WO2012018156A1 - Dispositif de transport d'oxygène et son procédé de fabrication - Google Patents

Dispositif de transport d'oxygène et son procédé de fabrication Download PDF

Info

Publication number
WO2012018156A1
WO2012018156A1 PCT/KR2010/006673 KR2010006673W WO2012018156A1 WO 2012018156 A1 WO2012018156 A1 WO 2012018156A1 KR 2010006673 W KR2010006673 W KR 2010006673W WO 2012018156 A1 WO2012018156 A1 WO 2012018156A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxygen donor
donor particles
particles
weight
oxygen
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.)
Ceased
Application number
PCT/KR2010/006673
Other languages
English (en)
Korean (ko)
Inventor
류청걸
백점인
류정호
이중범
엄태형
김경숙
양석란
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.)
Korea Electric Power Corp
Original Assignee
Korea Electric Power Corp
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 Korea Electric Power Corp filed Critical Korea Electric Power Corp
Publication of WO2012018156A1 publication Critical patent/WO2012018156A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/016—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on manganites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/322—Transition aluminas, e.g. delta or gamma aluminas
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3263—Mn3O4
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • 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
    • F23C2900/10001—Use of special materials for the fluidized 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 
    • 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 present invention relates to an oxygen donor particle and a method for producing the same.
  • Thermal power plants are the largest source of anthropogenic carbon dioxide emissions.
  • CCS carbon dioxide capture and storage
  • Chemical looping combustion (CLC) technology is attracting attention as a technology that can separate CO 2 source without degrading power generation efficiency. Since the medium-circulating gas combustion technology burns fuel with oxygen contained in metal oxides instead of air, the gas discharged after combustion of the fuel includes only water vapor and CO 2 . Therefore, when only the removal of condensed water vapor exhaust gas is possible because the CO 2 source separated, leaving the CO 2.
  • Media circulating gas combustion technology uses oxygen donor particles as the oxygen delivery medium. In the medium-circulating gas combustion process, a fluidized bed reactor (reduction reactor) and a reduced oxygen donor particle receive oxygen from the air in which oxygen contained in the oxygen donor particle is delivered to the fuel while the oxygen donor particle is reduced.
  • a circulating fluidized-bed process is used in which a fluidized bed reactor (oxidation reactor) in which an oxidizing reaction takes place is composed of a combination connected to each other.
  • the oxygen donor particles must satisfy various conditions suitable for the fluidized bed process characteristics.
  • it should have a pore structure that is advantageous for the fluidized bed process, that is, sufficient strength, shape suitable for flow, packing density or packing density, average particle size, particle size distribution and diffusion of the reaction gas.
  • it has a high oxygen transfer capacity in terms of reactivity so that it can supply enough oxygen for combustion of fuel while it passes through the fuel reactor.
  • Oxygen donor particles can also be used for media circulation reforming.
  • the medium circulation reforming is a technique for producing hydrogen from a fuel by using oxygen exchange characteristics of oxygen donor particles, and may use a circulating fluidized bed process.
  • Oxygen donor particles that use nickel oxide (NiO) as a metal oxide that exchanges oxygen are formed by impregnation, coprecipitation, and raw materials mixed with water, kneaded, dried, calcined and ground. Physical mixing methods and freeze granulation methods for forming particles are mainly used.
  • the oxygen donor particles prepared by these methods are not suitable for the fluidized bed process, such as the shape after filling, the filling density, particle size and strength, or the NiO content is low, or is not suitable for mass production.
  • Spray-drying method has been used as a method for producing large quantities of oxygen donor particles having suitable physical properties for fluidized bed process.
  • a manufacturing process for making the slurry to have homogeneous and stable fluidity characteristics is very important.
  • Incorrect control of the slurry properties creates particles of elliptical, donut, and grooved shapes rather than spherical shape, which causes large particle wear loss in the fluidized bed process.
  • Oxygen donor particles produced by the spray drying method shown in the literature is a significant portion of the prepared particles are shown in the form of doughnut or grooved, there is a need for improvement.
  • Ni-based oxygen donor particles are composed of an active material NiO and a support.
  • the support serves to increase the dispersion of NiO, to impart strength to the particles, and to suppress sintering of NiO, which may occur during the calcination process and the circulating combustion process operated at high temperature.
  • the reactivity and physical properties of the final oxygen donor particles are different.
