water feed for steam generating tubes 220.
  • the 99+% pure hydrogen gas is recovered and utilized, preferably as a gas tubine engine fuel.

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Abstract

Un générateur compact d'hydrogène à trois étages (10) comprend un étage (12) de production de gaz contenant de l'oxyde de carbone et de l'hydrogène, de faible énergie calorifique, un deuxième étage de réacteur (14) servant à réduire exothermiquement l'oxyde ferrique avec le gaz de faible énergie calorifique et à produire de la vapeur surchauffée et un troisième étage de réacteur (16) servant à faire réagir endothermiquement la vapeur et le fer pour produire du gaz d'hydrogène sensiblement pur. Le gaz d'hydrogène avec la vapeur n'ayant pas réagi est dirigé depuis le troisième étage (16) vers un condenseur (18), de préférence une unité à refroidissement par air, où l'on condense la vapeur et l'on extrait le gaz hydrogène. Le condensat (20) est recyclé vers le deuxième réacteur (14) lorsque l'eau d'alimentation servant à produire la vapeur surchauffée et l'air de refroidissement chauffé (22) sont dirigés vers le premier étage (12) où ils sont utilisés dans la production du gaz de faible énergie calorifique. Au moins un et de préférence tous les étages utilisent un lit fluidifié rotatif. Il est souhaitable que le condenseur (18) soit un échangeur de chaleur à lit fluidifié rotatif. Le générateur d'hydrogène à multi-étages (10) est spécialement utile pour l'alimentation de turbines à gaz où la place représente un problème à cause de la congestion et/ou des limitations dans l'emplacement des installations.
PCT/US1979/001089 1979-12-10 1979-12-10 Procede et systeme de production d'hydrogene au moyen d'un lit fluidifie rotatif WO1983000638A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2449635A (en) * 1943-03-19 1948-09-21 Standard Catalytic Co Production of hydrogen
US3031287A (en) * 1958-06-23 1962-04-24 Homer E Benson Process for manufacturing mixtures of hydrogen, carbon monoxide, and methane
US3222147A (en) * 1962-02-12 1965-12-07 Con Gas Service Corp Process for the preparation of mixtures of hydrogen, carbon monoxide and methane
US3421869A (en) * 1964-06-01 1969-01-14 Con Gas Service Corp Method for the production of a mixture of hydrogen and steam
US3442619A (en) * 1968-03-27 1969-05-06 Consolidation Coal Co Production of hydrogen via the steam-iron process utilizing dual solids recycle
US3442620A (en) * 1968-04-18 1969-05-06 Consolidation Coal Co Production of hydrogen via the steam-iron process
US3619142A (en) * 1969-02-11 1971-11-09 Consolidation Coal Co Continuous steam-iron process
US4039272A (en) * 1975-09-26 1977-08-02 Stone-Platt Fluidfire Limited Apparatus and method for carrying out reactions in a fluidized bed
US4148186A (en) * 1976-07-17 1979-04-10 Stone-Platt Fluid Fire Limited Engine
US4183208A (en) * 1977-12-15 1980-01-15 United Technologies Corporation Fluidized bed gasifier

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2449635A (en) * 1943-03-19 1948-09-21 Standard Catalytic Co Production of hydrogen
US3031287A (en) * 1958-06-23 1962-04-24 Homer E Benson Process for manufacturing mixtures of hydrogen, carbon monoxide, and methane
US3222147A (en) * 1962-02-12 1965-12-07 Con Gas Service Corp Process for the preparation of mixtures of hydrogen, carbon monoxide and methane
US3421869A (en) * 1964-06-01 1969-01-14 Con Gas Service Corp Method for the production of a mixture of hydrogen and steam
US3442619A (en) * 1968-03-27 1969-05-06 Consolidation Coal Co Production of hydrogen via the steam-iron process utilizing dual solids recycle
US3442620A (en) * 1968-04-18 1969-05-06 Consolidation Coal Co Production of hydrogen via the steam-iron process
US3619142A (en) * 1969-02-11 1971-11-09 Consolidation Coal Co Continuous steam-iron process
US4039272A (en) * 1975-09-26 1977-08-02 Stone-Platt Fluidfire Limited Apparatus and method for carrying out reactions in a fluidized bed
US4148186A (en) * 1976-07-17 1979-04-10 Stone-Platt Fluid Fire Limited Engine
US4183208A (en) * 1977-12-15 1980-01-15 United Technologies Corporation Fluidized bed gasifier

Non-Patent Citations (4)

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Title
G.C. LINDAUER ET AL; EXPERIMENTAL STUDIES ON HIGH GRAVITY ROTATING FLUIDUZED BED, 1966, U.S. ATOMIC ENERGY COMMISION; UPTON, NEW YORK; BNL-50013 *
I. CHEM. E. SYMPOSIUM SERIES NO. 43 (PAPER PRESENTED AT JUNE, 1975 MEETING), HEAT TRANSFER AND COMBUSTION IN CENTRIFUGAL FLUIDIZED BEDS, J. BROUGHTON ET AL; PAGES 1-5 *
J. SWITHENBANK, ROTATING FLUIDIZED BED COMBUSTOR/GASIFIER, UNIVERSITY OF SHEFFIELD. *
N. DEMIRCAN ET AL; ROTATING FLUIDIZED BED COMBUSTOR, FLUIDIZATION, 1978, CAMBRIDGE UNIVERSITY PRESS, ENGLAND, PAGE 1 *

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