KR20200048157A - Adsorbent for selective separation of carbon monoxide and preparation method thereof - Google Patents

Abstract

The present invention relates to an adsorbent with high carbon monoxide selectivity for selectively adsorbing, separating and purifying carbon monoxide, and a method for manufacturing the same. More particularly, the present invention relates to an adsorbent with carbon monoxide selectivity, including bayerite or a bayerite-like substrate in which a copper compound is dispersed, and the selectivity of carbon monoxide to at least one selected from the group consisting of carbon dioxide, methane, nitrogen and hydrogen is 15 or more. The present invention also relates to a manufacturing method of the adsorbent.

Description

Carbon monoxide selective adsorbent and its manufacturing method {ADSORBENT FOR SELECTIVE SEPARATION OF CARBON MONOXIDE AND PREPARATION METHOD THEREOF}

The present invention relates to a carbon monoxide high selectivity adsorbent for selectively adsorbing carbon monoxide, separation and purification, and a method for manufacturing the same.

LDG (Linz-Donawitz Gas), a by-product of ironworks, contains carbon monoxide (65-80%), carbon dioxide (5-7%), and trace amounts of nitrogen, and BFG (Blast Furnace Gas) is carbon monoxide (20-36%) , Carbon dioxide (4 ~ 13%), nitrogen (55 ~ 61%), hydrogen (1.5 ~ 8%), carbon monoxide generated by the by-product gas is 3 million tons per year, but most of the carbon monoxide currently emitted is recovered It is not being burned as a heat source.

As diversification of carbon monoxide production and generation sources is made, and interest in application to resource recovery and high value-added products (acetic acid, polyurethane, polycarbonate, formic acid, acrylic acid, phosgene, etc.) is increased, it is necessary to adsorb and separate carbon monoxide. The demand for technology development is increasing.

Currently, as a technique for separating carbon monoxide, a deep cooling method, an absorption method, an adsorption method, and the like are mainly used, and among these, the adsorption method uses a carbon monoxide adsorbent, which is advantageous in terms of cost to separate small and medium-sized carbon monoxide.

Since the constituents of the by-product gas such as LDG, BFG, etc. are composed of a large amount of carbon monoxide, carbon dioxide, and a trace gas, an adsorbent having excellent carbon monoxide adsorption at room temperature and pressure and carbon monoxide selectivity is required to adsorb a large amount of carbon monoxide. .

In general, the carbon monoxide adsorbent is a form in which the first copper is supported, and is used for selectively adsorbing and separating carbon monoxide from a steam reforming gas composed of hydrogen and carbon monoxide, or syngas. This carbon monoxide adsorbent is difficult to disperse uniformly because the first copper compound is not soluble in a general solvent, and then converts the first copper salt to the first copper state by reducing the copper salt after depositing it on the solid support or converting the first copper salt onto the solid support. The method of impregnating (adhering) after evaporation has been used, but there is a problem in that the first copper salt is not uniformly dispersed on the solid support or the adsorption properties for carbon monoxide are lowered.

The present invention is to solve the above problems, the object of the present invention is to provide a carbon monoxide selective adsorbent having a high selectivity to carbon monoxide and a Bayerite or similar Bayerite substrate in which copper compounds are dispersed.

In addition, to provide a method for producing a carbon monoxide selective adsorbent comprising the step of uniformly distributing a copper compound on a Bayerite or similar Bayerite substrate.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

The carbon monoxide selective adsorbent according to an embodiment of the present invention includes a Bayerite or similar Bayerite substrate in which a copper compound is dispersed, and includes at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen. Selectivity is 15 or more.

According to one aspect, the specific surface area of the Bayerite or similar Bayerite substrate may be 350 m ² g ^-1 or more.

According to one aspect, the pore volume of the Bayerite or similar Bayerite substrate may be 0.10 cm ³ g ^-1 or more.

According to one aspect, the copper compound may be thermally dispersed or impregnated into pores, surfaces, or both of the bayerite or similar bayerite substrate.

