KR20210144169A - Nox adsorbent manufacturing method - Google Patents

Abstract

Disclosed in the present invention is a method for preparing a NO_x absorbent capable of overcoming a limitation of a conventional NO_x removal means. The method for preparing a NO_x absorbent comprises: (S10) a step of producing a preparation solution containing manganese dioxide particles, prepared by titrating potassium acetate (Mn(CH_3COO)_2) into a potassium permanganate (KMnO_4) solution, potassium acetate (CH_3COOK) and acetic acid (CH_3COOH); (S20) a step of removing remaining ions from the manganese dioxide particles, dispersing the manganese dioxide particles in distilled water, and performing solid-liquid separation to wash the manganese dioxide particles; (S30) a step of drying the manganese dioxide particles in a wet cake state in a drying process at a preset temperature and time; (S40) a step of crushing the manganese dioxide particles to produce adsorbent powder made of manganese dioxide particles; (S50) a step of stirring an organic-inorganic binder in the adsorbent powder to produce stirred powder; (S60) a step of forming the stirred powder into a NO_x adsorbent by adding moisture to the stirred powder and then extruding the same; and (S70) a step of drying the NO_x absorbent to prepare a final NO_x absorbent.

Description

NOx adsorbent manufacturing method

The present invention relates to a method for manufacturing a NOx adsorbent, and more particularly, to a method for manufacturing a NOx adsorbent capable of improving the limitations of conventional NOx removal means.

The electronics industry is an industry that manufactures devices that apply the motion characteristics of electrons or parts or materials mainly used here. And it means an industry for producing electronic components such as household devices such as video and sound devices and semiconductors/other electronic components.

In the process of the electronics industry, nitrogen oxide (hereinafter referred to as NOx), which is an air pollutant, is generated in the process of manufacturing devices, parts, or materials, and there is a problem that NOx may be discharged at a high concentration.

In addition, as the scrubber uses high temperature and high energy to remove the gas that is hardly decomposable, there is a problem in that a high concentration of NOx is inevitably discharged from the rear end of the scrubber.

Accordingly, in the electronics industry and scrubbers, means for removing high concentrations of NOx must be essential.

As a means for removing NOx, technologies applicable to general industries such as flue gas recirculation, multi-stage combustion, SCR, SNCR, and solution absorption are being adopted.

However, the NOx removal means has a problem in that it is difficult to actually apply due to reasons such as structural limitations and restrictions on FAB import of chemicals.

Republic of Korea Patent Publication No. 10-2012003 Japanese Patent Laid-Open No. 2000-521306

The present invention has been devised to solve the above problems, and in order to improve the structural limitations of the conventional NOx removal means, etc., a method of manufacturing a manganese dioxide particle-based NOx adsorbent produced by titration of manganese acetate with a solution of potassium permanganate. It is intended to provide

In addition, the present invention is to provide a method for preparing a manganese dioxide particle-based NOx adsorbent produced by titrating manganese acetate to a solution of potassium permanganate to produce a preparation solution, and then further titrating copper acetate or copper nitrate to the preparation solution. There is this.

And in the present invention, potassium hydroxide is further titrated to the production solution produced by titrating manganese acetate and copper nitrate to a solution of potassium permanganate, and after stirring the production solution, copper hydroxide is co-precipitated upon completion of stirring. An object of the present invention is to provide a method for preparing a NOx adsorbent based on manganese dioxide particles produced by

However, the technical problems to be achieved in the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned are clearly to those of ordinary skill in the art to which the present invention belongs from the description below. can be understood

As a technical method for achieving the above object, in the NOx adsorbent manufacturing method of the present invention, the particle maker 10 titrates manganese acetate (Mn(CH ₃ COO) ₂ ) to _{a solution of potassium permanganate (KMnO 4 )} Manganese dioxide (MnO ₂ ) and particles, and residual ions potassium acetate (CH ₃ COOK) and acetic acid (CH ₃ COOH) to generate a preparation solution containing (S10); After the washing machine 20 removes the residual ions from the manganese dioxide particles by solid-liquid separation, the manganese dioxide particles are dispersed in distilled water, and solid-liquid separation is performed again to remove the remaining residual ions by washing the manganese dioxide particles (S20); Step (S30) of drying, by the first dryer 30, the manganese dioxide particles in a wet cake state in a drying process at a preset temperature and time by the washing process; The crusher 40 crushes the dried manganese dioxide particles by a drying process to generate an adsorbent powder composed of manganese dioxide particles of a predetermined size (S40); The stirrer 50 stirs the organic-inorganic binder of a predetermined content in the adsorbent powder to generate a stirred powder (S50); The extruder 60 adds moisture to the stirred powder and then extrudes it to mold the stirred powder into a NOx adsorbent (S60); and a second dryer 70 drying the NOx adsorbent in a drying process at a preset temperature and time to prepare a final NOx adsorbent (S70).

In addition, the particle maker 10 may set the molar ratio of potassium permanganate and manganese acetate to 0 to 0.6:1.

And the particle maker 10 may produce manganese dioxide particles by further titrating _{copper acetate (Cu(CH 3} COO) ₂ ) or copper nitrate (Cu(NO ₃ ) _{2 ) in the preparation solution.}

In addition, the particle maker 10 may titrate copper acetate to the production solution by 10 to 15 wt% of the production solution.

And the particle maker 10 titrates copper nitrate with manganese acetate to a solution of potassium permanganate to produce a preparation solution, further titrates potassium hydroxide (KOH) to the preparation solution, and after stirring the preparation solution, copper hydroxide (Cu) (OH) ₂ ) can be co-precipitated to produce manganese dioxide particles.

