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WO2010052417A1 - Process for the continuous production of an oxygen-rich gas at high temperature - Google Patents

Process for the continuous production of an oxygen-rich gas at high temperature Download PDF

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Publication number
WO2010052417A1
WO2010052417A1 PCT/FR2009/052112 FR2009052112W WO2010052417A1 WO 2010052417 A1 WO2010052417 A1 WO 2010052417A1 FR 2009052112 W FR2009052112 W FR 2009052112W WO 2010052417 A1 WO2010052417 A1 WO 2010052417A1
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Prior art keywords
oxygen
fluidized bed
boiler
fast fluidized
loop
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French (fr)
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Jean-Xavier Morin
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/83—Solid phase processes with moving reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0233—Chemical processing only
    • C01B13/0237—Chemical processing only by oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0233—Chemical processing only
    • C01B13/024—Chemical processing only by reduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/06—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B01D53/10—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00176—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles outside the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00203—Coils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00327—Controlling the temperature by direct heat exchange
    • B01J2208/00336—Controlling the temperature by direct heat exchange adding a temperature modifying medium to the reactants
    • B01J2208/0038—Solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00504—Controlling the temperature by means of a burner
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen
    • 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
    • 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 invention relates to a process for the continuous production of a gas rich in oxygen at high temperature.
  • Oxygen production is commonly obtained by distillation of atmospheric air.
  • the cold necessary for the industrial liquefaction of the air is obtained by relaxation using the phenomenon of Joule-Thomson.
  • the air is dusted, freed of its carbon dioxide and moisture, compressed to 200 bar, cooled in a heat exchanger, and then relaxed to 25 bar.
  • a series of compressions and relaxations leads to liquefaction. This fractional distillation separates oxygen, nitrogen and noble gases.
  • Perovskite is a crystalline structure common to many oxides. This name first designated calcium titanate CaTiO3 formula, before being extended to all oxides of general formula ABO3 having the same structure. Perovskites are of great interest because of the great variety of properties according to the choice of the elements A and B. An example of these properties is described in the following article: "Mixed conduction and oxygen permeation in the oxides for CaTiO3" , IWAHARA H. (1); ESAKA T.; MANGAHARA T.; (1) Tottori University, College. eng., dep. Environmental Chemistry Technology, Tottori 680, JAPAN Journal of Applied Electrochemistry 1988, vol. 18, no. 2, pp. 173-177.
  • a process for producing an oxygen-rich gas by means of perovskites is described in US patent document 2003/0138747.
  • This method consists in putting air streams in contact with a perovskite material in a fixed bed and thus retaining or adsorbing oxygen on the perovskite.
  • the corresponding installation comprises two fixed beds filled with perovskites, one of which receives compressed air and heated and the other saturated with oxygen receives recycled gases from a boiler system, cooled and compressed.
  • This oxygen production process utilizes these perovskite oxygen storage properties at high temperatures to adsorb oxygen from the air into a fixed bed of particles and then release it by scavenging recycled gases.
  • the method operates substantially continuously by combining the operation of the two fixed beds in cyclic mode by means of a circulation circuit comprising a large number of valves, of the order of eight valves, controlled in sequence. Such an installation therefore poses mechanical problems in the operation of these valves.
  • the invention proposes a process for the continuous production of an oxygen-rich gas for supplying an existing boiler by means of an installation comprising two fast fluidized-bed loops, the first of which is fluidized by a an oxygen-containing gas providing an exothermic reaction and the second of which is fluidized by recycled gases from said boiler, interconnected, to produce a thermochemical loop containing only mixed oxide particles with perovskite structure, each of said fast fluidized bed comprising a reactor filled with said particles and connected to a separation cyclone and a return line of the solids to the reactor downstream of said cyclone
  • the invention proposes to use a new architecture of two interconnected high-flux fast fluidized-bed solid-gas loops of circulating solids, only able, thanks to this high and continuous circulation of mixed oxide particles with perovskite structures, to transfer the oxygen required selectively and to perform on the circulating solids the heat exchanges created by the exothermicity and endothermicity of the reactions with oxygen.
  • This new architecture ensures the production of a gas rich in oxygen by means of a thermochemical loop containing only particles of mixed oxides with perovskite structure for the supply of an existing boiler using any combustible, fossil or non-fossil. No other fuel is introduced into said loops, in particular in the fluidized reduction loop by recycled gases from said boiler.
  • the process according to the invention is perfectly adapted to the high temperature, in order to accelerate the exchange kinetics, and makes it possible to achieve total autothermicity by means of specific oxide formulations and by circulating dozens of thousands of tons per hour of solids, flow required by large applications.
  • said gas containing oxygen is air.
  • said recycled gases are a mixture of carbon dioxide and water vapor from an oxy-combustion boiler or a fast fluidized bed boiler.