According to one aspect, the copper compound, the first copper salt, copper chloride, copper fluoride, copper iodide, copper bromide, copper nitrate, copper acetate, copper thiocyanate, copper thiobenzoate, thiobutyl It may include at least one selected from the group consisting of copper, cuprous benzoate, cuprous sulfate and cuprous thiosulfate.

According to one aspect, among the entire carbon monoxide selective adsorbent, it may be to include 5% to 50% by weight of the copper compound.

According to one aspect, the selectivity of carbon monoxide to at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen may be 35 or more.

According to one aspect, the carbon monoxide adsorption amount may be 40 cm ³ g ^-1 or more and the carbon dioxide adsorption amount may be 3 cm ³ g ^-1 or less under a temperature condition of 20 ° C and a pressure of 100 kPa.

A method for preparing a carbon monoxide selective adsorbent according to an embodiment of the present invention includes preparing a Bayerite or similar Bayerite substrate; Preparing a mixture of the Bayerite or similar Bayerite substrate and a copper compound; And thermally dispersing the copper compound on the bayerite or similar bayerite substrate.

According to one aspect, the Bayerite or similar Bayerite substrate is fired at a temperature of 200 ° C to 400 ° C for 1 hour to 12 hours, such that the specific surface area is 350 m ² g ^-1 or more, and the pore volume is It may be to be 0.1 cm ³ g ^-1 or more.

According to one aspect, the step of heat dissipation may be performed for 1 hour to 48 hours at a heat dispersion temperature of 250 ° C to 350 ° C.

According to one aspect, the heat dispersing step, vacuum; Or an atmosphere containing an inert gas, a reducing gas, or both; It may be performed in.

Method for producing a carbon monoxide selective adsorbent according to another embodiment of the present invention, the step of preparing an impregnation solution containing a copper compound and a solvent; A baerite or similar bayer having a specific surface area of 350 m ² g ^-1 or higher and a pore volume of 0.1 cm ³ g ^-1 or higher by firing the bayerite or similar bayerite at a temperature of 200 ° C to 400 ° C for 1 to 12 hours. Preparing a light substrate; Impregnating the Bayerite or similar Bayerite substrate with the Bayerite or similar Bayerite substrate by contacting the impregnation solution; Drying the Bayerite or similar Bayerite substrate impregnated with the copper compound; And calcining the Bayerite or similar Bayerite substrate impregnated with the dried copper compound.

According to one aspect, the drying step, the temperature and vacuum of 30 ℃ to 60 ℃; Or performing in an atmosphere containing an inert gas, a reducing gas or both for 1 hour to 50 hours, the firing step, the temperature and vacuum of 110 ℃ to 400 ℃; Or it may be performed for 10 minutes to 20 hours in an atmosphere containing an inert gas, a reducing gas, or both.

According to one aspect, the impregnating step may be performed at a temperature of 15 ° C to 60 ° C using an initial wetting technique.

According to one aspect, the solvent comprises at least one selected from the group consisting of water, toluene, ethyl acetate and acetonitrile, and the impregnating solution comprises at least one selected from the group consisting of ammonia, nitric acid, hydrochloric acid and sulfuric acid. It may be included.

According to the present invention, a carbon monoxide selective adsorbent having a selectivity of at least 15 carbon monoxide for at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen can be implemented by applying a Bayerite or similar Bayerite substrate.

The highly selective adsorbent of carbon monoxide according to the present invention has a very high selectivity of carbon monoxide compared to at least one selected from the group consisting of carbon dioxide, methane, nitrogen and hydrogen in a mixed gas, and can be effectively applied to selective adsorption and separation of carbon monoxide. .

In addition, according to the method for producing a carbon monoxide selective adsorbent of the present invention, it is possible to implement a carbon monoxide selective adsorbent in which copper compounds are uniformly distributed on a Bayerite or similar Bayerite substrate.

