KR102122327B1 - Raw material composition for oxygen carrier, oxygen carrier using the same and method of manufacturing the oxygen carrier - Google Patents

Abstract

The present invention is a copper oxide; Manganese oxide; Magnesium oxide or magnet?? hydroxide; And alumina oxide in a sol or powder form. The raw material composition for preparing the oxygen transfer particles of the present invention is prepared as oxygen transfer particles according to a method for preparing oxygen transfer particles described below by controlling the composition, the formulation of the raw materials, and the degree of homogenization, followed by a fluidized bed. Or, it has physical properties such as shape, particle size, and particle size distribution suitable for high-speed fluidized bed processes, and is commercial grade at a low firing temperature without using expensive nickel-based oxides compared to the prior art. Oxygen transfer particles having the oxygen transfer performance and durability of can be prepared.

Description

Raw material composition for oxygen transport particle production, oxygen transport particle and oxygen transport particle production method using the same{RAW MATERIAL COMPOSITION FOR OXYGEN CARRIER, OXYGEN CARRIER USING THE SAME AND METHOD OF MANUFACTURING THE OXYGEN CARRIER}

The present invention relates to a raw material composition for producing oxygen transfer particles, an oxygen transfer particle and a method for producing oxygen transfer particles produced using the same.

As the average temperature of the earth rises due to the greenhouse effect caused by an increase in the concentration of carbon dioxide (CO ₂ ) in the atmosphere, the damage of climate change continues to appear. Thermal power plants are the largest sources of artificial carbon dioxide emissions. Reduction of carbon dioxide emissions from thermal power plants can be achieved through carbon capture and storage (CCS). However, when the conventional CCS technology is applied to a power plant, a significant reduction in power generation efficiency and an increase in power generation cost follow. Accordingly, new technologies are required to minimize the reduction in power generation efficiency and lower the CO ₂ capture cost.

Chemical Looping Combustion (CLC) technology is drawing attention as a technology capable of separating CO ₂ while reducing power generation efficiency. In the CLC technology, oxygen and fuel contained in solid particles (oxygen transfer particles), which are mainly composed of metal oxide instead of air, react with fuel, so combustion occurs, and thus the exhaust gas contains only water vapor and CO ₂ . Therefore, if the water vapor is condensed and removed, only CO ₂ remains, so it is possible to separate the CO ₂ source. In the CLC process, as the oxygen contained in the oxygen transport particles is delivered to the fuel, the oxygen transport particles receive the oxygen contained in the air and the fuel reactor in which the reaction occurs as a reduction, and the reduced oxygen transport particles are oxidized again. It consists of a combination of air reactors that are regenerated in their initial state. Both reactors use a fluidized bed reactor, and the entire process is a circulating fluidized-bed process.

The oxygen transfer particles applied to the CLC process must satisfy various conditions suitable for fluid bed process characteristics. First of all, it is necessary to have properties suitable for a fluidized bed process, i.e., sufficient strength, shape and packing density (packing density or tapped density), average particle size and particle size distribution suitable for flow. In addition, it has a high oxygen transfer capacity in terms of reactivity, so it must be able to supply sufficient oxygen required for combustion of fuel while the fuel passes through the fuel reactor.

However, the conventional oxygen transfer particles are manufactured in a method unsuitable for mass production, or properties such as shape, strength, density, etc. are inadequate or necessary to be applied to the fluidized bed process, and in order to reduce the interaction strength between the metal oxide and the support. By using a support having a stable crystal structure, the oxygen transfer performance decreases due to an increase in the firing temperature to obtain sufficient strength, or it is not fluidized due to aggregation between particles during the reaction, or the content of metal oxides is low, resulting in a small amount of oxygen transfer. have.

Particularly, the conventional oxygen transfer particles mainly used NiO-based oxygen transfer particles, which are expensive metals, because of their excellent oxygen transfer rate, oxygen transfer amount, and durability. Therefore, in order to improve the technical, economic, and environmental aspects of the chemical roofing technology, there is a need to develop low-cost oxygen transfer particles having excellent oxygen transfer rate, oxygen transfer amount and wear resistance without using NiO.

Therefore, while having adequate properties and sufficient strength for the fluidized bed process, it is possible to suppress the aggregation phenomenon between particles that may occur during the oxidation-reduction cycle reaction, to reduce the oxygen transfer performance even at high temperature firing, and to lower the firing temperature. Development of delivery particles is required.

One object of the present invention is to provide a raw material composition for the production of oxygen-transfer particles having physical properties including strength, which are suitable for a fluidized bed process, are inexpensive compared to conventional techniques, and have excellent oxygen transfer rate, oxygen transfer amount, and wear resistance.

Another object of the present invention is to prepare a stable fluid colloidal slurry (colloidal slurry) homogeneously dispersed using the raw material composition and use it to form a particle shape (shape), particle size (size) suitable for the chemical looping circulating fluidized bed process ), has a particle distribution (size distribution), strength (mechanical strength or attrition resistance), low cost compared to the prior art, and provides an oxygen transfer rate, oxygen transfer amount and abrasion resistance excellent oxygen transfer particles and a method for manufacturing the same .

Another object of the present invention is to effectively capture and collect carbon dioxide generated by combustion while effectively burning fuel using the oxygen-transferring particles, the amount of particle filling in the chemical roofing combustion process, and wear generated during long-term operation It is to provide a chemical roofing combustion method that prevents a decrease in system thermal efficiency due to carbon dioxide capture while reducing the amount of replenishment due to loss.

An embodiment of the present invention is 30% to 50% by weight of copper oxide; 20% to 40% by weight of manganese oxide; 5 to 20% by weight of magnesium oxide or magnesium hydroxide; 10% to 30% by weight of aluminum oxide or aluminum hydroxide in sol or powder form; It relates to a raw material composition for the production of oxygen transfer particles comprising a.

The copper oxide may have an average particle size of more than 0 to 5 μm, and a purity of 98% or more.

The manganese oxide may have an average particle size of more than 0 to 5 μm, and a purity of 98% or more.

The magnesium oxide or magnesium hydroxide may have an average particle size of greater than 0 to 5 μm, and a purity of 98% or more.

The sol or powdered aluminum oxide or aluminum hydroxide may have an average particle size of greater than 0 to 5 μm and a purity of 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 comprising 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 Formula 1 below.

