KR102213381B1 - A magnesium oxide hollow sphere and method for manufacturing the same - Google Patents

Abstract

In one embodiment of the present invention, (a) preparing a precursor solution by dissolving magnesium salt, polystyrene, and carboxylic acid in a solvent; (b) applying ultrasonic waves to the precursor solution to generate droplets, and spraying the droplets into the reactor using a carrier gas; And (c) pyrolyzing the droplet to obtain a magnesium oxide hollow sphere; containing, it provides a magnesium oxide hollow sphere and a method for producing the same.

Description

A magnesium oxide hollow sphere and its manufacturing method {A MAGNESIUM OXIDE HOLLOW SPHERE AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a magnesium oxide hollow sphere and a method of manufacturing the same, and more particularly, to a method of manufacturing the magnesium oxide hollow sphere having bimodal pores and a polystyrene template and a spray pyrolysis method using oxalic acid.

Greenhouse gases include carbon dioxide (CO ₂ ), methane (CH ₄ ), and nitrous oxide (N ₂ O), and these gases are discharged into the atmosphere in human industrial activities and daily life. Among them, carbon dioxide is mainly produced when fossil fuels such as coal and petroleum are combusted, methane is a main component of natural gas and is generated from animal waste, and nitrous oxide is generated from industrial processes or fertilizers. Among the six major greenhouse gases, carbon dioxide has the lowest global warming index of 1, but it accounts for more than 80% of the total greenhouse gas emissions, and the contribution to global warming is the highest at 65%.

Therefore, various adsorbents have been developed to reduce such carbon dioxide, and among them, the process of adsorption using an amine-based solution has been commercialized, but the amine-based adsorbent has a disadvantage that the adsorption amount decreases to 1/3 when reused, so periodic replacement There is a disadvantage that it is inefficient because it is required.

Theoretically, magnesium-based adsorbents with high carbon dioxide absorption and excellent reusability are suitable for use in the process of capturing carbon dioxide from flue gas. In addition, if a magnesium oxide adsorbent having a large specific surface area and a uniform pore distribution can be mass-produced, it can be applied to various industrial fields emitting carbon dioxide.

The present invention is to solve the problems of the prior art described above, and an object of the present invention is to provide a magnesium oxide hollow sphere having bimodal pores and a method for manufacturing the same.

One aspect of the present invention, (a) preparing a precursor solution by dissolving magnesium salt, polystyrene, and carboxylic acid in a solvent; (b) applying ultrasonic waves to the precursor solution to generate droplets, and spraying the droplets into the reactor using a carrier gas; And (c) pyrolyzing the droplet to obtain a magnesium oxide hollow sphere; containing, it provides a method for producing a magnesium oxide hollow sphere.

In one embodiment, the magnesium salt is magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate, magnesium bromide, and magnesium iodide. ) And a combination of two or more of them may be one selected from the group consisting of.

In one embodiment, the average particle size of the polystyrene may be 50 to 500 nm.

In one embodiment, the carboxylic acid may be one selected from the group consisting of oxalic acid, succinic acid, tartaric acid, glutamic acid, adipic acid, terephthalic acid, phthalic acid, malonic acid, maleic acid, fumaric acid, and a combination of two or more of them.

In one embodiment, the solvent is methanol, ethanol, propanol, iso-propanol, tert-butanol, n-butanol, methoxyethanol, ethoxyethanol, dimethylacetamide, dimethylformamide, n-methyl-2-pi It may be one selected from the group consisting of rolidone (NMP), formic acid, nitromethane, acetic acid, water, and combinations of two or more of them.

In one embodiment, the thermal decomposition in step (c) may be performed at 300 to 1,000°C.

In one embodiment, after the step (c), (d) annealing the magnesium oxide hollow sphere at 100 ~ 500 ℃; may further include.

Another aspect of the present invention provides a magnesium oxide hollow sphere manufactured by the above-described manufacturing method and having bimodal pores.

In one embodiment, at least a portion of the magnesium oxide may be modified with carboxylic acid.

In one embodiment, the pore diameter distribution of the magnesium oxide hollow sphere is a first peak included in the range of 1 to 10 nm; And a second peak included in the range of 10 to 50 nm.