1 is a flow chart showing a method for producing a carbon monoxide selective adsorbent according to an embodiment of the present invention.
2 is a carbon monoxide adsorption curve graph and a carbon dioxide adsorption curve graph of the carbon monoxide selective adsorbent according to the weight of the copper compound included.
3 is a carbon monoxide adsorption curve graph and a carbon dioxide adsorption curve graph of the carbon monoxide selective adsorbent according to the heat dispersion temperature.
4 is a graph showing adsorption curves of carbon monoxide, carbon dioxide, methane, hydrogen, and nitrogen of an adsorbent in which 30 wt% of the best copper salt is heat-dispersed on a Bayerite substrate at 300 ° C.
5 is a flowchart illustrating a method of manufacturing a carbon monoxide selective adsorbent according to another embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, when it is determined that a detailed description of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, terms used in the present specification are terms used to appropriately represent a preferred embodiment of the present invention, which may vary depending on a user, an operator's intention, or a custom in the field to which the present invention pertains. Therefore, definitions of these terms should be made based on the contents throughout the specification. The same reference numerals in each drawing denote the same members.

Throughout the specification, when one member is positioned “on” another member, this includes not only the case where one member abuts another member, but also the case where another member exists between the two members.

Throughout the specification, when a part “includes” a certain component, it means that the other component may be further included instead of excluding the other component.

Hereinafter, the carbon monoxide selective adsorbent of the present invention and a method for manufacturing the same will be described in detail with reference to examples and drawings. However, the present invention is not limited to these examples and drawings.

The carbon monoxide selective adsorbent according to an embodiment of the present invention includes a Bayerite or similar Bayerite substrate in which a copper compound is dispersed, and includes at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen. Selectivity is 15 or more. The selectivity means “CO adsorption amount / CO ₂ , CH ₄ , N ₂ or H ₂ adsorption amount”. The bayerite or pseudo bayerite may have some changes in atomic arrangement and structure in a process such as pretreatment such as firing, and the bayerite or pseudo bayerite of the present invention includes a case of such a modification.

The carbon monoxide selective adsorbent according to an embodiment of the present invention is one in which a copper compound is dispersed on a Bayerite or similar Bayerite substrate, for example, a pore, a surface, or both, for example, a pore, a surface of the substrate , Or a Bayerite or similar Bayerite substrate with copper compounds dispersed in both. Alternatively, it may include a Bayerite or similar Bayerite substrate impregnated with copper compounds on the surface, pores, surface, or both of the substrate.

The carbon monoxide selective adsorbent according to an embodiment of the present invention has the characteristics of a copper compound and a bayerite or similar bayerite substrate at the same time, thereby providing a higher selectivity of carbon monoxide compared to a conventional carbon monoxide adsorbent using a zeolite or alumina substrate. Carbon dioxide, methane, nitrogen and hydrogen, and the selectivity of carbon monoxide to at least one selected from the group can provide a high selectivity of carbon monoxide compared to a carbon monoxide selective adsorbent to which a boehmite or similar boehmite substrate is applied. .

Specifically, the carbon monoxide selective adsorbent according to an embodiment of the present invention has a selectivity of carbon monoxide for at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen, and is 15 or more.

According to one aspect, the specific surface area of the Bayerite or similar Bayerite substrate may be 350 m ² g ^-1 or more. The Bayerite substrate has a large specific surface area, which is advantageous for better dispersion of the copper compound, and thus the carbon monoxide adsorption performance is significantly increased.

According to one aspect, the pore volume of the Bayerite or similar Bayerite substrate may be 0.1 cm ³ g ^-1 or more. The Bayerite substrate has a large pore volume, which is advantageous for better dispersion of the copper compound, and thus, the carbon monoxide adsorption performance is significantly increased.

According to one aspect, the Bayerite or similar Bayerite substrate may be one having a higher specific surface area and pore volume by firing at a high temperature in advance before impregnation or thermal dispersion of a copper compound.

According to one aspect, the copper compound may be thermally dispersed or impregnated into pores, surfaces, or both of the bayerite or similar bayerite substrate.

