KR20130035642A - Oxygen carriers and manufacturing method thereof - Google Patents
Oxygen carriers and manufacturing method thereof Download PDFInfo
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- KR20130035642A KR20130035642A KR1020110100067A KR20110100067A KR20130035642A KR 20130035642 A KR20130035642 A KR 20130035642A KR 1020110100067 A KR1020110100067 A KR 1020110100067A KR 20110100067 A KR20110100067 A KR 20110100067A KR 20130035642 A KR20130035642 A KR 20130035642A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/08—Preparation of oxygen from air with the aid of metal oxides, e.g. barium oxide, manganese oxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23D—BURNERS
- F23D14/00—Burners for combustion of a gas, e.g. of a gas stored under pressure as a liquid
- F23D14/32—Burners for combustion of a gas, e.g. of a gas stored under pressure as a liquid using a mixture of gaseous fuel and pure oxygen or oxygen-enriched air
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1027—Oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
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Abstract
The present invention is an active substance; A support; And a binder containing calcium oxide, barium oxide and boron oxide.
By using the oxygen donor particle raw material composition according to the present invention excellent in strength at a lower firing temperature compared to the prior art while excellent oxygen transfer capacity, fluidized bed process
Oxygen donor particles having suitable physical properties can be provided.
Description
The present invention relates to an oxygen donor particle and a method for producing the same.
Due to the greenhouse effect of increasing atmospheric CO2 concentrations, the global average temperature has risen, causing damage to climate change. Thermal power plants are the largest source of anthropogenic carbon dioxide emissions.
Reduction of carbon dioxide emissions from thermal power plants can be achieved through carbon dioxide capture and storage (CCS) technology. However, when CCS technology is applied to power plants, power generation efficiency is reduced, resulting in an increase in power generation costs. Therefore, new technologies are required to minimize the reduction of power generation efficiency and to lower the cost of CO 2 capture.
Chemical looping combustion (CLC) technology is attracting attention as a technology that can separate CO 2 source without compromising power generation efficiency. Since the media circulating combustion technology burns fuel with oxygen contained in metal oxides instead of air, only gas and CO 2 are included in the gas discharged after combustion of the fuel. Therefore, when only the removal of condensed water vapor exhaust gas is possible because the CO 2 source separated, leaving the CO 2. Media circulating combustion technology uses oxygen donor particles as the oxygen transfer medium. In the medium circulating combustion process, a fluidized bed reactor (reduction reactor) and a reduced oxygen donor particle receive oxygen from air and oxidize when oxygen contained in the oxygen donor particle is delivered to the fuel and the oxygen donor particle is reduced. A circulating fluidized-bed process is used in which a fluidized bed reactor (oxidation reactor) in which an oxidizing reaction takes place is composed of a combination connected to each other.
Therefore, the oxygen donor particles must satisfy various conditions suitable for the fluidized bed process characteristics. First of all, it should have a pore structure that is advantageous for the fluidized bed process, that is, sufficient strength, shape suitable for flow, packing density or packing density, average particle size, particle size distribution and diffusion of the reaction gas. In addition, it has a high oxygen transfer capacity in terms of reactivity so that it can supply enough oxygen for combustion of fuel while it passes through the fuel reactor.
Oxygen donor particles can also be used for media circulation reforming. The medium circulation reforming is a technique for producing hydrogen from a fuel by using oxygen exchange characteristics of oxygen donor particles, and may use a circulating fluidized bed process.
Impregnation, coprecipitation, physical mixing method of mixing raw materials with water, kneading, drying, sintering and pulverizing to form particles ) And freeze granulation are mainly used. However, the oxygen donor particles prepared by these methods are not suitable for the fluidized bed process due to the physical properties such as shape after filling, particle size and strength, or low metal oxide content, and thus are not suitable for mass production or mass production. .
Spray-drying method has been used as a method for producing large quantities of oxygen donor particles having suitable physical properties for fluidized bed process. In order to form a spherical particle having a particle size distribution of several tens to several hundred microns by spraying a slurry obtained by mixing a raw material with water using a nozzle, a manufacturing process for making the slurry to have homogeneous and stable fluidity characteristics is very important. Incorrect control of the slurry properties results in the formation of ellipsoidal, donut-shaped, grooved particles rather than spherical particles, which increases the wear of the particles during the fluidized bed process. Oxygen donor particles produced by the spray drying method shown in the literature is a significant portion of the prepared particles are shown in the form of doughnut or grooved, there is a need for improvement.
