EP1021499A1 - Procede et appareil de gazeification de matieres carbonees solides - Google Patents

Procede et appareil de gazeification de matieres carbonees solides

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Publication number
EP1021499A1
EP1021499A1 EP98958839A EP98958839A EP1021499A1 EP 1021499 A1 EP1021499 A1 EP 1021499A1 EP 98958839 A EP98958839 A EP 98958839A EP 98958839 A EP98958839 A EP 98958839A EP 1021499 A1 EP1021499 A1 EP 1021499A1
Authority
EP
European Patent Office
Prior art keywords
reaction chamber
char
cfb
particles
product gas
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.)
Granted
Application number
EP98958839A
Other languages
German (de)
English (en)
Other versions
EP1021499B1 (fr
Inventor
Peder Christian Stoholm
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.)
PYRONEER AS
Original Assignee
DANISH FLUID BED TECHNOLOGY AP
Danish Fluid Bed Technology APS
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 DANISH FLUID BED TECHNOLOGY AP, Danish Fluid Bed Technology APS filed Critical DANISH FLUID BED TECHNOLOGY AP
Priority to EP20100183554 priority Critical patent/EP2284245A1/fr
Publication of EP1021499A1 publication Critical patent/EP1021499A1/fr
Application granted granted Critical
Publication of EP1021499B1 publication Critical patent/EP1021499B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—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
    • C10J3/46—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
    • C10J3/72—Other features
    • C10J3/80—Other features with arrangements for preheating the blast or the water vapour
    • 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
    • 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
    • C10K1/026—Dust removal by centrifugal forces
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C10/00—Fluidised bed combustion apparatus
    • F23C10/02—Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed
    • F23C10/04—Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed the particles being circulated to a section, e.g. a heat-exchange section or a return duct, at least partially shielded from the combustion zone, before being reintroduced into the combustion zone
    • F23C10/08—Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed the particles being circulated to a section, e.g. a heat-exchange section or a return duct, at least partially shielded from the combustion zone, before being reintroduced into the combustion zone characterised by the arrangement of separation apparatus, e.g. cyclones, for separating particles from the flue gases
    • F23C10/10—Fluidised bed combustion apparatus with means specially adapted for achieving or promoting a circulating movement of particles within the bed or for a recirculation of particles entrained from the bed the particles being circulated to a section, e.g. a heat-exchange section or a return duct, at least partially shielded from the combustion zone, before being reintroduced into the combustion zone characterised by the arrangement of separation apparatus, e.g. cyclones, for separating particles from the flue gases the separation apparatus being located outside the combustion chamber
    • 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
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
    • 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
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2206/00—Fluidised bed combustion
    • F23C2206/10—Circulating fluidised bed
    • F23C2206/101—Entrained or fast fluidised bed
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2206/00—Fluidised bed combustion
    • F23C2206/10—Circulating fluidised bed
    • F23C2206/103—Cooling recirculating particles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F23G2201/40—Gasification
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2203/00—Furnace arrangements
    • F23G2203/50—Fluidised bed furnace
    • F23G2203/501—Fluidised bed furnace with external recirculation of entrained bed material