  • alumina Al 2 O 3
  • oxygen donor particles of high strength can be obtained.
  • alumina is mainly used as the support.
  • NiO nickel aluminate
  • Conventional techniques for NiO oxygen donor particles include structurally stable forms of alpha alumina ( ⁇ -Al 2 O 3 ), nickel aluminate (NiAl 2 O 4 ), magnesium aluminate ( MgAl 2 O 4 ) is mainly used as a support material.
  • alpha alumina ( ⁇ -Al 2 O 3 ) and magnesium aluminate (MgAl 2 O 3 ) were used as a support.
  • the support was structurally stable, so that the spray-molded particles were fired at a high temperature of 1400 ° C. or more to obtain the strength required for the fluidized bed process application.
  • the firing cost also increases due to high temperature firing. Since high temperature firing increases the production cost of the particles when producing a large amount of oxygen donor particles, it is necessary to lower the firing temperature necessary to obtain the strength required in the fluidized bed process.
  • magnesia and alumina as a support for oxygen donor particles, it is possible to provide oxygen donor particles having excellent reactivity with physical properties such as strength even at low firing temperatures, and excellent reactivity.
  • the present invention is an active material including a metal oxide
  • It relates to an oxygen donor particle having a support comprising gamma alumina and magnesia.
  • the present invention also relates to a slurry composition in which a solid raw material comprising a metal oxide, gamma alumina and magnesia is mixed in a solvent.
  • the present invention comprises the steps of (A) mixing a solid material comprising a metal oxide, gamma alumina and magnesia with a solvent; (B) preparing a homogenized slurry; (C) spray drying the slurry to form oxygen donor particles; And
  • (D) a method of producing oxygen donor particles comprising the step of dry firing the molded oxygen donor particles to produce the final oxygen donor particles.
  • the present invention comprises the steps of reacting the oxygen donor particles including a metal oxide supported on a support including gamma alumina and magnesia with gaseous fuel to reduce the oxygen donor particles and to burn fuel gas;
  • It relates to a medium-circulating gas combustion method comprising the step of reacting the reduced oxygen donor particles with oxygen to oxidize.
  • the present invention comprises a reduction reactor for reacting oxygen donor particles with gaseous fuel to reduce the oxygen donor particles and burn fuel gas; And a oxidation reactor for reacting the reduced oxygen donor particles with oxygen to oxidize them.
  • the oxygen donor particle relates to a medium-circulating gas combustion device including a metal oxide supported on a support including gamma alumina and magnesia.
  • magnesia and alumina as a support for oxygen donor particles, even at low firing temperatures, physical properties such as strength can be provided for fluidized bed processes, and oxygen donor particles having excellent reactivity can be provided.
  • FIG. 1 is a process chart showing a process for preparing oxygen donor particles using a mixture of gamma alumina ( ⁇ -Al 2 O 3 ) and magnesia (MgO) according to the present invention as a support material.
  • FIG. 2 is a process chart showing a process of preparing a homogenized slurry after mixing a solid raw material in water.
  • FIG. 3 is a process chart showing a process of forming oxygen donor particles by spray drying the slurry.
  • Figure 4 is a process diagram showing a process for producing the final oxygen donor particles by dry firing the oxygen donor particles formed by the spray drying method.
  • FIG. 6 is a basic conceptual view of a medium purifying gas combustion apparatus.
  • the present invention is an active material including a metal oxide
  • It relates to an oxygen donor particle having a support comprising gamma alumina and magnesia.
  • Oxygen donor particles comprising gamma alumina and magnesia according to the present invention may have a shape suitable for a circulating fluidized-bed process, particle size, particle size distribution, packing density, and oxygen transfer ability. It can be produced at a lower firing temperature than the conventional firing temperature.
  • the shape of the oxygen donor particles of the present invention may be spherical. If the shape is not spherical but elliptical, donut-shaped or grooved, the wear loss of the particles increases.
  • the average particle size of the oxygen donor particles of the present invention is not particularly limited, and may be, for example, 50 ⁇ m to 150 ⁇ m.
  • the particle size distribution of the oxygen donor particles is not particularly limited, and may be, for example, 30 ⁇ m to 400 ⁇ m.
  • the packing density of the oxygen donor particles is not particularly limited, and may be, for example, 1.0 g / mL to 3.0 g / mL.
  • the specific surface area (BET) of the oxygen donor particles is not particularly limited, and may be, for example, 0.1 m 2 / g to 100 m 2 / g.
  • the wear resistance is represented by the wear index (AI), which means that the lower the wear index is the better the wear resistance.
  • AI wear index
