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WO2020004751A1 - Composition de matière première pour la fabrication de particules de transfert d'oxygène, particules de transfert d'oxygène fabriquées à l'aide de celle-ci, et méthode de fabrication de particules de transfert d'oxygène - Google Patents

Composition de matière première pour la fabrication de particules de transfert d'oxygène, particules de transfert d'oxygène fabriquées à l'aide de celle-ci, et méthode de fabrication de particules de transfert d'oxygène Download PDF

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Publication number
WO2020004751A1
WO2020004751A1 PCT/KR2019/000135 KR2019000135W WO2020004751A1 WO 2020004751 A1 WO2020004751 A1 WO 2020004751A1 KR 2019000135 W KR2019000135 W KR 2019000135W WO 2020004751 A1 WO2020004751 A1 WO 2020004751A1
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Prior art keywords
oxygen transfer
particles
transfer particles
oxygen
slurry
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PCT/KR2019/000135
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English (en)
Korean (ko)
Inventor
김의식
백점인
엄태형
이중범
조현근
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Korea Electric Power Corp
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Korea Electric Power Corp
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Publication of WO2020004751A1 publication Critical patent/WO2020004751A1/fr
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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
    • C01B13/02—Preparation of oxygen
    • C01B13/08—Preparation of oxygen from air with the aid of metal oxides, e.g. barium oxide, manganese oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/08—Preparation of oxygen from air with the aid of metal oxides, e.g. barium oxide, manganese oxide
    • C01B13/086—Preparation of oxygen from air with the aid of metal oxides, e.g. barium oxide, manganese oxide with manganese oxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C10/00—Fluidised bed combustion apparatus
    • F23C10/01—Fluidised bed combustion apparatus in a fluidised bed of catalytic particles

Definitions

  • the present invention relates to a raw material composition for preparing oxygen transfer particles, an oxygen transfer particle and an oxygen transfer particle manufacturing method produced using the same.
  • thermal power plants are the largest source of anthropogenic carbon dioxide emissions. Reduction of carbon dioxide emissions from thermal power plants can be achieved through carbon capture and storage (CCS).
  • CCS carbon capture and storage
  • new new technologies are required to minimize the reduction in power generation efficiency and to lower the cost of CO 2 capture.
  • Chemical Looping Combustion (CLC) technology is attracting attention as a technology that can separate CO 2 with reduced power generation efficiency.
  • CLC Chemical Looping Combustion
  • oxygen and fuel contained in solid particles (oxygen transfer particles) mainly composed of metal oxides instead of air react with each other to cause combustion, and thus, only the water vapor and CO 2 are included in the exhaust gas. Therefore, when the water vapor condenses, so removed, leaving the CO 2 may be the CO 2 source separated.
  • oxygen contained in oxygen transfer particles is transferred to a fuel, and oxygen transfer particles undergo a reaction in which a reduction reaction occurs, and oxygen transfer particles reduced by receiving oxygen contained in air are oxidized again.
  • the initial stages of regenerated air reactors consist of a combination of interconnections. Both reactors use a fluidized bed reactor and the whole process is a circulating fluidized-bed process.
  • Oxygen transfer particles applied to the CLC process must satisfy various conditions suitable for the fluidized bed process characteristics. First, they must have adequate physical properties, i.e. sufficient strength, shape and packing density (packing density or tapped density), average particle size and particle size distribution for the fluidized bed process. In addition, it has a high oxygen transfer capacity in terms of reactivity so that it can supply enough oxygen for the combustion of the fuel while the fuel passes through the fuel reactor.
  • conventional oxygen transfer particles are manufactured by methods that are not suitable for mass production, or properties such as shape, strength, density, etc. are inappropriate or need to be improved for the fluidized bed process, and in order to reduce interaction strength between metal oxides and supports.
  • a support having a stable crystal structure the oxygen transfer performance is reduced due to the increase of the firing temperature to obtain sufficient strength, or the fluidization is not performed due to the aggregation phenomenon between the particles during the reaction, or the oxygen transfer amount is low due to the low content of metal oxides. have.
  • the conventional oxygen transfer particles NiO-based oxygen transfer particles, which are expensive metals, are mainly used because of excellent oxygen transfer rate, oxygen transfer amount, and durability. Therefore, in order to improve the technical, economical and environmental aspects of the chemical looping technology, it is required to develop low-cost oxygen transfer particles having excellent oxygen transfer rate, oxygen transfer amount, and wear resistance without using NiO.
  • One object of the present invention is to provide a raw material composition for preparing oxygen-transfer particles having a physical property including strength, which is suitable for a fluidized bed process, which is inexpensive compared to the prior art, and which has an excellent oxygen transfer rate, oxygen transfer amount, and wear resistance.
  • Another object of the present invention is to prepare a homogeneously dispersed stable colloidal slurry using the raw material composition, and using the same, the shape and particle size (size) suitable for chemical looping combustion circulating fluidized bed process ), Particle distribution (size distribution), mechanical strength or attrition resistance, and provides a low-cost, high oxygen transfer rate, oxygen transfer amount and abrasion resistance compared to the prior art and the oxygen transfer particles and a method for producing the same. .
  • Another object of the present invention is to separate and collect carbon dioxide generated by combustion while burning the fuel effectively using the oxygen transfer particles, the particle filling amount in the chemical looping combustion process and abrasion generated during long time operation It is to provide a chemical looping combustion method that prevents a decrease in system thermal efficiency due to carbon dioxide capture while reducing the replenishment amount due to loss.
  • One embodiment of the present invention comprises about 30% to about 50% copper oxide; About 20% to about 40% manganese oxide; About 5% to about 20% magnesium oxide or magnesium hydroxide; About 10 wt% to about 30 wt% of aluminum oxide or aluminum hydroxide in sol or powder form; It relates to a raw material composition for producing oxygen transfer particles comprising a.
