KR101778412B1 - Adsorbent for selective adsorption of carbon monoxide and method for preparation thereof - Google Patents

Abstract

The present invention relates to a selective adsorbent and a method of manufacturing the carbon monoxide, more particularly, solid additives, including the clay in step, the adsorbent powder mixture for preparing a sorbent powder mixture was then dried and ground mixture of CuCl and Al ₂ O ₃ To produce a solid mixture, to prepare a liquid mixture comprising silica sol and water, and to mix the solid mixture with a liquid mixture to produce an adsorbent composition. ≪ RTI ID = 0.0 >Way; And an adsorbent produced by such a method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a selective adsorbent for carbon monoxide,

The present invention relates to a selective adsorbent for carbon monoxide and a method for producing the same, and more particularly, to a carbon monoxide adsorbent which maintains a state in which CuCl is dispersed in a support and is excellent in selectivity and adsorption to carbon monoxide in a mixed gas, .

Many studies have been conducted on the selective adsorption and separation of carbon monoxide (CO) in a mixed gas after the fact that carbon monoxide can be selectively absorbed by using an ammonium chloride compound solution.

As a metal component that can be combined with a solid material to more effectively separate carbon monoxide, various metals including nickel, cobalt, copper, and silver can be used. Among them, an adsorbent containing a copper compound is most effective for adsorption of carbon monoxide .

On the other hand, as a method of dispersing the copper compound in the support, the following method is used. More specifically, first, a method in which an aqueous solution of a copper (Cu (II)) compound is dispersed in a support and reduced to a copper (Cu (I) A method in which a compound is mixed with a support by a physical method using a solvent or nonsolvent and then stabilized at a high temperature, and third, a method in which a copper (Cu (I)) compound is vaporized and deposited on the inner surface of a support . Furthermore, a method of producing a carbon monoxide adsorbent by immersing an aqueous solution of a cuprous compound in which a cuprous salt is dissolved in a solvent in a support is also known.

However, a method of dissolving a cupric (Cu (II)) compound or a cuprous (Cu (I)) compound in a solution and dispersing the cupric solution in a solution may be carried out by using a reducing agent or an antioxidant The generation of byproducts and over-reduction in the process of stabilization cause a problem that the performance of the adsorbent including adsorption / desorption characteristics is not properly manifested. Further, a method of vaporizing a cuprous (Cu (I)) compound and depositing it on the inner surface of a support has a problem of requiring a large capacity and high cost of facilities for vaporizing a copper (Cu (I)) compound, The process of dispersing copper (Cu (I)) compounds was small. On the other hand, it is the simplest method that the copper (Cu (I)) compound is mixed with the support by a physical method and stabilized at a high temperature. However, in the process of making the pellet in a powder form for practical use in the field, And contact with water and air is inevitable in the course of making dough, and there is a problem that the performance of the adsorbent varies depending on drying and calcination processes after molding.

On the other hand, in the process of separating and recovering carbon monoxide after the use of the adsorbent, development of an adsorbent excellent in selectivity for carbon monoxide and adsorption / desorption performance compared with gases which can coexist in a mixed gas phase such as carbon dioxide, nitrogen,

Therefore, it is an object of the present invention to provide a high selectivity, high adsorptive and / or high selectivity adsorbent which can selectively remove and recover the carbon monoxide-containing component in the mixed gas by improving selectivity and adsorption / desorption performance for the carbon monoxide during selective adsorption and separation of carbon monoxide in the mixed gas When an adsorbent having a high crush strength and a method for producing the same are provided, it is expected that the adsorbent can be widely applied in related fields.

Accordingly, one aspect of the present invention is to provide a selective adsorbent of carbon monoxide which maintains CuCl dispersed in a support and is excellent in selectivity and adsorption to carbon monoxide in a mixed gas.

Another aspect of the present invention is to provide a method for producing a selective adsorbent of carbon monoxide as described above.

According to one aspect of the present invention, there is provided a method for producing a powdery alumina powder, comprising: drying and pulverizing and mixing CuCl and Al ₂ O ₃ to prepare an adsorbent powder mixture; Further adding a solid additive including clay to the adsorbent powder mixture to prepare a solid mixture; Preparing a liquid mixture comprising silica sol and water; And mixing the solid mixture with a liquid mixture to produce an adsorbent composition.

According to another aspect of the present invention, there is provided a selective adsorbent of carbon monoxide produced by the production method of the present invention and having a specific surface area of 30 to 200 m ² / g.

According to still another aspect of the present invention, CuCl, Al ₂ O _3, comprises a clay, silica sol, and water, wherein the CuCl and Al ₂ O ₃ were prepared by the adsorbent composition of 20 to 50: 50 to 80 weight ratio, A selective adsorbent of carbon monoxide having a specific surface area of 30 to 200 m ² / g is provided.