Definitions

  • the invention relates to a method and an apparatus for gasification of solid carbonaceous material in a circulating fluidised bed (CFB) gasifier, which comprise a CFB reaction chamber, a particle separator for separation of particles containing char from the exit gas of the CFB reaction chamber and a particle re-circulation duct for re-circulation of the separated particles to the CFB reaction chamber.
  • the re-circulation duct comprises a char reaction chamber for gasification of char contained in the separated particles.
  • the re-circulation duct may comprise a particle accumulation for the purpose of preventing that a large amount of gas flows from the CFB reaction chamber to the particle separator via the re-circulation duct, and/or for the purpose of controlling the rate of particle re-circulation.
  • Such constructions are often designated as "non mechanical particle locks" and in English literature one distinguishes between subtypes that are typically designated: seal pots, J-valves, and L-valves.
  • the function is based on the addition of a gas for mobilising, i.e. ejecting and/or fluidisation of particles in the particle valve.
  • the added gas flow is small compared to the gas flow that is further added to the CFB reaction chamber.
  • a gas with a low oxygen content as mobilising gas because the use of a oxygen containing gas such as atmospheric air may course damages on construction materials and particle sintering due to more or less locally increased temperatures.
  • CFB gasifiers wherein re-circulation of particles takes place via a char combustion chamber are also known.
  • the heating of the re-circulating particles means that the addition of oxidising agent to the CFB reaction chamber can be reduced.
  • some major disadvantages are that the choice of combustion conditions leads to a need for a large square section in the char reaction chamber and that a considerable part of the fuel energy is converted to thermal energy in a considerable stream of hot flue gasses from the char combustion chamber.
  • the invention provides a method for gasification of solid carbonaceous material in a circulating fluidised bed (CFB) gasifier, which method comprises addition of the carbonaceous material to a CFB reaction chamber in the gasifier, addition of oxygen-containing gasification agent to the gasifier, rejection of particle loaded product gas from the reaction chamber, separation of particles from the product gas and re-circulation of separated particles to the reaction chamber, and the method of the invention is characterised by converting char contained in the re-circulating particles to a combustible gas by adding a considerable part, preferably the main part and even better at least 75 % of the amount of oxygen added to the CFB gasifier in the form a oxygen- containing gasification agent to a char reaction chamber which exist in the re-circulation path for the separated particles.
  • CFB circulating fluidised bed
  • the above mentioned definition of the distribution of added oxygen not only consider the mass of free molecular oxygen but also oxygen bound in water vapour, carbon dioxide and other oxidising components that may be added to the CFB gasifier.
  • oxygen bound in components such as SiO 2 and Al 2 O 3. which in the sense of gasification are not acting as oxidising, are disregarded as also oxygen chemically bound in the fuel.
  • the invention provides improved possibilities for converting solid carbonaceous fuel to a combustible gas. Compared to simple CFB gasifiers without a separate char reaction chamber, it is not least advantageous that a low temperature can be maintained in the CFB reaction chamber meaning that:
  • the method of the invention is very advantageous because:
  • the primary function of the CFB reaction chamber is to secure an effective pyrolyse-wise (by pyrolysis a thermal decomposition only due to heating is to be understood, i.e. excluding decomposition due to oxidation) conversion of the fuel, which typically can be achieved at a considerably lower temperature than necessary for effectively oxidising the char particles in a low oxygen atmosphere.
  • a thermal decomposition only due to heating is to be understood, i.e. excluding decomposition due to oxidation
  • conversion of the fuel which typically can be achieved at a considerably lower temperature than necessary for effectively oxidising the char particles in a low oxygen atmosphere.
  • volatile fuels such as biomass and household waste achieve a high pyrolyse-wise conversion to gas.
  • the char is transported to the top of the CFB reaction chamber together with the further content of particular material of the product gas.
  • the limited extend of char oxidation in the CFB reaction chamber is lowering the tendency for the creation of a large amount of fine char and ash particles in the CFB reaction chamber, which improves the possibilities for effectively separating char and ash particles by the aid of the following particle separator.
  • the major part of the separated particles and preferably at least 90 % thereof is transferred to the char reaction chamber, wherein the char is converted by adding a proper oxygen containing gasification agent such as atmospheric air, pure oxygen, water vapour or mixtures thereof.
  • a proper oxygen containing gasification agent such as atmospheric air, pure oxygen, water vapour or mixtures thereof.
  • the mentioned conversion of the char is mainly performed in a single reaction chamber but naturally the char conversion could be distributed on several more or less physically separated reaction chambers.
  • the need for adding oxygen to the char reaction chamber will depend on the amount of char produced in the CFB reaction chamber which amount depends on the fuel as well as the more specifically chosen reaction conditions in the CFB reaction chamber, including particularly the temperature, mixing conditions and the size of the fuel particles.
  • An effective gasification of the char added to the char reaction chamber as well as a proper release of thermal energy may however be anticipated by adding free molecular oxygen to an amount which is below 0.8 and preferably below 0.6 times the amount which would be necessary for a stoichiometric combustion of the char.
  • lower consumption and higher heating value can be pursued by optimising the process conditions for achieving high concentrations of oxygen-lean or oxygen free components such as CH-t and higher hydrocarbons in the outlet gas. This e.g.
  • the invention allows a reduction of the square section of the char reaction chamber and that the char reaction chamber contributes to the production of combustible gas.
  • the conversion of the fuel by pyrolysis in the CFB reaction chamber do not need the addition of oxygen, which means that especially highly volatile fuels such as many types of biomass can be gasified effectively in the gasification process by adding less than 0.4 and preferably less than 0.3 kg of free molecular oxygen per kg of dry fuel.
  • the CFB reaction chamber as well as the char reaction chamber may additionally be fed with further gas such as water vapour, re-circulated product gas and flue gas.
