Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D49/00—Separating dispersed particles from gases, air or vapours by other methods
• • 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
• • 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
  • F23C10/005—Fluidised bed combustion apparatus comprising two or more beds
• • 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 
  • F23C99/00—Subject-matter not provided for in other groups of this subclass
• • 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 
  • F23C2900/00—Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
  • F23C2900/99008—Unmixed combustion, i.e. without direct mixing of oxygen gas and fuel, but using the oxygen from a metal oxide, e.g. FeO
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J2217/00—Intercepting solids
  • F23J2217/60—Intercepting solids using settling/precipitation chambers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E20/00—Combustion technologies with mitigation potential
  • Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery

Definitions

• the field of the invention is that of the separation of particles, and more specifically metal oxide particles, on the one hand, and unburnt particles possibly associated with fly ash, on the other hand, in the context chemical loop combustion to produce energy, synthesis gas and / or hydrogen.
• the chemical looping combustion (abbreviation CLC for Chemical Looping Combustion) consists of bringing into contact, in a high-temperature chamber, a gaseous, liquid and / or solid hydrocarbon feedstock with a solid of the metal oxide and oxygen-carrying type.
• the metal oxide gives up some of the oxygen it contains, the latter participating in the combustion of hydrocarbons.
• the fumes mainly contain carbon oxides, water and possibly hydrogen. Indeed, it is not necessary to put the hydrocarbon feedstock in contact with air and the fumes are therefore mainly composed of combustion gases and possibly a dilution gas used for transporting and fluidizing the particles or a gas (for example water vapor) promoting the gasification of solid fuel.
• the patent application FR 2,850,156 describes a chemical loop combustion process for which the fuel is ground before entering the reduction reactor operating in a circulating fluidized bed.
• the small size of the solid fuel particles allows a more complete and faster combustion.
• the downstream separation of the circulating bed is first provided by a cyclone and then by a device for separating the unburnt particles from the metal oxide particles. Thus, it avoids the entrainment of unburnt in the oxidation zone and thus the CO 2 emissions in the effluents of the oxidation reactor.
• the separation device is fluidized by water vapor, which separates the fine and light particles, such as the carbonaceous residue, and reintroduces the latter into the reactor, while the denser and larger particles of oxides are transferred to the oxidation reactor.
• the patent application FR 2 896 709 relates to a particle separator operating in a chemical loop process.
• This separator is fed by the flow of particles carrying the oxygen and mixed with the solid fuel.
• the particles flow in a dense phase following a tortuous path and passing through baffles, which makes it possible to control the residence time and to promote the separation of the light particles (unburnt particles) from the particles. heavy (metal oxides).
• the particles are then introduced into a fluidization zone, said fluidization being controlled by means located at the base of the separator but also at the wall of the baffles, which makes it possible to entrain the lighter particles which are then recycled to the reactor. fluidization.
• the separation efficiency is reduced in view of a limitation in the driving capacity of the particles in the gas phase. Indeed, to drive large quantities of particles, it is necessary to implement large amounts of gas and free sections.
• the geometry of the FR 2 896 709 separator is very complicated by the presence of internals, in particular asymmetrical internals. This geometry is problematic given the mechanical stresses experienced by the materials constituting the separator under the temperature conditions of the CLC process, generally above 800 ° C. Indeed, if the outer walls are often protected by a refractory cement and remain at low temperature, this is not the case of internal walls that are brought to the conditions of the process.
• Applicants have developed a novel separator wherein the mixture of particles from the combustion zone is contacted with a gas stream from the combustion zone and / or an external gas source. This mixture then enters the dilute phase of the separator. In the separator, the velocity of the gas flow is controlled so as to allow sedimentation of the heavier particles (essentially metal oxide particles), the lighter particles (essentially unburnt particles) being drawn towards the top of the separator to be recycled to the combustion zone.
• the separator according to the invention has an improved efficiency of separation of unburnt particles and particles of metal oxides.
