EP2473581A2 - Verfahren und vorrichtung zur nutzung von sauerstoff bei der dampfreformierung von biomasse - Google Patents

Verfahren und vorrichtung zur nutzung von sauerstoff bei der dampfreformierung von biomasse

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Publication number
EP2473581A2
EP2473581A2 EP10757567A EP10757567A EP2473581A2 EP 2473581 A2 EP2473581 A2 EP 2473581A2 EP 10757567 A EP10757567 A EP 10757567A EP 10757567 A EP10757567 A EP 10757567A EP 2473581 A2 EP2473581 A2 EP 2473581A2
Authority
EP
European Patent Office
Prior art keywords
gas
fluidized bed
bed reactor
oxygen
porous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10757567A
Other languages
German (de)
English (en)
French (fr)
Inventor
Karl-Heinz Tetzlaff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP2473581A2 publication Critical patent/EP2473581A2/de
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72Other features
    • C10J3/80Other features with arrangements for preheating the blast or the water vapour
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005Separating solid material from the gas/liquid stream
    • B01J8/0055Separating solid material from the gas/liquid stream using cyclones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818Feeding of the fluidising gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical 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
    • B01J8/26Chemical 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 two or more fluidised beds, e.g. reactor and regeneration installations
    • B01J8/28Chemical 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 two or more fluidised beds, e.g. reactor and regeneration installations the one above the other
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/48Apparatus; Plants
    • C10J3/50Fuel charging devices
    • C10J3/503Fuel charging devices for gasifiers with stationary fluidised bed
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60Processes
    • C10J3/64Processes with decomposition of the distillation products
    • C10J3/66Processes with decomposition of the distillation products by introducing them into the gasification zone
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C10/00Fluidised bed combustion apparatus
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C10/00Fluidised bed combustion apparatus
    • F23C10/18Details; Accessories
    • F23C10/20Inlets for fluidisation air, e.g. grids; Bottoms
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23LSUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
    • F23L7/00Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
    • F23L7/007Supplying oxygen or oxygen-enriched air
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00513Controlling the temperature using inert heat absorbing solids in the bed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00522Controlling the temperature using inert heat absorbing solids outside the bed
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00Details of gasification apparatus
    • C10J2200/09Mechanical details of gasifiers not otherwise provided for, e.g. sealing means
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0956Air or oxygen enriched air
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0959Oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/12Heating the gasifier
    • C10J2300/1269Heating the gasifier by radiating device, e.g. radiant tubes
    • C10J2300/1276Heating the gasifier by radiating device, e.g. radiant tubes by electricity, e.g. resistor heating
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2700/00Special arrangements for combustion apparatus using fluent fuel
    • F23C2700/04Combustion apparatus using gaseous fuel
    • F23C2700/043Combustion apparatus using gaseous fuel for surface combustion
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/34Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage

Definitions

  • the invention relates to a fluidized bed reactor for
  • Heating the fluidized bed of the fluidized bed reactor wherein the heating device has at least one cavity.
  • the invention relates to a process for the gasification and / or pyrolysis of solid fuels, preferably biomass, in a fluidized bed reactor, preferably of the aforementioned type.
  • Biomass by steam reforming is endothermic. So thermal energy has to be coupled into the process. This can be done by partial combustion of the biomass.
  • a temperature level of about 800 ° C is not easy, because a high oxygen supply locally high temperatures are achieved, which lead to a melting of the ash components of the biomass. Therefore, the oxygen must either be diluted with water vapor or nitrogen or the biomass must be present as a small proportion in the inert bed material in the form of small coke particles, which quickly pass the heat to the bed material. That's why
  • Fluidized bed reactors mostly operated with air.
  • Fluidized bed reactors which are interconnected by a sand cycle.
  • the burner called the burner is operated with air.
  • the coke particles are burned and heated the circulating sand bed to about 950 ° C.
  • the temperature of the coke particles may be more than 1100 ° C under these oxidizing conditions. Therefore, this type of reactor is safe to operate only with wood.
  • the use of stalk biomass would lead to clumping of the sand due to its low ash melting point.
