WO2019078413A1 - Material composition for preparing oxygen transfer particles, oxygen transfer particles prepared using same, and method for preparing oxygen transfer particles - Google Patents

Abstract

One embodiment of the present invention relates to a material composition for preparing oxygen transfer particles, comprising: nickel hydroxide; cerium oxide or cerium hydroxide; and titanium oxide. The material composition for preparing 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 compositional state, the formulation of materials, and the degree of homogenization, so as to have physical properties, such as shape, particle size and size distribution, suitable for a fluidized-bed or high velocity fluidized-bed process, and oxygen transfer particles having improved abrasion resistance, long-term durability and oxygen transfer performance can be prepared even while firing temperature is lowered, in comparison with a conventional technique.

Description

Raw material composition for producing oxygen-transferring particles, oxygen-transferring particles prepared by using the same and method for producing oxygen-transferring particles

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a raw material composition for producing oxygen-transferring particles, oxygen-transferring particles prepared using the same, and a process for producing oxygen-transferring particles.

Climate change is continuing to suffer as the average global temperature rises due to the greenhouse effect resulting from increased CO ₂ concentrations in the atmosphere. The thermal power plant is the stationary source with the greatest anthropogenic 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, the power generation efficiency is greatly reduced and the cost of power generation is increased accordingly. Therefore, new technologies are required to minimize power generation efficiency and reduce CO ₂ capture cost.

Chemical Looping Combustion (CLC) technology is attracting attention as a technology capable of separating CO ₂ from power generation while reducing power generation efficiency. The CLC technology includes only water vapor and CO ₂ because the fuel contained in the solid particles (oxygen transfer particles), which is the main component of the metal oxide instead of air, reacts with the fuel and burns. Therefore, CO ₂ can be separated from CO ₂ by condensing water vapor. In the CLC process, the oxygen contained in the oxygen transfer particles is transferred to the fuel, and the oxygen transfer particles are oxidized again due to the oxygen contained in the air and the fuel reactors in which the reduction reaction occurs. The air reactors regenerated in an initial state are constituted by a combination of the two. Both reactors use a fluidized bed reactor and the whole process becomes a circulating fluidized-bed process.

Oxygen transferring particles used in this CLC process must satisfy various conditions suitable for fluidized bed process characteristics. First of all, suitable properties for the fluidized bed process, namely sufficient strength, suitable shape for flow and packing density or tapped density, average particle size and particle size distribution should be provided. In addition, it has a high oxygen transfer capacity in terms of reactivity, so that it must be able to supply enough oxygen for the fuel to pass through the fuel reactor as it passes through the fuel reactor.

However, the conventional oxygen transfer particles are produced by a method unsuitable for mass production, or the physical properties such as shape, strength and density are not suitable for application to the fluidized bed process or need to be improved. In order to reduce the strength of interaction between the metal oxide and the support The use of a support having a stable crystal structure results in a decrease in the oxygen delivery performance due to a rise in firing temperature to obtain sufficient strength or a problem of fluidization due to the agglomeration phenomenon during the reaction or a problem that the content of oxygen is low due to the low content of metal oxides have.

Therefore, it is possible to provide a method for producing a metal oxide which has suitable physical properties and sufficient strength for a fluidized bed process, inhibits coagulation between particles that may occur during an oxidation-reduction cycle reaction, reduces oxygen transfer performance even at high temperature firing, Development of transmission particles is required.

It is an object of the present invention to provide a raw material composition for producing oxygen-transferring particles which is suitable for fluidized bed processes, including strength, and which has improved abrasion resistance, long-term durability and oxygen delivery performance while lowering the firing temperature as compared with conventional techniques.

It is another object of the present invention to provide a stable colloidal slurry which is homogeneously dispersed by using the above raw material composition and to make it suitable for a chemical roofing combustion circulating fluidized bed process, ), A particle size distribution, mechanical strength or attrition resistance, and is superior in wear resistance and oxygen transmission performance even at a low firing temperature compared with the prior art, and a method for producing the same.

It is still another object of the present invention to provide a method and apparatus for efficiently collecting and collecting carbon dioxide generated by combustion while effectively combusting a fuel using the oxygen transfer particles and to reduce the amount of particles charged in a chemical roofing combustion process, And to provide a chemical roofing combustion method that prevents decrease in system thermal efficiency due to carbon dioxide capture while reducing a replenishment amount due to loss.

One embodiment of the present invention is directed to a process for the preparation of a composition comprising: nickel hydroxide; And cerium oxide or cerium hydroxide; To a raw material composition for producing oxygen-transferring particles.

The raw material composition for producing an oxygen-transferring particle may further include titanium oxide.

Wherein the raw material composition for producing oxygen-transferring particles comprises about 55% to about 80% by weight of nickel hydroxide; From about 10% to about 45% by weight of cerium oxide or cerium hydroxide; And from about 0% to about 20% by weight of titanium oxide.

The nickel hydroxide may have an average particle size of greater than about 0 to about 5 microns and a purity of greater than about 98%.

The cerium oxide or cerium hydroxide may have an average particle size of greater than about 0 to about 5 microns and a purity of greater than about 98%.

The titanium oxide may have an average particle size of greater than about 0 to about 5 microns and a purity of greater than about 95%.

Another embodiment of the present invention relates to an oxygen-transferring particle formed from the above-described raw material composition for producing oxygen-transferring particles and comprising nickel oxide and cerium oxide.

The oxygen transfer particles were subjected to 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, and the abrasion index represented by the following formula 1 was about 25% .

[Formula 1]

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

In the above Equation 1, W1 is the unit weight in g before the abrasion test of the sample, and W2 is the unit weight in g of the fine particles collected for 5 hours after the abrasion test of the sample.

Wherein the oxygen-transferring particles are spherical in shape, non-blowhole, have an average particle size of from about 60 占 퐉 to about 150 占 퐉, a particle size distribution of from about 30 占 퐉 to about 400 占 퐉, a packing density of from about 1.5 g / mL to about 4.0 g / mL.

The oxygen transfer particles may have an oxygen transfer amount of about 10 wt% to about 25 wt% of the total weight of the oxygen transfer particles.

Another embodiment of the present invention is a process for producing an oxygen-transferring particle, comprising the steps of: (A) mixing a raw material composition for producing oxygen-transferring particles with a solvent to prepare a slurry for producing oxygen- (B) stirring the slurry to produce a homogenized slurry; (C) spray drying the slurry to form solid particles; And (D) drying and firing the molded solid particles to produce oxygen-transferring particles.

In the step (A) of preparing the slurry for producing an oxygen-transferring particle, the raw material composition for producing oxygen-transferring particles and the solvent are mixed at a weight ratio of about 15 to 40: about 60 to 85, and the solvent may be water.

In the step (A) of preparing the slurry for producing an oxygen-transferring particle, the slurry may further comprise at least one of a dispersant, a defoaming agent and an organic binder.

The dispersant may include at least one of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

The anionic surfactant may include at least one of a polycarboxylic acid salt and a polycarboxylic acid amine salt.