The carbon monoxide selective adsorbent of the present invention has high selectivity, high adsorptivity and high crush strength, and therefore, various molded articles using the carbon monoxide selective adsorbent of the present invention can be used as an adsorbent for the separation process for high CO concentration and in H ₂ -PSA Since it can be used as a CO adsorption remover, utilization of steel byproduct gas process etc. is various. Particularly, the process efficiency of the adsorbent of the present invention can be improved, and when the adsorbent of the present invention is applied to a pressure swing adsorption process to separate carbon monoxide from a mixed gas containing carbon monoxide, the selectivity of carbon monoxide increases, , The amount of adsorption to gases such as nitrogen and hydrogen is rapidly reduced, and carbon monoxide of high purity can be produced. Also, the amount of adsorbed / desorbed working CO is higher than that of a commercial adsorbent, which can reduce the size of the adsorption tower or reduce the number of adsorption towers, thereby significantly lowering the investment cost. Further, when the hydrogen adsorbent of the present invention separates hydrogen from a hydrogen mixture partially containing carbon monoxide, carbon monoxide can be adsorbed and removed due to high selectivity of carbon monoxide, so that the adsorbent can also be used for obtaining high purity hydrogen.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates an exemplary process for preparing the adsorbent of the present invention.
2 shows XRD graphs showing changes in Cu phase according to dough and aging time, and changes in Cu phase due to vacuum heat treatment of the dough in the process of producing the adsorbent of the present invention, and (b) (C) a graph showing an XRD graph showing changes in Cu phase during the drying, firing and reduction processes of the pellet carbon monoxide adsorbent made in the manufacturing process, and XRD graph showing the change in Cu phase.
FIG. 3 is a thermogravimetric analysis graph showing the weight loss of CuCl in the N ₂ , CO and H ₂ gas atmospheres according to temperature rise. FIG.
4 shows photographs of (a) post-kneading and (b) pelletized adsorbents during the adsorbent pelletizing process of the present invention.
5 is a graph _{showing the relationship between the} adsorbent CuCl-Al ₂ O ₃ (a) synthesized in Production Example 1 and the adsorbent CO, CO ₂ , N ₂ And shows the adsorption isotherm (isotherm) of the graph at 25 ℃ for CH _4.
6 shows the adsorption amount ratio (selectivity) of the CuCl-Al ₂ O ₃ adsorbent (a) synthesized in Production Example 1 and the commercial adsorbent (b) of Comparative Production Example 2 to CO / CO ₂ at 25 ° C Graph.
Figure 7 is a graph which shows the adsorption and desorption on pure CO gas of the commercial adsorbent of the adsorbent CuCl-Al ₂ O ₃ (a) and Comparative Preparation Example 2 (b) synthesized in Preparation Example 1.
Figure 8 Preparation of CuCl-Al ₂ O prepared in ₁₃ adsorbent (a) and Comparative Production Example 2 Commercial CO and CO ₂ gas mixture in the adsorbent (b) of _{(CO: CO 2 = 75 ~} 50: 25 ~ 50 ). ≪ / RTI >
9 is a graph showing the relative CO adsorption amount according to the amount of CuCl-Al ₂ O ₃ adsorbent synthetic CuCl in Production Example 1.
10 is a graph showing the relative amount of CO adsorption depending on the kind of support of CuCl.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

According to the present invention, there is provided a method for producing an adsorbent having high selectivity, high adsorptivity and high crush strength against carbon monoxide. The process of the process for producing an exemplary adsorbent of carbon monoxide of the present invention is shown in FIG.

More specifically, the method for producing a selective adsorbent of carbon monoxide according to the present invention comprises the steps of: drying and pulverizing CuCl and Al ₂ O ₃ to prepare an adsorbent powder mixture; Further adding a solid additive including clay to the adsorbent powder mixture to prepare a solid mixture; Preparing a liquid mixture comprising silica sol and water; And mixing the solid mixture and the liquid mixture to produce an adsorbent composition.

That is, in the present invention, in order to produce adsorbents having high selectivity and high adsorption to carbon monoxide, they are supported on an alumina-based support. Further, a process of separately preparing solid components by mixing and grinding is carried out for uniformly supporting CuCl, In order to solve the problem that the mixing of a liquid component including water is inevitable and a cuprous compound is oxidized / reduced to a copper (Cu (II)) compound or a copper metal in this process, a solid mixture And the liquid mixture were prepared independently, and the mixing time was controlled, and the drying, calcination and reduction steps were performed.

The Al ₂ O ₃ used as a support in the present invention preferably has an average particle size of 0.1 to 10 μm, and the particles falling within the above range preferably occupy 20 wt% or more of the total Al ₂ O ₃ .

The CuCl and Al ₂ O ₃ are mixed in a ratio of 20 to 50:50 to 80, more preferably 30 to 40:60 to 70, and CuCl is contained in a content of less than the above range There is a problem that the amount of CO adsorbed by the CO adsorbent is low. When the amount of CO adsorbed exceeds the above range, the amount of adsorbed CO is not increased due to the low dispersion on the Al - ₂ O ₃ support such as CuCl, There is a problem that only the production cost of adsorption is increased. In consideration of the adsorption amount and the cost of preparing the adsorbent, it is preferable to mix the components at a ratio of 30 to 40: 60 to 70 by weight.

Meanwhile, the CuCl and Al ₂ O ₃ may be independently mixed with each other after drying and crushing, or may be mixed together after drying and crushing, and the drying is preferably carried out to such an extent that crushing is possible.

In the present invention, the clay contained in the solid additive is preferably bentonite-based clay, Wherein the solid mixture further comprises at least one of methyl cellulose (MC), starch and polyethylene (PE), the liquid mixture comprising at least one selected from the group consisting of glycerol, polyethylene glycol (PEG) and polyvinyl alcohol It is preferable to further include one species. More preferably, the solid mixture comprises bentonite-based clay and methylcellulose. When methylcellulose is included together with the clay, it is possible to increase the degree of mixing and obtain the desired extrusion dough state.

In the present invention, the clay serves as a low-temperature inorganic binder, a plasticizer, a wetting agent and the like, and is preferably contained in an amount of 3 to 20 parts by weight per 100 parts by weight of the powder mixture. If the amount of the clay is less than 3 parts by weight per 100 parts by weight of the powder mixture of the adsorbent, it is impossible to obtain a kneaded state having a suitable viscosity for extrusion kneading, which is problematic in producing a pellet type adsorbent, and 20 parts by weight per 100 parts by weight of the adsorbent powder mixture There is a problem that the performance of the selective carbon monoxide adsorbent is deteriorated due to excessive incorporation of the bentonite-based clay having the characteristic that the CO adsorption property is poor and the CO ₂ adsorption is good.

On the other hand, the methylcellulose serves as an emulsifier, an organic binder, etc., and is preferably contained in an amount of 0.5 to 3 parts by weight per 100 parts by weight of the powder mixture of the adsorbent. The starch serves as an organic binder, Preferably, the polyethylene (PE) is included in an amount of 2 to 5 parts by weight per 100 parts by weight of the mixture, and the polyethylene (PE) is included in an amount of 1 to 3 parts by weight per 100 parts by weight of the powder mixture. On the other hand, carboxylmethylcellulose (CMC) can also be used for the same purpose as methylcellulose and has the same effect.

