WO2011052825A1 - Oxygen donor particles for chemical looping combustion or chemical looping reforming, and preparation method thereof - Google Patents

Oxygen donor particles for chemical looping combustion or chemical looping reforming, and preparation method thereof Download PDF

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WO2011052825A1
WO2011052825A1 PCT/KR2009/006364 KR2009006364W WO2011052825A1 WO 2011052825 A1 WO2011052825 A1 WO 2011052825A1 KR 2009006364 W KR2009006364 W KR 2009006364W WO 2011052825 A1 WO2011052825 A1 WO 2011052825A1
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oxygen donor
oxygen
particles
donor particles
reforming
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PCT/KR2009/006364
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French (fr)
Korean (ko)
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백점인
류청걸
전원식
이중범
엄태형
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한국전력공사
한국남동발전 주식회사
한국중부발전(주)
한국서부발전 주식회사
한국남부발전 주식회사
한국동서발전(주)
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Priority to PCT/KR2009/006364 priority Critical patent/WO2011052825A1/en
Publication of WO2011052825A1 publication Critical patent/WO2011052825A1/en

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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/42—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts using moving solid particles
    • C01B3/44—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts using moving solid particles using the fluidised bed technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/725—Redox processes
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • C—CHEMISTRY; METALLURGY
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1606—Combustion processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • 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 for media circulating combustion or medium circulation reforming and a method for producing the same, in particular for minimizing the consumption of oxygen donor particles and having physical properties suitable for fluidized bed process, and for excellent media circulation combustion or media circulation reforming.
  • An oxygen donor particle and a method for producing the same are provided.
  • the largest share of anthropogenic carbon dioxide sources is coal-fired power plants that burn large amounts of fossil fuel for energy supply. Reduction of carbon dioxide emissions in the power sector can be achieved through improved power generation and consumption efficiency, increased nuclear and renewable energy, and carbon dioxide capture and storage (CCS). Post-combustion capture, pre-combustion and oxy-fuel combustion technologies are being developed as CO2 capture technologies for thermal power plants. The biggest barrier to applying this carbon dioxide capture technology to coal-fired power plants is the reduction of power generation efficiency and the increase in power generation cost.
  • CLC Chemical looping combustion
  • syngas and hydrogen production are increasing as energy sources to replace oil.
  • Current technologies for mass production of syngas and hydrogen utilize syngas obtained by gasifying coal or reforming natural gas or biogas with steam.
  • Chemical looping reforming (CLR) is drawing attention as a new method of syngas production that can produce syngas at a lower cost and reduce the energy consumption required for syngas production.
  • Medium circulation combustion and medium circulation reforming are a fluidized bed reactor in which a reaction in which oxygen is oxidized by receiving oxygen from air or water vapor and a reaction in which the medium is reduced as oxygen in the medium is transferred to the fuel
  • oxygen donor particles, a medium for obtaining oxygen from air or water vapor and delivering to fuel must satisfy various conditions suitable for fluidized bed process characteristics.
  • it must have sufficient physical properties, namely sufficient strength, suitable shape and packing density (packing density or tapped density), average particle size and particle size distribution, and pore structure favorable for diffusion of reaction gas and sufficient contact area for fluidized bed process.
  • the method of molding oxygen donor particles is impregnation, coprecipitation, physical mixing of raw materials by mixing them with water, kneading, drying and sintering and then grinding to form particles. (physical mixing method), freeze granulation method and the like were used.
  • the spray-drying method or the spin-flash drying technique which is commercially used to produce a large amount of oxygen donor particles suitable for a fluidized bed process according to the scale of the medium circulation process, has recently been used. have.
  • spherical particles are molded, which is the most suitable shape to minimize particle loss due to wear in shape. Freeze granulation and spray-drying methods are used for mass production. Drying method is more advantageous.
  • a spherical particle having a particle size distribution of several tens to hundreds of microns by spraying a slurry in which raw materials are mixed with water in a freeze granulation or spray-drying method using a nozzle.
  • additives such as antifoaming agents, organic binders and the like to make the slurry homogeneous and stable fluidity is very important. Incorrect control of the slurry properties results in the formation of particles of elliptical, donut, or grooved shapes rather than spherical shape, which causes large wear losses of the fluidized bed process.
  • An object of the present invention is to provide an oxygen donor particle for medium circulation combustion or medium circulation reforming, which has been devised to solve the above-mentioned problems, minimizes consumption, has physical properties suitable for a fluidized bed process, and is highly reactive.
  • Still another object of the present invention is to provide oxygen circulating combustion or medium circulation reforming for producing oxygen donor particles having a shape, particle size, particle size distribution, packing density, pore structure, and oxygen transfer ability suitable for a fluidized bed process. It is to provide a method for producing the particles.
  • the medium-circulating combustion or the oxygen donor particles for medium-circuit reforming are used for medium-circuit reforming for producing syngas or hydrogen through medium-circulating combustion or partial oxidation of fuel combusting gas or solid phase fuel.
  • the solid raw material of the oxygen donor particles is 40 to 80% by weight of nickel oxide (NiO) as an active material, and 20 to 60% by weight of ceramics and clays as a support for imparting specific surface area and strength. Is made of.
  • the present invention provides a method for preparing the medium-circulating combustion or medium-circulating reforming oxygen donor particles, comprising: preparing a slurry using a solid raw material, and firstly forming the oxygen donor particles using a spray spray dryer. And dry-firing the primary shaped oxygen donor particles to form the final oxygen donor particles.
  • a medium circulation combustion or medium circulation reforming oxygen donor particles according to the present invention, by improving the degree of completion of the technology development of medium circulation combustion or media circulation reform, where high-performance oxygen donor particles are essential, the existing combustion method or synthesis gas production Alternative methods can be used to separate carbon dioxide without compromising thermal efficiency, or to produce syngas at low cost.
  • the spherical shape and particle size, particle size distribution, packing density and strength, high porosity and porosity which are favorable for the fluidized bed process Oxygen donor particles having a structure and excellent oxygen transfer capacity can be prepared.
  • the present invention replaces a facility such as a thermal power plant or a cogeneration plant that requires a carbon dioxide capture facility in the future to prevent climate change due to an increase in the concentration of carbon dioxide in the atmosphere, and a facility that produces syngas through gasification of fuel or natural gas reforming. It is expected to be used in industry as a core technology of media circulation combustion and media circulation reform, which is emerging as a new technology that can be rapidly developed.
  • FIG. 1 is a process chart showing a process for producing the oxygen circulation particles for medium circulation combustion or medium circulation reforming according to the present invention.
  • FIG. 2 is a process chart showing a process for preparing a slurry using a solid raw material.
  • Figure 3 is a process diagram showing the process of primary molding oxygen donor particles.
  • Figure 4 is a process chart showing the process of forming the final oxygen donor particles by dry firing the primary molded oxygen donor particles.
  • 5 and 6 are photographs showing the shape of each oxygen donor particles prepared in the embodiment of the present invention.
  • the solid raw material constituting the oxygen circulation particles for medium circulation combustion or medium circulation reforming according to the present invention is composed of an active material and a support.
  • the active material is a metal or metal oxide capable of delivering oxygen to fuel and receiving oxygen back from air or water vapor.
  • active materials include nickel oxide (NiO) and make up 40 to 80% by weight of the total solid raw materials.
  • the support is a material that provides the pore structure necessary for diffusion and gives oxygen donor particles sufficient strength required in the fluidized bed process after firing.
  • the supporter simultaneously serves 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 suppress the aggregation of each other during the redox cycle, and serve to create a passage for gas to flow in and out (diffusion) to the outside of the particle and the active material before and after the reaction.
  • Such a support includes ceramics such as gamma alumina ( ⁇ - Al 2 O 3 ) or pseudo-boehmite, and clays include bentonite.
  • the support constitutes 20 to 60% by weight of the total solids. At this time, ceramics account for 0.1 to 60% by weight of the total solid raw materials, clays account for 0.1 to 30% by weight of the total solid raw materials.
  • an organic additive such as a dispersant, an antifoaming agent, and an organic binder is required in preparing a slurry.
  • the dispersant is used to prevent the phenomenon of agglomeration of the solid raw material particles with each other.
  • anionic and nonionic surfactants are used as the dispersant.
  • Dispersants comprise 0.01 to 10% by weight of the total solid raw material weight.
  • Anionic surfactants include poly carboxylate ammonium salts or poly carboxylate amine salts.
  • the antifoaming agent is used to suppress or remove the foam that may be generated during the slurry manufacturing process.
  • Antifoaming agents include, for example, silica-silicone, silicon-based, metal soap-based, amido-based, polyether-based, polyglycol-based, organophosphorous-based, higher alcohol-based and lactic-acid-based. These defoamers account for 0.001 to 1% by weight of the total solid raw material weight.
  • Organic binder is added in the slurry manufacturing step to impart plasticity and fluidity of the slurry, to maintain the shape of the particles during spray-drying molding, and to give strength to the oxygen donor particles after molding, thereby providing the oxygen donor particles prior to pre-drying and firing.
  • Organic binders include polyvinyl alcohols (polyvinylalcohols), polyethylene glycol (polyethyleneglycols), methyl cellulose (methylcelluloses), polyethylene oxide (polyethylenoxide) and the like. Such organic binder accounts for 0.5 to 5% by weight based on the total weight of solid raw materials.
  • FIG. 1 is a process chart showing a process for preparing oxygen donor particles for medium circulation combustion or medium circulation reforming according to the present invention.
  • the step of preparing a slurry using a solid raw material (S10) the step of spray drying the prepared slurry to primary molding the oxygen donor particles (S20) ), And drying and calcining the primary molded oxygen donor particles (S30).
  • FIG. 2 is a process chart showing a process of preparing a slurry using a solid raw material.