The antifoaming agent may include at least one of a silicone type antifoaming agent, a metal soap type antifoaming agent, an amide type antifoaming agent, a polyether type antifoaming agent, a polyester type antifoaming agent, a polyglycol type antifoaming agent and an alcohol type antifoaming agent.

The organic binder may include at least one of polyvinyl alcohol, polyethylene glycol, and methyl cellulose.

Wherein the additive comprises from about 0.01 to about 5.0 parts by weight of the dispersant, from about 0.01 to about 1.0 part by weight of the defoamer, and from about 0.01 to about 5.0 parts by weight of the defoamer, based on 100 parts by weight of the raw material composition for producing oxygen- The organic binder may be added in an amount of about 1.0 part by weight to about 5.0 parts by weight.

The step (B) of agitating the slurry to produce a homogenized slurry may further comprise removing impurities in the agitated and pulverized slurry.

(C) spraying and drying the slurry to form solid particles, the homogenized slurry is introduced into a spray drier, the inlet temperature is about 260 ° C to about 300 ° C, and the outlet temperature is about 90 ° C to about 150 ° C And spraying to form solid particles.

The step (D) of producing the oxygen-transferring particles by drying and firing the molded solid particles comprises drying the molded solid particles at about 110 ° C to about 150 ° C for about 2 hours to about 24 hours, Lt; 0 > C to about 1350 < 0 > C at a rate of about 1 [deg.] C / min to about 5 [deg.] C / min and firing for about 2 hours to about 10 hours.

Another embodiment of the present invention includes the steps of reacting the above-mentioned oxygen transfer particles 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 To a chemical roofing combustion method.

The present invention relates to a raw material composition for producing oxygen-transporting particles which is suitable for a fluidized bed process and which has physical properties including strength and which is improved in abrasion resistance, long-term durability and oxygen delivery performance while lowering a firing temperature as compared with conventional techniques, Oxygen transfer particles with excellent shape, particle size, size distribution, mechanical strength or attrition resistance and excellent wear resistance, long-term durability and oxygen delivery performance suitable for combustion circulating fluidized bed processes And by using such oxygen transfer particles, it is possible to reduce the replenishment amount of the particle filling amount in the chemical roofing combustion process and the abrasion loss occurring during the long-time operation, and to prevent deterioration of the system thermal efficiency due to carbon dioxide capture Which can provide a chemical roofing combustion method.

Fig. 1 is a photograph of the shapes of oxygen transfer particles of Examples 1 to 6 of the present invention using an industrial microscope. Fig.

Fig. 2 is a photograph of the shape of oxygen transfer particles of Comparative Examples 4 and 7 of the present invention, taken using an industrial microscope.

FIG. 3 is a flowchart illustrating a method of manufacturing an oxygen-transferring particle according to an embodiment of the present invention.

4 is a flow chart showing steps (A) and (B) of the oxygen transfer particle production method according to an embodiment of the present invention.

FIG. 5 is a flow chart showing the step (C) of the oxygen transfer particle production method according to an embodiment of the present invention.

FIG. 6 is a flow chart showing step (D) of the oxygen transfer particle production method according to an embodiment of the present invention.

7 is a schematic diagram of a chemical loop combustion method according to an embodiment of the present invention.

≪ Raw material composition for producing oxygen-transferring particles >

One embodiment of the present invention is directed to a process for the preparation of a composition comprising: nickel hydroxide; And cerium oxide or cerium hydroxide.

The raw material composition for producing oxygen-transferring particles of the present invention may be prepared as oxygen-transferring particles according to the oxygen-transferring particle production method described below by controlling the composition, formulation and homogenizing degree of the raw materials, Or physical properties such as shape, particle size and particle size distribution suitable for high-speed fluidized bed processes, and which has improved wear resistance, long-term durability and oxygen delivery performance while lowering the firing temperature as compared with the prior art Transfer particles can be produced.

In addition, the oxygen transfer particles produced by the oxygen transfer particle-forming raw material composition transfer oxygen to a gaseous fuel such as a natural gas, a shale gas or a syngas as well as a solid fuel, Is excellent in fast-regenerating characteristics, and can be used repeatedly in succession. Accordingly, when the oxygen transfer particles are applied to the chemical roofing combustion process (CLC process) of the gaseous fuel and / or the solid fuel, the replenishment amount due to the particle filling amount and the wear loss occurring during the long- There is an effect that the process (CLC process) is simplified and the economical efficiency is improved.

The raw material composition for producing an oxygen-transferring particle of the present invention contains nickel hydroxide (Ni (OH) ₂ ) as an active material raw material. Nickel hydroxide is nickel oxide (NiO) as the water exits during the firing process in the production of oxygen transfer particles. When nickel oxide formed from nickel hydroxide is applied to a chemical roofing combustion reaction (CLC process) or the like, it is reduced to nickel (Ni) while efficiently burning the fuel by transferring oxygen to the fuel, It plays the role of receiving and playing.

Further, the raw material composition for producing oxygen-transferring particles of the present invention can be produced by using nickel hydroxide (Ni (OH) ₂ ) instead of nickel oxide (NiO) (Mg) content can be increased while maintaining excellent oxygen delivery performance, thereby solving the problem of coagulation between particles which may appear during the oxidation and reduction cycle reaction of chemical roofing combustion. . In addition, nickel hydroxide (Ni (OH) ₂ ) is advantageous for sphering the shape of the oxygen-transferring particles.

The nickel hydroxide may be a commercial nickel hydroxide having an average particle size of greater than about 0 to about 5 microns, specifically greater than about 0 and about 5 microns. Within this range, sufficient strength suitable for use in the fluidized bed process can be obtained even at lower firing temperatures, and the degree of dispersion between particles can be made more uniform.

The nickel hydroxide may have a purity of greater than about 98%, such as greater than about 99%. Within this range, the strength and the oxygen transmission amount of the oxygen transfer particles can be further improved.

The raw material composition for producing oxygen-transferring particles of the present invention may use only nickel hydroxide as a raw material for the active material, or a mixture of nickel hydroxide and another metal oxide may be used.

The kind of the metal oxide which can be mixed with the nickel hydroxide (Ni (OH) ₂ ) is not particularly limited. Specifically, it includes a nickel-based oxide including nickel oxide (NiO) and the like, a copper-based oxide including copper oxide (CuO, Cu ₂ O), iron oxide (FeO, Fe ₂ O ₃ , Fe ₃ O ₄ ) illustrates the cobalt-based oxides, including iron oxide, manganese oxide _{(MnO, MnO 2, Mn 2} O 3, Mn 3 O 4) manganese-based oxide and cobalt oxide (CaO, Co ₃ O _4), or the like, such as can do.

The content of nickel hydroxide may be about 55 wt% to about 80 wt%, specifically about 60 wt% to about 80 wt%, of the total raw material composition for producing oxygen-transporting particles. Within the above range, the oxygen transferring particles have improved oxygen transfer capacity and are excellent in physical properties such as wear resistance of the oxygen transferring particles after firing, and are excellent in nickel oxide (NiO) grains in the oxygen transferring particles in the firing process. It is possible to suppress the sintering phenomenon.