  • fluidized-bed reactors can also be operated autothermally by direct supply of pure oxygen.
  • the ash melting point of biomass is exceeded, even if the oxygen in half with
  • the invention has the object, the
  • Fluidized bed reactors to allow.
  • pure oxygen for the steam reforming of biomass with low ash melting point to be made usable.
  • the heater has a
  • Oxygen supply for supplying an oxygen-containing gas into the cavity of the heater and adjoins the cavity to a porous, gas-permeable portion of the heater In this way, a controlled oxidation by means of oxygen of an oxygen-containing gas is possible. This can be about air. However, technically pure oxygen is preferred. In addition, it can be achieved by the porous and gas-permeable section that the oxygen-containing gas comes into contact with a combustible gas and oxidizes as a result, without at the same time coke particles of the fluidized bed being able to react directly with the oxygen. The coke particles therefore become
  • the heater can be designed very differently. Due to the porous design it is made
  • Heating device may be provided.
  • the oxygen-containing gas is supplied to the cavity of the heating device and the oxygen-containing gas and / or a combustible gas flows through the porous, gas-permeable section of the heating device.
  • the combustible gas is oxidized at least partially with heat release by the oxygen-containing gas.
  • the heat of oxidation is then released to the fluidized bed of the fluidized bed reactor.
  • the tubes are preferably in
  • Fluidized bed reactor provided, wherein at least
  • the heating device has a plurality of concentrically arranged tubes. So there are several groups of provided at least two tubes, which are each provided concentrically with each other.
  • each group of tubes an inner tube and an outer tube, wherein at least the inner tube or the outer tube are porous and gas permeable.
  • an annular space between the inner tube and the outer tube is obtained, can be provided in the other internals.
  • the annular space can serve as a further flow channel for the appropriate flow of the gases involved.
  • the outer tube can also act as a shield against the high temperature in the annulus as needed, so that it can not come in the fluidized bed to exceed the ash melting point of the coke particles.
  • the combustible gas does not enter the annulus through the corresponding porous and gas-permeable outer tube from the fluidized bed, but is fed directly from the outside of the annular gap, can also be provided
  • the fuel gas supply for supplying combustible gas may be provided such that the fuel gas is supplied to the inner tube or the annulus between the outer tube and / or the inner tube. So it can be ensured that the combustible gas depending on the preferred
  • Process management of the heater can be supplied.
  • both the respective inner tube and the respective outer tube can be porous and gas-permeable.
  • gas-permeable heat shield This can serve, for example, the thermal shield against the coke particles in the fluidized bed.
  • the outer tube may be enclosed by at least one gas-impermeable jacket.
  • the jacket is then heated from the inside, so to speak, by the oxidation of the combustible gas and gives the
  • the jacket can itself be designed as a concentric tube.
  • the oxygen supply one Nozzle bottom for supplying oxygen-containing gas to
  • Cavity and at the same time for supplying fluidizing gas to the fluidized bed of the fluidized bed reactor include.
  • the fuel gas supply may also be integrated into the nozzle bottom to simultaneously supply the oxygen-containing gas and the combustible gas to the cavity of the heater and the fluidizing gas to the fluidized bed of the fluidized bed reactor.
  • the heating device is provided in a stationary fluidized bed and / or a circulating fluidized bed.
  • the heat transfer is particularly good and much better than outside the fluidized bed.
  • Fluidized bed may comprise an inert bed material. But this can also be dispensed with, so that, for example, the fluidized bed is formed from coke particles.
  • coke particles can heat via the heater well, for example for steam reforming, fed.
  • Heater preferably the at least one porous, gas-permeable tube, at least partially
  • Catalyst material is made, can be carried out a catalytic reaction of tars.
  • a tar-containing pyrolysis gas is preferably used as the combustible gas, which in a fluidized bed reactor upstream
  • Process step is formed in a pyrolysis reactor.
  • the combustible gas can then, preferably after a
  • the effectiveness of the heater can be increased without sacrificing the advantages described above, when the porous, gas-permeable section, in particular a porous, gas-permeable tube, is formed electrically heated.