  • the solid raw material is mixed with water with stirring so that the concentration of the slurry (weight ratio of solid material to liquid water) is 15 to 50% by weight. At this time, the solid raw materials are prevented from agglomeration with each other and mixed together by adding a dispersant and an antifoaming agent together as organic additives for smooth mixing.
  • the slurry in which the mixing of the solid raw materials is completed is crushed to several microns ( ⁇ m) or less in the slurry using a wet mill.
  • the particles pulverized in this process are more homogeneously dispersed in the slurry, and aggregation of the particles in the slurry is suppressed by the already added dispersant, thereby producing a homogeneous and stable slurry.
  • the grinding process can be repeated several times and a dispersant and an antifoaming agent are added between each grinding process to control the fluidity of the slurry. And an organic binder is added to maintain the particle shape during spray drying.
  • the wet grinding process can be omitted.
  • the slurry is sieved to remove foreign substances or lumpy raw materials which may cause nozzle clogging during spray molding.
  • the flowability of the final slurry in the present invention and any viscosity transferable to the pump is possible.
  • FIG. 3 is a process chart showing a process of primary molding oxygen donor particles.
  • the particle size distribution of the oxygen donor particles is preferably 30 to 303 ⁇ m.
  • the fluidized slurry is sprayed by countercurrent spray method that sprays in the opposite direction to the flow of drying air using a pressurized nozzle to form oxygen donor particles.
  • the spray dryer inlet temperature is 260-300 °C and outlet temperature is 90-150 It is preferable to maintain the temperature.
  • Figure 4 is a process diagram showing the process of forming the final oxygen donor particles by dry firing the primary molded oxygen donor particles.
  • the primary molded oxygen donor particles are preliminarily dried (S31) and then molded into final oxygen donor particles through a sintering process (S32).
  • the primary molded oxygen donor particles are dried for 2 hours or more in a reflux dryer in an air atmosphere of 110 ⁇ 130 °C.
  • the pre-dried oxygen donor particles are put into a high-temperature firing furnace in an air atmosphere, and the dispersing agent is added during slurry production while firing for 2 to 10 hours at a firing temperature of 900 to 1300 ° C. at a rate of 1 to 5 ° C./min,
  • the antifoaming agent and the organic binder are combusted and the strength of the particles is improved by the bonding between the raw materials.
  • the final formed oxygen donor particles through the above process is to deliver oxygen in the range of 400 ⁇ 1400 °C, and has the conditions suitable for the fluidized bed reaction. That is, the shape of the oxygen donor particles is spherical, the average particle size is 50 ⁇ 200 ⁇ m, the particle size distribution is 30 ⁇ 500 ⁇ m, the filling density is 0.6 ⁇ 3.0g / mL, Hg porosity is more than 30% , Specific surface area is more than 0.1m2 / g, wear resistance is less than 60%, oxygen transfer capacity is more than 5wt%.
  • ⁇ - Al 2 O 3 20 having 60 to 70% by weight of NiO in powder form as an active ingredient in a total of 8 kg of solid raw materials and having a purity of at least 95% as a support and a specific surface area of 150 m 2 / g It relates to the production of oxygen donor particles having a composition ratio of 0.1 to 10% by weight of pseudo-boehmite and 0.1 to 5% by weight of sodium bentonite having a ⁇ 40% by weight, a purity of 70% or more and a specific surface area of 310 m 2 / g.
  • a mixed slurry was prepared by adding a raw material to water with stirring using a stirrer so that the slurry concentration was 33 to 35% by weight. In this process, a dispersant and an antifoam were added.
  • the mixed slurry was pulverized with a high energy ball mill three times, and after the second crushing, an antifoaming agent, a dispersant, and an organic binder were added, followed by the third pulverization to obtain a stable and homogeneous colloidal slurry. Prepared. At this time, the viscosity of the slurry is 600 ⁇ 29,000 cP, and the final slurry solid concentration was 30 ⁇ 34% by weight after removing the foreign matter through a sieve sieve pulverized slurry.
  • Oxygen donor particles prepared by transporting the stable and homogeneous fluid colloidal slurry prepared by the pump to the spray dryer and spray-dried were dried at 120 ° C. in an air atmosphere reflux dryer for 2 hours or longer, and at a heating rate of 5 ° C./min in an air atmosphere in a kiln.
  • Oxygen donor particles were prepared by raising the temperature to 950-1300 ° C. and firing for at least 4 hours. Before reaching the firing temperature, the mixture was maintained at isothermal temperature for about 1 hour at 200, 400, 500, and 650 ° C.
  • the oxygen donor particles thus prepared are labeled as A, B, C, D, E, F according to the active ingredient and the support composition. Table 1 summarizes the characteristics of the oxygen donor particles prepared in Example 1.
  • Example 1 the physical properties of the oxygen donor particles A to F prepared by molding after spray drying were characterized by the following analysis method. Specifically, the shape of the absorbent is SEM, the packing density is tap density meter (ASTM D 4164-88), the particle size and particle size distribution is the particle size analyzer (or sieve), the specific surface area and pore volume is standard BET. , Pore volume and porosity were measured using a Hg porosimeter.
  • the wear resistance of the absorbent in the fluidized bed was measured with a three-hole air-jet abrasion tester modified according to 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.
  • the wear index is expressed as the percentage of fines generated over 5 hours.
  • Materials with less than 30% AI in high speed fluidized bed reactors and even less than 60% in bubbling fluidized bed reactors can be used sufficiently at atmospheric pressure, and the materials will be able to be used in fluidized bed media circulation and media circulation reforming processes.
  • Lower wear index (AI) means better wear resistance of the bulk particles.
  • Oxygen transfer capacity of the absorbents A to F prepared in Example 1 was evaluated using thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the composition of the reaction gas used for the reduction of oxygen donor particles was 10 vol% CH 4 , 90 vol% CO 2, and air was used as a reaction gas to oxidize the reduced oxygen donor particles. 100% nitrogen was supplied between the oxidation and reduction reactions to prevent direct fuel and air contact in the reactor.
  • the sample amount of oxygen donor particles used in the experiment was about 30 mg.
  • the flow rate of each reaction gas was 150 std mL / min, and the oxygen transfer capacity was measured by repeating the oxidation / reduction reaction of the oxygen donor particles at least five times, where the oxygen transfer capacity was obtained when the oxygen donor particles were completely oxidized.
  • wear resistance means wear index (Atrition index, AI), the smaller the better the wear resistance.
  • 5 and 6 show SEM images showing that the shape of each oxygen donor particle prepared in the present invention is spherical and the particle size of the raw material in the slurry after grinding by a wet mill is several microns or less.
  • Oxygen donor particles Firing temperature, °C shape Average particle size, ⁇ m Particle size distribution, ⁇ m Filling density, g / mL Hg porosity,% Specific Surface Area (BET), m 2 / g Wear resistance (AI),% Oxygen transfer capacity, wt%
  • the oxygen donor particles prepared according to the present example have suitable conditions for the fluidized bed process. That is, the shape of the oxygen donor particles is spherical, the average particle size is within the range of 50 ⁇ 200 ⁇ m, the particle size distribution is within the range of 30 ⁇ 500 ⁇ m, the filling density is within the range of 0.6 ⁇ 3.0g / mL, Hg pores The degree is more than 30%, the specific surface area is more than 0.1m2 / g, the wear resistance is less than 60%, and the oxygen transfer capacity is 5wt% That's it.
  • the spherical shape and particle size, particle size distribution, packing density, and high porosity which are suitable for fluidized bed process, It can be seen that oxygen donor particles having a pore structure and an excellent oxygen transfer capacity that are favorable for the reaction can be prepared.
  • the existing combustion method or the synthesis gas production method is improved by improving the completion of technology development of medium-circulating combustion or medium circulation reforming, in which high-performance oxygen donor particles are essential.
  • carbon dioxide can be separated at source without lowering thermal efficiency, or syngas can be produced at low cost.
  • the spherical shape and particle size, particle size distribution, packing density and strength, high porosity and porosity which are favorable for the fluidized bed process Oxygen donor particles having a structure and excellent oxygen transfer capacity can be prepared.
  • the present invention replaces a facility such as a thermal power plant or a cogeneration plant that requires a carbon dioxide capture facility in the future to prevent climate change due to an increase in the concentration of carbon dioxide in the atmosphere, and a facility that produces syngas through gasification of fuel or natural gas reforming. It is expected to be used in industry as a core technology of media circulation combustion and media circulation reform, which is emerging as a new technology that can be rapidly developed.

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Abstract

The present invention relates to oxygen donor particles for chemical looping combustion or chemical looping reforming, having minimized consumption of oxygen donor particles, physical characteristics suitable for a fluidized bed process, and excellent reactivity. The present invention relates to oxygen donor particles used in chemical looping combustion for burning gaseous, solid fuel or chemical looping reforming for producing a synthetic gas or hydrogen through partial oxidation of fuel, wherein a solid material of the oxygen donor particles comprises 40-80 wt% of nickel oxide (NiO) as an active material, and 20-60 wt% of ceramic and clay as a support for providing specific surface area and strength. Therefore, carbon dioxide can be fundamentally separated without deterioration of thermal efficiency or a synthetic gas can be produced with low cost by developing chemical looping combustion or chemical looping reforming by essentially using high performance oxygen donor particles with a high level of technical quality and by replacing known combustion methods or synthetic gas production methods.