The raw material composition for producing oxygen-transferring particles of the present invention contains cerium oxide (CeO ₂ ) or cerium hydroxide (Ce (OH) ₄ ) as a raw material of a support. The cerium hydroxide is cerium oxide (CeO 2) as the water exits during firing during the production of the oxygen-transferring particles. In this process, the nickel oxide particles as the active ingredient are supported so as to be uniformly distributed throughout the oxygen- It can improve the usability and promote the oxygen transfer. In addition, cerium hydroxide is advantageous in sphericalizing the shape of the oxygen-transferring particles. In addition, the cerium oxide itself has a function of exchanging oxygen, so that the oxygen transfer amount can be improved and the oxygen transfer particles can be realized in a spherical shape.

Cerium oxide (CeO ₂₎ or cerium hydroxide (Ce (OH) ₄₎ is able to provide a sufficient strength required by the fluidized bed process after the firing, by performing the role as the inorganic binder, at the same time the oxygen transfer particles.

That is, cerium oxide (CeO ₂ ) or cerium hydroxide (Ce (OH) ₄ ) has a function of supporting a metal oxide, ie, nickel oxide (NiO) An inorganic binder, an oxygen transfer performance promoter, and the like.

In addition, cerium oxide (CeO ₂ ) or cerium hydroxide (Ce (OH) ₄ ) is a phenomenon in which oxygen transfer particles aggregate with each other during repetition of a redox cycle at high temperature and sintering of the active material (NiO) And the gas before and after the reaction can act as a pathway for facilitating the flow of gas between the outside of the oxygen transfer particle and the active material.

The cerium oxide (CeO ₂ ) or cerium hydroxide (Ce (OH) ₄ ) may have an average particle size of from about 0 to about 5 μm and a purity of about 98% or more when dispersed in a solvent. Within this range, a sufficient strength suitable for use in the fluidized bed process can be obtained, and the degree of dispersion of the active material in the oxygen delivery particles can be made more uniform.

The content of cerium oxide (CeO ₂ ) or cerium hydroxide (Ce (OH) ₄ ) may be from about 10 wt.% To about 45 wt.% Of the total oxygen transfer particle-forming raw material composition. Within this range, the effect of increasing the porosity, improving the physical properties, and preventing the sintering of the active material in the oxygen transfer particles can be more excellent. Further, the oxygen transfer amount can be further improved within the above range.

The cerium oxide (CeO ₂ ) or cerium hydroxide (Ce (OH) ₄ ) is not limited in the form in which it is supplied, and may be, for example, supplied in a solid powder state. In this case, the finally produced oxygen transfer particles have properties more suitable for the fluidized bed process and can realize a lower firing temperature and excellent strength.

The raw material composition for producing oxygen-transferring particles of the present invention may further comprise titanium oxide (TiO ₂ ). The titanium oxide is supported in such a manner that nickel oxide or nickel oxide formed from nickel hydroxide in the firing process is uniformly distributed throughout the oxygen transferring particles together with cerium oxide or cerium hydroxide used as a support raw material used together in the firing process, The sintering phenomenon of the active material is suppressed, and the inorganic binder acts simultaneously. Through this, titanium oxide can provide oxygen-transfer particles after firing with sufficient strength required in a fluidized bed process. In particular, titanium oxide can lower the firing temperature of the oxygen-transferring particles necessary for realizing a sufficiently high-strength characteristic.

The titanium oxide (Ti0 ₂₎ has an average particle size of from about greater than 0 to about 5 ㎛ a commercial nickel hydroxide. Within this range, sufficient strength suitable for use in the fluidized bed process can be obtained even at lower firing temperatures, and the degree of dispersion between particles can be made more uniform.

The titanium oxide (TiO ₂ ) may have a purity of about 95% or more, for example, about 97% or more. Within this range, the strength and the oxygen transmission amount of the oxygen transfer particles can be further improved.

The content of the titanium oxide (TiO ₂ ) may be from about 0 wt% to about 20 wt% or from about 0 wt% to about 20 wt% of the total oxygen transfer particle raw composition. Within the above range, it is possible to lower the sintering temperature while suppressing the sintering phenomenon between the active materials, thereby improving the oxygen transfer rate, the oxygen transfer rate, and the oxidation reaction It is possible to further improve the oxygen delivery performance as it is regenerated in the initial state.

The titanium oxide (TiO ₂ ) is not limited in the form in which it is supplied, and may be, for example, supplied in a solid powder state. In this case, the finally produced oxygen transfer particles have properties more suitable for the fluidized bed process and can realize a lower firing temperature and excellent strength.

<Oxygen Transmission Particle>

Another embodiment of the present invention relates to an oxygen-transferring particle formed from the above-described raw material composition for producing oxygen-transferring particles and comprising nickel oxide and cerium oxide.

The raw material composition for producing an oxygen-transferring particle may include nickel hydroxide; Cerium oxide or cerium hydroxide; And titanium oxide; specifically, from about 55% to about 80% by weight of nickel hydroxide; From about 10% to about 45% by weight of cerium oxide or cerium hydroxide; And from about 0% to about 20% by weight of titanium oxide.

Accordingly, the oxygen transfer particles of the present invention realize excellent oxygen transfer rate, oxygen transfer amount and durability by the composition and structural characteristics of the constituent metals. In addition, when such oxygen transfer particles are applied to the chemical roofing combustion process and apparatus, the amount of charged particles and wear loss required for long-time operation can be reduced.

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

In addition, the oxygen transferring particles of the present invention are stable and uniformly dispersed in the oxygen transferring particles in an average particle size of 5 μm or less, for example, 1 μm or less in the slurry state, It has excellent long-term durability of particles and has spherical shape and particle size, particle size distribution, filling density, strength, low firing temperature and excellent oxygen transfer performance suitable for fluidized bed process.

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

The oxygen transfer particles were subjected to 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, and the abrasion index expressed by the following formula 1 was about 20% .

[Formula 1]

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

In the above Equation 1, W1 is the unit weight in g before the abrasion test of the sample, and W2 is the unit weight in g of the fine particles collected for 5 hours after the abrasion test of the sample.

The lower limit of the abrasion index is not particularly limited, and the closer to 0% the better. Within this range, when the oxygen transfer particles are used for chemical roofing combustion, the loss of wear loss is further reduced, the amount of oxygen transfer particles to be supplemented during the process operation can be reduced, and the generation rate of fine powder, It is more advantageous to be applied to a circulating fluidized bed process or the like.

Wherein the oxygen-transferring particles are spherical in shape, non-blowhole, have an average particle size of from about 60 占 퐉 to about 150 占 퐉, a particle size distribution of from about 30 占 퐉 to about 400 占 퐉, From about 1.5 g / mL to about 4.0 g / mL. In this case, when the oxygen transfer particles are used for chemical roofing combustion, the loss rate of abrasion is further reduced, the amount of oxygen transfer particles to be supplemented during the process operation can be reduced, and the generation rate of fine powder, Process and the like.