[Formula 1]

Cu _a Mn _b Mg _c Al _d O _x

In Formula 1, a, b, c, and d are each independently 0.1 to 2.7, the sum of a + b + c + d is 3, and x is 0 to 4.

The oxygen transfer particles were subjected to abrasion testing for 5 hours at a flow rate of 10.00 l/min (273.15 K, 1 bar) according to ASTM D5757-95 using an abrasion tester, and the abrasion index represented by Equation 1 below may be 20% or less. have.

[Equation 1]

AI(%) = [(W2)/(W1)]

In Equation 1, W1 is the g unit weight before the abrasion test of the sample, and W2 is the g unit weight of the microparticles collected for 5 hours during which the abrasion test of the sample was performed.

The oxygen transport particles have a non-blowhole spherical shape, an average particle size of 60 μm to 150 μm, a particle size distribution of 30 μm to 400 μm, and a packing density of 1.5 g/mL to 4.0. g/mL.

The oxygen transfer particles may have an oxygen transfer amount of 7 to 15% by weight of the total weight of the oxygen transfer particles.

Another embodiment of the present invention (A) mixing the above-described raw material composition for preparing oxygen transport particles with a solvent to prepare a slurry for preparing oxygen transport particles; (B) preparing a homogenized slurry by stirring the slurry; (C) spray drying the slurry to form solid particles; And (D) drying and calcining the molded solid particles to prepare oxygen transfer particles.

In the step (A) of preparing the slurry for preparing the oxygen transport particles, the raw material composition for preparing the oxygen transport particles and the solvent are mixed in a weight ratio of 15 to 40:60 to 85, and the solvent may be water.

In the step (A) of preparing the slurry for preparing the oxygen transport particles, the slurry may further include at least one additive of a dispersant, an antifoaming agent, and an organic binder.

The dispersant may include one or more 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 both a dispersant, an antifoaming agent and an organic binder, and the additive is 0.01 to 5.0 parts by weight of a dispersant, 0.01 to 1.0 parts by weight of an antifoaming agent, and 1.0 to 5.0 parts by weight of an organic binder relative to 100 parts by weight of a raw material composition for preparing oxygen transport particles. Can be added.

The step (B) of preparing the homogenized slurry by stirring the slurry may further include removing foreign substances in the stirred and pulverized slurry.

In the step (C) of spray-drying the slurry to form solid particles, the homogenized slurry is introduced into a spray dryer, and then sprayed while maintaining an inlet temperature of 260°C to 300°C and an outlet temperature of 90°C to 150°C. And molding into solid particles.

In the step (D) of drying and firing the molded solid particles to prepare oxygen-transferring particles, the molded solid particles are dried at 110°C to 150°C for 2 to 24 hours, and put into a high-temperature firing furnace at 1°C/min to It may include heating at a rate of 5°C/min to 1000°C to 1350°C for 2 to 10 hours.

Another embodiment of the present invention comprises the steps of reacting the aforementioned oxygen transport particles with fuel to reduce the oxygen transport particles and burning the fuel, and reacting the reduced oxygen transport particles with oxygen to regenerate the particles. It relates to a chemical roofing combustion method.

The present invention is suitable for a fluidized bed process, including physical properties, strength, and low cost, compared to the prior art, oxygen transfer rate, oxygen transfer amount and abrasion resistance. Compared to the prior art, it has excellent particle wear, long-term durability, and oxygen transfer performance, while having a suitable particle shape, particle size, particle size distribution, and mechanical strength or attrition resistance. It is possible to provide an oxygen transfer particle that can replace the expensive nickel-based oxide and a method for manufacturing the same, and by using such an oxygen transfer particle, the amount of particle filling in the chemical roofing combustion process and the amount of replenishment due to wear loss occurring during long-time operation It is possible to provide a chemical looping combustion method that can prevent the reduction of the thermal efficiency of the system due to the capture of carbon dioxide. In particular, since the oxygen transfer particles made of low-cost raw materials can reduce the operating cost of the chemical roofing combustion process, it is possible to improve the economic efficiency of the chemical roofing combustion process.

1 is a photograph of the shape of the oxygen transfer particles of Example 1 of the present invention using an industrial microscope.
Figure 2 is a photograph of the shape of the oxygen transfer particles of Comparative Example 1 of the present invention using an industrial microscope.
Figure 3 is a photograph of the shape of the oxygen transfer particles of Example 2 of the present invention using an industrial microscope.
4 is a flow chart showing a method of manufacturing oxygen transfer particles according to an embodiment of the present invention.
5 is a flow chart showing the steps (A) and (B) of the method for producing oxygen transfer particles according to an embodiment of the present invention.
6 is a flow chart showing the step (C) of the method for producing oxygen transfer particles according to an embodiment of the present invention.
7 is a flow chart showing the step (D) of the method for producing oxygen transfer particles according to an embodiment of the present invention.
8 is a schematic diagram of a chemical loop combustion method according to an embodiment of the present invention.

<Raw material composition for oxygen delivery particle production>

One embodiment of the invention copper oxide; Manganese oxide; Magnesium oxide or magnesium hydroxide; And a sol or powder-form aluminum oxide or aluminum hydroxide; and a raw material composition for preparing oxygen-transmitting particles comprising the following raw material composition for preparing oxygen-transmitting particles.

The raw material composition for preparing the oxygen transfer particles of the present invention is prepared as oxygen transfer particles according to a method for preparing oxygen transfer particles described below by controlling the composition, the formulation of the raw materials, and the degree of homogenization, followed by a fluidized bed. Alternatively, it has physical properties such as shape, particle size, and particle size distribution suitable for a high-speed fluidized bed process, and can replace nickel-based oxides that are inexpensive and relatively expensive compared to conventional techniques. It is possible to manufacture oxygen transfer particles having excellent transfer rate, oxygen transfer amount, and wear resistance.

The raw material composition for preparing the oxygen transport particles is copper oxide; Manganese oxide; Magnesium hydroxide; And aluminum hydroxide in the form of sol or powder. It may be to include.

The oxygen transfer particle production raw material composition is copper oxide 30% to 50% by weight; 20% to 40% by weight of manganese oxide; 5 to 20% by weight of magnesium oxide or magnesium hydroxide; 10% to 30% by weight of aluminum oxide or aluminum hydroxide in sol or powder form; It can contain.