  • a major purpose may be to keep up proper temperatures and fluid dynamic conditions in the respective reaction chambers during varying choice of fuel and load.
  • the char oxidation in the char reaction chamber will result in that the particles re-circulating in the CFB gasifier achieve a temperature increase in the char reaction chamber and due to that, the thermal energy necessary for sustaining the mainly endothermal pyrolysis processes in the CFB reaction chamber can fully or partly be added by the addition of the circulating particles.
  • the method according to the invention may of course comprise further characteristics such as: • the process may be fed with others than the mentioned particular materials for the purpose of stabilising the particle size distribution and/or absorption of various components such as components containing sulphur- and alkaline,
  • one or several particle streams may be drained from the process, e.g. for the purpose of changing the particle size distribution and/or the chemical composition of the particular material and/or to avoid accumulation in the system and/or for the purpose of utilising the drained materials in other relations,
  • drained particles may fully or partly be returned to the gasification process after a proper processing such as size classification, crushing, agglomeration as well as any other mechanical, thermal and chemical treatment, • larger or smaller parts of the main components and connection ducts of the process including e.g. the char reaction chamber may be composed of cooled or uncooled components,
  • the described process may be used at pressures being considerably higher as well as considerably lower than atmospheric pressure, • the char bed may be utilised as a "loop seal", which e.g. is achieved by letting the particle inlet duct from the re-circulating particle separator exhaust at a level below the bed surface in the char reaction chamber,
  • one CFB reaction chamber may be equipped with two or more particle re-circulation ducts, • one particle re-circulation ducts may serve several CFB reaction chambers,
  • particle separators as well as other components of the process may be integrated in the CFB reaction chamber construction and/or in each other.
  • the fuel addition to the CFB reaction chamber happens in a way that gives an intensive contact between the fuel and the particles in the CFB reaction chamber, i.e. it is appropriate that the feeding happens to a turbulent area that has a high particle concentration.
  • the desired effective contact may also be achieved by adding the fuel to a process stream which brings the fuel into the CFB reaction chamber and preferably to the bottom of the CFB reaction chamber.
  • the above mentioned low temperatures also enhance the possibilities for binding chlorine contained in e.g. straw, household waste and certain types of plastic into e.g. materials containing calcium such as limestone added to the process.
  • a further important characteristic may be the addition of calcium containing materials to the gasification process such as to the CFB reaction chamber.
  • the particle separation in order to re-circulate particles via the char reaction chamber may be performed using any type of particle separator, such as:
  • dynamic separators such as turn chamber-, labyrinth-, and cyclone separators
  • barrier filters such as high temperature bag filters, porous ceramic filters and granular bed filters, including using various combinations of e.g. the mentioned separators.
  • the product gas from the CFB reaction chamber is at first cleaned in a primary dynamic type of particle separator and thereafter in a secondary separator of more effective type.
  • the re-circulation of particles through the char reaction chamber is in this case primarily performed from the first mentioned primary dynamic separator.
  • the secondary separator may e.g. be a highly efficient barrier filter, but also a cyclone separator being more efficient than the primary separator including a multi cyclone separator. Further particle separation/gas cleaning may also in this version take place prior to the primary separator (using a pre-separator) as well as after the secondary separator.
  • a proper dynamic type primary separator where as a barrier filter is better suited for fulfilling potential severe demands about low content of particles and other problematic components in the product gas.
  • improved possibilities for binding problematic components such as chlorine, sulphur and alkalines in the filter cake as well as possibilities for oxidation of fine char particles are achieved by using a barrier filter.
  • Improved char oxidation can be achieved by adding a proper oxidation agent such as atmospheric air, oxygen, or water vapour in the gas path prior to the filter.
  • the filter may be used as an alternative to more traditional gas coolers, i.e. considerable cooling of the product gas may be achieved by cooling a particle circuit comprising the granular bed filter,
  • the cooling of the product gas may this way be achieved without heat absorption surfaces being in direct contact with corrosive components in the product gas, and this way cooling medias cooling the particle circuit may be heated to high temperatures such as above 500 °C, which allows a more efficient utilisation of the subtracted heat,
  • the heat obtained by cooling the particle circuit may e.g. be returned to the gasification process by fully or partly using the heat for e.g. preheating the gasification agent or fuel drying and/or the heat can be used for heating a working media in an electricity producing process such as by superheating water vapour or heating a gas stream which is afterwards expanded in a gas turbine.
  • the product gas from the CFB reaction chamber is passing a filter of the type moving granular bed.
  • additional gas cleaning can be achieved by the aid of separators/filters located prior to as well as after the moving granular bed filter, and particles may be re-circulated and/or drained from all of the included filters.
  • a barrier filter such as a granular bed filter as a re-circulating and possibly the only separator.
  • the drains from the CFB process such as to selectively drain the reaction products which are aimed to be removed from the process.
  • the particles separated from the barrier filter may be partitioned in two or several size classes and afterwards the smallest particles may be extracted from the gasifier.
  • the later mentioned controlled agglomeration of ash particles is a further example of how such selective draining can be established.
  • the granular bed filter In order to avoid an excessive pressure loss and that the product gas to a large extent carry small particles through the filter, the granular bed filter typically has to be dimensioned for low gas velocities such as below 3 m/s and preferably below 1.5 m/s which corresponds to a large flow square section compared to e.g. the flow square section of the CFB reaction chamber.