In addition, the particle maker 10 may titrate copper nitrate to a solution of potassium permanganate by 12 to 20 wt% of the production solution.

And the particle maker 10 may titrate potassium hydroxide to the preparation solution so that the pH of the preparation solution becomes pH 10 or less.

In addition, the washer 20 sets the volume ratio of the manganese dioxide particles to the distilled water to 1.6:2, and the washing process may be performed once to prevent dissolution of surface OH functional groups of the NOx adsorbent while removing residual ions. .

And the first dryer 30 can dry the manganese dioxide particles in a wet cake state at 100° C. or more for 20 hours or more.

In addition, the crusher 40 may crush the dried manganese dioxide particles to 1 to 1.4 mm.

And the stirrer 50, the content of the organic-inorganic binder may be set to 1 to 3%.

In addition, the second dryer 70 can dry the NOx adsorbent at 100° C. or higher for 20 hours or more.

According to the present invention, it is possible to manufacture a manganese dioxide particle-based NOx adsorbent with improved adsorption performance of the conventional NOx adsorbent.

However, the effects obtainable in the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those of ordinary skill in the art to which the present invention belongs from the following description. will be able

1 is a block diagram showing the configuration of an apparatus for producing a NOx adsorbent of the present invention.
2 is a flow chart showing the process of the NOx adsorbent manufacturing method according to the first manufacturing process of manganese dioxide particles.
3 is a flowchart of the manganese dioxide particle generation step of the first manganese dioxide particle manufacturing process.
4 is a flow chart of the manganese dioxide particle washing step of the first manganese dioxide particle manufacturing process.
5 is a flowchart of the manganese dioxide particle generation step of the second manganese dioxide particle manufacturing process.
6 is a graph comparing the adsorption performance of the NOx adsorbent in the manufacturing process of the second manganese dioxide particle and the conventional adsorbent.
7 is a flowchart of the manganese dioxide particle generation step of the third manganese dioxide particle manufacturing process.
8 is a graph comparing the adsorption performance of the NOx adsorbent according to whether or not copper hydroxide co-precipitation.
9 is a graph comparing adsorption performance between NOx adsorbents according to the number of washings.
10 is a graph comparing adsorption performance between NOx adsorbents according to copper content.
11 is a graph comparing adsorption performance between NOx adsorbents according to an organic-inorganic binder addition content.
12 is a graph comparing adsorption performance between NOx adsorbents according to whether water is injected or not.
13 is a graph comparing the adsorption performance of the NOx adsorbent in the manufacturing process of the third manganese dioxide particle and the conventional adsorbent.

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings. DETAILED DESCRIPTION The detailed description set forth below in conjunction with the appended drawings is intended to describe exemplary embodiments of the present invention and is not intended to represent the only embodiments in which the present invention may be practiced. The following detailed description includes specific details in order to provide a thorough understanding of the present invention. However, one of ordinary skill in the art to which the present invention pertains will recognize that the present invention may be practiced without these specific details. In addition, throughout the specification, when a part is said to "comprising or including" a certain component, it does not exclude other components, but may further include other components unless otherwise stated. means that In addition, in the description of the embodiments of the present invention, if it is determined that a detailed description of a well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to intentions or customs of users and operators. Therefore, the definition should be made based on the content throughout this specification.

NOx adsorbent manufacturing device

Hereinafter, the NOx adsorbent manufacturing apparatus 1 of the preferred embodiment will be described in detail with reference to FIG. 1 .

Referring to Figure 1, the NOx adsorbent manufacturing apparatus 1 of the preferred embodiment is a particle maker 10, a washing machine 20, a first dryer 30, a crusher 40, a stirrer 50, an extruder 60 and a second dryer 70 .

The particle maker 10 generates a preparation solution by titrating manganese acetate (Mn(CH ₃ COO) _{2 ) with a solution of potassium permanganate (KMnO 4} ) in order to generate manganese dioxide particles constituting the NOx adsorbent.

In the process of generating the preparation solution, potassium permanganate and manganese acetate cause an oxidation reaction in the preparation solution by titration of manganese acetate, and in the preparation solution, potassium acetate (CH ₃ COOK) and acetic acid ( CH ₃ COOH) is produced.

In addition, the particle maker 10 titrates only manganese acetate to a solution of potassium permanganate to produce manganese dioxide particles (hereinafter, the first manganese dioxide particle production process) as well as a process added during the first manganese dioxide particle production process. Manganese dioxide particles may be produced through an additional manufacturing process (hereinafter, a second manufacturing process of manganese dioxide particles).

In the second manufacturing process of manganese dioxide particles, the particle maker 10 titrates manganese acetate with a solution of potassium permanganate to produce a preparation solution, and then, copper acetate (Cu(CH ₃ COO) ₂ ) or copper nitrate (Cu) to the preparation solution (NO ₃ ) ₂ ) may be more titrated.

Furthermore, the particle maker 10 may generate manganese dioxide particles by a manufacturing process (hereinafter, a third manganese dioxide particle manufacturing process) modified from the first and second manufacturing processes of the manganese dioxide particles.

In the third manufacturing process of manganese dioxide particles, the particle maker 10 titrates manganese acetate and copper nitrate together with a solution of potassium permanganate to produce a preparation solution, and then further titrates potassium hydroxide (KoH) to the preparation solution, and the preparation solution After stirring, copper hydroxide (Cu(OH) ₂ ) may be co-precipitated (or precipitated) to produce manganese dioxide particles.