In general, oxygen donor particles are composed of an active material metal oxide and a support. Here, the support serves to increase the dispersion of the metal oxides, to impart strength to the particles, and to suppress sintering of the metal oxides that may occur during the medium circulation combustion process. That is, the reactivity and physical properties of the oxygen donor particles finally prepared according to the type of the support will show a difference.
Conventionally, oxygen donor particles using alumina (Al 2 O 3 ) as a support material of a NiO active material have been proposed. Oxygen donor particles prepared using the alumina have high strength. In addition, oxygen donor particles prepared by adding magnesia (MgO) to a support material containing alumina have been proposed to increase fuel conversion of oxygen donor particles and to suppress agglomeration between particles. However, when the oxygen donor particles are manufactured, sprayed and dried particles (Green body) are subjected to a sintering process to achieve strength, and at this time, part of NiO strongly interacts with the support material to form a stable compound, thereby delivering oxygen. There is a problem that causes a decrease in capacity. For example, when NiO and alumina are used, nickel aluminate (NiAl 2 O 4 ) is produced during the firing process.
Accordingly, alpha alumina (α-Al 2 O 3 ), which is a structurally stable form, to reduce the interaction between the metal oxide and the support material; Nickel oxide oxygen donor particles prepared by spray drying using magnesium aluminate (MgAl 2 O 4 ) and / or a mixture of alpha alumina and magnesia (MgO) as a support material have been proposed. However, in this case, since the support is structurally very stable form, the spray-formed particles should be fired at a high temperature of 1400 ° C. or more in order to obtain the strength required for the fluidized bed process application. When the firing is performed at a high temperature of 1400 ° C. or higher, the packing density of the particles is increased after firing, so that more energy is consumed in the fluidization, and the interaction between the active material and the support is increased by the high temperature firing, resulting in a problem of lowering oxygen transfer ability. Done. In addition, there is a problem that the firing cost due to high temperature firing also rises.
Therefore, there is a need for a method for producing oxygen donor particles that can secure sufficient strength required in a fluidized bed process while lowering the firing temperature in order to improve oxygen transfer capacity of oxygen donor particles and to reduce particle manufacturing costs due to high temperature firing of large oxygen donor particles. Do.
The present invention is a fertilizer comprising a mixture of calcium oxide (CaO), barium oxide (BaO) and boron oxide (B 2 O 3 ) as a binder in addition to the metal oxide and the support component, which has been mainly used to prepare oxygen donor particles Oxygen donor particles are produced by spray-drying method using CBB as a raw material for particle production, and oxygen donor has excellent strength at lower firing temperature and excellent oxygen transfer ability and suitable properties for fluidized bed process. Particles can be provided.
Active substance; A support; And
An oxygen donor particle raw material composition comprising a binder containing calcium oxide, barium oxide and boron oxide.
Hereinafter, the oxygen donor particle raw material composition according to the present invention will be described in more detail.
In the present invention, the active material means a material capable of delivering oxygen to fuel and receiving oxygen from air or steam again. In the present invention, the type of the active material is not particularly limited and may be, for example, a metal oxide. Specific examples of the metal oxides include copper oxides such as copper oxide (CuO and Cu 2 O), nickel oxides such as nickel oxide (NiO) and iron oxides such as iron oxide (FeO, Fe 2 O 3 , and Fe 3 O 4 ). Oxides, manganese oxides such as manganese oxides (MnO, MnO 2 , Mn 2 O 3 , Mn 3 O 4 ), and cobalt oxides such as cobalt oxides (CaO, Co 3 O 4 ). In the present invention, it is preferable to use nickel oxide (NiO) as the active material.
In the present invention, the content of the active substance is not particularly limited, and may be included in an amount of 50 parts by weight to 80 parts by weight based on 100 parts by weight of the oxygen donor particle raw material composition, and preferably may be included in an amount of 60 parts by weight to 75 parts by weight. have. If the content is less than 50 parts by weight, the oxygen transport capacity is reduced, the interaction strength with the support increases, there is a fear that the reactive capacity is lowered. If the content is more than 80 parts by weight, physical properties such as porosity decreases, particles There is a fear of sintering between the active materials and cohesion between indenters.
The support included in the oxygen donor particle composition of the present invention may support the active material to be evenly distributed throughout the particle, and provide oxygen donor particles with sufficient strength required in the fluidized bed process after firing. That is, the support may simultaneously serve as a binder that gives strength to the oxygen donor particles while binding to each other during the function of supporting the active material and firing. In addition, it may serve to suppress the phenomenon that the metals aggregate with each other during the redox cycle at a high temperature.