  • low gas velocities such as below 3 m/s and preferably below 1.5 m/s which corresponds to a large flow square section compared to e.g. the flow square section of the CFB reaction chamber.
  • it is therefore an interesting possibility to integrate the granular bed filter in the top of the CFB reaction chamber i.e. in a way that makes the granular bed filter more or less surround the top and while the product gas is added to the granular bed filter more or less directly from the top of the CFB reaction chamber and preferably in a rotational symmetric way.
  • a pre-separation of particles may be performed by initially passing the product gas from the top of the CFB reaction chamber through a pre-separator such as a turn chamber separator, which may also be fully or partly integrated in the CFB reaction chamber and surrounding it in a more or less rotational symmetric way.
  • a pre-separator such as a turn chamber separator
  • mean temperature of the char reaction chamber being higher than the mean temperature of the CFB reaction chamber and preferably at least 50 °C higher. Regardless the potential choice of controlling the process on the basis of temperatures measured in other levels, mean temperatures here are to be understood as the temperatures existing in approximately half the height of the respective reaction chambers.
  • the addition of the thermal energy needed for the predominantly endothermal pyrolysis processes is fully or partly obtained by adding particles from the char reaction chamber to the CFB reaction chamber, which particles have a higher and preferably at least a 25 °C higher temperature than the temperature of the product gas leaving the CFB reaction chamber.
  • Further preferred characteristics of the invention may contribute to forms of the char reaction chamber aiming a further optimised char conversion. This is by e.g.:
  • the horizontal square section of the char reaction chamber being larger than the square section of the CFB reaction chamber and preferably at least twice as large. This is in order to allow a sufficient supply of gasification agent at a low superficial gas velocity
  • the innovation may be improved by arranging the char reaction chamber as several mutually super posed char reaction chambers in order to achieve this way a more compact version of the gasification process.
  • the square section area of the char reaction chamber shall be understood as the sum of the horizontal square section areas of the supe ⁇ osed char reaction chambers.
  • the mentioned tendency for char particles to concentrate in the top of the char reaction chamber is partly due to these particles appearing more fluid dynamically light due to a tendency for being less spherical than e.g. particles fluidised in a long time as well as low density/high porosity. Furthermore, some of the char particles will be relatively small. The tendency for lower char density and the formation of small particles is enhanced by the oxidation of the char particles in the char reaction chamber.
  • a further possibility for improving the method of the invention is to support the mentioned tendency for segregation in the char reaction chamber. This is by choosing one or several of the following conditions:
  • a large bed height such as more than 1 m and preferably more than 2 m
  • the gasification of many fuels relevant for the method will result in a weak and fine ash, which is difficult to retain using especially dynamic particle separators, and which may give a tendency for fast blocking a barrier filter. Furthermore, it may be a problem to retain especially the smallest char particles in the process in the sufficient time for achieving a satisfying char gasification. It is therefore interesting to pursue a sintering and possibly an agglomeration of the ash- /char particles. E.g. this may be achieved by arranging or controlling the process with the intention of achieving a properly increased temperature in more or less extended fractions of the upper part of the char reaction chamber, where the concentration of fine ash-/char particles will be the highest due to the earlier mentioned segregation.
  • an important improvement of the invention may be achieved by the addition of (temperature increasing) oxygen and/or (temperature decreasing) water vapour predominantly in respectively the upper and the lower part of the char reaction chamber.
  • the earlier mentioned large bed height will also improve the possibilities for creating considerable temperature differences in the char reaction chamber.
  • a possible tendency for major temperature differences may of course also be counteracted by the mentioned mechanisms, as also asymmetric addition of a controllable part of the fluidisation gas can moderate the temperature difference due to the increased thermal mixing created this way in the char reaction chamber.
  • agglomeration is pursued through the above mentioned methods and to an extent that makes the agglomerated and i.e. enlarged ash particles sink to the bottom of the bed in order to be drained either directly from the bottom or through a compartment to which the particles are added.
  • This method provides the opportunity of selectively and e.g. continuously draining non-combustible components such as alkalines having a large tendency to form chemical components having low melting points Some of these components, such as alkali chlonde are relatively easy to separate, e g by water washing, which gives the opportunity of re-introducing particles refined this way to the process
  • a further possible and considerable improvement of the invention is to cool the particles in the char reaction chamber by a therein located heat abso ⁇ tion surface and preferably a surface in the lower part of the char reaction chamber Hence, a number of advantages may be achieved
  • the heat abso ⁇ tion via the mentioned heat abso ⁇ tion surface may be made controllable by e g. • varying the fluidisation velocity in the part of the bed containing the heat abso ⁇ tion surface
  • re-circulation of particles from the char reaction chamber to the CFB reaction chamber may in a further improved version of the invention be performed via one or several ducts which may contain control means that makes it possible to control the flow of particles.
  • control means that makes it possible to control the flow of particles.
  • improved possibilities for temperature control may be achieved by bringing the particles into contact with a heat abso ⁇ tion surface in one or several of the mentioned return ducts.
  • the mentioned possible control means are preferably of a non mechanical type, i.e. the particle flow rate is controlled by adding a gas that mobilise the particles to an extend that depends on the gas addition.
  • particles are transferred from the char reaction chamber to the CFB reaction chamber via at least one particle re-circulation duct that adds particles into the bottom of the CFB-reaction chamber via a predominantly vertical connection duct.
  • the mentioned predominantly vertical connection duct is surrounded by the char reaction chamber and this preferably in a way that the char reaction chamber surround the re-circulation duct as a rotation symmetric ring chamber.
