WO2012043960A1 - Oxygen carrier particles and method for manufacturing same - Google Patents

Oxygen carrier particles and method for manufacturing same Download PDF

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Publication number
WO2012043960A1
WO2012043960A1 PCT/KR2011/003957 KR2011003957W WO2012043960A1 WO 2012043960 A1 WO2012043960 A1 WO 2012043960A1 KR 2011003957 W KR2011003957 W KR 2011003957W WO 2012043960 A1 WO2012043960 A1 WO 2012043960A1
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Prior art keywords
oxygen donor
particles
slurry
raw material
oxygen
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PCT/KR2011/003957
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French (fr)
Korean (ko)
Inventor
류청걸
백점인
이중범
류정호
엄태형
Original Assignee
한국전력공사
한국남동발전 주식회사
한국중부발전 주식회사
한국서부발전 주식회사
한국남부발전 주식회사
한국동서발전 주식회사
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Publication of WO2012043960A1 publication Critical patent/WO2012043960A1/en

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    • 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
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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 CO2 without reducing power generation efficiency. Since the media circulating gas combustion technology burns fuel with oxygen contained in metal oxides instead of air, only gas and CO 2 are included in the gas discharged after combustion of the fuel. Therefore, only condensation and removal of water vapor in the exhaust gas, leaving only CO2, CO2 source separation is possible.
  • 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 air while oxygen contained in the oxygen donor particle is delivered to a fuel, and the oxygen donor particle is reduced.
  • a circulating fluidized-bed process is used in which a fluidized bed reactor (oxidation reactor) in which a reaction which receives and oxidizes is formed is connected to each other.
  • the oxygen donor particles must satisfy various conditions suitable for the fluidized bed process characteristics.
  • it should have a suitable pore structure 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.
  • Impregnation, coprecipitation, physical mixing method of mixing raw materials with water, kneading, drying, sintering and pulverizing to form particles ) And freeze granulation are mainly used.
  • the oxygen donor particles prepared by these methods are not suitable for the fluidized bed process due to the physical properties such as shape after filling, particle size and strength, or low metal oxide content, and thus are not suitable for mass production or 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 have homogeneous and stable fluidity characteristics is very important.
  • Inadequate slurry property control results in the formation of non-spherical oval, donut or grooved particles, which increases the wear loss of the particles when applied to a fluidized bed process.
  • Oxygen donor particles produced by the spray drying method shown in the literature a substantial portion of the prepared particles show a doughnut or grooved form, there is a need for improvement.
  • oxygen donor particles are composed of an active material metal oxide and a support.
  • the support serves to increase the dispersion of the metal oxides, to impart strength to the particles, and to suppress sintering of the metal oxides that may occur during the medium circulation combustion process. That is, the reactivity and physical properties of the oxygen donor particles finally prepared according to the type of the support will show a difference.
  • oxygen donor particles using alumina (Al 2 O 3) as a support material of a nickel oxide (NiO) active material have been proposed.
  • Oxygen donor particles using the alumina have a high strength.
  • magnesia (MgO) is added to the support material including the alumina, and then oxygen donor particles prepared by spray drying are presented. It became.
  • the particles formed after spray drying (Green body) is subjected to a sintering process to achieve strength, at this time, a portion of the nickel oxide (NiO) strongly interacts with the support raw material and a stable compound Since it may form, it may cause a problem that the oxygen transfer capacity is reduced.
  • nickel oxide (NiO) and alumina are used, nickel aluminate (NiAl 2 O 4) is produced during the firing process.
  • the spray-formed particles should be fired at a high temperature of 1400 ° C. or more to obtain the strength required for the fluidized bed process application.
  • the firing is performed at a high temperature of 1400 ° C. or higher, the packing density of the particles is increased after firing, and more energy is consumed in fluidization, and the shrinkage of the particles causes a problem that the specific surface area decreases and the reactivity decreases.
  • the firing cost due to high temperature firing also increases.
  • the present invention uses hydrotalcite or a mixture of gamma alumina and hydrotalcite as a support material for oxygen donor particles, thereby achieving strength even at a lower firing temperature than in the prior art of preparing oxygen donor particles containing magnesium (Mg) components. It is possible to provide oxygen donor particles having excellent reactivity and suitable for the circulating fluidized bed process.
  • the present invention as a means for solving the above problems, an active material containing a metal oxide;
  • An oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite is provided.
  • the present invention provides a slurry composition comprising a solid raw material and a solvent containing the oxygen donor particle raw material composition as another means for solving the above problems.
  • the present invention provides another means for solving the above problems, (A) preparing a mixture by mixing the above-described oxygen donor particle raw material composition with a solvent as a solid raw material;
  • (D) providing a method for producing oxygen donor particles comprising the step of dry baking the molded solid particles to produce oxygen donor particles.
  • the present invention provides an oxygen donor particle produced by the above production method as another means for solving the above problems.
  • 1 is a process chart showing a process for producing an acid donor particle according to the present invention.
  • 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 5 is an industrial micrograph of the oxygen donor particles according to the present invention.
  • 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
  • An oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
  • oxygen donor particle raw material composition according to the present invention will be described in more detail.
  • the active material means a material capable of delivering oxygen to fuel and receiving oxygen from air or steam again.
  • the type of the active material is not particularly limited and may be, for example, a metal oxide.
  • the metal oxides include copper oxides such as copper oxide (CuO and Cu 2 O), nickel oxides such as nickel oxide (NiO), iron oxides such as iron oxide (FeO, Fe 2 O 3 and Fe 3 O 4), manganese oxide (MnO, Manganese oxides, such as MnO2, Mn2O3, Mn3O4), and cobalt oxides, such as cobalt oxide (CaO, Co3O4), etc. are mentioned.
  • the content of the active substance is not particularly limited, and may be used in an amount of 50 to 80 parts by weight, preferably 60 to 70 parts by weight, based on the oxygen donor particle raw material composition.
  • the support material included in the oxygen donor particle composition of the present invention supports the active material to be evenly distributed throughout the particle, provides a pore structure necessary for diffusion of the reaction gas, and provides sufficient strength required for the oxygen donor particle in the fluidized bed process after firing.
  • the support raw material 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 during the redox cycle, and the gas before and after the reaction may serve to create a passage for smooth entry and exit (diffusion) between the outside of the particle and the active material.
  • the support material may be a mixture of hydrotalcite or gamma alumina ( ⁇ -Al 2 O 3) and hydrotalcite.
  • the gamma alumina ( ⁇ -Al 2 O 3) makes it possible to obtain high-strength oxygen donor particles.
  • the content of gamma alumina ( ⁇ -Al 2 O 3) is not particularly limited, and may be 0 to 45 parts by weight, preferably 0 to 20 parts by weight, based on the oxygen donor particle raw material composition.
  • the hydrotalcite (Mg-Al layered double hydroxide) is the oxygen donor particles to obtain the sufficient strength required in the fluidized bed process at a lower firing temperature than the prior art to prepare oxygen donor particles containing Mg component To be able.
  • the content of hydrotalcite is not particularly limited, and may be used in an amount of 5 to 50 parts by weight, preferably 20 to 50 parts by weight, based on the oxygen donor particle raw material composition.
  • the support material that is, a mixture of hydrotalcite or gamma alumina and hydrotalcite is preferably used in an amount of 20 parts by weight to 50 parts by weight based on the oxygen donor particle composition.
  • the present invention also relates to a slurry composition comprising the solid raw material and the solvent using the above-described oxygen donor particle raw material composition, that is, a raw material composition containing the active material and the support raw material as a solid raw material.
  • the kind of the solvent is not particularly limited, and a solvent generally used in the art may be used. Specifically, water may be used as the solvent.
  • the solid raw material may be included, for example, in an amount of 15 to 50 parts by weight based on the slurry composition. If the content of the solid raw material is less than 15 parts by weight, the amount of the slurry for the production of oxygen donor particles may increase and ultimately reduce the production efficiency. If the content of the solids exceeds 50 parts by weight, the viscosity of the slurry according to the concentration of the slurry is increased. There is a fear that the fluidity is lowered due to the increase, making it difficult to perform spray drying.
  • the slurry composition according to the present invention further comprises at least one organic additive selected from the group consisting of dispersants, antifoaming agents and organic binders for controlling homogenization of solid raw materials, concentration, viscosity, stability, flowability and strength and density of slurry. It may include.
  • a dispersant is used to prevent agglomeration between particles in the grinding process, which will be described below. That is, in the pulverization process for controlling the particle size of the solid raw material constituting the oxygen donor particles, the dispersant may be used to prevent the reduction of the pulverization efficiency due to the aggregation of the pulverized fine powder particles.
  • the type of dispersant in the present invention for example, at least one selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be used, and preferably anionic Surfactants and nonionic surfactants can be used.
  • anionic surfactant poly carboxylate ammonium salts or poly carboxylate amine salts may be used.
  • the dispersant may be used in an amount of 0.01 to 10 parts by weight based on the solid raw material. In this range, the dispersion effect of the particles is excellent.
  • a defoamer may be used to remove bubbles in the slurry to which the dispersant and the organic binder are applied.
  • the type of the antifoaming agent for example, one or more selected from the group consisting of silicon-based, metal soap-based, amide-based, polyether-based, alcohol-based and the like can be used.
  • the antifoaming agent may be used in 0.001 to 1 parts by weight based on the solid raw material.
  • the organic binder imparts plasticity and fluidity to the slurry and ultimately gives strength to the solid particles formed during spray drying, thereby facilitating handling of the particles before drying and firing.
  • the type of the organic binder in the present invention for example, one or more selected from the group consisting of polyvinyl alcohol, polyethylene glycol, methyl cellulose and the like can be used.
  • the content of the organic binder is not particularly limited. For example, 0.5 to 5 parts by weight may be used based on the solid raw material. When the content is less than 0.05 parts by weight, it may be difficult to maintain the spherical shape before drying and firing due to a decrease in the bonding strength of the molded solid particles during spray drying, if the content exceeds 5 parts by weight of the final material by the residual ash after firing There is a fear that the performance of the.
  • the method for producing the oxygen donor particles in the present invention is not particularly limited.
  • (D) may be prepared by a method comprising the step of dry firing the molded solid particles to produce oxygen donor particles.
  • the mixture may be prepared by mixing the aforementioned solid raw material in a solvent.
  • the solid raw material may include an active material and a support material, the active material and the support material may be used without limitation the above-described type, the content may also be used within the above-described content range.
  • the solvent may be used without limitation the above-described type, specifically, water may be used.
  • the content of the solid raw material in the present invention may be 15 to 50 parts by weight based on the slurry composition.
  • Step (B) according to the invention comprises adding to the slurry at least one organic additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder;
  • the slurry may be stirred and pulverized.
  • the 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 of the above may be used.
  • the dispersant, the antifoaming agent and the organic binder may be used without limitation the above-described kind, the content thereof is as described above.
  • agitation may be performed in the process of adding the components included in the mixture and / or in a state where all of them are added. At this time, stirring may be performed using a stirrer.
  • the solid raw material particles can be more homogeneously dispersed in the slurry.
  • additional antifoaming agent and dispersant may be added if necessary.
  • a wet milling method may be used to improve the grinding effect and to solve problems such as blowing of particles generated during dry grinding.
  • the pulverized slurry can be characterized by using a dispersant, antifoaming agent or additional solvent to adjust characteristics such as concentration and viscosity.
  • the grinding process may be omitted.
  • a step of removing foreign matter in the stirred and pulverized slurry may be further performed.
  • the above step it is possible to remove the foreign matter or agglomerated raw materials that may cause clogging of the nozzle during spray molding. Removal of the foreign matter may be carried out through sieving.
  • Step (C) of the present invention is a step of spray drying the slurry to form the solid particles, the molding of the slurry can be carried out using a spray dryer.
  • the slurry may be transferred to a spray dryer using a pump, and then the solid slurry may be molded by spraying the transferred slurry composition into the spray dryer through a pump or the like.
  • the operating conditions of the spray dryer for forming the oxygen donor particles in the spray dryer of the present invention can be applied to the operating conditions generally used in this field.
  • step (D) is a step of preparing the oxygen donor particles by dry firing the solid particles prepared in step (C).
  • the molded solid particles may be dried and then fired to prepare oxygen donor particles.
  • Drying in the present invention may be carried out by drying the molded solid particles in a reflux dryer of 110 to 150 °C for 2 to 24 hours. At this time, drying is performed in an air atmosphere.
  • the dried particles are placed in a high temperature baking furnace to raise the final firing temperature to 1000 to 1400 °C at a rate of 1 to 5 °C / min, and then fire for 2 to 10 hours.