  • the copper oxide may have an average particle size of greater than about 0 to about 5 ⁇ m, and purity of about 98% or more.
  • the manganese oxide may have an average particle size of greater than about 0 to about 5 ⁇ m, and purity of about 98% or more.
  • the magnesium oxide or magnesium hydroxide may have an average particle size greater than about 0 to about 5 ⁇ m, and purity may be about 98% or more.
  • the aluminum oxide or aluminum hydroxide in the form of a sol or powder may have an average particle size of greater than about 0 to about 5 ⁇ m and a purity of about 95% or more.
  • Another embodiment of the present invention relates to an oxygen transfer particle formed from the above-described raw material composition for preparing oxygen transfer particles and including copper oxide, manganese oxide, magnesium oxide and aluminum oxide.
  • the oxygen transfer particles may be nickel oxide-free oxygen transfer particles that do not contain nickel oxide.
  • the oxygen transfer particles may have a structure of the following formula (1).
  • a, b, c, and d are each independently about 0.1 to about 2.7, the sum of a + b + c + d is about 3, and x is about 0 to about 4.
  • the oxygen transfer particles were subjected to abrasion test at a flow rate of 10.00 l / min (273.15 K, 1 bar) for 5 hours using an abrasion tester, and the wear index represented by the following Equation 1 was about 20% or less. Can be.
  • W1 is the weight in grams before the abrasion test of the sample
  • W2 is the weight in grams of the fine particles collected during the five hours the wear test of the sample.
  • the oxygen carrier particles are non-blowhole spherical, have an average particle size of about 60 ⁇ m to about 150 ⁇ m, a particle size distribution of about 30 ⁇ m to about 400 ⁇ m, and a packing density of about 1.5. g / mL to about 4.0 g / mL.
  • the oxygen transfer particles may have an oxygen transfer amount of about 7% by weight to about 15% by weight of the total oxygen transfer particles.
  • Another embodiment of the present invention comprises the steps of (A) mixing the above-described raw material composition for preparing oxygen transfer particles with a solvent to prepare a slurry for preparing oxygen transfer particles; (B) stirring the slurry to produce a homogenized slurry; (C) spray drying the slurry to form solid particles; And (D) drying and sintering the molded solid particles to produce oxygen transfer particles.
  • step (A) of preparing a slurry for preparing oxygen transport particles the raw material composition for preparing oxygen transport particles and the solvent may be mixed in a weight ratio of about 15 to 40: about 60 to 85, and the solvent may be water.
  • the slurry may further include at least one additive of a dispersant, an antifoaming agent, and an organic binder.
  • the dispersant may include at least one of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants.
  • the anionic surfactant may include at least one of polycarboxylate and polycarboxylic acid amine salt.
  • the antifoaming agent may include at least one of a silicone antifoaming agent, a metal soap antifoaming agent, an amide antifoaming agent, a polyether antifoaming agent, a polyester antifoaming agent, a polyglycol antifoaming agent, and an alcohol antifoaming agent.
  • the organic binder may include one or more of polyvinyl alcohol, polyethylene glycol, and methyl cellulose.
  • the additive includes all of the dispersant, the antifoaming agent and the organic binder, the additive is about 0.01 parts by weight to about 5.0 parts by weight of the dispersant, about 0.01 parts by weight to about 1.0 parts by weight of the antifoaming agent with respect to 100 parts by weight of the raw material composition for preparing oxygen transfer particles, and
  • the organic binder may be added in an amount of about 1.0 part by weight to about 5.0 parts by weight.
  • Step (B) of preparing a homogenized slurry by stirring the slurry may further include removing foreign matter in the stirred and ground slurry.
  • step (C) of spray drying the slurry to form the solid particles after injecting the homogenized slurry into the spray dryer, the inlet temperature is about 260 ° C to about 300 ° C and the outlet temperature is about 90 ° C to about 150 ° C. It may include forming a solid particle by spraying while maintaining.
  • Drying and firing the molded solid particles to prepare oxygen-transfer particles (D) is to dry the molded solid particles from about 110 °C to about 150 °C for about 2 hours to about 24 hours, and put into a high temperature kiln Heating to about 1000 ° C. to about 1350 ° C. at a rate of about 1 ° C./min to about 5 ° C./min, and firing for about 2 hours to about 10 hours.
  • Another embodiment of the present invention includes the steps of reacting the aforementioned oxygen transfer particles with a fuel to reduce the oxygen transfer particles and combust the fuel, and reacting the reduced oxygen transfer particles with oxygen to regenerate the particles. It relates to a chemical looping combustion method.
  • the present invention is suitable for the fluidized bed process including the physical properties including the strength, the raw material composition for the production of oxygen transfer particles and the oxygen delivery rate, oxygen transfer amount and wear resistance excellent compared to the prior art and chemical loop loop combustion fluidized bed using the raw material composition It has excellent abrasion resistance, long-term durability and oxygen transfer performance compared to the prior art because of its shape shape, particle size, particle distribution and mechanical strength or attrition resistance, which are suitable for the process. It is possible to provide an oxygen transfer particle and a manufacturing method thereof that can replace expensive nickel-based oxide, and the amount of filling in the chemical looping combustion process and the amount of replenishment due to abrasion loss generated during a long operation using the oxygen transfer particle. Can reduce the thermal efficiency of the system due to carbon dioxide capture. It can provide a chemical looping combustion method. In particular, the oxygen transfer particles made of a low cost raw material can reduce the operating cost of the chemical looping combustion process can improve the economics of the chemical looping combustion process.
  • FIG. 1 is a flow chart showing a method for producing oxygen transfer particles according to an embodiment of the present invention.
  • Figure 2 is a flow chart showing steps (A) and (B) of the method for producing oxygen transfer particles according to an embodiment of the present invention.
