KR20120025679A - Carbon dioxide sorbent and preparation method thereof - Google Patents

Abstract

PURPOSE: A carbon dioxide absorbent and a method for preparing the same are provided to improve yield and to implement mass-product by improving physical characteristic, carbon dioxide conversion rate, carbon dioxide absorbing capability, and regenerating performance of the carbon dioxide absorbent. CONSTITUTION: A composition for a carbon dioxide absorbent includes active components, support, inorganic binder, and metal oxide containing transition metals. The active components are one or more selected from a group including alkali metal oxide, alkali earth metal oxide, alkali metal carbonate, alkali earth metal carbonate, alkali metal bicarbonate, alkali earth metal bicarbonate, alkali metal hydroxide, alkali earth metal hydroxide, and the precursors of the same. The support is one or more selected from a group including alumina, hydrotalcite, silica, ceramic, and magnesia. The inorganic binder is one or more selected from a group including cements, clays, and ceramics. The metal oxide is one or more selected from a group including titanium oxide, zirconium oxide, barium titania, molybdenum oxide, nickel oxide, cobalt oxide, iron oxide, copper oxide, zinc oxide, and yttria-stabilizer zirconia.

Description

Carbon dioxide sorbent and preparation method

The present invention relates to a carbon dioxide absorbent comprising a metal oxide containing an active ingredient, a support, an inorganic binder and a transition metal.

In response to the occurrence of climate change due to global warming, climate change response has emerged as a top priority for the international and domestic sectors. Therefore, countries around the world have secured measures to reduce their own greenhouse gases through technology development, creating new growth engines and preoccupying the global market.

Carbon dioxide (CO ₂ ) is recognized as one of the major substances that cause climate change, and there are more than 7900 large-scale facilities that emit more than 100,000 tons of CO ₂ annually, and about 13.5 billion tons Emits carbon dioxide. This accounts for 55% of the global annual emissions of 22.4 billion tons. Therefore, in order to stabilize carbon dioxide in the atmosphere, it is desirable to first remove carbon dioxide from a large-scale carbon dioxide emission facility.

There are various methods of removing carbon dioxide from the large-scale carbon dioxide discharge facility, such as wet chemical absorption, absorption, membrane separation, or low temperature cooling separation. However, these methods have a high recovery cost or are difficult to apply to power plants or large industries.

There is a way to efficiently remove carbon dioxide from the off-gas dry CO ₂ capture technology (Dry CO ₂ capture technology). The method uses solid particles instead of the liquid solvent used in conventional wet chemical cleaning, reacts the solid particles with carbon dioxide present in the exhaust gas to form a stable compound, and then uses pure water and additional heat sources to produce pure carbon dioxide. Separate. The absorbent in which the carbon dioxide is separated can be recycled and reused repeatedly and continuously. In addition, by applying a fluidized bed process, the installation area is small, excellent heat transfer characteristics and easy to operate.

In addition, the regeneration absorption technology generates little wastewater, less corrosion problems, and can be used for various materials at low cost. In addition, there are many potential for sustainable growth compared to other technologies in terms of design flexibility, eco-friendliness, low energy recovery and high efficiency CO2 absorption (absorption and reactivity).

Conventional patents related to this dry regeneration carbon dioxide capture technology include US 7045483, US 6280503, US 7314847, US7314847B1, US 7314877B1, US 4515900, US7067456, US 5214019, JP2007-090208A and US20070072769A1.

The above patents are mainly for application of active materials, supports, combinations of inorganic and organic binders, combinations of active materials and supports, or the active ingredient itself or for applications in completely different applications. In addition, the production methods such as the production by physical mixing and the production by a supporting method are different, and are not suitable for producing the absorbent in large quantities. Particularly, the solid absorbent particles are not suitable for the process of continuously collecting and separating carbon dioxide while continuously circulating between two reactors for absorption and regeneration of the fluidized bed process.

In some, and efficient for the application to industrial processes that discharge a large amount of carbon dioxide, such as power plants, steel, refining and cement industry, in particular the long-term use of the solid absorbent can not minimize the effect of the SO ₂ contained in the industrial off-gas There is a problem.

The present invention effectively captures carbon dioxide while minimizing the effects of sulfur dioxide contained in the flue-gas before discharging it to the atmosphere, and can be easily regenerated by an additional heat source, repeatedly absorbing and regenerating between the two reactors. It is an object of the present invention to provide a carbon dioxide absorbent that can be used for a long time and a method for producing the same.

The present invention is an active ingredient, a support, an inorganic binder and

A carbon dioxide absorbent comprising a metal oxide containing a transition metal.

Hereinafter, the carbon dioxide absorbent according to the present invention will be described in more detail.

In the present invention, the active ingredient is a substance that selectively reacts with carbon dioxide to efficiently collect and separate carbon dioxide from the gas stream.

Examples of the active ingredient include, for example, alkali metal oxides, alkaline earth metal oxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal carbonates, alkaline earth metal bicarbonates, alkali metal hydroxides, alkaline earth metal hydroxides and carbonate precursors. You can use one or more selected. Here, the carbonate precursor means a material that can be converted to carbonate.

In the present invention, the active ingredient may specifically include at least one selected from the group consisting of potassium carbonate, potassium bicarbonate, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydroxide, calcium hydroxide, magnesium hydroxide, magnesium oxide, calcium oxide and zinc oxide. .

In the present invention, the content of the active ingredient may include 5 to 70 parts by weight, and preferably 10 to 60 parts by weight with respect to the absorbent composition. If the content is less than 10 parts by weight, there is a possibility that the collection efficiency of carbon dioxide is lowered, if it exceeds 70 parts by weight, the active ingredient can not be used efficiently, the spherical shape of the absorbent may be deformed, and the physical properties (Strength, Filling Density) may be lowered.

In the present invention, the purity of the active ingredient is preferably 98% or more.

In the present invention, the support of the absorbent is a substance which makes the active ingredient well distributed in the absorbent particles, thereby increasing the utility of the active ingredient and facilitating adsorption and absorption of carbon dioxide and water required for the reaction. The type of the support may have a large specific surface area, and for example, one or more selected from the group consisting of alumina, hydrotalcite, silica, ceramic, and magnesia may be used. Preferably, when the active ingredient for high temperature is used, one or more selected from the group consisting of alumina and hydrotalside may be used. When the active ingredient for low temperature is used, one or more selected from the group consisting of alumina and magnesia may be used. . In this case, the alumina used may have an Al ₂ O ₃ content of about 99.8% and a specific surface area of 150 to 300 m 2 / g. In addition, the hydrotalcite may include 20 wt% or more of magnesium oxide (MgO), the specific surface area may be 100 to 300 m 2 / g, and the magnesia may have a specific surface area of 20 to 100 m 2 / g.

In the present invention, the content of the support may include 5 to 70 parts by weight, and preferably 10 to 60 parts by weight with respect to the absorbent composition. If the content is less than 10 parts by weight, there is a fear that the physical strength is lowered, if it exceeds 70 parts by weight, the active ingredient is relatively low, there is a fear that the performance is lowered.

In the present invention, the inorganic binder can be densely packed between the absorbent compositions to prepare a high density absorbent, increase the binding strength of the active ingredient and the support, give strength to the absorbent, and can use the absorbent without loss due to prolonged wear. It is a substance to make. As the type of the inorganic binder in the present invention, for example, one or more selected from the group consisting of cements, clays, ceramics, and the like may be used. At this time, specific types of the clays include bentonite or kaolin, and specific types of ceramics include alumina sol, silica sol or boehmite, and the like. Silicates, calcium aluminate, and the like.