Description

매체순환연소 또는 매체순환개질용 산소공여입자 및 그 제조방법Oxygen donor particles for medium circulation combustion or medium circulation reforming and preparation method thereof
본 발명은 매체순환연소 또는 매체순환개질용 산소공여입자 및 그 제조방법에 관한 것으로, 특히 산소공여입자의 소모량을 최소화하고 유동층공정에 적합한 물리적 특성을 지니고 반응성이 우수한 매체순환연소 또는 매체순환개질용 산소공여입자 및 그 제조방법에 관한 것이다.The present invention relates to an oxygen donor particle for media circulating combustion or medium circulation reforming and a method for producing the same, in particular for minimizing the consumption of oxygen donor particles and having physical properties suitable for fluidized bed process, and for excellent media circulation combustion or media circulation reforming. An oxygen donor particle and a method for producing the same.
산업화, 경제성장 및 인간 활동에 필요한 에너지 확보를 목적으로 화석연료 사용은 지속적으로 증가하고 있으며, 화석연료 사용증가에 따라 이산화탄소의 배출량도 증가하고 있다. 대기 중의 이산화탄소 농도가 증가하면서 온실효과로 인한 지구의 평균기온이 상승하면서 기후변화의 피해가 지속적으로 나타나고 있다. 따라서 화석연료로부터의 이산화탄소 배출을 줄이기 위한 다양한 방법이 요구된다.The use of fossil fuels is increasing continuously for the purpose of industrialization, economic growth, and securing energy for human activities, and carbon dioxide emissions are increasing with increasing use of fossil fuels. As the concentration of carbon dioxide in the atmosphere increases, the average temperature of the earth due to the greenhouse effect rises, causing damage to climate change continuously. Therefore, various methods are needed to reduce carbon dioxide emissions from fossil fuels.
인위적인 이산화탄소 배출원 중 가장 큰 비중을 차지하는 것은 에너지 공급을 위해 대량의 화석연료를 연소시키는 화력발전소이다. 전력부문에서의 이산화탄소 배출 저감은 전력생산 및 소비 효율 향상, 원자력 및 재생 에너지 확대, 이산화탄소 포집 저장(Carbon Dioxide Capture and Storage: CCS)을 통해 달성할 수 있다. 화력발전소에서의 이산화탄소 포집 기술로 연소후(post-combustion) 포집, 연소전 포집(pre-combustion), 순산소(oxy-fuel) 연소 기술이 개발되고 있다. 이러한 이산화탄소 포집 기술을 화력발전소에 적용함에 있어 가장 큰 장벽은 이산화탄소 포집 설비를 설치하여 운전함에 따른 발전효율 감소와 이에 따른 발전원가 상승이다.The largest share of anthropogenic carbon dioxide sources is coal-fired power plants that burn large amounts of fossil fuel for energy supply. Reduction of carbon dioxide emissions in the power sector can be achieved through improved power generation and consumption efficiency, increased nuclear and renewable energy, and carbon dioxide capture and storage (CCS). Post-combustion capture, pre-combustion and oxy-fuel combustion technologies are being developed as CO2 capture technologies for thermal power plants. The biggest barrier to applying this carbon dioxide capture technology to coal-fired power plants is the reduction of power generation efficiency and the increase in power generation cost.
이에 따라 발전효율 감소를 최소화하고 CO2 포집 비용을 낮추기 위한 새로 신기술이 요구된다. 매체순환 연소기술은 이러한 목적에 부합되며 장기적으로 발전효율 감소 및 CO2 포집 비용을 최소화할 수 있는 연소기술로 2000년 이후 차세대 연소 및 발전기술로 부상하고 있다. 매체순환연소(CLC, chemical looping combustion)는 공기대신 금속산화물에 포함된 산소로 연료를 연소시키므로 산소분리설비 없이 순산소연소를 할 수 있는 새로운 개념이다. 즉, 연료 연소 후 배출되는 가스에는 수증기와 CO2만 포함되어 있어 수증기만 응축 제거하면 CO2만 남게 되므로 CO2 원천분리가 가능한 기술이다. 매체순환연소는 NOx의 배출이 거의 없고 별도의 CO2 포집 공정이 없이도 고농도(98%)의 CO2를 포집할 수 있다. Accordingly, new technologies are needed to minimize the reduction of power generation efficiency and to lower the cost of CO 2 capture. Media circulating combustion technology meets this purpose and has been emerging as the next generation combustion and power generation technology since 2000 as a combustion technology that can reduce power generation efficiency and minimize CO 2 capture costs in the long run. Chemical looping combustion (CLC) is a new concept that allows oxy-fuel combustion without oxygen separation, as it burns fuel with oxygen contained in metal oxides instead of air. In other words, the fuel combustion and then discharged when the gas, because it contains only water vapor and CO 2 removal only water vapor condenses, so, leaving the CO 2 source CO 2 separation is possible techniques. Media circulating combustion can capture high concentrations (98%) of CO 2 without any NOx emissions and without a separate CO 2 capture process.
한편 석유 사용량 증가에 따른 석유 매장량이 줄어들면서 석유를 대체할 에너지원으로 합성가스 및 수소 생산량이 증가하고 있다. 합성가스 및 수소를 대량으로 생산하기 위한 현재의 기술은 석탄을 가스화하거나 천연가스나 바이오가스를 수증기로 개질하여 얻은 합성가스를 이용하고 있다. 매체순환개질(CLR, chemical looping reforming)은 기존의 기술에 비해 합성가스 생산에 필요한 에너지 소모를 줄이고 저비용으로 합성가스를 생산할 수 있는 새로운 방식의 합성가스 생산기술로 주목되고 있다.Meanwhile, as oil reserves decrease due to increased oil consumption, syngas and hydrogen production are increasing as energy sources to replace oil. Current technologies for mass production of syngas and hydrogen utilize syngas obtained by gasifying coal or reforming natural gas or biogas with steam. Chemical looping reforming (CLR) is drawing attention as a new method of syngas production that can produce syngas at a lower cost and reduce the energy consumption required for syngas production.
매체순환연소와 매체순환개질은 공기 또는 수증기로부터 산소를 받아 매체(medium)가 산화(oxidation)되는 반응이 일어나는 유동층 반응기와 매체에 함유된 산소가 연료로 전달되면서 매체는 환원(reduction)이 되는 반응이 일어나는 유동층 반응기가 서로 연결된 조합으로 구성되는 순환유동층공정(circulating fluidized-bed process)을 사용한다. 이때 공기 또는 수증기로부터 산소를 얻어 연료에 전달하는 매체인 산소공여입자는 유동층 공정특성에 적합한 여러 가지 조건을 만족시켜야 한다. 우선 유동층 공정에 적합한 물성, 즉 충분한 강도, 유동에 적합한 형상과 충진밀도(packing density 또는 tapped density), 평균 입자크기 및 입자크기 분포, 반응가스의 확산에 유리한 기공구조와 충분한 접촉면적을 지녀야 한다. 또한 반응성 측면에서 높은 산소전달능력(oxygen transfer capacity)을 지니고 있어 연료의 연소나 부분산화에 필요한 충분한 산소를 연료가 연료반응기를 통과하는 동안 공급할 수 있어야 한다. 매체순환연소 및 매체순환개질에 있어 산소공여입자 개발은 전체 기술의 성공 여부를 결정짓는 핵심기술로 인식되고 있다. Medium circulation combustion and medium circulation reforming are a fluidized bed reactor in which a reaction in which oxygen is oxidized by receiving oxygen from air or water vapor and a reaction in which the medium is reduced as oxygen in the medium is transferred to the fuel This happens using a circulating fluidized-bed process in which the fluidized bed reactors are composed of interconnected combinations. At this time, oxygen donor particles, a medium for obtaining oxygen from air or water vapor and delivering to fuel, must satisfy various conditions suitable for fluidized bed process characteristics. First, it must have sufficient physical properties, namely sufficient strength, suitable shape and packing density (packing density or tapped density), average particle size and particle size distribution, and pore structure favorable for diffusion of reaction gas and sufficient contact area for fluidized bed process. In addition, it has a high oxygen transfer capacity in terms of reactivity so that it can supply enough oxygen for fuel combustion or partial oxidation while passing through the fuel reactor. The development of oxygen donor particles in medium circulation combustion and medium circulation reform is recognized as a key technology that determines the success of the whole technology.
기존의 특허나 논문에 따르면 산소공여입자를 성형하는 방법으로 함침법(impregnation)이나, 공침법 (coprecipitation), 원료물질을 물에 혼합하여 반죽하고 건조 및 소성한 후 분쇄하여 입자를 성형하는 물리적 혼합 (physical mixing method), 동결 건조 (freeze granulation)법 등이 이용되었다. 그러나, 매체순환 공정 규모격상에 따라 유동층 공정에 적합한 대량의 산소공여입자를 생산하기 위해 상업용으로 사용되고 있는 분무건조법(spray-drying method)이나 방사열풍건조(spin-flash drying) 기술 등이 최근 들어 사용되고 있다. 이중 유동층 공정에서 형상면에서 마모로 인한 입자 손실을 최소화할 수 있는 가장 적합한 형상인 구형의 입자가 성형되는 기술은 동결건조(freeze granulation)와 분무건조법(spray-drying method)이며 대량생산 측면에서 분무건조법이 더 유리하다.According to existing patents or papers, the method of molding oxygen donor particles is impregnation, coprecipitation, physical mixing of raw materials by mixing them with water, kneading, drying and sintering and then grinding to form particles. (physical mixing method), freeze granulation method and the like were used. However, the spray-drying method or the spin-flash drying technique, which is commercially used to produce a large amount of oxygen donor particles suitable for a fluidized bed process according to the scale of the medium circulation process, has recently been used. have. In the double fluidized bed process, spherical particles are molded, which is the most suitable shape to minimize particle loss due to wear in shape. Freeze granulation and spray-drying methods are used for mass production. Drying method is more advantageous.