In general, the carbon monoxide adsorbent is a form in which the first copper is supported, and is used for selectively adsorbing and separating carbon monoxide from a steam reforming gas composed of hydrogen and carbon monoxide, or syngas. This carbon monoxide adsorbent is difficult to disperse uniformly because the first copper compound is not soluble in a general solvent, and then converts the first copper salt to the first copper state by reducing the copper salt after depositing it on the solid support or converting the first copper salt onto the solid support. The method of impregnating (adhering) after evaporation has been used, but there is a problem in that the first copper salt is not uniformly dispersed on the solid support or the adsorption properties for carbon monoxide are lowered.

On the other hand, a Bayerite or similar Bayerite substrate having a large specific surface area as described above is advantageous for heat dissipation or impregnation of a copper compound, and a copper compound other than a carbon monoxide adsorbent in which the copper compound is generally mixed or supported is thermally dispersed or impregnated. It is possible to implement a carbon monoxide selective adsorbent in the form.

According to one aspect, the copper compound, the first copper salt, copper chloride, copper fluoride, copper iodide, copper bromide, copper nitrate, copper acetate, copper thiocyanate, copper thiobenzoate, thiobutyl It may include at least one selected from the group consisting of copper, cuprous benzoate, cuprous sulfate and cuprous thiosulfate.

According to one aspect, among the entire carbon monoxide selective adsorbent, it may be to include 5% to 50% by weight of the copper compound. More specifically, it may be 20 to 45% by weight. When the copper compound contains less than 5% by weight or more than 50% by weight, the adsorption amount of carbon monoxide is lowered, and the adsorption amount of at least one selected from the group consisting of carbon dioxide, methane, nitrogen and hydrogen is increased, and carbon dioxide is increased. A problem may arise in that the selectivity of carbon monoxide to at least one selected from the group consisting of methane, nitrogen, and hydrogen is lowered.

According to one aspect, the selectivity of carbon monoxide to at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen may be 35 or more.

According to one aspect, the adsorption amount of carbon monoxide at a temperature condition of 20 ° C. and a pressure of 100 kPa is 40 cm ³ g ⁻¹ or more, and at least one adsorption amount selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen is 3 cm ³ g It may be less than ^-1 .

For example, by adjusting the manufacturing conditions, the adsorption amount of carbon monoxide at 20 ° C and 100 kPa of pure gas can be maximized to 48.5 cm ³ g ^-1 , and for at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen. It is possible to implement a carbon monoxide selective adsorbent having a selectivity of carbon monoxide of 16.8.

As another example, when the manufacturing conditions are adjusted, the carbon monoxide adsorption amount at 20 ° C. and 100 kPa of pure gas is slightly reduced to 41.6 cm ³ g ⁻¹ , but for at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen. A carbon monoxide selective adsorbent that maximizes the selectivity of carbon monoxide to 35.5 can be realized.

1 is a flow chart showing a method for producing a carbon monoxide selective adsorbent according to an embodiment of the present invention. Hereinafter, the present invention will be described with reference to FIG. 1.

Method for producing a carbon monoxide selective adsorbent according to an embodiment of the present invention, preparing a Bayerite or similar Bayerite substrate (S110); Preparing a mixture of the bayerite or similar bayerite substrate and a copper compound (S120); And thermally dispersing the copper compound on the Bayerite or similar Bayerite substrate (S130).

According to one aspect, the Bayerite or similar Bayerite substrate is fired at a temperature of 200 ° C to 400 ° C for 1 hour to 12 hours, such that the specific surface area is 350 m ² g ^-1 or more, and the pore volume is It may be to be 0.10 cm ³ g ^-1 or more. The pre-fired Bayerite substrate has a large specific surface area and a large pore volume, which is advantageous for better dispersion of the copper compound, and thus the carbon monoxide adsorption performance is significantly increased.

According to one aspect, the step of preparing a mixture of the Bayerite or similar Bayerite substrate and the copper compound (S120) may be a step of grinding and mixing the Bayerite or similar Bayerite substrate and the copper compound. The grinding and mixing may use a device used in the technical field of the present invention, for example, a ball mill, a mixer, and the like.