Here, bentonite may use any commercial bentonite including natural sodium bentonite, synthetic sodium bentonite, and is not particularly limited thereto, and specifically, synthetic sodium bentonite (63.1% SiO ₂ , 16.6% Al ₂ O ₃ , 3.28% Fe ₂ O ₃ , 3.07% CaO, 2.82% MgO, 3.86% Na ₂ O, 8.11% moisture).

In addition, boehmite has similar characteristics to alumina sol in water, acidic and basic aqueous solution, and all types of boehmite can be used. Specifically, boehmite (pseudo-Boehmite: Versal 900, size 60) can be used. -65 mu m) can be used.

In the present invention, the content of the inorganic binder may include 5 to 70 parts by weight, and preferably 10 to 60 parts by weight with respect to the absorbent composition. If the content is less than 5 parts by weight, physical properties may be reduced by lowering the bonding strength between the raw materials (active ingredient, support and inorganic binder), and if it exceeds 70 parts by weight, the content of the active ingredient is relatively reduced This may fall.

In the present invention, the metal oxide containing the transition metal serves as an accelerator, and can repeatedly use the absorption reaction and the regeneration reaction without degrading the reaction caused by the repeated use of the absorbent, and at the same time, It is a material that minimizes the effect and facilitates long-term use of the absorbent. Examples of the metal oxide containing the transition metal include, for example, titanium oxide, zirconium oxide, barium titania (BaTiO ₂ ), molybdenum oxide, nickel oxide, cobalt oxide, iron oxide, copper oxide, zinc oxide, and the like. One or more selected from the group consisting of Yttria-stabilized zirconia and the like may be used, and preferably, titanium dioxide (TiO ₂ ) and zinc oxide (ZnO) may be used.

In the present invention, the content of the metal oxide containing the transition metal may include 5 to 70 parts by weight, and preferably 5 to 60 parts by weight based on the absorbent composition. If the content is less than 5 parts by weight, there is a fear that the role of the accelerator may not be fully exhibited. If the content is more than 70 parts by weight, the content of the active ingredient may be relatively reduced, resulting in the use of the accelerator as an accelerator.

The present invention also relates to a slurry composition comprising the above-mentioned solid raw material and a solvent by using the above-described absorbent composition, that is, a composition comprising a metal oxide containing an active ingredient, a support, an inorganic binder, and a transition metal.

In the present invention, the metal oxide containing the active ingredient, the support, the inorganic binder, and the transition metal may be used without limitation the above-described kind, and the content thereof may also be used in the above-mentioned amounts.

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 or alcohols such as methanol and ethanol can be used, and water is preferably used.

In addition, the content of the solid raw material in the present invention may be included, for example, 20 to 50 parts by weight with respect to the slurry composition, preferably 20 to 40 parts by weight. If the content of the solid raw material is less than 20 parts by weight, the amount of the slurry for the absorbent preparation is increased and ultimately the absorbent manufacturing efficiency may be lowered. If it exceeds 50 parts by weight, the viscosity of the slurry increases with increasing the concentration of the slurry The fluidity of the furnace may be lowered, 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 a dispersant, an antifoaming agent and an 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 absorbent, the dispersant may be used to prevent the reduction of the grinding efficiency by 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 dispersants, cationic dispersants, amphoteric dispersants and nonionic dispersants may be used, and preferably anionic dispersants and nonionics. Systemic dispersants can be used. As the anionic dispersant, polycarboxylic acid, polycarboxylic acid amine, polycarboxylic acid amine salt, polycarboxylic acid soda salt, or the like may be used. As the nonionic dispersant, a fluorine-based surfactant may be used.

The anionic dispersant may be used in an amount of 0.1 to 10 parts by weight based on a solid raw material, and a nonionic dispersant may be used in an amount of 0.01 to 0.3 parts by weight based on a solid raw material. In this range, the dispersion effect of the particles is excellent.

In the present invention, a defoager may be used to remove bubbles in the slurry to which the dispersant and the organic binder are applied. The antifoaming agent may include, for example, at least one selected from the group consisting of silicone, metal soap, amide, polyether, polyester, polyglycol, organophosphoric acid and alcohol. Preferably, a metal soap type and polyester type nonionic surfactant can be used.

The antifoaming agent may be used in an amount of 0.01 to 0.2 parts by weight based on the solid raw material.

In the present invention, the organic binder imparts plasticity and fluidity to the slurry and ultimately gives strength to the solid particles formed during spray drying, thereby facilitating handling of the particles before drying and firing. . In the present invention, as the type of the organic binder, for example, one or more selected from the group consisting of polyvinyl alcohol, polyglycol, 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 0.05 parts by weight, it may be difficult to maintain the spherical shape until the 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.

In the present invention, a pH adjusting agent may be further added to adjust the pH of the slurry composition. As a kind of said pH adjuster, organic amine, aqueous ammonia, etc. can be used, for example. The pH adjusting agent may be used in an amount of 0.01 to 10 parts by weight based on the solid material.

The method for producing the carbon dioxide absorbent in the present invention is not particularly limited. In the present invention, for example, (A) drying the slurry composition to produce solid particles; And

(C) it may be prepared by a method comprising the step of preparing a water absorbent by dry firing the prepared solid particles.

In the present invention, the slurry composition in step (A) may be prepared by mixing the aforementioned solid raw material in a solvent.

The solid raw material may include a metal oxide containing an active ingredient, a support, an inorganic binder, and a transition metal, and the metal oxide containing the active ingredient, the support, an inorganic binder, and a transition metal may be used without limitation. Its content may also be used within the aforementioned content range.

The slurry composition according to the present invention comprises the steps of preparing a mixture of a solvent and a solid raw material;

Adding at least one organic additive selected from the group consisting of a dispersing agent, an antifoaming agent and an organic binder to the mixture; And

The mixture may be prepared by a method including stirring and pulverizing.

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, as described above, may be included in 20 to 50 parts by weight based on the slurry composition.

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.

The mixture of the present invention may further add a pH adjusting agent in addition to the organic additive.

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. Examples of the type of agitator used include, for example, a general mechanical stirrer, a double helix mixer, a high speed emulsifier, a homogenizer, a high shear blender, or an ultrasonic homogenizer. Ultrasonic homogenizer) may be used and may be selectively used depending on the amount of raw material to be added.

By carrying out the grinding in the present invention, the solid raw material particles can be dispersed more homogeneously in the slurry. In the present invention, additional defoaming and dispersing agents may be added as necessary during the grinding, and a more stable slurry may be prepared using a pH adjuster.

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.

In the present invention, the pulverization is performed using a pulverizer, in which the kind of pulverizer used is, for example, a roller mill, a ball mill, an attrition mill, a preener A mill mill, bead mill, or high energy bead mill may be used. In the present invention, a high energy bead mill can be preferably used.

In the case of using the high energy bead mill, the filling amount of the bead (grind), which is the pulverization medium, is preferably 60% to 80% based on the volume of the grinding container when grinding and homogenizing. Beads, which are grinding media, may use Yttria stabilized zirconia beads, which are excellent in strength and stability. The size of the ball is preferably 0.3 mm to 1.25 mm.