  • Figure 3 is a flow chart showing step (C) of the method for producing oxygen transfer particles according to an embodiment of the present invention.
  • Figure 4 is a flow chart showing step (D) of the method for producing oxygen transfer particles according to an embodiment of the present invention.
  • FIG. 5 is a schematic diagram of a chemical loop combustion method according to an embodiment of the present invention.
  • One embodiment of the present invention is copper oxide; Manganese oxide; Magnesium oxide or magnesium hydroxide; And it relates to a raw material composition for producing oxygen transfer particles comprising a raw material composition for preparing oxygen transfer particles, including aluminum oxide or aluminum hydroxide in the form of a sol or powder.
  • the raw material composition for preparing the oxygen transfer particles of the present invention is prepared by the oxygen transfer particles according to the oxygen transfer particle production method described below by adjusting the composition (composition), formulation and homogenizing degree of the raw material, fluidized bed Alternatively, it is possible to replace oxygen, which is inexpensive and relatively expensive compared to the prior art, and has physical properties such as shape, particle size and particle distribution suitable for high speed fluidized bed process, and oxygen Oxygen transfer particles having excellent delivery rate, oxygen transfer amount and wear resistance can be prepared.
  • the raw material composition for producing oxygen transport particles is copper oxide; Manganese oxide; Magnesium hydroxide; And aluminum hydroxide in sol or powder form; It may be to include.
  • the raw material composition for preparing oxygen transfer particles may include about 30 wt% to about 50 wt% of copper oxide; About 20% to about 40% manganese oxide; About 5% to about 20% magnesium oxide or magnesium hydroxide; About 10 wt% to about 30 wt% of aluminum oxide or aluminum hydroxide in sol or powder form; It may include.
  • Oxygen transfer particles produced by the raw material composition for the production of oxygen transfer particles deliver oxygen to gaseous fuels such as natural gas, shale gas, syngas as well as solid fuel, and again obtains oxygen from a gas containing oxygen such as air Fast regeneration characteristics are excellent and can be used repeatedly. Accordingly, when the oxygen transfer particles are applied to the chemical looping combustion process (CLC process) of gaseous fuel and / or solid fuel, the amount of refilling due to the particle filling amount and the abrasion loss generated during long time operation can be reduced, thereby reducing the chemical looping combustion. There is an effect of improving the economics while simplifying the process (CLC process). In particular, the oxygen transfer particles made of a low cost raw material can reduce the operating cost of the chemical looping combustion process can improve the economics of the chemical looping combustion process.
  • gaseous fuels such as natural gas, shale gas, syngas as well as solid fuel
  • F regeneration characteristics are excellent and can be used repeatedly. Accordingly, when the oxygen transfer particles are applied to the chemical loop
  • the raw material composition for preparing oxygen transfer particles of the present invention includes copper oxide and manganese oxide as active material raw materials.
  • Oxygen transfer particles composed of copper oxides and manganese oxides transfer oxygen while being reduced to copper (Cu) and manganese (Mn) when applied to chemical roofing combustion reactions without nickel oxide, and regenerated by receiving oxygen from air or water vapor. Play a role.
  • the copper oxide (CuO, Cu 2 O, etc.) may be a commercial copper oxide having an average particle size of greater than about 0 to about 5 ⁇ m. Within this range, the oxygen transfer rate and the oxygen transfer rate may be similar or improved to those of nickel oxide.
  • the copper oxide may have a purity of at least about 98%, for example at least about 99%. Within this range, the oxygen transfer particle rate and oxygen transfer amount can be further improved.
  • the manganese oxide (MnO, MnO 2 , Mn 2 O 3 , Mn 3 O 4, etc.) may be a commercial manganese oxide having an average particle size of more than about 0 to about 5 ⁇ m. Within this range, it is possible to produce oxygen transfer particles excellent in heat resistance and durability.
  • the manganese oxide may have a purity of at least about 98%, for example at least about 99%. Within this range, the wear resistance can be further improved.
  • the raw material composition for preparing oxygen transfer particles of the present invention may use only a mixture of copper oxide and manganese oxide as an active material raw material, or may be used by mixing some other metal oxides.
  • the kind of metal oxide that can be used in admixture with the copper oxide and manganese oxide is not particularly limited. Specifically, iron oxides containing iron oxides (FeO, Fe 2 O 3 , Fe 3 O 4 ) and the like and cobalt oxides containing cobalt oxides (CaO, Co 3 O 4 ) and the like can be exemplified.
  • the raw material composition for the production of oxygen transfer particles of the present invention can increase the magnesium (Mg) content while maintaining excellent oxygen transfer performance, which has the effect of solving the problem of coagulation between particles that may appear during oxidation and reduction cycle reaction of chemical looping combustion. have.
  • the magnesium oxide or magnesium hydroxide may be a commercial magnesium oxide or hydroxide having an average particle size of greater than about 0 to about 5 ⁇ m. Within this range, the problem of aggregation phenomenon of oxygen transfer particles can be solved.
  • the magnesium oxide or hydroxide may have a purity of at least 98%, for example at least 99%. Within this range, the aggregation phenomenon can be further prevented.
  • the raw material composition for preparing oxygen transfer particles of the present invention includes aluminum oxide or aluminum hydroxide as a support material.
  • Aluminum oxide or aluminum hydroxide is used as an inorganic binder in the oxygen carrier particles, thus providing sufficient strength required for fluidized bed processes.
  • aluminum oxide or aluminum hydroxide may be supported such that copper oxide and manganese oxide, which are active ingredients of the oxygen transfer particles, are uniformly distributed throughout the oxygen transfer particles, thereby increasing the utility of the active ingredient and promoting oxygen transfer performance.
  • the aluminum oxide or aluminum hydroxide may be a commercial aluminum oxide having an average particle size of greater than about 0 to about 5 ⁇ m in sol or powder form. Within this range, the durability of the oxygen transfer particles is improved and the degree of dispersion of the active material is made uniform.