  • a high temperature baking furnace to raise the final firing temperature to 1000 to 1400 °C at a rate of 1 to 5 °C / min, and then fire for 2 to 10 hours.
  • after the stagnation section of each 30 minutes or more at the stagnation temperature of two or more steps up to the final firing temperature can be baked.
  • firing may use a firing furnace such as a muffle furnace, a tubular furnace, or a kiln.
  • a firing furnace such as a muffle furnace, a tubular furnace, or a kiln.
  • the organic additives (dispersant, antifoaming agent and organic binder) introduced during the preparation of the slurry are burned, and the strength of the particles is improved by bonding between the raw materials.
  • the present invention is an active material containing a metal oxide
  • An oxygen donor particle prepared using an oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
  • the shape of the oxygen donor particles according to the present invention may be spherical. If the shape is not spherical, but donut-shaped or grooved, the wear loss of the particles is increased.
  • the average particle size and particle distribution of the oxygen donor particles may be, for example, 50 to 150 ⁇ m and 30 to 400 ⁇ m, respectively.
  • the packing density of the oxygen donor particles of the present invention may be, for example, 1.0 to 3.0 g / cc.
  • the porosity of the oxygen donor particles is 5 to 80%, the specific surface area may be 0.1 to 100 m 2 / g.
  • the wear resistance is represented by the wear index (AI), the lower the wear index means that the wear resistance is better.
  • the wear resistance of the oxygen donor particles may be 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 the closer to 0%, the better.
  • the oxygen transfer capacity of the oxygen donor particles is not particularly limited, for example, may be 1 wt% to 17 wt%.
  • the present invention is an active material containing a metal oxide
  • Oxygen donor particles prepared using an oxygen donor particle raw material composition comprising a support material containing a mixture of hydrotalcite or gamma alumina and hydrotalcite are reacted with gaseous fuel to reduce the oxygen donor particles and burn fuel gas. Making a step; And
  • 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 for example, at least one selected from the group consisting of methane, hydrogen, carbon monoxide, alkanes (CnH 2 n + 2), natural gas (LNG) and syngas (syngas). Can be.
  • 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 particles may include an active material containing a metal oxide; And an oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
  • 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
  • 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.
  • spray drying the slurry to form the oxygen donor particles is the step of transporting 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 combustion device.
  • methane may be used as the gaseous fuel.
  • 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 reduced oxygen donor particles (M) are moved to an oxidation reactor, and reacted with oxygen in the air in the oxidation reactor to be oxidized again.
  • the oxidized oxygen donor particles are 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.
  • 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 40 to 50 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 final slurry solids concentration was 34.8 parts by weight after removing the foreign matter by sieving the slurry after the grinding.
  • 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 at least 2 hours, and at a heating temperature of 5 ° C./min in an air atmosphere in a kiln at 1300 ° C./min. After raising to °C, it was calcined for 5 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.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 NiO, parts by weight 70 70 70 61 65 Mn 3 O 4 , parts by weight 5 70 61 Hydrotalcite, parts by weight 30 15 25 39 21 30 39 ⁇ -Al 2 O 3 , parts by weight 15 14 ⁇ -Al 2 O 3 , parts by weight MgO, parts by weight MgAl 2 O 4 parts by weight Total solids content, parts by weight 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • the shape of the oxygen donor particles was measured using an industrial microscope.
  • 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.
  • Hg porosity of oxygen donor particles was measured using a pore meter (Micromeritics, AutoPore IV 9500).
  • 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 is expressed as the percentage of fines generated over 5 hours.
  • Materials with a wear index (AI) of less than 30% in high speed fluidized bed reactors and even less than 60% in bubbling fluidized bed reactors are fully usable at atmospheric pressure and can also be used in fluidized bed media and process reforming processes. .
  • 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 reaction of the oxygen donor particles was 10 vol% CH4, 90 vol% CO2 in Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, and Comparative Examples 6, 7 and In Example 3, it was 60 vol% CO, 30 vol% H2, and 10 vol% CO2.
  • air was used as a 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 is determined by the weight of the metal oxide included in the raw material. Based on the theoretical maximum oxygen donor particle weight when the oxygen donor particle is completely oxidized, the oxygen donor particle completely subtracts the weight change obtained by subtracting the weight of the oxygen donor particle measured at the end of the reduction reaction of the oxygen donor particle under the given experimental conditions. It is expressed as a percentage by weight divided by the theoretical maximum oxygen donor particle weight when oxidized.
  • Example 1 1300 rectangle 114 41.5-302.5 2.57 23.1 1.1 12.8 14.3
  • Example 2 1300 rectangle 93 41.5-302.5 2.13 16.6 1.6 27.0 13.6
  • Example 3 1200 rectangle 94 49.0-302.5 2.89 5.3 0.1 2.2 15.7
  • Example 4 1200 rectangle 78 37.0-231.0 1.89 22.1 4.7 13.1 13.2
  • Example 5 1300 rectangle 86 37.0-196.0 2.17 19.4 2.1 26.4 12.9
  • Example 6 1000 rectangle 98 41.5-302.5 1.84 16.0 0.70 21.2 6.4 1100 rectangle 97 41.5-231.0 2.21 7.7 0.16 2.3 6.4
  • Example 7 1100 rectangle 100 37.0-302.5 2.09 10.8 0.34 3.9 6.0 Comparative Example 1 1300 rectangle 112 41.5-302.5 1.78 24.4
  • Figure 5 shows an industrial micrograph of the oxygen donor particles according to the Examples and Comparative Examples of the present invention.
  • A is Example 1
  • B is Example 2
  • C is Example 3
  • D is Example 4
  • E is Example 5
  • F is Example 6
  • G is Example 7, H.
  • I is Comparative Example 2
  • J represents the oxygen donor particles of Comparative Example 3.
  • the oxygen donor particles produced by Examples and Comparative Examples have a spherical shape.
  • the oxygen donor particles according to the embodiment using nickel oxide (NiO) and / or manganese oxide (Mn 3 O 4) as the active material, and using hydrotalcite as the support material is calcined at 1300 °C or less Even when manufactured at a temperature, it can be seen that they have suitable conditions for the fluidized bed process.
  • the shape of the oxygen donor particles is spherical, the average particle size is 78 to 115 ⁇ m, the particle size distribution is 37.0 to 302.5 ⁇ m, the filling density is 1.8 to 2.9 g / ml, Hg porosity is 5% or more, specific surface area is 0.1 More than m 2 / g, wear index is less than 40% and oxygen transfer capacity is more than 5 wt%.
  • the oxygen donor particles containing magnesium (Mg) components may be used at lower firing temperatures than at the prior art. It is possible to provide oxygen donor particles having good physical properties and suitable for fluidized bed process and having high reactivity.

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Abstract

The present invention relates to oxygen carrier particles, the material composition of which includes: an active material containing a metal oxide; and a support material which contains hydrotalcite or a mixture of hydrotalcite and gamma-alumina. The use of the support material of the present invention enables the manufacture of oxygen carrier particles having high reactivity and physical characteristics, such as high strength, even at a low firing temperature so as to be suitable for use in a liquid layer process.

Description

산소공여입자 및 그 제조방법Oxygen donor particle and its manufacturing method
본 발명은 산소공여입자 및 그 제조방법에 관한 것이다.The present invention relates to an oxygen donor particle and a method for producing the same.
대기 중 이산화탄소 농도의 증가에 따른 온실효과로 인해 지구의 평균기온이 상승하면서 기후변화의 피해가 지속적으로 나타나고 있다. 화력발전소는 인위적 이산화탄소 배출이 가장 많은 고정 배출원이다.Due to the greenhouse effect of increasing atmospheric CO2 concentrations, the global average temperature has risen, causing damage to climate change. Thermal power plants are the largest source of anthropogenic carbon dioxide emissions.
화력발전소에서의 이산화탄소 배출 저감은 이산화탄소 포집 및 저장(Carbon Dioxide Capture and Storage: CCS) 기술을 통해 달성할 수 있다. 하지만 CCS 기술을 발전소에 적용할 경우 발전효율이 감소되고, 이에 따라 발전원가가 상승되는 문제점이 생긴다. 따라서 발전효율의 감소를 최소화하고, CO2 포집 비용을 낮추기 위한 새로 신기술이 요구되고 있다.  Reduction of carbon dioxide emissions from thermal power plants can be achieved through carbon dioxide capture and storage (CCS) technology. However, when CCS technology is applied to power plants, power generation efficiency is reduced, resulting in an increase in power generation costs. Therefore, new technologies are required to minimize the reduction of power generation efficiency and to lower the cost of CO2 capture.
매체순환식 가스연소(CLC, chemical looping combustion)기술은 발전효율의 저하없이 CO2를 원천분리할 수 있는 기술로 주목 받고 있다. 상기 매체순환식 가스연소 기술은 공기대신 금속 산화물에 포함된 산소로 연료를 연소시키므로, 연료의 연소 후 배출되는 가스에는 수증기와 CO2만 포함되어 있다. 따라서, 배출 가스 중 수증기만 응축 제거하면 CO2만 남게 되므로, CO2 원천분리가 가능하다. 매체순환식 가스연소 기술은 산소전달 매체로 산소공여입자를 사용한다. 상기 매체순환식 가스연소 공정은 산소공여입자에 함유된 산소가 연료로 전달되면서 상기 산소공여입자는 환원(reduction)되는 반응이 일어나는 유동층 반응기(환원 반응기) 및 환원된 산소공여입자가 공기로부터 산소를 받아 산화(oxidation)되는 반응이 일어나는 유동층 반응기(산화 반응기)가 서로 연결된 조합으로 구성되는 순환유동층공정(circulating fluidized-bed process)을 사용한다. Chemical looping combustion (CLC) technology is attracting attention as a technology that can separate CO2 without reducing power generation efficiency. Since the media circulating gas combustion technology burns fuel with oxygen contained in metal oxides instead of air, only gas and CO 2 are included in the gas discharged after combustion of the fuel. Therefore, only condensation and removal of water vapor in the exhaust gas, leaving only CO2, CO2 source separation is possible. 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 air while oxygen contained in the oxygen donor particle is delivered to a fuel, and the oxygen donor particle is reduced. A circulating fluidized-bed process is used in which a fluidized bed reactor (oxidation reactor) in which a reaction which receives and oxidizes is formed is connected to each other.
따라서, 상기 산소공여입자는 유동층 공정특성에 적합한 여러 가지 조건을 만족시켜야 한다. 우선, 유동층 공정에 적합한 물성, 즉 충분한 강도, 유동에 적합한 형상, 충진밀도(packing density 또는 tapped density), 평균 입자크기, 입자크기 분포 및 반응 가스의 확산에 유리한 기공 구조를 지녀야 한다. 또한 반응성 측면에서 높은 산소전달능력(oxygen transfer capacity)을 지니고 있어 연료의 연소에 필요한 충분한 산소를 연료가 연료반응기를 통과하는 동안 공급할 수 있어야 한다. Therefore, the oxygen donor particles must satisfy various conditions suitable for the fluidized bed process characteristics. First of all, it should have a suitable pore structure 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. In addition, 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.
산소공여입자는 매체순환개질에도 이용될 수 있다. 상기 매체순환개질은 산소공여입자의 산소를 주고받는 특성을 이용하여 연료로부터 수소를 생산하는 기술이며, 순환유동층 공정을 사용할 수 있다.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.
산소를 주고받는 산소공여입자의 성형 방법으로 함침법(impregnation), 공침법 (coprecipitation), 원료물질을 물에 혼합하여 반죽하고 건조 및 소성한 후 분쇄하여 입자를 성형하는 물리적 혼합법 (physical mixing method) 및 동결 건조법 (freeze granulation) 등이 주로 이용되고 있다. 하지만 이들 방법들로 제조된 산소공여입자는 성형 후 형상을 비롯한 충진밀도, 입자크기 및 강도 등의 물성이 유동층 공정에 부적합하거나 또는 금속산화물의 함량이 낮아 산소전달량이 낮거나, 대량생산에 부적합하다. Impregnation, coprecipitation, physical mixing method of mixing raw materials with water, kneading, drying, sintering and pulverizing to form particles ) And freeze granulation are mainly used. However, the oxygen donor particles prepared by these methods are not suitable for the fluidized bed process due to the physical properties such as shape after filling, particle size and strength, or low metal oxide content, and thus are not suitable for mass production or mass production. .