  • the above mentioned preferred rotation symmetric construction of the char reaction chamber gives also the possibility of performing the earlier mentioned sintering and potentially also agglomeration in a particularly simple and well controlled way.
  • the addition of gas containing oxygen in order to create a zone with increased temperature in preferably the upper ash and char rich part of the char reaction chamber may be to some few locations and possibly only to a single location in the char reaction chamber.
  • the mentioned rotation may simply be established by adding one or several process streams such as the gasification agent, the oxidising agent creating increased temperature and re-circulating particles with some momentum in a direction supporting the mentioned rotating movement
  • connection duct allows the flow of particles through the connection duct to be simply controlled by adding a gas which to an extend depending on the added amount creates a transport of particles upwards into the CFB reaction chamber
  • the flow square section of the duct can be less than 25 % and preferably less than 10 % of the horizontal square section area of the CFB reaction chamber
  • connection duct may also be given a considerably larger horizontal square section area and e g appear as a downwards extension of the CFB reaction chamber
  • a larger part of the oxidation agent added to the process may be added to the connection duct, and this way, char oxidation in the connection duct may to a considerable extent supplement the char oxidation in the char reaction chamber
  • char particles brought out of the char reaction chamber along with the circulating inert particles leads to losses of unconverted char and also that large char particles accumulates in the bottom of the CFB reaction chamber
  • the possibility of counteracting the accumulation of large particles is especially an advantage when the expenses for reducing the particle size are to be minimised
  • a further simple possibility is to drain out potential larger non-combustible particles (which e g are added to the CFB reaction chamber with the fuel or which are formed as a consequence of agglomeration) from the bottom of the above mentioned predominantly vertical connection duct
  • the product gas from the char reaction chamber may fully or partly be added to e g the CFB reaction chamber, the outlet product gas from the CFB reaction chamber or to applications external to the gasification process
  • a considerable part and e g at least 50 % and preferable at least 75 % of the product gas from the char reaction chamber is transferred to the CFB reaction chamber and preferably to the bottom of the CFB reaction chamber m order to make the gas serve as fluidisation gas
  • a particularly simple and therefore attractive possibility is to add essentially all of the product gas from the char reaction chamber to the CFB reaction chamber.
  • the need for a separate system for exhausting and cleaning the product gas from the char reaction chamber may this way be minimised and potentially fully avoided, and moreover, the need for adding further fluidising gas in the CFB reaction chamber can be minimised.
  • the product gas added from the char reaction chamber constitutes at least 50 % and preferable at least 80 % of the total stream of gas added to the CFB reaction chamber.
  • the addition of product gas from the char reaction chamber to the CFB reaction chamber happens in approximately the same vertical level as the surface of the bed in the char reaction chamber. This way the ducting of product gas from the char reaction chamber to the CFB reaction chamber can be short and simple and in the same time there is easy access for achieving a simple and well controlled transfer of particles via a duct connecting the bottom of the char reaction chamber by the bottom of the CFB reaction chamber.
  • the product gas from the char reaction chamber is fully or partly passing one or several of the following process steps:
  • a particle separator for re-circulation of particles to the char reaction chamber. This is in order to optimise the char conversion and gas production and in order to achieve an increased retention of ash, including the content of mineral components in the char. • a reaction chamber to which an oxidation agent such as air is also added in order to oxidise fine char particles. This is also for the pu ⁇ ose of increased conversion of char, but the pu ⁇ ose may also be to modify the ash into a more appropriate form, including sintering, agglomerating and/or melting the ash,
  • a particle separator • a particle separator and preferably a barrier filter for removing fine ash particles.
  • the temperature of the re-circulating particles including by controlling the temperature of the char reaction chamber and/or by controlling the heat abso ⁇ tion via potential heat abso ⁇ tion surfaces, including by controlling the re-circulation through potential cooled particle recirculation ducts.
  • a preferred version of the invention is mainly controlled in the following way: • desired temperature in the CFB reaction chamber is achieved by controlling the flow of particles from the char reaction chamber to the CFB reaction chamber • desired temperature in the char reaction chamber is achieved by controlling the amount and/or composition of gasification agent added to the char reaction chamber.
  • the desired temperatures in the respective reaction chambers may additionally or alternatively be achieved by the aid of one of the mentioned methods for controllable cooling.
  • the method and apparatus according to the invention are, due to the mentioned characteristics, especially advantageous for fuels with one or several of the following characteristics:
  • the fraction of product gas produced by pyrolysing the fuel in the CFB reaction chamber will contain a large fraction of heavy organic components, which, if condensing, may cause problematic depositions and perhaps blockages in ducts and process equipment.
  • the process is therefore of primary interest for system applications wherein the product gas is transferred to its use at a temperature of at least 200 °C and preferably at least 400 °C.
  • Such hot and preferably adiabatic transfer of the product gas in the same time minimises the thermodynamic irreversibility and the plant expenses and potential operational problems related to cooling such gasses.
  • the gas is treated in order to decompose the mentioned heavy organic components.
  • the method of the invention is particularly interesting in relation to using the product gas as a fuel in an electricity-producing process, and preferably processes wherein the product gas is used as fuel in a steam boiler, gas turbine, combustion engine, or a fuel cell plant.
  • the gas is applied in solid fuel fired combustion chambers such as in steam boilers, a particularly interesting option is fully or partly using the product gas as so called "re-burning" gas, i.e. for the pu ⁇ ose of reducing the emission of nitrogen oxides.