동결건조(freeze granulation)나 분무건조법(spray-drying method)에서 원료를 물에 혼합한 슬러리를 노즐을 이용하여 분무하여 수십에서 수백 마이크론 크기의 입자크기 분포를 갖는 구형의 입자로 성형하기 위해서는 분산제, 소포제, 유기결합제 등의 첨가제를 사용하여 슬러리를 균질하고 안정된 유동성 특성을 갖도록 하는 제조 과정이 매우 중요하다. 슬러리 특성 제어가 잘못된 경우 구형이 아닌 타원형이나 도우넛형, 홈이 파인 형태의 입자가 만들어져 유동층 공정 적용시 입자의 마모손실이 크지는 원인이 된다.In order to form a spherical particle having a particle size distribution of several tens to hundreds of microns by spraying a slurry in which raw materials are mixed with water in a freeze granulation or spray-drying method using a nozzle, The use of additives such as antifoaming agents, organic binders and the like to make the slurry homogeneous and stable fluidity is very important. Incorrect control of the slurry properties results in the formation of particles of elliptical, donut, or grooved shapes rather than spherical shape, which causes large wear losses of the fluidized bed process.
이러한 산소공여입자 및 그 제조방법과 관련된 종래의 특허로는 미국특허 제5447024호, 미국공개특허 US 2005/0175533, 미국공개특허 US 2007/0049489, 미국공개특허 US 2009/002045 등이 있다.Conventional patents related to such oxygen donor particles and preparation methods thereof include US Patent 5447024, US Patent Publication US 2005/0175533, US Patent Publication US 2007/0049489, US Patent Publication US 2009/002045, and the like.
상기 특허들은 대량생산에 부적합한 방법으로 성형되었거나 성형 후 형상을 비롯한 충진밀도, 입자크기, 강도 등의 물성이 유동층 공정에 부적합하거나 조성이나 물성, 반응성에 대한 기준이 제시되지 않아 고온에서 운전되는 매체순환연소 또는 매체순환개질의 순환유동층 공정에 적용할 수 있는 형상과 성능을 갖추고 있지 못한 문제점이 있다.These patents are formed by methods that are not suitable for mass production, or physical properties such as shape after packing, such as packing density, particle size, and strength are not suitable for fluidized bed processes, or standards for composition, physical properties, and reactivity are not provided. There is a problem that does not have the shape and performance that can be applied to the circulating fluidized bed process of the combustion or media circulation reform.
본 발명의 목적은 상술한 문제점을 해소하기 위해 안출된 것으로, 소모량을 최소화하고 유동층 공정에 적합한 물리적 특성을 지니고 반응성이 우수한 매체순환연소 또는 매체순환개질용 산소공여입자를 제공하는데 있다.Disclosure of Invention An object of the present invention is to provide an oxygen donor particle for medium circulation combustion or medium circulation reforming, which has been devised to solve the above-mentioned problems, minimizes consumption, has physical properties suitable for a fluidized bed process, and is highly reactive.
본 발명의 또 다른 목적은, 유동층 공정에 적합한 형상, 입자크기, 입자크기 분포, 충진밀도, 기공구조 및 산소전달능력을 갖는 산소공여입자를 제조할 수 있는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법을 제공하는데 있다. Still another object of the present invention is to provide oxygen circulating combustion or medium circulation reforming for producing oxygen donor particles having a shape, particle size, particle size distribution, packing density, pore structure, and oxygen transfer ability suitable for a fluidized bed process. It is to provide a method for producing the particles.
상기 목적을 달성하기 위해 본 발명 매체순환연소 또는 매체순환개질용 산소공여입자는, 가스 또는 고체상 연료를 연소시키는 매체순환연소나 연료의 부분산화를 통해 합성가스 또는 수소를 생산하는 매체순환개질에 사용되는 산소공여입자에 있어서, 상기 산소공여입자의 고체원료는, 활성물질인 니켈옥사이드(NiO) 40~80 중량%, 비표면적과 강도를 부여하기 위한 지지체로 세라믹류 및 점토류 20~60중량%로 이루어진다.In order to achieve the above object, the medium-circulating combustion or the oxygen donor particles for medium-circuit reforming are used for medium-circuit reforming for producing syngas or hydrogen through medium-circulating combustion or partial oxidation of fuel combusting gas or solid phase fuel. In the oxygen donor particles, the solid raw material of the oxygen donor particles is 40 to 80% by weight of nickel oxide (NiO) as an active material, and 20 to 60% by weight of ceramics and clays as a support for imparting specific surface area and strength. Is made of.
또한, 상기 목적을 달성하기 위해 본 발명 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법은, 고체원료를 이용해 슬러리를 제조하는 단계, 슬러리를 분무 건조기를 이용해 산소공여입자를 일차 성형하는 단계, 및 일차 성형된 산소공여입자를 건조 소성시켜 최종 산소공여입자를 성형하는 단계를 포함한다.In addition, in order to achieve the above object, the present invention provides a method for preparing the medium-circulating combustion or medium-circulating reforming oxygen donor particles, comprising: preparing a slurry using a solid raw material, and firstly forming the oxygen donor particles using a spray spray dryer. And dry-firing the primary shaped oxygen donor particles to form the final oxygen donor particles.
이와 같은 본 발명에 따른 매체순환연소 또는 매체순환개질용 산소공여입자에 의하면, 고성능 산소공여입자가 필수인 매체순환연소나 매체순환개질의 기술개발 완성도를 높임으로써, 기존의 연소방식이나 합성가스생산방식을 대체하여 열효율 저하 없이 이산화탄소를 원천적으로 분리하거나, 저비용으로 합성가스를 생산할 수 있다.According to such a medium circulation combustion or medium circulation reforming oxygen donor particles according to the present invention, by improving the degree of completion of the technology development of medium circulation combustion or media circulation reform, where high-performance oxygen donor particles are essential, the existing combustion method or synthesis gas production Alternative methods can be used to separate carbon dioxide without compromising thermal efficiency, or to produce syngas at low cost.
본 발명에 따른 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법에 의하면, 유동층 공정에 적합한 구형의 형상과 입자크기, 입자크기분포, 충진 밀도와 강도, 그리고 높은 기공도, 반응에 유리한 기공구조 및 우수한 산소전달능력(oxygen transfer capacity)를 가지는 산소공여입자를 제조할 수 있다.According to the method for producing oxygen circulation particles for medium circulation combustion or medium circulation reforming according to the present invention, the spherical shape and particle size, particle size distribution, packing density and strength, high porosity and porosity which are favorable for the fluidized bed process Oxygen donor particles having a structure and excellent oxygen transfer capacity can be prepared.
따라서, 본 발명은 대기 중 이산화탄소 농도 증가로 인한 기후변화 예방을 위해 향후 이산화탄소 포집설비가 필요한 화력발전소나 열병합발전소 등의 설비와 연료의 가스화나 천연가스개질을 통해 합성가스를 생산하고 있는 설비를 대체할 수 있는 신기술로 급부상하고 있는 매체순환연소 및 매체순환개질의 핵심기술로 산업상 그 이용이 크게 기대된다.Therefore, the present invention replaces a facility such as a thermal power plant or a cogeneration plant that requires a carbon dioxide capture facility in the future to prevent climate change due to an increase in the concentration of carbon dioxide in the atmosphere, and a facility that produces syngas through gasification of fuel or natural gas reforming. It is expected to be used in industry as a core technology of media circulation combustion and media circulation reform, which is emerging as a new technology that can be rapidly developed.
도 1은 본 발명에 따른 매체순환연소 또는 매체순환개질용 산소공여입자를 제조하는 과정을 나타낸 공정도.1 is a process chart showing a process for producing the oxygen circulation particles for medium circulation combustion or medium circulation reforming according to the present invention.
도 2는 고체원료를 이용해 슬러리를 제조하는 과정을 나타낸 공정도.2 is a process chart showing a process for preparing a slurry using a solid raw material.
도 3은 산소공여입자를 일차 성형하는 과정을 나타낸 공정도.Figure 3 is a process diagram showing the process of primary molding oxygen donor particles.
도 4는 일차 성형된 산소공여입자를 건조 소성시켜 최종 산소공여입자를 성형하는 과정을 나타낸 공정도.Figure 4 is a process chart showing the process of forming the final oxygen donor particles by dry firing the primary molded oxygen donor particles.
도 5 및 도 6은 본 발명의 실시예에서 제조한 각 산소공여입자의 형상을 나타낸 사진.5 and 6 are photographs showing the shape of each oxygen donor particles prepared in the embodiment of the present invention.
이하, 본 발명에 따른 바람직한 실시예를 첨부한 도면에 따라 상세하게 설명한다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
먼저, 본 발명에 따른 매체순환연소 또는 매체순환개질용 산소공여입자를 구성하는 고체원료는 활성물질과 지지체로 구성된다.First, the solid raw material constituting the oxygen circulation particles for medium circulation combustion or medium circulation reforming according to the present invention is composed of an active material and a support.
상기 활성물질은 연료로 산소를 전달하고 공기나 수증기로부터 산소를 다시 받을 수 있는 금속 또는 금속산화물이다. 이러한 활성물질로는 니켈옥사이드(NiO)가 있으며 총 고체원료 중 40~80 중량%를 차지한다.The active material is a metal or metal oxide capable of delivering oxygen to fuel and receiving oxygen back from air or water vapor. These active materials include nickel oxide (NiO) and make up 40 to 80% by weight of the total solid raw materials.
상기 지지체는 확산(diffusion)에 필요한 기공구조를 제공하고 소성 후 산소공여입자에 유동층 공정에서 요구하는 충분한 강도를 주는 물질이다. 즉, 지지체는 활성물질을 지지하는 기능과 소성시 서로 결합하면서 산소공여입자에 강도를 주는 바인더로서의 역할을 동시에 한다. 또한, 고온에서 금속이 산화 환원 사이클을 반복하는 동안 서로 응집되는 현상을 억제하며 반응 전후에 가스가 입자 외부와 활성물질까지 입출입(확산)이 원활하도록 통로를 만들어주는 역할을 한다.The support is a material that provides the pore structure necessary for diffusion and gives oxygen donor particles sufficient strength required in the fluidized bed process after firing. In other words, the supporter simultaneously serves 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 suppress the aggregation of each other during the redox cycle, and serve to create a passage for gas to flow in and out (diffusion) to the outside of the particle and the active material before and after the reaction.