In the third manufacturing process of manganese dioxide, the particle maker 10 may titrate copper nitrate to a solution of potassium permanganate in an amount of 12 to 20 wt% of the preparation solution to produce manganese dioxide particles, and the pH of the preparation solution is pH 10 or less. Potassium hydroxide may be titrated to the preparation solution as much as possible.

In addition, it is preferable that the particle maker 10 is provided with a stirring means to perform stirring in the manufacturing process of the third manganese dioxide particles.

And the stirring means of the particle maker 10 causes a reaction by stirring the preparation solution, and when the stirring of the preparation solution is finished, co-precipitation of copper hydroxide generated in the stirring process may occur.

Here, co-precipitation refers to a phenomenon in which other substances or ions that have not yet reached solubility are precipitated together when a certain substance is precipitated. That is, the co-precipitation of copper hydroxide is preferably understood as a phenomenon in which copper hydroxide is precipitated in a prepared solution produced by titrating together manganese acetate and copper nitrate in a solution of potassium permanganate.

As described above, the particle maker 10 may perform the first, second, and third manganese dioxide particle production processes, but it is preferable to perform at least one of the first, second, and third manganese dioxide particle production processes. However, since the NOx adsorbent finally selected through the third manganese dioxide particle manufacturing process has relatively improved adsorption performance than the Nox adsorbent finally selected in the first and second manganese dioxide particle manufacturing process, the particle maker 10 is the first 3 It is more preferable to carry out the manufacturing process of manganese dioxide particles.

The washer 20 receives the preparation solution from the particle maker 10 and removes residual ions by washing the manganese dioxide particles.

The washing machine 20 performs the washing process in the order of solid-liquid separation, distilled water mixing, and solid-liquid separation at least once to wash the manganese dioxide particles contained in the prepared solution, and the solid-liquid separation means and the distilled water mixing means are used to perform the washing process. It is preferable to be provided.

Here, when the washing machine 20 performs the washing process in the order of solid-liquid separation, distilled water washing, and solid-liquid separation, the separation efficiency of manganese dioxide particles and residual ions in one solid-liquid separation is lowered, and when the washing process is finished by washing with distilled water, manganese dioxide is included This is because unfiltered residual ions may remain in distilled distilled water.

In addition, the solid-liquid separation means that the washer 20 separates the solid manganese dioxide particles and the liquid residual ions constituting the manufacturing solution from each other, and the distilled water mixing means that the washing machine 20 mixes the solid-liquid separated manganese dioxide particles with distilled water to obtain manganese dioxide It means dispersing the particles in distilled water.

As such, when the first and second manganese dioxide particle manufacturing processes are performed in the particle maker 10, the washing machine 20 uses distilled water at least twice the volume (L) of the manganese dioxide particles to wash the manganese dioxide particles. .

Furthermore, when the third manganese dioxide particle manufacturing process is performed in the particle maker 10, the washing machine 20 sets the volume (L) ratio of the manganese dioxide particles and distilled water to 1.6:2 to remove residual ions, but to be manufactured later To prevent dissolution of the surface OH functional groups of the NOx adsorbent, the washing process may be performed once.

As such, the manganese dioxide particles washed by the washing machine 20 may be in a wet cake state.

The first dryer 30 receives the manganese dioxide particles of the wet cake from the washer 20 and dries the manganese dioxide particles in the wet cake state at a preset temperature and time to generate dried manganese dioxide particles.

Here, the preset temperature of the first dryer 30 may be 100° C. or more, and the preset time may be 20 hours or more.

However, it is preferable that the first dryer 30 dry the manganese dioxide particles of the wet cake by setting the preset temperature to 110° C. and the preset time to 24 hours to completely dry the manganese dioxide particles in the wet cake state.

The crusher 40 receives the dried manganese dioxide particles from the first dryer 30 and crushes the dried manganese dioxide particles to generate an adsorbent powder composed of manganese dioxide particles of a predetermined size.

Here, the crusher 40 crushes the dried manganese dioxide particles to produce an adsorbent powder composed of manganese dioxide particles of 1-1.4 mm.

The agitator 50 receives the adsorbent powder from the crusher 40 , and stirs the adsorbent powder and an organic-inorganic binder of a predetermined content to generate a stirred powder.

Here, the stirrer 50 may set the pre-existing content of the organic-inorganic binder to 1 to 3% so that the stirred powder is molded with the NOx adsorbent.

Also, in the organic-inorganic binder, a ratio of the organic binder to the inorganic binder may be 3:7.

The extruder 60 receives the agitated powder from the agitator 50, adds moisture to the agitated powder, and then extrudes it to mold the stirred powder into a NOx adsorbent.

The second dryer 70 receives the NOx adsorbent from the extruder 60, and by drying the NOx adsorbent at a preset temperature and time, a final NOx adsorbent is manufactured.

Here, the preset temperature of the second dryer 70 may be 100° C. or more, and the preset time may be 20 hours or more.

However, it is preferable that the second dryer 30 prepares the final NOx adsorbent by setting the preset temperature to 110° C. and the preset time to 24 hours in order to produce the NOx adsorbent as the final NOx adsorbent.