On the other hand, in the liquid mixture separately prepared from the solid mixture, the silica sol serves as an inorganic binder after firing, and when 30 wt% silica sol is used, it is contained in an amount of 4 to 25 wt% When the amount of the silica sol is less than 4% by weight based on the weight of the adsorbent composition, a carbon monoxide adsorbent having a weak crushing strength after firing is produced. When the amount exceeds 25% by weight based on the weight of the adsorbent composition, There is a problem that the carbon monoxide adsorbing ability per unit weight is lowered because it is incorporated into the carbon monoxide adsorbent in the form of SiO ₂ which is a substance which does not adsorb carbon monoxide.

On the other hand, the liquid mixture may further comprise glycerin. The glycerin is preferably contained in an amount of 0.5 to 5% by weight, based on the weight of the adsorbent composition, such that when the dough is mixed with the solid mixture, a dough of suitable viscosity suitable for use in an extruder is easily obtained When the glycerin is less than 0.5% by weight based on the weight of the adsorbent composition, the viscosity of the dough is low, so that when it is used in a compressor, the productivity may be lowered and continuous troubles such as raw material supply may occur. %, There is a problem that the extrusion molding becomes difficult due to an excessively high viscosity, or an excess amount of carbon remains after firing, the crushing strength of the adsorbent is lowered, and the cost of producing the adsorbent is increased by inefficient use of glycerin.

The polyethylene glycol (PEG) is preferably present in an amount of 0.5 to 5% by weight, based on the weight of the adsorbent composition, and the polyvinyl alcohol (PVA) is included in an amount of 0.5 to 5% .

On the other hand, in the present invention, water is preferably contained in an amount of 7 to 30% by weight based on the weight of the adsorbent composition, and when the water is less than 7% by weight based on the weight of the adsorbent composition, And when it exceeds 30% by weight based on the weight of the adsorbent composition, it is difficult to use it in a compressor because of too much kneading, and there is a problem of deformation of CuCl in the adsorbent or moisture removal The adsorbent performance and the manufacturing cost increase.

The liquid mixture may further contain ammonia water, and the ammonia water may further reduce the ammonia water. When ammonia water is used, 28 wt% ammonia water may be mixed into the liquid mixture in an amount of 1 to 10 wt% based on the weight of the adsorbent composition. If a different weight ratio of ammonia water is used, a weight ratio such that the content of ammonia components except moisture is the same can be used.

Here, the content of water refers to all the H ₂ O contained in the liquid mixture, which means the amount of water in the silica sol and the total amount of water contained in the ammonia water.

The step of preparing the adsorbent composition by mixing the solid mixture and the liquid mixture is preferably performed by mixing, kneading and aging for 3 to 20 hours. When the time is less than 3 hours, mixing may be insufficient, (Cu (I)) copper compound is excessively oxidized to a copper (Cu (II)) compound or a copper metal when the time exceeds 20 hours.

More specifically, the step of preparing the adsorbent composition includes spraying a liquid mixture while stirring the solid mixture, kneading the resultant mixture, further kneading the resultant mixture, and further forming a molding device such as extruding, milling, And then molding it using the mold.

Further, the method for producing a selective adsorbent of carbon monoxide according to the present invention may further comprise the step of extruding and drying the adsorbent composition following the step of preparing the adsorbent composition by mixing the solid mixture and the liquid mixture, And firing.

More preferably, the drying is performed at a temperature of 80 to 250 ° C in a nitrogen atmosphere or a vacuum atmosphere, and more preferably at a temperature of 120 to 200 ° C. If the drying temperature is lower than 80 ° C., excessive drying time is required or drying is not properly performed. If the drying temperature is higher than 250 ° C., pores may be generated in the adsorbent due to rapid evaporation of the remaining water, There is a problem that arises.

The drying method is not particularly limited, and may preferably be performed for 5 to 48 hours.

The firing is preferably performed at a temperature of 200 to 400 ° C in a nitrogen atmosphere or a vacuum atmosphere, and more preferably at a temperature of 250 to 350 ° C. When the calcination temperature is lower than 200 ° C, silica sol and bentonite-based clay do not react with siloxane bond and the crushing strength is lowered. When the calcination temperature is higher than 400 ° C, CuCl, which is the active site of the pellet- There is a problem that it is converted into metal. In order to enhance the adsorption property of the carbon monoxide adsorbent, it is more preferable to perform calcination at 250 to 300 ° C.

Furthermore, the calcined adsorbent composition may further be reduced, wherein the reduction comprises at least one of CO, H ₂ and N ₂ , and O ₂ In an atmosphere in which H ₂ is not contained in an atmosphere limited to 1 volume% or less, it is preferably performed at a temperature of 150 to 400 ° C., more preferably 200 to 300 ° C., and when H ₂ is contained It is preferable that the reaction is carried out at a temperature of 150 to 350 ° C, more preferably 200 to 250 ° C.

When the reduction temperature is lower than 150 ℃ is Cu (II) is in reducing conditions, including the H _2, if it exceeds 400 ℃ in reducing conditions that do not include, H ₂ has a problem that is not converted to Cu (I) 350 C, there is a problem that Cu (II) is reduced to Cu metal. In order to maximize the Cu (I) and to increase the dispersion degree and improve the performance of the CO adsorbent, it is more preferable that the reduction is performed at a temperature of 200 to 300 ° C.

According to another aspect of the present invention, there is provided a selective adsorbent of carbon monoxide, which is produced by the method for producing a selective adsorbent of carbon monoxide according to the present invention and has a specific surface area of 30 to 200 m ² / g.

According to another aspect of the present invention, there is provided a method for producing a powder mixture, comprising: mixing CuCl and Al ₂ O ₃ at a ratio of 20 to 50:50 to 80; Drying the powder mixture at 80 to 250 占 폚; Calcining the dried powder mixture at 200 to 400 캜; And reducing the calcined powder mixture. ≪ Desc / Clms Page number 5 >

At this time, the drying may be performed in a nitrogen atmosphere, and the reducing step may be CO or H ₂ , But is not limited thereto.

According to still another aspect of the present invention, CuCl and Al ₂ O ₃ is 20 to 50:50 to 80, and mixed at a ratio by weight, the selective adsorbent for carbon monoxide ratio of 10 or more the amount of adsorption of CO and CO ₂ available from 3 bar to 20 bar In particular, the selective adsorbent of carbon monoxide has a difference between adsorption amount at CO adsorption at 7 bar and adsorption amount at CO desorption at 0.5 bar of 2.5 mmol / g or more.