In the present invention, the support may be one or more selected from the group consisting of gamma alumina (γ-Al 2 O 3 ), hydrotalcite and magnesia (MgO), preferably gamma alumina, hydrotalcite , A mixture of gamma alumina and magnesia (MgO) or a mixture of gamma alumina and hydrotalcite may be used.
The gamma alumina (γ-Al 2 O 3 ) makes it possible to obtain oxygen donor particles of high strength. In the present invention, the content of gamma alumina (γ-Al 2 O 3 ) is not particularly limited and may be included in an amount of 0 to 48 parts by weight based on 100 parts by weight of the oxygen donor particle raw material composition.
In addition, the magnesia (MgO), hydrotalcite (Mg-Al layered double hydroxide) serves to reduce the aggregation phenomenon that may appear during high temperature operation by leaving the Mg component in the final oxygen donor particles after firing.
In the present invention, the content of the support is not particularly limited, and may be included in an amount of 15 to 50 parts by weight, and preferably 20 to 40 parts by weight, based on 100 parts by weight of the oxygen donor particle raw material composition. If the content is less than 15 parts by weight, the physical properties such as decrease in porosity is lowered, there is a fear that sintering and indentation between the active material in the particles may occur, when exceeding 50 parts by weight, oxygen transfer capacity is reduced, active There is a fear that the reactivity is reduced by increasing the interaction strength with the substance. Specifically, magnesia and hydrotalcite may be included in an amount of 2 to 15 parts by weight based on 100 parts by weight of the oxygen donor particle raw material composition, and preferably 3 to 15 parts by weight. In addition, the hydrotalcite may be included in an amount of 5 to 48 parts by weight, and preferably in an amount of 15 to 48 parts by weight.
The binder included in the oxygen donor particle composition of the present invention serves to make the oxygen donor particles have the strength required for the fluidized bed process even at a low firing temperature. That is, the binder serves to increase the strength of the oxygen donor particles to lower the firing temperature to obtain the strength required in the fluidized bed process, and to improve the wear resistance.
In the present invention, as a binder, a mixture of calcium oxide, barium oxide and boron oxide may be used. In the present invention, the mixture of calcium oxide, barium oxide and boron oxide may be referred to as CB. As the CBI, a commonly used product may be used.
The content of the binder in the present invention is not particularly limited, and may be included in an amount of 1 to 10 parts by weight, and preferably 2 to 8 parts by weight, based on 100 parts by weight of the oxygen donor particle raw material composition.
The present invention also relates to a slurry composition comprising the solid raw material and the solvent using the oxygen donor particle raw material composition, that is, the raw material composition including the active material, the support and the binder as a solid raw material.
In the present invention, the kind of the solvent is not particularly limited, and a solvent generally used in the art may be used. Specifically, water may be used as the solvent.
In addition, in the present invention, the solid raw material may be included in an amount of 15 to 50 parts by weight, preferably 30 to 40 parts by weight, based on the slurry composition. If the content of the solid raw material is less than 15 parts by weight, the amount of the slurry for the production of oxygen donor particles may increase and ultimately reduce the production efficiency. If the content of the solids exceeds 50 parts by weight, the viscosity of the slurry according to the concentration of the slurry is increased. There is a fear that the fluidity decreases due to the increase, making it difficult to carry out spray drying.
The slurry composition according to the present invention further comprises at least one organic additive selected from the group consisting of dispersants, antifoaming agents and organic binders for controlling homogenization of solid raw materials, concentration, viscosity, stability, flowability and strength and density of slurry. It may include.
In the present invention, it is preferable to use both the dispersant, the antifoaming agent and the organic binder.
In the present invention, a dispersant is used to prevent agglomeration between particles in the grinding process, which will be described below. That is, in the grinding process for controlling the particle size of the solid raw material constituting the oxygen donor particles, the dispersant may be used to prevent the reduction of the grinding efficiency due to the agglomeration of the pulverized fine powder particles.
As the type of dispersant in the present invention, for example, at least one selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be used, preferably anionic. Surfactants and nonionic surfactants can be used. As the anionic surfactant, poly carboxylate ammonium salts or poly carboxylate amine salts may be used.
The dispersant may be used in an amount of 0.01 to 1 part by weight based on the solid raw material. In this range, the dispersion effect of the particles is excellent.
In the present invention, a defoamer may be used to remove bubbles in the slurry to which the dispersant and the organic binder are applied. As the kind of the antifoaming agent, for example, at least one selected from the group consisting of silicon, metal soap, amide, polyether and alcohol can be used.