In one embodiment, the BET specific surface area of the magnesium oxide hollow sphere may be 160 m ² /g or more.

In one embodiment, the pore volume of the magnesium oxide hollow sphere may be 0.30 cm ³ /g or more.

In one embodiment, the amount of CO ₂ adsorption of the hollow magnesium oxide sphere may be 0.150 mol/kg or more.

According to an aspect of the present invention, it is possible to provide a magnesium oxide hollow sphere having bimodal pores and a method of manufacturing the same.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 schematically shows a method of manufacturing a bimodal MgO hollow sphere according to an embodiment of the present invention.
2 shows the results of analyzing the morphology of the MgO hollow spheres prepared in an embodiment of the present invention and the MgO prepared in a comparative example.
3 shows the results of analyzing the crystal structure and pore distribution of the MgO hollow spheres prepared in one embodiment of the present invention and the MgO prepared in Comparative Example.
Figure 4 is an analysis of the difference according to the pore distribution by measuring the CO ₂ adsorption amount of the MgO hollow sphere prepared in an embodiment of the present invention and the MgO prepared in the comparative example.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

When a range of numerical values is described herein, the value has the precision of significant figures provided according to the standard rules in chemistry for significant figures, unless a specific range thereof is stated otherwise. For example, 10 includes a range of 5.0 to 14.9, and the number 10.0 includes a range of 9.50 to 10.49.

In the present specification, "hollow sphere" may mean spherical particles having a cavity formed therein.

In the present specification, "mesoporous" may mean pores having a pore diameter of 2 to 50 nm, and "microporous" may mean pores having a pore diameter of 50 nm or more.

In the present specification, "bimodal" may mean that a distribution of a specific physical property has two peaks.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Method for producing magnesium oxide hollow spheres

A method for producing a magnesium oxide hollow sphere according to an aspect of the present invention includes the steps of: (a) dissolving a magnesium salt, polystyrene, and carboxylic acid in a solvent to prepare a precursor solution; (b) applying ultrasonic waves to the precursor solution to generate droplets, and spraying the droplets into the reactor using a carrier gas; And (c) thermally decomposing the droplets to obtain hollow magnesium oxide spheres.

In the step (a), the magnesium salt is magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate, magnesium bromide, and magnesium iodide. iodide) and may be one selected from the group consisting of a combination of two or more of them, preferably magnesium acetate, more preferably, magnesium acetate tetrahydrate ((CH ₃ COO) ₂ Mg·4H ₂ O) May be, but is not limited thereto.

The average particle size of the polystyrene may be 50 nm or more, 75 nm or more, 100 nm or more, 125 nm or more, or 150 nm or more, and 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm Hereinafter, it may be 225 nm or less or 200 nm or less. When the average particle size of the polystyrene satisfies the above range, the specific surface area and CO ₂ adsorption amount of the prepared magnesium oxide hollow spheres may be excellent.

The polystyrene may function as a template material for manufacturing the magnesium oxide hollow sphere. Accordingly, the size and pore size distribution of the magnesium oxide hollow spheres can be controlled by adjusting the average particle size of the polystyrene.

The carboxylic acid may be one selected from the group consisting of oxalic acid, succinic acid, tartaric acid, glutamic acid, adipic acid, terephthalic acid, phthalic acid, malonic acid, maleic acid, fumaric acid, and a combination of two or more of them, and preferably oxalic acid. It is not limited thereto.

Since magnesium salt and polystyrene are easily separated from each other, in general, when a magnesium oxide structure is manufactured using a polystyrene template, a segregation phenomenon in which the composition is non-uniform may occur, and when such segregation occurs, the shape of the manufactured magnesium oxide structure , The size and pore distribution may be uneven. However, in the present invention, the magnesium salt can be strongly bonded to the polystyrene by treating the magnesium salt with the carboxylic acid, and accordingly, uniform magnesium oxide hollow spheres can be prepared.

According to the manufacturing method of the present invention, due to the difference between the surface charge of carboxylic acid-treated magnesium and the surface charge of polystyrene, polystyrene is decomposed in a state of being located inside the particles, thereby forming hollow particles having a smooth surface.