유동층 공정에 적합한 물성을 갖는 산소공여입자를 대량으로 생산하기 위한 방법으로 분무건조법(spray-drying method)이 사용되고 있다. 원료를 물에 혼합한 슬러리를 노즐을 이용하여 분무하여, 수십 내지 수백 마이크론의 입자크기 분포를 갖는 구형 입자로 성형하기 위해서는, 슬러리를 균질하고 안정된 유동성 특성을 갖도록 하는 제조 과정이 매우 중요하다. 슬러리 특성 제어가 잘못된 경우, 구형이 아닌 타원형, 도우넛형 또는 홈이 파인 형태의 입자가 만들어져, 유동층 공정에 적용 시 입자의 마모손실이 커지는 원인이 된다. 문헌에 나타난 분무건조법으로 제조된 산소공여입자는, 상기 제조된 입자의 상당 부분이 도우넛형 또는 홈이 파인 형태를 보이고 있어, 이에 대한 개선이 필요하다.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. In order to form a spherical particle having a particle size distribution of several tens to hundreds of microns by spraying a slurry obtained by mixing a raw material with water using a nozzle, a manufacturing process for making the slurry have homogeneous and stable fluidity characteristics is very important. Inadequate slurry property control results in the formation of non-spherical oval, donut or grooved particles, which increases the wear loss of the particles when applied to a fluidized bed process. Oxygen donor particles produced by the spray drying method shown in the literature, a substantial portion of the prepared particles show a doughnut or grooved form, there is a need for improvement.
일반적으로, 산소공여입자는 활성물질인 금속산화물과 지지체로 구성된다. 여기서, 지지체는 금속산화물의 분산도(dispersion)를 높이고, 입자에 강도를 부여하며, 매체순환연소 과정에서 발생할 수 있는 금속산화물의 소결(Sintering)현상을 억제하는 역할을 한다. 즉, 상기 지지체의 종류에 따라 최종 제조된 산소공여입자의 반응성 및 물성은 차이를 나타내게 된다. In general, oxygen donor particles are composed of an active material metal oxide and a support. Here, the support serves to increase the dispersion of the metal oxides, to impart strength to the particles, and to suppress sintering of the metal oxides that may occur during the medium circulation combustion process. That is, the reactivity and physical properties of the oxygen donor particles finally prepared according to the type of the support will show a difference.
종래, 산화니켈(NiO) 활성물질의 지지체 원료로 알루미나(Al2O3)를 사용한 산소공여입자가 제시되었다. 상기 알루미나를 사용한 산소공여입자는 높은 강도를 지닌다. 한편, 산소공여입자의 연료 전환율을 높이고 입자간의 응집현상(agglomeration)을 억제하기 위해 상기 알루미나를 포함하는 지지체 원료에 마그네시아(MgO)를 첨가한 후, 분무건조법을 이용하여 제조한 산소공여입자가 제시되었다. 그러나, 상기 산소공여입자의 제조 시, 분무건조 후 성형된 입자(Green body)는 강도 구현을 위해 소성 과정을 거치게 되는데, 이때, 산화니켈(NiO)의 일부는 지지체 원료와 강하게 상호작용하여 안정한 화합물을 형성하므로, 산소전달능력이 감소하는 문제점을 초래할 수 있다. 일례로 산화니켈(NiO) 및 알루미나를 사용하는 경우, 소성과정에서 니켈알루미네이트(NiAl2O4)가 생성된다. Conventionally, oxygen donor particles using alumina (Al 2 O 3) as a support material of a nickel oxide (NiO) active material have been proposed. Oxygen donor particles using the alumina have a high strength. Meanwhile, in order to increase fuel conversion of oxygen donor particles and to suppress agglomeration between particles, magnesia (MgO) is added to the support material including the alumina, and then oxygen donor particles prepared by spray drying are presented. It became. However, in the production of the oxygen donor particles, the particles formed after spray drying (Green body) is subjected to a sintering process to achieve strength, at this time, a portion of the nickel oxide (NiO) strongly interacts with the support raw material and a stable compound Since it may form, it may cause a problem that the oxygen transfer capacity is reduced. For example, when nickel oxide (NiO) and alumina are used, nickel aluminate (NiAl 2 O 4) is produced during the firing process.
상기 문제점을 해결하기 위하여, 구조적으로 안정된 형태인 알파알루미나(α-Al2O3) 및/또는 마그네슘알루미네이트(MgAl2O4)를 지지체 원료로 사용하여 금속산화물과 지지체 원료간의 상호작용을 감소시킨 산소공여입자가 제시되었다. 또한, 마그네슘 성분을 포함하는 산화니켈(NiO) 산소공여입자를 분무건조법으로 제조한 종래의 기술에서도, 산화니켈(NiO)과 지지체 원료간의 상호작용을 최소화하기 위해 구조적으로 안정된 형태인 알파알루미나(α-Al2O3) 또는 마그네슘알루미네이트(MgAl2O4)를 지지체 원료로 사용하였다. 이 경우, 지지체가 구조적으로 안정된 형태이므로 유동층 공정 적용에 필요한 강도를 얻기 위해 분무성형한 입자를 1400℃ 이상의 고온으로 소성해야 한다. 상기 소성을 1400℃ 이상의 고온에서 수행하면, 소성 후 입자의 충진밀도가 높아져 유동화에 더 많은 에너지가 소모되며, 입자의 수축에 의해 비표면적이 작아지고 반응성이 떨어지는 문제점을 초래하게 된다. 또한 고온 소성으로 인한 소성비용도 상승하는 문제점이 있다. In order to solve the above problems, oxygen donor particles having reduced structural interaction between metal oxide and support material using alpha alumina (α-Al2O3) and / or magnesium aluminate (MgAl2O4), which are structurally stable forms, as support materials It became. In addition, even in the conventional technique in which nickel oxide (NiO) oxygen donor particles including magnesium components are manufactured by spray drying, alpha alumina (α), which is a structurally stable form, is minimized in order to minimize interaction between nickel oxide (NiO) and a support material. -Al2O3) or magnesium aluminate (MgAl2O4) was used as support material. In this case, since the support is structurally stable, the spray-formed particles should be fired at a high temperature of 1400 ° C. or more to obtain the strength required for the fluidized bed process application. When the firing is performed at a high temperature of 1400 ° C. or higher, the packing density of the particles is increased after firing, and more energy is consumed in fluidization, and the shrinkage of the particles causes a problem that the specific surface area decreases and the reactivity decreases. In addition, there is a problem that the firing cost due to high temperature firing also increases.
따라서, 산소공여입자의 물성 및 반응성을 향상시키고, 대량의 산소공여입자 제조 시 고온 소성에 따른 입자 제조 비용을 낮추기 위해 유동층 공정에서 요구되는 강도를 얻는데 필요한 소성온도를 최대한 낮출 필요가 있다.Therefore, in order to improve the physical properties and reactivity of the oxygen donor particles, and to lower the particle manufacturing cost due to high temperature firing in the production of 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.
본 발명은 산소공여입자의 지지체 원료로 하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 사용함으로써, 마그네슘(Mg) 성분을 포함하는 산소공여입자를 제조하는 종래 기술에 비해 더 낮은 소성온도에서도 강도 등의 물리적 특성이 순환유동층 공정에 적합하고, 반응성이 우수한 산소공여입자를 제공할 수 있다.The present invention uses hydrotalcite or a mixture of gamma alumina and hydrotalcite as a support material for oxygen donor particles, thereby achieving strength even at a lower firing temperature than in the prior art of preparing oxygen donor particles containing magnesium (Mg) components. It is possible to provide oxygen donor particles having excellent reactivity and suitable for the circulating fluidized bed process.
본 발명은 상기 과제를 해결하기 위한 수단으로서, 금속 산화물을 함유하는 활성물질; 및The present invention as a means for solving the above problems, an active material containing a metal oxide; And
하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 산소공여입자 원료 조성물을 제공한다.An oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite is provided.
본 발명은 상기 과제를 해결하기 위한 다른 수단으로서, 상기 산소공여입자 원료 조성물을 함유하는 고체원료 및 용매를 포함하는 슬러리 조성물을 제공한다.The present invention provides a slurry composition comprising a solid raw material and a solvent containing the oxygen donor particle raw material composition as another means for solving the above problems.
본 발명은 상기 과제를 해결하기 위한 다른 수단으로서, (A) 고체원료로서 상기 전술한 산소공여입자 원료 조성물을 용매와 혼합하여 혼합물을 제조하는 단계; The present invention provides another means for solving the above problems, (A) preparing a mixture by mixing the above-described oxygen donor particle raw material composition with a solvent as a solid raw material;
(B) 균질화된 슬러리를 제조하는 단계; (B) preparing a homogenized slurry;
(C) 슬러리를 분무건조하여 고체 입자를 성형하는 단계; 및 (C) spray drying the slurry to form solid particles; And
(D) 성형된 고체 입자를 건조 소성시켜 산소공여입자를 제조하는 단계를 포함하는 산소공여입자의 제조방법을 제공한다. (D) providing a method for producing oxygen donor particles comprising the step of dry baking the molded solid particles to produce oxygen donor particles.
본 발명은 상기 과제를 해결하기 위한 다른 수단으로서, 상기 제조방법에 의해 제조된 산소공여입자를 제공한다. The present invention provides an oxygen donor particle produced by the above production method as another means for solving the above problems.
도 1은 본 발명에 따른 산공여입자를 제조하는 과정을 나타낸 공정도이다.1 is a process chart showing a process for producing an acid donor particle according to the present invention.
도 2는 고체원료를 물에 혼합한 후 균질화된 슬러리로 제조하는 과정을 나타낸 공정도이다.2 is a process chart showing a process of preparing a homogenized slurry after mixing a solid raw material in water.
도 3은 슬러리를 분무건조하여 산소공여입자를 성형하는 과정을 나타낸 공정도이다.3 is a process chart showing a process of forming oxygen donor particles by spray drying the slurry.
도 4는 분무건조법으로 성형된 산소공여입자를 건조 소성시켜 최종 산소공여입자를 제조하는 과정을 나타낸 공정도이다.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.
도 5는 본 발명에 따른 산소공여입자의 산업용 현미경 사진이다.5 is an industrial micrograph of the oxygen donor particles according to the present invention.
도 6은 매체순화식 가스연소 장치의 기본 개념도이다.6 is a basic conceptual view of a medium purifying gas combustion apparatus.
본 발명은 금속 산화물을 포함하는 활성물질; 및The present invention is an active material including a metal oxide; And
하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 산소공여입자 원료 조성물에 관한 것이다. An oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
이하, 본 발명에 따른 산소공여입자 원료 조성물을 보다 상세하게 설명한다. Hereinafter, the oxygen donor particle raw material composition according to the present invention will be described in more detail.
본 발명에서 활성물질은 연료로 산소를 전달하고 공기나 수증기로부터 산소를 다시 받을 수 있는 물질을 의미한다. 본 발명에서 상기 활성물질의 종류는 특별히 제한되지 않으며, 예를 들면 금속 산화물일 수 있다. 상기 금속 산화물의 구체적인 예로는, 산화구리(CuO, Cu2O) 등의 구리계 산화물, 산화니켈(NiO) 등의 니켈계 산화물, 산화철(FeO, Fe2O3, Fe3O4) 등의 철계 산화물, 산화망간(MnO, MnO2, Mn2O3, Mn3O4) 등의 망간계 산화물 및 산화코발트(CaO, Co3O4) 등의 코발트계 산화물 등을 들 수 있다. 본 발명에서는 활성물질로 산화니켈(NiO), 산화망간(Mn3O4) 또는 산화니켈(NiO)과 산화망간(Mn3O4)의 혼합물을 사용하는 것이 바람직하다.In the present invention, the active material means a material capable of delivering oxygen to fuel and receiving oxygen from air or steam again. In the present invention, the type of the active material is not particularly limited and may be, for example, a metal oxide. Specific examples of the metal oxides include copper oxides such as copper oxide (CuO and Cu 2 O), nickel oxides such as nickel oxide (NiO), iron oxides such as iron oxide (FeO, Fe 2 O 3 and Fe 3 O 4), manganese oxide (MnO, Manganese oxides, such as MnO2, Mn2O3, Mn3O4), and cobalt oxides, such as cobalt oxide (CaO, Co3O4), etc. are mentioned. In the present invention, it is preferable to use nickel oxide (NiO), manganese oxide (Mn 3 O 4) or a mixture of nickel oxide (NiO) and manganese oxide (Mn 3 O 4) as the active material.