The oxygen transfer particles produced by the raw material composition for preparing the oxygen transfer particles transmit oxygen to gas fuels such as natural gas, shale gas, and synthetic gas as well as solid fuels, and again obtain oxygen from gases containing oxygen such as air. It has excellent reproducing properties and can be used continuously and repeatedly. Accordingly, when the oxygen transfer particles are applied to a chemical fuel combustion process of gas fuel and/or solid fuel (CLC process), the amount of particle filling and the amount of replenishment due to abrasion loss generated during long-time operation can be reduced. It has the effect of improving economic efficiency while simplifying the process (CLC process). In particular, since the oxygen transfer particles made of low-cost raw materials can reduce the operating cost of the chemical roofing combustion process, it is possible to improve the economic efficiency of the chemical roofing combustion process.

The raw material composition for preparing oxygen transfer particles of the present invention includes copper oxide and manganese oxide as raw materials for active materials. Oxygen transport particles composed of copper oxide and manganese oxide are reduced to copper (Cu) and manganese (Mn) when they are applied to chemical roofing combustion reactions without nickel oxide, and transfer oxygen, and receive oxygen from air or water vapor to regenerate It plays a role.

The copper oxide (CuO, Cu ₂ O, etc.) may be a commercial copper oxide having an average particle size of greater than 0 to 5 μm. Within this range, it is possible to have a similar or improved level of oxygen transfer rate and oxygen transfer amount to that of nickel oxide.

The copper oxide may have a purity of 98% or more, for example, 99% or more. Within the above range, the oxygen transfer particle speed and the oxygen transfer amount can be further improved.

Further, 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 greater than 0 to 5 μm. Within the above range, it is possible to manufacture oxygen-transfer particles having excellent heat resistance and durability.

The manganese oxide may have a purity of 98% or more, for example, 99% or more. Within the above range, wear resistance may be further improved.

The raw material composition for preparing oxygen transport 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 partially mixing other metal oxides.

The type of metal oxide that can be used in combination with the copper oxide and manganese oxide is not particularly limited. Specifically, iron oxides including iron oxides (FeO, Fe ₂ O ₃ , Fe ₃ O ₄ ) and cobalt oxides including cobalt oxide (CaO, Co ₃ O ₄ ) and the like can be exemplified.

In addition, in the raw material composition for preparing oxygen transfer particles of the present invention, it is possible to increase the magnesium (Mg) content while maintaining excellent oxygen transfer performance, and thus has an effect of solving the problem of aggregation between particles that may appear during the oxidation and reduction cycle reaction of chemical roofing combustion. have.

The magnesium oxide or magnesium hydroxide (MgO, Mg(OH) _2, etc.) may be commercial magnesium oxide or hydroxide having an average particle size of greater than 0 to 5 μm. Within the above range, it is possible to solve the problem of the aggregation phenomenon of the oxygen transport particles.

The magnesium oxide or hydroxide may have a purity of 98% or more, for example, 99% or more. Within this range, agglomeration 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 raw material. Aluminum oxide or aluminum hydroxide is used as an inorganic binder in the oxygen transport particles, so it can provide sufficient strength required in the fluidized bed process.

In addition, the aluminum oxide or aluminum hydroxide supports copper oxides and manganese oxides, which are the active ingredients of the oxygen transport particles, to be uniformly distributed throughout the oxygen transport particles, thereby increasing the utilization of the active ingredients and promoting oxygen transport performance.

The aluminum oxide or aluminum hydroxide may be a commercial aluminum oxide having an average particle size of greater than 0 to 5 μm in a sol or powder form. Within this range, the durability of the oxygen-transmitting particles is improved and the degree of dispersion of the active material is uniform.

The aluminum oxide or aluminum hydroxide may have a purity of 95% or more, for example, 99% or more. Within the above range, the oxygen transfer rate, the oxygen transfer amount and the wear resistance of the oxygen transfer particles can be further improved.

In one embodiment, the raw material composition for preparing the oxygen transport particles of the present invention is an active material raw material by using the active ingredient of copper oxide and manganese oxide in combination with the magnesium hydroxide and aluminum hydroxide, the active ingredient and magnesium oxide and / or aluminum oxide When using, or when using only one of the magnesium compound and the aluminum compound as a hydroxide, it is possible to further improve the oxygen transfer amount, strength, and sintering prevention effect of the oxygen transfer particles.

<Oxygen transport 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 comprising copper oxide, manganese oxide, magnesium oxide, and aluminum oxide.

By using the above-described raw material composition to prepare the oxygen transfer particles, while having a particle shape (shape), particle size (size), particle distribution (size distribution), strength (mechanical strength or attrition resistance) suitable for the chemical looping combustion circulating fluidized bed process , Excellent abrasion resistance, long-term durability and excellent oxygen transfer performance, it is possible to provide an oxygen transfer particle and a method for manufacturing the same, which can replace the expensive nickel-based oxide compared to 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 have a structure represented by Formula 1 below.

[Formula 1]

Cu _a Mn _b Mg _c Al _d O _x

In Formula 1, a, b, c and d are each independently 0.1 to 2.7, the sum of a + b + c + d is 3, and x is greater than 0 to 4.

Through this, the oxygen transfer particles of the present invention realize excellent oxygen transfer rate, oxygen transfer amount and wear resistance by the composition and structural properties of the component metal. In addition, when the oxygen transfer particles are applied to a chemical roofing combustion process and apparatus, it is possible to reduce the amount of particle filling and wear loss required during long-time operation.

In addition, it can be used not only for gas fuel, but also for chemical roofing of solid fuel, and can be effectively used in partial oxidation of fuel, reforming of fuel, hydrogen production, and the like.

In addition, the oxygen transport particles of the present invention are stable and evenly dispersed in the oxygen transport particle solid raw materials pulverized to a size of 5 µm or less, for example, 1 µm or less in the slurry state, resulting in final oxygen transfer fired after spray drying. It has excellent long-term durability of particles, and has a spherical shape and particle size, particle size distribution, filling density, strength, low calcination temperature, and excellent oxygen transfer performance suitable for fluidized bed processes.