The non-blowhole refers to a sphere having a shape other than a shape including a blowhole such as dimple, hollow, and the like.

The average particle size and particle size distribution of the oxygen-transferring particles may be specifically from about 60 탆 to about 150 탆, more specifically from about 70 탆 to about 130 탆, and the particle size distribution is about 30 탆 To about 400 microns, and more specifically from about 38 microns to about 350 microns.

The oxygen transfer particles may have an oxygen transfer amount of from about 10 wt% to about 25 wt%, specifically from about 11 wt% to about 25 wt%, more specifically from about 12.5 wt% to about 20 wt% .

&Lt; Production method of oxygen transfer particles >

Another embodiment of the present invention relates to a method for producing an oxygen-transferring particle, comprising the steps of: (A) mixing a raw material composition for producing oxygen-transferring particles with a solvent to prepare a slurry for producing oxygen- (B) stirring the slurry to produce a homogenized slurry; (C) spray drying the slurry to form solid particles; And (D) drying and firing the molded solid particles to produce oxygen-transferring particles.

The slurry for preparing oxygen transfer particles may be prepared by mixing the above-mentioned raw material composition for producing oxygen transfer particles with a solvent.

The raw material composition for producing an oxygen-transferring particle may include nickel hydroxide; Cerium oxide or cerium hydroxide; And titanium oxide; specifically, from about 55% to about 80% by weight of nickel hydroxide; From about 10% to about 45% by weight of cerium oxide or cerium hydroxide; And from about 0% to about 20% by weight of titanium oxide.

The slurry for preparing the oxygen-transferring particles in the step (A) of preparing the slurry for producing the oxygen-transferring particles is prepared by mixing the above-mentioned raw material composition for producing oxygen-transferring particles of the present invention into a solvent.

The raw material composition for producing oxygen-transferring particles and the solvent may be mixed at a weight ratio of about 15 to 40: about 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 producing oxygen-transferring particles are maintained within an appropriate range, the viscosity is kept within an appropriate range to improve the fluidity, Excellent manufacturing efficiency can be realized.

The type of the solvent is not particularly limited, and solvents generally used in this field can be used. Specifically, water can be used as the solvent. In this case, workability and manufacturing efficiency in the homogenization and firing process can be further improved.

In step (A) of preparing the slurry for producing oxygen-transferring particles, the slurry may further comprise at least one additive selected from dispersing agents, antifoams and organic binders.

Specifically, the additive may be mixed with the raw material composition for producing an oxygen-transferring particle in a state previously introduced into the above-mentioned solvent. In this case, the dispersibility and the ability to mix with the solvent of the raw material composition for producing oxygen-transferring particles can be further improved.

The above dispersant can prevent the components contained in the raw material composition for producing oxygen-transferring particles from agglomerating with each other when the slurry is crushed as described below. In addition, 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.

Specifically, at least one of an anionic surfactant, a cationic surfactant, and a nonionic surfactant may be used as the dispersing agent. The anionic surfactant may be, for example, a poly carboxylate ammonium salt or a polycarboxylate amine salt. In this case, the function of controlling the charge control, dispersion and agglomeration of the particle surface by the dispersant can be further improved, and the slurry can be highly concentrated.

In addition, the dispersant can improve the efficiency of manufacturing the shaped body (oxygen transfer particle assembly) produced by spray drying the slurry, that is, the shape of the green body, not the donut shape, the dimple shape, or the blow shape.

The content of the dispersant may be about 0.01 parts by weight to about 5 parts by weight based on 100 parts by weight of the raw material composition for producing oxygen-transferring particles. Within this range, the dispersing effect of the oxygen-transferring particles can be more excellent.

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

Specifically, the antifoaming agent may include at least one of a silicone-based antifoaming agent, a metal soap-based antifoaming agent, an amide-based antifoaming agent, a polyether-based antifoaming agent, a polyester-based antifoaming agent, a polyglycol-based antifoaming agent and an alcohol- based antifoaming agent. In this case, the compatibility of the defoamer is more excellent.

The amount of the defoaming agent may be about 0.01 part by weight to about 1.0 part by weight based on 100 parts by weight of the raw material composition for producing oxygen-transferring particles. Within this range, it is possible to reduce the occurrence of bubbles during the slurry production process, to further improve the efficiency of producing spherical oxygen transfer particles during spray drying, to further reduce the content of residual ash after firing, have. The more specific content of the antifoaming agent can be adjusted depending on the bubble generation amount.

The organic binder may be added in the slurry preparation step to impart plasticity and fluidity to the slurry and ultimately provide strength to the oxygen delivery particles assembled by spray drying to form an assembly prior to preliminary drying and firing, The handling of the green body can be facilitated.

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

The content of the organic binder may be about 1 part by weight to about 5 parts by weight based on 100 parts by weight of the raw material composition for producing oxygen-transferring particles. Within the above range, the bonding force of the solid particles formed by the spray drying is improved, the characteristics of maintaining the shape of the spherical shape before drying and firing can be improved, and the content of residual ash after firing is reduced, .

In one embodiment, the additive comprises both a dispersant, a defoamer, and an organic binder, wherein the additive comprises about 0.01 to about 5.0 parts by weight of the dispersant, about 1.0 part by weight of the organic binder, To about 5.0 parts by weight of the defoaming agent, and from about 0.01 to about 1.0 part by weight of the defoaming agent. In this case, it is advantageous to control the average particle size, particle size distribution and shape of the oxygen delivery particles while further improving the oxygen delivery amount of the oxygen delivery 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 the homogenized slurry by stirring the slurry may include homogenizing the slurry prepared above by stirring and pulverizing the slurry using a stirrer. In this case, the controllability such as the homogenization characteristics of the slurry, the concentration of the slurry, the viscosity, the stability, the fluidity and the strength and density of the particles after spray drying can be further improved.

The stirring may be carried out in the course of adding the components contained in the mixture or in the state in which all of the components contained therein are added. At this time, stirring may be performed using, for example, a stirrer.

Specifically, the slurry prepared by mixing the solvent and / or additive with the composition for producing oxygen-transferring particles may be pulverized using a pulverizer after stirring to make the particle size in the slurry to be several microns (쨉 m) or less. In this process, the pulverized particles are more uniformly dispersed in the slurry and the aggregation of the particles in the slurry is inhibited, so that a homogeneous and stable slurry can be produced.

If necessary, the pulverization process can be repeated several times, and the fluidity of the slurry can be controlled by adding the dispersant and defoamer during each pulverization process.

For example, a wet milling method may be used as a milling method. In this case, it is possible to improve the pulverizing effect and to solve the problems such as fly-off of particles generated during dry pulverization. On the other hand, when the particle diameter of the raw material composition is several microns or less, a separate pulverization process may be omitted.