In summary, the NOx adsorbent manufacturing apparatus 1 of the present invention generates manganese dioxide particles in the third manganese dioxide particle manufacturing process in the particle manufacturing machine 10, and the volume ratio of the manganese dioxide particles and distilled water in the washing unit 20 is 1.6: After setting to 2, the washing process in the order of solid-liquid separation, distilled water mixing, and solid-liquid separation is performed once, and the manganese dioxide particles of the wet cake are dried in the first dryer 30 at 110° C. for 24 hours, and in the crusher 40 An adsorbent powder composed of 1 to 1.4 mm of manganese dioxide particles is produced, and the stirred powder and 1-3% organic-inorganic half-inder are stirred in a stirrer 50 to produce a stirred powder, and the agitation in the extruder 50 In consideration of the adsorption performance of the NOx adsorbent, it is most preferable to mold the powder into a NOx adsorbent and dry the NOx adsorbent at 110° C. for 24 hours in a second dryer 70 to prepare the final NOx adsorbent.

In Example 1, in order to proceed with the screening test for selecting a sample of the NOx adsorbent, a commercial metal material having an affinity for NOx gas and a high specific surface area metal material capable of replacing the commercial metal material were selected, and the results of the screening test were It is shown in [Table 1] below.

sample adsorption time Fe ₂ O ₃ Break through within 30 seconds MG(OH) ₂ Break through within 30 seconds Cr ₂ O ₃ Break through within 30 seconds CuO Break through within 30 seconds FeO(OH) 1 minute later Cu-Mg-Fe(OH) 1 minute later Cu-Mg-Al(OH) 1 minute later Mg-Al-Si(OH) 1 minute later MnO ₂ Break after 7 minutes

As shown in [Table 1], as the commercial metal material, iron oxide (Fe ₂ O ₃ ), magnesium hydroxide (MG(OH) ₂ ), chromium oxide (Cr ₂ O ₃ ) and copper oxide (CuO) were selected. , high specific surface area metal materials include goethite (FeO(OH)), copper-magnesium-iron alloy (Cu-Mg-Fe(OH)), copper-magnesium-aluminum alloy (Cu-Mg-Al(OH)), magnesium -Aluminum-silicon-based alloy (Mg-Al-Si(OH)) and manganese dioxide (MnO ₂ ) were selected.

In this screening test, it was obtained that the adsorption time for all commercial metals was broken within 30 seconds, while the high specific surface area metals broke through after 1 minute or more. In particular, manganese dioxide was relatively It was confirmed that the adsorption performance was excellent.

Based on the results of the screening test of Example 1 as described above, manganese dioxide was selected as a sample to be applied to the NOx adsorbent.

In Example 2, a process of manufacturing the NOx adsorbent by the particle maker 10 performing the first manufacturing process of manganese dioxide particles will be described in detail.

Referring to FIG. 2 , the particle maker 10 may produce manganese dioxide particles by titrating manganese acetate with a solution of potassium permanganate ( S10 ).

In the manganese dioxide particle generation step (S10), as shown in FIG. 3, the particle maker 10 titrates manganese acetate to a solution of potassium permanganate (S11), and can produce a preparation solution (S12), thereby Manganese dioxide particles may be generated in the preparation solution (S13).

Referring back to FIG. 2 , the washing machine 20 may wash the manganese dioxide particles through one or more washing processes after the manganese dioxide particle generation step ( S10 ) ( S20 ).

The washing process of the washing machine 20 is as shown in FIG. 4, after the washing machine 20 removes potassium acetate and acetic acid, which are residual ions, from the manganese dioxide particles through solid-liquid separation (S21), the solid-liquid separated manganese dioxide particles are separated from the The manganese dioxide particles can be dispersed in distilled water by mixing with distilled water twice the volume of the manganese dioxide particles (S22), and the solid-liquid separation is performed again to remove residual ions from the manganese dioxide particles (S23). It may be a process.

In the manganese dioxide particle washing step (S20), manganese dioxide particles in a wet cake state may be generated.

Referring back to FIG. 2 , the first dryer 30 may dry the manganese dioxide particles in a wet cake state at a preset temperature and time after the manganese dioxide particle washing step ( S20 ) ( S30 ).

In the manganese dioxide particle drying step (S30), the first dryer 30 may produce dried manganese dioxide particles by drying the manganese dioxide particles in a wet cake state at 110° C. for 24 hours.

The crusher 40 may generate an adsorbent powder composed of manganese dioxide particles of a predetermined size by crushing the dried manganese dioxide particles after the manganese dioxide particle drying step (S30) (S40).

In the manganese dioxide particle crushing step (S40), the crusher 40 may crush the dried manganese dioxide particles into 1 to 1.4 mm of manganese dioxide particles.

The stirrer 50 may generate a stirred powder by stirring the adsorbent powder and an organic-inorganic binder of a predetermined content after the manganese dioxide crushing step (S40) (S50).

In the stirring powder generating step (S50), the stirrer 50 may be stirred with the adsorbent powder by adding 1 to 3% organic-inorganic binder.

The extruder 60 may mold the stirred powder into a NOx adsorbent by extruding after adding moisture to the stirred powder after the stirring powder generating step (S50) (S60).

The second dryer 70 may dry the NOx adsorbent at a preset temperature and time after the NOx adsorbent forming step (S60) (S70).

In the NOx adsorbent drying step ( S70 ), the second dryer 70 may dry the NOx adsorbent at 110° C. for 24 hours, thereby manufacturing the final NOx adsorbent.

In Example 3, in order to titrate manganese acetate to a solution of potassium permanganate in the manganese dioxide particle generation step (S10) of Example 2, a NOx adsorbent according to the molar ratio of potassium permanganate and manganese acetate was prepared and adsorption performance was evaluated, and the results of the adsorption performance evaluation are shown in [Table 2] below.