  • the wear resistance of the oxygen donor particles is not particularly limited, and may be, for example, 40% or less. When the wear resistance exceeds 40%, a lot of fine powder is generated, which makes it difficult to use the circulating fluidized bed process.
  • the lower limit of the wear resistance is not particularly limited and is preferably 1% or more.
  • the oxygen transfer capacity of the oxygen donor particles is not particularly limited, for example, may be 5 wt% to 17 wt%.
  • Oxygen donor particles according to the present invention may include an active material and a support.
  • the active material means a material capable of delivering oxygen to fuel and receiving oxygen from air or water vapor again.
  • the type of the active material is not particularly limited and may be, for example, a metal oxide.
  • the metal oxides include nickel oxides such as nickel oxide (NiO) and manganese oxides such as manganese oxide (MnO, MnO 2 , Mn 2 O 3 , Mn 3 O 4 ).
  • NiO nickel oxide
  • MnO 2 , Mn 2 O 3 , Mn 3 O 4 manganese oxide
  • the content of the active substance is not particularly limited.
  • the active substance may be included in an amount of 50 parts by weight to 80 parts by weight with respect to the oxygen donor particles, and preferably may be included in an amount of 60 parts by weight to 70 parts by weight. .
  • the support included in the oxygen donor particles of the present invention supports the active material to be dispersed evenly throughout the particles, provides a pore structure necessary for diffusion of the reaction gas, and provides the oxygen donor particles with sufficient strength required in the fluidized bed process after firing.
  • the support may simultaneously serve as a binder that gives strength to the oxygen donor particles while binding to each other during the function of supporting the active material and firing.
  • metals may be prevented from agglomerating with each other while repeating a redox cycle, and the gas before and after the reaction may serve to make a passage to facilitate the ingress and diffusion (diffusion) from the outside of the particles to the active material.
  • the type of the support is not particularly limited.
  • ceramics may be used, and gamma alumina ( ⁇ -Al 2 O 3 ) and magnesia (MgO) may be preferably used.
  • the gamma alumina ( ⁇ -Al 2 O 3 ) makes it possible to obtain oxygen donor particles of high strength.
  • the content of gamma alumina ( ⁇ -Al 2 O 3 ) is not particularly limited, and may be included, for example, in an amount of 10 parts by weight to 49 parts by weight with respect to the oxygen donor particles, preferably 20 parts by weight to It may be included in an amount of 40 parts by weight.
  • magnesia is used to increase the fuel conversion rate of the oxygen donor particles and to suppress the aggregation phenomenon between the particles.
  • the content of magnesia (MgO) is not particularly limited, and may be included, for example, in an amount of 1 to 20 parts by weight based on the oxygen donor particles.
  • the support that is gamma alumina and magnesia, is preferably used in an amount of 20 parts by weight to 50 parts by weight based on the oxygen donor particles.
  • the present invention also relates to a slurry composition in which a solid raw material comprising a metal oxide, gamma alumina and magnesia is mixed in a solvent.
  • the metal oxide, gamma alumina, and magnesia may use the aforementioned materials.
  • the content of each of the metal oxide, gamma alumina, and magnesia included in the solid raw material may use the aforementioned range.
  • the solvent in the present invention is not particularly limited, and water may be used, for example.
  • the content of the solid raw material in the present invention is not particularly limited, for example, 15 parts by weight to 50 parts by weight based on 100 parts by weight of the slurry composition may be used.
  • the slurry composition according to the present invention may further comprise at least one organic additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder.
  • a dispersant selected from the group consisting of a dispersant, an antifoaming agent and an organic binder.
  • an organic additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder.
  • the dispersant is used to suppress the phenomenon that the solid raw material is well mixed with water and aggregates with each other.
  • the type of dispersant is not particularly limited, and for example, anionic surfactant or nonionic surfactant can be used.
  • Specific examples of the anionic surfactant include poly carboxylate ammonium salts or poly carboxylate amine salts.
  • the content of the dispersant is not particularly limited, and for example, 0.01 part by weight to 10 parts by weight may be used based on 100 parts by weight of the solid raw material.
  • Antifoaming agent in the present invention can be used to suppress or remove the foam that may be generated during the production of the slurry.
  • the kind of the antifoaming agent is not particularly limited, and for example, silicone, metal soap, amide, polyether or alcohol may be used.
  • the content of the antifoaming agent is not particularly limited.
  • 0.001 part by weight to 1 part by weight based on 100 parts by weight of the solid raw material may be used.
  • the organic binder is used to impart plasticity and fluidity to the slurry and to maintain the shape of the particles during spray drying.