In the present invention, it is further possible to remove foreign matter in the slurry which has been stirred and pulverized. Through the above steps, it is possible to remove foreign matter or agglomerated raw materials that may cause nozzle clogging or the like during spray molding. The removal of the foreign matter can be performed, for example, by sieving.

There is no particular limitation on the fluidity of the homogenized slurry, and any viscosity is possible if it can be transported by a pump.

(C) spraying and drying the slurry to form solid particles, the homogenized slurry is introduced into a spray drier, the inlet temperature is maintained at about 260 ° C. to about 300 ° C., and the outlet temperature is maintained at about 90 ° C. to about 150 ° C. And then shaping into solid particles by spraying.

The slurry may be molded using a spray dryer. Specifically, the homogenized slurry may be transferred to a spray dryer through a pump, and then the transferred slurry composition may be sprayed into a spray dryer to form solid particles.

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

The type and operating conditions of the spray dryer for forming the oxygen transfer particles in the spray dryer may be those operating conditions commonly used in this field.

More specifically, the oxygen delivery particles can be formed by spraying the fluidized homogeneous slurry in a countercurrent spraying method in which the pressurized nozzle is sprayed in a direction opposite to the flow of the drying air.

At this time, the inlet temperature of the spray dryer may be maintained at about 260 ° C to about 300 ° C, and the outlet temperature may be maintained at about 90 ° C to about 150 ° C. The efficiency of producing spherical oxygen transfer particles within the above temperature range can be further improved.

The step (D) of producing the oxygen-transferring particles by drying and firing the molded solid particles is carried out by drying the molded solid particles at about 110 ° C to about 150 ° C for about 2 hours to about 24 hours, Lt; 0 &gt; C to about 1350 &lt; 0 &gt; C at a rate of 1 [deg.] C / min to about 5 [deg.] C / min and calcining for about 2 hours to about 10 hours.

When the drying is performed under the above-mentioned temperature and time conditions, it is possible to prevent cracks from occurring in the particles due to expansion of moisture in the particles during firing. At this time, drying can be performed in an air atmosphere.

When the drying is completed, the dried particles are put into a high-temperature firing furnace and the final firing temperature is raised from about 1050 ° C to about 1350 ° C at a rate of about 1 ° C / min to about 5 ° C / min, Lt; / RTI &gt; It is possible to prevent the strength of the particles from becoming weak or the firing cost from being excessively increased within the firing time range. In this case, the organic additives (dispersant, antifoaming agent, and organic binder) introduced during the production of the slurry by firing are burned and bonding between the raw materials is performed to improve the strength of the particles. Further, within the above-mentioned firing temperature range, it is possible to sufficiently improve the oxygen transmission amount while preventing the firing temperature from being insufficient and preventing the strength of the oxygen transfer particles from being lowered.

More specifically, the firing may be performed by a method of imparting stagnation zones of at least about 30 minutes each at a stagnation temperature of two or more stages until reaching a final firing temperature. In this case, it is possible to prevent the particle shape destruction due to the gas generated by the evaporation of water and the combustion of the organic additive inside the produced oxygen transfer particles.

The firing can be performed by using a firing furnace such as a muffle furnace, a tubular furnace or a kiln.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings in order to facilitate a person skilled in the art to which the present invention belongs. The scope of the invention is not limited by the examples given below.

3 is a schematic view showing a process (S100) for producing oxygen transfer particles using the oxygen transfer particle raw material composition according to the present invention. As shown in FIG. 3, the oxygen-transferring particles are prepared by mixing (A) adding a raw material composition for producing oxygen-transferring particles to a solvent and mixing the mixture, (B) preparing a homogenized slurry by pulverizing and dispersing the mixed slurry, (D) a step (C) of spray-drying the homogenized slurry to form solid particles and a step (D) of drying and firing the molded solid particles (green body of oxygen transfer particles) .

4 is a process drawing showing an exemplary process for preparing a mixture of a raw material composition and water as a slurry. As shown in FIG. 4, the preparation of the slurry includes the steps of adding the additive to water (S11), mixing the solid raw material into water (S12), adding the organic additive to the mixture (S21) And a step (S22) of homogenizing and dispersing and pulverizing and dispersing the slurry and preparing a dispersed slurry, and removing the foreign substances contained in the slurry (S23).

5 is a process drawing showing an exemplary process of spray-drying slurry to form oxygen-transfer particles. As shown in FIG. 5, the step (S30) of spray-drying the slurry to form the oxygen transfer particles (S30) includes transferring the slurry to the spray dryer (S31) and injecting the transferred slurry into the spray dryer Step S32.

6 is a process drawing showing an exemplary process of drying and firing an oxygen transfer particle green body formed by a spray drying method to form final oxygen transfer particles. As shown in FIG. 6, the formed oxygen transfer particle green body can be manufactured as a final oxygen transfer particle through a preliminary drying step (S41) and a firing step (S42).

<Chemical roofing combustion method>

Another embodiment of the present invention is a process for the production of a chemical roofing combustion comprising reacting the oxygen transfer particles described above with a fuel to burn the fuel and reduce the oxygen transfer particles and to regenerate the reduced oxygen transfer particles by reacting with oxygen &Lt; / RTI &gt;

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

A schematic view of the chemical roofing combustion method of the present invention is shown in Fig.

When the oxygen transfer particles are reacted with the fuel, the oxygen transfer particles are reduced while transferring oxygen to the fuel, generating carbon dioxide and water. When the reduced oxygen transfer particles are reacted with oxygen, they are oxidized and regenerated again. In the chemical roofing combustion method of the present invention, the above process is repeated. In addition, the provision of oxygen to the reduced oxygen transfer particles can be effected through contact of air and oxygen transfer particles.

When the oxygen transfer particles of the present invention are applied to the chemical roofing combustion process (CLC process), carbon dioxide can be originally separated and collected while reducing the system thermal efficiency deterioration due to carbon dioxide capture compared to the conventional combustion system. In addition, due to the nature of the chemical roofing combustion process, carbon dioxide is not captured by using the solution, so there is an advantage that the amount of water used is small and no waste water is generated.

In addition, the 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 the fuel; And an air reactor for oxidizing and reacting the reduced oxygen transfer particles with oxygen.

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

The reactions in the fuel reactor and in the air reactor are shown in Schemes 1 and 2 below. The following reaction scheme 1 is the reaction in the fuel reactor and the reaction scheme 2 is the reaction occurring in the air reactor.

<Reaction 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 Schemes 1 and 2, M represents a metal, and X and Y represent the ratio of each atom in the metal oxide molecule.

In the schemes 1 and 2, one oxygen atom (O) is transferred from one molecule of the metal oxide, but one or more oxygen atoms (O) may be delivered. In this case, the equations 1 and 2 are changed according to the number of delivered oxygen .