More specifically, the carbon monoxide selective adsorbent of the present invention to CuCl, Al ₂ O _3, comprises a clay, silica sol, and water, wherein the CuCl and Al ₂ O ₃ 20 to 50: 50 to 80 weight ratio of adsorbent compositions And has a specific surface area of 30 to 200 m ² / g.

The content of the carbon monoxide selective adsorbent of the present invention and the content of the carbon monoxide selective adsorbent are as described above in the process for producing the selective adsorbent of carbon monoxide.

That is, the adsorbent composition further comprises at least one of methyl cellulose (MC), starch and polyethylene (PE) as the solid mixture, and the liquid mixture comprises glycerol, polyethylene glycol (PEG) and polyvinyl alcohol It is preferable to further include at least one species selected from the group consisting of The clay is CuCl and Al ₂ O ₃ mixture is 3 to 20 per 100 parts by weight By weight.

Meanwhile, the adsorbent composition preferably contains silica sol in an amount of 4 to 25% by weight based on the weight of the adsorbent composition together with water, which is a weight ratio when 30 wt% silica sol is used, , A weight ratio of the silica sol components other than moisture is the same, and further, at least one liquid additive may be further included, for example, 0.5 to 5 wt%, based on the weight of the adsorbent composition, (PEG) based on the weight of the adsorbent composition, 0.5 to 5 wt% of polyvinyl alcohol (PVA) based on the weight of the adsorbent composition, and the like.

Meanwhile, the adsorbent of the present invention preferably has a carbon content of 0.5 to 7 wt% in the pellet-type carbon monoxide adsorbent after sintering.

The adsorbent of the present invention is a selective adsorbent of carbon monoxide which exhibits low carbon monoxide adsorption characteristics at a specific temperature below a certain pressure and exhibits rapid CO adsorption at a specific pressure of a specific temperature.

More particularly, FIG. 5 (a) and Figure 5 (b) first With reference to th figure, the commercial adsorbent of Comparative Production with CuCl-Al ₂ O ₃ adsorbent (a) prepared in Preparation Example 1, Example 2 (b) of It can be seen that the CO adsorption amount at 25 ° C shows a sharp increase between 1 and 2 bar in the case of Production Example 1 while the CO adsorption amount of the commercial adsorbent of Comparative Production Example 2 shows a gentle curve to 1 to 5 bar You can see that you draw.

The selective adsorbent of the carbon monoxide produced by the present invention is improved in selectivity and adsorption / desorption performance for the carbon monoxide during the selective adsorption / separation of carbon monoxide in the mixed gas by applying pressure swing adsorption (PSA) Can be used to effectively separate and recover or remove the carbon monoxide component.

Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Example

1. Preparation of adsorbent

Manufacturing example  One

Alumina and CuCl having an average particle diameter of 2 μm as a support were dried at 150 ° C. or less to remove moisture and were pulverized by mixing at a ratio of 70% by weight of alumina and 30% by weight of CuCl for 5 hours or more and pulverized at 80 to 150 ° C. Dried, heated to 300 ° C, and then reduced in a 5% CO or H ₂ atmosphere at 300 ° C to prepare CuCl-Al ₂ O ₃ .

Comparative Manufacturing Example  One

Alumina supported was calcined at 900 캜, and CuCl was mixed and calcined at a ratio of 70% by weight of alumina and 30% by weight of CuCl, dried at 110 캜 in a nitrogen atmosphere under the same conditions as Comparative Production Example 1, Thereafter, CuCl-sintered Al ₂ O ₃ was prepared by reducing at 300 ° C in 5% CO or H ₂ atmosphere.

Comparative Manufacturing Example  2

A zeolite-based HX-CO adsorbent from China P was used.

Comparative Manufacturing Example  3

The support zeolite 5A was dried at 110 DEG C to remove moisture and CuCl was mixed with 70 wt% of zeolite 5A and 30 wt% of CuCl and pulverized and dried at 110 DEG C under nitrogen atmosphere under the same conditions as Comparative Production Example 1 , Followed by calcination at 300 ° C, followed by reduction in a 5% CO or H ₂ atmosphere at 300 ° C to prepare CuCl-5A zeolite.

Example  And Comparative Example

Alumina and CuCl having an average particle size of 2 μm were dried at a temperature of 150 ° C. or lower and were pulverized by mixing at a ratio of 70 wt% of alumina and 30 wt% of CuCl for 1 hour or longer. The solid mixture shown in the following Table 1 was first milled in a ribbon mixer Hour, and the liquid mixture and the solid mixture were mixed and kneaded under the conditions shown in Table 1 below.

The liquid mixture was mixed using a sprayer while operating the ribbon mixer, and then kneaded for 30 minutes or more. Thereafter, kneading was performed by using an extruder several times to make a dough and compression molded.

Further, in order to make the adsorbent uniform in size, a molder having a plurality of 2-pit holes in front of the extruder is installed, and a cutting knife is installed on the geodemother, and the molding is performed at regular intervals.

The pellet adsorbent is dried at a temperature of 110 to 160 ° C. under nitrogen atmosphere or in a vacuum state by a vacuum pump and calcined at a temperature of 200 to 350 ° C. in a nitrogen atmosphere or a vacuum state to obtain a pellet The pellet CO ₂ adsorbent based on CuCl-Al ₂ O ₃ was prepared by reduction in -70% CO or H ₂ atmosphere.