  • the organic binder may facilitate handling of the oxygen donor particles before drying and firing by imparting strength to the oxygen donor particles after molding.
  • the type of the organic binder is not particularly limited, and for example, polyvinylalcohols, polyethyleneglycols or methylcelluloses may be used.
  • the content of the organic binder is not particularly limited.
  • 0.5 parts by weight to 5 parts by weight may be used based on 100 parts by weight of the solid raw material.
  • the method for producing the oxygen donor particles according to the present invention is not particularly limited.
  • the oxygen donor particles may be prepared using a spray drying method.
  • Oxygen donor particles of the present invention comprises the steps of (A) mixing a solid material comprising a metal oxide, gamma alumina and magnesia with a solvent; (B) preparing a homogenized slurry; (C) spray drying the slurry to form oxygen donor particles; And
  • (D) may be prepared by a method comprising the step of dry firing the molded oxygen donor particles to produce the final oxygen donor particles.
  • Step (A) is a step of mixing a solid raw material with a solvent, the solid raw material including a metal oxide, gamma alumina and magnesia.
  • the metal oxide, gamma alumina, and magnesia may use the aforementioned materials.
  • the content of each of the metal oxide, gamma alumina, and magnesia included in the solid raw material may use the aforementioned range.
  • the kind of solvent used in the present invention is not particularly limited, and water may be preferably used.
  • the content of the solid raw material is not particularly limited, and may be, for example, 15 parts by weight to 50 parts by weight based on 100 parts by weight of the mixture (or the following slurry).
  • step (B) is a step of preparing a homogenized slurry of the mixture prepared by step (A), the step of adding a dispersant; Adding an antifoam; And
  • steps selected from adding an organic binder it is preferable to include all three steps.
  • the dispersant, the antifoaming agent, and the organic binder may be used in the above-mentioned kinds and contents.
  • the method may further include grinding the particles in the slurry.
  • the milling may be performed using a wet mill, and it is preferable to mill the particles in the slurry to several microns or less.
  • the particles pulverized by the above step are more homogeneously dispersed in the slurry, and the added dispersant suppresses the aggregation of the particles in the slurry, so that a homogeneous and stable slurry can be produced.
  • the grinding step may be repeated several times, and the flowability of the slurry may be adjusted by further adding a dispersant and an antifoaming agent between each grinding step.
  • an organic binder may be added to maintain the particle shape during spray drying.
  • the wet grinding process may be omitted.
  • Oxygen donor particle production method may further comprise the step of removing foreign matter in the prepared slurry.
  • the step of removing foreign matter in the prepared slurry Through the above step, it is possible to remove the foreign matter or agglomerated raw materials that may cause the nozzle clogging during spray molding. Removal of the foreign matter may be carried out through sieving.
  • Step (C) of the present invention is a step of molding the oxygen donor particles using a spray dryer of the slurry prepared by step (B).
  • the step may transfer the slurry prepared in step (B) to the spray dryer using a pump, and then spray the transferred slurry into the spray dryer to form oxygen donor particles.
  • the operating conditions of the spray dryer for molding the oxygen donor particles in the spray dryer may be applied to the operating conditions generally used in this field.
  • the spraying method of the slurry is not particularly limited, and for example, a countercurrent spraying method may be used in which the spray nozzle is sprayed in a direction opposite to the flow of drying air.
  • Inlet temperature of the spray dryer in the present invention is 260 °C to 300 °C, the outlet temperature may be 90 °C to 150 °C.
  • the particle size distribution of the oxygen donor particles prepared in the step is 30 ⁇ m to 303 ⁇ m.
  • Step (D) of the present invention is a step of producing a final oxygen donor particles by dry firing the molded oxygen donor particles.
  • step (D) the oxygen donor particles formed by step (C) are preliminarily dried and then calcined to produce final oxygen donor particles.
  • the preliminary drying may be performed by drying the molded oxygen donor particles in a reflux dryer at 110 ° C to 130 ° C for at least 2 hours.
  • the predrying is done in an air atmosphere.
  • the dried oxygen donor particles are placed in a high temperature kiln and the firing temperature is raised to 1100 ° C to 1300 ° C at a rate of 1 ° C / min to 5 ° C / min, and calcined for 2 to 10 hours.
  • the organic additives (dispersant, antifoaming agent and organic binder) introduced during the preparation of the slurry by the firing are burned, and the strength of the particles is improved by bonding between the raw materials.
  • the final formed oxygen donor particles through this step may deliver oxygen at 600 °C to 1400 °C, may have conditions suitable for fluidized bed reaction.