  • the aluminum oxide or aluminum hydroxide may have a purity of at least about 95%, for example at least about 99%. Within this range, it is possible to further improve the oxygen transfer rate, oxygen transfer amount and wear resistance of the oxygen transfer particles.
  • the raw material composition for the production of oxygen transfer particles of the present invention by using a combination of the active ingredient of copper oxide and manganese oxide and the magnesium hydroxide and aluminum hydroxide as an active material raw material, the active ingredient and magnesium oxide and / or aluminum oxide
  • the active ingredient and magnesium oxide and / or aluminum oxide When compared to the case of using only one of the magnesium compound and aluminum compound as a hydroxide, it is possible to further improve the oxygen transfer amount, strength, sintering prevention effect of the oxygen transfer particles.
  • Another embodiment of the present invention relates to an oxygen transfer particle formed from the above-described raw material composition for preparing oxygen transfer particles and including copper oxide, manganese oxide, magnesium oxide and aluminum oxide.
  • Oxygen transfer particles are prepared using the above-described raw material composition, thereby having a particle shape, particle size, particle distribution, and mechanical strength or attrition resistance suitable for chemical looping combustion circulating fluidized bed process. It is possible to provide an oxygen transfer particle and a method of manufacturing the same, which are excellent in wear resistance, long-term durability and oxygen transfer performance, and can replace nickel-based oxide, which is more expensive than the prior art.
  • the oxygen transfer particles may be nickel oxide-free oxygen transfer particles that do not contain nickel oxide.
  • the oxygen transfer particles may be a structure represented by the following formula (1).
  • a, b, c, and d are each independently about 0.1 to about 2.7, the sum of a + b + c + d is about 3, and x is greater than about 0 to about 4.
  • the a, b, c and d are each, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, and the sum of a + b + c + d is, for example, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, wherein x is for example, 0.1, 0.2,
  • the oxygen transfer particle of the present invention implements an excellent oxygen transfer rate, oxygen transfer amount and wear resistance by the composition and structural characteristics of the component metal.
  • the oxygen transfer particles are applied to chemical looping combustion process and apparatus, it is possible to reduce the amount of particle filling and wear loss required for long time operation.
  • the oxygen carrier particles of the present invention are stable and evenly dispersed oxygen solid particles in the slurry state to an average size of about 5 ⁇ m or less, for example, about 1 ⁇ m or less, so that the final firing after spray drying Long-term durability of oxygen transfer particles is excellent, and it has spherical shape and particle size, particle size distribution, packing density, strength, low firing temperature and excellent oxygen transfer performance suitable for fluidized bed process.
  • the raw material composition for preparing oxygen transfer particles may be about 30 wt% to about 50 wt%, for example, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt% of copper oxide.
  • the raw material composition for producing oxygen transport particles is copper oxide; Manganese oxide; Magnesium hydroxide; And aluminum hydroxide in sol or powder form; It may be to include.
  • the oxygen transfer particles were subjected to abrasion test at a flow rate of 10.00 l / min (273.15 K, 1 bar) for 5 hours using an abrasion tester, followed by a wear index of 20% or less. For example, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5 %, 4%, 3%, 2%, 1%.
  • W1 is the weight in grams before the abrasion test of the sample
  • W2 is the weight in grams of the fine particles collected during the five hours the wear test of the sample.
  • the lower limit of the wear index is not particularly limited, and the closer to 0% is, the better. Within the above range, when the oxygen transfer particles are used for chemical looping combustion, the wear loss rate is further reduced, thereby reducing the amount of oxygen transfer particles to be replenished during the process operation, and reducing the production rate of the fine powder generated during the process. It is more advantageous for application to a circulating fluidized bed process.
  • the oxygen carrier particles are non-blowhole spherical, have an average particle size of about 60 ⁇ m to about 150 ⁇ m, a particle size distribution of about 30 ⁇ m to about 400 ⁇ m, and a packing density of about 1.5 g / mL to about 4.0 g / mL.
  • the wear loss rate is further reduced, so that the amount of oxygen transfer particles to be replenished during the process operation can be reduced, and the production rate of the fine powder generated during the process is lowered to circulate the fluidized bed. It has more advantageous properties for application to processes and the like.
  • the non-blowhole means a spherical shape except for a shape including a blowhole such as a dimple shape and a hollow shape.
  • the average particle size and particle size distribution of the oxygen transfer particles may be about 60 ⁇ m to about 150 ⁇ m, more specifically about 70 ⁇ m to about 130 ⁇ m, particle size distribution is about 30 ⁇ m About 400 ⁇ m, more specifically about 38 ⁇ m to about 350 ⁇ m.
  • the packing density of the oxygen transfer particles may be specifically about 1.5 g / mL to about 3.0 g / mL, specifically about 2 g / mL to about 2.5 g / mL.
  • the oxygen transfer particles may have an oxygen transfer amount of about 7 wt% to about 15 wt%, specifically about 9 wt% to about 12 wt%, for example, 7 wt%, 8 wt%, and 9 wt% of the total oxygen transfer particle weight. %, 10%, 11%, 12%, 13%, 14%, 15% by weight.
  • Another embodiment of the present invention comprises the steps of (A) mixing the above-described raw material composition for preparing oxygen transfer particles with a solvent to prepare a slurry for preparing oxygen transfer particles; (B) stirring the slurry to produce a homogenized slurry; (C) spray drying the slurry to form solid particles; And (D) drying and sintering the molded solid particles to produce oxygen transfer particles.
  • the slurry for preparing oxygen transfer particles may be prepared by mixing the aforementioned raw material composition for preparing oxygen transfer particles with a solvent.