이러한 지지체로는 세라믹류로 감마알루미나(γ-Al2O3) 또는 유사 보에마이트가 있으며, 점토류로는 벤토나이트가 있다. 지지체는 총 고체원료중 20~60 중량%를 차지한다. 이 때, 세라믹류는 총 고체원료중 0.1~60중량%를 차지하며, 점토류는 총 고체원료중 0.1~30중량%를 차지한다.Such a support includes ceramics such as gamma alumina ( γ- Al 2 O 3 ) or pseudo-boehmite, and clays include bentonite. The support constitutes 20 to 60% by weight of the total solids. At this time, ceramics account for 0.1 to 60% by weight of the total solid raw materials, clays account for 0.1 to 30% by weight of the total solid raw materials.
본 발명에 따른 산소공여입자를 제조하는 과정에서, 고체원료를 유동층 공정에 적합한 물성을 갖는 구형의 입자로 분무 성형하기 위해서는 안정하고 균질화된 슬러리의 제조가 필요하다. 이를 위해 슬러리 제조시 분산제, 소포제, 유기결합제 등의 유기첨가제가 필요하다.In the process of preparing the oxygen donor particles according to the present invention, in order to spray-form the solid raw material into spherical particles having suitable properties for the fluidized bed process, it is necessary to prepare a stable and homogenized slurry. For this purpose, an organic additive such as a dispersant, an antifoaming agent, and an organic binder is required in preparing a slurry.
상기 분산제는 고체원료 입자끼리 서로 응집되는 현상을 방지하는데 사용된다. 이러한 분산제로는 음이온계(anionic)와 비이온계(nonionic) 계면활성제(surfactant)가 사용된다. 분산제는 총 고체원료 중량 대비 0.01~10 중량%를 차지한다. 음이온계 계면활성제로는 암모늄폴리카르복실산(Poly carboxylate ammonium salts) 또는 아민폴리카르복실산(Poly carboxylate amine salts)이 있다.The dispersant is used to prevent the phenomenon of agglomeration of the solid raw material particles with each other. As the dispersant, anionic and nonionic surfactants are used. Dispersants comprise 0.01 to 10% by weight of the total solid raw material weight. Anionic surfactants include poly carboxylate ammonium salts or poly carboxylate amine salts.
상기 소포제는 슬러리 제조과정에서 발생될 수 있는 거품을 억제 또는 제거하기 위해 사용된다. 소포제로는 시리카실리콘계, 실리콘계, 금속비누계, 아미도계, 폴리에테르계, 폴리글라이콜계, 유기인산계, 고급알콜계, 유산지방계 등이 있다. 이러한 소포제는 총 고체원료 중량 대비 0.001~1 중량%를 차지한다.The antifoaming agent is used to suppress or remove the foam that may be generated during the slurry manufacturing process. Antifoaming agents include, for example, silica-silicone, silicon-based, metal soap-based, amido-based, polyether-based, polyglycol-based, organophosphorous-based, higher alcohol-based and lactic-acid-based. These defoamers account for 0.001 to 1% by weight of the total solid raw material weight.
상기 유기결합제는 슬러리 제조 단계에서 첨가하여 슬러리의 가소성(plasticity)과 유동성을 부여하고 분무건조 성형시 입자의 형상을 유지하고 성형 후의 산소공여입자에 강도를 부여함으로써 예비건조 및 소성 전에 산소공여입자의 취급이 용이하도록 하는 기능을 가진다. 유기결합제로는 폴리비닐알콜계(polyvinylalcohols), 폴리에틸렌글라이콜계(polyethyleneglycols), 메틸셀룰로즈계(methylcelluloses), 폴리에틸렌옥사이드계(polyethylenoxide) 등이 있다. 이러한 유기결합제는 총 고체원료 중량 대비 0.5~5 중량%를 차지한다.The organic binder is added in the slurry manufacturing step to impart plasticity and fluidity of the slurry, to maintain the shape of the particles during spray-drying molding, and to give strength to the oxygen donor particles after molding, thereby providing the oxygen donor particles prior to pre-drying and firing. Has a function to facilitate handling. Organic binders include polyvinyl alcohols (polyvinylalcohols), polyethylene glycol (polyethyleneglycols), methyl cellulose (methylcelluloses), polyethylene oxide (polyethylenoxide) and the like. Such organic binder accounts for 0.5 to 5% by weight based on the total weight of solid raw materials.
도 1은 본 발명에 따른 매체순환연소 또는 매체순환개질용 산소공여입자를 제조하는 과정을 나타낸 공정도이다.1 is a process chart showing a process for preparing oxygen donor particles for medium circulation combustion or medium circulation reforming according to the present invention.
본 발명에 따른 매체순환연소 또는 매체순환개질용 산소공여입자를 제조하기 위해서는, 고체원료를 이용해 슬러리를 제조하는 단계(S10), 제조된 슬러리를 분무 건조시켜 산소공여입자를 일차 성형하는 단계(S20), 및 일차 성형된 산소공여입자를 건조 소성시켜 최종 산소공여입자를 성형하는 단계(S30)로 이루어진다.In order to prepare the oxygen circulation particles or medium circulation reforming oxygen donor particles according to the present invention, the step of preparing a slurry using a solid raw material (S10), the step of spray drying the prepared slurry to primary molding the oxygen donor particles (S20) ), And drying and calcining the primary molded oxygen donor particles (S30).
도 2는 고체원료를 이용해 슬러리를 제조하는 과정을 나타낸 공정도이다.2 is a process chart showing a process of preparing a slurry using a solid raw material.
균질하고 안정된 유동성 슬러리를 제조하기 위해서는, 고체원료를 배합비에 따라 물에 첨가하여 혼합하는 단계(S11), 유기첨가제를 첨가하여 물에 고체원료가 잘 혼합되도록 하는 단계(S12), 혼합된 슬러리를 습식 분쇄기를 이용하여 분쇄하여 균질하고 분산된 슬러리를 제조하는 단계(S13), 및 슬러리에 포함된 이물질을 제거하는 단계(S14)로 이루어진다.In order to prepare a homogeneous and stable flowable slurry, adding a solid raw material to water according to the mixing ratio and mixing (S11), adding an organic additive to mix the solid raw material with water well (S12), the mixed slurry Grinding using a wet mill to produce a homogeneous and dispersed slurry (S13), and removing the foreign matter contained in the slurry (S14).
고체원료는 슬러리의 농도(고체원료 대 액상인 물의 중량비)가 15~50 중량%가 되도록 물에 교반하면서 혼합한다. 이때 고체원료가 서로 덩어리지는 것을 억제하고 원만한 혼합을 위하여 유기 첨가제로 분산제와 소포제를 함께 첨가하여 혼합한다.The solid raw material is mixed with water with stirring so that the concentration of the slurry (weight ratio of solid material to liquid water) is 15 to 50% by weight. At this time, the solid raw materials are prevented from agglomeration with each other and mixed together by adding a dispersant and an antifoaming agent together as organic additives for smooth mixing.
고체 원료의 혼합이 완료된 슬러리는 습식 분쇄기를 사용하여 슬러리 중의 입자를 수 마이크론(㎛) 이하로 분쇄한다. 이 과정에서 분쇄된 입자는 슬러리 내에 더욱 균질하게 분산되고, 이미 첨가한 분산제에 의해 슬러리내 입자의 응집이 억제되므로 균질하고 안정한 슬러리가 제조된다. 필요에 따라 분쇄 과정은 수회 반복할 수 있으며 각 분쇄 과정 사이에 분산제와 소포제를 첨가하여 슬러리의 유동성을 조절한다. 그리고 유기결합제를 첨가하여 분무 건조시 입자 형상을 유지하도록 한다. 한편, 원료입자가 수 마이크론 이하이면 습식 분쇄과정을 생략할 수 있다.The slurry in which the mixing of the solid raw materials is completed is crushed to several microns (μm) or less in the slurry using a wet mill. The particles pulverized in this process are more homogeneously dispersed in the slurry, and aggregation of the particles in the slurry is suppressed by the already added dispersant, thereby producing a homogeneous and stable slurry. If necessary, the grinding process can be repeated several times and a dispersant and an antifoaming agent are added between each grinding process to control the fluidity of the slurry. And an organic binder is added to maintain the particle shape during spray drying. On the other hand, if the raw material particles are several microns or less, the wet grinding process can be omitted.
분쇄를 완료한 슬러리는 체로 쳐서 분무 성형시 노즐 막힘의 원인이 될 수 있는 이물질이나 덩어리진 원료를 제거한다. 본 발명에서 최종 슬러리의 유동성에 대한 특별한 제한은 없으며 펌프로 이송가능한 어떤 점도도 가능하다.After completion of the grinding, the slurry is sieved to remove foreign substances or lumpy raw materials which may cause nozzle clogging during spray molding. There is no particular limitation on the flowability of the final slurry in the present invention and any viscosity transferable to the pump is possible.
도 3은 산소공여입자를 일차 성형하는 과정을 나타낸 공정도이다.3 is a process chart showing a process of primary molding oxygen donor particles.