  • the mixture of oxygen, carbon dioxide and water vapor from said second fast fluidized bed loop can be transferred to said boiler operating in oxy-combustion or in said fast fluidized bed boiler.
  • Said mixed oxide particles with perovskite structures preferably have a particle size of between 10 and 100 microns.
  • Said mixed oxide particles with perovskite structures may have a Calcium Iron Titanium, Calcium Cobalt Titanium and / or Calcium Nickel composition with the addition of copper and / or manganese.
  • Said reactors preferably operate at a temperature of between 750 and 1150 ° C.
  • the temperature of said first fast fluidized bed loop is advantageously controlled by means of an exchanger.
  • the temperature control of the first fast fluidized bed loop is provided by the adjustable cooling of the solids taken from said thermochemical loop.
  • the invention also relates to an installation for implementing such a method, characterized in that said exchanger is disposed in said return line of said first fast fluidized bed loop.
  • Said exchanger may also be implanted in said reactor of said first fast fluidized bed loop.
  • said first fast fluidized bed loop comprises a heat exchanger for controlling its temperature.
  • Figure 1 is a view of an installation according to the invention according to a first embodiment.
  • Figure 2 is a view of an installation according to the invention according to a second embodiment.
  • FIG. 1 is a detailed view of an installation according to the invention.
  • a continuous production facility for an oxygen-rich gas comprises two reactors 1, 2 filled with mixed oxides with a perovskite structure and whose first 1 operates at a high temperature. between 750 and 1150 ° C. and is fluidized by an oxygen-containing gas, preferably air, supplied by line 3 and the second of which is fluidized by recycled gases from a boiler 5 fed by the pipe 4.
  • These two reactors are fast fluidized bed loops and are interconnected, in order to achieve a thermochemical mouth.
  • thermochemical loop is drawn off by a pipe 7 a flow of mixed oxides with perovskite structures, high temperature particles having absorbed oxygen from the air in the first fast fluidized bed loop 1 where the reaction is exothermic, to the first fast fluidized bed loop 2 with recycled gases, preferably carbon dioxide mixed with water vapor, and in which will release the oxygen.
  • the reaction in this second fast fluidized bed loop 2 is endothermic and utilizes the heat of the solids from the first fast fluidized bed loop 1 to effect this release.
  • the solids flow taken from the first fast fluidized bed loop 1 must therefore satisfy this heat requirement.
  • the oxygen free solids are transferred via line 8 to the first fast fluidized bed loop 1 for a new cycle.
  • the temperature control of the second endothermic fast fluid bed loop 2 between 750 and 1150 ° C. is ensured by the addition of solids from the first exothermic fast fluidized-bed loop 1.
  • the plant comprises a fresh solid introduction device 9 in the first fast fluidized bed loop 1 and used solids extraction devices 10, 11 of each fast fluidized bed loop 1, 2.
  • the gaseous streams 12, 13 from each fast fluidized bed loop 1, 2 are partially cooled in exchangers 14, 15 for example steam water type.
  • the gaseous stream containing the oxygen-depleted air 12 coming from the first fast fluidized-bed loop 1 is discharged to the atmosphere after cooling to 90 ° C. and filtration by means of a filtration device 17.
  • the stream 13 of oxygen and scavenging gas comprising carbon dioxide and water vapor from the second fast fluidized bed loop 2 is transferred at high temperature by a special jacketed jacket 16 to the hearth 5C of the boiler 5 operating in oxy-combustion, in order to avoid any safety problem relating to the transport of oxygen at high temperature.
  • the outer annular space of the jacket of this jacket 16 under light pressure contains carbon dioxide and water vapor from the boiler 5 operating in oxy-combustion and cooling the oxygen and the hot sweep gas 13 .
  • Part of this flow of oxygen, carbon dioxide and water vapor can be recycled to the first fast fluidized bed loop 1 by mixing with fluidization pair 3 to drive the autothermicity of the assembly and the levels.
  • the mixed oxides with perovskite structures used must have sufficient mechanical resistance for the resistance to abrasion and erosion created by the fluidization and shocks, and have a particle size of between 10 and 100 microns adapted to the beds. fast fluidized and their interconnection. Given the wide range of possible composition of perovskites, it appears that the mixed oxides of structure Calcium Iron Titanium, Calcium Cobalt Titanium, Calcium Nickel Titanium are adapted to this transfer of oxygen at high temperature. The addition of copper and / or manganese mixed or substituted with iron and nickel is also proposed in view of their oxidation properties.
  • the boiler 5 is an oxy-combustion boiler comprising a furnace 5C supplied with charcoal 18 and equipped with a filtration device 5A and a condenser 5B.
  • the invention can also be applied to a fast fluidized bed boiler 5 'also equipped with a filtration device 5'A and a condenser 5'B as shown in FIG. 2.
  • this boiler with Fast fluidized bed comprises a 5'C focal point whose output is connected to a separation cyclone 5'D provided with a 5'E solids return line towards the hearth.
  • the two fast fluidized bed loops 1, 2 are shown in detail in FIG.
  • Each consists of a reactor IA, 2A whose output is connected to a separation cyclone IB, 2B provided with a solid return line IC, 2C to the reactor which is provided with a siphon.
  • the exothermic nature of the oxygen adsorption / absorption reaction in the first fast fluidized-bed loop 1 is controlled by a heat exchanger 6A, 6B arranged on the path of the circulating solids whose adjustable flow rate makes it possible to precisely adjust the temperature optimal adsorption in the fast fluidized bed loop.
  • This exchanger may be arranged on the return line IC downstream of the cyclone IB, such as the exchanger 6A, and / or be implanted in the reactor IA, such as the exchanger 6B.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Combustion & Propulsion (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