The oxygen transfer particle production raw material composition is copper oxide 30% to 50% by weight; 20% to 40% by weight of manganese oxide; 5 to 20% by weight of magnesium oxide or magnesium hydroxide; 10% to 30% by weight of aluminum oxide or aluminum hydroxide in sol or powder form; It can contain.

The raw material composition for preparing the oxygen transport particles is copper oxide; Manganese oxide; Magnesium hydroxide; And aluminum hydroxide in the form of sol or powder. It may be to include.

When the high-performance oxygen transfer particles are applied to the chemical roofing combustion process (CLC process), carbon dioxide can be separated and collected by the source while reducing the system thermal efficiency reduction due to carbon dioxide capture compared to the conventional combustion method.

The oxygen transfer particles were subjected to abrasion testing for 5 hours at a flow rate of 10.00 l/min (273.15 K, 1 bar) according to ASTM D5757-95 using an abrasion tester, and the abrasion index represented by Equation 1 below may be 20% or less. have.

[Equation 1]

AI(%) = [(W2)/(W1)]

In Equation 1, W1 is the g unit weight before the abrasion test of the sample, and W2 is the g unit weight of the microparticles collected for 5 hours during which the abrasion test of the sample was performed.

The lower limit of the wear index is not particularly limited, and the closer to 0%, the better. Within the above range, when the oxygen transfer particles are used for chemical roofing combustion, the wear loss rate is further reduced, thereby reducing the amount of oxygen transfer particles to be supplemented during the process operation, and lowering the production rate of fine powders generated during the process. It has more advantageous properties for application to a circulating fluidized bed process or the like.

The oxygen-transmitting particles have a non-blowhole spherical shape, an average particle size of 60 µm to 150 µm, a particle size distribution of 30 µm to 400 µm, and a filling density of 1.5 g/mL to 4.0. g/mL. In this case, when the oxygen transfer particles are used for chemical roofing combustion, the wear loss rate is further reduced, thereby reducing the amount of oxygen transfer particles to be supplemented during the process operation, and lowering the production rate of fine powders generated during the process to reduce the circulation rate of the circulating fluidized layer. It has more advantageous properties for application to processes and the like.

The non-blowhole (non-blowhole) means a spherical shape of a shape other than a shape including a blowhole, such as a dimple type, a hollow type.

The average particle size and particle size distribution of the oxygen transfer particles, specifically, the average size of the particles may be 60㎛ to 150㎛, more specifically 70㎛ to 130㎛, the particle size distribution is 30㎛ to 400㎛, more Specifically, it may be 38 μm to 350 μm.

The oxygen transfer particles may have an oxygen transfer amount of 7 wt% to 15 wt%, specifically 9 wt% to 12 wt%, of the total weight of the oxygen transport particles.

<Method of manufacturing oxygen transfer particles>

Another embodiment of the present invention (A) mixing the above-described raw material composition for preparing oxygen transport particles with a solvent to prepare a slurry for preparing oxygen transport particles; (B) preparing a homogenized slurry by stirring the slurry; (C) spray drying the slurry to form solid particles; And (D) drying and calcining the molded solid particles to prepare oxygen transfer particles.

The oxygen transport particle production slurry may be prepared by mixing the above-described oxygen transport particle production raw material composition with a solvent.

The oxygen transfer particle production raw material composition is copper oxide 30% to 50% by weight; 20% to 40% by weight of manganese oxide; 5 to 20% by weight of magnesium oxide or magnesium hydroxide; 10% to 30% by weight of aluminum oxide or hydroxide in sol or powder form; It can contain.

In the step (A) of preparing a slurry for preparing oxygen transport particles, the slurry for preparing oxygen transport particles is prepared by mixing the above-described raw material composition for preparing oxygen transport particles of the present invention with a solvent.

The raw material composition for preparing the oxygen transport particles and the solvent may be mixed in a weight ratio of 15 to 40:60 to 85. Within the above range, the amount of the 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 grinding is more easily performed when homogenized, Excellent manufacturing efficiency can be achieved.

The type 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.

In the step (A) of preparing a slurry for preparing oxygen transport particles, the slurry may further include at least one additive of a dispersant, an antifoaming agent, and an organic binder.

Specifically, the additive may be mixed with the raw material composition for the production of oxygen transfer particles in a pre-injected state in the above-described solvent. In this case, it is possible to further improve the dispersibility of the raw material composition for preparing oxygen transfer particles and the mixing property with a solvent.

The dispersant may prevent the components included in the raw material composition for preparing oxygen transfer particles from agglomerating with each other when the slurry to be described below is crushed. In addition, the efficiency of controlling the particle size of the raw material components constituting the oxygen transport particles in the homogenization process can be further improved.

Specifically, 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 this case, it is possible to further improve the function of controlling the charge control, dispersion and aggregation of the particle surface by the dispersant, and make the slurry highly concentrated.

In addition, the dispersant can improve the efficiency in which the shape of the formed body (oxygen transfer particle assembly), that is, the green body, produced during spray drying of the slurry is spherical rather than donut-shaped, dimple-shaped, or blow-shaped.

The content of the dispersing agent may be from 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the raw material composition for preparing oxygen transfer particles. Within the above range, the dispersion effect of the oxygen transport particles may be more excellent.

The defoamer may be used to remove air bubbles in the slurry to which the dispersant and the organic binder are applied.

Specifically, 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. In this case, the compatibility of the antifoaming agent is more excellent.

The content of the antifoaming agent may be from 0.01 parts by weight to 1.0 parts by weight based on 100 parts by weight of the raw material composition for preparing oxygen transfer particles. Within the above range, it is possible to reduce the generation of bubbles during the slurry production process, to further improve the efficiency of producing 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. The more specific content of the anti-foaming agent may be adjusted depending on the amount of bubbles generated.

The organic binder is added in the slurry preparation step to impart plasticity and fluidity to the slurry and ultimately to give strength to the oxygen-transferred particles assembled by spray drying, thereby pre-drying and firing the assembly. It can facilitate handling of the green body.

Specifically, as the type of the organic binder, one or more of polyvinyl alcohol, polyethylene glycol, and methyl cellulose may be used.

The content of the organic binder may be 1 part by weight to 5 parts by weight based on 100 parts by weight of the raw material composition for preparing oxygen transfer particles. Within the above range, the bonding strength of the solid particles formed by spray drying is improved, and characteristics of maintaining a spherical shape before drying and firing can be improved, and the amount of residual ash after firing is reduced to further improve the oxygen transfer amount. I can do it.