균질하고 안정된 유동성 슬러리를 분무 건조기로 성형하여 구형의 산소공여입자를 제조하는 단계(S20)는, 성형된 슬러리를 펌프를 이용해 분무 건조기로 이송하는 단계(S21)와, 이송된 슬러리를 분무 건조기 내로 분사하여 산소공여입자를 성형하는 단계(S22)를 거친다.Forming a homogeneous and stable flowable slurry with a spray dryer to produce spherical oxygen donor particles (S20), transferring the shaped slurry to a spray dryer using a pump (S21), and transferring the transferred slurry into the spray dryer Injection is performed to form the oxygen donor particles (S22).
분무 건조기 내에서 산소공여입자를 성형하기 위해서는 적합한 분무 건조기의 운전조건이 필요하다. 산소공여입자의 입자 크기 분포는 30~303㎛가 되는 것이 바람직하다. 유동성 슬러리는 가압노즐을 사용하여 건조용 공기의 흐름과 반대 방향으로 분사하는 향류식 분무방식으로 분사하여 산소공여입자를 성형하게 되며, 분무 건조기 입구온도는 260~300 ℃, 출구온도는 90~150 ℃를 유지하는 것이 바람직하다.In order to mold the oxygen donor particles in the spray dryer, operating conditions of a suitable spray dryer are required. The particle size distribution of the oxygen donor particles is preferably 30 to 303 µm. The fluidized slurry is sprayed by countercurrent spray method that sprays in the opposite direction to the flow of drying air using a pressurized nozzle to form oxygen donor particles.The spray dryer inlet temperature is 260-300 ℃ and outlet temperature is 90-150 It is preferable to maintain the temperature.
도 4는 일차 성형된 산소공여입자를 건조 소성시켜 최종 산소공여입자를 성형하는 과정을 나타낸 공정도이다.Figure 4 is a process diagram showing the process of forming the final oxygen donor particles by dry firing the primary molded oxygen donor particles.
일차 성형된 산소공여입자는 예비 건조과정(S31)을 거친 후, 소성과정(S32)을 통해 최종 산소공여입자로 성형된다.The primary molded oxygen donor particles are preliminarily dried (S31) and then molded into final oxygen donor particles through a sintering process (S32).
상기 예비 건조과정(S31)에서는 일차 성형된 산소공여입자를 110~130 ℃ 공기분위기의 환류 건조기에서 2시간 이상 건조하게 된다.In the preliminary drying step (S31), the primary molded oxygen donor particles are dried for 2 hours or more in a reflux dryer in an air atmosphere of 110 ~ 130 ℃.
상기 소성과정(S32)에서는 예비 건조된 산소공여입자를 공기분위기의 고온 소성로에 넣고 1~5℃/min의 속도로 소성온도 900~1300 ℃까지 올려 2~10시간 소성시키면서 슬러리 제조시 투입된 분산제, 소포제, 유기결합제를 연소시키고 원료물질들 간의 결합에 의해 입자의 강도를 향상시키게 된다.In the sintering process (S32), the pre-dried oxygen donor particles are put into a high-temperature firing furnace in an air atmosphere, and the dispersing agent is added during slurry production while firing for 2 to 10 hours at a firing temperature of 900 to 1300 ° C. at a rate of 1 to 5 ° C./min, The antifoaming agent and the organic binder are combusted and the strength of the particles is improved by the bonding between the raw materials.
전술한 과정을 통해 최종 성형된 산소공여입자는 400~1400℃의 범위에서 산소를 전달하게 되며, 유동층 반응에 적합한 조건들을 갖는다. 즉, 산소공여입자의 형상은 구형이며, 평균 입자크기가 50~200㎛이고, 입자크기 분포는 30~500㎛이며, 충진밀도는 0.6~3.0g/mL이고, Hg 기공도가 30%이상이며, 비표면적은 0.1㎡/g이상이고, 내마모도는 60%이하이며, 산소전달능력은 5wt%이상이다.The final formed oxygen donor particles through the above process is to deliver oxygen in the range of 400 ~ 1400 ℃, and has the conditions suitable for the fluidized bed reaction. That is, the shape of the oxygen donor particles is spherical, the average particle size is 50 ~ 200㎛, the particle size distribution is 30 ~ 500㎛, the filling density is 0.6 ~ 3.0g / mL, Hg porosity is more than 30% , Specific surface area is more than 0.1㎡ / g, wear resistance is less than 60%, oxygen transfer capacity is more than 5wt%.
(실시예1) Example 1
본 실시예는 총 8 kg의 고체원료 중 활성성분으로 순도 98% 이상의 분말 형태의 NiO 60~70 중량%, 지지체로 순도 95% 이상이며 비표면적이 150㎡/g인 γ-Al2O3 20~40 중량%, 순도 70% 이상이며 비표면적이 310㎡/g인 유사 보에마이트 0.1~10 중량%, 소디움 벤토나이트 0.1~5 중량%를 조성비로 하는 산소공여입자 제조에 관한 것이다.In this example, γ- Al 2 O 3 20 having 60 to 70% by weight of NiO in powder form as an active ingredient in a total of 8 kg of solid raw materials and having a purity of at least 95% as a support and a specific surface area of 150 m 2 / g It relates to the production of oxygen donor particles having a composition ratio of 0.1 to 10% by weight of pseudo-boehmite and 0.1 to 5% by weight of sodium bentonite having a ˜40% by weight, a purity of 70% or more and a specific surface area of 310 m 2 / g.
슬러리 농도가 33~35 중량%가 되도록 물에 원료를 교반기로 교반하면서 첨가하여 혼합 슬러리를 제조하였다. 이 과정에서 분산제, 소포제도 첨가하였다. 혼합 슬러리는 3차례에 걸쳐 고에너지볼밀(High Energy Ball Mill)로 분쇄하였고 2차 분쇄 후 소포제와 분산제, 유기결합제를 첨가하고 3차 분쇄를 진행하여 안정되고 균질한 유동성 콜로이드 슬러리(colloidal slurry)를 제조하였다. 이 때, 슬러리의 점도는 600~29,000 cP이며, 분쇄를 마친 슬러리를 체거름을 통해 이물질을 제거하고 측정한 최종 슬러리 고체농도는 30~34 중량%이었다.A mixed slurry was prepared by adding a raw material to water with stirring using a stirrer so that the slurry concentration was 33 to 35% by weight. In this process, a dispersant and an antifoam were added. The mixed slurry was pulverized with a high energy ball mill three times, and after the second crushing, an antifoaming agent, a dispersant, and an organic binder were added, followed by the third pulverization to obtain a stable and homogeneous colloidal slurry. Prepared. At this time, the viscosity of the slurry is 600 ~ 29,000 cP, and the final slurry solid concentration was 30 ~ 34% by weight after removing the foreign matter through a sieve sieve pulverized slurry.
제조된 안정되고 균질한 유동성 콜로이드 슬러리를 펌프로 분무건조기로 이송하고 분무건조하여 제조한 산소공여입자를 120℃ 공기분위기 환류 건조기에서 2시간 이상 건조하고 소성로에서 공기 분위기에서 승온 속도 5℃/min으로 950~1300 ℃로 온도를 올린 후 4시간 이상 소성하여 산소공여입자를 제조하였다. 소성온도에 도달하기 전 200, 400, 500, 650 ℃ 온도에서 각각 1시간 정도 등온으로 유지하였다. 이렇게 제조된 산소공여입자를 활성성분과 지지체 조성에 따라 A, B, C, D, E, F로 표기하였다. <표-1>은 실시예 1에서 제조한 산소공여입자의 특성을 요약한 것이다.Oxygen donor particles prepared by transporting the stable and homogeneous fluid colloidal slurry prepared by the pump to the spray dryer and spray-dried were dried at 120 ° C. in an air atmosphere reflux dryer for 2 hours or longer, and at a heating rate of 5 ° C./min in an air atmosphere in a kiln. Oxygen donor particles were prepared by raising the temperature to 950-1300 ° C. and firing for at least 4 hours. Before reaching the firing temperature, the mixture was maintained at isothermal temperature for about 1 hour at 200, 400, 500, and 650 ° C. The oxygen donor particles thus prepared are labeled as A, B, C, D, E, F according to the active ingredient and the support composition. Table 1 summarizes the characteristics of the oxygen donor particles prepared in Example 1.
표 1 산소공여입자의 조성 및 슬러리 특성
산소공여입자 A B C D E F
NiO, wt% 70 70 70 70 70 60
γ-Al2O3, wt% 20 20 20 25 30 40
유사 보에마이트, wt% 5 7 10 5 0 0
소디움벤토나이트,wt% 5 3 0 0 0 0
총 고체 함량, wt% 100 100 100 100 100 100
분산제, wt% 0.15 0.25 0.2 0.15 0.22 0.4
소포제, wt% 0.05 0.075 0.15 0.1 0.1 0.05
유기결합제, wt% 1.25 1.25 1.25 1.25 1.25 1.25
슬러리 고체농도, wt% 30 31 33 30 34 31
슬러리 점도, cP 11,300 2,360 1,330 1,100 630 29,200
Table 1 Composition and Slurry Characteristics of Oxygen Donor Particles
Oxygen donor particles A B C D E F
NiO, wt% 70 70 70 70 70 60
γ-Al 2 O 3 , wt% 20 20 20 25 30 40
Pseudoboehmite, wt% 5 7 10 5 0 0
Sodium Bentonite, wt% 5 3 0 0 0 0
Total solids content, wt% 100 100 100 100 100 100
Dispersant, wt% 0.15 0.25 0.2 0.15 0.22 0.4
Antifoam, wt% 0.05 0.075 0.15 0.1 0.1 0.05
Organic binder, wt% 1.25 1.25 1.25 1.25 1.25 1.25
Slurry solid concentration, wt% 30 31 33 30 34 31
Slurry viscosity, cP 11,300 2,360 1,330 1,100 630 29,200
상기 실시예1에서 분무건조법으로 성형 후 소성하여 제조한 산소공여입자 A~F의 물성을 다음과 같은 분석 방법에 의해 특성화하였다. 구체적으로, 흡수제의 형상은 SEM을, 충진 밀도는 탭(tap) 밀도계(ASTM D 4164-88)를, 입도 및 입도 분포는 입도 분석기(또는 체)를, 비표면적 및 기공 부피는 표준 BET를, 기공 부피 및 기공률은 Hg 기공 측정기를 이용하여 측정하였다.In Example 1, the physical properties of the oxygen donor particles A to F prepared by molding after spray drying were characterized by the following analysis method. Specifically, the shape of the absorbent is SEM, the packing density is tap density meter (ASTM D 4164-88), the particle size and particle size distribution is the particle size analyzer (or sieve), the specific surface area and pore volume is standard BET. , Pore volume and porosity were measured using a Hg porosimeter.