The invention relates to a process for the continuous production of an oxygen-rich gas for supplying an existing boiler (5, 5') by means of an installation comprising two rapid fluidized-bed loops, the first of which (1) is fluidized by a gas containing oxygen that ensures an exothermic reaction and the second of which (2) is fluidized by recycled gases originating from said boiler (5, 5'), which loops are interconnected (7, 8), in order to produce a thermochemical loop containing only particles of mixed oxides of perovskite structure, each of said rapid fluidized-bed loops (1, 2) comprising a reactor (1A, 2A) filled with said particles and connected to a cyclone separator (1B, 2B) and a return line (1C, 2C) for returning solids to the reactor downstream of said cyclone.

Description

PROCEDE DE PRODUCTION CONTINUE D'UN GAZ RICHE EN OXYGENE A HAUTE TEMPERATURE PROCESS FOR THE CONTINUOUS PRODUCTION OF OXYGEN RICH GAS AT HIGH TEMPERATURE

L'invention concerne un procédé de production continue d'un gaz riche en oxygène à haute température.The invention relates to a process for the continuous production of a gas rich in oxygen at high temperature.

La production d'oxygène est couramment obtenue par distillation de l'air atmosphérique. Le froid nécessaire à la liquéfaction industrielle de l'air est obtenu par détente en utilisant le phénomène de Joule- Thomson. L'air est dépoussiéré, débarrassé de son gaz carbonique et de son humidité, comprimé vers 200 bars, refroidi dans un échangeur, puis détendu jusqu'à 25 bars. Une série de compressions et de détentes aboutit à la liquéfaction. Cette distillation fractionnée sépare l'oxygène, l'azote et les gaz nobles.Oxygen production is commonly obtained by distillation of atmospheric air. The cold necessary for the industrial liquefaction of the air is obtained by relaxation using the phenomenon of Joule-Thomson. The air is dusted, freed of its carbon dioxide and moisture, compressed to 200 bar, cooled in a heat exchanger, and then relaxed to 25 bar. A series of compressions and relaxations leads to liquefaction. This fractional distillation separates oxygen, nitrogen and noble gases.

Il existe une technologie récente de production d'oxygène utilisant des céramiques appelées pérovskites ayant une structure et des propriétés particulières connues depuis 1860.There is a recent oxygen production technology using ceramics called perovskites having a particular structure and properties known since 1860.

La pérovskite est une structure cristalline commune à de nombreux oxydes. Ce nom a d'abord désigné le titanate de calcium de formule CaTiO3, avant d'être étendu à l'ensemble des oxydes de formule générale ABO3 présentant la même structure. Les pérovskites présentent un grand intérêt en raison de la très grande variété de propriétés selon le choix des éléments A et B. Un exemple de ces propriétés est décrit dans l'article suivant : « Mixed conduction and oxygen permeation in the substituted oxides for CaTiO3 », IWAHARA H. (1) ; ESAKA T. ; MANGAHARA T. ; (1) Tottori univ., fac. eng., dep. environmental chemistry technology, Tottori 680, JAPON Journal of applied electrochemistry 1988, vol. 18, no2, pp. 173-177.Perovskite is a crystalline structure common to many oxides. This name first designated calcium titanate CaTiO3 formula, before being extended to all oxides of general formula ABO3 having the same structure. Perovskites are of great interest because of the great variety of properties according to the choice of the elements A and B. An example of these properties is described in the following article: "Mixed conduction and oxygen permeation in the oxides for CaTiO3" , IWAHARA H. (1); ESAKA T.; MANGAHARA T.; (1) Tottori University, College. eng., dep. Environmental Chemistry Technology, Tottori 680, JAPAN Journal of Applied Electrochemistry 1988, vol. 18, no. 2, pp. 173-177.

Un procédé de production d'un gaz riche en oxygène au moyen de pérovskites est décrit dans le document de brevet US 2003/0138747. Ce procédé consiste à mettre des flux d'air en contact avec un matériau pérovskite dans un lit fixe et ainsi d'en retenir ou adsorber l'oxygène sur la pérovskite. L'installation correspondante comprend deux lits fixes remplis de pérovskites dont l'un reçoit de l'air comprimé et chauffé et l'autre saturé d'oxygène reçoit des gaz recyclés provenant d'un système de chaudière, refroidis et comprimés.A process for producing an oxygen-rich gas by means of perovskites is described in US patent document 2003/0138747. This method consists in putting air streams in contact with a perovskite material in a fixed bed and thus retaining or adsorbing oxygen on the perovskite. The corresponding installation comprises two fixed beds filled with perovskites, one of which receives compressed air and heated and the other saturated with oxygen receives recycled gases from a boiler system, cooled and compressed.

Ce procédé de production d'oxygène utilise ces propriétés de stockage d'oxygène des pérovskites à haute température pour adsorber l'oxygène de l'air dans un lit fixe de particules puis le libérer par balayage de gaz recyclés. Le procédé fonctionne de façon sensiblement continue en combinant le fonctionnement des deux lits fixes en mode cyclique au moyen d'un circuit de circulation comprenant un nombre important de vannes, de l'ordre de huit vannes, commandées en séquence. Une telle installation pose donc des problèmes mécaniques tenant au fonctionnement de ces vannes.This oxygen production process utilizes these perovskite oxygen storage properties at high temperatures to adsorb oxygen from the air into a fixed bed of particles and then release it by scavenging recycled gases. The method operates substantially continuously by combining the operation of the two fixed beds in cyclic mode by means of a circulation circuit comprising a large number of valves, of the order of eight valves, controlled in sequence. Such an installation therefore poses mechanical problems in the operation of these valves.