In the present invention, the grinding may be performed two or more times to produce a homogeneous slurry. After pulverization, a dispersant and an antifoaming agent may be added to the slurry (mixture) in order to perform the next pulverization, thereby controlling the fluidity of the slurry to facilitate the transfer through the pump.

In addition, prior to final grinding, an organic binder may be added to uniformly mix the slurry.

After the grinding is complete, the average diameter of the particles in the ground mixture may be 3 μm or less, preferably 1 μm or less.

The pulverized slurry can be dispersed, defoamer, or additional solvent to adjust the specificity 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.

Preparation of the slurry composition of the present invention may further comprise the step of removing the foreign matter contained in the slurry after preparing the slurry composition. 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 composition produced by the present invention, and any viscosity is possible if it can be transferred to a pump.

Drying of the slurry composition in the step of drying the slurry composition of the present invention into solid particles may be performed using a spray dryer, and preferably, may be performed using a spray dryer.

In the step, the slurry composition is transferred to a spray dryer using a pump, and then the transferred slurry composition is sprayed into the spray dryer through a pump or the like to form solid particles. The viscosity of the slurry transferable to the pump is not particularly limited, but may be sprayed at 300 cP or more.

The operating conditions of the spray dryer for forming the catalyst in the spray dryer in the present invention may apply the operating conditions generally used in this field.

In addition, in the present invention, the spraying method of the slurry composition is not particularly limited, and for example, a countercurrent spraying method may be used in which the spray nozzle is sprayed in a direction opposite to the flow of drying air. That is, in order to control the average particle size of the catalyst in the spray dryer, a countercurrent spray method may be used in which a pressurized nozzle is installed at the bottom of the dryer to increase the residence time of the particles injected in the dryer.

Since the shape, particle size, particle distribution, and absorbent structure of the integral catalyst / absorber particles are affected by the concentration, viscosity, dispersion degree, slurry injection pressure, injection amount, drying capacity and temperature of the spray dryer, etc., The structure and spray form of the spray dryer can be adjusted accordingly.

In the present invention, the injection pressure of the spray dryer is 5 to 15 kg / cm ² , the inner diameter of the pressure nozzle is 0.4 to 1.6 mm, the inlet temperature of the dryer may be 260 to 300 ℃ and the outlet temperature may be 90 to 150 ℃.

The particle size distribution of the solid particles produced in the step is preferably 30 to 330 ㎛.

In the present invention, step (B) is a step of preparing a catalyst by dry firing the solid particles prepared in step (A).

In step (C), the solid particles may be dried and then calcined to prepare a catalyst.

Drying in the present invention may be carried out by drying the molded solid particles in a reflux dryer of 110 to 150 ℃ or more for 2 hours. At this time, drying is performed in an air atmosphere.

When the drying is completed, the dried particles are placed in a high temperature firing furnace to raise the final firing temperature to 350 to 1000 ° C. at a rate of 0.5 to 10 ° C./min, and then fired for 2 hours or more. 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 addition, the firing in the present invention may be carried out in the atmosphere of air, nitrogen, Hellum, hydrogen, water or reducing gas, wherein the flow rate of the atmosphere gas may be 60 ml / min or more.

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 ingredient, a support, an inorganic binder and

A carbon dioxide absorbent comprising a metal oxide containing a transition metal.

The absorbent according to the invention may be spherical in shape. If the shape is not spherical, but donut-shaped or grooved, the wear loss of the particles is increased.

The particle size and particle distribution of the absorbent may be, for example, 100 to 150 μm and 30 to 303 μm, respectively.

The packing density of the absorbent of the present invention may be, for example, 0.6 to 2.0 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 of the absorbent may be, for example, 40% or less, and preferably 30% or less. When the wear resistance exceeds 40%, a lot of fine powder may be generated, which may make it difficult to use the carbon dioxide removal process. The lower limit of the wear resistance is not particularly limited, but is preferably more than 0%.

In the present invention, the absorbent capacity of the absorbent may be, for example, 3 to 10% by weight.

In addition, the regeneration performance of the absorbent of the present invention may be, for example, 70% or more, preferably 80% or more. The upper limit of the regeneration performance may be 100%, the regeneration performance is excellent in the above range can be reused the absorbent many times.

In addition, the present invention is 5 to 40 parts by weight of at least one active ingredient selected from the group consisting of alkali metal carbonate, alkali metal bicarbonate, and alkali metal hydroxide;

0 to 40 parts by weight of one or more additional active ingredients selected from the group consisting of alkaline earth metal oxides and alkaline earth metal hydroxides;

30 to 70 parts by weight of at least one support selected from the group consisting of alumina and hydrotalcite;

5 to 30 parts by weight of at least one inorganic binder selected from the group consisting of calcium silicate, bentonite, and boehmite; And

It relates to a carbon dioxide absorbent comprising 1 to 20 parts by weight of a metal oxide containing a transition metal.

In addition, the present invention is 30 to 50 parts by weight of at least one active ingredient selected from the group consisting of alkali metal carbonate and alkali metal bicarbonate;

20 to 50 parts by weight of at least one support selected from the group consisting of alumina and magnesia;

10 to 25 parts by weight of at least one inorganic binder selected from the group consisting of calcium silicate, bentonite, and boehmite; And

It relates to a carbon dioxide absorbent comprising 1 to 30 parts by weight of a metal oxide containing a transition metal.

In addition, the present invention comprises the first step of converting carbon monoxide into carbon dioxide and hydrogen at the same time to capture the carbon dioxide in the absorbent; And

In the carbon dioxide separation method comprising a second step of regenerating the absorbent trapped by the carbon dioxide,

 The absorbent may provide a carbon dioxide separation method comprising a metal oxide containing an active ingredient, a support, an inorganic binder, and a transition metal.

The carbon dioxide absorbent used in the carbon dioxide separation method may include the aforementioned absorbent component.

Syngas produced in a gasifier or the like contains carbon monoxide and hydrogen as main components.

In the first step, carbon monoxide in the synthesis gas reacts with water and is converted into carbon dioxide and hydrogen as shown in Scheme 1 below.

<Scheme 1>

CO + H ₂ O → CO ₂ + H ₂

The conversion of carbon monoxide may be activated by a catalyst. Here, the catalyst may be used a general catalyst used in this field.

Carbon dioxide produced by the reaction may be captured by the absorbent.

In the present invention, the first step may be performed at 150 to 300 ° C.

The second step is to regenerate the absorbent trapped carbon dioxide, the regeneration may be carried out by reacting the absorbent with water vapor.

Feeding the absorbent with water vapor and additional heat sources separates the carbon dioxide in the absorbent and regenerates the absorbent.

The absorbent regenerated in the present invention may be carried out again in the first step of capturing carbon dioxide.

In addition, the present invention comprises the steps of collecting the carbon dioxide contained in the exhaust gas as an absorbent; And

In the carbon dioxide separation method comprising the step of regenerating the collected carbon dioxide,

The absorbent may provide a carbon dioxide separation method comprising a metal oxide containing an active ingredient, a support, an inorganic binder, and a transition metal.

In the present invention, the step of collecting the carbon dioxide contained in the exhaust gas as an absorbent may be performed at 50 to 150 ℃.