유동층에서 흡수제의 내마모도는 ASTM D 5757-95에 따라 변형된 3-홀 에어-젯 마모 시험기로 측정하였다. 마모 지수(AI)는 상기 ASTM 방법에 기재된 바대로 5시간에 걸쳐 10 slpm (분당 표준 부피)에서 결정하였다. 마모 지수는 5시간에 걸쳐 발생된 미세분말(fine)의 비율로 나타낸다. 고속 유동층 반응기에서 30% 미만, 나아가 버블링 유동층 반응기에서 60% 미만의 AI를 갖는 물질은 대기압에서도 충분히 사용 가능하고, 이 물질은 유동층 매체순환공정 및 매체순환개질 공정에서도 사용 가능할 것이다. 마모 지수(AI)가 낮을수록 벌크 입자의 내마모도가 좋다는 것을 의미한다.The wear resistance of the absorbent in the fluidized bed was measured with a three-hole air-jet abrasion tester modified according to 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. The wear index is expressed as the percentage of fines generated over 5 hours. Materials with less than 30% AI in high speed fluidized bed reactors and even less than 60% in bubbling fluidized bed reactors can be used sufficiently at atmospheric pressure, and the materials will be able to be used in fluidized bed media circulation and media circulation reforming processes. Lower wear index (AI) means better wear resistance of the bulk particles.
실시예1에서 제조된 흡수제 A~F의 산소전달능력(oxygen transfer capacity)은 열중량 분석법(thermogravimetric analysis, TGA)를 이용하여 평가하였다. 산소공여입자의 환원반응에 사용한 반응가스의 조성은 10 vol% CH4, 90 vol% CO2 이었고 환원된 산소공여입자를 산화시키기 위한 반응가스는 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 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 the absorbents A to F prepared in Example 1 was evaluated using thermogravimetric analysis (TGA). The composition of the reaction gas used for the reduction of oxygen donor particles was 10 vol% CH 4 , 90 vol% CO 2, and air was used as a reaction gas to oxidize the reduced oxygen donor particles. 100% nitrogen was supplied between the oxidation and reduction reactions to prevent direct fuel and air contact in the reactor. The sample amount of oxygen donor particles used in the experiment was about 30 mg. The flow rate of each reaction gas was 150 std mL / min, and the oxygen transfer capacity was measured by repeating the oxidation / reduction reaction of the oxygen donor particles at least five times, where the oxygen transfer capacity was obtained when the oxygen donor particles were completely oxidized. The theoretical maximum oxygen donor particle weight when the oxygen donor particle is completely oxidized by the weight change obtained by subtracting the oxygen donor particle weight measured at the end of the reduction reaction of the oxygen donor particle at the given experimental conditions at the theoretical maximum oxygen donor particle weight. Divided by the weight percentage.
실시예1에서 제조한 흡수제 A∼F에 관한 물리적 특성과 반응 특성을 <표-2>에 요약하였다. 여기서 내마모도는 마모지수(attrition index, AI)를 의미하며, 작을수록 내마모성이 우수한 것이다. 본 발명에서 제조한 각 산소공여입자의 형상이 구형이며 습식분쇄기로 분쇄 후 슬러리내 원료의 입자크기가 수 마이크론 이하임을 보여주는 SEM 사진을 도 5 및 도 6에 나타내었다.Physical and reaction characteristics of the absorbents A to F prepared in Example 1 are summarized in <Table-2>. Here, wear resistance means wear index (Atrition index, AI), the smaller the better the wear resistance. 5 and 6 show SEM images showing that the shape of each oxygen donor particle prepared in the present invention is spherical and the particle size of the raw material in the slurry after grinding by a wet mill is several microns or less.
표 2 산소공여입자의 물리적 특성 및 산소전달 능력
산소공여입자 소성온도,℃ 형상 평균입자크기,㎛ 입자크기분포,㎛ 충진밀도,g/mL Hg기공도,% 비표면적(BET),m2/g 내마모도(AI),% 산소전달능력,wt%
A 950 구형 86 42~303 1.23 62.9 32 58.4 14.7
1100 82 42~303 1.63 64.8 15.3 28.9 14.2
1250 76 37~303 2.01 69.1 3.2 12.0 12.5
B 950 구형 107 37~355 1.38 74.7 27.1 52.9 15.1
1100 98 37~303 1.65 56.8 12.4 30.6 13.8
1250 96 37~303 2.12 48.7 3.4 9.6 13.4
C 950 구형 95 42~303 1.46 64.2 21.0 42.2 15.5
1100 78 37~303 1.87 53.3 7.8 16.9 15.5
D 950 구형 93 42~355 1.48 61.5 20.1 39.2 15.4
1100 76 37~303 1.87 53.1 7.7 16.5 14.5
E 950 구형 93 37~303 1.40 70.0 21.9 52.3 15.3
1100 86 37~303 1.86 56.4 9.2 15.5 13.2
1300 75 37~303 2.35 62.4 2.3 18.2 12.6
F 1000 구형 126 37~303 0.96 63.0 35.9 55.2 8.8
1100 110 37~303 1.37 56.3 3.0 20.5 6.5
TABLE 2 Physical Properties and Oxygen Transfer Capacity of Oxygen Donor Particles
Oxygen donor particles 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%
A 950 rectangle 86 42-303 1.23 62.9 32 58.4 14.7
1100 82 42-303 1.63 64.8 15.3 28.9 14.2
1250 76 37-303 2.01 69.1 3.2 12.0 12.5
B 950 rectangle 107 37-355 1.38 74.7 27.1 52.9 15.1
1100 98 37-303 1.65 56.8 12.4 30.6 13.8
1250 96 37-303 2.12 48.7 3.4 9.6 13.4
C 950 rectangle 95 42-303 1.46 64.2 21.0 42.2 15.5
1100 78 37-303 1.87 53.3 7.8 16.9 15.5
D 950 rectangle 93 42-355 1.48 61.5 20.1 39.2 15.4
1100 76 37-303 1.87 53.1 7.7 16.5 14.5
E 950 rectangle 93 37-303 1.40 70.0 21.9 52.3 15.3
1100 86 37-303 1.86 56.4 9.2 15.5 13.2
1300 75 37-303 2.35 62.4 2.3 18.2 12.6
F 1000 rectangle 126 37-303 0.96 63.0 35.9 55.2 8.8
1100 110 37-303 1.37 56.3 3.0 20.5 6.5
상기 표-2에서 보는 바와 같이, 본 실시예에 의해 제조된 산소공여입자들은 유동층 공정에 적합한 조건들을 갖추고 있음을 알 수 있다. 즉, 산소공여입자의 형상은 구형이며, 평균 입자크기가 50~200㎛ 범위 이내이고, 입자크기 분포는 30~500㎛ 범위 이내이며, 충진밀도는 0.6~3.0g/mL 범위 이내이고, Hg 기공도가 30%이상이며, 비표면적은 0.1㎡/g이상이고, 내마모도는 60%이하이며, 산소전달능력은 5wt% 이상이다.As shown in Table 2, it can be seen that the oxygen donor particles prepared according to the present example have suitable conditions for the fluidized bed process. That is, the shape of the oxygen donor particles is spherical, the average particle size is within the range of 50 ~ 200㎛, the particle size distribution is within the range of 30 ~ 500㎛, the filling density is within the range of 0.6 ~ 3.0g / mL, Hg pores The degree is more than 30%, the specific surface area is more than 0.1㎡ / g, the wear resistance is less than 60%, and the oxygen transfer capacity is 5wt% That's it.
상기의 실시예에서 보는 바와 같이 본 발명 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법에 의하면, 유동층 공정에 적합한 구형의 형상과 입자크기, 입자크기분포, 충진 밀도, 그리고 높은 기공도, 반응에 유리한 기공구조 및 우수한 산소전달능력(oxygen transfer capacity)를 가진 산소공여입자를 제조할 수 있음을 알 수 있다.As can be seen from the above examples, according to the method for producing oxygen circulation particles or medium circulation reforming oxygen donor particles of the present invention, the spherical shape and particle size, particle size distribution, packing density, and high porosity, which are suitable for fluidized bed process, It can be seen that oxygen donor particles having a pore structure and an excellent oxygen transfer capacity that are favorable for the reaction can be prepared.
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, although described based on the preferred embodiment according to the present invention, the present invention is not limited to the specific embodiment, can be changed within the scope described in the claims by those of ordinary skill in the art have.
본 발명에 따른 매체순환연소 또는 매체순환개질용 산소공여입자에 의하면, 고성능 산소공여입자가 필수인 매체순환연소나 매체순환개질의 기술개발 완성도를 높임으로써, 기존의 연소방식이나 합성가스생산방식을 대체하여 열효율 저하 없이 이산화탄소를 원천적으로 분리하거나, 저비용으로 합성가스를 생산할 수 있다.According to the medium-circulating combustion or the medium-circulating reforming oxygen donor particles according to the present invention, the existing combustion method or the synthesis gas production method is improved by improving the completion of technology development of medium-circulating combustion or medium circulation reforming, in which high-performance oxygen donor particles are essential. Alternatively, carbon dioxide can be separated at source without lowering thermal efficiency, or syngas can be produced at low cost.