• the present invention relates to a chemical loop combustion device using a solid fuel generating unburnt particles and implementing oxygen carrier particles, such as metal oxides, and comprising at least one zone of combustion and separator of particles contained in a gas mixture from said combustion zone, wherein the separator comprises an enclosure with at least one intake pipe of said mixture, an exhaust pipe located in the lower part of the enclosure and a pipe outlet located in the upper part of the device, the inlet and outlet / outlet parameters being chosen to create in the enclosure a dense phase in the lower part and a diluted phase in the upper part, and wherein said intake pipe opens in the diluted phase.
• the separator enclosure may further include a supply line for a gas from an external source.
• the outlet pipe may be connected to a gas-solid separator for evacuating a gas depleted of unburnt particles by a pipe, and recycling the unburnt particles via a communication pipe with the combustion zone.
• the intake pipe can enter the chamber substantially axially and with a length of between 1 and 5 times the diameter of the chamber.
• the intake pipe can penetrate through the lower part of the enclosure.
• the lower part of the enclosure may comprise an annular space between the outer wall of the intake pipe and the wall of the separator.
• the combustion zone may comprise at least one solid feed line, an oxygen carrier particle feed line, a fluidization gas feed line, to form said gas mixture.
• the invention also relates to a chemical loop combustion method using a solid fuel generating unburnt particles and implementing oxygen carrier particles, such as metal oxides, and comprising at least one combustion zone and one combustion zone.
• particle separator contained in a gas mixture from the combustion zone, a method according to which a mixture of particles and gas is admitted into the separator enclosure, the particles are extracted by an outlet at the top of the enclosure and a evacuation in the lower part of this chamber, the intake and extraction parameters being chosen to create in the chamber a lower dense phase and an upper dilute phase, dilute phase in which said mixture is admitted.
• the separator enclosure may be powered by a gas from an external source.
• the superficial velocity of the gas in the dilute phase of the chamber of the device can be set at a value between 30 and 300% of the average terminal rate of drop of the oxygen carrier particles.
• the superficial velocity of the gas in the dilute phase of the chamber of the device can be set at a value between 75 and 125% of the average terminal rate of drop of the oxygen carrier particles.
• the gas velocity in the upper part of the combustion zone can be between 3 and 10 m / s.
• the separator can be placed above the combustion zone.
• the enclosure may be powered by a gas from an external source representing less than 20% of the total gas flow in the separator.
• the combustion zone can operate in a dense phase fluidized bed, the particles of which are transported to the separator, the transport being controlled by an L-shaped valve.
• the combustion zone can operate in a dense phase fluidized bed, the particles of which are transported to the separator through a gas / solid separator at the exit of which the particles flow inside the separator.
• FIGS. 1 to 5 represent, solely by way of example and in a nonlimiting manner, various implementations and integration of the device according to the invention at the exit of a combustion zone. a CLC unit.
• FIG. 5 illustrates a particular geometry of the device according to the invention.
• Figure 1 describes the invention integrated in a global scheme.
• Zone (2) represents the combustion zone of a chemical looping combustion process (CLC) in which a solid charge is introduced via a pipe (7), particles of oxygen carrier via a pipe (8) from the oxidation zone (not shown) of the CLC process and a fluidization gas supplied by a pipe (17) such as, for example, steam or water.
• CLC chemical looping combustion process
• the solid charge (or fuel) treated in the combustion zone is generally composed of a hydrocarbon solid source containing predominantly carbon and hydrogen.
• the filler is advantageously selected from coal, coke, petcoke, biomass, oil sands and household waste.
• This combustion zone (2) can operate in a fluidized bed in dense phase or circulating fluidized bed or in a bed arrangement consisting of a dense phase and a transport phase.
• the gas velocity in the upper part of the combustion zone is between 3 and 10 m / s.
• a flow of particles containing particles of metal oxides, called heavy particles, and light particles comprising unburnt particles and possibly fly ash, all in a gas stream is extracted from the zone (2) to be is then introduced into a separator (1) by an intake pipe (4).
• the gaseous flow comes wholly or partly from the combustion zone (2) and consists mainly of CO, CO 2 , H 2 and H 2 O, the complement may come from an external source containing, for example, recycled CO 2 and / or water vapor, introduced through the conduit (11) in the lower part of the separator (1).
• all the off-gases used for combustion are used for the separation and, very preferably, it consists of at least 80% of the effluents from the combustion zone.
• this cyclone is to separate the unburned gas into unburnt particles which is then extracted via a pipe (10) and the unburnt particles entrained with the metal oxide particles extracted by a pipe (9) and recycled to the combustion zone (2).