KMnO ₄ (mol) Mn(CH ₃ COO) ₂ (mol) Adsorption capacity (mg/g) One One X 0.7 One X 0.6 One 4.5 0.3 One 4.9

Referring to [Table 2], when the molar ratio of potassium permanganate was 0.7 to 1 in the adsorption performance evaluation of Example 3, an unreacted solution of potassium permanganate was generated, and the adsorption performance of the NOx adsorbent was not derived. In contrast, when the molar ratio of potassium permanganate was 0.6 or less, the adsorption capacity of the NOx adsorbent was confirmed.

According to the result of the evaluation of the adsorption performance of Example 3, it is preferable that the particle maker 10 set the molar ratio of potassium permanganate and manganese acetate to 0 to 0.6:1 in the manganese dioxide particle generation step (S10) of Example 2 got the result that

However, when the amount of potassium permanganate is small or large, an unreacted solution of potassium permanganate is generated. In Example 3, the particle maker 10 of Example 2 has a molar ratio of potassium permanganate and manganese acetate to 0.6:1. It was found that it is more preferable to set

In Example 4, a process of manufacturing the NOx adsorbent by the particle maker 10 performing the second manufacturing process of manganese dioxide particles will be described in detail.

Furthermore, the NOx adsorbent manufacturing method of Example 4 differs only in the detailed process of the manganese dioxide particle generation step (S10) compared to the NOx adsorbent manufacturing method of Example 2, and the remaining manufacturing steps (S20, S30, S40) , S50, S60, and S70) are the same, so the description of the remaining manufacturing steps (S20, S30, S40, S50, S60, S70) will be omitted for convenience.

5, in the manganese dioxide particle generation step (S10) of Example 4, the particle maker 10 titrates manganese acetate to a solution of potassium permanganate (S110), so as to produce a preparation solution (S111), the preparation solution By further titrating copper acetate or copper nitrate to (S112), manganese dioxide particles may be generated in the preparation solution (S113).

In Example 5, the adsorption performance of the NOx adsorbent according to the content of copper acetate was evaluated in order to confirm the effect of adding copper acetate that can be titrated to the preparation solution in the manganese dioxide particle generation step (S10) of Example 4. , the results of the adsorption performance evaluation are shown in [Table 3] below.

KMnO ₄ (mol) Mn(CH ₃ COO) ₂ (mol) Cu(CH ₃ COO) ₂ (wt%) Adsorption capacity (mg/g) 0.6 One 5 5.911 0.6 One 10 13.266 0.6 One 15 10.044

Referring to [Table 3], the adsorption performance evaluation of Example 5 was carried out by fixing the molar ratio of potassium permanganate and manganese acetate to 0.6:1, and increasing the content of copper acetate by 5 wt%.

In addition, in the adsorption performance evaluation of Example 5, when the content of copper acetate is 5 wt%, the adsorption capacity of the NOx adsorbent is 5.911 mg/g, and when the content of copper acetate is 10 wt%, the adsorption capacity of the NOx adsorbent is 13.266 mg/g/g g, it was confirmed that the adsorption capacity of the NOx adsorbent was 10.044 mg/g when the content of copper acetate was 15 wt%. In addition, it was confirmed that when the content of copper acetate was increased from 5 wt% to 10 wt%, the adsorption performance of the Nox adsorbent was significantly improved.

As such, in Example 5, considering the adsorption performance of the NOx adsorbent through the results of the adsorption performance evaluation, in the manganese dioxide particle generation step (S10) of Example 4, the particle maker 10 determines the content of copper acetate in the production solution. It was set to 10-15 wt%, but in order to maximize the adsorption performance of the NOx adsorbent, it was found that it is preferable to set the content of copper acetate to 10 wt% of the prepared solution.

In Example 6, by reflecting the evaluation of the adsorption performance of Example 5, the particle maker 10 adsorbed the NOx adsorbent and the conventional adsorbent (eg, carulite) in which the content of copper acetate in the prepared solution was adjusted to 10 wt% of the prepared solution. The performance was compared, and the adsorption performance test results are shown in FIG. 6 and [Table 4] below.

sample KMnO ₄
(mol) Mn(CH ₃ COO) ₂
(mol) Cu(CH ₃ COO) ₂
(wt%) particle size
(mm) adsorption capacity
(mg/g) Copper acetate 10 wt% 0.6 One 10 around 1 mm 13.266 conventional adsorbent - 10.311

6, the adsorption performance experiment of Example 6 was an initial NO concentration of 2,000 ppm, an initial temperature of 21 ° C., a flow rate of 500 ml/min, a filling volume of 10 ml, a space velocity of 3,000 hr ^-1 , a breakthrough point of 1 ppm, an outflow starting point, The size of the adsorbent was about 1 mm, and the experimental conditions were set with NDIR analysis equipment.

Referring to [Table 4], in the adsorption performance test under the experimental conditions, the adsorption capacity of the NOx adsorbent to which the copper acetate content was applied as 10 wt% was 13.266 mg/g, and the adsorption capacity of the conventional adsorbent was 10.311 mg/g. was confirmed to be

Accordingly, in Example 6, it was obtained that the NOx adsorbent in which the content of copper acetate in the preparation solution was adjusted to 10 wt% of the preparation solution by the particle maker 10 had improved adsorption performance compared to the conventional adsorbent.