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It should be understood, however, that this is provided as illustrative of the present invention and is not to be construed as limiting the invention in any way.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

The following examples illustrate the use of nickel hydroxide (Ni (OH) ₂ ) to provide the active ingredient nickel oxide (NiO); Cerium oxide (CeO ₂ ) or cerium hydroxide (Ce (OH) ₄ ) in powder form as a support material for imparting dispersion and strength of nickel oxide (NiO) and promoting oxygen transfer reaction; (NiO) -based oxygen transfer particles using titanium oxide (TiO ₂ ) as a raw material for enhancing physical properties through reduction of sintering temperature of oxygen transfer particles.

When nickel hydroxide (Ni (OH) ₂ ) and cerium hydroxide (Ce (OH) ₄ ) are calcined at a high temperature, water (H ₂ O) is released and becomes nickel oxide and cerium oxide, respectively.

In the following examples, nickel oxide (NiO) is 70 parts by weight, cerium oxide (CeO ₂ ) is 20 parts by weight to 30 parts by weight based on 100 parts by weight of a dry raw material sample in which H ₂ O is discharged by high- , And titanium oxide (TiO ₂ ) in an amount of more than 0 parts by weight to 10 parts by weight.

More specifically, the oxygen transfer particles of Examples 1 to 6 were produced by the following method.

Example 1

Industrial Ni (OH) to produce the oxygen transfer particles ₂ (purity 98% or higher, powder form), CeO ₂ (powder, average particle size of 1 ㎛ or less, purity more than 99%), TiO ₂ (powder, average particle size of 1 탆 or less, purity of 95% or more).

NiO (OH) ₂ and CeO ₂ (6.95 kg, 2.4 kg) were weighed such that NiO was added in an amount of 70 parts by weight and CeO ₂ was added in an amount of 30 parts by weight, and 18 liters of a dispersant Surfactant) and antifoaming agent (metal soap system) were added and the solid raw material composition was mixed with a stirrer. The solid raw material composition was added to water mixed with an organic additive, and the mixture was stirred with a stirrer to prepare a mixed slurry. The total amount of additive is as shown in Table 1.

The mixed slurry was first pulverized with a high energy ball mill. In order to proceed smoothly, water and a dispersant were further added after the first grinding. After the second milling, polyethylene glycol was added and the third milling proceeded to produce a stable and homogeneous flowable colloidal slurry. The pulverized slurry was sieved to remove foreign matter and the solid concentration in the final slurry was measured. The amount of total added additive and the solids concentration in the final slurry measured are as shown in Table 1.

The prepared colloidal slurry was transferred by a pump to a spray drier and spray dried to form oxygen transfer particles. The thus formed oxygen transfer particle assembly, that is, a green body was preliminarily dried in an air atmosphere reflux dryer at 120 ° C for 12 hours and fired at 1100 ° C to 1300 ° C for 5 hours in a firing furnace to prepare oxygen transfer particles . 300 ° C, 400 ° C, 500 ° C, 650 ° C, 800 ° C and 950 ° C for 1 hour before reaching the firing temperature, and the rate of temperature rise was about 5 ° C / min.

Example 2

Initial water dose is changed to 32 liters, and cerium oxide instead of cerium hydroxide (Ce (OH) _4, in powder form, the average particle size of 1 ㎛ or less, and the purity 99% or more), using, and high-temperature firing, H ₂ O is discharged Dried raw material sample was measured in the same manner as in Example 1, except that the amount of NiO was 70 parts by weight and CeO ₂ was 30 parts by weight based on 100 parts by weight of the dried raw material sample.

Table 1 shows the contents of raw material materials for producing NiO-based oxygen-transferring particles according to Examples 1 and 2 and the characteristics of the fluid colloidal slurry.

Examples 3 to 6

Oxygen transferring particles were prepared in the same manner as in Example 1, except that the initial water input amounts in Examples 3 and 5 were 22 liters, and Examples 4 and 5 were 25 litters and the composition was changed as shown in Table 1 below.

ingredient	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
Nickel hydroxide (Ni (OH) 2 )	74.3	70.6	74.3	71.1	74.3	71.8
Cerium oxide (CeO 2)	25.7	-	21.4	-	17.1	-
Cerium hydroxide (Ce (OH) 4 )	-	29.4	-	24.8	-	20.0
Titanium oxide (TiO 2)	-	-	4.3	4.1	8.6	8.2
Total solids content	100	100	100	100	100	100
Dispersant	2.4	2.9	1.0	1.2	1.0	1.0
Defoamer	0.4	0.4	0.3	0.3	0.3	0.5
Organic binder	3.0	3.8	3.6	3.0	2.5	3.0
Slurry solid concentration	31.0	20.0	23.1	20.1	24.5	22.0

Comparative Examples 1 to 8

Comparative Examples 1 to 8 were prepared in the same manner as in Example 1 except that the composition was changed as shown in Table 2 below.

ingredient	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6	Comparative Example 7	Comparative Example 8
Nickel oxide (NiO)	70	70	70	70	65.8	66.5	70	67.2
Gamma alumina (γ-Al 2 O 3)	30	-	-	-	-	-	-	-
Alpha-alumina (α-Al 2 O 3)	-	30	-	-	-	-	-	-
Magnesium aluminate (MgAl 2 O 4 )	-	-	30	-	-	-	-	-
Cerium oxide (CeO 2)	-	-	-	30	-	-	20	-
Cerium hydroxide (Ce (OH) 4 )	-	-	-	-	34.2	28.7	-	23.2
Titanium oxide (TiO 2)	-	-	-	-	-	4.8	10	9.6
Total solids content	100	100	100	100	100	100	100	100
Dispersant	0.2	0.2	0.2	1.0	1.5	1.0	0.8	1.3
Defoamer	0.1	0.1	0.1	0.4	0.3	0.4	0.4	0.4
Organic binder	1.3	2.4	3.8	3.0	2.4	2.4	2.5	2.4
Slurry solid concentration	34.0	75.5	60.4	58.9	40.2	43.9	61.1	42.6

&Lt; Evaluation of physical properties &

(1) Measurement of shape of oxygen transfer particles

The shapes of the oxygen transfer particles prepared in Examples and Comparative Examples were measured using an industrial microscope and the results are shown in Fig. 1 (Examples 1 to 6) and Fig. 2 (Comparative Examples 4 and 7).

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

The average particle size and particle size distribution of the oxygen transfer particles were determined using a MEINZER-II Sheaker and a standard, based on ASTM E-11 of the American Society for Testing Materials (ASTM) Respectively.

(3) Filling density measurement

The packing density of oxygen transfer particles was measured using an AutoTap (Quantachrome) packing density meter according to ASTM D 4164-88.

(4) Wear resistance measurement

The wear resistance of oxygen transfer particles was measured by an abrasion tester in accordance with ASTM D 5757-95. The wear index (AI) was determined at 10 std L / min (standard volume per minute) over 5 hours as described in the ASTM method, and the wear index represents the ratio of fine powder generated over 5 hours. The lower the wear index (AI), the stronger the particle strength. For comparison, the wear index (AI) of the fluid catalytic cracking (AkzoFCC) catalyst used in the oil companies measured by the same method was 22.5%.