Par ailleurs, pour lisser la production d'oxygène vis à vis de l'utilisation, un réservoir de stockage d'oxygène basse pression dilué est nécessaire. Il s'agit là d'un véritable inconvénient d'investissement et d'exploitation. Enfin ce procédé repose sur l'utilisation de lits fixes opérés en mode cyclique, ce qui le rend inadapté à satisfaire les besoins en oxygène de 15 000 tonnes/jour des grandes centrales à combustibles solides fossiles sauf à multiplier les lits fixes par dizaines, ce qui ne serait pas économique. L'invention résout ces problèmes en fournissant une procédé de production continue d'un gaz riche en oxygène à haute température totalement continu, pour l'alimentation d'une chaudière existante, pouvant être extrapolé à de très grandes capacités de production, de l'ordre de 15 000 à 20 000 tonnes/jour, minimisant la consommation électrique des équipements auxiliaires, minimisant également la consommation d'eau de refroidissement et capable de suivre les variations de charge des chaudières que l'installation alimente en comburant. La capacité à effectuer cette production par une seule unité et non pas par des trains multiples amène à des réductions très importantes de coût d'investissement.Furthermore, to smooth the production of oxygen with respect to use, a dilute low pressure oxygen storage tank is required. This is a real disadvantage of investment and exploitation. Finally, this method relies on the use of fixed beds operated in cyclic mode, which makes it unsuited to meeting the oxygen needs of 15 000 tonnes / day of large fossil fuel solid power plants except to multiply the fixed beds by tens, which would not be economical. The invention solves these problems by providing a process for the continuous production of a high-temperature oxygen-rich gas at a totally continuous temperature, for supplying an existing boiler, which can be extrapolated to very large production capacities. 15,000 to 20,000 tonnes / day, minimizing the power consumption of ancillary equipment, also minimizing consumption of cooling water and able to follow the load variations of the boilers that the installation supplies with oxidizer. The ability to perform this production by a single unit and not by multiple trains leads to very significant reductions in investment cost.

Pour ce faire, l'invention propose un procédé de production continue d'un gaz riche en oxygène pour l'alimentation d'une chaudière existante au moyen d'une installation comprenant deux boucles à lit fluidisé rapide, dont la première est fluidisée par un gaz contenant de l'oxygène assurant une réaction exothermique et dont la seconde est fluidisée par des gaz recyclés provenant de ladite chaudière, interconnectées, afin de réaliser une boucle thermochimique contenant uniquement des particules d'oxydes mixtes à structure de pérovskites, chacune desdites boucles à lit fluidisé rapide comprenant un réacteur rempli desdites particules et connecté à un cyclone de séparation et une conduite de retour des solides au réacteur en aval dudit cycloneTo this end, the invention proposes a process for the continuous production of an oxygen-rich gas for supplying an existing boiler by means of an installation comprising two fast fluidized-bed loops, the first of which is fluidized by a an oxygen-containing gas providing an exothermic reaction and the second of which is fluidized by recycled gases from said boiler, interconnected, to produce a thermochemical loop containing only mixed oxide particles with perovskite structure, each of said fast fluidized bed comprising a reactor filled with said particles and connected to a separation cyclone and a return line of the solids to the reactor downstream of said cyclone

L'invention propose d'utiliser une nouvelle architecture de deux boucles gaz solides à lit fluidisé rapide interconnectés à très fort flux de solides circulants, seuls capables grâce à cette circulation élevée et continue de particules d'oxydes mixtes à structures de pérovskites, de transférer l'oxygène nécessaire de façon sélective et d'effectuer sur les solides en circulation les échanges de chaleur créés par l'exothermicité et l'endothermicité des réactions avec l'oxygène.The invention proposes to use a new architecture of two interconnected high-flux fast fluidized-bed solid-gas loops of circulating solids, only able, thanks to this high and continuous circulation of mixed oxide particles with perovskite structures, to transfer the oxygen required selectively and to perform on the circulating solids the heat exchanges created by the exothermicity and endothermicity of the reactions with oxygen.

Cette nouvelle architecture assure la production d'un gaz riche en oxygène au moyen d'une boucle thermochimique contenant uniquement des particules d'oxydes mixtes à structure de pérovskites pour l'alimentation d'une chaudière existante utilisant tout combustible, fossile ou non fossile. Aucun autre combustible n'est introduit dans lesdites boucles, en particulier dans la boucle de réduction fluidisée par des gaz recyclés provenant de ladite chaudière. Le procédé conforme à l'invention est parfaitement adapté à la haute température, afin d'accélérer les cinétiques d'échange, et permet d'atteindre la totale autothermicité grâce à des formulations spécifiques d'oxydes et grâce au fait de circuler des dizaines de milliers de tonnes par heure de solides, débit exigé par les applications de grande taille.This new architecture ensures the production of a gas rich in oxygen by means of a thermochemical loop containing only particles of mixed oxides with perovskite structure for the supply of an existing boiler using any combustible, fossil or non-fossil. No other fuel is introduced into said loops, in particular in the fluidized reduction loop by recycled gases from said boiler. The process according to the invention is perfectly adapted to the high temperature, in order to accelerate the exchange kinetics, and makes it possible to achieve total autothermicity by means of specific oxide formulations and by circulating dozens of thousands of tons per hour of solids, flow required by large applications.

Selon un mode de réalisation préféré, ledit gaz contenant de l'oxygène est de l'air.According to a preferred embodiment, said gas containing oxygen is air.

De préférence, lesdits gaz recyclés sont un mélange de dioxyde de carbone et de vapeur d'eau provenant d'une chaudière fonctionnant en oxy-combustion ou d'une chaudière à lit fluidisé rapide.Preferably, said recycled gases are a mixture of carbon dioxide and water vapor from an oxy-combustion boiler or a fast fluidized bed boiler.