In one embodiment, the additive includes all of a dispersant, an antifoaming agent, and an organic binder, and the additive is 0.01 to 5.0 parts by weight of a dispersant, 1.0 to 5.0 parts by weight of an organic binder, and 0.01 of an antifoaming agent relative to 100 parts by weight of a raw material composition for preparing oxygen transfer particles. To 1.0 part by weight may be added into the slurry. In this 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 fluid colloidal slurry. In this case, workability and manufacturing efficiency in the homogenization and firing process can be further improved.

The step (B) of preparing a homogenized slurry by stirring the slurry may include homogenizing the slurry prepared above by stirring and pulverizing it using a stirrer. In this case, control properties such as homogenization characteristics of the slurry, concentration of the slurry, viscosity, stability, fluidity, and strength and density of particles after spray drying may be further improved.

The stirring may be performed in a process of adding components included in the mixture or in a state in which all components included are added. At this time, stirring may be performed using, for example, a stirrer.

Specifically, the slurry prepared by mixing the solvent and/or additives with the composition for preparing oxygen-transmitting particles is completed and then pulverized using a grinder to stir the particle size in the slurry to several microns (µm) or less. In this process, the pulverized particles are more homogeneously dispersed in the slurry, and since aggregation of the particles in the slurry is suppressed, a homogeneous and stable slurry can be produced.

If necessary, the grinding process may be repeated several times, and the fluidity of the slurry may be controlled while a dispersant and an antifoaming agent are added between each grinding process.

For example, a wet milling method may be used as a grinding method. In this case, the crushing effect can be improved, and problems such as blowing of particles generated during dry grinding can be solved. On the other hand, if the particle diameter of the raw material composition particles is a few microns or less, a separate grinding process may be omitted.

In the present invention, it is possible to further perform the removal of foreign substances in the stirred and pulverized slurry. Through the above steps, foreign matter or lumped raw materials that may cause clogging of the nozzle during spray molding may be removed. Removal of the foreign material may be performed, for example, through a sieve.

There is no particular limitation on the flowability of the homogenized slurry, and any viscosity is possible if it can be transferred to the pump.

In the step (C) of spray-drying the slurry to form solid particles, the homogenized slurry is introduced into the spray dryer, and then sprayed while maintaining the inlet temperature at 260°C to 300°C and the outlet temperature at 90°C to 150°C. And molding into particles.

Molding of the slurry can be carried out using a spray dryer, and specifically, after transferring the homogenized slurry to a spray dryer through a pump, solid particles can be molded by spraying the transferred slurry composition into a spray dryer.

Molding of the slurry may be more advantageous in that when the organic binder is added, the particle shape is maintained in a spherical shape during spray drying.

The shape and operating conditions of the spray dryer for forming oxygen-transfer particles in the spray dryer can be applied to the operating conditions generally used in this field.

More specifically, the oxygen-transmitting particles may be formed by spraying a homogenized slurry of fluidity using a pressurized nozzle using a countercurrent spraying method in which the flow of drying air is sprayed in the opposite direction.

At this time, the inlet temperature of the spray dryer may be maintained at 260 ℃ to 300 ℃, the outlet temperature is 90 ℃ to 150 ℃. The efficiency of producing spherical oxygen-transfer particles within the temperature range may be further improved.

In the step (D) of drying and firing the molded solid particles to prepare the oxygen-transfer particles, the molded solid particles are dried at 110°C to 150°C for 2 to 24 hours, and put into a high-temperature firing furnace at 1°C/min to 5 It may include heating at 1050°C to 1350°C at a rate of °C/min and firing for 2 to 10 hours.

When drying is performed under the above temperature and time conditions, moisture in the particles expands during firing, thereby preventing cracks in the particles. At this time, drying may be performed in an air atmosphere.

When the drying is completed, the dried particles are placed in a high temperature firing furnace, and the final firing temperature is raised to 1050 °C to 1350 °C at a rate of 1 °C/min to 5 °C/min, followed by firing for 2 to 10 hours. Within the firing time range, it is possible to prevent the strength of the particles from becoming weak or excessively increasing the firing cost. In this case, the organic additives (dispersants, antifoaming agents and organic binders) introduced during the preparation of the slurry by firing are burned and bonds between the raw materials are formed to improve the strength of the particles. In addition, within the firing temperature range, it is possible to sufficiently improve the amount of oxygen transfer while preventing the strength of the oxygen transfer particles from being lowered due to insufficient firing temperature.

More specifically, the firing may be performed by a method of imparting a stagnation section of 30 minutes or more at stagnation temperatures of two or more steps up to the final firing temperature. In this case, it is possible to prevent the evaporation of moisture inside the oxygen transfer particles to be produced and the destruction of the particle shape by the gas generated due to combustion of the organic additive.

The firing may be performed by using a firing furnace such as a muffle furnace, a tubularfurnace, or a kiln.

Hereinafter, the present invention will be described in more detail through examples according to the present invention in accordance with the accompanying drawings so that those skilled in the art to which the present invention pertains can easily practice, but the scope of the present invention is the examples presented below It is not limited by.

4 is a process diagram schematically showing a method (S100) of manufacturing oxygen transfer particles using the oxygen transfer particle raw material composition according to the present invention. As shown in FIG. 4, the oxygen transfer particles are mixed by adding a raw material composition for preparing oxygen transfer particles to a solvent (A), and preparing the mixed slurry into a homogenized slurry through pulverization and dispersion (B), Spray drying the homogenized slurry to form solid particles (C) and drying and firing the molded solid particles (green body of the oxygen transfer particles) to prepare the final oxygen transfer particles (D) It includes.

5 is a process chart showing an exemplary process for preparing a mixture of a raw material composition and water as a slurry. As shown in FIG. 5, the preparation of the slurry comprises adding an additive to water (S11), mixing a solid raw material into water (S12), adding an organic additive to the mixture (S21) and the mixed slurry. It may include a step (S22) of homogenizing and dispersing the slurry by grinding and dispersing, and may further include a step (S23) of removing foreign substances contained in the slurry.

6 is a process diagram showing an exemplary process for forming the oxygen transport particles by spray drying the slurry. As shown in FIG. 6, the step of spray drying the slurry to form the oxygen transfer particles (S30) is the step of 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.