• the heavy particles extracted in the lower part of the separator consist mainly of metal oxides and can be sent to a second combustion zone in which the oxygen carrier will be reduced, or to an oxidation zone allowing the oxygen carrier recovering at least a part of the oxidation state that it had at the entrance to the combustion zone (2) and the lighter unburned particles are recycled to the combustion zone, after separation of the gaseous effluent .
• the inlet and outlet / outlet parameters are chosen so as to create a dense phase in the enclosure in the lower part and a diluted phase in the upper part, and the intake pipe (4) opens into the dilute phase.
• the particles that sediment in the lower part form a dense phase consisting of the heavier particles, of greater or lesser height in the separator, depending, among other things, on the density of the particles, the feed and extraction rates, but the level of said dense phase, forming the interface with the dilute phase, is in all cases located below the inlet (4) opening into the separator for the introduction of the mixture of particles extracted from the combustion zone.
• rapid separation is meant a separation taking place in less than 1 minute and preferably in less than 20 seconds, this time corresponding to the residence time of the light particles in the dilute phase of the separator.
• the dilute phase generally has a solids content of less than 5%, or even less than 1% vol.
• X amount of unburnt particles entrained with the gas / total amount of unburnt particles in the mixture of particles entering the separator
• the superficial velocity of the flow in the separation zone must be greater than the final rate of fall of the unburnt fuel particles to allow their entrainment with the gas.
• the superficial gas velocity in the dilute phase of the separation zone is set at a value generally comprised between 30 and 300% of the average terminal rate of drop of the oxygen carrier particles, preferably between 75 and 125%.
• the particle flow entrained in the dilute phase of the separator remains less than 5 kg / s / m2, preferably less than 1 kg / s / m2.
• Vt ( 4d p ⁇ p - P g ) g ) 1/2 where: dp is the average particle diameter
• p s is the density of the particles (kg / m 3 )
• p g is the density of the gas (kg / m 3 )
• the geometry of the separator may be parallelepipedal, cylindrical or any other three-dimensional geometry and preferably it has a symmetry of revolution.
• the material used to make the enclosure of the separator may be selected from special steels such as Phastelloy or even ceramics.
• the outlet of the pipe (4) enters the enclosure on an axial depth preferably between 1 to 5 times the diameter of the enclosure, preferably from 1 to 2 times the diameter of the enclosure.
• the height of the enclosure available above the outlet of the intake pipe (4) in the enclosure is generally between 1, 5 to 10 times the diameter of the enclosure.
• the metal oxide particles such as, for example, oxides of Fe, Ti, Ni, Cu, Mn, Co, V, are used alone or as a mixture, and have an average size generally greater than 50 microns, preferably between 100 and 500 microns.
• the metal oxides, synthetic or mineral, supported or not, generally have a density greater than 1500 kg / m 3 .
• the nickel oxide particles supported on alumina generally have a grain density of between 2500 and 3500 kg / m 3 depending on the porosity of the support and the oxide content.
• nickel typically about 3200 kg / m 3 .
• Ilmenite a combination of titanium and iron, has a density of 4700 kg / m 3 .
• the separation device according to the present invention is advantageously used for separating unburnt particles from metal oxide particles having a density greater than 2500 kg / m 3 , preferably greater than 4000 kg / m 3.
• Oxygen carrier particles are generally much larger in size and density than fly ash and unburnt particles that have previously been in contact with the oxygen carrying particles in the high temperature combustion zone. At the outlet of the combustion zone, it is estimated that the size of the unburned coal particles is less than 100 microns and that the majority of the particles are less than 50 microns in size. The density of these particles is generally between 1000 and 1500 kg / m 3 .
• Figure 2 differs from Figure 1 in that the intake duct (4) opens axially directly into the separator (1) which is placed above the combustion zone (2).
• the upper part of the combustion zone is narrowed, which makes it possible to accelerate and transport the gas-particle mixture leaving the combustion zone, and comprising combustion fumes, unburnt particles and possibly fly ash.
• the gas velocity in the upper part of the combustion zone is preferably between 3 and 10 m / s and the flow of particles transported in this part is between 25 and 500 kg / s / m 2 , preferably between 60 and 300 kg / s / m 2 .
• the conduit (4) opens into the separator in a dilute phase consisting essentially of gas (at least 95% by volume). Due to the imposed velocity of the gas in the separator (1), the heavy particles sediment in the lower part of the separator and are extracted by the pipe (5), while the light particles are entrained in the upper part of the separator (1). and are evacuated by the pipe (6).
• the flow of light particles entrained relative to the section of the separator (1) is less than 5 kg / s / m 2 , is generally between 0.02 and 1.0 kg / s / m 2 and contains at least 50% of the unburnt particles from the combustion zone (2).
• the fluidization of the dense phase is performed by adding a gas external to the combustion zone by a conduit (11).