본 발명에 따른 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법에 의하면, 유동층 공정에 적합한 구형의 형상과 입자크기, 입자크기분포, 충진 밀도와 강도, 그리고 높은 기공도, 반응에 유리한 기공구조 및 우수한 산소전달능력(oxygen transfer capacity)를 가지는 산소공여입자를 제조할 수 있다.According to the method for producing oxygen circulation particles for medium circulation combustion or medium circulation reforming according to the present invention, the spherical shape and particle size, particle size distribution, packing density and strength, high porosity and porosity which are favorable for the fluidized bed process Oxygen donor particles having a structure and excellent oxygen transfer capacity can be prepared.
따라서, 본 발명은 대기 중 이산화탄소 농도 증가로 인한 기후변화 예방을 위해 향후 이산화탄소 포집설비가 필요한 화력발전소나 열병합발전소 등의 설비와 연료의 가스화나 천연가스개질을 통해 합성가스를 생산하고 있는 설비를 대체할 수 있는 신기술로 급부상하고 있는 매체순환연소 및 매체순환개질의 핵심기술로 산업상 그 이용이 크게 기대된다.Therefore, the present invention replaces a facility such as a thermal power plant or a cogeneration plant that requires a carbon dioxide capture facility in the future to prevent climate change due to an increase in the concentration of carbon dioxide in the atmosphere, and a facility that produces syngas through gasification of fuel or natural gas reforming. It is expected to be used in industry as a core technology of media circulation combustion and media circulation reform, which is emerging as a new technology that can be rapidly developed.

Claims (12)

  1. 가스 또는 고체상 연료를 연소시키는 매체순환연소나 연료의 부분산화를 통해 합성가스 또는 수소를 생산하는 매체순환개질에 사용되는 산소공여입자에 있어서,Oxygen donor particles used in the medium circulation reforming to burn gas or solid fuel or the medium circulation reforming to produce syngas or hydrogen through partial oxidation of fuel,
    상기 산소공여입자의 고체원료는,The solid raw material of the oxygen donor particles,
    활성물질인 니켈옥사이드(NiO) 40~80 중량%, 비표면적과 강도를 부여하기 위한 지지체로 세라믹류 및 점토류 20~60중량%로 이루어진 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자.Nickel oxide (NiO) as active material 40 to 80% by weight, support for imparting specific surface area and strength, oxygen circulation for medium circulation combustion or media circulation reforming, characterized in that consisting of 20 to 60% by weight of ceramics and clays particle.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 지지체로 세라믹류는 감마알루미나(γ-Al2O3) 또는 유사 보에마이트로 총 고체원료중 0.1~60 중량%를 차지하고, 점토류는 벤토나이트로 총 고체원료중 0.1~30 중량%를 차지하는 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자.As the support, ceramics are gamma alumina ( γ- Al 2 O 3 ) or pseudo boehmite, which accounts for 0.1 to 60% by weight of the total solid material, and clays are bentonite, which accounts for 0.1 to 30% by weight of the total solid material. Oxygen donor particles for medium circulation combustion or medium circulation reforming, characterized in that.
  3. 상기 제1항 또는 제2항의 고체원료를 이용해 슬러리를 제조하는 단계;Preparing a slurry using the solid raw material of claim 1 or 2;
    슬러리를 분무 건조기를 이용해 산소공여입자를 일차 성형하는 단계;및Primary molding the slurry using a spray dryer for oxygen donor particles; and
    일차 성형된 산소공여입자를 건조 소성시켜 최종 산소공여입자를 성형하는 단계를 포함하는 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.Method for producing a medium-circulating combustion or medium-circulation reforming oxygen donor particles comprising the step of drying the primary molded oxygen donor particles to dry firing.
  4. 제 3 항에 있어서,The method of claim 3, wherein
    상기 슬러리 제조단계에서 제조된 슬러리의 농도는 15~50중량%인 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.The concentration of the slurry produced in the slurry production step is a method for producing oxygen circulation particles or medium circulation reforming, characterized in that the 15 to 50% by weight.
  5. 제 4 항에 있어서,The method of claim 4, wherein
    상기 슬러리 제조단계는,The slurry manufacturing step,
    고체원료가 물에 잘 섞이고 서로 응집되지 않도록 분산제를 첨가하는 단계;Adding a dispersant such that the solid raw material mixes well with water and does not aggregate with each other;
    교반 또는 분쇄시 발생될 수 있는 거품을 억제 또는 제거하기 위해 소포제를 첨가하는 단계; 및Adding an antifoaming agent to inhibit or remove foam which may occur upon stirring or grinding; And
    분무 건조시 입자 형상을 유지하기 위해 유기결합제를 첨가하는 단계를 포함하는 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.Method for producing oxygen-circulating combustion medium or oxygen circulation particles for media circulating combustion comprising the step of adding an organic binder to maintain the particle shape during spray drying.
  6. 제 5 항에 있어서,The method of claim 5,
    상기 분산제는 음이온계 또는 비이온계이며 상기 고체원료 총중량 대비 0.01~10중량%를 첨가하며, 상기 소포제는 시리카실리콘계, 실리콘계, 금속비누계, 아미도계, 폴리에테르계, 폴리글라이콜계, 유기인산계, 고급알코올계 또는 유산지방계이며 상기 고체원료 총중량 대비 0.001~1중량%를 첨가하며, 상기 유기결합제는 폴리비닐알콜계, 폴리에틸렌글라이콜계, 메틸셀룰로즈계 또는 폴리에틸렌옥사이드계이며 상기 고체원료 총중량 대비 0.5~5중량%를 첨가하는 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.The dispersant is an anionic or nonionic and adds 0.01 to 10% by weight relative to the total weight of the solid raw material, and the antifoaming agent is a silica silicon-based, silicon-based, metal soap-based, amido-based, polyether-based, polyglycol-based, organic phosphorus Acid-based, higher alcohol-based or lactic acid-based, add 0.001 ~ 1% by weight to the total weight of the solid material, the organic binder is polyvinyl alcohol, polyethylene glycol, methyl cellulose or polyethylene oxide based on the total weight of the solid material Method for producing oxygen circulation particles for medium circulation combustion or medium circulation reforming, characterized in that 0.5 to 5% by weight is added.
  7. 제 3 항에 있어서,The method of claim 3, wherein
    상기 슬러리 제조단계에서 이물질을 제거하는 과정을 포함하는 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.Method for producing a medium circulation combustion or medium circulation reforming oxygen donor particles comprising the step of removing the foreign matter in the slurry manufacturing step.
  8. 제 7 항에 있어서,The method of claim 7, wherein
    이물질을 제거하는 과정에서 체거름을 통해 이물질을 제거하는 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.Method for producing a medium circulation combustion or medium circulation reforming oxygen donor particles, characterized in that to remove the foreign matter through a sieving in the process of removing the foreign matter.
  9. 제 3 항에 있어서,The method of claim 3, wherein
    상기 소성과정에서는 건조된 상기 산소공여입자를 공기 분위기의 고온 소성로에 넣고 1~5℃/min의 속도로 900~1300℃로 상승시킨 후 2~10시간 소성시키는 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.In the firing process, the dried oxygen donor particles are placed in a high temperature firing furnace in an air atmosphere, and then heated to 900 to 1300 ° C. at a rate of 1 to 5 ° C./min, and then calcined for 2 to 10 hours. Method for preparing oxygen donor particles for circulation reforming.
  10. 제 9 항에 있어서,The method of claim 9,
    상기 소성과정에서의 소성시간은 4~6시간인 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.The firing time in the firing process is a method for producing oxygen circulation particles or medium circulation reforming oxygen donor particles, characterized in that 4 to 6 hours.
  11. 제 9 항 또는 제 10 항에 있어서,The method according to claim 9 or 10,
    일차 성형된 상기 산소공여입자를 건조시키는 과정에서는 110~130℃의 건조온도에서 2~100시간 건조시키는 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.In the process of drying the primary molded oxygen donor particles, the method for producing oxygen circulation particles or medium circulation reforming, characterized in that the drying for 2 to 100 hours at a drying temperature of 110 ~ 130 ℃.
  12. 제 3 항에 있어서,The method of claim 3, wherein
    상기 최종 성형된 산소공여입자는, 형상이 구형이며, 평균 입자크기가 50~200㎛ 범위 이내이고, 입자크기 분포는 30~500㎛ 범위 이내이며, 충진밀도는 0.6~3.0g/mL 범위 이내이고, Hg 기공도가 30~80% 범위 이내이며, 비표면적은 0.1~100㎡/g 범위 이내이고, 내마모도는 0초과 60%이하의 범위 이내이며, 산소전달능력은 5~17wt% 범위 이내인 것을 특징으로 하는 매체순환연소 또는 매체순환개질용 산소공여입자의 제조방법.The final molded oxygen donor particles, the shape is spherical, the average particle size is within the range of 50 ~ 200㎛, the particle size distribution is within the range of 30 ~ 500㎛, the filling density is within the range of 0.6 ~ 3.0g / mL , Hg porosity is within the range of 30 ~ 80%, specific surface area is within the range of 0.1 ~ 100㎡ / g, wear resistance is within the range of more than 0 and less than 60%, oxygen transfer capacity is within the range of 5 ~ 17wt%. Method for producing oxygen circulation particles for medium circulation combustion or medium circulation reforming characterized in that.
PCT/KR2009/006364 2009-10-30 2009-10-30 Oxygen donor particles for chemical looping combustion or chemical looping reforming, and preparation method thereof WO2011052825A1 (en)

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