(5) Measurement of oxygen transfer performance

The oxygen delivery performance of the oxygen delivery particles prepared in the examples was evaluated using thermogravimetric analysis (TGA). The reaction gas used in the reduction reaction of oxygen transfer particles in Examples and Comparative Examples was composed of 15 vol% CH ₄ mixed with 85 vol% CO ₂ and the reaction gas for oxidizing the reduced oxygen transfer particles was air Respectively. 100% nitrogen was supplied between the oxidation reaction and the reduction reaction so that the fuel and air were not in direct contact with each other in the reactor. The amount of oxygen transfer particles used in the experiment was about 30 mg. The flow rate of each reaction gas was 300 ml / min (273.5K, 1 bar), and the oxidation / reduction reaction of the oxygen transfer particles was repeated at least 10 times at 850 ° C. The amount of oxygen transfer was calculated from the redox weight difference. The oxygen transfer amount is an amount of oxygen delivered by the oxygen transfer particles to the fuel. 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 terminated based on the weight of the complete oxidation state of the oxygen transfer particles, Divided by the weight of the particle's complete oxidation state and expressed as a weight percentage.

	Firing temperature (캜)	Oxygen transfer particle shape	Average particle size (占 퐉)	Particle size distribution (탆)	Filling density (g / ml)	Wear Index AI (%)	Oxygen transfer amount (parts by weight)
Example 1	1100	rectangle	-	-	-	64	-
	1200		83	37 ~ 302.5	2.9	19.7	15.0
	1300		76	37 ~ 302.5	3.5	3.3	14.9
Example 2	1100	rectangle	73	37 ~ 302.5	2.7	21.2	-
	1200		67	37 ~ 302.5	3.3	16.4	15.9
	1300		65	37 ~ 302.5	3.6	2.3	15.8
Example 3	1000	rectangle	-	-	-	41.0	-
	1100		71	37 to 231	3.56	2.1	15.6
Example 4	1000	rectangle	95	37 ~ 302.5	2.1	23.5	-
	1100		84	37 ~ 302.5	3.6	1.3	16.3
Example 5	1000	rectangle	-	-	-	30.1	-
	1100		82	37 to 231	3.6	1.6	15.6
Example 6	1000	rectangle	84	37 ~ 302.5	2.1	21.5	-
	1100		76	37 to 231	3.7	0.9	16.3

	Firing temperature (캜)	Oxygen transfer particle shape	Average particle size (占 퐉)	Particle size distribution (탆)	Filling density (g / ml)	Wear Index AI (%)	Oxygen transfer amount (parts by weight)
Comparative Example 1	1300	rectangle	75	37 ~ 302.5	2.4	18.2	11.9
	1400		74	37 ~ 302.5	2.5	1.1	11.2
Comparative Example 2	1300	rectangle	-	-	-	61.7	-
	1400		114	37 ~ 302.5	2.6	9.0	10.8
Comparative Example 3	1300	rectangle	-	-	-	50.7	-
	1400		99	41.5 to 231	2.6	22.1	-
	1500		98	41.5 to 231	2.6	22.0	-
Comparative Example 4	1200	Dimple	-	-	-	66.3	-
	1300		87	49 ~ 302.5	3.1	17.9	14.7
	1400		78	41.5 to 302.5	3.4	5.6	14.5
Comparative Example 5	1300	rectangle	90	41.5 to 231	3.4	26.8	-
	1400		83	37 to 231	3.7	3.8	15.9
Comparative Example 6	1200	rectangle	-	-	-	24.9	-
	1300		91	41.5 to 231	3.66	2.6	16.3
Comparative Example 7	1200	Dimple	-	-	-	32.9	-
	1300		71	37 to 231	2.6	6.1	15.6
Comparative Example 8	1200	rectangle	-	-	-	84.5	-
	1300		84	37 to 231	3.42	1.8	16.2

The oxygen transfer particles of Examples 1 to 6 were prepared using Ni (OH) ₂ as the raw material of the active material, CeO ₂ or Ce (OH) ₄ as the support raw material, and TiO ₂ as the additive raw material. As shown in Table 3, the oxygen-transferring particles prepared from the composition according to the present invention show high strength at a sintering temperature of 1100 to 1300 ° C and a wear index of 5% or less and have properties suitable for a commercial fluidized bed process have.

That is, the shape of the oxygen transfer particles is spherical and has an average particle size of 65 to 85 占 퐉, a particle size distribution of 37 to 302.5 占 퐉, a filling density of about 3.6 g / ml, and a wear index of 5% . FIG. 5 shows an industrial micrograph of oxygen transfer particles according to an embodiment of the present invention.

Further, as can be seen from the attached FIG. 1, the oxygen-transferring particles produced by the examples have a spherical shape. The oxygen delivery amount of the oxygen delivery particles was as high as 14.9 to 16.3 parts by weight. Oxygen transfer particles of TiO embodiment ₂ is added for example, 3 to 6 Examples 1 and compared to 2 exhibits a high strength characteristic of 5% or less abrasion index at 1100 ℃ temperature 200 ℃ low firing TiO ₂ added to the sintering temperature drop In the case of the present invention.

The oxygen transfer particles of Comparative Examples 1 to 3 proposed in the prior art use NiO as the raw material of the active material. The oxygen transfer particles of Comparative Example 1 and Comparative Example 2 prepared using γ-alumina or α-alumina as a support material exhibited high strength characteristics with a wear index of less than 10% at a firing temperature of 1400 ° C. and had properties suitable for commercial fluidized bed processes . However, the amount of oxygen delivered was 11.2 parts by weight or less, which is much lower than in the Examples.

The oxygen transfer particles of Examples 1 to 6 show an oxygen transmission amount of 30% or more higher than that of the oxygen transfer particles of Comparative Examples 1 to 2 of the prior art. The oxygen delivery particles of Comparative Example 3 prepared using magnesium aluminate as a support material could not obtain high strength properties even at a sintering temperature of 1500 ° C.

On the other hand, in the oxygen transfer particles of Comparative Example 4 and Comparative Example 5 in which NiO was used as a raw material for the active material instead of Ni (OH) ₂ as the raw material of the active materials of the Examples, the oxygen transfer amount and the wear index were equivalent to those of Example 1 and Example 2 It was found that a sintering temperature of 1400 ° C or more, which is 100 ° C higher than that of Example 1 and Example 2, was required in order to obtain a high strength property with a wear index of 5% or less. In particular, Comparative Example 4 was formed in the form of a dimple or a donut having a hollow shape at the center, which was unsuitable for fluidized bed process applications. When dimples or donut-shaped particles are used for a long time in a fluidized bed process, the amount of particle loss replenishment may increase due to more particle wear loss than spherical shape. The oxygen transfer particles of Comparative Examples 6 to 8 in which TiO ₂ was added had the same values of oxygen transfer amount and wear index as those of Examples 3 to 6. However, in order to obtain a high strength characteristic of a wear index of 5% or less, A higher sintering temperature of 1300 DEG C or higher was required.