7 is a process chart showing an exemplary process for preparing a final oxygen delivery particle by drying and firing the oxygen carrier particle formed by the spray drying method. As shown in FIG. 7, the formed oxygen carrier particle biomaterial may be prepared as a final oxygen carrier particle through a preliminary drying process (S41), followed by a firing process (S42).

<Chemical roofing combustion method>

Another embodiment of the present invention is a chemical roofing combustion comprising reacting the aforementioned oxygen transport particles with a fuel, burning fuel and reducing the oxygen transport particles, and reacting the reduced oxygen transport particles with oxygen to regenerate them. It's about how.

Here, the fuel is not particularly limited, and a solid phase, a liquid phase, and a gas phase may be used. Preferably, the fuel may be a gaseous fuel. Gas fuel used in the present invention is not particularly limited, for example, hydrogen, carbon monoxide, alkanes (alkane, C _n H _{2n + 2} ), natural gas (LNG) and one selected from the group consisting of syngas (syngas) It may be abnormal.

8 is a schematic diagram of the chemical roofing combustion method of the present invention.

When the oxygen transport particles react with the fuel, the oxygen transport particles are reduced while delivering oxygen to the fuel and generate carbon dioxide and water. When the reduced oxygen transfer particles react with oxygen, they are oxidized and regenerated. In the chemical roofing combustion method of the present invention, the above process is repeated. In addition, the supply of oxygen to the reduced oxygen transport particles may be achieved through contact of air and oxygen transport particles.

When the oxygen transfer particles of the present invention are applied to a chemical roofing combustion process (CLC process), carbon dioxide can be separated and collected by source while reducing the system thermal efficiency reduction due to carbon dioxide capture compared to a conventional combustion method. In addition, because of the nature of the chemical roofing combustion process, since the solution does not capture carbon dioxide, there is an advantage of low water consumption and little waste water generation.

In addition, such a chemical roofing combustion method (CLC process) includes a fuel reactor for reacting oxygen transfer particles with fuel to reduce the oxygen transfer particles and burn fuel; And an air reactor that reacts and oxidizes the reduced oxygen-transfer particles with oxygen.

Specifically, in the fuel reactor, the metal oxide (M _x O _y ) in the oxygen transport particles reacts with the fuel to become a reduced metal oxide (M _x O _{y -1} ). At this time, the fuel is burned and reduced. The reduced oxygen transfer particles are oxidized again by reacting with oxygen in the air by moving to the air reactor. The oxidized oxygen transport particles are circulated to the fuel reactor to repeat the above process.

The reactions in the fuel reactor and the air reactor are shown in the following reaction formulas 1 and 2. The following Reaction Scheme 1 is a reaction in a fuel reactor, and Reaction Scheme 2 shows a reaction occurring in an air reactor.

<Scheme 1>

4M _x O _y + CH ₄ → 4M _x O _y-1 + 2H ₂ O + CO ₂

<Reaction Scheme 2>

M _x O _y-1 + 0.5O ₂ → M _x O _y

In the above reaction schemes 1 and 2, M represents a metal, and X and Y represent a ratio occupied by 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 may be delivered. Can be.

Examples and comparative examples

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a part of the examples of the present invention and cannot be interpreted as limiting the present invention by any means.

The contents not described here will be sufficiently technically inferred by those skilled in the art, and thus the description thereof will be omitted.

The following examples are copper oxide (CuO) for providing copper oxide which is the active ingredient of the oxygen transfer particles; Manganese oxide (MnO) to provide another active ingredient, manganese oxide; Magnesium hydroxide (Mg(OH) ₂ ) to provide magnesium oxide to prevent aggregation of oxygen transfer particles; It is an example of the production of oxygen transfer particles using sol-form boehmite (AlOOH) as a raw material composition as a support raw material for imparting dispersion and strength of an active substance and enhancing an oxygen transfer reaction.

In the raw material composition, magnesium hydroxide (Mg(OH) ₂ ) becomes magnesium oxide while water (H ₂ O) is discharged when calcined at a high temperature.

Among the raw material compositions, sol-form boehmite (AlOOH) becomes aluminum oxide when water (H ₂ O) is discharged when fired at a high temperature.

More specifically, the oxygen transfer particles of Examples 1 to 2 and Comparative Example 1 were prepared by the following method.

Example 1

Industrial CuO (purity 98% or more, average particle size 0 to 5㎛ or less in powder form), MnO (average particle size 0 to 5㎛ or less in powder form, purity 98% or more), Mg( OH) ₂ (powder form, average particle size 4.5 µm, purity 98.% or more), AlOOH (sol form, sol form AlOOH in a sol form in which the solvent is water, alumina (Al ₂ O ₃ when the sol is dried and calcined) ) 20 parts by weight of the form, AlOOH in the form of a powder was prepared with a purity of 99% or more and an average particle size of 1 μm or less in a state dispersed in a solvent).

After calcining each material at high temperature, CuO, MnO, Mg(OH) ₂ and AlOOH are 2.43 kg so that 40.5 parts by weight, 36.2 parts by weight, 10.3 parts by weight, and 13 parts by weight based on CuO, MnO, MgO, and Al ₂ O ₃ , respectively. , 2.17 kg, 0.89 kg, 3.90 kg were weighed, and a dispersant (anionic surfactant) and an antifoaming agent (metal soap system) were added to 9 liters of water to mix the solid raw material composition with a stirrer. The organic raw material was added to the mixed raw material composition while stirring with a stirrer to prepare a mixed slurry.

The mixed slurry was first crushed with a High Energy Ball Mill. Water and a dispersing agent were additionally added after the first pulverization in order to facilitate the pulverization. After the second pulverization, polyethylene glycol was added and the third pulverization was performed to prepare a stable and homogeneous fluid colloidal slurry. The crushed slurry was removed by sieving and the solid concentration in the final slurry was measured. Table 1 shows the total amount of additives added and the solid concentration in the final slurry measured.

The prepared colloidal slurry was transferred to a spray dryer by a pump and spray dried to form oxygen-transfer particles. The thus prepared oxygen-transferred particle assembly, 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-transferred particles. Before reaching the firing temperature, it stayed at 200° C., 300° C., 400° C., 500° C., 650° C., 800° C. and 950° C. for about 1 hour, and the rate of temperature increase was about 5° C./min.