The antifoaming agent may be used in 0.001 to 0.5 parts by weight based on the solid material. If the amount of the antifoaming agent is too small, there is a fear that bubbles are generated during the slurry manufacturing process to obtain a spherical shape during spray drying, and if the amount of the antifoaming agent is too large, harmful gas may occur during the firing process. The amount of the antifoaming agent can be adjusted according to the amount of bubbles generated.
In the present invention, the organic binder imparts plasticity and fluidity to the slurry and ultimately gives strength to the molded solid particles upon spray drying, thereby facilitating handling of the particles before drying and firing. As the type of the organic binder in the present invention, for example, one or more selected from the group consisting of polyvinyl alcohol, polyethylene glycol and methyl cellulose may be used.
In the present invention, the content of the organic binder is not particularly limited. For example, 0.5 to 5 parts by weight may be used based on the solid raw material. If the content is less than 0.5 parts by weight, it may be difficult to maintain the spherical shape before drying and firing due to a decrease in the bonding strength of the spray-dried solid particles, if the content exceeds 5 parts by weight of the final material There is a risk of deterioration in performance.
The method for producing the oxygen donor particles in the present invention is not particularly limited. In the present invention, for example, (A) preparing a mixture by mixing the above-described oxygen donor particle raw material composition with a solvent as a solid raw material;
(B) preparing a homogenized slurry;
(C) spray drying the slurry to form solid particles; And
(D) may be prepared by a method comprising the step of dry firing the molded solid particles to produce oxygen donor particles.
In step (A) of the present invention, the mixture may be prepared by mixing the aforementioned solid raw material in a solvent.
The solid raw material may include an active material and a support material, the active material and the support material may be used without limitation the above-described type, the content may also be used within the above-described content range.
In the present invention, the solvent may be used without limitation the above-described type, specifically, water may be used.
In addition, the content of the solid raw material in the present invention may be included in an amount of 15 to 50 parts by weight based on the slurry composition.
Step (B) according to the invention, ie preparing a homogenized slurry, comprises adding to the slurry at least one organic additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder; And
Stirring and grinding the slurry may be further included.
In the step of adding the organic additive to the mixture of the present invention, as the organic additive, one or more selected from the group consisting of a dispersant, an antifoaming agent and an organic binder may be used, and preferably all of the above are used. The dispersant, the antifoaming agent and the organic binder may be used without limitation the above-described kind, the content thereof is as described above.
In the present invention, the stirring may be performed in the process of adding the components included in the mixture, and / or in a state where all of them are added, and may be performed using a stirrer.
In the present invention, by performing the grinding, the solid raw material particles can be more homogeneously dispersed in the slurry. In the present invention, additional defoaming and dispersing agents may be added as necessary during the grinding.
In the present invention, a wet milling method may be used to improve the grinding effect and to solve problems such as blowing of particles generated during dry grinding.
The pulverized slurry can be characterized by using a dispersant, antifoaming agent or additional solvent to adjust characteristics such as concentration and viscosity.
On the other hand, if the particle size of the solid raw material particles are several microns or less, the grinding process may be omitted.
In the present invention, a step of removing foreign matter in the stirred and pulverized slurry may be further performed. Through the above step, it is possible to remove the foreign matter or agglomerated raw materials that may cause the nozzle clogging during spray molding. Removal of the foreign matter may be carried out through sieving.
There is no particular limitation on the flowability of the final slurry produced by the present invention, and any viscosity is possible if it can be transferred to a pump.
Step (C) of the present invention is a step of spray drying the slurry to form the solid particles, the molding of the slurry can be carried out using a spray dryer.
In the step, the slurry may be transferred to a spray dryer using a pump, and then the transferred slurry composition may be sprayed into a spray dryer through a pump to form solid particles.
In the present invention, the operating conditions of the spray dryer for molding the oxygen donor particles in the spray dryer may be applied to the operating conditions generally used in this field.
In the present invention, step (D) is a step of preparing the oxygen donor particles by dry firing the solid particles prepared in step (C).
In step (D), the molded solid particles may be dried and then fired to prepare oxygen donor particles.
Drying in the present invention may be carried out by drying the molded solid particles in a reflux dryer of 110 to 150 ℃ for 2 to 24 hours. By carrying out the drying at the temperature and time, it is possible to prevent the phenomenon that the water in the particles during the sintering to cause cracks in the particles. At this time, drying is performed in an air atmosphere.
When the drying is completed, the dried particles are placed in a high temperature baking furnace to raise the final firing temperature to 1000 to 1200 ℃ at a rate of 1 to 5 ℃ / min, and then baked for 3 to 10 hours. If the firing time is less than 3 hours, the interaction between the raw materials in the particles may not be sufficient, and the strength of the particles may be weakened. If the firing time exceeds 10 hours, the firing cost may increase. In the present invention, after the stagnation section of each 30 minutes or more at a stagnation temperature of two or more steps up to the final firing temperature may be fired.