Le mélange d'oxygène, de dioxyde de carbone et de vapeur d'eau issu de ladite seconde boucle à lit fluidisé rapide peut être transféré vers ladite chaudière fonctionnant en oxy-combustion ou dans ladite chaudière à lit fluidisé rapide. Lesdites particules d'oxydes mixtes à structures de pérovskites ont de préférence une granulométrie comprise entre 10 et 100 microns.The mixture of oxygen, carbon dioxide and water vapor from said second fast fluidized bed loop can be transferred to said boiler operating in oxy-combustion or in said fast fluidized bed boiler. Said mixed oxide particles with perovskite structures preferably have a particle size of between 10 and 100 microns.

Lesdites particules d'oxydes mixtes à structures de pérovskites peuvent avoir une composition Calcium Fer Titane, Calcium Cobalt Titane et/ou Calcium Nickel avec adjonction de cuivre et/ou de manganèse.Said mixed oxide particles with perovskite structures may have a Calcium Iron Titanium, Calcium Cobalt Titanium and / or Calcium Nickel composition with the addition of copper and / or manganese.

Lesdits réacteurs fonctionnent de préférence à une température comprise entre 750 à 1150 0C.Said reactors preferably operate at a temperature of between 750 and 1150 ° C.

La température de ladite première boucle à lit fluidisé rapide est avantageusement contrôlée au moyen d'un échangeur. En variante, le contrôle de température de la première boucle à lit fluidisé rapide est assuré par le refroidissement réglable des solides prélevés sur ladite boucle thermochimique.The temperature of said first fast fluidized bed loop is advantageously controlled by means of an exchanger. Alternatively, the temperature control of the first fast fluidized bed loop is provided by the adjustable cooling of the solids taken from said thermochemical loop.

L'invention concerne également une installation pour la mise en œuvre d'un tel procédé, caractérisé en ce que ledit échangeur est disposé dans ladite conduite de retour de ladite première boucle à lit fluidisé rapide.The invention also relates to an installation for implementing such a method, characterized in that said exchanger is disposed in said return line of said first fast fluidized bed loop.

Ledit échangeur peut également être implanté dans ledit réacteur de ladite première boucle à lit fluidisé rapide. De préférence, ladite première boucle à lit fluidisé rapide comporte un échangeur de contrôle de sa température.Said exchanger may also be implanted in said reactor of said first fast fluidized bed loop. Preferably, said first fast fluidized bed loop comprises a heat exchanger for controlling its temperature.

L'invention est décrite ci-après plus en détail à l'aide de figures ne représentant que des modes de réalisation préférés de l'invention.The invention is described below in more detail with the aid of figures representing only preferred embodiments of the invention.

La figure 1 est une vue d'une installation conforme à l'invention selon un premier mode de réalisation.Figure 1 is a view of an installation according to the invention according to a first embodiment.

La figure 2 est une vue d'une installation conforme à l'invention selon un second mode de réalisation.Figure 2 is a view of an installation according to the invention according to a second embodiment.

La figure 3 est une vue de détail d'une installation conforme à l'invention. Comme représenté sur la figure 1, une installation de production continue d'un gaz riche en oxygène, conforme à l'invention, comprend deux réacteurs 1, 2 remplis d'oxydes mixtes à structure de pérovskites et dont le premier 1 fonctionne à haute température comprise entre 750 à 1150 0C et est fluidisé par un gaz contenant de l'oxygène, de préférence de l'air, alimenté par la conduite 3 et dont le second est fluidisé par des gaz recyclés d'une chaudière 5 alimenté par la conduite 4. Ces deux réacteurs sont des boucles à lit fluidisé rapide et sont interconnectés, afin de réaliser une bouche thermochimique.Figure 3 is a detailed view of an installation according to the invention. As represented in FIG. 1, a continuous production facility for an oxygen-rich gas, according to the invention, comprises two reactors 1, 2 filled with mixed oxides with a perovskite structure and whose first 1 operates at a high temperature. between 750 and 1150 ° C. and is fluidized by an oxygen-containing gas, preferably air, supplied by line 3 and the second of which is fluidized by recycled gases from a boiler 5 fed by the pipe 4. These two reactors are fast fluidized bed loops and are interconnected, in order to achieve a thermochemical mouth.

Sur cette boucle thermochimique est soutiré par une conduite 7 un débit d'oxydes mixtes à structures de pérovskites, particules à haute température ayant absorbé l'oxygène de l'air dans la première boucle à lit fluidisé rapide 1 où la réaction est exothermique, vers la première boucle à lit fluidisé rapide 2 par des gaz recyclés, de préférence du dioxyde de carbone mélangé à de la vapeur d'eau, et dans lequel va s'effectuer la libération d'oxygène. La réaction dans cette seconde boucle à lit fluidisé rapide 2 est endothermique et utilise la chaleur des solides en provenance de la première boucle à lit fluidisé rapide 1 pour effectuer cette libération. Le débit de solides prélevés de la première boucle à lit fluidisé rapide 1 doit donc satisfaire à ce besoin de chaleur. Puis les solides débarrassés de leur oxygène sont transférés par une conduite 8 vers la première boucle à lit fluidisé rapide 1 pour un nouveau cycle.On this thermochemical loop is drawn off by a pipe 7 a flow of mixed oxides with perovskite structures, high temperature particles having absorbed oxygen from the air in the first fast fluidized bed loop 1 where the reaction is exothermic, to the first fast fluidized bed loop 2 with recycled gases, preferably carbon dioxide mixed with water vapor, and in which will release the oxygen. The reaction in this second fast fluidized bed loop 2 is endothermic and utilizes the heat of the solids from the first fast fluidized bed loop 1 to effect this release. The solids flow taken from the first fast fluidized bed loop 1 must therefore satisfy this heat requirement. Then the oxygen free solids are transferred via line 8 to the first fast fluidized bed loop 1 for a new cycle.