In Example 7, the adsorption performance of the NOx adsorbent according to the content of copper nitrate was evaluated in order to confirm the effect of adding copper nitrate that can be titrated to the manufacturing solution in the manganese dioxide particle generation step (S10) of Example 4 , the results of the adsorption performance evaluation are shown in [Table 5] below.

KMnO ₄ (mol) Mn(CH ₃ COO) ₂ (mol) Cu(NO ₃ ) ₂ (wt%) Adsorption capacity (mg/g) 0.6 One 4 6.289 0.6 One 6 6.861 0.6 One 8 7.434 0.6 One 10 6.443 0.6 One 15 6.948 0.6 One 20 7.760

Referring to [Table 5], the adsorption performance evaluation of Example 7 showed that the content of copper nitrate was 4, 6, 8, 10, 15, 20 wt% while fixing the molar ratio of potassium permanganate and manganese acetate to 0.6:1. in the process of increasing it.

In addition, in the adsorption performance evaluation of Example 7, the adsorption capacity of the NOx adsorbent was 6.289 mg/g when the content of copper nitrate was 4 wt%, and the adsorption capacity of the NOx adsorbent was 6.861 mg/g when the content of copper nitrate was 6 wt%. g, when the content of copper nitrate is 8 wt%, the adsorption capacity of the NOx adsorbent is 7.434 mg/g, when the content of copper nitrate is 10 wt%, the adsorption capacity of the NOx adsorbent is 6.443 mg/g, and the content of copper nitrate is 15 In the case of wt%, the adsorption capacity of the NOx adsorbent was 6.948 mg/g, and when the content of copper nitrate was 20 wt%, the adsorption capacity of the NOx adsorbent was 7.760 mg/g.

As described above, in the evaluation of the adsorption performance of Example 7, it was obtained that the adsorption performance of the NOx adsorbent was not correlated with whether the copper nitrate was titrated or not.

Furthermore, in Example 7, according to the result of the adsorption performance evaluation, when considering the adsorption performance of Nox in the manganese dioxide particle generation step (S10) of Example 4, the particle maker 10 prepares copper acetate in the production solution The most preferable result was obtained by titrating more by 10 wt% of

In Example 8, a process of manufacturing the NOx adsorbent by the particle maker 10 performing the third manufacturing process of manganese dioxide particles will be described in detail.

Furthermore, in the NOx adsorbent manufacturing method of Example 8, there is only a difference in the detailed process of the manganese dioxide particle generation step (S10) compared to the NOx adsorbent manufacturing method of Examples 2 and 4, and the remaining manufacturing steps (S20, S30) , S40, S50, S60, and S70) are the same, so the description of the remaining manufacturing steps (S20, S30, S40, S50, S60, S70) will be omitted for convenience.

Referring to Figure 7, in the manganese dioxide particle generation step (S10) of Example 8, the particle maker 10 titrates manganese acetate and copper nitrate together with a solution of potassium permanganate (S1110), so that the production solution is generated (S1111) ), by further titrating potassium hydroxide to the preparation solution (S1112), and stirring the preparation solution (S1113), manganese dioxide particles may be generated in the preparation solution (S1114).

In addition, between the stirring step (S1113) of the preparation solution and the net dioxide particle generation step (S1114), as the particle maker 10 ends the stirring of the preparation solution, co-precipitation of copper hydroxide may occur.

In Example 9, the adsorption performance of the NOx adsorbent of Example 8, the NOx adsorbent of Example 4, and the conventional adsorbent was compared to confirm the effect of co-precipitation of copper hydroxide generated in Example 8. The performance test results are shown in [Table 6] below.

absorbent KMnO ₄
(mol) Mn(CH ₃ COO) ₂
(mol) CU
Raw material addition amount
(wt%) Cu(OH) ₂
co-aggression particle size
(mm) adsorption capacity
(mg/g) conventional adsorbent 0.6 One 10 - 1-1.4 16.61 Example 2 0.6 One 10 X pellet 16.53 Example 3 0.6 One 10 O pellet 33.83

Referring to Figure 8, the adsorption performance experiment of Example 9 was an initial NO concentration of 2,000 ppm, an initial temperature of 21 °C, a flow rate of 500 ml/min, a filling volume of 10 ml, a space velocity of 3,000 hr ^-1 , a breakthrough point of 1 ppm, an outflow starting point, It was conducted under the experimental conditions set by the size of the adsorbent pellet and the analysis equipment NDIR.

Referring to [Table 6], the adsorption performance test of Example 9 under the experimental conditions showed that the addition amount of copper (copper nitrate) was 10 wt% of the preparation solution while fixing the molar ratio of potassium permanganate and manganese acetate to 0.6:1. was carried out under the conditions of fixing to , and the NOx adsorbent of Example 8 was the only one in which co-precipitation of copper hydroxide occurred.

In the adsorption performance test of Example 9, the adsorption capacity of the conventional adsorbent was 16.61 mg/g, the Nox adsorbent of Example 4 was 16.53 mg/g, and the NOx adsorbent of Example 8 was 33.83 mg/g. was found to be g.

Accordingly, in Example 9, it was obtained that the NOx adsorbent of Example 8 improved the adsorption performance by more than twice that of the NOx adsorbent of Example 4 and the conventional adsorbent.

In Example 10, after the copper hydroxide co-precipitation of Example 9, the adsorption performance of the NOx adsorbent while changing the number of times of washing the manganese dioxide particles in order to confirm the effect of the washing of the manganese dioxide particle washing step (S20) of Example 8 was evaluated, and the results of the adsorption performance evaluation are shown in FIG. 9 and [Table 7] below.