  • the raw material composition for preparing oxygen transfer particles may include about 30 wt% to about 50 wt% of copper oxide; About 20% to about 40% manganese oxide; About 5% to about 20% magnesium oxide or magnesium hydroxide; About 10% to about 30% by weight of aluminum oxide or hydroxide in sol or powder form; It may include.
  • the slurry for preparing oxygen transport particles is prepared by mixing the above-described raw material composition for preparing oxygen transport particles in a solvent.
  • the raw material composition for preparing oxygen transport particles and the solvent may be mixed in a weight ratio of about 15 to 40: about 60 to 85.
  • the amount of solvent to be evaporated during spray drying and the solid content of the raw material composition for preparing oxygen-transfer particles are maintained in an appropriate range, the viscosity is maintained within an appropriate range to improve fluidity, and more easily grind when homogenizing, Excellent manufacturing efficiency can be achieved.
  • the kind of the solvent is not particularly limited, and a solvent generally used in this field may be used. Specifically, water may be used as the solvent. In this case, workability and manufacturing efficiency in the homogenization and firing process can be further improved.
  • the slurry may further include at least one additive of a dispersant, an antifoaming agent, and an organic binder.
  • the additive may be mixed with the raw material composition for preparing oxygen transfer particles in a state previously added to the solvent described above.
  • the dispersibility of the raw material composition for preparing oxygen transfer particles and the mixing property with the solvent can be further improved.
  • the dispersant may prevent a phenomenon in which the components included in the raw material composition for preparing oxygen transfer particles are agglomerated with each other when the slurry is crushed to be described below.
  • the efficiency of controlling the particle size of the raw material components constituting the oxygen transfer particles in the homogenization process can be further improved.
  • the dispersant may use one or more of anionic surfactants, cationic surfactants and nonionic surfactants.
  • the anionic surfactant may be, for example, poly carboxylate ammonium salts or poly carboxylate amine salts. In such a case, the function of controlling charge control, dispersion and aggregation of the particle surface by the dispersant can be further improved, and the slurry can be made highly concentrated.
  • the dispersing agent may improve the efficiency in which the shape of the molded body (oxygen transfer particle assembly), ie, the green body, produced when the slurry is spray-dried is manufactured into a spherical shape other than a donut type, dimple type and blow type.
  • the content of the dispersant is about 0.01 part by weight to about 5 parts by weight, for example 0.01 part by weight, 0.05 part by weight, 0.1 part by weight, 0.5 part by weight, 1 part by weight, based on 100 parts by weight of the raw material composition for preparing oxygen transfer particles. 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts by weight. Within this range, the dispersion effect of the oxygen transfer particles may be more excellent.
  • the defoamer may be used to remove bubbles in the slurry to which the dispersant and the organic binder are applied.
  • the antifoaming agent may include at least one of a silicone antifoaming agent, a metal soap antifoaming agent, an amide antifoaming agent, a polyether antifoaming agent, a polyester antifoaming agent, a polyglycol antifoaming agent, and an alcohol antifoaming agent.
  • a silicone antifoaming agent e.g., silicone antifoaming agent
  • a metal soap antifoaming agent e.g., a metal soap antifoaming agent
  • an amide antifoaming agent e.g., a polyether antifoaming agent
  • a polyester antifoaming agent e.glycol antifoaming agent
  • an alcohol antifoaming agent e.glycol antifoaming agent
  • the amount of the antifoaming agent may be about 0.01 parts by weight to about 1.0 parts by weight, for example, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, and 1 parts by weight based on 100 parts by weight of the raw material composition for preparing oxygen transfer particles. have. Within the above range, it is possible to reduce the generation of bubbles during the slurry manufacturing process, to improve the efficiency of producing the spherical oxygen transfer particles during spray drying, and to further improve the oxygen transfer amount by reducing the content of residual ash after firing. have. More specific content of the antifoaming agent can be added or subtracted according to the amount of foaming.
  • the organic binder is added in the slurry manufacturing step to impart plasticity and fluidity to the slurry and ultimately to give strength to the oxygen-transferred particles assembled by spray-drying molding, that is, before drying and firing Handling of the green body can be facilitated.
  • the organic binder may be used at least one of polyvinyl alcohol, polyethylene glycol, and methyl cellulose.
  • the content of the organic binder is about 1 part by weight to about 5 parts by weight, for example 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, based on 100 parts by weight of the raw material composition for preparing oxygen transfer particles. , 3.5 parts, 4 parts, 4.5 parts, 5 parts by weight.
  • the binding force of the solid particles formed by spray drying is improved, so that the property of maintaining a spherical shape before drying and firing can be improved, and the content of residual ash after firing is further reduced to further improve oxygen transfer amount. You can.
  • the additive includes all of the dispersant, the antifoaming agent and the organic binder, the additive is about 0.01 parts by weight to about 5.0 parts by weight of dispersant and about 1.0 parts by weight of organic binder based on 100 parts by weight of the raw material composition for preparing oxygen transfer particles.
  • the additive is about 0.01 parts by weight to about 5.0 parts by weight of dispersant and about 1.0 parts by weight of organic binder based on 100 parts by weight of the raw material composition for preparing oxygen transfer particles.
  • an antifoaming agent may be added in the slurry. In such a case, it is advantageous to control the average particle size, particle size distribution and shape of the oxygen transfer particles while further improving the oxygen transfer amount of the oxygen transfer particles.
  • the slurry may be a flowable colloidal slurry. In this case, workability and manufacturing efficiency in the homogenization and firing process can be further improved.
  • Step (B) of preparing a homogenized slurry by stirring the slurry may include homogenizing the slurry prepared by stirring and pulverizing the slurry prepared above using a stirrer.
  • control properties such as the homogenization properties of the slurry, the concentration of the slurry, the viscosity, the stability, the flowability and the strength and density of the particles after spray drying can be further improved.