CO ₂ absorbent according to the present invention is excellent in physical properties such as packing density and wear resistance, CO conversion rate, CO ₂ absorption capacity and regeneration performance, SO ₂ It has excellent endothelial toxicity and can effectively capture and separate carbon dioxide contained in the synthesis gas of fossil fuel. In addition, by applying the spray technology, mass production is easy, and the production yield is high and the cost is low, so it can be used as a low cost pre-combustion CO ₂ recovery technology for coal gasification combined cycle, fuel cell, coal liquefaction process, compound production process.

In addition, in the case of using the active material for high temperature, the synthesis gas conditions of high temperature and high pressure can be used as it is in the process such as accelerated water gas conversion reaction, so that the reduction of efficiency due to the recovery of CO ₂ can be minimized, and the compression cost is remarkably reduced. Can be lowered. In addition, when the low temperature active material is used, the absorption reaction and the regeneration reaction proceed under low temperature synthesis gas conditions such as power plants, steelmaking, oil refining and cement industries, thereby improving energy efficiency and reducing costs.

1 is a process chart showing a process for preparing a carbon dioxide absorbent according to the present invention.
2 is a process chart illustrating a process of preparing a mixture of a solid raw material and a solvent into a slurry.
3 is a process chart showing a process of forming a solid particle by spray drying the slurry.
Figure 4 is a process chart showing a process of manufacturing the absorbent by dry baking the solid particles molded by the spray drying method.
5 is a SEM photograph of the absorbent prepared by Example 1 according to the present invention.
Figure 6 is a graph showing the results of evaluating the CO ₂ absorption capacity of the absorbent prepared in Example 1 according to the present invention.
7 is a SEM photograph of the absorbent prepared by Example 2 according to the present invention.
8 is a SEM photograph of the absorbent prepared by Example 3 according to the present invention.
9 is a graph showing the sulfur dioxide impact evaluation of the absorbent prepared in Example 2 according to the present invention.
10 is a SEM photograph of the absorbent prepared by Example 4 according to the present invention.
11 is a graph showing the sulfur dioxide impact evaluation of the absorbent prepared in Example 3 according to the present invention.

Hereinafter, a method of manufacturing a carbon dioxide absorbent according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 is a process chart showing a process for preparing a carbon dioxide absorbent according to the present invention.

As shown in FIG. 1, in the preparation of the absorbent, a step of preparing a slurry by mixing a solid material with a solvent (10) and spray drying the prepared slurry to prepare solid particles (primary manufactured absorbent) (20) And drying 30 the solid particles to prepare a final absorbent.

Figure 2 of the present invention is a process chart showing a process for producing a mixture of a solid raw material and a solvent as a slurry.

As shown in Figure 2, the slurry is prepared by mixing a solid raw material in water (solvent) to prepare a mixture (11), adding an organic additive, etc. to the mixture (12), stirring the mixture ( 13), pulverizing and homogenizing the solid raw material 14 and removing the foreign matter contained in the slurry (15).

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 a solid particle by spray drying the slurry.

As shown in FIG. 3, the spray drying of the slurry to form the solid particles comprises a step 21 of transferring the slurry to the spray dryer and a step 22 of spraying the transferred slurry into the spray dryer.

Figure 4 is a process chart showing a process of manufacturing the absorbent by dry baking the solid particles molded by the spray drying method.

As shown in FIG. 4, the solid particles (absorbent) firstly dried in the spray drying step are prepared through the drying process 31 and then the final absorbent through the calcination process 32.

Example

<Measurement of Physical Properties of Absorbents Prepared in Examples>

1) Measurement of the shape of the catalyst

The shape of the catalyst was measured using a naked eye, an industrial microscope or an electron scanning microscope (SEM).

2) Measurement of Average Particle Size and Particle Size Distribution

Average particle size and particle size distribution of the catalyst were measured according to the standard method ASTM E-11. At this time, 10 g of the absorbent sample was sieved in a sieve shaker for 30 minutes, and then the average particle size and size distribution were calculated according to the calculation method presented.

3) Fill density measurement

The packing density of the catalyst was measured according to the apparatus and method presented in the standard specification ASTM D 4164-88.

4) Specific surface area (BET) and pore volume measurement

The specific surface area and pore volume of the catalyst were measured using a quantachrome multi BET surface area meter and a Hg porosity meter, respectively.

5) Wear Resistance (AI) Measurement

Abrasion resistance of the catalyst was measured in accordance with the test method and sequence proposed in the specification using a 3-hole attrition tester manufactured in accordance with ASTM D 5757-95.

The wear index (AI), calculated according to the method proposed by ASTM, is the ratio of the initial sample volume (50 g) of the fine powder collected and collected due to wear in the wear tubes for 5 hours at a flow rate of 10 slpm (standard liters per minute). . One of the important indicators of the (fluidized bed or high velocity fluidized bed) process is that less than 30% is preferred for the (fluidized bed) process. The wear index (AI) expressed in wear resistance indicates that the smaller the value, the higher the wear strength.

6) Carbon dioxide absorption capacity and regeneration performance measurement

The absorption and regeneration reactions of the prepared absorbents were measured using pressurized thermogravimetric analysis. The weight and total flow rate of the sample used were 10 mg and 50 ml / min in Example 1, respectively, and 10 mg and 60 ml / min in Examples 2 to 4, respectively.

In Example 1 using the active ingredient for high temperature, the CO ₂ absorption reaction was measured at 200 ℃ and 20 bar, the regeneration reaction was measured at 400 ℃ and 20 bar.

At this time, the calcined composition used for the absorption reaction was 37% carbon dioxide in volume percentage, 10% water as steam, and 57% nitrogen as balance gas. The gas composition used for the regeneration reaction is nitrogen containing 10% of water as steam.

In Examples 2 to 4 using the active ingredient for low temperature, the CO ₂ absorption reaction was measured at 70 ℃, regeneration reaction was measured at 140 ℃.

At this time, the calcined composition used in the absorption reaction was 14.4% carbon dioxide, 5.4% oxygen, 10% water as steam, and 70.2% nitrogen as balance gas. The gas composition used for the regeneration reaction is nitrogen.

Absorption and regeneration of the absorbent were performed by using a Batch fluidized bed (2 cm ID) reactor for at least 1.5 cycles (absorption-regeneration-absorption) to evaluate the absorbent's first and second CO ₂ absorption capacity. Denotes the ratio of the second absorbent capacity to the first absorbent capacity as a percentage.

7) Sulfur dioxide endothelial toxicity evaluation

Sulfur dioxide endothelial toxicity of the prepared absorbents was performed using a thermogravimetric analyzer at least 4 cycles (absorption-regeneration-absorption).

The first absorption reaction to SO ₂ Assessment is carried out in the absence of the SO ₂ gas and 2 in the second absorption reaction fourth absorption reaction is Rate CO ₂ absorption capacity in terms containing SO ₂ gas of 40 ppm and SO ₂ is It was compared with the first absorption capacity and fourth absorption capacity not included.

Example 1

Magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate and sodium hydroxide 20 to 50 parts by weight, so that the total mass is 8 kg, gamma alumina (γ-Al2O3) as a support And 20 to 60 parts by weight of hydrotalcite, 5 to 20 parts by weight of calcium silicate, bentonite and similar boehmite as an inorganic binder, and 5 to 20 parts by weight of titanium dioxide as an additive.