Le contrôle de température de la seconde boucle à lit fluidisé rapide 2 endothermique comprise entre 750 à 1150 0C est assuré par l'apport de solides provenant de la première boucle à lit fluidisé rapide 1 exothermique.The temperature control of the second endothermic fast fluid bed loop 2 between 750 and 1150 ° C. is ensured by the addition of solids from the first exothermic fast fluidized-bed loop 1.

L'installation comporte un dispositif d'introduction de solides frais 9 dans la première boucle à lit fluidisé rapide 1 et des dispositifs d'extraction de solides usagés 10, 11 de chaque boucle à lit fluidisé rapide 1, 2.The plant comprises a fresh solid introduction device 9 in the first fast fluidized bed loop 1 and used solids extraction devices 10, 11 of each fast fluidized bed loop 1, 2.

Les courants gazeux 12, 13 issus de chaque boucle à lit fluidisé rapide 1, 2 sont refroidis partiellement dans des échangeurs 14, 15 par exemple de type eau vapeur. Le courant gazeux contenant l'air appauvri en oxygène 12 issu de la première boucle à lit fluidisé rapide 1 est rejeté à l'atmosphère après refroidissement à 9O0C et filtration au moyen d'un dispositif de filtration 17. Le courant 13 d'oxygène et de gaz de balayage comportant du dioxyde de carbone et de la vapeur d'eau issu de la seconde boucle à lit fluidisé rapide 2 est transféré à haute température par une gaine spéciale 16 à double enveloppe vers le foyer 5C de la chaudière 5 fonctionnant en oxy-combustion, afin d'éviter tout problème de sécurité relatif au transport d'oxygène à haute température. L'espace annulaire externe de la double enveloppe de cette gaine 16 sous légère pression contient du dioxyde de carbone et de la vapeur d'eau provenant de la chaudière 5 fonctionnant en oxy- combustion et refroidissant l'oxygène et le gaz de balayage chauds 13. Une partie de ce courant d'oxygène, de dioxyde de carbone et de vapeur d'eau peut être recyclée vers la première boucle à lit fluidisé rapide 1 par mélange avec Pair 3 de fluidisation pour piloter l'autothermicité de l'ensemble et les niveaux de température de fonctionnement de chaque boucle à lit fluidisé rapide 1, 2, comme illustré en pointillés 3'. Ceci peut entraîner une légère perte de dioxyde de carbone à l'atmosphère par la sortie de la première boucle à lit fluidisé rapide mais procure un ajustement de réglage ultime de température d'ensemble. Les oxydes mixtes à structures de pérovskites utilisés doivent posséder suffisamment de résistance mécanique pour la tenue à l'abrasion et à l'érosion créées par la mise en fluidisation et les chocs, ainsi que posséder une granulométrie comprise entre 10 et 100 microns adaptée aux lits fluidisés rapides et à leur interconnexion. Compte tenu de la large plage de composition possible des pérovskites, il apparaît que les oxydes mixtes de structure Calcium Fer Titane, Calcium Cobalt Titane, Calcium Nickel Titane sont adaptées à ce transfert d'oxygène à haute température. L'adjonction de cuivre et/ou de manganèse en mélange ou substitution au fer et au nickel est également proposée compte tenu de leurs propriétés d'oxydation.The gaseous streams 12, 13 from each fast fluidized bed loop 1, 2 are partially cooled in exchangers 14, 15 for example steam water type. The gaseous stream containing the oxygen-depleted air 12 coming from the first fast fluidized-bed loop 1 is discharged to the atmosphere after cooling to 90 ° C. and filtration by means of a filtration device 17. The stream 13 of oxygen and scavenging gas comprising carbon dioxide and water vapor from the second fast fluidized bed loop 2 is transferred at high temperature by a special jacketed jacket 16 to the hearth 5C of the boiler 5 operating in oxy-combustion, in order to avoid any safety problem relating to the transport of oxygen at high temperature. The outer annular space of the jacket of this jacket 16 under light pressure contains carbon dioxide and water vapor from the boiler 5 operating in oxy-combustion and cooling the oxygen and the hot sweep gas 13 . Part of this flow of oxygen, carbon dioxide and water vapor can be recycled to the first fast fluidized bed loop 1 by mixing with fluidization pair 3 to drive the autothermicity of the assembly and the levels. operating temperature of each fast fluidized bed loop 1, 2, as shown in dashed lines 3 '. This can result in a slight loss of carbon dioxide to the atmosphere by the exit of the first fast fluidized bed loop but provides an ultimate set temperature adjustment. The mixed oxides with perovskite structures used must have sufficient mechanical resistance for the resistance to abrasion and erosion created by the fluidization and shocks, and have a particle size of between 10 and 100 microns adapted to the beds. fast fluidized and their interconnection. Given the wide range of possible composition of perovskites, it appears that the mixed oxides of structure Calcium Iron Titanium, Calcium Cobalt Titanium, Calcium Nickel Titanium are adapted to this transfer of oxygen at high temperature. The addition of copper and / or manganese mixed or substituted with iron and nickel is also proposed in view of their oxidation properties.