Comparative Example 1

Comparative Example 1 also prepared oxygen-transfer particles in the same manner as in Example 1. The main differences in Example 1 and the manufacturing method are as follows. After calcining the raw material at high temperature, CuO, MnO, Mg(OH) ₂ and AlOOH are 2.15 kg, so that 35.9 parts by weight, 32.0 parts by weight, 9.1 parts by weight, and 23 parts by weight based on CuO, MnO, MgO, and Al ₂ O ₃ , respectively. 1.92 kg, 0.79 kg, and 6.90 kg were weighed and water was prepared by adding 12 liters. Table 1 shows the total amount of additives added and the solid concentration in the final slurry measured.

Example 2

In Example 2, oxygen transfer particles were prepared in the same manner as in Example 1. The main differences in Example 1 and the manufacturing method are as follows. After calcining the raw material at high temperature, CuO, MnO, Mg(OH) ₂ and AlOOH are 2.74 kg, such that 45.7 parts by weight, 27.1 parts by weight, 7.7 parts by weight, and 19.5 parts by weight based on CuO, MnO, MgO, and Al ₂ O ₃ , respectively. 1.63 kg, 0.67 kg, and 5.85 kg were weighed and water was prepared by adding 10 liters. Table 1 shows the total amount of additives added and the solid concentration in the final slurry measured.

Oxygen transport particle composition
(Unit, parts by weight, based on solid samples) Example 1 Comparative Example 1 Example 2 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 solid content 100 100 100 Dispersant 1.0 1.0 1.0 Antifoam 0.03 0.03 0.03 Organic binder 3.0 3.0 3.0 Slurry solid concentration 33.3 27.3 29.6

<Physical property evaluation>

(1) Measurement of shape of oxygen transfer particles

The shape of the oxygen transfer particles prepared in Examples and Comparative Examples was measured using an industrial microscope, and the results are shown in FIG. 1 (Example 1) and FIG. 2 (Comparative Example 1) and FIG. 3 (Example 2).

(2) Measurement of average particle size and particle size distribution

The average particle size and particle size distribution of the oxygen-transmitting particles were classified using MEINZER-IIShaker and a standard body for 10 minutes using MEINZER-IIShaker and a standard body based on ASTM E-11 of the American Society for Testing Materials (ASTM). Was calculated. The results are shown in Table 2 below.

(3) Fill density measurement

The filling density of the oxygen transport particles was measured using an AutoTap (Quantachrome) filling density meter according to ASTM D 4164-88. The results are shown in Table 2 below.

(4) Wear resistance measurement

The wear resistance of the oxygen transfer particles was measured by an abrasion tester according to ASTM D 5757-95. The abrasion index (AI) was determined at 10 stdL/min (standard volume per minute) over 5 hours as described in the ASTM method above, and the abrasion index represents the ratio of fines generated over 5 hours. The lower the wear index (AI), the stronger the strength of the particles. For comparison, the abrasion index (AI) of the AkzoFCC (Fluid Catalytic Cracking) catalyst used by the refinery measured by the same method was 22.5%, respectively. The results are shown in Table 2 below.

(5) Measurement of oxygen transfer performance

The oxygen transfer performance of the oxygen transfer particles prepared in Examples and Comparative Examples was evaluated using thermogravimetric analysis (TGA). In Examples and Comparative Examples, the composition of the reaction gas used for the reduction reaction of the 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. Did. Between the oxidation and reduction reactions, 100% nitrogen was supplied to prevent direct contact between the fuel and air in the reactor. The sample amount of oxygen transfer particles used in the experiment was about 30 mg. The flow rate of each reaction gas was 300 ml/min (273.5 K, based on 1 bar), and the oxidation/reduction reaction of the oxygen transport particles was repeated at least 10 times at 950°C. The amount of oxygen delivered was calculated from the difference in redox weight. The amount of oxygen delivered is the amount of oxygen delivered to the fuel by the oxygen transfer particles, and the weight change amount obtained by subtracting the weight of the oxygen transfer particles measured when the reduction reaction of the oxygen transfer particles is completed based on the weight of the fully oxidized state of the oxygen transfer particles is oxygen transfer. It is the value expressed by the weight percentage divided by the weight of the fully oxidized state of the particles. The results are shown in Table 2 below.

Firing temperature
(℃) Average particle size (㎛) Particle size distribution
(㎛) Fill density (g/ml) Wear Index Al (%) Oxygen transfer amount (wt%) Example 1 1100 97 37~302.5 2.5 2.4 11.8 Comparative Example 1 1100 82 37-196 2.0 15.2 9.5 Example 2 1100 98 37~302.5 2.44 2.2 10.9

The oxygen transfer particles of Examples 1 to 2 and Comparative Example 1 were prepared using CuO, MnO as the active material, AlOOH as the support material, and Mg(OH) ₂ as the additive material. As shown in Table 2, the oxygen transfer particles prepared by the composition according to the present embodiment had a high strength property of a wear index of 3% or less at a firing temperature of 1100°C and a property of 15.2% superior to a commercial fluid bed catalyst standard (22.5%). It can be seen that it possesses properties suitable for commercial fluidized bed processes.

In addition, the shape of the oxygen transfer particles is spherical, the average particle size is 82 to 98 μm, the particle size distribution is within the range of 37 to 302.5 μm, the filling density is about 2.5 g/ml, and the wear index is 5% or less. . 1 to 3 are presented industrial micrographs of oxygen transfer particles according to Examples and Comparative Examples of the present invention.

In addition, as can be seen in the attached Figures 1 to 3, the oxygen transfer particles prepared by Examples and Comparative Examples have a spherical shape. The oxygen transfer amount of the oxygen transfer particles prepared in Examples 1 to 2 and Comparative Example 1 was high in 9.5 to 11.8 parts by weight.

From the above results, a high-performance and low-cost oxygen transfer particle in a form suitable for a fluidized bed process capable of effectively burning fuel in a chemical roofing combustion technology using the oxygen transfer particle raw material composition proposed in the present invention and a method for manufacturing the oxygen transfer particle using the same. It was shown that it can be prepared. Oxygen transfer particles according to the raw material composition and the manufacturing method can be a competitive technology because mass production is easy and economic efficiency of the chemical roofing combustion process is reduced by reducing particle usage and reducing process size due to improved particle performance.