For example, in the step (S120) of preparing a mixture of the Bayerite or similar Bayerite substrate and a copper compound, the Bayerite or similar Bayerite substrate to the copper compound is 90:10 to 50:50 (mass ratio) or 80 : 20 to 60: 40 (mass ratio) may be mixed, and among all the carbon monoxide selective adsorbents finally produced, the copper compound may contain 5% to 50% by weight.

2 is a carbon monoxide adsorption curve graph and a carbon dioxide adsorption curve graph of the carbon monoxide selective adsorbent according to the weight of the copper compound included.

Specifically, Figure 2 (a) is a carbon monoxide adsorption curve graph according to the weight of the copper compound contained, Figure 2 (b) is a carbon monoxide adsorption curve graph of the carbon monoxide selective adsorbent according to the weight of the copper compound included .

Referring to Figure 2 (a) and (b), if the total amount of the carbon monoxide selective adsorbent, the copper compound containing 5% to 50% by weight, the selectivity of carbon monoxide to carbon dioxide (CO adsorption amount / CO ₂ adsorption amount) ) Is 15 or more, it can be seen that the carbon monoxide selective adsorbent is implemented, especially when the copper compound contains 30% by weight, it can be seen that the carbon monoxide adsorption amount is greatly increased.

According to one aspect, the heat dissipation step (S130) may be performed for 1 hour to 48 hours at a heat dispersion temperature of 250 ° C to 350 ° C.

According to one aspect, the step of dispersing the heat (S130), the heat dissipation temperature 250 ℃ to 350 ℃; 250 ° C to 330 ° C; Or it may be a heat dispersion in an inert gas atmosphere at a temperature of 270 ℃ to 300 ℃. When included within the temperature range, it prevents the conversion to AlOOH, crystalline or amorphous aluminum oxide and maintains the properties of the Bayerite or similar Bayerite substrate, while retaining the properties of the Bayerite or similar Bayerite substrate. It is possible to induce uniform heat dissipation of a high concentration copper compound. In addition, it is possible to prevent the conversion of the copper compound to metallic copper (Cu) according to an increase in temperature, so that the properties of the copper compound are maintained in the carbon monoxide selective adsorbent.

For example, the step of dispersing the heat (S130) may be performed for 1 hour to 48 hours, and when included in the time range, while maintaining the properties of the copper compound, it is uniform on the Bayerite or similar Bayerite substrate. Can be heat dissipated.

According to one aspect, the step of dispersing the heat (S130), vacuum; Or an atmosphere containing an inert gas, a reducing gas, or both; It may be performed in.

3 is a carbon monoxide adsorption curve graph and a carbon dioxide adsorption curve graph of the carbon monoxide selective adsorbent according to the heat dispersion temperature.

Specifically, Figure 3 (a) is a carbon monoxide adsorption curve graph of the carbon monoxide selective adsorber according to the heat dissipation temperature, Figure 3 (b) is a carbon monoxide adsorption curve graph of the carbon monoxide selective adsorber according to the heat dispersion temperature.

Referring to FIG. 3, referring to (a) and (b), the carbon monoxide selective adsorbent prepared at a heat dissipation temperature of 250 ° C. (523 K) to 350 ° C. (723 K) selectivity of carbon monoxide to carbon dioxide (CO It can be seen that the adsorption amount / CO ₂ adsorption amount) is very high. In particular, it can be seen that the carbon monoxide adsorption amount is significantly increased when it is prepared at a heat dissipation temperature of 300 ° C (573 K).

As a result, it can be seen that, among the adsorbents, the adsorbent obtained by thermally dispersing 30% by weight of the best copper salt at 300 ° C. on the Bayerite substrate shows the highest carbon monoxide adsorption capacity and excellent carbon monoxide selectivity compared to carbon dioxide. It can be seen that this adsorbent has a very large carbon monoxide selectivity compared to methane, nitrogen and hydrogen as well as carbon dioxide.