• This gas passes through the separation zone (1) and advantageously participates in the physical separation process of the particles before leaving the separator via the pipe (6).
• FIG. 3 differs from FIG. 2 in that the combustion zone (2) in which the solid charge introduced by the pipe (7) is burned in contact with the oxygen carrier particles brought by a pipe (8) in a fluidized bed in dense phase, the fluidization being operated through the introduction of a gas supplied by a pipe (17) and containing for example water vapor and / or carbon dioxide.
• the combustion fumes are discharged from the combustion zone (2) through a conduit (15) located in the upper portion of the fluidized bed of this zone.
• the particles are withdrawn into the dense phase of the fluidized bed and transported independently of the combustion fumes in lines (4) and (4 ') to the separation zone (1).
• the transport means represented by the pipes (4) and (4 ') include, for example, a device for drawing off in a dense phase, a vertical tube in which the particles flow downwards, a non-mechanical valve, such as a valve in L, for controlling the flow rate of particles by controlled injection of an insufflation gas upstream of a bend in a transport lift in which a gas external to the combustion zone (2) is injected to transport the particles.
• the particles therefore arrive in the separator (1) in the presence of a gas allowing their upward transport.
• the gas-particle mixture originating from the combustion zone (2) opens into the separator (1) through the end of the pipe (4 ') in a dilute phase consisting essentially of gases (at least 95% by volume) in which the superficial velocity is controlled by adding gas through the pipe (11).
• the adjustment of the superficial velocity in the separator (1) makes it possible to control the quantity of particles entrained towards the outlet (6). Particles not entrained towards this outlet (6) sediment in the dense phase of the separator (1) and are collected in the lower part of the separator (1) and discharged via a pipe (5) to another reaction zone.
• FIG. 4 describes another embodiment of the invention, which differs from that of FIG. 3 in that the particles entering the separator (1) are introduced from a downcomer (4 ") in which the particles arrive in a descending transport mode in dense phase, the movement of the particles depending on the gravity and not on the speed of the surrounding gas.
• a prior separation of the mixture transported in the intake duct (4) is carried out, for example in a gas-solid separator (12).
• the solid particles then flow through the pipe (4 ") inside the separator (1) and are distributed over the entire section of the separator (1) through a deflector (14), such as for example a" hat “ Chinese “, with a hollow cone of larger section than the duct (4").
• a deflector such as for example a" hat “ Chinese ", with a hollow cone of larger section than the duct (4"). Due to this new mode of introduction, the gas involved in the separation of the particles in the separator (1) is introduced substantially at the base of the chamber by a conduit (11), the interstitial gas introduced through the conduit.
• FIG. 5 describes a particular geometry of the device according to the invention, which comprises in its lower part a circular recess or annular space (200) between the wall of the pipe (4) opening into the dilute phase and the outer wall (300) of the smaller diameter separator, whereby all the surfaces of the device have an outer face, which can be easily cooled, and it is possible to coat all internal surfaces with a refractory cement (100). Under these conditions, the outer walls are no longer exposed to high temperature levels and are protected from contact with gas and particle currents.
• the tests to quantify the performance of the device according to the invention were conducted on a cold model simulating the flows.
• the model includes a transport tube with an internal diameter of 2 cm, in which the particles are transported by air under ambient conditions, the air simulating the combustion fumes.
• the transport tube opens into the dilute phase of a cylindrical separation chamber of constant section (internal diameter of 12.5 cm).
• the tube enters the chamber to a depth of 20 cm, which leaves a height of 80 cm above the outlet of the conduit in the diluted phase to effect the separation.
• the separation chamber is equipped at its base with a gas distribution box for fluidizing the particles around the transport conduit. The level of the fluidized dense phase is maintained under the outlet of the transport conduit opening into the separation chamber.
• Vsg The superficial velocity of the gas in the dilute phase above the outlet of the transport tube.
• the gas velocity in the transport tube is equal to 3m s.
• the flow of solids circulating in the transport tube, feeding the separation zone is equal to 140 kg / h, which corresponds to a flow of 123 kg / s / m 2 .
• the mass concentration of light particles in all the particles entering the separator is called Cl.
• Oxygen carrier particles consisting of a heavy ore of iron and titanium (ilmenite), whose properties are as follows:
• FCC catalyst particles smaller and less dense, simulating coke particles or unburned carbon at process conditions, the properties of which are as follows:
• the separation efficiency is important.
• the gas velocity in the dilute phase is 1, 0 or 1, 1 m / s, the recovery efficiency of the light particles can be greater than 70%.