In the present invention, firing may use a firing furnace such as a muffle furnace, a tubular furnace, or a kiln.
In the present invention, the organic additives (dispersant, antifoaming agent and organic binder) introduced during the preparation of the slurry by the firing are burned, and the strength of the particles is improved by bonding between the raw materials.
In addition, the present invention is an active substance; A support; And
An oxygen donor particle prepared using an oxygen donor particle raw material composition comprising a binder containing calcium oxide, barium oxide and boron oxide.
The shape of the oxygen donor particles according to the present invention may be spherical. If the shape is not spherical, but donut-shaped or grooved, the wear loss of the particles is increased.
The average particle size and particle distribution of the oxygen donor particles may be, for example, 50 to 150 μm and 30 to 400 μm, respectively.
The packing density of the oxygen donor particles of the present invention may be, for example, 1.0 to 3.0 g / cc.
In the present invention, the wear resistance is represented by the wear index (AI), the lower the wear index means that the wear resistance is better. The wear resistance is a value measured by a wear tester according to ASTM D5757-95 for 5 hours at a flow rate of 10.00 l / min (273.15K, 1 bar basis). In the present invention, the wear resistance of the oxygen donor particles may be 15% or less. When the wear resistance exceeds 15%, a lot of fine powder is generated, and thus it is difficult to use the circulating fluidized bed process. In the present invention, the lower limit of the wear resistance is not particularly limited, and the closer to 0%, the better.
In addition, in the present invention, the oxygen transfer capacity of the oxygen donor particles is not particularly limited, for example, may be 10 wt% to 17 wt%.
In addition, the present invention is an active substance; A support; And
Reacting the oxygen donor particles prepared using the oxygen donor particle raw material composition comprising a binder containing calcium oxide, barium oxide and boron oxide with gaseous fuel to reduce the oxygen donor particles and combust the fuel gas; And
It relates to a medium-circulating gas combustion method comprising the step of reacting the reduced oxygen donor particles with oxygen to oxidize.
Here, the oxygen donor particles may use the oxygen donor particles described above.
When the oxygen donor particles are reacted with the gaseous fuel, the metal oxides of the oxygen donor particles are reduced to form metal particles and generate carbon dioxide and water. When the metal particles in the reduced oxygen donor particles react with oxygen, the metal particles are oxidized to form a metal oxide again.
In the medium circulation gas combustion method of the present invention, the above process is repeated.
The gaseous fuel used in the present invention is not particularly limited, and may be, for example, one or more selected from the group consisting of hydrocarbon, hydrogen, and carbon monoxide, including natural gas (LNG) and syngas.
In addition, the provision of oxygen to the reduced oxygen donor particles may be made through air.
The present invention also comprises a reduction reactor for reacting oxygen donor particles with gaseous fuel to reduce the oxygen donor particles and burn fuel gas; And a oxidation reactor for reacting the reduced oxygen donor particles with oxygen to oxidize them.
The oxygen donor particle is an active material; A support; And
It relates to a medium-circulating gas combustor produced using an oxygen donor particle raw material composition comprising a binder containing calcium oxide, barium oxide and boron oxide.
The oxygen donor particles of the present invention may use the oxygen donor particles described above.
In the present invention, the oxidation reactor and the reduction reactor may be composed of a combination connected to each other.
In the present invention, by using the CBI (CBB) composed of a mixture of calcium oxide (CaO), barium oxide (BaO) and boron oxide (B 2 O 3 ) as the binding particles, the strength is excellent at a lower firing temperature than the prior art At the same time, it is possible to provide an oxygen donor particle having excellent oxygen transfer ability and suitable physical properties for a fluidized bed process.
1 is a process chart showing a process for preparing the oxygen donor particles according to the present invention.
2 is a process chart showing a process of preparing a homogenized slurry after mixing a solid raw material in water.
3 is a process chart showing a process of forming oxygen donor particles by spray drying the slurry.
Figure 4 is a process diagram showing a process for producing the final oxygen donor particles by dry firing the oxygen donor particles formed by the spray drying method.
5 is an industrial micrograph of the oxygen donor particles according to the present invention.
6 is a basic conceptual view of a media circulating gas combustion device.
The content of the present invention will be described in detail with reference to the following drawings.
1 is a process chart showing a process for preparing nickel oxide (NiO) oxygen donor particles using CBB particles containing calcium oxide, barium oxide and boron oxide according to the present invention as a binder.