  • the stirring may be performed in the process of adding the components included in the mixture or in a state in which all the components included are added. At this time, the stirring may be performed using, for example, a stirrer.
  • the slurry prepared by mixing the solvent and / or additives with the composition for preparing oxygen-transfer particles is pulverized using a pulverizer after stirring to make the particle size in the slurry to several microns ( ⁇ m) or less.
  • the particles pulverized in this process are more homogeneously dispersed in the slurry, and aggregation of the particles in the slurry is suppressed, so that a homogeneous and stable slurry can be produced.
  • the grinding process may be repeated several times, and the fluidity of the slurry may be controlled by adding a dispersant and an antifoaming agent between each grinding process.
  • a wet milling method may be used as the grinding method.
  • the grinding effect can be improved, and problems such as blowing out of particles generated during dry grinding can be solved.
  • the particle diameter of the raw material composition particles are several microns or less, a separate grinding process may be omitted.
  • removing the foreign matter in the stirred and pulverized slurry may be further performed.
  • step (C) of spray drying the slurry to form the solid particles the homogenized slurry is introduced into a spray dryer, and then the inlet temperature is about 260 ° C to about 300 ° C, for example, 260 ° C, 270 ° C, 280 ° C, 290 °C, 300 °C, outlet temperature is about 90 °C to about 150 °C, for example, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C while maintaining the spray to form a solid particle It may include.
  • Molding of the slurry may be performed using a spray dryer, and specifically, the homogenized slurry may be transferred to a spray dryer through a pump, and then the solid particles may be molded by spraying the transferred slurry composition into the spray dryer.
  • Molding of the slurry may be more advantageous in that the particle shape remains spherical during spray drying when an organic binder is added.
  • the shape and operating conditions of the spray dryer for forming the oxygen transfer particles in the spray dryer may apply the operating conditions generally used in this field.
  • the fluidized homogenized slurry may be sprayed by a countercurrent spray method in which the fluid is sprayed in a direction opposite to that of the drying air using a pressurized nozzle, thereby forming oxygen transfer particles.
  • the inlet temperature of the spray dryer may be maintained at 260 °C to 300 °C, the outlet temperature is 90 °C to 150 °C.
  • the efficiency of producing the spherical oxygen transfer particles within the temperature range can be further improved.
  • Drying and firing the molded solid particles to prepare oxygen-transfer particles (D) comprises drying the molded solid particles at 110 ° C. to 150 ° C. for 2 to 24 hours, and putting the molded solid particles into a high temperature baking furnace at about 1 ° C./min to Heating to about 1050 ° C. to about 1350 ° C. at a rate of about 5 ° C./min, and firing for about 2 hours to about 10 hours.
  • the drying When the drying is performed at the above temperature and time conditions, it is possible to prevent the phenomenon of cracking in the particles due to expansion of moisture in the particles during firing.
  • the drying may be performed in an air atmosphere.
  • the dried particles are placed in a high temperature kiln, about 1 °C / min to about 5 °C / min, for example 1 °C / min, 2 °C / min, 3 °C / min, 4 °C / min, 5 Raising the final firing temperature at about 1050 ° C. to about 1350 ° C., for example 1050 ° C., 1100 ° C., 1150 ° C., 1200 ° C., 1250 ° C., 1300 ° C., 1350 ° C., at a rate of C. min.
  • the organic additives disersant, antifoaming agent and organic binder
  • the raw materials are bonded to each other to improve the strength of the particles.
  • the firing temperature range it is possible to sufficiently improve the oxygen transfer amount while preventing the firing temperature from being insufficient to lower the strength of the oxygen transfer particles.
  • the firing may be performed by a method of giving a stagnation section of about 30 minutes or more at stagnation temperatures of two or more stages up to the final firing temperature.
  • a method of giving a stagnation section of about 30 minutes or more at stagnation temperatures of two or more stages up to the final firing temperature it is possible to prevent the destruction of the particle shape by the gas generated by the water evaporation and combustion of the organic additive inside the oxygen transfer particles to be produced.
  • the firing may be performed by using a firing furnace such as a muffle furnace, tubular furnace or kiln.
  • a firing furnace such as a muffle furnace, tubular furnace or kiln.
  • the oxygen transfer particles are prepared by adding a raw material composition for preparing oxygen transfer particles to a solvent (A), preparing a mixed slurry into a homogenized slurry through grinding and dispersing (B), Spray drying the homogenized slurry into solid particles (C) and drying and firing the molded solid particles (green body of oxygen carrier particles) to prepare final oxygen carrier particles (D) It includes.
  • FIG. 2 is a flow chart showing steps (A) and (B) of the method for producing oxygen transfer particles according to an embodiment of the present invention.
  • 2 shows an exemplary process of preparing a mixture of raw material composition and water into a slurry.
  • the slurry is prepared by adding an additive to water (S11), mixing a solid raw material into water (S12), adding an organic additive to the mixture (S21), and mixing the slurry. Grinding and dispersing to homogenize and prepare a dispersed slurry (S22), and may further comprise a step (S23) of removing foreign matter contained in the slurry.
  • FIG. 3 is a flow chart showing step (C) of the method for producing oxygen transfer particles according to an embodiment of the present invention.
  • 3 illustrates an exemplary process of spray drying the slurry to form oxygen transfer particles.
  • the step of spray drying the slurry to form oxygen transfer particles (S30) may include transferring the slurry to the spray dryer (S31) and spraying the transferred slurry into the spray dryer to form the oxygen transfer particles.
  • Step S32 may be included.
  • Figure 4 is a flow chart showing step (D) of the method for producing oxygen transfer particles according to an embodiment of the present invention. 4 shows an exemplary process of dry firing the oxygen carrier particles formed by spray drying to produce final oxygen transfer particles. As shown in FIG. 4, the molded oxygen transfer particle biomaterial may be prepared as a final oxygen transfer particle through a preliminary drying process (S41) and then through a sintering process (S42).