  • heat abso ⁇ tion surfaces are cooled by a process stream from the connected gas consuming system, e.g. cooling is by water vapour from a steam circuit or by combustion air for e.g. a boiler, gas turbine or fuel cell.
  • the cooling energy may also be used for drying of potential fuels with high water content and/or for heating any other process stream.
  • an apparatus of the type having a circulating fluidised bed (CFB) gasifier for the gasification of solid carbonaceous material and comprising a CFB reaction chamber, which is connected to a particle separator, from which particles separated from product gas from the CFB reaction chamber can be returned to the CFB reaction chamber via a particle re-circulation duct, the apparatus also comprising means for adding the carbonaceous material to the CFB reaction chamber and means for adding a gasification agent to the gasifier, and the apparatus according to the invention is characterised by the forming of a char reaction chamber in the re-circulation duct and by that the means for adding the gasification agent are designed for supplying a considerable part and preferably the main part of the amount of oxygen added to the CFB gasifier to the char reaction chamber in form of an oxygen containing gasification agent for converting char, which is contained in the re-circulating particles, to a combustible gas.
  • CFB circulating fluidised bed
  • figure 1 schematically shows a simple version of the apparatus according to the invention-
  • FIG 2 schematically shows another version of the apparatus according to the invention.
  • figure 3 schematically shows a version of the char reaction chamber, which in a simple way makes it possible to perform sintering and/or agglomeration of ash-/cha ⁇ articles.
  • FIG. 1 shows schematically an apparatus in the form of a CFB gasifier, that has a CFB reaction space or -chamber 1 with an outlet 4 for particle loaded gas 32, a cyclone separator 2 for separation of particles from the gas and a char reaction chamber 3, to which the separated particles 33 are added from the separator via a duct 5.
  • Fuel 40 is added to the CFB-reaction chamber at its bottom and in the reaction chamber 1, the fuel is pyrolysing as the consequence of an effective contact to particles 35, which are re-circulated from the char reaction chamber 3.
  • the char reaction chamber 3 which is functioning as a gasifier, is primarily a slowly fluidised bubbling bed of the separated particles 33.
  • Oxygen-containing gasification agent such as air and potentially water vapour is added as fluidising gas 36.
  • a heat abso ⁇ tion surface 8 located in the bottom of the char reaction chamber 3 a part of the thermal energy from the char gasification is transferred to the cooling media 43.
  • Particles 35 are re-circulated from the bottom of the char reaction chamber 1 via a predominantly vertical duct 6, while the rate of re-circulation is controlled by adding a variable gas stream 38 to the vertical duct.
  • a further added gas stream 37 ascertain the mobility of the particles in a short horizontal duct connecting the char reaction chamber 3 to the vertical duct 6.
  • a particle stream 42 may be drained from the lower part of the vertical duct 6
  • Product gas 34 is transferred from the top of the char reaction chamber into the bottom of the CFB reaction chamber 1 via a duct 7, where this gas serves as fluidising gas.
  • Additional fluidising gas 39 such as flue gas from the process using the produced product gas 41, may be added in order to impact the flow condition of gas and particles 31 up through the CFB reaction chamber in a preferred direction
  • Figure 2 shows another version of the apparatus according to the invention, which comprises a number of further possibilities for optimising the gasification process in relation to given fuels and applications
  • the CFB-gasifier may, besides the already mentioned items, comprise a pre-separator 9 for re- circulating particles directly to the CFB reaction chamber 1, and after the re-circulating separator 2 there may be a secondary separator 10, from which further particles 58 can be re-circulated to the char reaction chamber 3 or be drained at 54 As it is shown, it can also be chosen to drain a partial stream of particles 53 from the primary separator 2, which is particularly relevant, if a highly effective filter is chosen as the primary and potentially the only separator
  • An oxygen-containing gas 44 can, as it is shown, be added in the char reaction chamber for the pu ⁇ ose of creating an increased temperature in locations in the upper part of the fluidised bed This is primarily done in order to give the ash particles existing in the upper part of the bed a heat treatment.
  • the possibilities for retaining the ash by the following particle separators are improved and/or the ash can be made to agglomerate to an extent that it achieves a sufficient size and mechanical stability to supplement the circulating particular media in the gasifier and/or it may be drained as a relatively coarse particle stream, respectively 50 and 42 through respectively the bottom of the char reaction chamber 3 and the bottom of the CFB reaction chamber 1
  • heat may be extracted by the aid of a heat transmission media 51, added to a heat abso ⁇ tion surface 1 1 which i located in e g one of two parallel ducts for the re-circulation of particles to the CFB reaction chamber 1
  • control means 15 are preferably a non-mechanical type and may be combined in a single control mean deciding the share of the re-circulating particle stream that has to pass the heat abso ⁇ tion surface.
  • the particle separator 14 may e.g. be a highly effective barrier filter, which cleans the gas in order to fully or partly extract it as a stream 56 in stead of as also shown, adding it to the CFB reaction chamber 1 or to the exit gas from this chamber.
  • additives 52 such as limestone may be added to the CFB reaction chamber. This is in order to enhance the retention of problematical gasses, such as gasses containing chlorine.
  • Figure 3 further illustrates the possibility of sintering and possibly agglomerating ash-/ char particles in the char reaction chamber 3.
  • a directional addition of gasification agent 36 as well as the oxygen containing gas 44 to the creation of an overall movement of the particles in the char reaction chamber. This movement makes the ash-/char particles pass a zone having an increased temperature, which appears as a consequence of exothermic reactions between the oxygen-containing gas 44 and combustible components in the char reaction chamber.
  • the possibility of giving the ash-/char particles a well defined heat treatment by this simple method is particularly present when the char reaction chamber is constructed rotational symmetric and e.g. as a ring chamber.
  • the horizontal movement of particles indicated in figure 3 corresponds in this case to a rotating movement of particles in the char reaction chamber.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Industrial Gases (AREA)
  • Fluidized-Bed Combustion And Resonant Combustion (AREA)