  • the porous, gas-permeable section in particular a porous, gas-permeable tube
  • the porous, gas-permeable tube if necessary serve as a heating resistor.
  • the porous, gas-permeable portion, in particular the porous, gas-permeable tube is formed of a metallic, electrically conductive material.
  • the heating resistor is segmented over the height of the fluidized-bed reactor, so that the electrical heating power of the heating device in the corresponding segments can be set and / or controlled independently of one another. segmented
  • Heating devices may be particularly useful, even if the fluidized bed reactor is divided into different sections, such as through the use of perforated plates.
  • the perforated plates can then for example for
  • Voltage supply of the individual electrical segments of the heater are used.
  • the method is in a particularly preferred
  • Embodiment provided that the oxygen-containing gas through the porous, gas-permeable portion of the
  • Heating device in the direction of the fluidized bed of the
  • Fluidized bed reactor flows and in the porous, gas-permeable section and / or immediately adjacent to the
  • Fluidized bed side of the porous, gas-permeable section oxidize the combustible gas in the fluidized bed. In this way, a spatial separation of the
  • Oxidation and the coke particles are achieved, leaving a
  • the combustible gas of the fluidized bed of the fluidized bed reactor through the porous, gas-permeable portion of the heater in the direction of the cavity of the
  • Heating device of the oxygen-containing gas to be oxidized. Also in this case, the previously mentioned
  • oxygen-containing gas supplied to at least one inner porous and gas-permeable tube, wherein the oxygen-containing gas through the pore system of the inner tube in a
  • the combustible gas is ultimately oxidized in the annulus by the oxygen-containing gas, after which the at least partially oxidized gas exits the heater through the pore system of the outer tube.
  • At least partially oxidized gas preferably flows into the fluidized bed reactor in order to heat it.
  • the at least partially oxidized gas flows into the fluidized bed of the fluidized bed reactor where the heat of the at least partially oxidized gas also flows to the fluidized bed reactor
  • the at least partially oxidized gas flows through a porous, gas-permeable tube and / or a heat shield between the inner tube and the outer tube, preferably in the fluidized bed reactor, more preferably in the fluidized bed of the fluidized bed reactor. In this way, a better heat shield over the
  • oxygen-containing gas is supplied to at least one inner porous and gas-permeable tube, from where it passes through the
  • Pore system of the inner tube flows into an annular space between the inner tube and an outer tube.
  • the annular space is further combustible gas "fed by the there
  • oxygen-containing gas is oxidized.
  • the thus at least partially oxidized gas is withdrawn via an outlet from the fluidized bed reactor and not directly into the Fluidized bed of the fluidized bed reactor introduced.
  • a corresponding mixing can be prevented in this way.
  • the combustible gas is supplied to at least one inner porous and gas-permeable tube and flows through the pore system of the inner tube in an annular space between the inner tube and an outer tube to which the oxygen-containing gas is supplied.
  • the combustible gas is thus in the annulus of
  • the at least partially oxidized gas is then removed via a discharge from the
  • Fluidized bed reactor deducted.
  • a pyrolysis gas preferably tar-containing, from a pyrolysis reactor upstream of the fluidized-bed reactor is used as combustible gas.
  • Another method variant provides that
  • oxygen-containing gas is supplied to at least one inner porous and gas-permeable tube and then flows through the pore system of the inner tube into an annular space between the inner tube and an outer tube.
  • the combustible gas flows out of the fluidized bed of the
  • gas-permeable tube in the direction of the annular space between the inner and the outer tube.
  • the flammable Gas ultimately oxidized by the oxygen-containing gas and the at least partially oxidized reaction gas withdrawn via an outlet from the fluidized bed reactor.
  • the combustible gas and / or the oxygen-containing gas can in a simple constructive manner and for easy
  • Fluidized bed is supplied.
  • oxygen is understood here as an oxygen-containing gas, but preferably technically pure oxygen.
  • the fluidized bed can be inert
  • Bedding material such as sand
  • the invention can be applied to a classical stationary fluid bed with and without sand, a circulating fluidized bed or a cocaine cloud.