  • the present invention comprises the steps of reacting the oxygen donor particles including a metal oxide supported on a support including gamma alumina and magnesia with gaseous fuel to reduce the oxygen donor particles and to burn fuel gas;
  • It relates to a medium-circulating gas combustion method comprising the step of reacting the reduced oxygen donor particles with oxygen to oxidize.
  • the oxygen donor particles may use the oxygen donor particles described above.
  • the metal oxides of the oxygen donor particles are reduced to form metal particles and generate carbon dioxide and water.
  • the metal particles in the reduced oxygen donor particles react with oxygen, the metal particles are oxidized to form a metal oxide again.
  • the gaseous fuel used in the present invention is not particularly limited and may be, for example, one or more selected from the group consisting of methane, hydrogen, carbon monoxide, alkanes (C n H 2n + 2 ), LNG, and syngas.
  • the provision of oxygen to the reduced oxygen donor particles may be made through air.
  • the present invention also comprises a reduction reactor for reacting oxygen donor particles with gaseous fuel to reduce the oxygen donor particles and burn fuel gas; And a oxidation reactor for reacting the reduced oxygen donor particles with oxygen to oxidize them.
  • the oxygen donor particle relates to a medium-circulating gas combustion apparatus including a metal oxide supported on a support including gamma alumina and magnesia.
  • the oxygen donor particles of the present invention may use the oxygen donor particles described above.
  • the oxidation reactor and the reduction reactor may be composed of a combination connected to each other.
  • NiO nickel oxide
  • MgO magnesia
  • the preparation of the oxygen donor particles by adding a solid material to the water mixing step (S10), preparing a mixture of water and a solid material into a homogenized slurry through grinding and dispersion (S20) , Spray drying the prepared slurry to form oxygen donor particles (S30) and drying firing the molded oxygen donor particles to prepare final oxygen donor particles (S40).
  • Figure 2 of the present invention is a process chart showing a process for producing a mixture of a solid raw material and water into a slurry.
  • the preparation of the slurry is a step of mixing the solid material in water (S11), the step of mixing the water and the solid material by adding an organic additive (S21), by grinding and dispersing the mixed slurry It comprises a step of preparing a homogeneous and dispersed slurry (S22) and removing the foreign matter contained in the slurry (S23).
  • organic additive one or more selected from the group consisting of a dispersant, an antifoaming agent, and an organic binder may be used, and preferably all may be used.
  • FIG. 3 is a process chart showing a process of forming oxygen donor particles by spray drying the slurry.
  • the step of spray drying the slurry to form oxygen donor particles includes transferring the slurry to the spray dryer (S31) and spraying the transferred slurry into the spray dryer to form the oxygen donor particles. Step S32 is made.
  • Figure 4 is a process diagram showing a process for producing the final oxygen donor particles by dry firing the oxygen donor particles formed by the spray drying method.
  • the molded oxygen donor particles are prepared as final oxygen donor particles through a preliminary drying process (S41), and then calcined (S42).
  • FIG. 6 is a basic conceptual view of a medium-circulating gas fuel device.
  • the metal oxide (MO) in the oxygen donor particles reacts with the gaseous fuel and is reduced to become metal particles (M). At this time, the gaseous fuel is burned.
  • the metal particles (M) in the reduced oxygen donor particles move to an oxidation reactor, and react with oxygen in the air in the oxidation reactor to be oxidized back to the metal oxide.
  • the oxidized metal oxide is circulated to a reduction reactor to repeat the above process.
  • Schemes 1 and 2 The reactions in the reduction reactor and the metal reactor are shown in Schemes 1 and 2 below.
  • Scheme 1 below is a reaction in a reduction reactor
  • Scheme 2 shows a reaction occurring in an oxidation reactor.
  • nickel oxide at least 98% pure, in powder form
  • gamma alumina at least 95% pure, specific surface area 150 m 2 / g
  • magnesia at least 98.2% pure, specific surface area 45 m 2 / g
  • a solid slurry was added to water while stirring with a stirrer to prepare a mixed slurry.
  • the content of the solid raw material was about 40 parts by weight based on 100 parts by weight of the mixed slurry.
  • a dispersant anionic surfactant
  • an antifoaming agent metal soap system
  • the mixed slurry was ground three times in a high energy ball mill.
  • a polyethylene glycol-based organic binder was added and the third grinding was performed to prepare a stable and homogeneous colloidal slurry.
  • the viscosity of the slurry was 2800 cP, and the final slurry solid concentration was 35.8 parts by weight after removing the foreign matter by sieving the finished slurry.
  • Oxygen donor particles prepared by transferring the prepared colloid slurry to a spray dryer with a pump and spray drying are dried in an air atmosphere reflux dryer at 120 ° C. for 2 hours or more, and at a heating temperature of 5 ° C./min in an air atmosphere in a firing furnace at 1100. After raising the temperature to °C to 1,300 °C, firing for at least 4 hours to prepare oxygen donor particles. Before reaching the firing temperature, the mixture was maintained at isothermal temperature for about 1 hour at 200 ° C, 400 ° C, 500 ° C and 650 ° C.