As shown in Figure 1, the preparation of the oxygen donor particles by adding a solid material to the water mixing step (S10), preparing a mixture of water and a solid material into a homogenized slurry through grinding and dispersion (S20) , Spray drying the prepared slurry to form oxygen donor particles (S30) and drying firing the molded oxygen donor particles to prepare final oxygen donor particles (S40).
Figure 2 of the present invention is a process chart showing a process for producing a mixture of a solid raw material and water into a slurry.
As shown in Figure 2, the preparation of the slurry is a step of mixing the solid material in water (S11), the step of mixing the water and the solid material by adding an organic additive (S21), by grinding and dispersing the mixed slurry It comprises a step of preparing a homogeneous and dispersed slurry (S22) and removing the foreign matter contained in the slurry (S23).
Here, as the organic additive, one or more selected from the group consisting of a dispersant, an antifoaming agent, and an organic binder may be used, and preferably all may be used.
3 is a process chart showing a process of forming oxygen donor particles by spray drying the slurry.
As shown in FIG. 3, the step of spray drying the slurry to form oxygen donor particles (S30) includes transferring the slurry to the spray dryer (S31) and spraying the transferred slurry into the spray dryer to form the oxygen donor particles. Step S32 is made.
Figure 4 is a process diagram showing a process for producing the final oxygen donor particles by dry firing the oxygen donor particles formed by the spray drying method.
As shown in FIG. 4, the molded oxygen donor particles are prepared as final oxygen donor particles through a preliminary drying process (S41), and then calcined (S42).
6 is a basic conceptual view of a medium-circulating gas fuel device.
In the above, gaseous fuel may be methane.
In the reduction reactor, the metal oxide (MO) in the oxygen donor particles reacts with the gaseous fuel and is reduced to become metal particles (M). At this time, the gaseous fuel is burned.
The reduced oxygen donor particles (M) are moved to an oxidation reactor, and reacted with oxygen in the air in the oxidation reactor to be oxidized again.
The oxidized oxygen donor particles are circulated to a reduction reactor to repeat the above process.
The reactions in the reduction reactor and the metal reactor are shown in Schemes 1 and 2 below. Scheme 1 below is a reaction in a reduction reactor, and Scheme 2 shows a reaction occurring in an oxidation reactor.
<Reaction Scheme 1>
CH 4 + 4MO → CO 2 + 2H 2 O + 4M
<Reaction Scheme 2>
M + 1 / 2O 2 → MO
Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples.
Example
Example 1
70 parts by weight of nickel oxide (purity 98% or more, powder form), 25 parts by weight of gamma alumina (γ-Al 2 O 3 ) and 5 parts by weight of CBB (NICHIA, NP970-05) were mixed so that the total mass was 8 kg. Solid raw materials were prepared.
A solid slurry was added to water while stirring with a stirrer to prepare a mixed slurry. Here, the content of the solid raw material was 40 parts by weight based on 100 parts by weight of the mixed slurry. In this process, a dispersant (anionic surfactant) and an antifoaming agent (metal soap system) were added. The mixed slurry was ground three times in a high energy ball mill. In the above process, after the second grinding, a polyethylene glycol-based organic binder was added and the third grinding was performed to prepare a stable and homogeneous colloidal slurry. The final slurry solids concentration was 34.8 parts by weight after removing the foreign matter through a sieved sieve slurry.
Oxygen donor particles prepared by transferring the prepared colloid slurry to a spray dryer with a pump and spray drying are dried in an air atmosphere reflux dryer at 120 ° C. for 2 hours or more, and at a heating temperature of 5 ° C./min in an air atmosphere in a firing furnace at 1100. After raising the temperature to ℃, it was baked for 5 hours to prepare oxygen donor particles.
The content and slurry properties of the components used to prepare the oxygen donor particles are shown in Table 1 below.
Examples 2-5 and Comparative Examples 1-8
Oxygen donor particles were prepared in the same manner as in Example 1, but the content and slurry properties of the components used in the preparation are shown in Tables 1 and 2 below.
(Oxygen Carrier)
(Oxygen Carrier)
Experimental Example
(1) Measurement of shape of oxygen donor particles
The shape of the oxygen donor particles was measured using an industrial microscope.
(2) measurement of average particle size and particle size distribution
Average particle size and particle size distribution of the oxygen donor particles were measured using a standard sieve according to ASTM E-11.
(3) filling density measurement
The packing density of the oxygen donor particles was measured using a packing density meter (Quantachrome Autotap) according to ASTM D 4164-88.