  • Heating device forming structure arranged
  • preferably has a large surface area and is at least partially gas-permeable.
  • Oxygen can be used to heat by oxidation or partial oxidation of a gas, the structure that gives off its heat by conduction, convection and thermal radiation to the fluidized bed.
  • a structure for industrial gasification may preferably consist essentially of a
  • the tubes can be arranged in large numbers in a fluidized bed of a fluidized bed reactor. Depending on the process, some pipes may be gas permeable and others gas tight. Gas-permeable are, for example, sintered tubes with connected pore space, tissue or tubes which are perforated. Advantageous process control can be achieved with tubes having a porous structure known from candle filters. Suitable are ceramic and metallic materials. In the tubes further tubes may be arranged, which also have a gas-permeable structure or may be formed gas-impermeable.
  • the heating of the structures, in particular the outer tubes of the structures can be done for example as follows.
  • the oxygen supplied to the structure, in particular the tubes flows via corresponding lines by applying a sufficient positive pressure difference the pressure in the reaction space of the fluidized-bed reactor is smaller than in the porous structure, from the inside to the outside through the gas-permeable outer tube wall in the direction of the reaction space of the fluidized-bed reactor.
  • Fluidized bed reactor So here is an autothermal gasification.
  • Oxidation preferably takes place on the inner wall in analogy to case (a).
  • the oxidized or partially oxidized gases, i. the reaction products are withdrawn from the tube for further use.
  • the further use may be, for example, to make the sensible heat available for the entire process. It can also be provided to bring the oxidized or partially oxidized gases to a higher pressure level and the
  • Feed reaction space of the fluidized bed reactor Feed reaction space of the fluidized bed reactor.
  • the structure is composed of several porous layers, preferably of several concentric porous tubes, one can use any combustible gas to heat the structure.
  • the structure then has at least two concentric, porous tubes.
  • the combustible gas can be introduced into the intermediate space of the porous layers of the structure, in particular into the annular space between the concentric tubes, or into the interior of the structure or the interior of the respective inner concentric tube.
  • the oxygen is then in the other room, the space, annulus or interior
  • gas-permeable tube is introduced and the gas in the annular gap, then the oxygen flows at a positive pressure difference in the annulus, where the gas is at least partially oxidized.
  • the inner tube is thereby hot and transfers the heat to the outer tube, which in turn gives off the heat to the fluidized bed of the fluidized bed reactor.
  • a tar-containing pyrolysis gas is selected as the gas, it is desirable for the inner tube to reach the highest possible temperature. In this case it is
  • Heat shield roughly in the form of a rolled
  • Heat shield can be designed so that the highest possible turbulence, so that the gas molecules get in contact with the hot pipe wall as often as possible. To assist tar destruction, it is advantageous to catalytically coat at least the inner tube.
  • nickel-based ones are suitable for this purpose.
  • Catalysts from Group VIII of the Periodic Table which can also destroy ammonia.
  • the doping of nickel-based catalysts with MgO, Zr0 2 or Zr0 2 - A1 2 0 3 is also advantageous.
  • the outer tube is gas-permeable, the partially oxidized pyrolysis gas, the tar content was largely catalytically and / or thermally reacted by applying a corresponding pressure difference in the
  • the largely tarry pyrolysis gas can also be used as synthesis gas from the
  • the outer tube may be gas tight.
  • Oxygen can also be outside the structure.
  • the at least partially oxidized gas then heats up the structure as it flows through it.
  • the structure then transfers the heat to the fluidized bed of the fluidized bed reactor.
  • the at least partially Oxidation of the gas can also be carried out entirely outside the fluidized-bed reactor or directly below the structure, in particular of the tubes.
  • the combination of combustible gas and oxygen can also take place within the structure, in particular within the tubes. Even in these cases, a gas-permeable tube may be advantageous because it can be achieved in the axial direction low temperature differences.
  • tarry pyrolysis gas is used as combustible gas, it is advantageous to use at least the
  • Structure in particular the at least one inner tube, to be provided with a catalyst.