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 about 25 parts by weight based on 100 parts by weight of the mixed slurry. The dispersant was added prior to the input of raw materials for easy mixing and dispersion of the solid material, or a small amount of the dispersant was added depending on the viscosity of the mixed slurry and the degree of agitation in the sequential loading of the raw materials. The antifoaming agent was added in small amounts depending on the degree of bubbles generated after the dispersant was added or during the stirring of the slurry.

The slurry was sufficiently stirred for 10 minutes or more at a speed of 10000 to 25000 rpm using a double spiral stirrer to prevent sedimentation of particles having a relatively high specific gravity or large sizes in the solid raw material.

After stirring, the slurry was pulverized and homogenized using a high energy bead mill two or more times to prepare a final slurry. At this time, additional water, a dispersant, an antifoaming agent, and a pH adjusting agent (organic amine) were added to control the properties of the slurry, such as the viscosity of the slurry, the concentration of the solid material, and the pH, or to facilitate the operation. Polyethylglycol as an organic binder was added before final grinding to homogeneously disperse the slurry.

The final slurry obtained through the characteristics control of the slurry as described above was sieved to remove foreign matter that can be introduced during the manufacturing process.

After drying the prepared slurry for 2 hours or more at 120 ℃ in a dryer of an air atmosphere, the final temperature after raising the temperature at a heating rate of 0.5 to 10 ℃ / min to a final firing temperature 500 ℃ to 650 ℃ in a Muffle Furnace (Muffle Furnace) The final absorbent was prepared by maintaining at least for 2 hours.

In order to effectively remove the organic additives and the organic binder added during the slurry manufacturing process, each one hour was maintained at 200 ° C., 400 ° C. and 500 ° C. before reaching the final firing temperature.

The content and slurry properties of the components used in the preparation of the absorbent are shown in Table 1 below.

A B C D F G H I J K L M MgO (parts by weight) 15 15 20 Mg (OH) ₂ (parts by weight) 30 CaO (parts by weight) 20 Ca (OH) ₂ (parts by weight) 20 K ₂ CO ₃ (parts by weight) 15 15 35 25 KHCO ₃ (parts by weight) 25 Na ₂ CO ₃ (parts by weight) 10 10 10 10 25 NaHCO ₃ (parts by weight) 25 NaOH (part by weight) 25 γ-Alumina
(Parts by weight) 43 43 43 43 43 43 40 40 40 40 MgO / Al ₂ O ₃
(Parts by weight) 43 33 17 20 20 20 20 Calcium silicate
(Parts by weight) 10 10 7 10 10 10 10 Bentonite
(Parts by weight) 5 5 5 5 5 5 5 5 5 5 5 5 Pseudoboehmite-A (parts by weight) 5 5 5 5 5 5 5 5 Pseudoboehmite-B (parts by weight) 5 5 5 5 TiO ₂ (parts by weight) 7 7 5 5 7 7 7 7 5 5 5 5 ZnO (parts by weight) 10 Total Solid Raw Material
(Parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100 Nonionic Dispersant
(Parts by weight) 0.01 to 0.1 Anionic Dispersant
(Parts by weight) 0.1 to 3 Defoamer (part by weight) 0.01 to 0.1 Organic binder
(Parts by weight) 1.0 to 5.0 Slurry concentration
(Parts by weight) 25.1 27.5 29.8 25.7 27.1 25.5 30.5 29.8 26.2 32.9 30.4 27.0 Slurry pH 11.98 11.18 11.24 10.93 11.71 10.88 10.66 11.04 8.98 10.67 11.68 8.66 Viscosity (cP) 56000 56000 2160 1300 97000 21000 11100 23300 16100 54000 30960 30130

Table 2 shows the results measured by measuring the physical properties and carbon dioxide reaction characteristics of the absorbent (A ~ M) prepared in Example 1.

Production Example
A B C D F G H I J K L M shape ss ss ss ss ss ss ss ss ss ss ss ss Particle Size μm 124 135 112 108 135 143 163 179 150 137 128 144 Particle Distribution μm 42-303 49-303- 43-303 42-303 49-303 37-303 37-303 49-303 42-303 37-303 37-303 37-303 Packing density g / ml 0.63 0.70 0.84 0.76 0.55 0.51 0.58 0.61 0.65 0.70 1016 0.60 Wear resistance
% 11.88 13.14 4.44 2.64 16.32 31.94 13.42 26.23 13.80 4.40 1.44 11.60 TGA CO2 Absorption Capacity 1 st 9.0 6.10 9.70 17.60 6.70 11.60 7.90 10.80 14.10 8.60 14.90 13.80 2st 8.60 7.00 10.00 16.20 6.00 7.50 - 6.60 11.90 8.30 10.40 9.40 Regeneration performance,% 96 100 100 92 90 65 - 61 84 97 70 68 Final firing temperature 600 600 600 600 600 600 600 600 600 600 600 600

Figure 5 shows the shape of the absorbent prepared in Example 1, the shape of the absorbent is spherical.

6 is a graph showing the results of evaluating absorbency for the absorbent prepared in Example 1;

As shown in Figure 6, the CO ₂ absorption capacity has a high value of more than 6% by weight even if the absorbent is reused several times.

Absorbent according to Example 1 of the present invention has a spherical shape, the particle size of 100 to 180㎛, particle distribution 30 to 330㎛, filling density 0.5g / cc or more, CO ₂ absorption capacity 6 to 17% by weight, regeneration performance More than 60% and wear resistance of less than 40% to meet all the physical properties required in the fluidized bed promoted water gas shift process, it can be easily used in the fluidized bed promoted water gas shift reaction. .

Example 2

20 to 50 parts by weight of potassium carbonate or potassium bicarbonate as active ingredient for low temperature, 20 to 50 parts by weight of gamma alumina (γ-Al2O3) as support, calcium silicate, bentonite and similar boehmite as inorganic binder Solid materials were prepared using 15 to 20 parts by weight and 3 to 20 parts by weight of titanium dioxide and zirconium dioxide as additives.

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 about 25 to 40 parts by weight based on 100 parts by weight of the mixed slurry. The dispersant was added prior to the input of raw materials for easy mixing and dispersion of the solid material, or a small amount of the dispersant was added depending on the viscosity of the mixed slurry and the degree of agitation in the sequential loading of the raw materials. The antifoaming agent was added in small amounts depending on the degree of bubbles generated after the dispersant or stirring the slurry.

The slurry was sufficiently stirred for 10 minutes or more at a speed of 10000 to 25000 rpm using a double spiral stirrer to prevent sedimentation of particles having a relatively high specific gravity or large sizes in the solid raw material.

After stirring, the slurry was pulverized and homogenized using a high energy bead mill two or more times to prepare a final slurry. At this time, additional water, a dispersant, an antifoaming agent, and a pH adjusting agent (organic amine) were added to control the properties of the slurry, such as the viscosity of the slurry, the concentration of the solid material, and the pH, or to facilitate the operation. Polyethylglycol as an organic binder was added before final grinding to homogeneously disperse the slurry.

The final slurry obtained through the characteristics control of the slurry as described above was sieved to remove foreign matter that can be introduced during the manufacturing process.

After drying the prepared slurry for 2 hours or more at 120 ℃ in a dryer of an air atmosphere, the final temperature after raising the temperature at a heating rate of 0.5 to 10 ℃ / min to a final firing temperature 500 ℃ to 650 ℃ in a Muffle Furnace (Muffle Furnace) The final absorbent was prepared by maintaining at least for 2 hours.