본 발명에서 활성물질의 함량은 특별히 제한되지 않고, 산소공여입자 원료 조성물에 대하여 50 내지 80 중량부를 사용할 수 있으며, 바람직하게는 60 내지 70 중량부를 사용할 수 있다. In the present invention, the content of the active substance is not particularly limited, and may be used in an amount of 50 to 80 parts by weight, preferably 60 to 70 parts by weight, based on the oxygen donor particle raw material composition.
본 발명의 산소공여입자 조성물에 포함되는 지지체 원료는 활성물질이 입자 전체에 고루 분포되도록 지지하고, 반응가스의 확산에 필요한 기공구조를 제공하며, 소성 후 산소공여입자에 유동층 공정에서 요구하는 충분한 강도를 제공해 줄 수 있다. 즉, 상기 지지체 원료는 활성물질을 지지하는 기능과 소성 시 서로 결합하면서 산소공여입자에 강도를 주는 바인더로서의 역할을 동시에 할 수 있다. 또한, 고온에서 금속이 산화 환원 사이클을 반복하는 동안 서로 응집하는 현상을 억제하며, 반응 전후의 가스가 입자 외부와 활성물질사이에서 입출입(확산)이 원활하도록 통로를 만들어주는 역할을 할 수 있다.The support material included in the oxygen donor particle composition of the present invention supports the active material to be evenly distributed throughout the particle, provides a pore structure necessary for diffusion of the reaction gas, and provides sufficient strength required for the oxygen donor particle in the fluidized bed process after firing. Can provide That is, the support raw material 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. In addition, at a high temperature, metals may be prevented from agglomerating with each other during the redox cycle, and the gas before and after the reaction may serve to create a passage for smooth entry and exit (diffusion) between the outside of the particle and the active material.
본 발명에서 상기 지지체 원료로는 하이드로탈사이트(hydrotalcite) 또는 감마알루미나(γ-Al2O3)와 하이드로탈사이트의 혼합물을 사용할 수 있다.In the present invention, the support material may be a mixture of hydrotalcite or gamma alumina (γ-Al 2 O 3) and hydrotalcite.
상기 감마알루미나(γ-Al2O3)는 높은 강도의 산소공여입자를 얻을 수 있게 한다. 본 발명에서 감마알루미나(γ-Al2O3)의 함량은 특별히 제한되지 않고, 산소공여입자 원료 조성물에 대하여 0 내지 45 중량부를 사용할 수 있으며, 바람직하게는 0 내지 20 중량부를 사용할 수 있다.The gamma alumina (γ-Al 2 O 3) makes it possible to obtain high-strength oxygen donor particles. In the present invention, the content of gamma alumina (γ-Al 2 O 3) is not particularly limited, and may be 0 to 45 parts by weight, preferably 0 to 20 parts by weight, based on the oxygen donor particle raw material composition.
또한, 상기 하이드로탈사이트(hydrotalcite, Mg-Al layered double hydroxide)는 Mg 성분을 포함하는 산소공여입자를 제조하는 종래 기술에 비해 산소공여입자가 더 낮은 소성온도에서도 유동층 공정에서 요구되는 충분한 강도를 얻을 수 있게 한다. In addition, the hydrotalcite (Mg-Al layered double hydroxide) is the oxygen donor particles to obtain the sufficient strength required in the fluidized bed process at a lower firing temperature than the prior art to prepare oxygen donor particles containing Mg component To be able.
본 발명에서 하이드로탈사이트의 함량은 특별히 제한되지 않고, 산소공여입자 원료 조성물에 대하여 5 내지 50 중량부를 사용할 수 있으며, 바람직하게는 20 내지 50 중량부를 사용할 수 있다.In the present invention, the content of hydrotalcite is not particularly limited, and may be used in an amount of 5 to 50 parts by weight, preferably 20 to 50 parts by weight, based on the oxygen donor particle raw material composition.
본 발명에서 지지체 원료, 즉 하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물은 산소공여입자 조성물에 대하여 20 중량부 내지 50 중량부의 함량으로 사용되는 것이 바람직하다.In the present invention, the support material, that is, a mixture of hydrotalcite or gamma alumina and hydrotalcite is preferably used in an amount of 20 parts by weight to 50 parts by weight based on the oxygen donor particle composition.
또한, 본 발명은 전술한 산소공여입자 원료 조성물, 즉, 활성물질 및 지지체 원료를 포함하는 원료 조성물을 고체원료로 하여, 상기 고체원료 및 용매를 포함하는 슬러리 조성물에 관한 것이다.The present invention also relates to a slurry composition comprising the solid raw material and the solvent using the above-described oxygen donor particle raw material composition, that is, a raw material composition containing the active material and the support raw material as a solid raw material.
본 발명에서 상기 용매의 종류는 특별히 제한되지 않으며, 이 분야에서 일반적으로 사용되는 용매를 사용할 수 있다. 구제적으로는 상기 용매로 물을 사용할 수 있다.In the present invention, the kind of the solvent is not particularly limited, and a solvent generally used in the art may be used. Specifically, water may be used as the solvent.
본 발명에서 고체원료는, 예를 들면, 슬러리 조성물에 대하여 15 내지 50 중량부의 함량으로 포함될 수 있다. 상기 고체원료의 함량이 15 중량부 미만이면, 산소공여입자 제조를 위한 슬러리의 양이 증가하여 궁극적으로 제조 효율이 저하될 우려가 있으며, 50 중량부를 초과하면, 슬러리의 농도 증가에 따른 슬러리의 점도 증가로 유동성이 저하되어 분무건조의 수행이 어려워질 우려가 있다. In the present invention, the solid raw material may be included, for example, in an amount of 15 to 50 parts by weight based on the slurry composition. If the content of the solid raw material is less than 15 parts by weight, the amount of the slurry for the production of oxygen donor particles may increase and ultimately reduce the production efficiency. If the content of the solids exceeds 50 parts by weight, the viscosity of the slurry according to the concentration of the slurry is increased. There is a fear that the fluidity is lowered due to the increase, making it difficult to perform spray drying.
본 발명에 따른 슬러리 조성물은 고체원료의 균질화, 슬러리의 농도, 점도, 안정성, 유동성과 강도 및 밀도 등을 제어를 위하여, 분산제, 소포제 및 유기결합제로 이루어진 그룹으로부터 선택되는 하나 이상의 유기첨가제를 추가로 포함할 수 있다. The slurry composition according to the present invention further comprises at least one organic additive selected from the group consisting of dispersants, antifoaming agents and organic binders for controlling homogenization of solid raw materials, concentration, viscosity, stability, flowability and strength and density of slurry. It may include.
본 발명에서는 상기 분산제, 소포제 및 유기결합제를 모두 사용하는 것이 좋다. In the present invention, it is preferable to use both the dispersant, the antifoaming agent and the organic binder.
본 발명에서 분산제(dispersant)는 하기에 설명할 분쇄 과정에서 입자끼리 응집되는 현상을 방지하기 위해 사용된다. 즉, 산소공여입자를 구성하는 고체원료들의 입자크기를 제어하기 위한 분쇄 과정에서, 분쇄된 미세 분말 입자들의 응집에 의한 분쇄 효율의 저하를 방지하기 위해 상기 분산제를 사용할 수 있다.In the present invention, a dispersant is used to prevent agglomeration between particles in the grinding process, which will be described below. That is, in the pulverization process for controlling the particle size of the solid raw material constituting the oxygen donor particles, the dispersant may be used to prevent the reduction of the pulverization efficiency due to the aggregation of the pulverized fine powder particles.
본 발명에서 분산제의 종류로는, 예를 들면, 음이온계 계면활성제, 양이온계 계면활성제, 양쪽성 계면활성제 및 비이온계 계면활성제로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있으며, 바람직하게는 음이온계 계면활성제 및 비이온계 계면활성제를 사용할 수 있다. 상기 음이온계 계면활성제로는 폴리카르복실산암모늄염(Poly carboxylate ammonium salts) 또는 폴리카르북실산아민염(Poly carboxylate amine salts) 등을 사용할 수 있다. As the type of dispersant in the present invention, for example, at least one selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be used, and preferably anionic Surfactants and nonionic surfactants can be used. As the anionic surfactant, poly carboxylate ammonium salts or poly carboxylate amine salts may be used.
상기 분산제는 고체원료를 기준으로, 0.01 내지 10 중량부를 사용할 수 있다. 상기 범위에서, 입자들의 분산 효과가 우수하다.The dispersant may be used in an amount of 0.01 to 10 parts by weight based on the solid raw material. In this range, the dispersion effect of the particles is excellent.
본 발명에서 소포제(defoamer)는 분산제 및 유기결합제가 적용된 슬러리의 기포를 제거하기 위해 사용될 수 있다. 상기 소포제의 종류로는, 예를 들면, 실리콘계, 금속비누계, 아마이드계, 폴리에테르계 및 알코올계 등으로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있다. In the present invention, a defoamer may be used to remove bubbles in the slurry to which the dispersant and the organic binder are applied. As the type of the antifoaming agent, for example, one or more selected from the group consisting of silicon-based, metal soap-based, amide-based, polyether-based, alcohol-based and the like can be used.
상기 소포제는 고체원료를 기준으로, 0.001 내지 1 중량부를 사용할 수 있다. The antifoaming agent may be used in 0.001 to 1 parts by weight based on the solid raw material.
본 발명에서 유기결합제(organic binder)는 슬러리에 가소성 및 유동성을 부여하고, 궁국적으로는 분무건조 시 성형된 고체 입자에 강도를 부여함으로써, 건조 및 소성 전에 상기 입자의 취급을 용이하게 할 수 있다. 본 발명에서 상기 유기결합제의 종류로는, 예를 들면, 폴리비닐알코올계, 폴리에틸렌글라이콜계 및 메틸셀룰로즈 등으로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있다.In the present invention, the organic binder imparts plasticity and fluidity to the slurry and ultimately gives strength to the solid particles formed during spray drying, thereby facilitating handling of the particles before drying and firing. . As the type of the organic binder in the present invention, for example, one or more selected from the group consisting of polyvinyl alcohol, polyethylene glycol, methyl cellulose and the like can be used.
본 발명에서 상기 유기결합제의 함량은 특별히 제한되지 않으며, 예를 들면, 고체원료를 기준으로, 0.5 내지 5 중량부를 사용할 수 있다. 상기 함량이 0.05 중량부 미만이면, 분무건조 시 성형된 고체 입자의 결합력 저하로 건조 및 소성 전까지 구형의 형상을 유지하는 것이 어려워질 우려가 있으며, 5 중량부를 초과하면 소성 후 잔여 회분에 의해 최종물질의 성능이 저하될 우려가 있다.In the present invention, the content of the organic binder is not particularly limited. For example, 0.5 to 5 parts by weight may be used based on the solid raw material. When the content is less than 0.05 parts by weight, it may be difficult to maintain the spherical shape before drying and firing due to a decrease in the bonding strength of the molded solid particles during spray drying, if the content exceeds 5 parts by weight of the final material by the residual ash after firing There is a fear that the performance of the.
본 발명에서 산소공여입자를 제조하는 방법은 특별히 제한되지 않는다. 본 발명에서는, 예를 들면, (A) 고체원료로서 전술한 산소공여입자 원료 조성물을 용매와 혼합하여 혼합물을 제조하는 단계; The method for producing the oxygen donor particles in the present invention is not particularly limited. In the present invention, for example, (A) preparing a mixture by mixing the above-described oxygen donor particle raw material composition with a solvent as a solid raw material;
(B) 균질화된 슬러리를 제조하는 단계; (B) preparing a homogenized slurry;
(C) 슬러리를 분무건조하여 고체 입자를 성형하는 단계; 및 (C) spray drying the slurry to form solid particles; And
(D) 성형된 고체 입자를 건조 소성시켜 산소공여입자를 제조하는 단계를 포함하는 방법으로 제조할 수 있다. (D) may be prepared by a method comprising the step of dry firing the molded solid particles to produce oxygen donor particles.
본 발명의 단계 (A)에서 혼합물은 앞에서 전술한 고체원료를 용매에 혼합하여 제조할 수 있다.In step (A) of the present invention, the mixture may be prepared by mixing the aforementioned solid raw material in a solvent.
상기 고체원료는 활성물질 및 지지체 원료를 포함할 수 있고, 상기 활성물질 및 지지체 원료는 앞에서 전술한 종류를 제한 없이 사용할 수 있으며, 그 함량도 앞에서 전술한 함량 범위 내에서 사용할 수 있다.The solid raw material may include an active material and a support material, the active material and the support material may be used without limitation the above-described type, the content may also be used within the above-described content range.
본 발명에서 용매는 앞에서 전술한 종류를 제한 없이 사용할 수 있으며, 구체적으로는 물을 사용할 수 있다.In the present invention, the solvent may be used without limitation the above-described type, specifically, water may be used.