Abstract

L'invention porte sur la gazéification d'une matière carbonée solide s'effectuant dans un gazéifieur à lit fluidisé circulant comprenant une chambre de réaction (1) à lit fluidisé circulant, un séparateur de particules (2) pour la séparation de particules contenant du charbon et provenant du gaz (32) d'émission de la chambre de réaction, et un conduit de recirculation (5) pour la recirculation des particules séparées dans la chambre de réaction. Le conduit de recirculation (5) des particules comprend une chambre (3) de réaction dans laquelle s'effectue la gazéification du charbon contenu dans les particules de recirculation. La fonction du gazéifieur peut être commandée de différentes manières. Comparé à l'utilisation de gazéifieurs à lit fluidisé circulant plus traditionnels dans lesquels le charbon doit être transformé dans la chambre de réaction, on obtient, par exemple, avec une structure meilleure marché et plus compacte, une plus grande efficacité et une plus grande flexibilité du combustible. Le processus de gazéification est tout à fait approprié également pour les biocombustibles et les produits résiduaires qui ont une teneur élevée en alcalins et en chlore.
EP98958839.7A 1997-12-09 1998-12-09 Procede et appareil de gazeification de matieres carbonees solides Expired - Lifetime EP1021499B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20100183554 EP2284245A1 (fr) 1997-12-09 1998-12-09 Réacteur à lit fluidisé avec séparateur de particules et chambre de reaction.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK142397 1997-12-09
DK142397 1997-12-09
PCT/DK1998/000541 WO1999032583A1 (fr) 1997-12-09 1998-12-09 Procede et appareil de gazeification de matieres carbonees solides