As described above, the configuration and operation of the present invention has been described based on the preferred embodiment according to the present invention, but the present invention is not limited to a specific embodiment, and a person having ordinary knowledge in the field will describe the patent to be described later. Various modifications and changes can be made to the present invention without departing from the spirit and technical scope of the present invention as set forth in the claims.

Claims (23)

Copper oxide 40.5% to 50% by weight;
Manganese oxide 27.1 wt% to 36.2 wt%;
Magnesium oxide or magnesium hydroxide 7.7 wt% to 10.3 wt%; And
It is a raw material composition for the production of oxygen transfer particles containing; aluminum oxide or aluminum hydroxide 13% by weight to 19.5% by weight,
The raw material composition for preparing the oxygen transport particles is a nickel oxide-free type that does not contain nickel oxide,
The copper oxide has an average particle size of more than 0 and less than or equal to 5 μm,
The manganese oxide has an average particle size of more than 0 and less than 5 μm,
The magnesium oxide or magnesium hydroxide has an average particle size of greater than 0 and less than or equal to 5 μm, and
The aluminum oxide or aluminum hydroxide has an average particle size of greater than 0 and less than or equal to 5 μm, a raw material composition for preparing oxygen transfer particles.
delete delete delete delete It is formed from a raw material composition for the production of oxygen transfer particles according to claim 1, and is an oxygen transfer particle comprising copper oxide, manganese oxide, magnesium oxide and aluminum oxide,
The oxygen transfer particles are nickel oxide-free, nickel oxide-free, non-blowhole spherical, average particle size of 60 µm to 150 µm, and particle size distribution of 30 µm to 400 Μm, the filling density is 1.5 g/mL to 4.0 g/mL, and the oxygen transfer particles have the structure of Formula 1,
After the abrasion test was conducted for 5 hours at a flow rate of 10.00 l/min (273.15 K, 1 bar) according to ASTM D5757-95 using an abrasion tester, the oxygen transfer particles having an abrasion index of 3% or less represented by the following Equation 1:
[Formula 1]
Cu _a Mn _b Mg _c Al _d O _x
(In Formula 1, a, b, c, and d are each independently 0.1 to 2.7, the sum of a + b + c + d is 3, and x is greater than 0 to 4)
[Equation 1]
AI(%) = [(W2)/(W1)]
(In Equation 1, W1 is the weight in g of the oxygen transfer particle sample before the abrasion test, and W2 is the weight in g of the microparticles collected for 5 hours during the abrasion test of the sample).
delete delete delete delete The method of claim 6,
The oxygen transfer particles are oxygen transfer particles having an oxygen transfer amount of 7 to 15% by weight of the total weight of the oxygen transfer particles.
(A) mixing the raw material composition for preparing oxygen transfer particles of claim 1 with a solvent to prepare a slurry for preparing oxygen transfer particles;
(B) preparing a homogenized slurry by stirring the slurry;
(C) spray drying the slurry to form solid particles; And
(D) drying and calcining the molded solid particles to prepare oxygen transfer particles;
The prepared oxygen transfer particles are nickel oxide-free, nickel oxide-free, non-blowhole spherical, average particle size of 60 μm to 150 μm, and particle size distribution of 30 μm to 400 μm, and the filling density is 1.5 g/mL to 4.0 g/mL,
Method for producing oxygen transfer particles having an abrasion index of 3% or less as shown in Equation 1 below after abrasion test for 5 hours at a flow rate of 10.00 l/min (273.15 K, 1 bar) according to ASTM D5757-95 using an abrasion tester :
[Equation 1]
AI(%) = [(W2)/(W1)]
(In Equation 1, W1 is the weight in g of the oxygen transfer particle sample before the abrasion test, and W2 is the weight in g of the microparticles collected for 5 hours during the abrasion test of the sample).
The method of claim 12,
In the step (A) of preparing the slurry for preparing the oxygen transfer particles, the raw material composition for preparing the oxygen transfer particles and the solvent are mixed in a weight ratio of 15 to 40:60 to 85, and the solvent is water.
The method of claim 12,
In the step (A) of preparing the slurry for preparing the oxygen transport particles, the slurry further comprises one or more additives among dispersants, antifoaming agents and organic binders.
The method of claim 14,
The dispersing agent is an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a method for producing oxygen-transporting particles containing at least one of a nonionic surfactant.
The method of claim 15,
The anionic surfactant is a method for producing oxygen-transmitting particles containing at least one of a polycarboxylate and a polycarboxylic acid amine salt.
The method of claim 14,
The antifoaming agent is 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 method of claim 14,
The organic binder is polyvinyl alcohol, polyethylene glycol, and a method for producing oxygen-transmitting particles comprising at least one of methyl cellulose.
The method of claim 14,
The additive includes both a dispersant, an antifoaming agent and an organic binder,
The additive is a method for producing oxygen-transferring particles that are added in an amount of 0.01 to 5.0 parts by weight of a dispersant, 0.01 to 1.0 parts by weight of an antifoaming agent, and 1.0 to 5.0 parts by weight of an organic binder relative to 100 parts by weight of a raw material composition for preparing oxygen-transmitting particles.
The method of claim 12,
The step (B) of preparing the homogenized slurry by stirring the slurry further comprises removing foreign substances in the stirred and pulverized slurry.
The method of claim 12,
In the step (C) of spray-drying the slurry to form solid particles, the homogenized slurry is introduced into a spray dryer, and then sprayed while maintaining an inlet temperature of 260°C to 300°C and an outlet temperature of 90°C to 150°C. A method for producing oxygen transfer particles comprising molding into solid particles.
The method of claim 12,
In the step (D) of drying and firing the molded solid particles to prepare oxygen-transferring particles, the molded solid particles are dried at 110° C. to 150° C. for 2 to 24 hours, and put into a high-temperature firing furnace at 1° C./min to A method for producing oxygen transfer particles comprising heating at 1000°C to 1350°C at a rate of 5°C/min and calcining for 2 to 10 hours.
A chemical roofing combustion method comprising reacting the oxygen transfer particles according to claim 6 with a fuel to reduce the oxygen transfer particles and burning the fuel, and reacting the reduced oxygen transfer particles with oxygen to regenerate the particles. .

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