In order to effectively remove the organic additives and the organic binder added during the slurry manufacturing process, each one hour was maintained at 200 ° C., 400 ° C. and 500 ° C. before reaching the final firing temperature.

The content and slurry properties of the components used in the preparation of the absorbent are shown in Table 1 below.

N O P Q R K ₂ CO ₃ (parts by weight) 35 35 35 35 KHCO ₃ (parts by weight) 35 γ-Alumina
(Parts by weight) 43 43 38 33 28 Calcium silicate
(Parts by weight) 7 7 7 7 7 Bentonite
(Parts by weight) 5 5 5 5 5 Pseudoboehmite-A (parts by weight) 5 5 Pseudoboehmite-B (parts by weight) 5 5 5 TiO ₂ (parts by weight) ZrO (parts by weight) 5 5 10 15 20 Hydrotalcite (parts by weight) Total Solid Raw Material
(Parts by weight) 100 100 100 100 100 Nonionic Dispersant
(Parts by weight) 0.01 to 0.1 Anionic Dispersant
(Parts by weight) 0.1 to 3 Defoamer (part by weight) 0.01 to 0.1 Organic binder
(Parts by weight) 1.0 to 5.0 Slurry concentration
(Parts by weight) 34.0 30.9 28.6 29.8 29.9 Slurry pH 10.8 8.8 11.7 11.7 11.3 pH adjuster (organic amine) (parts by weight) 0.10 Viscosity (cP) 1710 1790 1313 2130 2860

The results measured by measuring the physical properties and carbon dioxide reaction characteristics of the absorbents (N to R) prepared in Example 2 are shown in Table 4 below.

N O P Q R shape ss ss ss ss Ss Particle Size μm 112 150 122 107 114 Particle Distribution μm 37-303 68-303 53-212 45-180 53-250 Packing density g / ml 0.87 0.66 0.88 0.90 0.95 Specific surface area m ² / g 46.8 41.95 - - - Hg porosity% 52.64 64.84 - - - % Wear resistance 0.4 8.94 0.56 0.68 0.12 TGA CO2 Absorption Capacity 1 st 8.93 5.17 9.03 7.91 8.72 2st 7.04 5.20 7.05 6.03 6.90 Reburn performance,% 79 100 78 76 79 Final firing temperature 550 550 550 550 550

Figure 7 is a photograph of the SEM photograph of the absorbent prepared in Example 2, as shown above, the absorbent showed a spherical shape.

In particular, the solid absorbent according to the second embodiment of the present invention, spherical shape, particle size 100 to 150 ㎛, particle distribution 30 to 400 ㎛, packing density 0.6 g / cc or more, CO 2 absorption ability 5 wt% or more, regeneration performance 75 It can be seen that not only satisfies all the physical properties required by the dry carbon dioxide absorption process, but also has excellent carbon dioxide absorption ability and regeneration performance of less than 10% and less than 10% of abrasion resistance.

Example 3

20 to 50 parts by weight of potassium carbonate as a low temperature active ingredient, 20 to 50 parts by weight of gamma alumina (γ-Al2O3) as a support, a calcium silicate, bentonite and similar boehmite as inorganic binders so that the total mass is 8 kg Solid materials were prepared using at least 3 to 20 parts by weight selected from the group consisting of titanium dioxide, barium titania, molybdenum oxide, iron oxide, copper oxide and zinc oxide as parts by weight and additives.

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 about 20 parts by weight to 40 parts by weight based on 100 parts by weight of the mixed slurry. The dispersant was added prior to the input of raw materials for easy mixing and dispersion of the solid material, or a small amount of the dispersant was added depending on the viscosity of the mixed slurry and the degree of agitation in the sequential loading of the raw materials. The antifoaming agent was added in small amounts depending on the degree of bubbles generated after the dispersant or stirring the slurry.

The slurry was sufficiently stirred for 10 minutes or more at a speed of 10000 to 25000 rpm using a double spiral stirrer to prevent sedimentation of particles having a relatively high specific gravity or large sizes in the solid raw material.

After stirring, the slurry was pulverized and homogenized using a high energy bead mill two or more times to prepare a final slurry. At this time, additional water, a dispersant, an antifoaming agent, and a pH adjusting agent (organic amine) were added to control the properties of the slurry, such as the viscosity of the slurry, the concentration of the solid material, and the pH, or to facilitate the operation. Polyethylglycol as an organic binder was added before final grinding to homogeneously disperse the slurry.

The final slurry obtained through the characteristics control of the slurry as described above was sieved to remove foreign matter that can be introduced during the manufacturing process.

After drying the prepared slurry for 2 hours or more at 120 ℃ in a dryer of an air atmosphere, the final temperature after raising the temperature at a heating rate of 0.5 to 10 ℃ / min to a final firing temperature 500 ℃ to 650 ℃ in a Muffle Furnace (Muffle Furnace) The final absorbent was prepared by maintaining at least for 2 hours.

In order to effectively remove the organic additives and the organic binder added during the slurry manufacturing process, each one hour was maintained at 200 ° C., 400 ° C. and 500 ° C. before reaching the final firing temperature.

The content and slurry properties of the components used in the preparation of the absorbent are shown in Table 5 below.

S T U V W K ₂ CO ₃ (parts by weight) 35 35 35 35 35 γ-Alumina
(Parts by weight) 40 40 43 43 43 Calcium silicate
(Parts by weight) 7 7 7 7 7 Bentonite
(Parts by weight) 5 5 5 5 5 Pseudoboehmite-A (parts by weight) 5 5 5 5 5 TiO ₂ (parts by weight) 5 5 Fe ₂ O ₃ (parts by weight) 3 CuO (parts by weight) 3 BaTiO ₂ (parts by weight) 5 MoO ₃ (parts by weight) 5 ZnO (parts by weight) 5 Total Solid Raw Material
(Parts by weight) 100 100 100 100 100 Nonionic Dispersant
(Parts by weight) 0.01 to 0.1 Anionic Dispersant
(Parts by weight) 0.1 to 3 Defoamer (part by weight) 0.01 to 0.1 Organic binder
(Parts by weight) 1.0 to 5.0 Slurry concentration
(Parts by weight) 30.9 29.9 27.7 21.2 29.3 Slurry pH 11.69 11.65 11.46 10.74 11.87 pH adjuster (organic amine) (parts by weight) 0.10 Viscosity (cP) 537 613 1830 1270 4270

Table 6 shows the results measured by measuring the physical properties and carbon dioxide reaction characteristics of the absorbents (S to W) prepared in Example 3.

S T U V W shape ss ss ss ss Ss Particle Size μm 133 131 122 109 112 Particle Distribution μm 57-303 57-303 60-220 45-270 45-180 Packing density g / ml 0.95 0.98 0.81 0.93 0.87 Specific surface area m ² / g 17.93 12.96 Hg porosity% 65.45 69.64 % Wear resistance 15.10 30.0 0.90 10.40 1.06 TGA CO2 Absorption Capacity 1 st 6.40 7.17 9.57 7.35 8.08 2st 5.59 5.61 7.13 5.51 7.02 Reburn performance,% 87 78 85 85 87 Final firing temperature 550 550 550 550 550

Figure 8 is a SEM photograph of the absorbent prepared in Example 3, as shown above, the absorbent showed a spherical shape.