또한, 본 발명에서 고체원료의 함량은 전술한 바와 같이, 슬러리 조성물에 대하여 15 내지 50 중량부일 수 있다.In addition, the content of the solid raw material in the present invention may be 15 to 50 parts by weight based on the slurry composition.
본 발명에 따른 단계 (B), 즉 균질화된 슬러리를 제조하는 단계는 슬러리에 분산제, 소포제 및 유기결합제로 이루어진 그룹으로부터 선택된 하나 이상의 유기첨가제를 첨가하는 단계; 및 Step (B) according to the invention, ie preparing a homogenized slurry, comprises adding to the slurry at least one organic additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder; And
상기 슬러리를 교반하고 분쇄하는 단계로 이루어질 수 있다.The slurry may be stirred and pulverized.
본 발명의 혼합물에 유기첨가제를 첨가하는 단계에서 유기첨가제로는 분산제, 소포제 및 유기결합제로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있으며, 바람직하게는 상기를 모두 사용할 수 있다. 상기 분산제, 소포제 및 유기결합제는 앞에서 전술한 종류를 제한없이 사용할 수 있으며, 그 함량도 전술한 바와 같다. In the step of adding the organic additive to the mixture of the present invention, as the 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 of the above may be used. The dispersant, the antifoaming agent and the organic binder may be used without limitation the above-described kind, the content thereof is as described above.
본 발명에서 교반은 혼합물에 포함되는 성분들을 첨가하는 과정 또는/및 모두 첨가된 상태에서 이루어질 수 있다. 이 때, 교반은 교반기를 사용하여 수행할 수 있다. In the present invention, agitation may be performed in the process of adding the components included in the mixture and / or in a state where all of them are added. At this time, stirring may be performed using a stirrer.
본 발명에서는 분쇄를 수행함으로써, 고체원료 입자를 슬러리 내에 더욱 균질하게 분산시킬 수 있다. 본 발명에서는 상기 분쇄 시, 필요에 따라 추가의 소포제 및 분산제를 첨가할 수 있다. In the present invention, by pulverizing, the solid raw material particles can be more homogeneously dispersed in the slurry. In the present invention, when the above grinding, additional antifoaming agent and dispersant may be added if necessary.
본 발명에서는 분쇄효과를 향상시키고, 건식 분쇄 시 발생하는 입자의 날림 등의 문제를 해결하기 위하여 습식 분쇄(Wet milling) 방법을 사용할 수 있다. In the present invention, a wet milling method may be used to improve the grinding effect and to solve problems such as blowing of particles generated during dry grinding.
분쇄가 완료된 슬러리는 분산제, 소포제 또는 추가의 용매를 사용하여 농도 및 점도 등의 특징을 조절할 수 있다. The pulverized slurry can be characterized by using a dispersant, antifoaming agent or additional solvent to adjust characteristics such as concentration and viscosity.
한편, 고체원료 입자의 입경이 수 마이크론 이하이면, 분쇄과정을 생략할 수도 있다. On the other hand, if the particle size of the solid raw material particles are several microns or less, the grinding process may be omitted.
본 발명에서는 교반 및 분쇄된 슬러리 중의 이물질을 제거하는 단계를 추가로 수행할 수 있다. 상기 단계를 통하여, 분무 성형 시 노즐 막힘 등의 원인이 될 수 있는 이물질 또는 덩어리진 원료를 제거할 수 있다. 상기 이물질의 제거는 체거름을 통해 수행될 수 있다. In the present invention, a step of removing foreign matter in the stirred and pulverized slurry may be further performed. Through the above step, it is possible to remove the foreign matter or agglomerated raw materials that may cause clogging of the nozzle during spray molding. Removal of the foreign matter may be carried out through sieving.
본 발명에 의해 제조된 최종 슬러리의 유동성에 대한 특별한 제한은 없으며, 펌프로 이송이 가능하다면 어떤 점도도 가능하다.There is no particular limitation on the flowability of the final slurry produced by the present invention, and any viscosity is possible if it can be transferred to a pump.
본 발명의 단계 (C)는 슬러리를 분무건조하여 고체 입자로 성형하는 단계로, 상기 슬러리의 성형은 분무건조기를 사용하여 수행할 수 있다. Step (C) of the present invention is a step of spray drying the slurry to form the solid particles, the molding of the slurry can be carried out using a spray dryer.
상기 단계는 슬러리를 펌프를 이용해 분무건조기로 이송시킨 뒤, 상기 이송된 슬러리 조성물을 펌프 등을 통해 분무건조기 내로 분사함으로써 고체 입자를 성형할 수 있다. In the step, the slurry may be transferred to a spray dryer using a pump, and then the solid slurry may be molded by spraying the transferred slurry composition into the spray dryer through a pump or the like.
본 발명의 분무건조기에서 산소공여입자를 성형하기 위한 상기 분무건조기의 운전조건은 이 분야에서 일반적으로 사용되는 운전조건을 적용할 수 있다.The operating conditions of the spray dryer for forming the oxygen donor particles in the spray dryer of the present invention can be applied to the operating conditions generally used in this field.
본 발명에서 단계 (D)는 단계 (C)에서 제조된 고체 입자를 건조 소성시켜 산소공여입자를 제조하는 단계이다. In the present invention, step (D) is a step of preparing the oxygen donor particles by dry firing the solid particles prepared in step (C).
상기 단계 (D)에서는 성형된 고체 입자를 건조한 후, 소성시켜 산소공여입자를 제조할 수 있다.In the step (D), the molded solid particles may be dried and then fired to prepare oxygen donor particles.
본 발명에서 건조는 성형된 고체 입자를 110 내지 150℃의 환류 건조기에서 2 내지 24시간 동안 건조하여 수행할 수 있다. 이 때, 건조는 공기 분위기에서 이루어 진다.Drying in the present invention may be carried out by drying the molded solid particles in a reflux dryer of 110 to 150 ℃ for 2 to 24 hours. At this time, drying is performed in an air atmosphere.
상기 건조가 완료되면, 건조된 입자를 고온 소성로에 넣고 1 내지 5 ℃/min의 속도로 최종 소성 온도를 1000 내지 1400℃까지 상승시킨 뒤, 2 내지 10 시간 동안 소성시킨다. 본 발명에서는 최종 소성 온도에 이르기까지 2 단계 이상의 정체 온도에서 각 30 분 이상의 정체 구간을 부여한 뒤 소성할 수 있다. When the drying is completed, the dried particles are placed in a high temperature baking furnace to raise the final firing temperature to 1000 to 1400 ℃ at a rate of 1 to 5 ℃ / min, and then fire for 2 to 10 hours. In the present invention, after the stagnation section of each 30 minutes or more at the stagnation temperature of two or more steps up to the final firing temperature can be baked.
본 발명에서 소성은 박스형로(muffle furnace), 튜브형로(tubular furnace) 또는 킬른(kiln) 등의 소성로를 사용할 수 있다. In the present invention, firing may use a firing furnace such as a muffle furnace, a tubular furnace, or a kiln.
본 발명에서는 상기 소성에 의해, 슬러리의 제조 시 투입된 유기첨가제(분산제, 소포제 및 유기결합제)는 연소되고, 원료물질들 간의 결합이 이루어져 입자의 강도가 향상하게 된다.In the present invention, by the firing, the organic additives (dispersant, antifoaming agent and organic binder) introduced during the preparation of the slurry are burned, and the strength of the particles is improved by bonding between the raw materials.
또한, 본 발명은 금속 산화물을 함유하는 활성물질; 및In addition, the present invention is an active material containing a metal oxide; And
하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 산소공여입자 원료 조성물을 사용하여 제조된 산소공여입자에 관한 것이다. An oxygen donor particle prepared using an oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
본 발명에 따른 산소공여입자의 형상은 구형일 수 있다. 상기 형상이 구형이 아닌 도우넛 형 또는 홈이 파인 형태일 경우, 입자의 마모손실이 커지게 된다.The shape of the oxygen donor particles according to the present invention may be spherical. If the shape is not spherical, but donut-shaped or grooved, the wear loss of the particles is increased.
그리고, 상기 산소공여입자의 평균입자크기 및 입자분포는, 예를 들면, 각각 50 내지 150 ㎛ 및 30 내지 400 ㎛ 일 수 있다.The average particle size and particle distribution of the oxygen donor particles may be, for example, 50 to 150 μm and 30 to 400 μm, respectively.
본 발명의 산소공여입자의 충진밀도는, 예를 들면, 1.0 내지 3.0 g/cc 일 수 있다. The packing density of the oxygen donor particles of the present invention may be, for example, 1.0 to 3.0 g / cc.
또한, 상기 산소공여입자의 기공도는 5 내지 80%이고, 비표면적은 0.1 내지 100 m2/g일 수 있다. In addition, the porosity of the oxygen donor particles is 5 to 80%, the specific surface area may be 0.1 to 100 m 2 / g.
본 발명에서 내마모도는 마모지수(AI)로 표현되며, 상기 마모지수가 낮을수록 내마모도가 좋다는 것을 의미한다. 상기 산소공여입자의 내마모도는, 40% 이하일 수 있다. 상기 내마모도가 40%를 초과하면, 미세분말 등이 많이 발생하여 순환유동층 공정 등에 사용하기 어렵다. 본 발명에서 상기 내마모도의 하한은 특별히 제한되지 않으며, 0%에 근접할수록 좋다.In the present invention, the wear resistance is represented by the wear index (AI), the lower the wear index means that the wear resistance is better. The wear resistance of the oxygen donor particles may be 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. In the present invention, the lower limit of the wear resistance is not particularly limited, and the closer to 0%, the better.
또한, 본 발명에서, 산소공여입자의 산소전달능력은 특별히 제한되지 않으며, 예를 들면, 1 wt% 내지 17 wt% 일 수 있다.In addition, in the present invention, the oxygen transfer capacity of the oxygen donor particles is not particularly limited, for example, may be 1 wt% to 17 wt%.
또한, 본 발명은 금속 산화물을 함유하는 활성물질; 및In addition, the present invention is an active material containing a metal oxide; And
하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 산소공여입자 원료 조성물을 사용하여 제조된 산소공여입자를 기체연료와 반응시켜 상기 산소공여입자를 환원시키고 연료가스를 연소시키는 단계; 및 Oxygen donor particles prepared using an oxygen donor particle raw material composition comprising a support material containing a mixture of hydrotalcite or gamma alumina and hydrotalcite are reacted with gaseous fuel to reduce the oxygen donor particles and burn fuel gas. Making a step; And
상기 환원된 산소공여입자를 산소와 반응시켜 산화시키는 단계를 포함하는 매체순환식 가스연소 방법에 관한 것이다.It relates to a medium-circulating gas combustion method comprising the step of reacting the reduced oxygen donor particles with oxygen to oxidize.
여기서, 산소공여입자는 앞에서 전술한 산소공여입자를 사용할 수 있다. Here, the oxygen donor particles may use the oxygen donor particles described above.
산소공여입자를 기체연료와 반응시키면, 산소공여입자의 금속 산화물은 환원되어 금속 입자를 형성하고, 이산화탄소와 물을 발생시킨다. 상기 환원된 산소공여입자 중의 금속 입자를 산소와 반응시키면 상기 금속 입자는 산화하여 다시 금속 산화물 형태를 이루게 된다. When the oxygen donor particles are reacted with the gaseous fuel, the metal oxides of the oxygen donor particles are reduced to form metal particles and generate carbon dioxide and water. When the metal particles in the reduced oxygen donor particles react with oxygen, the metal particles are oxidized to form a metal oxide again.
본 발명의 매체순환식 가스연소 방법에서는 상기와 같은 과정을 반복하게 된다.In the medium circulation gas combustion method of the present invention, the above process is repeated.
본 발명에서 사용되는 기체연료는 특별히 제한되지 않으며, 예를 들면, 메탄, 수소, 일산화탄소, 알칸(alkane, CnH2n+2), 천연가스(LNG) 및 합성가스(syngas)로 이루어진 그룹으로부터 선택된 하나 이상일 수 있다. The gaseous fuel used in the present invention is not particularly limited, and for example, at least one selected from the group consisting of methane, hydrogen, carbon monoxide, alkanes (CnH 2 n + 2), natural gas (LNG) and syngas (syngas). Can be.
또한, 환원된 산소공여입자로의 산소의 제공은 공기를 통해 이루어 질 수 있다.In addition, the provision of oxygen to the reduced oxygen donor particles may be made through air.