(4) Wear resistance (AI) measurement
The wear resistance of the oxygen donor particles was measured by a wear tester in accordance with ASTM D 5757-95. The wear index (AI) was determined at 10 slpm (standard volume per minute) over 5 hours as described in the ASTM method above, and the wear index is expressed as the percentage of fines generated over 5 hours.
Materials with less than 30% AI in high speed fluidized bed reactors and even less than 60% in bubbling fluidized bed reactors are fully usable at atmospheric pressure and can also be used in fluidized bed media circulation and media circulation reforming processes. The lower the wear index (AI), the better the wear resistance of the bulk particles.
(5) Oxygen Transport Capacity Measurement
Oxygen transfer capacity of oxygen donor particles was evaluated using thermogravimetric analysis (TGA). The composition of the reaction gas used for the reduction reaction of the oxygen donor particles was 10 vol% CH 4 , 90 vol% CO 2 . In addition, air was used as a reaction gas for oxidizing the reduced oxygen donor particles. 100% nitrogen was supplied between the oxidation and reduction reactions to prevent direct fuel and air contact in the reactor. The sample amount of oxygen donor particles used in the experiment was about 30 mg. The flow rate of each reaction gas was 300 ml / min (0 ° C, 1 bar basis), and the oxygen transfer capacity was measured by repeating the oxidation / reduction reaction of the oxygen donor particles at least five times, where the oxygen transfer capacity was determined in the raw material. The weight obtained by subtracting the weight of oxygen donor particles measured at the end of the reduction reaction of oxygen donor particles under the experimental conditions at the theoretical maximum oxygen donor particle weight when the oxygen donor particles are completely oxidized based on the weight of the metal oxide contained. The change is expressed as a percentage by weight divided by the theoretical maximum oxygen donor particle weight when the oxygen donor particle is completely oxidized.
The results measured by measuring the physical properties and oxygen transfer capacity of the Examples 1 to 5 and Comparative Examples 1 to 8 are shown in Table 3 below.
Temperature,
℃
Size, ㎛
size
Distribution
density,
g / ml
(AI),
%
ability,
wt%
Figure 5 shows an industrial micrograph of the oxygen donor particles according to an embodiment of the present invention. In FIG. 5, A represents Example 1, B represents Example 2, C represents Example 3, D represents Example 4, and E represents Example 5 oxygen donor particles. As shown in the figure, the oxygen donor particles produced by the embodiment has a spherical shape.
As shown in Table 3, nickel oxide (NiO) is used as an active material, and a mixture of gamma alumina, hydrotalcite, gamma alumina and magnesia, or a mixture of gamma alumina and hydrotalcite is used as a support material. It can be seen that the oxygen donor particles (oxygen donor particles according to the embodiment) using zero CBB have sufficient strength and physical properties suitable for the fluidized bed process even at a firing temperature of 1200 ° C. or less. That is, the shape of the oxygen donor particles is spherical, the average particle size is 95 to 110 ㎛, the particle size distribution is 37.0 to 302.5 ㎛, the filling density is 1.9 to 2.5 g / ml, the wear index is less than 12% and the oxygen transfer capacity is 13.1 wt% or more. In particular, the addition of CBB can be seen that the strength is much increased even at a lower firing temperature than the comparative example.
Oxygen donor particles of Comparative Example 1 using gamma alumina as a support material had a wear index value of 15.5% at a firing temperature of 1100 ° C., whereas oxygen donor particles of Example 1 having 5 parts by weight of CBB added had a wear index at the same firing temperature. The value was 1.2%, which was much better than the strength, and the oxygen transfer capacity was 13.7 wt%, slightly higher than the 13.2 wt% of Comparative Example 1.
Oxygen donor particles of Comparative Example 2 using a mixture of gamma alumina and magnesia as the support material showed the strength applicable to the fluidized bed process with a wear index value of 14.7% at a firing temperature of 1300 ° C. The donor particles showed much better strength at the firing temperatures of 1200 ° C. and 1100 ° C. despite the lower firing temperatures of 2.5% and 4.8%, respectively. Oxygen donor particles of Examples 2 and 3 were 13.3 wt% and 13.1 wt%, respectively, higher than 11.2 wt% of Comparative Example 2.
Oxygen donor particles of Comparative Example 3 and Comparative Example 4 using hydrotalcite as the support material showed the strengths applicable to the fluidized bed process with wear index values of 26.4% and 13.1% at firing temperatures of 1300 ° C and 1200 ° C, respectively. Oxygen donor particles of Examples 4 and 5, each of which added 5 parts by weight of CBB to the same support material, had a wear index value of 1.1% and 0.5%, respectively, at a firing temperature of 1200 ° C., even at the same litigation or lower firing temperature. Excellent strength was shown. Oxygen donor particles of Examples 4 and 5 were 13.7 wt% and 13.8 wt%, respectively, higher than 12.9 wt% and 13.2 wt% of Comparative Examples 3 and 4.