Selon ce premier mode de réalisation illustré sur la figure 1, la chaudière 5 est une chaudière à oxy-combustion comportant un foyer 5C alimenté en charbon 18 et équipé d'un dispositif de filtration 5A et d'un condenseur 5B. L'invention peut également s'appliquer à une chaudière à lit fluidisé rapide 5' également équipé d'un dispositif de filtration 5'A et d'un condenseur 5'B comme représenté sur la figure 2. De façon classique, cette chaudière à lit fluidisé rapide comporte un foyer 5'C dont la sortie est raccordée à un cyclone de séparation 5'D pourvu d'une conduite de retour des solides 5'E vers le foyer. Les deux boucles à lit fluidisé rapide 1, 2 sont représentés en détail sur la figure 3.According to this first embodiment illustrated in FIG. 1, the boiler 5 is an oxy-combustion boiler comprising a furnace 5C supplied with charcoal 18 and equipped with a filtration device 5A and a condenser 5B. The invention can also be applied to a fast fluidized bed boiler 5 'also equipped with a filtration device 5'A and a condenser 5'B as shown in FIG. 2. In a conventional manner, this boiler with Fast fluidized bed comprises a 5'C focal point whose output is connected to a separation cyclone 5'D provided with a 5'E solids return line towards the hearth. The two fast fluidized bed loops 1, 2 are shown in detail in FIG.

Chacune est constituée d'un réacteur IA, 2A dont la sortie est raccordée à un cyclone de séparation IB, 2B pourvu d'une conduite de retour des solides IC, 2C vers le réacteur qui est pourvue d'un siphon.Each consists of a reactor IA, 2A whose output is connected to a separation cyclone IB, 2B provided with a solid return line IC, 2C to the reactor which is provided with a siphon.

Le caractère exothermique de la réaction d'adsorption/absorption de l'oxygène dans la première boucle à lit fluidisé rapide 1 est contrôlé par un échangeur 6A, 6B disposé sur le trajet des solides circulants dont le débit réglable permet d'ajuster précisément la température optimale d'adsorption dans la boucle à lit fluidisé rapide. Cet échangeur peut être disposé sur la conduite de retour IC en aval du cyclone IB, tel que l'échangeur 6A, et/ou être implanté dans le réacteur IA, tel que l'échangeur 6B.The exothermic nature of the oxygen adsorption / absorption reaction in the first fast fluidized-bed loop 1 is controlled by a heat exchanger 6A, 6B arranged on the path of the circulating solids whose adjustable flow rate makes it possible to precisely adjust the temperature optimal adsorption in the fast fluidized bed loop. This exchanger may be arranged on the return line IC downstream of the cyclone IB, such as the exchanger 6A, and / or be implanted in the reactor IA, such as the exchanger 6B.

Afin de contrôler le degré d'oxygénation et de désoxygénation dans les solides transférés, le prélèvement des solides sur chaque boucle à lit fluidisé rapide 1, 2 par les conduites 7, 8 est effectué en bas du conduit de retour correspondant IC, 2C en aval des cyclones IB,In order to control the degree of oxygenation and deoxygenation in the transferred solids, the sampling of the solids on each fast fluidized bed loop 1, 2 through the lines 7, 8 is carried out at the bottom of the corresponding return conduit IC, 2C downstream. cyclones IB,

2B, de façon à ce que les solides soient restés suffisamment longtemps dans chaque zone réactionnelle en termes de température et de temps de séjour. 2B, so that the solids remained long enough in each reaction zone in terms of temperature and residence time.