본 발명은 또한, 산소공여입자를 기체연료와 반응시켜 상기 산소공여입자를 환원시키고 연료가스를 연소시키는 환원반응기; 및 상기 환원된 산소공여입자를 산소와 반응시켜 산화시키는 산화반응기를 포함하는 매체 순환식 가스연소장치에 있어서,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.
상기 산소공여입자는 금속 산화물을 함유하는 활성물질; 및 하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 산소공여입자 원료 조성물을 사용하여 제조된 것인 매체 순환식 가스연소장치에 관한 것이다.The oxygen donor particles may include an active material containing a metal oxide; And an oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
본 발명의 산소공여입자는 앞에서 전술한 산소공여입자를 사용할 수 있다. The oxygen donor particles of the present invention may use the oxygen donor particles described above.
본 발명에서 산화반응기 및 환원반응기는 서로 연결된 조합으로 구성될 수 있다.In the present invention, the oxidation reactor and the reduction reactor may be composed of a combination connected to each other.
이하, 본 발명의 일 예에 따른 산소공여입자의 제조방법을 첨부한 도면을 따라 상세하게 설명한다.Hereinafter, a method of manufacturing oxygen donor particles according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명에 따른 하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 지지체 원료로 사용하여 산화니켈(NiO) 산소공여입자를 제조하는 과정을 나타낸 공정도이다.1 is a process chart showing a process for preparing nickel oxide (NiO) oxygen donor particles using a hydrotalcite or a mixture of gamma alumina and hydrotalcite as a support material.
도 1에 나타난 바와 같이, 상기 산소공여입자의 제조는 고체원료를 물에 첨가하여 혼합하는 단계(S10), 물 및 고체원료의 혼합물을 분쇄와 분산을 통해 균질화된 슬러리로 제조하는 단계(S20), 제조된 슬러리를 분무건조시켜 산소공여입자를 성형하는 단계(S30) 및 성형된 산소공여입자를 건조 소성시켜 최종 산소공여입자를 제조하는 단계(S40)를 포함한다.As shown in Figure 1, 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).
본 발명의 도 2는 고체원료 및 물의 혼합물을 슬러리로 제조하는 과정을 나타낸 공정도이다.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.
도 2에 나타난 바와 같이, 슬러리의 제조는 고체원료를 물에 혼합하는 단계(S11), 유기첨가제를 첨가하여 물과 고체원료가 잘 혼합되도록 하는 단계(S21), 혼합된 슬러리를 분쇄 및 분산시켜 균질하고 분산된 슬러리를 제조하는 단계(S22) 및 슬러리에 포함된 이물질을 제거하는 단계(S23)로 이루어진다.As shown in Figure 2, 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).
여기서, 유기첨가제로는 분산제, 소포제 및 유기결합제로 이루어진 그룹으로부터 선택된 하나 이상을 사용할 수 있으며, 바람직하게는 모두를 사용할 수 있다. Here, as the 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.
도 3은 슬러리를 분무건조하여 산소공여입자를 성형하는 과정을 나타낸 공정도이다.3 is a process chart showing a process of forming oxygen donor particles by spray drying the slurry.
도 3에 나타난 바와 같이, 슬러리를 분무건조하여 산소공여입자를 성형하는 단계(S30)는 슬러리를 분무건조기로 이송하는 단계(S31) 및 이송된 슬러리를 분무건조기 내로 분사하여 산소공여입자를 성형하는 단계(S32)로 이루어진다.As shown in Figure 3, spray drying the slurry to form the oxygen donor particles (S30) is the step of transporting 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.
도 4는 분무건조법으로 성형된 산소공여입자를 건조 소성시켜 최종 산소공여입자를 제조하는 과정을 나타낸 공정도이다.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.
도 4에 나타난 바와 같이, 성형된 산소공여입자는 예비 건조과정(S41)을 거친 후, 소성과정(S42)을 통해 최종 산소공여입자로 제조된다.As shown in FIG. 4, the molded oxygen donor particles are prepared as final oxygen donor particles through a preliminary drying process (S41), and then calcined (S42).
본 발명에서 도 6은 매체순환식 가스연소장치의 기본 개념도이다.6 is a basic conceptual view of a medium-circulating gas combustion device.
상기에서는 기체연료로 메탄을 사용할 수 있다.In the above, methane may be used as the gaseous fuel.
환원반응기에서 산소공여입자 내의 금속 산화물(MO)은 기체연료와 반응하여 환원되고, 금속 입자(M)가 된다. 이 때, 기체연료는 연소된다.In the reduction reactor, 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.
상기 환원된 산소공여입자(M)는 산화반응기로 이동하고, 상기 산화반응기에서 공기 중의 산소와 반응하여 다시 산화된다. The reduced oxygen donor particles (M) are moved to an oxidation reactor, and reacted with oxygen in the air in the oxidation reactor to be oxidized again.
상기 산화된 산소공여입자는 환원반응기로 순환되어 위의 과정을 반복하게 된다.The oxidized oxygen donor particles are circulated to a reduction reactor to repeat the above process.
상기 환원반응기 및 금속반응기 내에서의 반응을 하기 반응식 1 및 2로 나타내었다. 하기 반응식 1은 환원반응기 내에서의 반응이며, 반응식 2는 산화반응기 내에서 일어나는 반응을 나타낸 것이다.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, and Scheme 2 shows a reaction occurring in an oxidation reactor.
<반응식 1><Scheme 1>
CH4 + 4MO → CO2 + 2H2O + 4MCH4 + 4MO → CO2 + 2H2O + 4M
<반응식 2><Scheme 2>
M + 1/2O2 → MOM + 1 / 2O2 → MO
<실시예><Example>
실시예 1Example 1
총 질량이 8 kg이 되도록 산화니켈(순도 98% 이상, 분말형태) 70 중량부 및 하이드로탈사이트(Al2O3:MgO = 7:3, 비표면적 277㎡/g) 30 중량부를 혼합하여 고체원료를 제조하였다. A solid raw material was prepared by mixing 70 parts by weight of nickel oxide (purity 98% or more, powder form) and 30 parts by weight of hydrotalcite (Al 2 O 3: MgO = 7: 3, specific surface area 277㎡ / g) so that the total mass was 8 kg. It was.
물에 고체원료를 교반기로 교반하면서 첨가하여 혼합 슬러리를 제조하였다. 여기서, 혼합 슬러리 100 중량부에 대하여, 고체원료의 함량은 40 내지 50 중량부였다. 이 과정에서 분산제(음이온계 계면활성제) 및 소포제(금속비누계)를 첨가하였다. 상기 혼합 슬러리를 3차례에 걸쳐 고에너지볼밀(High Energy Ball Mill)로 분쇄하였다. 상기 과정에서 2차 분쇄 후 폴리에틸렌글라이콜계의 유기결합제를 첨가하고 3차 분쇄를 진행하여 안정되고 균질한 유동성 콜로이드 슬러리(colloidal slurry)를 제조하였다. 분쇄를 마친 슬러리를 체거름을 통해 이물질을 제거하고 측정한 최종 슬러리 고체농도는 34.8 중량부였다.A solid slurry was added to water while stirring with a stirrer to prepare a mixed slurry. Here, the content of the solid raw material was 40 to 50 parts by weight based on 100 parts by weight of the mixed slurry. In this process, a dispersant (anionic surfactant) and an antifoaming agent (metal soap system) were added. The mixed slurry was ground three times in a high energy ball mill. In the above process, after the second grinding, a polyethylene glycol-based organic binder was added and the third grinding was performed to prepare a stable and homogeneous colloidal slurry. The final slurry solids concentration was 34.8 parts by weight after removing the foreign matter by sieving the slurry after the grinding.
상기 제조된 콜로이드 슬러리를 펌프로 분무건조기로 이송하고 분무건조하여 제조한 산소공여입자를 120℃의 공기분위기 환류 건조기에서 2시간 이상 동안 건조하고, 소성로에서 공기 분위기에서 승온 속도 5 ℃/min으로 1300℃까지 올린 후, 5시간 동안 소성하여 산소공여입자를 제조하였다. 소성온도에 도달하기 전 200℃, 400℃, 500℃ 및 650℃ 온도에서 각각 1시간 정도 등온으로 유지하였다. 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 at least 2 hours, and at a heating temperature of 5 ° C./min in an air atmosphere in a kiln at 1300 ° C./min. After raising to ℃, it was calcined for 5 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.
상기 산소공여입자의 제조에 사용된 성분들의 함량 및 슬러리 특성을 하기 표 1에 나타내었다.The content and slurry properties of the components used to prepare the oxygen donor particles are shown in Table 1 below.
실시예 2 내지 7 및 비교예 1 내지 3Examples 2 to 7 and Comparative Examples 1 to 3
실시예 1과 같은 방법으로 산소공여입자를 제조하되, 제조에 사용된 성분들의 함량 및 슬러리 특성을 하기 표 1에 나타내었다.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.
표 1
산소공여입자(Oxygen Carrier) 실시예 1 실시예 2 실시예 3 실시예 4 실시예5 실시예6 실시예7
NiO, 중량부 70 70 70 61 65
Mn3O4, 중량부 5 70 61
하이드로탈사이트, 중량부 30 15 25 39 21 30 39
γ-Al2O3, 중량부 15 14
α-Al2O3, 중량부
MgO, 중량부
MgAl2O4 중량부
총 고체 함량, 중량부 100 100 100 100 100 100 100
분산제, 중량부 0.2 0.2 0.2 0.2 0.2 0.2 0.2
소포제, 중량부 0.1 0.1 0.1 0.1 0.1 0.1 0.1
유기결합제, 중량부 2.0 1.5 3.0 2.2 2.3 3.0 2.6
슬러리 고체농도, 중량부 34.8 37.3 35.8 25.2 36.6 46.5 27.8
Table 1
Oxygen Carrier Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
NiO, parts by weight 70 70 70 61 65
Mn 3 O 4 , parts by weight 5 70 61
Hydrotalcite, parts by weight 30 15 25 39 21 30 39
γ-Al 2 O 3 , parts by weight 15 14
α-Al 2 O 3 , parts by weight
MgO, parts by weight
MgAl 2 O 4 parts by weight
Total solids content, parts by weight 100 100 100 100 100 100 100
Dispersant, parts by weight 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Antifoam, weight part 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Organic binder, parts by weight 2.0 1.5 3.0 2.2 2.3 3.0 2.6
Slurry solid concentration, parts by weight 34.8 37.3 35.8 25.2 36.6 46.5 27.8
표 2
산소공여입자(Oxygen Carrier) 비교예 1 비교예 2 비교예 3
NiO, 중량부 70 70
Mn3O4, 중량부 70
하이드로탈사이트, 중량부
γ-Al2O3, 중량부
α-Al2O3, 중량부 21.5
MgO, 중량부 8.5
MgAl2O4 중량부 30 30
총 고체 함량, 중량부 100 100 100
분산제, 중량부 0.2 0.2 0.2
소포제, 중량부 0.1 0.1 0.1
유기결합제, 중량부 1.0 3.8 3.0
슬러리 고체농도, 중량부 35.2 60.4 41.4
TABLE 2
Oxygen Carrier Comparative Example 1 Comparative Example 2 Comparative Example 3
NiO, parts by weight 70 70
Mn 3 O 4 , parts by weight 70
Hydrotalcite, parts by weight
γ-Al 2 O 3 , parts by weight
α-Al 2 O 3 , parts by weight 21.5
MgO, parts by weight 8.5
MgAl 2 O 4 parts by weight 30 30
Total solids content, parts by weight 100 100 100
Dispersant, parts by weight 0.2 0.2 0.2
Antifoam, weight part 0.1 0.1 0.1
Organic binder, parts by weight 1.0 3.8 3.0
Slurry solid concentration, parts by weight 35.2 60.4 41.4
실험예Experimental Example
(1) 산소공여입자의 형상 측정(1) Measurement of shape of oxygen donor particles
산소공여입자의 형상은 산업용 현미경을 이용하여 측정하였다.The shape of the oxygen donor particles was measured using an industrial microscope.
(2) 평균 입자 크기 및 입자 크기 분포의 측정(2) measurement of average particle size and particle size distribution
산소공여입자의 평균 입자 크기 및 입자 크기 분포는 ASTM E-11에 따라 표준 체를 이용하여 측정하였다. Average particle size and particle size distribution of the oxygen donor particles were measured using a standard sieve according to ASTM E-11.
(3) 충진 밀도 측정 (3) filling density measurement
산소공여입자의 충진 밀도는 ASTM D 4164-88에 따라 탭(tap) 밀도계(Quantachrome Autotap)을 사용하여 측정하였다. The packing density of the oxygen donor particles was measured using a tap density meter (Quantachrome Autotap) according to ASTM D 4164-88.