Landscapes

• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Fluidized-Bed Combustion And Resonant Combustion (AREA)
• Solid-Fuel Combustion (AREA)
• Combined Means For Separation Of Solids (AREA)
• Filtering Of Dispersed Particles In Gases (AREA)

Priority Applications (12)

Applications Claiming Priority (2)

Publications (2)

Family

ID=43568210

Family Applications (1)

Country Status (14)

Cited By (6)

Families Citing this family (8)

Citations (2)

Family Cites Families (22)

• 2010
  • 2010-06-02 FR FR1002326A patent/FR2960941B1/fr not_active Expired - Fee Related
• 2011
  • 2011-05-27 KR KR1020127034347A patent/KR20130109991A/ko not_active Abandoned
  • 2011-05-27 JP JP2013512961A patent/JP2013532268A/ja active Pending
  • 2011-05-27 RU RU2012156927/06A patent/RU2568017C2/ru not_active IP Right Cessation
  • 2011-05-27 CN CN201180027105.0A patent/CN103080649B/zh active Active
  • 2011-05-27 ES ES11728314T patent/ES2748513T3/es active Active
  • 2011-05-27 AU AU2011260164A patent/AU2011260164B2/en not_active Ceased
  • 2011-05-27 CA CA2799139A patent/CA2799139C/fr active Active
  • 2011-05-27 EP EP11728314.3A patent/EP2577163B1/fr active Active
  • 2011-05-27 WO PCT/FR2011/000317 patent/WO2011151537A2/fr not_active Ceased
  • 2011-05-27 PL PL11728314T patent/PL2577163T3/pl unknown
  • 2011-05-27 US US13/701,587 patent/US9388979B2/en active Active
  • 2011-05-27 BR BR112012030797-5A patent/BR112012030797B1/pt not_active IP Right Cessation
• 2012
  • 2012-11-15 ZA ZA2012/08629A patent/ZA201208629B/en unknown

Patent Citations (2)

Also Published As

Similar Documents

Legal Events