The solvent is methanol, ethanol, propanol, iso-propanol, tert-butanol, n-butanol, methoxyethanol, ethoxyethanol, dimethylacetamide, dimethylformamide, n-methyl-2-pyrrolidone (NMP), Formic acid, nitromethane, acetic acid, water, and may be one selected from the group consisting of a combination of two or more thereof, preferably, may be a mixed solvent of water and ethanol, more preferably, water and ethanol are each 1: It may be mixed in a volume ratio of 0.5 to 1.5, but is not limited thereto.

When the precursor solution is granulated by the spray pyrolysis method of steps (b) and (c), spherical particles having cavities therein may be produced.

The carrier gas used for spraying the precursor solution may be one selected from the group consisting of air, nitrogen, oxygen, helium, argon, and a combination of two or more of them, and preferably, nitrogen, but is limited thereto. no. Since the residence time of the reactant in the reactor is determined according to the flow rate of the carrier gas, the flow rate of the carrier gas can be adjusted so that the residence time becomes about 2 seconds in consideration of productivity.

The flow rate of the carrier gas may be 6.5 L/min or more, 7.0 L/min or more, or 7.5 L/min or more, and 9.5 L/min or less, 9.0 L/min or less, 8.5 L/min or less, or 8.0 L/min or less. have. If the flow rate of the carrier gas is less than 6.5 L/min, productivity may decrease, and if it exceeds 9.5 L/min, the reaction time or residence time is short, so that the crystallinity and the uniformity of the particle size distribution of the magnesium oxide hollow spheres will be significantly reduced. I can.

In step (c), the pyrolysis may be performed at 300°C or higher, 350°C or higher, 400°C or higher, 450°C or higher, 500°C or higher, or 550°C or higher, and 1,000°C or lower, 950°C or lower, 900°C or lower , 850°C or less, 800°C or less, 750°C or less, 700°C or less, or 650°C or less.

After the (c) step, (d) annealing the magnesium oxide hollow sphere at 100 ~ 500 ℃; may further include. The annealing may be performed at 100°C or higher, 150°C or higher, 200°C or higher, or 250°C or higher, and may be performed at 500°C or lower, 450°C or lower, 400°C or lower, or 350°C or lower. When the step (d) is performed, the crystallinity of the magnesium oxide hollow sphere may be improved.

The manufacturing method of the magnesium oxide hollow sphere may be performed in a continuous process, unlike a conventional manufacturing method in which a batch process is performed, and thus productivity can be remarkably excellent. Specifically, this continuous process may be performed by separating into a first reactor for preparing the precursor solution and a second reactor for spraying pyrolysis reaction of the precursor solution.

Magnesium oxide hollow sphere

The magnesium oxide hollow sphere according to an aspect of the present invention is manufactured by the above-described manufacturing method, and may have bimodal pores.

The pore size distribution of the magnesium oxide hollow sphere may have at least one peak in the range of 2 to 50 nm. That is, the magnesium oxide hollow sphere may have at least one mesopore peak. When the magnesium oxide hollow spheres are prepared by the spray pyrolysis method described above,

At least part of the magnesium oxide may be modified with carboxylic acid. The kinds and effects of these carboxylic acids are the same as described above.

The pore diameter distribution of the magnesium oxide hollow spheres is 1 nm or more, 1.5 nm or more, 2 nm or more, or 2.5 nm or more, 10 nm or less, 9.0 nm or less, 8.0 nm or less, 7.0 nm or less, 6.0 nm or less, 5.0 nm or less, or A first peak included in the range of 4.0 nm or less; And 10 nm or more, 11 nm or more, 12 nm or more, 13 nm or more, 14 nm or more, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, The second peak included in the range of 19 nm or less, 18 nm or less, 17 nm or less, 16 nm or less, or 15 nm or less; may be included, but is not limited thereto. The pore size distribution of the magnesium oxide hollow spheres can be appropriately controlled by varying the manufacturing method according to the use.