As shown in Example 3, the present invention includes a regeneration enhancer containing a transition metal acid fraction, and an absorbent prepared by spray drying may be used in a fluidized bed dry carbon dioxide capture process.

In the present invention, Figure 9 is a graph showing the sulfur dioxide impact evaluation of the absorbent V prepared in Example 3.

The impact assessment was performed for at least 4 cycles (absorption-regeneration-absorption) using a thermogravimetric analyzer, as described above.

The carbon dioxide absorption capacity was about 7% under the condition of not containing sulfur dioxide gas (1 cycle), and 5 to 6% in the gas containing sulfur dioxide (2 to 4 cycles). The above results show that even if the absorbent is reused several times, there is no deterioration of the absorbent capacity, and in particular, since there is little change in the absorbent capacity in 2 cycles and 4 cycles, it can be seen that the absorbent is hardly affected by sulfur dioxide. .

That is, the solid absorbent according to Example 3 of the present invention has a spherical shape, particle size of 100 to 140 μm, particle distribution of 40 to 400 μm, packing density of 0.8 g / cc or more, CO ₂ absorption ability of 5% by weight or more, regeneration performance Not only satisfies all the physical properties required in the process with 75 to 87% and 30% or less abrasion resistance, and also has excellent CO ₂ absorption and reproducibility. It was found that this is a strong absorbent.

Example 4

20 to 50 parts by weight of potassium carbonate as active ingredient for low temperature, gamma alumina (γ-Al2O3) and magnesium oxide as support, 20 to 50 parts by weight, calcium silicate, bentonite and similar boehmite as inorganic binder Solid materials were prepared using 15 to 20 parts by weight and one or more 3 to 20 parts by weight of one selected from the group consisting of titanium dioxide, zirconia oxide, barium titania, molybdenum oxide, and yttria stabilized zirconia.

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 about 20 to 40 parts by weight based on 100 parts by weight of the mixed slurry. The dispersant was added prior to the input of raw materials for easy mixing and dispersion of the solid material, or a small amount of the dispersant was added depending on the viscosity of the mixed slurry and the degree of agitation in the sequential loading of the raw materials. The antifoaming agent was added in small amounts depending on the degree of bubbles generated after the dispersant or stirring the slurry.

The slurry was sufficiently stirred for 10 minutes or more at a speed of 10000 to 25000 rpm using a double spiral stirrer to prevent sedimentation of particles having a relatively high specific gravity or large sizes in the solid raw material.

After stirring, the slurry was pulverized and homogenized using a high energy bead mill two or more times to prepare a final slurry. At this time, additional water, a dispersant, an antifoaming agent, and a pH adjusting agent (organic amine) were added to control the properties of the slurry, such as the viscosity of the slurry, the concentration of the solid material, and the pH, or to facilitate the operation. Polyethylglycol as an organic binder was added before final grinding to homogeneously disperse the slurry.

The final slurry obtained through the characteristics control of the slurry as described above was sieved to remove foreign matter that can be introduced during the manufacturing process.

After drying the prepared slurry for 2 hours or more at 120 ℃ in a dryer of an air atmosphere, the final temperature after raising the temperature at a heating rate of 0.5 to 10 ℃ / min to a final firing temperature 500 ℃ to 650 ℃ in a Muffle Furnace (Muffle Furnace) The final absorbent was prepared by maintaining at least for 2 hours.

In order to effectively remove the organic additives and the organic binder added during the slurry manufacturing process, each one hour was maintained at 200 ° C., 400 ° C. and 500 ° C. before reaching the final firing temperature.

The content and slurry properties of the components used in the preparation of the absorbent are shown in Table 7 below.

Production Example
X Y Z AA AB AC AD AE AF AG K ₂ CO ₃ (parts by weight) 35 35 35 40 40 40 40 40 40 40 γ-Alumina
(Parts by weight) 38 33 23 38 38 MgO (parts by weight) 43 43 MgO (parts by weight) 23 18 18 Calcium silicate
(Parts by weight) 7 7 7 7 7 7 7 7 7 7 Bentonite (parts by weight) 5 5 5 5 5 5 5 5 5 5 Pseudoboehmite-A (parts by weight) 5 5 5 5 5 5 5 5 5 5 TiO ₂ (parts by weight) 5 20 ZrO ₂ (parts by weight) 5 5 5 20 20 20 Yitria atabilized zirconium (parts by weight) 5 BaTiO ₂ (parts by weight) 5 MoO ₃ (parts by weight) 5 5 5 5 Total Solid Raw Material
(Parts by weight) 100 100 100 100 100 100 100 100 100 100 Nonionic Dispersant
(Parts by weight) 0.01 to 0.1 Anionic Dispersant
(Parts by weight) 0.1 to 3 Defoamer (part by weight) 0.01 to 0.1 Organic binder
(Parts by weight) 1.0 to 5.0 Slurry concentration
(Parts by weight) 29.5 32.1 28.9 30.2 30.6 31.6 29.5 26.6 28.9 29.6 Slurry pH 13.65 13.73 10.99 11.06 11.68 13.93 13.2 10.68 11.91 11.81 Organic amine (parts by weight) 0.10 Viscosity (cP) 17000 2880 1280 1320 2130 2860 3030 9300 1580 1200

Table 8 shows the results measured by measuring the physical properties and carbon dioxide reaction characteristics of the absorbent (X to AG) prepared in Example 4.

X Y Z AA AB AC AF AG shape ss ss ss ss ss ss ss Ss Particle Size μm 110 113 139 112 109 105 119 119 Particle Distribution μm 53-110 53-212 45-230 80-303 45-270 45-250 45-250 45-212 Packing density g / ml 0.93 0.99 0.91 1.01 1.10 1.19 1.05 0.89 % Wear resistance 0.98 3.26 0.36 0.24 0.02 0.01 0.10 0.68 TGA CO2 Absorption Capacity 1 st 8.34 7.42 6.91 7.05 7.86 6.59 6.33 7.57 2st 7.90 6.47 5.16 7.93 6.17 5.67 5.57 7.63 Reburn performance,% 95 87 75 89 79 86 88 100 Final firing temperature 550 550 550 550 550 550 550 550

10 is a SEM photograph of the absorbent prepared in Example 4, as shown above, the absorbent exhibited a spherical shape.

Table 9 and Figure 11 is a table and graph showing the results of the sulfur dioxide evaluation of the absorbent prepared in Example 4.

Y AA AB AC AF AG TGA CO2 Absorption Capacity 1 st 8.64 7.05 7.86 6.59 6.33 7.57 2st 7.79 6.45 6.17 5.67 5.57 7.63 3st 7.64 5.91 5.86 5.54 5.88 6.12 4st 7.17 6.15 6.23 5.63 5.68 6.35 Reburn performance,% 83 87 79 86 90 84 Final firing temperature 550 550 550 550 550 550

As can be seen from FIG. 11 and Table 9, the absorbents (Y to AG) did not show a decrease in carbon dioxide absorption capacity or a decrease in regeneration even when repeated absorption and regeneration reactions were performed under conditions containing sulfur dioxide.

As shown in Example 4, the present invention includes a regeneration enhancer containing a transition metal acid fraction, and the absorbent prepared by the spray drying technique may be used in a fluidized bed dry carbon dioxide capture process.