  • Oxygen donor particles were prepared in the same manner as in Example 1, but the content and slurry properties of the components used in the preparation are shown in Table 1 below.
  • the shape of the oxygen donor particles was measured by SEM (JOEL JSM 6400) photograph.
  • Average particle size and particle size distribution of the oxygen donor particles were measured using a standard sieve according to ASTM E-11.
  • the packing density of the oxygen donor particles was measured using a tap density meter (Quantachrome Autotap) according to ASTM D 4164-88.
  • the specific surface area of the oxygen donor particles was measured using a specific surface area analyzer (Micromeritics, ASAP 2420).
  • the wear resistance of the oxygen donor particles was measured by a wear tester in accordance with ASTM D 5757-95.
  • the wear index (AI) was determined at 10 slpm (standard volume per minute) over 5 hours as described in the ASTM method above, and the wear index was expressed as the percentage of fines generated over 5 hours.
  • Oxygen transfer capacity of oxygen donor particles was evaluated using thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the composition of the reaction gas used for the reduction of the oxygen donor particles was 10 vol% CH 4 , 90 vol% CO 2 , and air was used as the reaction gas for oxidizing the reduced oxygen donor particles. 100% nitrogen was supplied between the oxidation and reduction reactions to prevent direct fuel and air contact in the reactor.
  • the sample amount of oxygen donor particles used in the experiment was about 30 mg.
  • the flow rate of each reaction gas was 150 std ml / min, and the oxygen transfer capacity was measured by repeating the oxidation / reduction reaction of the oxygen donor particles at least five times, where the oxygen transfer capacity was based on the NiO weight contained in the raw material.
  • the weight change obtained by subtracting the oxygen donor particle weight measured at the end of the reduction reaction of the oxygen donor particle at the given experimental conditions at the theoretical maximum oxygen donor particle weight may be completely oxidized.
  • Example 1 1200 rectangle 96 41.5-302.5 2.06 - 27.5 10.1 1300 88 41.5-302.5 2.49 0.85 5.2 8.7
  • Example 2 1100 rectangle 97 41.5-302.5 1.25 - 38.3 - 1200 94 41.5-302.5 2.02 - 28.3 10.4 1300 87 41.5-302.5 2.64 0.50 2.8 6.3
  • Example 3 1300 rectangle 91 41.5-302.5 2.60 0.16 4.1 12.7
  • Example 5 1100 rectangle 96 41.5-302.5 2.00 0.73 10.0 5.7 1300 95 41.5-302.5 2.39 0.12 0.6 - Comparative Example 1 1300 rectangle 111 49.0-302.5 1.78 1.71 70.2 - 1400 110 49
  • FIG. 5 is a SEM photograph of oxygen donor particles prepared according to an embodiment of the present invention, (B) shows examples of oxygen donor particles prepared by Example 2 and (C). As shown in FIG. 5, the prepared oxygen donor particles have a spherical shape.
  • Table 2 shows the physical properties of the NiO and Mn 3 O 4 oxygen donor particles prepared by the Examples and Comparative Examples, as shown in Table 2, NiO oxygen donor particle average particle size is 85 ⁇ m to 100 ⁇ m The particle size distribution is 41.5 ⁇ m to 302.5 ⁇ m.
  • the packing density is 1.3 g / ml to 2.8 g / ml, the specific surface area is 0.16 m 2 / g or more, the wear index is 60% or less, and the oxygen transfer capacity is 6 wt% or more.
  • Comparative Example 1 using a mixture of ⁇ -Al 2 O 3 and MgO as a support and Comparative Example 2 using MgAl 2 O 4 as the support were prepared according to the examples of oxygen produced by the example having a wear index of 50% or more at a firing temperature of 1300 ° C. Much weaker strength than donor particles. Therefore, the oxygen donor particles of Comparative Example 1 and Comparative Example 2 should be calcined at a temperature higher than 1300 ° C. in order to obtain higher strength. When the baking temperature is 1400 ° C in Comparative Example 2, the strength suitable for the fluidized bed process is shown.
  • the shape of the Mn 3 O 4 oxygen donor particles prepared in Example 5 is spherical, the average particle size is about 95 ⁇ m, and the particle size distribution is 41.5 ⁇ m to 302.5 ⁇ m.
  • the packing density is 2.0 g / ml to 2.5 g / ml
  • the specific surface area is 0.12 m 2 / g or more
  • the wear index is 10% or less
  • the oxygen transfer ability is 3 wt% or more.
  • Comparative Example 3 using MgAl 2 O 4 as the support shows a lower wear resistance at the same firing temperature as compared to the Mn 3 O 4 oxygen donor particles prepared in Example with a wear index of 27.2% at a firing temperature of 1300 °C.
  • the oxygen donor particles oxygen donor particles using gamma alumina and magnesia as support bodies
  • the examples can obtain stronger strength even at a lower firing temperature than the comparative example.
  • the oxygen donor particles according to the present invention is excellent in physical properties such as strength even at a low firing temperature, and can be preferably used in a fluidized bed process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