The BET specific surface area of the magnesium oxide hollow sphere may be 160 m ² /g or more, 180 m ² /g or more, 200 m ² /g or more or 220 m ² /g or more, and 300 m ² /g or less, 280 m ² /g or less, 260 m ² /g or less, or 240 m ² /g or less, but is not limited thereto. The BET specific surface area of these hollow magnesium oxide spheres can be appropriately controlled by varying the manufacturing method according to the use.

The pore volume of the magnesium oxide hollow sphere may be 0.30 cm ³ /g or more, 0.35 cm ³ /g or more, 0.40 cm ³ /g or more, 0.45 cm ³ /g or more, or 0.50 cm ³ /g or more, and 0.75 cm ³ / g or less, 0.70 cm ³ /g or less, 0.65 cm ³ /g or less, 0.60 cm ³ /g or less, or 0.55 cm ³ /g or less, but is not limited thereto. The pore volume of the magnesium oxide hollow sphere can be appropriately controlled by varying the manufacturing method according to the use.

The amount of CO ₂ adsorption of the magnesium oxide hollow spheres is 0.150 mol/kg or more, 0.200 mol/kg or more, 0.250 mol/kg or more, 0.300 mol/kg or more, 0.350 mol/kg or more, 0.400 mol/kg or more, or 0.450 mol/ kg or more, 0.800 mol/kg or less, 0.750 mol/kg or less, 0.700 mol/kg or less, 0.650 mol/kg or less, 0.600 mol/kg or less, 0.550 mol/kg or less, or 0.500 mol/kg or less.

The magnesium oxide hollow sphere can be used as a carbon dioxide adsorbent. The magnesium oxide hollow sphere is easily regenerated and has excellent high-temperature stability, and thus can be used as a carbon dioxide adsorbent for high-temperature flue gases such as various plants and power plants.

Hereinafter, embodiments of the present invention will be described in more detail. However, the following experimental results are only representative of the above examples, and the scope and contents of the present invention are reduced or limited by the examples and cannot be interpreted. Effects of each of the various embodiments of the present invention not explicitly presented below will be specifically described in the corresponding section.

sample

Magnesium acetate tetrahydrate ((CH ₃ COO) ₂ Mg·4H ₂ O, 98%), oxalic acid (HO ₂ CCO ₂ H, 98%), 4-styrene sulfonic acid sodium salt hydrate (4- styrenesufonic acid sodium salt hydrate, H ₂ C=CHC ₆ H ₄ SO ₃ Na·xH ₂ O) and potassium persulfate (K ₂ S ₂ O ₈ , 99%) were purchased from Sigma-Aldrich, and ethanol (ethanol, C ₂ H ₅ OH, 99.5%) was purchased from Daejeong, and deionized water was prepared using Aqua Max Ultra 360 of Younglin.

The sample was used without separate purification.

Preparation Example: Preparation of polystyrene beads

First, 0.083 g of 4-styrene sulfonic acid sodium salt hydrate and 0.14 g of sodium hydrogen carbonate were added to 250 g of deionized water to prepare a mixture. After placing the mixture in an oil bath, the mixture was stirred for 10 minutes at 350 rpm. While stirring was continued, 33 g of a styrene monomer was added to the mixture, followed by further stirring for 1 hour. Thereafter, 0.14 g of potassium persulfate was added and then aged for 20 hours to prepare polystyrene beads.

Example: Preparation of MgO hollow spheres

Hollow MgO spheres were prepared by ultrasonic spray pyrolysis process.

A precursor solution was prepared by dissolving magnesium acetate in a mixed solvent having a volume ratio of H ₂ O and ethanol of 1:1 until the solution became transparent. A solution containing polystyrene beads having an average particle size of 180 nm was added to the precursor solution. An oxalic acid solution containing 10 ml of ethanol and 3 g of oxalic acid was added to the precursor solution, mixed and immersed for 20 minutes to precipitate magnesium acetate.

The precursor solution was heated to 115° C. for 10 minutes in an oil bath, and then injected into an ultrasonic nebulizer for spray pyrolysis. Ultrasonic waves were applied to the precursor solution to generate droplets, and the droplets were transferred to an electric furnace at 600°C as an inert gas. After obtaining MgO using a cellulose thimble filter, it was annealed in an argon atmosphere at 300°C.