Industrial photomicrographs of oxygen transfer particles of Comparative Example 4 and Comparative Example 7 are shown in Fig. As a result, the oxygen transfer particles of Comparative Example 4 and Comparative Example 7 were formed into a dimpled shape and thus were not suitable for application to a fluidized bed process.

From the above results, it can be seen that by using the oxygen transfer particle raw material composition of the present invention and the oxygen transfer particle production method using the same, high-strength Ni-based oxygen transfer particles suitable for a fluidized bed process capable of effectively burning fuel in chemical roofing combustion technology And can be produced even at a firing temperature of 1000 ° C to 1250 ° C. Oxygen transfer particles by the raw material composition and the production method can be a competitive technique because mass production is easy and economical efficiency of the chemical roofing combustion process is improved due to improvement of particle performance. As shown in Table 3 and FIG. 7, the oxygen transfer particles of Examples 1 to 6 according to the present invention have physical properties and reactivity suitable for the fluidized bed process of the chemical roofing combustion technique. It is possible to obtain high strength characteristics even at lower firing temperature than Ni-based oxygen transfer particles manufactured by using NiO and other support materials, thereby lowering the manufacturing cost. Also, since the wear resistance is excellent, the wear due to the rapid solid circulation in the fluidized bed process The amount of particle replenishment can be reduced. In addition, since the oxygen transfer performance is excellent, the amount of particles used can be relatively reduced, and the process can be made compact, which is economical.

From the above results, it can be seen that by using the oxygen transfer particle raw material composition of the present invention and the oxygen transfer particle production method using the same, high-performance NiO-based oxygen transfer particles suitable for a fluidized bed process capable of effectively burning fuel in chemical roofing combustion technology I can do it. Oxygen transfer particles by the raw material composition and the production method can be a competitive technique because they are easy to mass-produce, reduce the amount of particles used due to particle performance improvement, and reduce the scale of the process, thereby improving the economical efficiency of the chemical roofing combustion process.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, The present invention can be variously modified and changed without departing from the spirit and scope of the present invention described in the claims.

Claims (22)

1. Nickel hydroxide; And

   Cerium oxide or cerium hydroxide; Wherein the raw material composition for producing an oxygen-transferring particle comprises:
2. The method according to claim 1,

   The raw material composition for producing an oxygen-transferring particle further comprises titanium oxide.
3. The method according to claim 1,

   The raw material composition for producing oxygen-

   From about 55% to about 80% by weight of nickel hydroxide;

   From about 10% to about 45% by weight of cerium oxide or cerium hydroxide; And

   About 0 wt% to about 20 wt% of titanium oxide;

   Wherein the raw material composition for producing an oxygen-transferring particle comprises:
4. The method according to claim 1,

   Wherein the nickel hydroxide has an average particle size of greater than about 0 microns to about 5 microns and a purity of greater than about 98 percent.
5. The method according to claim 1,

   Wherein the cerium oxide or cerium hydroxide has an average particle size of greater than about 0 microns to about 5 microns and a purity of at least about 98 percent.
6. The method according to claim 1,

   Wherein the titanium oxide has an average particle size of greater than about 0 microns to about 5 microns and a purity of greater than or equal to about 95 percent.
7. An oxygen-transferring particle formed from a raw material composition for producing oxygen-transferring particles according to any one of claims 1 to 6 and comprising nickel oxide and cerium oxide.
8. 8. The method of claim 7,

   The oxygen transfer particles were subjected to 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, and then oxygen Transfer particles:

   [Formula 1]

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

   In the above Equation 1, W1 is the unit weight in g before the abrasion test of the sample, and W2 is the unit weight in g of the fine particles collected for 5 hours after the abrasion test of the sample.
9. 8. The method of claim 7,

   Wherein the oxygen-transferring particles are spherical in shape, non-blowhole, have an average particle size of from about 60 占 퐉 to about 150 占 퐉, a particle size distribution of from about 30 占 퐉 to about 400 占 퐉, a packing density of from about 1.5 g / mL to about 4.0 g / mL.
10. 8. The method of claim 7,

    Wherein the oxygen transfer particles have an oxygen transfer amount of from about 10% to about 25% by weight of the total oxygen transfer particles.
11. (A) mixing the raw material composition for producing oxygen-transferring particles according to any one of claims 1 to 6 with a solvent to prepare a slurry for producing oxygen-transferring particles;

    (B) stirring the slurry to produce a homogenized slurry;

    (C) spray drying the slurry to form solid particles; And

    (D) drying and firing the molded solid particles to produce oxygen-transferring particles.
12. 12. The method of claim 11,

    In the step (A) of producing the slurry for producing oxygen transfer particles, the raw material composition for producing oxygen transfer particles and the solvent are mixed at a weight ratio of about 15 to 40: about 60 to 85, and the solvent is water .
13. 12. The method of claim 11,

    Wherein the slurry further comprises at least one additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder in the step (A) of producing the slurry for producing an oxygen-transferring particle.
14. 14. The method of claim 13,

    Wherein the dispersant comprises at least one of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
15. 15. The method of claim 14,

    Wherein the anionic surfactant comprises at least one of a polycarboxylic acid salt and a polycarboxylic acid amine salt.
16. 14. The method of claim 13,

    Wherein the defoaming agent comprises at least one of a silicone-based defoaming agent, a metal soap-based defoaming agent, an amide-based defoaming agent, a polyether-based defoaming agent, a polyester-based defoaming agent, a polyglycol-based defoaming agent, and an alcohol-based defoaming agent.
17. 14. The method of claim 13,

    Wherein the organic binder comprises at least one of polyvinyl alcohol, polyethylene glycol, and methyl cellulose.
18. 14. The method of claim 13,

    Wherein the additive comprises both a dispersant, a defoamer, and an organic binder,

    The additive is added in an amount of about 0.01 to about 5.0 parts by weight of the dispersant, about 0.01 to about 1.0 part by weight of the defoaming agent, and about 1.0 to about 5.0 parts by weight of the organic binder, based on 100 parts by weight of the raw material composition for producing oxygen- By weight based on the total weight of the particles.
19. 12. The method of claim 11,

    The step (B) of agitating the slurry to prepare a homogenized slurry further comprises removing impurities in the agitated and pulverized slurry.
20. 12. The method of claim 11,

    (C) spraying and drying the slurry to form solid particles, the homogenized slurry is introduced into a spray drier, the inlet temperature is about 260 ° C to about 300 ° C, and the outlet temperature is about 90 ° C to about 150 ° C And forming the solid particles by spraying.
21. 12. The method of claim 11,

    The step (D) of producing the oxygen-transferring particles by drying and firing the molded solid particles comprises drying the molded solid particles at about 110 ° C to about 150 ° C for about 2 hours to about 24 hours, Lt; 0 &gt; C to about 1350 DEG C at a rate of about 1 DEG C / min to about 5 DEG C / min and calcining for about 2 hours to about 10 hours.
22. Reacting the oxygen transfer particles according to claim 7 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. .

Images