  • the structure or the at least one tube can also be made of a catalytic material. The whole partially oxidized
  • Pyrolysis gas must then flow through at least one catalytically active structure, whereby the tar content of the pyrolysis gas can be reduced even more significantly than in case (c).
  • this tube can be provided with a catalyst. It is not mandatory to shift the catalytic process into the interior of the structure. This process can also be done in an apparatus outside the
  • a precursor for the production of pyrolysis gas is in
  • the combustible gas such as tarry pyrolysis gas, not or not completely as fluidizing gas for the
  • Fluidized bed reactor is used, but at least partially for the at least partial oxidation of the structure is supplied, may be part of the gas of the
  • Fluidized bed reactor circulated and used as fluidizing gas to provide sufficient fluidizing gas for the operation of the fluidized bed reactor.
  • a circulating fan may be required
  • Fluidized bed reactor returns to the input.
  • pyrolysis gas is to be used to heat the structure, it is advisable to dedust this gas in advance and, if appropriate, to liberate it from catalyst poisons, such as sulfur. Hot gas desulfurization is generally sufficient and known per se. Although dust from the pipes, as in filter cartridges usual, by a
  • the gas introduced is totally oxidized with technically pure oxygen, this may only be possible with a circulating fan.
  • the temperatures that occur can be limited and thus the structures can be protected from excessive temperatures.
  • the generation of synthesis gas is often followed by another process for processing this gas into gaseous or liquid substances, such as hydrogen, methane, methanol or fuels.
  • gaseous or liquid substances such as hydrogen, methane, methanol or fuels.
  • purification of these products are often flammable gases and vapors, which are useful for heating the structure in the fluidized bed reactor and as a combustible gas in the previously
  • Water vapor is for example as fluidizing gas for the one described here
  • Fluidized bed reactor for the homogeneous water vapor reaction (shift) or in the methanation well usable.
  • the device according to the invention and the method according to the invention are suitable for pressure-loaded process control and also for a non-pressurized process. Reiner
  • Oxygen is used for larger pressure-charged systems
  • air may be more advantageous because the production of small amounts of pure oxygen is relatively costly.
  • the direct contact between the coke particles and the oxygen is avoided or at least significantly reduced.
  • the heat is transferred to the coke particles by radiation, convection and heat conduction. Because of the endothermic reaction of the coke reaction, the coke particles are preferably always colder than the structure, the surrounding gas or an adjacent one
  • the difference in temperature between coke particles and structure can be controlled by the size of the structure surface so that temperature differences between 20 ° C and 300 ° C can be set.
  • the Invention is therefore also for low-biomass
  • Ash melting point suitable This applies to a large number of high-yielding stalk-like biomasses.
  • Reforming process ⁇ can be operated allothermically despite the use of oxygen. That increases the
  • the invention also enables a thermally catalytic reduction of the
  • the fluidized bed reactor can be used for pyrolysis of solid
  • Fluidized bed reactor can also be used for the production of
  • Synthesis gas from solid fuels preferably from a pyrolysis gas of the aforementioned pyrolysis, be formed.
  • Steam reforming comprising a pyrolysis in a first reactor part (pyrolysis reactor) and a syngas production in a second reactor part (synthesis gas reactor) may be formed.
  • FIG. 1 shows a fluidized bed reactor with stationary
  • FIG. 2 shows a longitudinal section of the porous tube from FIG. 1
  • FIG. 3 shows a cross section of the porous tube from FIG. 1
  • 4 shows a fluidized-bed reactor with circulating fluidized bed, in which oxygen is introduced through tubes with a porous wall
  • FIG. 5 shows a fluidized-bed reactor with an outer layer
  • FIG. 6 shows a fluidized bed reactor with two concentrically arranged gas-permeable tubes
  • Fig. 7 is a longitudinal section of the gas-permeable pipes
  • Fig. 8 is a cross section of the gas-permeable tubes
  • Fig. 9 shows a cross section of the gas-permeable pipes
  • FIG. 10 shows a cascaded fluidized-bed reactor with two concentrically arranged tubes, wherein only the inner tube is permeable to gas
  • FIG. 11 is a longitudinal section of the tubes of FIG. 10,
  • Fig. 12 is a cross-section of the tubes of Figs. 10 and 11 and
  • FIG. 13 shows a fluidized-bed reactor in which the oxidation of a gas takes place on the inside of a porous tube.