Claims

REVEN DICATIONS REVEN DICATIONS 1. Procédé de production continue d'un gaz riche en oxygène pour l'alimentation d'une chaudière existante (5, 5') au moyen d'une installation comprenant deux boucles à lit fluidisé rapide, dont la première (1) est fluidisée par un gaz contenant de l'oxygène assurant une réaction exothermique et dont la seconde (2) est fluidisée par des gaz recyclés provenant de ladite chaudière (5, 5'), interconnectées (7, 8), afin de réaliser une boucle thermochimique contenant uniquement des particules d'oxydes mixtes à structure de pérovskites, chacune desdites boucles à lit fluidisé rapide (1, 2) comprenant un réacteur (IA, 2A) rempli desdites particules et connecté à un cyclone de séparation (IB, 2B) et une conduite de retour (IC, 2C) des solides au réacteur en aval dudit cyclone.Process for the continuous production of an oxygen-rich gas for supplying an existing boiler (5, 5 ') by means of an installation comprising two fast fluidized-bed loops, the first of which (1) is fluidized by an oxygen-containing gas providing an exothermic reaction and the second (2) of which is fluidized by recycled gases from said interconnected boiler (5, 5 ') (7, 8), to produce a thermochemical loop containing only mixed oxide particles with a perovskite structure, each of said fast fluidized-bed loops (1, 2) comprising a reactor (IA, 2A) filled with said particles and connected to a separation cyclone (IB, 2B) and a pipe return (IC, 2C) of the solids to the reactor downstream of said cyclone. 2. Procédé selon la revendication précédente, caractérisée en ce que ledit gaz contenant de l'oxygène est de l'air.2. Method according to the preceding claim, characterized in that said gas containing oxygen is air. 3. Procédé selon l'une des revendications précédentes, caractérisée en ce que lesdits gaz recyclés sont un mélange de dioxyde de carbone et de vapeur d'eau provenant de ladite chaudière (5) fonctionnant en oxy-combustion ou de ladite chaudière à lit fluidisé rapide (5 Λ).3. Method according to one of the preceding claims, characterized in that said recycled gas is a mixture of carbon dioxide and water vapor from said boiler (5) operating in oxy-combustion or said fluidized bed boiler fast (5 Λ ). 4. Procédé selon la revendication précédente, caractérisée en ce que le mélange d'oxygène, de dioxyde de carbone et de vapeur d'eau issu de ladite seconde boucle à lit fluidisé rapide est transféré vers ladite chaudière (5) fonctionnant en oxy-combustion ou dans ladite chaudière à lit fluidisé rapide (5 Λ).4. Method according to the preceding claim, characterized in that the mixture of oxygen, carbon dioxide and water vapor from said second fast fluidized bed loop is transferred to said boiler (5) operating in oxy-combustion or in said fast fluidized bed boiler (5 Λ ). 5. Procédé selon l'une des revendications précédentes, caractérisée lesdites particules d'oxydes mixtes à structures de pérovskites ont une granulométrie comprise entre 10 et 100 microns. 5. Method according to one of the preceding claims, characterized in that said particles of mixed oxides with perovskite structures have a particle size of between 10 and 100 microns. 6. Procédé selon l'une des revendications précédentes, caractérisée lesdites particules d'oxydes mixtes à structures de pérovskites ont une composition Calcium Fer Titane, Calcium Cobalt Titane et/ou Calcium Nickel avec adjonction de cuivre et/ou de manganèse. 6. Process according to one of the preceding claims, characterized in that said particles of mixed oxides with perovskite structures have a composition Calcium Iron Titanium, Calcium Cobalt Titanium and / or Calcium Nickel with addition of copper and / or manganese. 7. Procédé selon l'une des revendications précédentes, caractérisée en ce que lesdites boucles à lit fluidisé rapide (1, 2) fonctionnent à une température comprise entre 750 à 1150 0C.7. Method according to one of the preceding claims, characterized in that said fast fluidized bed loops (1, 2) operate at a temperature between 750 to 1150 0 C. 8. Procédé selon l'une des revendications précédentes, caractérisée en ce que la température de ladite première boucle à lit fluidisé rapide (1) est contrôlée au moyen d'un échangeur (6A, 6B).8. Method according to one of the preceding claims, characterized in that the temperature of said first fast fluidized bed loop (1) is controlled by means of an exchanger (6A, 6B). 9. Installation pour la mise en œuvre du procédé selon la revendication précédente, caractérisé en ce que ledit échangeur (6A) est disposé dans ladite conduite de retour (IC) de ladite première boucle à lit fluidisé rapide (1). 9. Installation for implementing the method according to the preceding claim, characterized in that said exchanger (6A) is disposed in said return line (IC) of said first fast fluidized bed loop (1). 10. Installation pour la mise en œuvre du procédé selon la revendication 8, caractérisé en ce que ledit échangeur (6B) est implanté dans ledit réacteur (IA) de ladite première boucle à lit fluidisé rapide (1). 10. Installation for carrying out the method according to claim 8, characterized in that said exchanger (6B) is implanted in said reactor (IA) of said first fast fluidized bed loop (1).
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015087053A (en) * 2013-10-30 2015-05-07 三菱日立パワーシステムズ株式会社 Pulverized coal combustion boiler power generation system equipped with chemical loop combustor

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1044924A1 (en) * 1999-04-13 2000-10-18 The Boc Group, Inc. Hydrocarbon partial oxidation process
EP1052219A1 (en) * 1999-05-13 2000-11-15 The Boc Group, Inc. Production of hydrogen and carbon monoxide
US20030138747A1 (en) 2002-01-08 2003-07-24 Yongxian Zeng Oxy-fuel combustion process
US20050226798A1 (en) * 2003-12-22 2005-10-13 The Boc Group, Inc. Oxygen sorbent compositions and methods of using same
US20070124997A1 (en) * 2005-12-06 2007-06-07 General Electric Company System and method for producing synthesis gas
WO2008036902A2 (en) * 2006-09-21 2008-03-27 Eltron Research & Development, Inc. Cyclic catalytic upgrading of chemical species using metal oxide materials
WO2009013647A2 (en) * 2007-07-20 2009-01-29 Foster Wheeler Energy Corporation Method of and a plant for combusting carbonaceous fuel by using a solid oxygen carrier

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1044924A1 (en) * 1999-04-13 2000-10-18 The Boc Group, Inc. Hydrocarbon partial oxidation process
EP1052219A1 (en) * 1999-05-13 2000-11-15 The Boc Group, Inc. Production of hydrogen and carbon monoxide
US20030138747A1 (en) 2002-01-08 2003-07-24 Yongxian Zeng Oxy-fuel combustion process
US20050226798A1 (en) * 2003-12-22 2005-10-13 The Boc Group, Inc. Oxygen sorbent compositions and methods of using same
US20070124997A1 (en) * 2005-12-06 2007-06-07 General Electric Company System and method for producing synthesis gas
WO2008036902A2 (en) * 2006-09-21 2008-03-27 Eltron Research & Development, Inc. Cyclic catalytic upgrading of chemical species using metal oxide materials
WO2009013647A2 (en) * 2007-07-20 2009-01-29 Foster Wheeler Energy Corporation Method of and a plant for combusting carbonaceous fuel by using a solid oxygen carrier

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
IWAHARA H.; ESAKA T.; MANGAHARA T.: "Mixed conduction and oxygen permeation in the substituted oxides for CaTi03", JAPON JOURNAL OF APPLIED ELECTROCHEMISTRY, vol. 18, no. 2, 1988, pages 173 - 177

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015087053A (en) * 2013-10-30 2015-05-07 三菱日立パワーシステムズ株式会社 Pulverized coal combustion boiler power generation system equipped with chemical loop combustor

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