(4) Hg 기공도 측정(4) Hg porosity measurement
산소공여입자의 Hg 기공도는 기공 측정기 (Micromeritics, AutoPore IV 9500)를 사용하여 측정하였다. Hg porosity of oxygen donor particles was measured using a pore meter (Micromeritics, AutoPore IV 9500).
(5) 비표면적(BET) 측정(5) Measurement of specific surface area (BET)
산소공여입자의 비표면적은 비표면적분석기(Micromeritics, ASAP 2420)를 사용하여 측정하였다.The specific surface area of the oxygen donor particles was measured using a specific surface area analyzer (Micromeritics, ASAP 2420).
(6) 내마모도(AI) 측정(6) Wear resistance (AI) measurement
산소공여입자의 내마모도는 ASTM D 5757-95에 따라 마모 시험기로 측정하였다. 마모 지수(AI)는 상기 ASTM 방법에 기재된 대로 5시간에 걸쳐 10 slpm (분당 표준 부피)에서 결정하였으며, 상기 마모 지수는 5시간에 걸쳐 발생된 미세분말(fine)의 비율로 나타낸다. 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 is expressed as the percentage of fines generated over 5 hours.
고속 유동층 반응기에서 30% 미만, 나아가 버블링 유동층 반응기에서 60% 미만의 마모지수(AI)를 갖는 물질은 대기압에서도 충분히 사용 가능하고, 이 물질은 유동층 매체순환공정 및 매체순환개질 공정에서도 사용 가능하다. 마모지수(AI)가 낮을수록 벌크 입자의 내마모도는 향상한다.Materials with a wear index (AI) of less than 30% in high speed fluidized bed reactors and even less than 60% in bubbling fluidized bed reactors are fully usable at atmospheric pressure and can also be used in fluidized bed media and process reforming processes. . The lower the wear index (AI), the better the wear resistance of the bulk particles.
(7) 산소전달능력 측정(7) Oxygen Transport Capacity Measurement
산소공여입자의 산소전달능력(oxygen transfer capacity)은 열중량 분석법(thermogravimetric analysis, TGA)을 사용하여 평가하였다. 상기 산소공여입자의 환원반응에 사용한 반응가스의 조성은 실시예 1, 2, 3, 4, 5 및 비교예 1, 2에서는 10 vol% CH4, 90 vol% CO2 였고, 실시예 6, 7 및 비교예 3에서는 60 vol% CO, 30 vol% H2, 10 vol% CO2 였다. 또한, 환원된 산소공여입자를 산화시키기 위한 반응가스로는 공기를 사용하였다. 산화반응과 환원반응 사이에는 100% 질소를 공급하여 연료와 공기가 반응기 내에서 직접 접촉하지 않도록 하였다. 실험에 사용한 산소공여입자 샘플량은 약 30 mg이었다. 각 반응 가스의 유량은 150 std ml/분이었고, 산소공여입자의 산화/환원 반응을 최소 5회 이상 반복 실시하여 산소전달능력을 측정하였으며, 여기서 산소전달능력은 원료에 포함된 금속산화물의 중량을 기준으로 산소공여입자가 완전히 산화되었을 때의 이론적인 최대 산소공여입자 무게에서 주어진 실험조건에서 산소공여입자의 환원반응이 종료되었을 때 측정된 산소공여입자 무게를 감하여 얻은 무게변화량을 산소공여입자가 완전히 산화되었을 때의 이론적인 최대 산소공여입자 무게로 나누어 무게백분율로 표시한 값이다.Oxygen transfer capacity of oxygen donor particles was evaluated using thermogravimetric analysis (TGA). The composition of the reaction gas used for the reduction reaction of the oxygen donor particles was 10 vol% CH4, 90 vol% CO2 in Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, and Comparative Examples 6, 7 and In Example 3, it was 60 vol% CO, 30 vol% H2, and 10 vol% CO2. In addition, air was used as a 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 is determined by the weight of the metal oxide included in the raw material. Based on the theoretical maximum oxygen donor particle weight when the oxygen donor particle is completely oxidized, the oxygen donor particle completely subtracts the weight change obtained by subtracting the weight of the oxygen donor particle measured at the end of the reduction reaction of the oxygen donor particle under the given experimental conditions. It is expressed as a percentage by weight divided by the theoretical maximum oxygen donor particle weight when oxidized.
상기 실시예 1 내지 7 및 비교예 1 내지 3의 물성 및 산소전달능력을 측정하여 측정된 결과를 하기 표 3에 나타냈다.The results measured by measuring the physical properties and oxygen transfer capacity of the Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Table 3 below.
표 3
소성온도,℃ 형상 평균입자크기,㎛ 입자크기분포 충진밀도,g/ml Hg기공도,% 비표면적(BET),m2/g 내마모도(AI),% 산소전달능력,wt%
실시예 1 1300 구형 114 41.5-302.5 2.57 23.1 1.1 12.8 14.3
실시예 2 1300 구형 93 41.5-302.5 2.13 16.6 1.6 27.0 13.6
실시예 3 1200 구형 94 49.0-302.5 2.89 5.3 0.1 2.2 15.7
실시예 4 1200 구형 78 37.0-231.0 1.89 22.1 4.7 13.1 13.2
실시예 5 1300 구형 86 37.0-196.0 2.17 19.4 2.1 26.4 12.9
실시예 6 1000 구형 98 41.5-302.5 1.84 16.0 0.70 21.2 6.4
1100 구형 97 41.5-231.0 2.21 7.7 0.16 2.3 6.4
실시예 7 1100 구형 100 37.0-302.5 2.09 10.8 0.34 3.9 6.0
비교예 1 1300 구형 112 41.5-302.5 1.78 24.4 1.7 70.2 -
1400 구형 110 41.5-302.5 2.0 22.1 1.5 44.1 13.4
비교예 2 1300 구형 112 49.0-231.0 2.33 10.0 0.5 50.7 -
1400 구형 99 41.5-231.0 2.60 10.2 0.21 22.1 14.0
비교예 3 1100 구형 126 58.0-302.5 1.36 - - 86.0 -
1300 구형 122 49.0-302.5 1.61 2.8 0.24 27.2 4.7
TABLE 3
Firing temperature, ℃ shape Average particle size, ㎛ Particle Size Distribution Filling density, g / ml Hg porosity,% Specific Surface Area (BET), m 2 / g Wear resistance (AI),% Oxygen transfer capacity, wt%
Example 1 1300 rectangle 114 41.5-302.5 2.57 23.1 1.1 12.8 14.3
Example 2 1300 rectangle 93 41.5-302.5 2.13 16.6 1.6 27.0 13.6
Example 3 1200 rectangle 94 49.0-302.5 2.89 5.3 0.1 2.2 15.7
Example 4 1200 rectangle 78 37.0-231.0 1.89 22.1 4.7 13.1 13.2
Example 5 1300 rectangle 86 37.0-196.0 2.17 19.4 2.1 26.4 12.9
Example 6 1000 rectangle 98 41.5-302.5 1.84 16.0 0.70 21.2 6.4
1100 rectangle 97 41.5-231.0 2.21 7.7 0.16 2.3 6.4
Example 7 1100 rectangle 100 37.0-302.5 2.09 10.8 0.34 3.9 6.0
Comparative Example 1 1300 rectangle 112 41.5-302.5 1.78 24.4 1.7 70.2 -
1400 rectangle 110 41.5-302.5 2.0 22.1 1.5 44.1 13.4
Comparative Example 2 1300 rectangle 112 49.0-231.0 2.33 10.0 0.5 50.7 -
1400 rectangle 99 41.5-231.0 2.60 10.2 0.21 22.1 14.0
Comparative Example 3 1100 rectangle 126 58.0-302.5 1.36 - - 86.0 -
1300 rectangle 122 49.0-302.5 1.61 2.8 0.24 27.2 4.7
도 5는 본 발명의 실시예 및 비교예에 따른 산소공여입자의 산업용 현미경 사진을 나타낸다. 상기 도 5 상기 도 5에서 A는 실시예 1, B는 실시예 2, C는 실시예 3, D는 실시예 4, E는 실시예 5, F는 실시예 6, G는 실시예 7, H는 비교예 1, I는 비교예 2 및 J는 비교예 3의 산소공여입자를 나타낸다. 상기 도에서 보이는 바와 같이, 실시예 및 비교예에 의해 제조된 산소공여입자는 구형의 형상을 지닌다. Figure 5 shows an industrial micrograph of the oxygen donor particles according to the Examples and Comparative Examples of the present invention. 5, A is Example 1, B is Example 2, C is Example 3, D is Example 4, E is Example 5, F is Example 6, and G is Example 7, H. Is Comparative Example 1, I is Comparative Example 2 and J represents the oxygen donor particles of Comparative Example 3. As shown in the figure, the oxygen donor particles produced by Examples and Comparative Examples have a spherical shape.
상기 표 2에서 보는 바와 같이, 활성물질로 산화니켈(NiO) 및/또는 산화망간(Mn3O4)을 사용하고, 지지체 원료로 하이드로탈사이트를 사용하는 실시예에 따른 산소공여입자는 1300℃ 이하의 소성온도에서 제조되어도 유동층 공정에 적합한 조건들을 갖추고 있음을 알 수 있다. 즉, 산소공여입자의 형상은 구형, 평균 입자크기는 78 내지 115 ㎛, 입자크기 분포는 37.0 내지 302.5 ㎛, 충진밀도는 1.8 내지 2.9 g/ml, Hg 기공도는 5% 이상, 비표면적은 0.1 ㎡/g이상, 마모지수는 40%이하 및 산소전달능력은 5 wt% 이상이다.As shown in Table 2, the oxygen donor particles according to the embodiment using nickel oxide (NiO) and / or manganese oxide (Mn 3 O 4) as the active material, and using hydrotalcite as the support material is calcined at 1300 ℃ or less Even when manufactured at a temperature, it can be seen that they have suitable conditions for the fluidized bed process. That is, the shape of the oxygen donor particles is spherical, the average particle size is 78 to 115 ㎛, the particle size distribution is 37.0 to 302.5 ㎛, the filling density is 1.8 to 2.9 g / ml, Hg porosity is 5% or more, specific surface area is 0.1 More than m 2 / g, wear index is less than 40% and oxygen transfer capacity is more than 5 wt%.
지지체 원료로 알파알루미나(α-Al2O3)와 마그네시아(MgO)의 혼합물을 사용한 비교예 1 및 지지체 원료로 마그네슘알루미네이트(MgAl2O4)를 사용한 비교예 2의 경우, 1,300℃의 소성온도에서 내마모도가 각각 70.2% 및 50.7%로 실시예 1 내지 5에 비해 높은 값을 가졌으며, 실시예와 비슷한 값의 내마모도를 갖기 위해서는 소성온도를 1400℃ 이상으로 유지해야 하는 것으로 나타났다. 즉, NiO를 활성물질로 사용한 산소공여입자 제조 시 지지체 원료로 하이드로탈사이트를 사용할 경우 기존보다 낮은 소성온도에서 유동층 공정에 필요한 충분한 강도를 얻을 수 있다. In Comparative Example 1 using a mixture of alpha alumina (α-Al 2 O 3) and magnesia (MgO) as the support material and Comparative Example 2 using magnesium aluminate (MgAl 2 O 4) as the support material, the wear resistance was 70.2 at a firing temperature of 1,300 ° C., respectively. % And 50.7% had a higher value than Examples 1 to 5, and it was shown that the firing temperature should be maintained at 1400 ° C. or more in order to have a wear resistance similar to that of Example. That is, when hydrotalcite is used as a support material for preparing oxygen donor particles using NiO as an active material, sufficient strength required for the fluidized bed process at a lower firing temperature than before can be obtained.
또한, 활성물질로 산화망간(Mn3O4)을 사용하고, 지지체 원료로 마그네슘알루미네이트(MgAl2O4를 사용한 비교예 3의 경우에도, 활성물질로 산화망간(Mn3O4)을 사용하고, 지지체 원료로 하이드로탈사이트를 사용한 실시예 6 및 7에 비해 충분한 강도를 얻기 위해서는 더 높은 소성온도를 필요로 한다. In addition, in the case of Comparative Example 3 using manganese oxide (Mn3O4) as the active material, magnesium aluminate (MgAl2O4) as the support material, manganese oxide (Mn3O4) as the active material, and hydrotalcite as the support material Higher firing temperatures are required to obtain sufficient strength compared to Examples 6 and 7 used.