  • Fig. 1 shows a fluidized bed reactor 9a with a
  • the fluidized bed 10 may contain sand.
  • Fluidized bed is fluidized by a fluidizing gas 13, for example water vapor and / or pyrolysis gas.
  • Biomass 14 is fed to the fluidized bed reactor via a conveying member.
  • the synthesis gas 15 generated in the fluidized bed reactor 9a passes the space above the fluidized bed 11 (freeboard) and leaves the fluidized bed reactor 9a at its head end.
  • a heating device 28 comprising a plurality of porous, a cavity 29 having tubes la, which oxygen 6 via a
  • Oxygen supply 30 in the form of lines 5 is supplied.
  • the oxygen 6 flows through a porous gas-permeable section 31 of the heating device 28, formed by the porous tubes 1a, in the direction of the fluidized bed 10.
  • Coke particles in the fluidized bed are mainly heated indirectly by heat conduction of sand and gas. Since the gasification of coke is endothermic, the coke particles are the coldest particles in the fluidized bed 10. Porosity and pore size of the tubes la are suitably chosen so that the pressure drop of the oxygen is significantly greater than the pressure difference at the top and bottom of the fluidized bed 10. Thus an approximately uniform heating is achieved. At the same time, the porosity and the pore size of the tubes 1a become so chosen that the coke particles can not penetrate into the pore system of the tubes la and there come into contact with the oxygen 6.
  • Fig. 4 shows a fluidized bed reactor 9b with circulating fluidized bed. In this type of reactor is the
  • the bed material of the fluidized bed 10 is continuously circulated via a cyclone 27 and operated with Siphongas 8 siphon in a conventional manner.
  • the porous tubes la can therefore fill almost the entire reaction space.
  • the nozzle bottom 12 consists of a double bottom formed by the plates 17 and 18. This raised floor is used to distribute the oxygen 6. The distribution of oxygen 6 could also be done in other ways.
  • the heat transfer to the tubes la in the first few centimeters at the nozzle bottom is not as high as in the middle part of the fluidized bed reactor 9b. Therefore, it is expedient not to heat the tube la in the lower region or to form it non-porous. This can be done by inserting or sheathing the tube la with a protective tube 4 in the form of a short gas-tight tube. Due to the double bottom, the fluidizing gas 13 is passed through a plurality of tube nozzles 20, which pass through the double bottom formed by the plates 17 and 18. As a backstop 21, a plate is provided. The fluidizing gas is supplied to the fluidized bed reactor 9a in addition to the tubes 1a.
  • Fig. 5 shows a fluidized bed reactor 9a with stationary fluidized bed 10, in which an arbitrary from the outside via a BrenngasZu Entry 32 supplied, combustible gas 7 is oxidized in an apparatus provided for this purpose 22 at least partially with oxygen 6.
  • the heated and partially oxidized gas flows through a double bottom, as in FIG. 4
  • This construction is particularly suitable for the oxidation or partial oxidation of tarry pyrolysis gases, which should preferably be dedusted prior to oxidation.
  • the elevated temperature of the partially oxidized pyrolysis gas can be used for the catalytic destruction of tars. This can be done by providing the tubes la with a catalyst or by arranging a catalytic reactor outside the fluidized bed reactor. In the case of severe overheating of the gas by partial oxidation or catalytic reactions, care should be taken, preferably by means of a multiplicity of pipes 1 a, to ensure that the temperature of the pipes 1 a does not become so high that the ashes in the fluidized bed 10
  • Fig. 6 shows a fluidized bed reactor 9a with stationary fluidized bed 10, in which a further porous tube 2a is arranged concentrically in the tubes la whose porosity is chosen so that coke particles do not penetrate into the pore system of the tubes, at least the tube can not penetrate.