4 is a graph showing adsorption curves of carbon monoxide, carbon dioxide, methane, hydrogen, and nitrogen of an adsorbent in which 30 wt% of the best copper salt is heat-dispersed on a Bayerite substrate at 300 ° C. Referring to Figure 4, it can be seen that the carbon monoxide selective adsorbent according to an embodiment of the present invention has excellent carbon monoxide selectivity compared to methane, nitrogen and hydrogen as well as carbon dioxide.

5 is a flowchart illustrating a method of manufacturing a carbon monoxide selective adsorbent according to another embodiment of the present invention. Hereinafter, the present invention will be described with reference to FIG. 5.

Method for producing a carbon monoxide selective adsorbent according to another embodiment of the present invention, preparing an impregnation solution containing a copper compound and a solvent (S210); A baerite or similar bayer having a specific surface area of 350 m ² g ^-1 or higher and a pore volume of 0.1 cm ³ g ^-1 or higher by firing the bayerite or similar bayerite at a temperature of 200 ° C to 400 ° C for 1 to 12 hours. Preparing a light substrate (S220); Impregnating the Bayerite or similar Bayerite substrate with the Bayerite or similar Bayerite substrate by contacting the impregnation solution (S230); Drying the Bayerite or similar Bayerite substrate impregnated with the copper compound (S240); And firing the Bayerite or similar Bayerite substrate impregnated with the dried copper compound (S250).

According to one aspect, the step of preparing an impregnation solution containing the copper compound and the solvent (S210), the stirring the copper compound and the solvent at room temperature to 40 ℃ temperature for 30 minutes to 4 hours to prepare an impregnation solution May be

According to one aspect, in the step (S220) of preparing the Bayerite or similar Bayerite substrate, the Bayerite or similar Bayerite substrate may be fired at a high temperature to increase the specific surface area and pore volume.

According to one aspect, the Bayerite or similar Bayerite substrate is fired at a temperature of 200 ° C to 400 ° C for 1 hour to 12 hours, such that the specific surface area is 350 m ² g ^-1 or more, and the pore volume is It may be to be 0.1 cm ³ g ^-1 or more. The pre-fired Bayerite substrate has a large specific surface area and a large pore volume, which is advantageous for better dispersion of the copper compound, and thus the carbon monoxide adsorption performance is significantly increased.

According to one aspect, the impregnation step (S230) may be performed at a temperature of 15 ° C to 60 ° C using an initial wetting technique. Specifically, 15 ℃ to 60 ℃ temperature using an initial wetting technique; Or it may be carried out for 1 hour to 20 hours at a temperature of 30 ℃ to 40 ℃.

According to one aspect, the drying step (S240), the temperature and vacuum of 30 ℃ to 60 ℃; Or it may be performed for 1 hour to 50 hours in an atmosphere containing an inert gas, a reducing gas, or both. Specifically, the impregnated substrate is filtered after the impregnation step (S230), and a temperature of 30 ° C to 60 ° C; Or 40 ° C. to 50 ° C. and vacuum; Or it may be to dry for 1 hour to 50 hours, preferably 5 hours to 20 hours in an atmosphere containing an inert gas, a reducing gas or both.

The firing step (S250), the temperature and vacuum of 110 ℃ to 400 ℃; Or it may be performed for 10 minutes to 20 hours in an atmosphere containing an inert gas, a reducing gas, or both. Specifically, the dried substrate after the drying step (S240), a vacuum in a firing device such as an electric furnace, etc .; Or a temperature of 110 ° C. to 400 ° C. while flowing an inert gas, a reducing gas, or an atmosphere containing both; Or it may be calcined at a temperature of 250 ° C to 330 ° C for 10 minutes to 20 hours, preferably 5 hours to 15 hours.

According to one aspect, the solvent comprises at least one selected from the group consisting of water, toluene, ethyl acetate and acetonitrile, and the impregnating solution comprises at least one selected from the group consisting of ammonia, nitric acid, hydrochloric acid and sulfuric acid. It may be included.