In Comparative Examples 5 to 8 using structurally very stable alpha alumina, a mixture of alpha alumina and magnesia, or magnesium aluminate as a support material, the samples were fired at 1400 ° C., but showed strengths that can be used in a fluidized bed process. Lower intensity was shown.
As described above, when CBB is added as a binder in preparation of oxygen donor particles using nickel oxide as an active material, much higher strength can be obtained even at a lower firing temperature than before.
As described above, the present invention has been described based on the preferred embodiments, but the present invention is not limited to the specific embodiments, and those skilled in the art can change the scope within the scope of the claims. have.
Claims (24)
An oxygen donor particle raw material composition comprising a binder containing calcium oxide, barium oxide and boron oxide.
The active material is at least one metal oxide selected from the group consisting of copper-based, nickel-based, iron-based, manganese-based and cobalt-based oxides.
An oxygen donor particle raw material composition comprising 50 to 80 parts by weight of an active substance based on 100 parts by weight of the oxygen donor particle raw material composition.
The support is an oxygen donor particle raw material composition comprising at least one selected from the group consisting of gamma alumina, hydrotalcite and magnesia.
An oxygen donor particle raw material composition comprising 15 to 50 parts by weight of a support with respect to 100 parts by weight of the oxygen donor particle raw material composition.
An oxygen donor particle raw material composition comprising 1 to 10 parts by weight of a binder based on 100 parts by weight of the oxygen donor particle raw material composition.
Slurry composition comprising 15 to 50 parts by weight of the solid raw material relative to the slurry composition.
Slurry composition further comprising at least one organic additive selected from the group consisting of dispersants, defoamers and organic binders.
A dispersant comprises at least one selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
Antifoaming agent is a slurry composition comprising at least one selected from the group consisting of silicone, metal soap, amide, polyether and alcohol.
Organic binder is a slurry composition comprising at least one selected from the group consisting of polyvinyl alcohol-based, polyethylene glycol-based and methyl cellulose.
(B) preparing a homogenized slurry;
(C) spray drying the slurry to form solid particles; And
(D) drying the calcined solid particles to produce oxygen donor particles comprising the step of producing oxygen donor particles.
Step (B) comprises the steps of adding to the slurry at least one organic additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder; And
Method for producing oxygen donor particles comprising the step of stirring and grinding the slurry.
Method for producing oxygen donor particles further comprising the step of removing foreign matter in the stirred and pulverized slurry.
Step (C) is a method of producing the oxygen donor particles to form a slurry using a spray dryer.
The drying of step (D) is carried out for 2 to 24 hours in an air atmosphere and 10 to 130 ℃ method of producing oxygen donor particles.
The firing of step (D) is a method for producing oxygen donor particles which is carried out for 3 to 10 hours after raising the temperature to 1000 to 1200 ° C. at a rate of 1 to 5 ° C./min in a high temperature kiln.
An oxygen donor particle produced using an oxygen donor particle raw material composition comprising a binder containing calcium oxide, barium oxide and boron oxide.
Oxygen donor particles have an average particle size of 50 to 150 μm, a particle distribution of 30 to 400 μm, a packing density of 1.0 to 3.0 g / cc, and an oxygen transfer capacity of 10 to 17 wt%.
Oxygen donor particles with an abrasion resistance value of 15% or less, measured at a flow rate of 10.00 l / min (273.15 K, 1 bar) for 5 hours using a wear tester in accordance with ASTM D5757-95.
And oxidizing the reduced oxygen donor particles with oxygen to oxidize the reduced oxygen donor particles.
The oxygen-circulating gas combustion device is the oxygen donor particles according to claim 19.
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| KR1020110100067A KR20130035642A (en) | 2011-09-30 | 2011-09-30 | Oxygen carriers and manufacturing method thereof |
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| KR1020110100067A KR20130035642A (en) | 2011-09-30 | 2011-09-30 | Oxygen carriers and manufacturing method thereof |
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| WO2020004751A1 (en) * | 2018-06-25 | 2020-01-02 | 한국전력공사 | Raw material composition for manufacturing oxygen transfer particles, oxygen transfer particles manufactured using same, and manufacturing method for oxygen transfer particles |
| KR20220071529A (en) * | 2020-11-24 | 2022-05-31 | 한국전력공사 | Water splitting material, composition for water splitting material and manufacturing method for water splitting material using the same |
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2011
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