1 schematically shows a method of synthesizing hollow MgO spheres having bimodal pores. Referring to FIG. 1, the present invention can synthesize MgO hollow spheres having bimodal pores by spray pyrolysis using polystyrene beads. In addition, if the spray pyrolysis method is used, high purity MgO hollow spheres can be produced in a continuous process. When carrying out such a continuous process, it is very important to prepare a solution for producing a high purity material.

In the present invention, in order to prevent segregation of polystyrene due to the low melting point of a metal salt, mainly nitrate or chloride, a magnesium oxalate precipitate was prepared using magnesium acetate and oxalic acid, and then a polystyrene solution was added to the precipitate. The synthesized magnesium oxalate solution was sprayed in the form of droplets, and immediately decompressed with polystyrene in a high temperature furnace to form MgO hollow spheres having bimodal pores. Since the MgO hollow sphere is produced by passing through the high-temperature furnace for a short period of about 2 seconds, the crystallinity is increased by annealing in an argon atmosphere at 300°C.

Comparative example

A precursor solution was prepared by dissolving magnesium acetate in a mixed solvent having a volume ratio of H ₂ O and ethanol of 1:1 until the solution became transparent.

The precursor solution was heated to 115° C. for 10 minutes in an oil bath, and then injected into an ultrasonic atomizer for use in spray pyrolysis. An ultrasonic wave was applied to the precursor solution to generate droplets, and the droplets were transferred to an electric furnace at 600°C as an inert gas. After obtaining MgO using a cellulose thimble filter, it was annealed in an argon atmosphere at 300°C.

Experimental Example 1: Analysis of physical properties

Using a high-resolution field emission scanning electron microscope (HR FE-SEM, Merlin, Carl Zeiss) and a transmission electron microscope to analyze the MgO hollow spheres prepared in the above Example and the MgO morphology of the Comparative Example One result is shown in FIG. 2. Figure 2 (a) is a low magnification SEM image of the MgO hollow sphere of the embodiment, Figure 2 (b) is a high magnification SEM image of the MgO hollow sphere of the embodiment, Figure 2 (c) is a low magnification TEM image of the MgO hollow sphere of the embodiment , Figure 2 (d) is a high magnification TEM image of the MgO hollow spheres of the Example, Figure 2 (e) is a low MgO TEM image of the comparative example, Figure 2 (f) is the MgO high magnification TEM image of the comparative example.

Referring to the SEM images of the examples shown in FIGS. 2A and 2B, the products of the above examples were manufactured by ultrasonic spray pyrolysis, and there are some differences in size, but it can be seen that the majority are spheres. . It is believed that it is possible to maintain the spherical shape by the interaction between oxalic acid and polystyrene.

Referring to the TEM images of the examples shown in (c) and (d) of FIG. 2, it can be seen that the product of the example is porous and is a hollow sphere. This is because magnesium and polystyrene were not separated during the spray pyrolysis process and were dissolved in oxalic acid.

Referring to the TEM images of the comparative examples shown in (e) and (f) of FIG. 2, MgO without addition of polystyrene and oxalic acid also has a hollow structure and has a specific surface area of 150 m ² /g, but low melting of magnesium acetate Due to the dots, it can be seen that the sphere is not maintained and has a distorted shape.

Using Cu-Kα (λ=1.54 ÅA) radiation, X-ray diffraction analysis (X-ray diffraction, XRD, Miniflex 600, Rigaku Co., Ltd.) in the 2θ range of 5 to 45° was performed to obtain the MgO hollow spheres prepared in the above example. The results of analyzing the crystal structure are shown in Fig. 3 (a).

Using an N ₂ porosimeter (N ₂ porosimeter, BELSORP-max, MicrotracBEL) was used to analyze the BET surface area, the adsorption and desorption isotherm, and the BJH pore distribution, and are shown in FIGS. Degassing of the material was carried out at 150° C. for 12 hours.

Referring to (a) of FIG. 3, it can be seen that the XRD pattern of the MgO hollow sphere of the Example is all the same as the MgO XRD pattern of the Comparative Example.