In general, the carbon monoxide adsorbent is a form in which the first copper is supported, and is used for selectively adsorbing and separating carbon monoxide from a steam reforming gas composed of hydrogen and carbon monoxide, or syngas. This carbon monoxide adsorbent is difficult to disperse uniformly because the first copper compound is not soluble in a general solvent, and then converts the first copper salt to the first copper state by reducing the copper salt after depositing it on the solid support or converting the first copper salt onto the solid support. The method of impregnating (adhering) after evaporation has been used, but there is a problem in that the first copper salt is not uniformly dispersed on the solid support or the adsorption properties for carbon monoxide are lowered.

On the other hand, according to the method for producing a carbon monoxide selective adsorbent of the present invention, by applying a Bayerite or a similar Bayerite substrate having a large specific surface area, it is possible to implement a carbon monoxide selective adsorbent in which a copper compound is evenly thermally dispersed or impregnated.

According to an embodiment of the present invention, the method for producing a carbon monoxide highly selective adsorbent according to the present invention may further include post-treatment processes such as grinding, washing, and the like used in the technical field of the present invention. It is not specifically mentioned.

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are only for illustrating the present invention, and the contents of the present invention are not limited to the following examples.

Example 1

The 7 g Bayerite material was calcined for 4 hours while flowing nitrogen gas at 350 ° C. and then cooled to room temperature. 7 g of calcined bayerite material and 3 g of first copper salt were thoroughly mixed using a blender, and then heat-treated at 300 ° C. for 12 hours while maintaining a vacuum.

Example 2

6.4 g of Bayerite material was calcined at 350 ° C. with nitrogen gas for 4 hours and then cooled to room temperature. 6.4 g of calcined bayerite material and 3.6 g of first copper salt were thoroughly mixed using a blender, and then heat-treated at 300 ° C. for 12 hours while maintaining a vacuum.

Comparative example

After thoroughly mixing 7 g of boehmite material and 3 g of copper salt using a mixer, heat treatment was performed at 300 ° C. for 12 hours while maintaining a vacuum.

Table 1 shows the CO adsorption amount, CO ₂ adsorption amount, and selectivity of carbon monoxide to carbon dioxide (CO adsorption) of the carbon monoxide selective adsorbent prepared according to Examples 1 and 2 of the present invention, and the carbon monoxide selective adsorbent prepared according to Comparative Examples. Amount / CO ₂ adsorption amount).

The adsorption amount of carbon monoxide and carbon dioxide was measured under a temperature condition of 20 ° C and 100 kPa of pure gas.

Sample CO adsorption
(cm ³ g ^-1 ) CO2 adsorption
(cm ³ g ^-1 ) CO / CO ₂ Example 1 48.5 2.89 16.8 Example 2 41.6 1.17 35.5 Comparative Example 1 34.0 2.74 12.4

Referring to Table 1, the selectivity (CO adsorption amount / CO ₂ adsorption amount) of carbon monoxide to carbon dioxide of the carbon monoxide selective adsorbent prepared according to an embodiment of the present invention is found to be 15 or more. Accordingly, it can be seen that the selectivity is implemented by 35 or more.

This means that it shows higher carbon monoxide and carbon monoxide selectivity compared to carbon monoxide selective adsorbent (Comparative Example 1) prepared by thermally impregnating the first copper salt with boehmite, another alumina-like substance.

As described above, although the embodiments have been described by a limited embodiment and drawings, those skilled in the art can make various modifications and variations from the above description. For example, even if the described techniques are performed in a different order than the described method, and / or the described components are combined or combined in a different form from the described method, or replaced or replaced by another component or equivalent Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (16)