CU raw material content
(%) number of washes final filtrate
(pH) total water consumption
(L) adsorption capacity
(mg/g) 10 0 7.89 0 3.69 One 7.89 2 39.90 3 8.12 6 33.27 5 8.50 10 34.16 7 8.78 14 34.59 9 9.47 18 34.34

9, the evaluation of the adsorption performance of Example 10 is an initial NO concentration of 2,000 ppm, an initial temperature of 21 °C, a flow rate of 500 ml/min, a filling volume of 10 ml, a space velocity of 3,000 hr ^-1 , a breakthrough point of 1 ppm outflow starting point , the size of the adsorbent, pellet, and NDIR analysis equipment were used under experimental conditions.

Referring to [Table 7], in the evaluation of the adsorption performance of Example 10, the amount of water (distilled water) was set to 2L per one washing number, and the water usage was increased by 2L each time the number of washings increased by one.

In addition, in the adsorption performance evaluation of Example 10, a NOx adsorbent in which the volume ratio between the manganese dioxide particles and distilled water was set to 1.6:2 was used.

In this evaluation of the adsorption performance of Example 10, the adsorption capacity of the NOx adsorbent was 3.689 mg/g when the number of washings was 0, the adsorption capacity of the NOx adsorbent was 39.90 mg/g when the number of washings was 1, and NOx when the number of washings was 3 times. The adsorption capacity of the adsorbent is 33.27 mg/g, the adsorption capacity of the NOx adsorbent is 34.16 mg/g when the number of washes is 5 times, the adsorption capacity of the NOx adsorbent is 34,59 mg/g when the number of washes is 9 times It was confirmed that the adsorption capacity of the NOx adsorbent was 34.34 mg/g.

Furthermore, in the evaluation of the adsorption performance of Example 10, it was confirmed that the OH functional group on the surface of the NOx adsorbent was dissolved when the number of washings was 2 or more.

Accordingly, in Example 10, it was obtained that the NOx adsorbent had the best performance when the number of times of washing was one in the manganese dioxide particle washing step (S20) of Example 8 based on the results of the adsorption performance evaluation.

In Example 11, in order to confirm the effect of copper nitrate titrated to a solution of potassium permanganate in the manganese dioxide particle generation step (S10) of Example 8, the adsorption performance of the NOx adsorbent according to the content of copper nitrate was evaluated, The results of the adsorption performance evaluation are shown in FIG. 10 and [Table 8] below.

Cu raw material content
(%) absorbent
(g) particle size
(mm) adsorption time
(min) adsorption capacity
(mg/g) 12 3.841 pellet 125 39.90 14 4.257 168 48.39 15 4.178 166 48.72 17 3.592 163 47.31 20 4.302 132 40.15

10, the evaluation of the adsorption performance of Example 11 is an initial NO concentration of 2,000 ppm, an initial temperature of 21 ° C., a flow rate of 500 ml/min, a filling volume of 10 ml, a space velocity of 3,000 hr ^-1 , a breakthrough point of 1 ppm, an outflow starting point, It was conducted under the experimental conditions set by the size of the adsorbent pellet and the analysis equipment NDIR.

Referring to Table 8, in the evaluation of the adsorption performance of Example 11, the adsorption capacity of the NOx adsorbent was 48.39 mg/g when the copper nitrate content was 14%, and the NOx adsorbent was adsorbed when the copper nitrate content was 15%. With a capacity of 48.72 mg/g, the adsorption performance of the NOx adsorbent was the best when the copper nitrate content was 14 and 15%.

However, in consideration of the cost and performance according to the content of copper nitrate, in Example 11, it was found that setting the content of copper nitrate to 14% is suitable for manufacturing the NOx adsorbent.

In Example 12, in order to confirm the influence of the organic-inorganic binder added in the stirring powder generating step (S50) of Example 8, the adsorption performance of the NOx adsorbent according to the content of the organic-inorganic binder was evaluated. The results of the performance evaluation are shown in FIG. 11 and [Table 9] below.

Cu raw material amount
(%) binder content
(%) adsorbent weight
(g) adsorption time
(mm) NO adsorption capacity
(mg/g) 15 0 3.569 137 49.57 One 4.486 187 44.92 3 4.474 128 41.23 5 4.223 122 39.80 10 4.531 108 30.69

11, the adsorption performance evaluation of Example 12 is an initial NO concentration of 2,000 ppm, an initial temperature of 21 ° C., a flow rate of 500 ml/min, a filling volume of 10 ml, a space velocity of 3,000 hr ^-1 , a breakthrough point of 1 ppm, an outflow starting point, It was conducted under the experimental conditions set by the size of the adsorbent pellet and the analysis equipment NDIR.

Referring to [Table 9], in the adsorption performance evaluation of Example 12, the content of copper nitrate was fixed at 15%, and the organic-inorganic binder had a ratio of 3:7 to the organic binder, and the organic-inorganic binder was set to 3:7. The adsorption performance of the NOx adsorbent was evaluated while the content of the inorganic binder was changed in the order of 0, 1, 3, 5, and 10%.

In this evaluation of the adsorption performance of Example 12, when the content of organic-inorganic binder was 0%, the weight of the adsorbent was 3.569 g, the adsorption time was 137 min, and the adsorption capacity of NO gas was 49.57 mg/g, so the adsorption performance of the NOx adsorbent This was found to be the best. However, when the content of the organic-inorganic binder was 0%, mass production of the NOx adsorbent was impossible.