Referring to FIG. 3B, it can be seen that mesopores were formed in that both MgO of the Example and MgO of the Comparative Example exhibit hysteresis.

division BET specific surface area (m ² /g) Pore volume (cm ³ /g) Average pore diameter (nm) Example 221.75 0.541 8.28 Comparative example 150.39 0.260 5.23

Referring to Table 1, the hollow MgO spheres of Examples have a larger specific surface area and a larger pore volume compared to the MgO of Comparative Examples. This difference is because the hollow MgO spheres of the examples have additional pores formed by polystyrene.

Referring to the pore distribution curve shown in (c) of FIG. 3, it can be seen that, unlike MgO of the comparative example, in addition to pores having a pore diameter of 3.8 nm, pores having a pore diameter of 14.5 nm were further formed.

The MgO hollow spheres of the examples and the MgO of the comparative examples were subjected to a CO ₂ adsorption test at 25° C. to further analyze the difference according to the pores and shown in FIG. 4.

Referring to FIG. 4, the MgO hollow spheres of the examples and the MgO of the comparative examples exhibited adsorption amounts of 0.470 mol/kg and 0.125 mol/kg, respectively. From these results, it can be seen that the pores produced by polystyrene and oxalic acid increased the amount of CO ₂ adsorption.

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and the concept of equivalents thereof should be construed as being included in the scope of the present invention.

Claims (13)

(a) preparing a precursor solution by dissolving magnesium salt, polystyrene, and carboxylic acid in a solvent;
(b) applying ultrasonic waves to the precursor solution to generate droplets, and spraying the droplets into a reactor using a carrier gas; And
(c) pyrolyzing the droplet to obtain a magnesium oxide hollow sphere; including,
The magnesium oxide hollow spheres contain bimodal pores,
The pore size distribution of the magnesium oxide hollow sphere is a first peak included in the range of 1 to 10 nm; And a second peak included in the range of 10 to 50 nm; containing, a method for producing a magnesium oxide hollow sphere. The method of claim 1,
The magnesium salt is magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate, magnesium bromide, magnesium iodide, and two or more of them. One selected from the group consisting of a combination, a method for producing a magnesium oxide hollow sphere. The method of claim 1,
The average particle size of the polystyrene is 50 to 500 nm, the method of producing a magnesium oxide hollow sphere. The method of claim 1,
The carboxylic acid is one selected from the group consisting of oxalic acid, succinic acid, tartaric acid, glutamic acid, adipic acid, terephthalic acid, phthalic acid, malonic acid, maleic acid, fumaric acid, and a combination of two or more of them, a method for producing magnesium oxide hollow spheres. The method of claim 1,
The solvent is methanol, ethanol, propanol, iso-propanol, tert-butanol, n-butanol, methoxyethanol, ethoxyethanol, dimethylacetamide, dimethylformamide, n-methyl-2-pyrrolidone (NMP), Formic acid, nitromethane, acetic acid, water, and one selected from the group consisting of a combination of two or more of them, a method for producing magnesium oxide hollow spheres. The method of claim 1,
In the step (c), the thermal decomposition is performed at 300 to 1,000° C., a method for producing a magnesium oxide hollow sphere. The method of claim 1,
After step (c),
(d) annealing the magnesium oxide hollow spheres at 100 to 500°C; further comprising, a method of manufacturing a magnesium oxide hollow sphere. It is manufactured by the manufacturing method according to any one of claims 1 to 7,
With bimodal pores,
The pore size distribution of the magnesium oxide hollow sphere is a first peak included in the range of 1 ~ 10 nm; And a second peak included in the range of 10 to 50 nm; containing, magnesium oxide hollow spheres. The method of claim 8,
The magnesium oxide is at least partially modified with carboxylic acid, magnesium oxide hollow spheres. delete The method of claim 8,
The BET specific surface area of the magnesium oxide hollow spheres is 160 m ² /g or more, magnesium oxide hollow spheres. The method of claim 8,
The volume of the pores of the magnesium oxide hollow sphere is 0.30 cm ³ /g or more, the magnesium oxide hollow sphere. The method of claim 8,
The amount of CO ₂ adsorption of the magnesium oxide hollow spheres is 0.150 mol/kg or more, magnesium oxide hollow spheres.

Images