Solid mixture Liquid mixture No. PWD clay Starch MC SS Gly PEG PVA WTR AW One Comparative Example 1 80.0 - 2.5 - 4.0 22.0 - 2 Comparative Example 2 80.0 - 5.0 - 4.0 22.0 - 3 Comparative Example 3 80.0 - - 0.6 - 4.0 22.0 - 4 Comparative Example 4 80.0 - - 1.2 - 4.0 22.0 - 5 Comparative Example 5 80.0 3.0 - 1.2 - 4.0 22.0 - 6 Comparative Example 6 80.0 5.0 - 1.2 - 4.0 22.0 - 7 Comparative Example 7 80.0 10.0 - 0.6 - 4.0 22.0 - 8 Comparative Example 8 80.0 15.0 - 0.6 - 4.0 23.0 - 9 Example 1 80.0 6.0 - - 5.0 - 19.0 - 10 Example 2 80.0 6.0 - - 10.0 - 15.0 - 11 Example 3 80.0 6.0 - - 15.0 - 12.0 - 12 Example 4 80.0 3.0 - - 15.0 - 12.0 - 13 Example 5 80.0 6.0 - - 20.0 - 9.0 - 14 Example 6 80.0 6.0 - - 20.0 - 9.0 - 15 Example 7 80.0 8.0 - - 10.0 - 16.0 - 16 Example 8 80.0 15.0 - - 15.0 - 13.0 - 17 Example 9 80.0 8.0 - - 20.0 - 10.0 - 18 Example 10 80.0 7.0 - 1.5 15.0 - 13.0 - 19 Example 11 80.0 7.0 0.6 15.0 - 13.0 - 20 Example 12 80.0 7.0 3.0 0.6 15.0 - 13.0 - 21 Example 13 80.0 7.0 3.0 15.0 - 13.0 - 22 Example 14 80.0 7.0 - 1.5 15.0 2.5 13.0 3.0 23 Example 15 80.0 7.0 - 1.5 15.0 2.5 11.0 6.0 24 Example 16 80.0 7.0 - 1.5 15.0 2.5 15.0 - 25 Example 17 80.0 5.0 - 1.5 15.0 5.0 15.0 - 26 Example 18 80.0 10.0 - 0.7 20.0 2.5 15.0 - 27 Example 19 80.0 7.0 - 1.5 20.0 2.5 15.0 - 28 Example 20 80.0 3.0 - 1.5 20.0 5.0 15.0 - 29 Example 21 80.0 7.0 - 1.5 20.0 5.0 15.0 - 30 Example 22 80.0 7.0 - 1.5 20.0 5.0 3.0 15.0 - 31 Example 23 80.0 7.0 - 1.5 20.0 5.0 3.0 15.0 -

* The values shown in Table 1 indicate the weight ratio of the other components to the PWD 80 parts by weight. In Table 1, No. 1-18 used PWD to ~ 0.1 kg, No. 9-21 used PWD ~ 1 kg, No. 22 ~ 31 PWD ~ 30 kg was used.

- PWD: CuCl-Al ₂ O ₃ powder mixture

- SS: 30wt% silica sol (remaining 70wt% moisture)

- MC: methyl cellulose

- Gly: glycerin

- WTR: Water

- AW: 28% Ammonia water (remaining 78wt% moisture)

- PEG: Polyethylene glycol

- PVA: polyvinyl alcohol

Experiments 1 to 29 shown in Table 1 above were conducted in order to capture the condition of the moldable adsorbent composition including the condition of dough, which is a key process for pelletizing normally.

In Comparative Examples 1 to 4, kneading was performed without using a bentonite-based clay serving as an inorganic binder. As a result, it was not made into a viscous dough that could be used in an extruder or the like, and when the water content was low, When the amount of water becomes large, it becomes like flowing water, and it becomes a thin dough like a fluid having a low viscosity and can not be used.

In Comparative Examples 5 to 8, the kneaded state of the bentonite-based clay was added and the kneaded state appeared to be a compressible viscosity. However, the strength of the pellet adsorbent after drying and firing after pelletization was broken by hand, We could see weakness.

Example  24

(20 wt% (average particle size: 2 μm) and 80 wt% (average particle size: 100 μm)) and CuCl were dried at 150 ° C. or lower and CuCl was mixed with 70 wt% of alumina and CuCl 30% by weight. The solid components were first mixed in a ribbon mixer for at least 1 hour, and the liquid and solid mixture were mixed and kneaded under the following conditions. Mixing of the liquid mixture was carried out using a sprayer while operating the ribbon mixer, followed by kneading for 30 minutes or more. Thereafter, kneading was performed by using an extruder several times to make a dough and compression molded. In order to make the adsorbent uniform, a molder having a plurality of 2-pit holes was installed in front of the extruder, and a cutting knife was installed in the geared motor to cut the mold at regular intervals. The pelletized adsorbent is dried at a temperature of 110 to 160 ° C under nitrogen atmosphere or in a vacuum state by a vacuum pump, and is calcined at a temperature of 200 to 350 ° C in a nitrogen atmosphere or a vacuum state at a temperature of 200 to 350 ° C The pellet CO ₂ adsorbent based on CuCl-Al ₂ O ₃ was prepared by reducing in 5-70% CO or H ₂ atmosphere.

Comparative Example  9

The average particle size of support 2 mu m, gamma alumina and CuCl were dried at 150 DEG C or lower, CuCl was mixed and calcined at a ratio of 70 wt% of alumina and 30 wt% of CuCl, and HDPE (high density polyethylene ) 10 wt% was added and the remaining conditions were the same, the liquid and solid mixture were mixed and kneaded, followed by compression molding. More specifically, the solid mixture components were first mixed in a ribbon mixer for at least 1 hour, and the liquid and solid mixture were mixed and kneaded under the following conditions. Mixing of the liquid raw materials was carried out using a sprayer while operating the ribbon mixer, and then kneaded for 30 minutes or more. Thereafter, kneading was performed by using an extruder several times to make a dough and compression molded. In order to make the adsorbent uniform, a molder having a plurality of 2-pit holes was installed in front of the extruder, and a cutting knife was installed in the geared motor to cut the mold at regular intervals. The pelletized adsorbent is dried at a temperature of 110 to 160 ° C under nitrogen atmosphere or in a vacuum state by a vacuum pump, and is calcined at a temperature of 200 to 350 ° C in a nitrogen atmosphere or a vacuum state at a temperature of 200 to 350 ° C The pellet CO ₂ adsorbent based on CuCl-Al ₂ O ₃ was prepared by reducing in 5-70% CO or H ₂ atmosphere.