이상에서 설명한 바와 같이, 본 발명에 따른 바람직한 실시예를 기초로 설명하였으나, 본 발명은 특정 실시예에 한정되는 것은 아니며, 해당분야 통상의 지식을 가진 자가 특허청구범위 내에서 기재된 범주내에서 변경할 수 있다.As described above, the present invention has been described based on the preferred embodiments, but the present invention is not limited to the specific embodiments, and can be changed within the scope described in the claims by those skilled in the art. have.
본 발명은 산소공여입자의 지지체 원료로 하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 사용함으로써, 마그네슘(Mg) 성분을 포함하는 산소공여입자를 종래 기술에 비해 더 낮은 소성온도에서도 강도 등의 물리적 특성이 유동층 공정에 적합하고, 반응성이 우수한 산소공여입자를 제공할 수 있다.According to the present invention, by using hydrotalcite or a mixture of gamma alumina and hydrotalcite as a support material for oxygen donor particles, the oxygen donor particles containing magnesium (Mg) components may be used at lower firing temperatures than at the prior art. It is possible to provide oxygen donor particles having good physical properties and suitable for fluidized bed process and having high reactivity.

Claims (22)

  1. 금속 산화물을 함유하는 활성물질; 및Active materials containing metal oxides; And
    하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 산소공여입자 원료 조성물.An oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
  2. 제 1 항에 있어서, The method of claim 1,
    금속 산화물은 구리계, 니켈계, 철계, 망간계 및 코발트계 산화물로 이루어진 그룹으로부터 선택된 하나 이상을 포함하는 산소공여입자 원료 조성물.The metal oxide is an oxygen donor particle raw material composition comprising at least one selected from the group consisting of copper, nickel, iron, manganese and cobalt oxide.
  3. 제 1 항에 있어서,The method of claim 1,
    산소공여입자 원료 조성물에 대하여 활성물질로 금속산화물 50 내지 80 중량부, 지지체로 감마알루미나 0 내지 45 중량부 및 하이드로탈사이트 5 내지 50 중량부를 포함하는 산소공여입자 원료 조성물.An oxygen donor particle raw material composition comprising 50 to 80 parts by weight of a metal oxide as an active material, 0 to 45 parts by weight of gamma alumina and 5 to 50 parts by weight of hydrotalcite as an active material with respect to the oxygen donor particle raw material composition.
  4. 고체원료로서 제 1 항에 따른 산소공여입자 원료 조성물 및 용매를 포함하는 슬러리 조성물.Slurry composition comprising the oxygen donor particle raw material composition according to claim 1 and a solvent as a solid raw material.
  5. 제 4 항에 있어서, The method of claim 4, wherein
    슬러리 조성물에 대하여 고체원료를 15 내지 50 중량부를 포함하는 슬러리 조성물.Slurry composition comprising 15 to 50 parts by weight of the solid raw material relative to the slurry composition.
  6. 제 4 항에 있어서, The method of claim 4, wherein
    분산제, 소포제 및 유기결합제로 이루어진 그룹으로부터 선택된 하나 이상의 유기첨가제를 추가로 포함하는 슬러리 조성물.Slurry composition further comprising at least one organic additive selected from the group consisting of dispersants, defoamers and organic binders.
  7. 제 6 항에 있어서, The method of claim 6,
    분산제는 음이온계 계면활성제, 양이온계 계면활성제, 양쪽성 계면활성제 및 비이온계 계면활성제로 이루어진 그룹으로부터 선택된 하나 이상을 포함하는 슬러리 조성물.A dispersant comprises at least one selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
  8. 제 6 항에 있어서,The method of claim 6,
    소포제는 실리콘계, 금속비누계, 아마이드계, 폴리에테르계 및 알코올계로 이루어진 그룹으로부터 선택된 하나 이상을 포함하는 슬러리 조성물.Antifoaming agent is a slurry composition comprising at least one selected from the group consisting of silicone, metal soap, amide, polyether and alcohol.
  9. 제 6 항에 있어서,The method of claim 6,
    유기결합제는 폴리비닐알코올계, 폴리에틸렌글라이콜계 및 메틸셀룰로즈로 이루어진 그룹으로부터 선택된 하나 이상을 포함하는 슬러리 조성물.Organic binder is a slurry composition comprising at least one selected from the group consisting of polyvinyl alcohol-based, polyethylene glycol-based and methyl cellulose.
  10. (A) 고체원료로서 제 1 항에 따른 산소공여입자 원료 조성물을 용매와 혼합하여 혼합물을 제조하는 단계; (A) preparing a mixture by mixing the oxygen donor particle raw material composition according to claim 1 with a solvent as a solid raw material;
    (B) 균질화된 슬러리를 제조하는 단계; (B) preparing a homogenized slurry;
    (C) 슬러리를 분무건조하여 고체 입자를 성형하는 단계; 및 (C) spray drying the slurry to form solid particles; And
    (D) 성형된 고체 입자를 건조 소성시켜 산소공여입자를 제조하는 단계를 포함하는 산소공여입자의 제조방법.(D) drying the calcined solid particles to produce oxygen donor particles comprising the step of producing oxygen donor particles.
  11. 제 10 항에 있어서, The method of claim 10,
    단계 (B)는, 슬러리에 분산제, 소포제 및 유기결합제로 이루어진 그룹으로부터 선택된 하나 이상의 유기첨가제를 첨가하는 단계; 및 Step (B) comprises the steps of adding to the slurry at least one organic additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder; And
    상기 슬러리를 교반하고 분쇄하는 단계를 포함하는 산소공여입자의 제조 방법.Method of producing an oxygen donor particles comprising the step of stirring and grinding the slurry.
  12. 제 11 항에 있어서, The method of claim 11,
    교반 및 분쇄된 슬러리 중의 이물질을 제거하는 단계를 추가로 포함하는 산소공여입자의 제조 방법.Method for producing oxygen donor particles further comprising the step of removing foreign matter in the stirred and pulverized slurry.
  13. 제 10 항에 있어서,The method of claim 10,
    단계 (C)는 슬러리를 분무건조기를 사용하여 성형하는 산소공여입자의 제조 방법.Step (C) is a method for producing the oxygen donor particles to form a slurry using a spray dryer.
  14. 제 10 항에 있어서, The method of claim 10,
    단계 (D)의 건조는 공기 분위기 하에서 10 내지 130℃에서 2 내지 24 시간 동안 수행되는 산소공여입자의 제조 방법.The drying of step (D) is carried out at 10 to 130 ° C. for 2 to 24 hours under an air atmosphere.
  15. 제 10 항에 있어서, The method of claim 10,
    소성은 고온 소성로에서 1 내지 5℃/min의 속도로 1000 내지 1400℃로 상승시킨 후 2 내지 10 시간 동안 수행되는 산소공여입자의 제조 방법.Firing is carried out for 2 to 10 hours after raising to 1000 to 1400 ℃ at a rate of 1 to 5 ℃ / min in a high temperature kiln.
  16. 금속 산화물을 함유하는 활성물질; 및Active materials containing metal oxides; And
    하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 산소공여입자 원료 조성물을 사용하여 제조된 산소공여입자. Oxygen donor particles prepared using an oxygen donor particle raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
  17. 제 16 항에 있어서, The method of claim 16,
    산소공여입자의 평균 입자크기는 50 내지 150 ㎛이고, 입자분포는 30 내지 400 ㎛이며, 충진밀도는 1.0 내지 3.0 g/cc인 산소공여입자.Oxygen donor particles have an average particle size of 50 to 150 µm, a particle distribution of 30 to 400 µm, and a packing density of 1.0 to 3.0 g / cc.
  18. 제 16 항에 있어서, The method of claim 16,
    산소공여입자의 기공도는 5 내지 80%이고, 비표면적은 0.1 내지 100 m2/g이며, 산소전달능력은 1 내지 17 wt%인 산소공여입자.Oxygen donor particles have a porosity of 5 to 80%, specific surface area of 0.1 to 100 m 2 / g, oxygen transfer capacity of 1 to 17 wt%.
  19. 제 16 항에 있어서, The method of claim 16,
    내마모도는 40% 이하인 산소공여입자.Abrasion resistance is less than 40% oxygen donor particles.
  20. 금속 산화물을 함유하는 활성물질; 및Active materials containing metal oxides; And
    하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 원료 조성물을 사용하여 제조된 산소공여입자를 기체연료와 반응시켜 상기 산소공여입자를 환원시키고 연료가스를 연소시키는 단계; 및 Reacting oxygen donor particles prepared using a raw material composition comprising a support material containing a hydrotalcite or a mixture of gamma alumina and hydrotalcite with gaseous fuel to reduce the oxygen donor particles and burn fuel gas; And
    상기 환원된 산소공여입자를 산소와 반응시켜 산화시키는 단계를 포함하는 매체순환식 가스연소 방법.And oxidizing the reduced oxygen donor particles with oxygen to oxidize the reduced oxygen donor particles.
  21. 제 20 항에 있어서, 기체연료는 메탄, 수소, 일산화탄소, 알칸(alkane, CnH2n+2), 천연가스(LNG) 및 합성가스(syngas) 로 이루어진 그룹으로부터 선택된 하나 이상인 매체순환식 가스연소 방법.21. The method of claim 20, wherein the gaseous fuel is at least one selected from the group consisting of methane, hydrogen, carbon monoxide, alkanes (CnH2n + 2), natural gas (LNG) and syngas.
  22. 산소공여입자를 기체연료와 반응시켜 상기 산소공여입자를 환원시키고 연료가스를 연소시키는 환원반응기; 및 상기 환원된 산소공여입자를 산소와 반응시켜 산화시키는 산화반응기를 포함하는 매체순환식 가스연소장치에 있어서,A reduction reactor for reacting oxygen donor particles with gaseous fuel to reduce the oxygen donor particles and combust the fuel gas; And a oxidation reactor for reacting the reduced oxygen donor particles with oxygen to oxidize them.
    상기 산소공여입자는 금속 산화물을 함유하는 활성물질; 및The oxygen donor particles may include an active material containing a metal oxide; And
    하이드로탈사이트 또는 감마알루미나와 하이드로탈사이트의 혼합물을 함유하는 지지체 원료를 포함하는 원료 조성물을 사용하여 제조된 것인 매체순환식 가스연소장치.A medium-circulating gas-fired apparatus, comprising a raw material composition comprising a support material containing hydrotalcite or a mixture of gamma alumina and hydrotalcite.
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CN106669680A (en) * 2016-11-25 2017-05-17 中国科学院上海高等研究院 Rod-like nanometer nickel containing metal solid solution catalyst and preparation method thereof
CN106669680B (en) * 2016-11-25 2020-08-11 中国科学院上海高等研究院 Rod-shaped nano nickel-containing metal solid solution catalyst and preparation method thereof
CN110225795A (en) * 2016-12-23 2019-09-10 Ifp新能源公司 Macropore carrier of oxygen solid with refractory matrix, preparation method and its purposes in chemical chain oxide-reduction method
CN109054756A (en) * 2018-06-21 2018-12-21 昆明理工大学 A kind of core-shell structure Fe2O3-CeO2The preparation method of/(Al@C) the high temperature composite phase-change heat-storage carrier of oxygen
CN109054755A (en) * 2018-06-21 2018-12-21 昆明理工大学 A kind of core-shell structure Fe2O3-CeO2The preparation method of/(Al@C) the heat accumulating type carrier of oxygen
CN109054755B (en) * 2018-06-21 2020-10-27 昆明理工大学 Core-shell structure Fe2O3-CeO2Preparation method of heat storage type oxygen carrier
CN109054756B (en) * 2018-06-21 2020-10-27 昆明理工大学 Core-shell structure Fe2O3-CeO2Preparation method of (Al @ C) high-temperature composite phase-change heat-storage oxygen carrier
CN112844418A (en) * 2020-12-30 2021-05-28 内蒙古大学 Mesoporous NiO-Al with alkaline carrier material2O3Molybdenum-based catalyst for preparing low-carbon alcohol from synthesis gas as carrier and preparation method thereof
CN112844418B (en) * 2020-12-30 2022-04-29 内蒙古大学 Mesoporous NiO-Al with alkaline carrier material2O3Molybdenum-based catalyst for preparing low-carbon alcohol from synthesis gas as carrier and preparation method thereof
CN112675853A (en) * 2021-01-07 2021-04-20 中国石油化工股份有限公司 Hydrogen-producing oxygen carrier and preparation method and application thereof
CN113058542A (en) * 2021-03-25 2021-07-02 四川嘉禾共聚科技有限公司 Preparation method and application of copper oxide @ hydrotalcite hybrid material

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