La présente invention concerne un dispositif de transport d'oxygène comportant un support comprenant de la magnésie et un matériau actif comprenant un oxyde métallique. Le dispositif de transport d'oxygène selon la présente invention présente d'excellentes caractéristiques physiques, telles que l'intensité, même à une faible température de cuisson, et peut être utile dans le traitement à lit fluidisé.
PCT/KR2010/006673 2010-08-04 2010-09-30 Dispositif de transport d'oxygène et son procédé de fabrication Ceased WO2012018156A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100075358A KR101691899B1 (ko) 2010-08-04 2010-08-04 산소공여입자 및 그 제조방법
KR10-2010-0075358 2010-08-04

Publications (1)

Publication Number Publication Date
WO2012018156A1 true WO2012018156A1 (fr) 2012-02-09

Family

ID=45559644

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2010/006673 Ceased WO2012018156A1 (fr) 2010-08-04 2010-09-30 Dispositif de transport d'oxygène et son procédé de fabrication

Country Status (2)

Country Link
KR (1) KR101691899B1 (fr)
WO (1) WO2012018156A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121519040A (zh) * 2026-01-15 2026-02-13 广西海洋科学院(广西红树林研究中心) 一种基于co2一步原位氧-碳化制备耐氢蚀耐氯离子磨蚀钝化膜层的方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140000452A (ko) * 2012-06-22 2014-01-03 한국전력공사 스피넬 구조의 산소공여입자 및 그 제조방법
CA3032070C (fr) * 2016-09-23 2023-08-15 Korea Electric Power Corporation Composition de matiere premiere pour preparer des particules de transport d'oxygene, particules de transport d'oxygene preparees a l'aide de celle-ci, et procede de preparation de particules de transport d'oxygene
KR102000912B1 (ko) * 2017-10-17 2019-07-17 한국전력공사 산소전달입자 제조용 원료 조성물, 이를 이용하여 제조된 산소전달입자 및 산소전달입자 제조방법
KR102122327B1 (ko) * 2018-06-25 2020-06-12 한국전력공사 산소전달입자 제조용 원료 조성물, 이를 이용하여 제조된 산소전달입자 및 산소전달입자 제조방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5447024A (en) * 1992-06-03 1995-09-05 Tokyo Electric Power Co., Inc. Chemical-looping combustion power generation plant system
US20050175533A1 (en) * 2003-12-11 2005-08-11 Thomas Theodore J. Combustion looping using composite oxygen carriers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5447024A (en) * 1992-06-03 1995-09-05 Tokyo Electric Power Co., Inc. Chemical-looping combustion power generation plant system
US20050175533A1 (en) * 2003-12-11 2005-08-11 Thomas Theodore J. Combustion looping using composite oxygen carriers

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LEE, JI HYEON ET AL., THE KOREA SOCIETY FOR ENERGY ENGINEERING (2007) JOURNAL OF FALL CONFERENCE, 2007 *
PILAR GAYAN ET AL.: "Effect of support on reactivity and selectivity of Ni-based oxygen carriers for chemical-looping combustion", FUEL, vol. 87, no. 12, 2008, IPC SCIENCE AND TECHNOLOGY PRESS, GUILDFORD, GB, pages 2641 - 2650, XP022679796 *
RYU, HO-JUNG ET AL., KOREAN CHEM. ENG. RES., vol. 42, no. 5, 2004, pages 588 - 597 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121519040A (zh) * 2026-01-15 2026-02-13 广西海洋科学院(广西红树林研究中心) 一种基于co2一步原位氧-碳化制备耐氢蚀耐氯离子磨蚀钝化膜层的方法和应用