  • Another embodiment of the present invention includes chemical looping combustion comprising reacting the aforementioned oxygen transfer particles with a fuel to combust the fuel, reducing the oxygen transfer particles, and reacting the reduced oxygen transfer particles with oxygen to regenerate it. It is about a method.
  • the fuel is not particularly limited and may be used in solid, liquid and gas phases, and may preferably be a gas fuel.
  • the gaseous fuel used in the present invention is not particularly limited, and for example, one selected from the group consisting of hydrogen, carbon monoxide, alkanes (C n H 2n + 2 ), natural gas (LNG) and syngas (syngas). It may be abnormal.
  • FIG. 5 is a schematic view of the chemical looping combustion method of the present invention.
  • the oxygen carrier particles react with the fuel
  • the oxygen carrier particles are reduced while delivering oxygen to the fuel and generate carbon dioxide and water.
  • the reduced oxygen transfer particles react with oxygen, they are oxidized and regenerated. In the chemical looping combustion method of the present invention, the above process is repeated.
  • the provision of oxygen to the reduced oxygen transfer particles may be made through contact of air and oxygen transfer particles.
  • the oxygen transfer particle of the present invention When the oxygen transfer particle of the present invention is applied to a chemical looping combustion process (CLC process), carbon dioxide can be separated and collected at the source while reducing the system thermal efficiency deterioration due to carbon dioxide capture compared to the conventional combustion method.
  • carbon dioxide due to the nature of the chemical looping combustion process, carbon dioxide is not collected by using a solution, so there is an advantage in that the amount of water used is small and the generation of waste water is scarce.
  • the chemical looping combustion method includes a fuel reactor for reacting oxygen transfer particles with a fuel to reduce the oxygen transfer particles and burn the fuel; And an air reactor for reacting the reduced oxygen transfer particles with oxygen to oxidize it.
  • the metal oxide (M x O y ) in the oxygen transfer particles reacts with the fuel to become the reduced metal oxide (M x O y ⁇ 1 ).
  • the fuel is burned and reduced.
  • the reduced oxygen transfer particles move to the air reactor and react with oxygen in the air to oxidize again.
  • the oxidized oxygen transfer particles are circulated to the fuel reactor to repeat the above process.
  • reaction schemes 1 and 2 Reactions in the fuel reactor and the air reactor are shown in the following reaction schemes 1 and 2.
  • Scheme 1 is a reaction in a fuel reactor
  • Scheme 2 shows a reaction occurring in an air reactor.
  • M represents a metal
  • X and Y represent a proportion of each atom in the metal oxide molecule.
  • Schemes 1 and 2 show an example in which one oxygen atom (O) is transferred from one molecule of metal oxide, but one or more or more than one may be transferred, and in this case, schemes 1 and 2 may be changed according to the number of oxygen delivered. Can be.
  • the following examples are copper oxide (CuO) to provide a copper oxide as the active component of the oxygen transfer particles; Manganese oxide (MnO) to provide another active ingredient, manganese oxide; Magnesium hydroxide (Mg (OH) 2 ) to provide magnesium oxide for preventing aggregation of oxygen transfer particles;
  • the present invention relates to the preparation of oxygen transfer particles using a sol form boehmite (AlOOH) as a raw material composition to impart dispersion and strength of an active substance and to enhance oxygen transfer reaction.
  • magnesium hydroxide (Mg (OH) 2 ) is magnesium oxide as water (H 2 O) is discharged when fired at a high temperature.
  • the sol form boehmite (AlOOH) in the raw material composition is aluminum oxide as the water (H 2 O) is discharged when fired at a high temperature.
  • the oxygen transfer particles of Examples 1 to 3 were prepared by the following method.
  • the mixed slurry was first milled with a high energy ball mill. In order to facilitate the grinding, after the first grinding, water and a dispersant were further added. After the second milling, polyethylene glycol was added and the third milling was performed to prepare a stable and homogeneous colloidal slurry. After the grinding, the slurry was sieved to remove foreign substances and the solid concentration in the final slurry was measured. The total amount of additive added and the solid concentration in the final slurry measured are shown in Table 1.
  • the prepared colloidal slurry was transferred to a spray dryer by a pump and spray-dried to form oxygen transfer particles.
  • the oxygen transfer particle assembly thus formed that is, the green body was pre-dried for 12 hours in an air atmosphere reflux dryer at 120 ° C., and calcined at 1100 ° C. for 5 hours in a kiln to prepare oxygen transfer particles.
  • the temperature was maintained at 200 ° C, 300 ° C, 400 ° C, 500 ° C, 650 ° C, 800 ° C and 950 ° C for about 1 hour, and the temperature increase rate was about 5 ° C / min.
  • Example 2 also prepared oxygen transfer particles in the same manner as in Example 1.
  • the main differences between Example 1 and the manufacturing method are as follows. After the raw material was calcined at a high temperature, CuO, MnO, Mg (OH) 2 , and AlOOH were 2.15 kg, 35.9 parts, 32.0 parts, 9.1 parts, and 23 parts by weight based on CuO, MnO, MgO, and Al 2 O 3 , respectively. 1.92 kg, 0.79 kg, 6.90 kg were weighed and water was prepared by adding 12 liters. The total amount of additive added and the solid concentration in the final slurry measured are shown in Table 1.
  • Example 3 also prepared oxygen transfer particles in the same manner as in Example 1.
  • the main differences between Example 1 and the manufacturing method are as follows. 2.74 kg of CuO, MnO, Mg (OH) 2 , AlOOH so that the raw materials were calcined at a high temperature and then 45.7 parts by weight, 27.1 parts, 7.7 parts, and 19.5 parts by weight based on CuO, MnO, MgO, Al 2 O 3 , respectively. 1.63 kg, 0.67 kg, 5.85 kg were weighed and water was prepared by adding 10 liters. The total amount of additive added and the solid concentration in the final slurry measured are shown in Table 1.