Comparative Example  10

Alumina and CuCl having an average particle size of 30 mu m were dried at 150 DEG C or less to remove moisture and CuCl was mixed with 70 wt% of alumina and 30 wt% of CuCl, followed by pulverization. The conditions of Example 21 (No. 29) , A liquid and a solid mixture were mixed and kneaded, compression molded, dried at 110 ° C under a nitrogen atmosphere, and fired at 300 ° C to produce pellet CuCl-Al ₂ O ₃ .

Comparative Example  11

Alumina and CuCl having an average particle size of 100 μm supported were dried at 150 ° C. or below to remove moisture and CuCl was mixed with 70% by weight of alumina and 30% by weight of CuCl and pulverized. The conditions of Example 21 (No. 29) Similarly, liquid and solid additives were mixed and kneaded, compression molded, dried at 110 ° C in a nitrogen atmosphere, and fired at 300 ° C to produce pellet CuCl-Al ₂ O ₃ .

2. Dough condition and time and heat treatment according to mixing of adsorbent powder mixture and liquid additive CuCl Change confirmation experiment

(1) dough condition

In Comparative Examples 1 to 4, kneading was performed without using a bentonite-based clay serving as an inorganic binder. As a result, kneading was not made as a kneading dough which could be used in an extruder, etc. When the water content was low, When it becomes too much, it becomes like a running water and it can not be used as a thin dough like a fluid with a low viscosity. On the other hand, in Comparative Examples 5 to 8, after the pelletizing operation, the strength of the pellet adsorbent after drying and firing broke even when lightly pressed by hand, indicating that the strength was very weak.

(2) Changes in Cu phase when water is added to CuCl and alumina mixture

The use of water in the process of producing the adsorbent is unavoidable and it is difficult to use water in the course of mixing with water in the case where a cuprous (Cu (I)) compound (such as CuCl) is oxidized / reduced to a copper (Cu The change of CuCl was confirmed by XRD when CuCl and alumina were mixed and water was added to confirm the development.

2 (a) (alumina and CuCl were dried at 150 ° C or less to remove moisture, and the mixture was pulverized by mixing at 70% by weight of alumina and 30% by weight of CuCl for 5 hours or more. (Cu (II)) compound (Cu (II)) after mixing with water, as can be seen from the result of the kneaded sample to be 20 wt% of the total weight of the copper (Cu (II)) compound (Cu ₂ OH ₂ Cl ₂ , Cu ₂ OH ₃ Cl, etc.) after 20 hours of mixing was changed to the form of Cu ₂ Cl ₂ OH ₂ , Cu ₂ ClOH ₃ , ) XDR peak. That is, _x in Cu _x (OH) _y Cl _z in FIG. 2 (a) may be 2, y may be 3 or 2, and z may be 1 or 2.

On the other hand, in case of drying (vacuum heat treatment) before 20 hours, 80% or more of Cu (II) is converted to Cu (I) by referring to the peak intensity of XRD, , It was found that more than 30% of Cu (II) remained. This is the ratio of two of Cu (II) compound in the case when the Cu (II) phase of Cu and Cl as a Cu ₂ Cl ₂ OH ratio of 1 is easy to switch, but that the long contact with water such as Cu ₂ ClOH ₃ Cu and Cl Because it can not be converted to CuCl (the ratio of Cu to Cl is 1). From these results, it was confirmed that the contact time of water to the mixture of CuCl and alumina is preferably 3 hours to 20 hours.

(3) Identification of changes in the adsorbent manufacturing process

In the manufacturing process of Example 21 (No. 29), the change of the phase of the copper compound was confirmed by XRD according to processes such as drying, calcination, reduction and the like. CuCl was changed to Cu ₂ Cl _n (OH) _m as it was in contact with water and air in the mixing with the liquid additive containing water and in the dough.

2CuCl nH ₂ O + O ₂ ? Cu ₂ Cl _n (OH) _m (n = 1 or 2, m = 2 or 3)

Furthermore, changing the drying phase and in the following sintering process Cu ₂ Cl ₂ O, it was confirmed that the change in the reduction process in the CuCl.

Cu ₂ Cl _n (OH) _m → Cu ₂ Cl ₂ O (drying / calcination) → CuCl (reduction treatment)

On the other hand, FIG. 2 (b) shows the case of drying in air, heat treatment in a vacuum / nitrogen atmosphere, and reduction treatment after firing a CO atmosphere in the case of Example 21 (No. 29) It is confirmed. As shown in FIG. 2 (b), CuCl was converted into Cu (II) (Cu ₂ Cl _n (OH) _m ) when it was dried in the air and then Cu ₂ Cl ₂ O And converted to CuCl by heat treatment in CO atmosphere.

As can be seen from FIG. 2 (c) (the pre-reduction pellet carbon monoxide adsorbent prepared in Example 21 (No. 29)) to evaluate the appropriate heat treatment temperature in the heat treatment in the reducing atmosphere, 300, 350, and 400 ℃, respectively. As a result, it was confirmed by XRD that the Cu metal peak was not observed at 350 ℃ or less, and the peak of Cu metal was considerably grown at 400 ℃ reduction annealing. The Cu metal size judged to be the XRD peak is judged to be microsize. Since CuCl mainly determines the amount of CO adsorption, micro-sized Cu metal growth has a problem that CO adsorption amount is decreased although it can selectively increase CO adsorption amount.

3. Experiments to confirm adsorption characteristics of adsorbents

The adsorption characteristics of the CuCl-Al ₂ O ₃ adsorbent synthesized in Production Example 1 and the commercial adsorbent of Comparative Production Example 2 to CO, CO ₂ , N ₂ and CH ₄ were evaluated and shown in FIG.

As a result, as shown in FIG. 5, in the case of the CuCl-Al ₂ O ₃ adsorbent synthesized in Production Example 1, as shown in FIG. 5 (a) 2 higher than the commercial adsorbent (3.2 mmol / g).

In the case of the CuCl-Al ₂ O ₃ adsorbent synthesized in Production Example 1, as shown in FIG. 5 (a), in a process of adsorption-desorption while swinging pressure at a high pressure and a low pressure as in a PSA (pressure swing adsorption) The difference in adsorption amount between the adsorption amount at 7 bar and the adsorption amount at 0.5 bar during the CO adsorption (~ 2.0 mmol / g) was measured to be higher than ~ 3.5 mmol / g in the comparative example 2. This means that a very low vacuum level is required for adsorption / desorption of working CO in the adsorbent to desorb CuCl-Al ₂ O ₃ adsorbent.