In particular, the absorbent has a spherical shape, particle size of 100 to 140 μm, particle distribution of 40 to 303 μm, packing density of 0.9 g / cc or more, carbon dioxide absorbing ability of 5% by weight or more, regeneration performance of 75% or more, wear resistance of 5% or less, After assessing the impact of 4 cycles of sulfur dioxide, it not only satisfies all the physical properties required in the dry carbon dioxide capture process, such as maintaining more than 70% of the initial performance, but also shows excellent CO ₂ absorption and regeneration, and particularly good endothelial toxicity to SO ₂ . have

As described above, although described based on the preferred embodiment according to the present invention, the present invention is not limited to the specific embodiment, can be changed within the scope described in the claims by those of ordinary skill in the art have.

Claims (37)

Active ingredients, supports, inorganic binders and
Carbon dioxide absorbent composition comprising a metal oxide containing a transition metal.
The method of claim 1,
The active ingredient is at least one carbon dioxide absorbent composition selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, alkaline earth metal bicarbonates, alkali metal hydroxides, alkaline earth metal hydroxides and precursors thereof.
The method of claim 1,
The amount of the active ingredient is 5 to 70 parts by weight relative to the absorbent composition carbon dioxide absorbent composition.
The method of claim 1,
The support is at least one carbon dioxide absorbent composition selected from the group consisting of alumina, hydrotalcite, silica, ceramics and magnesia.
The method of claim 4, wherein
Hydrotalcite comprises at least 20 wt% magnesium oxide (MgO) carbon dioxide absorbent composition.
The method of claim 4, wherein
The specific surface area of alumina is 150 to 300 m 2 / g, the specific surface area of magnesia is 20 to 100 m 2 / g, and the specific surface area of hydrotalcite is 100 m 2 / g or more.
The method of claim 1,
The carbon dioxide absorbent composition has a content of 5 to 70 parts by weight based on the absorbent composition.
The method of claim 1,
Inorganic binder is at least one carbon dioxide absorbent composition selected from the group consisting of cements, clays and ceramics.
The method of claim 8,
Cement is calcium silicate or calcium aluminate, clay is bentonite or kaolin, and ceramics are alumina sol, silica sol or boehmite.
The method of claim 1,
The amount of the inorganic binder is 5 to 70 parts by weight based on the absorbent composition.
The method of claim 1,
Metal oxides containing transition metals include titanium oxide, zirconium oxide, barium titania (BaTiO ₂ ), molybdenum oxide, nickel oxide, cobalt oxide, iron oxide, copper oxide, zinc oxide and yttria stabilized zirconia. At least one carbon dioxide absorbent composition selected from the group consisting of:
The method of claim 1,
The amount of the metal oxide containing the transition metal is 5 to 70 parts by weight relative to the absorbent composition.
Slurry composition comprising the solvent and the absorbent composition according to claim 1 as a solid raw material.
The method of claim 13,
Slurry composition comprising 20 to 50 parts by weight of the solid raw material relative to the slurry composition.
The method of claim 13,
Slurry composition further comprising at least one organic additive selected from the group consisting of dispersants, defoamers and organic binders.
The method of claim 15,
The dispersant is at least one slurry composition selected from the group consisting of anionic dispersants, cationic dispersants, amphoteric dispersants and nonionic dispersants.
The method of claim 15,
Antifoaming agent is a slurry composition of at least one selected from the group consisting of silicone, metal soap, amide, polyether, polyester, polyglycol, organophosphate and alcohol.
The method of claim 15,
The organic binder is at least one slurry composition selected from the group consisting of polyvinyl alcohol, polyglycol, and methyl cellulose.
(A) drying the slurry composition according to claim 13 to produce solid particles; And;
(B) a method of producing a carbon dioxide absorbent comprising the step of drying and firing the prepared solid particles to prepare an absorbent.
The method of claim 19,
The slurry composition comprises the steps of preparing a mixture of a solvent and a solid raw material;
Adding at least one organic additive selected from the group consisting of a dispersing agent, an antifoaming agent and an organic binder to the mixture; And
A method for producing a carbon dioxide absorbent prepared by the method comprising the step of stirring and grinding the mixture.
The method of claim 20,
A method for producing a carbon dioxide absorbent, wherein the average diameter of the particles in the ground mixture is 3 μm or less.
The method of claim 20,
A method of producing a carbon dioxide absorbent further comprising the step of removing foreign matter in the stirred and pulverized slurry composition.
The method of claim 19,
The slurry composition of step (A) is dried using a spray dryer.
The method of claim 23,
Injection pressure of the spray dryer is 5 to 15 kg / ㎠, the inner diameter of the pressurized nozzle is 0.4 to 1.6 mm, the dryer inlet temperature is 260 to 300 ℃, dryer outlet temperature is 90 to 150 ℃ manufacturing method of carbon dioxide absorbent.
The method of claim 19,
The drying of step (B) is carried out at 110 to 150 ° C. under an air atmosphere.
The method of claim 19,
Firing is carried out at 350 to 1000 ° C.
The method of claim 19,
Firing is carried out in air, nitrogen, helium, hydrogen, water vapor or reducing gas atmosphere, the gas flow rate is 60 ml / min or more method of producing a carbon dioxide absorbent.
Active ingredients, supports, inorganic binders and
A carbon dioxide absorbent comprising a metal oxide containing a transition metal.
29. The method of claim 28,
The average particle size is 100 to 180 ㎛, the particle distribution is 30 to 310 ㎛, the packing density is 0.5 to 2.0 g / cc carbon dioxide absorbent.
29. The method of claim 28,
Abrasion resistance is 40% or less carbon dioxide absorbent.
29. The method of claim 28,
The carbon dioxide absorbent is 3 to 17% by weight, the regeneration performance is more than 60% carbon dioxide absorbent.
5 to 40 parts by weight of one or more active ingredients selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides;
0 to 40 parts by weight of one or more additional active ingredients selected from the group consisting of alkaline earth metal oxides and alkaline earth metal hydroxides;
30 to 70 parts by weight of at least one support selected from the group consisting of alumina and hydrotalcite;
5 to 30 parts by weight of at least one inorganic binder selected from the group consisting of calcium silicate, bentonite, and boehmite; And
Carbon dioxide absorbent comprising 1 to 20 parts by weight of a metal oxide containing a transition metal.
30 to 50 parts by weight of one or more active ingredients selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates;
20 to 50 parts by weight of at least one support selected from the group consisting of alumina and magnesia;
10 to 25 parts by weight of at least one inorganic binder selected from the group consisting of calcium silicate, bentonite, and boehmite; And
Carbon dioxide absorbent comprising 1 to 30 parts by weight of a metal oxide containing a transition metal.
Converting carbon monoxide into carbon dioxide and hydrogen and simultaneously trapping carbon dioxide in the absorbent; And
In the carbon dioxide separation method comprising a second step of regenerating the absorbent trapped by the carbon dioxide,
The absorbent comprises a metal oxide containing an active ingredient, a support, an inorganic binder and a transition metal.
35. The method of claim 34,
The first step of capturing carbon dioxide in the absorbent is carried out at 150 to 300 ℃.
Collecting carbon dioxide contained in the flue gas as an absorbent; And
In the carbon dioxide separation method comprising the step of regenerating the collected carbon dioxide,
The absorbent comprises a metal oxide containing an active ingredient, a support, an inorganic binder and a transition metal.
37. The method of claim 36,
Capturing the carbon dioxide contained in the exhaust gas with an absorbent is carried out at 50 to 150 ℃.

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