Bayerite or similar Bayerite substrate in which the copper compound is dispersed; including, carbon monoxide selectivity to at least one selected from the group consisting of carbon dioxide, methane, nitrogen and hydrogen, 15 or more,
Carbon monoxide selective adsorbent.
According to claim 1,
The specific surface area of the Bayerite or similar Bayerite substrate is 350 m ² g ^-1 or more,
Carbon monoxide selective adsorbent.
According to claim 1,
The pore volume of the Bayerite or similar Bayerite substrate is 0.1 cm ³ g ^-1 or more,
Carbon monoxide selective adsorbent.
According to claim 1,
The copper compound is thermally dispersed or impregnated into the pores, surfaces, or both of the bayerite or similar bayerite substrate,
Carbon monoxide selective adsorbent.
According to claim 1,
The copper compound,
Best copper salt, copper chloride, copper fluoride, copper iodide, copper bromide, copper nitrate, copper acetate, copper thiocyanate, copper thiobenzoate, copper thiobutyl, copper benzoate, copper sulfate It comprises at least one selected from the group consisting of cuprous thiosulfate,
Carbon monoxide selective adsorbent.
According to claim 1,
Of the entire carbon monoxide selective adsorbent, which comprises 5% to 50% by weight of the copper compound,
Carbon monoxide selective adsorbent.
According to claim 1,
The selectivity of carbon monoxide to at least one selected from the group consisting of carbon dioxide, methane, nitrogen and hydrogen is 35 or more,
Carbon monoxide selective adsorbent.
According to claim 1,
The carbon monoxide adsorption amount is at least 40 cm ³ g ^-1 and the adsorption amount of at least one selected from the group consisting of carbon dioxide, methane, nitrogen, and hydrogen is 3 cm ³ g ^-1 or less at a temperature condition of 20 ° C and a pressure of 100 kPa. ,
Carbon monoxide selective adsorbent.
Preparing a Bayerite or similar Bayerite substrate;
Preparing a mixture of the Bayerite or similar Bayerite substrate and a copper compound; And
Comprising the step of thermally dispersing the copper compound on the Bayerite or similar Bayerite substrate;
Method for producing carbon monoxide selective adsorbent.
The method of claim 9,
The Bayerite or similar Bayerite substrate,
Calcined at a temperature of 200 ° C to 400 ° C for 1 hour to 12 hours,
The specific surface area is to be 350 m ² g ^-1 or more, and the pore volume is to be 0.1 cm ³ g ^-1 or more,
Method for producing carbon monoxide selective adsorbent.
The method of claim 9,
The step of dispersing the heat,
It is carried out for 1 hour to 48 hours at a heat dispersion temperature of 250 ℃ to 350 ℃,
Method for producing carbon monoxide selective adsorbent.
The method of claim 9,
The heat dispersing step includes vacuum; Or an atmosphere containing an inert gas, a reducing gas, or both; Is performed in,
Method for producing carbon monoxide selective adsorbent.
Preparing an impregnation solution comprising a copper compound and a solvent;
A baerite or similar bayer having a specific surface area of 350 m ² g ^-1 or higher and a pore volume of 0.1 cm ³ g ^-1 or higher by firing the bayerite or similar bayerite at a temperature of 200 ° C to 400 ° C for 1 to 12 hours. Preparing a light substrate;
Impregnating the Bayerite or similar Bayerite substrate with the Bayerite or similar Bayerite substrate by contacting the impregnation solution;
Drying the Bayerite or similar Bayerite substrate impregnated with the copper compound; And
Comprising the step of firing the dried, copper compound impregnated Bayerite or similar Bayerite substrate; containing,
Method for producing carbon monoxide selective adsorbent.
The method of claim 13,
The drying step includes a temperature and vacuum of 30 ° C to 60 ° C; Or in an atmosphere containing an inert gas, a reducing gas, or both for 1 hour to 50 hours,
The firing step includes a temperature and vacuum of 110 ° C to 400 ° C; Or it is carried out for 10 minutes to 20 hours in an atmosphere containing an inert gas, a reducing gas or both,
Method for producing carbon monoxide selective adsorbent.
The method of claim 13,
The impregnation step,
It is carried out at a temperature of 15 ℃ to 60 ℃ using the initial wetting technique,
Method for producing carbon monoxide selective adsorbent.
The method of claim 13,
The solvent is to include at least one selected from the group consisting of water, toluene, ethyl acetate and acetonitrile,
The impregnation solution is to include at least one selected from the group consisting of ammonia, nitric acid, hydrochloric acid and sulfuric acid,
Method for producing carbon monoxide selective adsorbent.

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