In particular, as can be seen from FIG. 5, the adsorption amounts of CO ₂ , N ₂ and CH ₄ are much lower than those of the commercial adsorbent of Comparative Production Example 2 in the case of the CuCl-Al ₂ O ₃ adsorbent synthesized in Production Example 1 As a result, it was confirmed that the CO selectivity was very high.

In order to determine the more precise results, it showed the adsorption amount of CO and CO ₂ of a commercial adsorbent for the synthesis compared to the CuCl-Al ₂ O ₃ adsorbent Preparation 2 ratio, i.e., selectivity in Preparation Example 1 in Fig. 6 by calculating As can be seen in the case of Production Example 1 shown in FIG. 6 (a) and the case of Comparative Production Example 2 shown in FIG. 6 (b), when the adsorption amount ratio The CuCl-Al ₂ O ₃ adsorbent synthesized in Production Example 1 is about 16 but the commercial adsorbent of Comparative Production Example 2 is 3 or less.

4. Crushing strength (crushing maximum load)

As in Examples 1 to 9, the solid mixture was added to the clay, The addition of silica sol improved the molding strength (crush strength, crushing maximum load) and enabled the production of pellet adsorbents when silica sol was added in an amount of 4 to 20 wt% based on the weight of the adsorbent composition. In this case, the crushing strength was 0.3-0.5 kg / cm ² (maximum crushing load: 2-3 kgf), and the higher the content of silica sol, the higher the strength.

Further, even when pelletization is performed by adding clay to the solid mixture and silica sol to the liquid mixture and adding methyl cellulose and / or starch as an emulsifier to increase the mixing state of the dough, the extrusion in the compressor is performed smoothly , And the crushing strength was 0.5 kg / cm ² (maximum fracture load: ~ 3 kgf).

When pelletization is carried out by adding clay and methylcellulose to the solid mixture and silica sol to the liquid mixture and adding glycerol to increase the fluidity and viscosity of the dough for the purpose of improving moldability and ease of operation, The fracture strength was ~ 2 kg / cm ² (maximum fracture load: ~ 5 kgf).

On the other hand, the fracture strength (maximum fracture load) of the pellet carbon monoxide adsorbent according to the particle size of the alumina serving as a support was measured, and when using alumina having an average particle size of 20 μm or more, it was measured to be very low as ~ 1.5 kgf and alumina In case of ~ 4 kgf or more appeared. In addition, when pellets were made by mixing 20 wt% of 1-2 μm alumina particles with 100 μm of alumina, ~ 3 kgf or more appeared.

On the other hand, when the carbon content in the pellet carbon monoxide adsorbent after calcination was increased by increasing the HDPE content as in the sample of Comparative Example 9, which confirmed the effect of the carbon content in the pellet carbon monoxide adsorbent after firing on the crushing strength, the crushing strength ) Was measured to be ~ 1.5 kgf or very low. As shown in the third photograph of FIG. 4 (b), it can be seen that the higher the residual carbon content, the darker the color becomes, and when the residual carbon content is more than 7 wt%, the crushing intensity decreases to black and the crushing strength decreases. In the second photograph of FIG. 4 (b), when the residual carbon content is less than 7 wt%, CuCl reacts with moisture and oxygen in the atmosphere to delay the change to Cu (II), indicating that the pellet carbon monoxide adsorbent (the color of Cu _x (OH) _y Cl _z ) as compared with that of the light blue (see the first photograph of Fig. 2 (b)).

5. CuCl  Depending on the content CO  Adsorption characterization experiment

The relative CO adsorption amount according to the CuCl content was evaluated and shown in FIG. To confirm the relative adsorption amount of CO, the same amount of adsorbent is put into an empty vessel, and a valve connected to another vessel filled with carbon monoxide of 5 bar or more is opened to allow the pressure to be lowered And the relative CO adsorption amount was measured.

All adsorption experiments were performed under isothermal conditions (~ 25 ° C).

FIG. 9 shows the results of the relative CO adsorption amount according to the weight ratio of CuCl synthesized in the same manner as in Production Example 1. FIG. For a-Al ₂ O ₃ adsorbent synthetic CuCl by the present invention, the Cu content was confirmed that high amount of CO adsorbed in the 20 to 50% by weight.

6. Depending on the type of support and the degree of firing CO  Adsorption characterization experiment

The relative CO adsorption amount of the adsorbent prepared by Comparative Production Example 3, Production Example 1 and Comparative Production Example 1 was evaluated. In order to confirm the relative adsorption amount of CO, the same amount of adsorbent was placed in an empty vessel, Valves connected to other vessels filled with more than 5 bar carbon monoxide were opened and the relative CO adsorption amount was measured using the pressure drop for a period of time until the equilibrium was reached.

All adsorption experiments were performed under isothermal conditions (~ 25 ° C). As a result, as can be seen from FIG. 10, it was confirmed that Comparative Production Example 3 and Comparative Production Example 1 showed lower CO adsorption amount than Production Example 1.

7. Experiment to confirm reduction temperature of adsorbent

FIG. 3 shows the weight loss of CuCl in N ₂ , CO and H ₂ gas atmospheres according to the temperature rise as a TG graph.

As shown in FIG. 3, it was confirmed that the decomposition temperature of CuCl was 350 ° C for hydrogen, 450 ° C for nitrogen, and 450 ° C for CO according to the gas atmosphere, considering this, if not containing the H ₂ si reduction of the adsorbent of the present invention is preferably carried out at 150 to 400 ℃ temperature, more preferably performed at 200 to 300 ℃ and case comprise a H ₂ from 150 to It is preferable that the reaction is carried out at a temperature of 350 DEG C, more preferably 200 DEG C to 250 DEG C.