  • the concentrically arranged tubes la, 2a form an annular space 33 and allow a greater overheating of the combustible gas 7, because the oxidation or partial oxidation with oxygen 6 takes place on the inner tube 2a, which emits the heat predominantly as radiation to the outer tube la.
  • the temperature increase can be strengthened if an additional gas-permeable tube 3 is arranged in the annular space.
  • the tube 3 may for example be formed from a rolled sheet, in which the openings may be punched so that metal flags remain as baffles on the plate.
  • At least the inner tube 2a should have a catalytically active layer or be made entirely of a catalytic material.
  • the protective tube 4 should preferably be made longer, so that at the inlet of the tube 3, the then still cold and thus tarry pyrolysis gas does not enter the fluidized bed reactor 9a.
  • the heat shield 3 can be formed in this case as a porous tube with catalytically active layer for tar destruction.
  • FIGS. 6 to 9 show that the oxidized or
  • Fig. 10 shows a cascaded fluidized bed reactor 9c with a stationary fluidized bed 10, which is an inert
  • Bedding material such as sand
  • These fluidized beds 23 consist only of coke clouds, which have risen from the fluidized bed 10.
  • a reaction space 11 Between the further fluidized bed 23 and the stationary fluidized bed 10 is a reaction space 11.
  • the structure is formed of a plurality of tubes 1b, each of which is an additional concentric
  • the inner tube 2a In the area of the sand-containing fluidized bed 10, the inner tube 2a consists of a porous tube 2a and in the region of the further fluidized beds 23 and
  • Reaction space 11 from a perforated pipe 2b or a pipe 2b with higher flow resistance the less
  • Oxygen 6 passes as the porous tube in the stationary fluidized bed 10. This is useful because the heat transfer in the stationary fluidized bed 10 is significantly higher than in the other fluidized beds 23 and the reaction chamber 11.
  • the tube lb is gas-impermeable.
  • the oxidized or partially oxidized gas 24 must therefore be discharged into the space 26 formed by the intermediate bottom 25. It is used from there for further use in the overall process.
  • Fig. 13 shows a fluidized bed reactor 9a with a
  • porous tubes la in the field of fluidized bed 10, which pass in the space above the fluidized bed in a gas-tight tube lb.
  • another porous tube 2a is concentrically arranged, which allows oxygen 6 to flow into the annulus. The oxygen 6 flows through the
  • the combustible gas 7 is in this case by applying a negative pressure of the fluidized bed 10 taken.
  • the oxidized or partially oxidized gas 24 passes into the overall process for further use.
  • the process can be classified as allothermic gasification process, because the
  • Syngas is not contaminated with the formed carbon dioxide.
  • Carbon monoxide is formed again and again in the fluidized bed because it is an equilibrium reaction.

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EP10757567A 2009-09-03 2010-09-03 Verfahren und vorrichtung zur nutzung von sauerstoff bei der dampfreformierung von biomasse Withdrawn EP2473581A2 (de)

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DE102009039920A DE102009039920A1 (de) 2009-09-03 2009-09-03 Verfahren und Vorrichtung zur Nutzung von Sauerstoff bei der Dampfreformierung von Biomasse
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US8932373B2 (en) 2015-01-13
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SG178614A1 (en) 2012-04-27
CN102625821A (zh) 2012-08-01
US9404651B2 (en) 2016-08-02
TW201113479A (en) 2011-04-16
DE102009039920A1 (de) 2011-03-10
RU2012112833A (ru) 2013-10-10
KR20120073234A (ko) 2012-07-04
RU2555889C2 (ru) 2015-07-10
CA2772981A1 (en) 2011-03-10
US20120217440A1 (en) 2012-08-30
JP2013503923A (ja) 2013-02-04
BR112012004825A2 (pt) 2016-03-15
WO2011026630A3 (de) 2011-12-01
JP5827230B2 (ja) 2015-12-02
WO2011026630A2 (de) 2011-03-10
SG10201405442VA (en) 2014-10-30

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