Also Published As

Publication number Publication date
KR20120013151A (ko) 2012-02-14
KR101691899B1 (ko) 2017-01-03

Similar Documents

Publication Publication Date Title
WO2012043960A1 (fr) Particules transporteurs d'oxygène et leur procédé de fabrication
WO2020004751A1 (fr) Composition de matière première pour la fabrication de particules de transfert d'oxygène, particules de transfert d'oxygène fabriquées à l'aide de celle-ci, et méthode de fabrication de particules de transfert d'oxygène
CN101386539B (zh) 氮化铝陶瓷材料及其制备方法
WO2012018156A1 (fr) Dispositif de transport d'oxygène et son procédé de fabrication
WO2013065880A1 (fr) Absorbant solide de dioxyde de carbone comprenant une amine ou un composé de cette amine, destiné à être utilisé dans le procédé de capture du dioxyde de carbone par voie sèche, et procédé de fabrication dudit absorbant
WO2015046715A1 (fr) Composition pour absorbant solide de dioxyde de carbone et absorbant solide de dioxyde de carbone contenant la composition
WO2013176358A1 (fr) Procédé de fabrication de grains abrasifs à base d'alumine pour matériau abrasif, et grains abrasifs à base d'alumine pour la fabrication dudit matériau abrasif
WO2013048191A2 (fr) Absorbant de dioxyde de carbone, et son procédé de préparation
WO2012036336A1 (fr) Agent de désulfuration et procédé de préparation de celui-ci
WO2016052838A1 (fr) Sorbant solide actif mésophile du dioxyde de carbone, composition de suspension et son procédé de préparation
WO2012043904A1 (fr) Particule hybride destinée à un procédé de réaction de déplacement au gaz à l'eau à sorption sur lit fluidisé améliorée et procédé de préparation de celle-ci
WO2019078413A1 (fr) Composition de matériau pour préparer des particules de transfert d'oxygène, particules de transfert d'oxygène préparées à l'aide de celle-ci, et méthode de préparation de particules de transfert d'oxygène
WO2018066751A1 (fr) Matière première solide pour absorbant de dioxyde de carbone, composition de l'absorbant de dioxyde de carbone la comprenant, et absorbant de dioxyde de carbone préparé à l'aide de celle-ci
WO2018043800A1 (fr) Procédé de préparation de matériau actif d'électrode à base de carbone dur de surface spécifique élevée par commande de processus de carbonisation et matériau actif d'électrode préparé par ce procédé
WO2012043905A1 (fr) Catalyseur de déplacement au gaz à l'eau à sorption améliorée et procédé de préparation de celui-ci
WO2023095954A1 (fr) Corps fritté en alumine noire et son procédé de fabrication
WO2018056766A1 (fr) Composition de matière première pour préparer des particules de transport d'oxygène, particules de transport d'oxygène préparées à l'aide de celle-ci, et procédé de préparation de particules de transport d'oxygène
WO2022025479A1 (fr) Catalyseur de reformage à sec comprenant un matériau à structure de pérovskite ayant un élément de transition élué, son procédé de fabrication, système de catalyseur de reformage à sec le comprenant, et pile à combustible à oxyde solide le comprenant
WO2024123020A1 (fr) Catalyseur supporté pour la production de nanotubes de carbone enchevêtrés et procédé de production de nanotubes de carbone enchevêtrés faisant appel à celui-ci
WO2014175519A1 (fr) Composition d'encre pour céramique pour impression par jet d'encre et procédé de préparation de celle-ci
KR20130035642A (ko) 산소공여입자 및 그 제조방법
WO2023090583A1 (fr) Catalyseur de reformage de méthane et son procédé de production
WO2024205353A1 (fr) Solution de revêtement pour la préparation d'un catalyseur de reformage auquel un support d'isolation est appliqué, et procédé de préparation de catalyseur de reformage
WO2022154148A1 (fr) Corps fritté en grenat d'yttrium et d'aluminium de grande pureté et de grande densité et son procédé de fabrication
WO2023277220A1 (fr) Liant solide pour matériau réfractaire et matériau réfractaire le comprenant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10855669

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10855669

Country of ref document: EP

Kind code of ref document: A1