8. Adsorbent Absorption / desorption  And mixed gas CO  Adsorption amount confirmation experiment

(1) Confirmation of adsorption / desorption ability of adsorbent

Evaluation of adsorption / desorption characteristics in which CuCl-Al ₂ O ₃ adsorbent synthesized in Production Example 1 and adsorbent of Comparative Example 2 were adsorbed on pure CO gas at 7 bar and desorbed at 0.5 bar (adsorption / desorption temperature: 50 < 0 > C), and the results are shown in the graph of Fig.

As can be found at 7, in the case of desorption at 0.5bar case of the Al ₂ O ₃ adsorbent synthetic-CuCl in Production Example 1 (Fig. 7 (a)) Comparative Production Example 2 commercial adsorbent (Fig. 7 (b) ) Than that of the control group.

(2) Confirmation of CO adsorption amount in the mixed gas

The CuCl-Al ₂ O ₃ adsorbent synthesized in Production Example 1 and the commercial adsorbent of Comparative Production Example 2 were adsorbed at 7 bar (CO / CO ₂ = 50-75 / 25-50) mixed with CO and CO ₂ The remaining amount of gas was analyzed to analyze the adsorption amount of CO. The adsorption temperature was 30 캜. The results are shown in the graph of Fig.

9, in the case of the CuCl-Al ₂ O ₃ adsorbent synthesized in Production Example 1 under the condition of a mixed gas of CO: CO ₂ = 3: 1 to 1: 1, as compared with the commercial adsorbent of Comparative Production Example 2 It was confirmed that the amount of CO adsorbed in the mixed gas was doubled.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be obvious to those of ordinary skill in the art.

Claims (26)

After drying and milling the CuCl and Al ₂ O ₃ comprising: mixing to prepare a powder mixture to the adsorbent;
Further adding a solid additive including clay to the adsorbent powder mixture to prepare a solid mixture;
Preparing a liquid mixture comprising silica sol and water;
Mixing the solid mixture and the liquid mixture to produce an adsorbent composition;
Extruding and drying the adsorbent composition;
Calcining the dried adsorbent composition; And
Reducing the calcined adsorbent composition
≪ / RTI >
2. The method of claim 1, wherein CuCl, and Al ₂ O ₃ is a method of manufacturing a selective adsorbent for carbon monoxide which is mixed with 20 to 50: 50 to 80 weight ratio.
The method of claim 1, wherein the CuCl and Al ₂ O ₃ are independently mixed after drying and crushing, or are mixed together after drying and crushing.
The method of claim 1, wherein the solid mixture further comprises at least one of methyl cellulose (MC), starch and polyethylene (PE), the liquid mixture comprising glycerol, polyethylene glycol (PEG), and polyvinyl alcohol (PVA) ≪ / RTI > further comprising at least one member selected from the group consisting of carbon monoxide, carbon monoxide and carbon monoxide.
The method of claim 1, wherein the clay is included in an amount of 3 to 20 parts by weight per 100 parts by weight of the adsorbent powder mixture.
The method of claim 1, wherein the silica sol is included in an amount of from 4 to 25% by weight, based on the weight of the adsorbent composition.
5. The method of claim 4, wherein the methylcellulose is included in an amount of 0.5 to 3 parts by weight per 100 parts by weight of the adsorbent powder mixture.
The method of claim 1, wherein the water is included in an amount of 7 to 30 weight percent based on the weight of the adsorbent composition.
2. The method of claim 1, wherein the liquid mixture further comprises ammonia water in an amount of 1 to 10 weight percent based on the weight of the adsorbent composition.
The method of claim 1, wherein the step of mixing the solid mixture with the liquid mixture to produce the adsorbent composition is carried out by mixing and kneading for 3 to 20 hours.
delete The method of claim 1, wherein the drying is performed at a temperature of 80 to 250 ° C in a nitrogen atmosphere or a vacuum atmosphere.
The method of claim 1, wherein the calcination is performed at a temperature of 200 to 400 캜 in a nitrogen atmosphere or a vacuum atmosphere.
delete The method of claim 1, wherein the reduction of the selective adsorbent for carbon monoxide, is carried out in CO, H ₂ and N ₂ of containing one or more ingredients and, O ₂ 150 of the atmosphere is limited to not more than 1% by volume to 400 ℃ temperature Gt;
A selective adsorbent of carbon monoxide, produced by the process of any one of claims 1 to 10, 12, 13 and 15, having a specific surface area of 30 to 200 m ² / g.
A mixture of CuCl, and Al ₂ O ₃ from 20 to 50:50 to 80 by weight to prepare a powder mixture;
Drying the powder mixture at 80 to 250 占 폚;
Calcining the dried powder mixture at 200 to 400 캜; And
Reducing the calcined powder mixture
≪ / RTI >
delete delete CuCl, Al ₂ O _3, comprises a clay, silica sol, and water, wherein the CuCl and Al ₂ O ₃ were prepared by the adsorbent composition of 20 to 50: 50 to 80 weight ratio, a specific surface area of 30 to 200m ² / g Selective adsorbent of carbon monoxide.
21. The adsorbent composition of claim 20, wherein the adsorbent composition comprises at least one of a solid mixture and a liquid mixture selected from the group consisting of starch, polyethylene glycol (PEG), polyvinyl alcohol (PVA) and polyethylene (PE) Lt; / RTI >
21. The method of claim 20, wherein the clay adsorbent is selective for carbon monoxide, contained in an amount of CuCl and Al ₂ O ₃ mixture of 100 parts by weight of 3 to 20 parts by weight of sugar.
21. The selective adsorbent of claim 20, wherein the adsorbent composition comprises silica sol in an amount of from 4 to 25% by weight, based on the weight of the adsorbent composition.
21. The selective adsorbent of claim 20, wherein the adsorbent composition comprises water in an amount of from 7 to 20% by weight, based on the weight of the adsorbent composition.
21. The method of claim 20, wherein the sorbent composition comprises an adsorbent selective for carbon monoxide further comprises a cellulose CuCl and Al ₂ O ₃ mixture of 100 parts by weight from 0.5 to 3 parts by weight per part.
21. The selective adsorbent of claim 20, wherein the adsorbent has a carbon content in the pelletized carbon monoxide adsorbent after sintering of 0.5 to 7 wt%.

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