Related Child Applications (1)

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EP10183554.4 Division-Into 2010-09-30

Publications (2)

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EP1021499A1 true EP1021499A1 (fr) 2000-07-26
EP1021499B1 EP1021499B1 (fr) 2013-04-17

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EP20100183554 Withdrawn EP2284245A1 (fr) 1997-12-09 1998-12-09 Réacteur à lit fluidisé avec séparateur de particules et chambre de reaction.
EP98958839.7A Expired - Lifetime EP1021499B1 (fr) 1997-12-09 1998-12-09 Procede et appareil de gazeification de matieres carbonees solides

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AU (1) AU1484399A (fr)
DK (1) DK1021499T3 (fr)
ES (1) ES2424815T3 (fr)
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WO (1) WO1999032583A1 (fr)

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FI20010570A (fi) 2001-03-20 2002-09-21 Fortum Oyj Menetelmä ja erotuslaite kahden faasin erottamiseksi toisistaan
FI120770B (fi) * 2001-10-02 2010-02-26 Valtion Teknillinen Menetelmä ja laitteisto polttoaineen kaasuttamiseksi leijukerrosreaktorissa
US8512451B1 (en) 2011-10-07 2013-08-20 William L. Heumann Cyclone separator arrangement
GB2503065B (en) 2013-02-20 2014-11-05 Recycling Technologies Ltd Process and apparatus for treating waste comprising mixed plastic waste
WO2015007285A1 (fr) 2013-07-17 2015-01-22 Pyroneer A/S Appareil et procédés de gazéification
CN108329948A (zh) * 2018-04-24 2018-07-27 合肥德博生物能源科技有限公司 一种污泥秸秆共气化制备燃气联产炭基脱硫剂的装置及其方法
CN112824502B (zh) * 2019-11-21 2022-04-15 中国科学院工程热物理研究所 循环流化床气化装置以及循环流化床气化方法
CN110791326B (zh) * 2019-11-21 2021-10-12 中国科学院工程热物理研究所 带气化辅床的循环流化床气化装置以及气化方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2662816A (en) * 1948-07-20 1953-12-15 Hydrocarbon Research Inc Gasification of carbonaceous materials containing volatile constituents
US4386940A (en) * 1981-10-08 1983-06-07 Cogas Development Company Gasification of carbonaceous solids
GB8330606D0 (en) * 1983-11-16 1983-12-21 Shell Int Research Preparation of hydrocarbons and fuel gas
FR2556983B1 (fr) * 1983-12-23 1986-05-16 Creusot Loire Procede et installation de traitement de matieres en lit fluidise, en particulier pour la combustion ou gazeification de matiere combustible
FR2586941B1 (fr) * 1985-09-09 1987-12-04 Framatome Sa Dispositif de traitement de matieres solides sous forme de particules, en lit fluidise circulant, en particulier dispositif de gazeification
SE457905B (sv) * 1986-08-28 1989-02-06 Abb Stal Ab Saett vid foerbraenning i fluidiserad baedd
US4709662A (en) * 1987-01-20 1987-12-01 Riley Stoker Corporation Fluidized bed heat generator and method of operation
FI873735A0 (fi) * 1987-08-28 1987-08-28 Ahlstroem Oy Foerfarande och anordning foer foergasning av fast kolhaltigt material.
US4896717A (en) * 1987-09-24 1990-01-30 Campbell Jr Walter R Fluidized bed reactor having an integrated recycle heat exchanger
DK633488D0 (da) * 1988-11-11 1988-11-11 Risoe Forskningscenter Reaktor
FI85909C (fi) * 1989-02-22 1992-06-10 Ahlstroem Oy Anordning foer foergasning eller foerbraenning av fast kolhaltigt material.
US5228981A (en) * 1990-10-01 1993-07-20 Exxon Research & Engineering Company Coal as an additive to accelerate thermal cracking in coking
US5140950A (en) * 1991-05-15 1992-08-25 Foster Wheeler Energy Corporation Fluidized bed combustion system and method having an integral recycle heat exchanger with recycle rate control and backflow sealing
US20060130401A1 (en) * 2004-12-16 2006-06-22 Foster Wheeler Energy Corporation Method of co-producing activated carbon in a circulating fluidized bed gasification process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9932583A1 *

Also Published As

Publication number Publication date
ES2424815T3 (es) 2013-10-08
EP2284245A1 (fr) 2011-02-16
DK1021499T3 (da) 2013-07-29
EP1021499B1 (fr) 2013-04-17
PT1021499E (pt) 2013-08-26
AU1484399A (en) 1999-07-12
WO1999032583A1 (fr) 1999-07-01

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