  • Example 1 Example 2
  • Example 3 CuO 40.5 35.9 45.7 MnO 36.2 32.0 27.1 Mg (OH) 2 10.3 9.1 7.7 MgO 0 0 0 AlOOH 13.0 23.0 19.5 Al 2 O 3 0 0 0
  • Total solids content 100 100
  • Dispersant 1.0 1.0
  • Organic binder 3.0 3.0
  • Slurry solid concentration 33.3 27.3 29.6
  • the shape of the oxygen transfer particles prepared in Examples and Comparative Examples was measured using an industrial microscope.
  • the average particle size and particle size distribution of the oxygen carrier particles were sorted for 10 minutes using a MEINZER-II shaker and standard for 30 minutes based on ASTM E-11 of the American Society for Testing Materials (ASTM). Calculated by The results are shown in Table 2 below.
  • the packing density of the oxygen carrier particles was measured using an AutoTap (Quantachrome) packing density meter according to ASTM D 4164-88. The results are shown in Table 2 below.
  • the wear resistance of the oxygen transfer particles was measured by a wear tester in accordance with ASTM D 5757-95.
  • the wear index (AI) was determined at 10 stdL / min (standard volume per minute) over 5 hours as described in the ASTM method above, and the wear index represents the proportion of fines generated over 5 hours. The lower the wear index (AI), the stronger the particle.
  • the abrasion index (AI) of the AkzoFCC (Fluid Catalytic Cracking) catalyst used by the refinery was 22.5%, respectively. The results are shown in Table 2 below.
  • Oxygen transfer performance of the oxygen transfer particles prepared in Examples was evaluated using thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the composition of the reaction gas used for the reduction reaction of oxygen transfer particles was used by mixing 15 vol% CH 4 with 85 vol% CO 2 and the reaction gas for oxidizing the reduced oxygen transfer particles using air. It was. 100% nitrogen was supplied between the oxidation and reduction reactions to prevent direct fuel and air contact in the reactor.
  • the oxygen transfer particle sample amount used for the experiment was about 30 mg.
  • the flow rate of each reaction gas was 300 ml / min (273.5 K, 1 bar basis), and the oxidation / reduction reaction of the oxygen carrier particles was repeated at least 10 times at 950 ° C. Oxygen transfer amount was calculated from redox weight difference.
  • Oxygen transfer amount is the amount of oxygen delivered to the fuel by the oxygen transfer particle, and the weight change obtained by subtracting the weight of the oxygen transfer particle measured at the end of the reduction reaction of the oxygen transfer particle based on the weight of the oxygenated particle is completed.
  • Example 1 1100 97 37-302.5 2.5 2.4 11.8
  • Example 2 1100 82 37-196 2.0 15.2 9.5
  • Example 3 1100 98 37-302.5 2.44 2.2 10.9
  • Oxygen transfer particles of Examples 1 to 3 were prepared using CuO, MnO as an active material, AlOOH as a support material, and Mg (OH) 2 as an additive material. As shown in Table 2, the oxygen transfer particles prepared by the composition according to the present embodiment has a high strength property of 3% or less of wear index at a firing temperature of 1100 ° C. and a characteristic of 15.2% superior to that of a commercial fluidized bed catalyst (22.5%). It can be seen that it possesses suitable physical properties for the commercial fluidized bed process.
  • the shape of the oxygen transfer particles is spherical, the average particle size is 82 to 98 ⁇ m, the particle size distribution is in the range of 37 to 302.5 ⁇ m, the packing density is about 2.5 g / ml, the wear index is 5% or less .
  • Oxygen transfer amount of the oxygen transfer particles prepared in Examples 1 to 3 was found to be high as 9.5 to 11.8 parts by weight.
  • the high-performance and low-cost oxygen-transferring particles suitable for the fluidized bed process capable of effectively burning fuel in chemical looping combustion technology by using the oxygen-transferring particle raw material composition and the method for preparing oxygen-transferring particles using the same are presented. It has been shown that it can be prepared. Oxygen transfer particles by such a raw material composition and a manufacturing method can be a competitive technology because it is easy to mass-produce, and the economical efficiency of the chemical looping combustion process is brought about by the reduction of the particle usage and the size of the process according to the improvement of the particle performance.

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Abstract

La présente invention concerne une composition de matière première pour la fabrication de particules de transfert d'oxygène, la composition de matière première comprenant : de l'oxyde de cuivre ; de l'oxyde de manganèse ; de l'oxyde de magnésium ou de l'hydroxyde de magnésium ; et de l'oxyde d'alumine de type sol ou poudre. La composition de matière première pour fabriquer des particules de transfert d'oxygène de la présente invention est transformée en particules de transfert d'oxygène par contrôle de la composition, de la formulation de matières premières, et du degré d'homogénéisation selon la méthode de fabrication de particules de transfert d'oxygène, ultérieurement décrite, et par la suite, des particules de transfert d'oxygène peuvent être fabriquées qui ont des propriétés physiques, telles qu'une forme, une taille de particule et une distribution de taille, qui sont appropriées pour un procédé à lit fluidisé ou à lit fluidisé à haut débit, et conservent des performances de transfert d'oxygène de qualité commerciale et une durabilité à une basse température de combustion tout en ne faisant pas appel à un oxyde à base de nickel à prix élevé comme dans l'état actuel de la technique.
PCT/KR2019/000135 2018-06-25 2019-01-04 Composition de matière première pour la fabrication de particules de transfert d'oxygène, particules de transfert d'oxygène fabriquées à l'aide de celle-ci, et méthode de fabrication de particules de transfert d'oxygène Ceased WO2020004751A1 (fr)

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