Accordingly, in Example 12, based on the results of the adsorption performance evaluation, the NOx adsorbent has excellent adsorption performance when the organic-inorganic binder content is 1, 3%, except for the case where the organic-inorganic binder content is 0%. got the result.

In Example 13, in order to confirm the influence of moisture in the NOx gas adsorption process, the adsorption performance of the NOx adsorbent of Example 8 was evaluated under certain conditions. ] is the same as

NO gas
(ppm) No ₂ gas
(ppm) O ₂
(%) hydration
Whether adsorption time
(min) NO adsorption capacity (mg/g) NO ₂ adsorption capacity (mg/g) NOx adsorption capacity (mg/g) 1935 676 4.7 X 1,307 36.92 19.76 56.67 1935 676 4.7 O 1,073 30.29 16.21 46/69 1935 119 4.5 X 1,411 39.72 3.68 43.40 1935 119 4.5 O 1,137 32.09 3.00 35.09

12, the evaluation of the adsorption performance of Example 13 is an initial NO concentration of 1,935 ppm, an initial temperature of 21 ° C., a flow rate of 1,100 ml/min, a filling volume of 200 ml, a space velocity of 3,30 hr ^-1 , a breakthrough point of 1 ppm outflow It was conducted under experimental conditions set by the starting point, the size of the adsorbent pellet, and the analysis equipment NDIR.

Referring to [Table 10], in the adsorption performance evaluation of Example 13, the ratio of NO gas to NO2 gas was set to 7:3 and 9:1, and moisture was injected under the conditions of 7:3 and 9:1. .

In this evaluation of the adsorption performance of Example 13, when the ratio of NO gas to NO2 gas was 7:3, when moisture was not injected and when moisture was injected, the adsorption capacity of the NOx adsorbent was 9.98 mg/g when moisture was injected. (17.61%) as a result.

In addition, when the ratio of NO gas to NO2 gas was 9:1, when no moisture was injected and when moisture was injected, the adsorption capacity of the NOx adsorbent was reduced by 8.31 mg/g (19.14%) when moisture was injected. got the result

Accordingly, in Example 13, in the process of adsorbing NOx gas by the NOx adsorbent, it was obtained that whether or not water was injected affects the adsorption performance.

In Example 14, the performances of the NOx adsorbent of Example 8, the conventional adsorbent 1 to 1.4 mm, and the conventional adsorbent 4 to 5 mm were compared, and the adsorption performance was compared. 11] as shown.

sample absorbent
(g) adsorption time
(min) particle size
(mm) adsorption capacity
(mg/g) Example 8 4.178 166 pellet 48.72 conventional adsorbent
1-1.4 mm 8.17 114 1-1.4 16.60 conventional adsorbent
4-5 mm 7.046 12 4-5 2.09

13, the adsorption performance experiment of Example 14 was an initial NO concentration of 2,000 ppm, an initial temperature of 21 ° C., a flow rate of 500 ml/min, a filling volume of 10 ml, a space velocity of 3,000 hr ^-1 , a breakthrough point of 1 ppm, an outflow starting point, It was conducted under the experimental conditions set by the size of the adsorbent pellet and the analysis equipment NDIR.

Referring to Table 11, in the adsorption performance test of Example 14, it was confirmed that the NOx adsorbent of Example 8 had an adsorption capacity of 48.72 mg/g, and that of the conventional adsorbent was 16.60 mg/g and 2.09 mg/g. .

Accordingly, in Example 14, it was obtained that the NOx adsorbent of Example 8 had superior adsorption performance than the conventional adsorbent.

In summary, through Examples 1 to 14, as the final NOx adsorbent prepared by the NOx adsorbent manufacturing method of Example 8 has the best adsorption performance, the final NOx adsorbent of the present invention is the NOx of Example 8. It was found that it is preferable to be prepared by the method for preparing an adsorbent.

The above description of the present invention is for illustration, and those of ordinary skill in the art to which the present invention pertains can 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 restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

1: NOx adsorbent manufacturing device,
10: particle maker,
20: washing machine,
30: first dryer;
40: shredder.
50: agitator,
60: extruder,
70: second dryer.

Claims (12)

The particle maker 10 titrates manganese acetate (Mn(CH ₃ COO) _{2 ) to a solution of potassium permanganate (KMnO 4} ) to obtain manganese dioxide (MnO ₂ ) particles, and residual ions potassium acetate (CH ₃ COOK) and acetic acid ( CH ₃ COOH) to generate a preparation solution containing (S10);
After the washer 20 removes the residual ions from the manganese dioxide particles by solid-liquid separation, the manganese dioxide particles are dispersed in distilled water, and the solid-liquid separation is performed again to remove the remaining residual ions. step (S20);
The first dryer 30 drying the manganese dioxide particles in a wet cake state by the washing process in a drying process at a preset temperature and time (S30);
The crusher 40 crushes the manganese dioxide particles dried by the drying process to generate an adsorbent powder composed of manganese dioxide particles of a predetermined size (S40);
The stirrer 50 stirs an organic-inorganic binder of a predetermined content in the adsorbent powder to generate a stirred powder (S50);
The extruder 60 adds moisture to the stirred powder and then extrudes it to mold the stirred powder into a NOx adsorbent (S60); and
A second dryer (70) drying the NOx adsorbent in a drying process at a preset temperature and time to prepare a final NOx adsorbent (S70). According to claim 1,
The particle maker 10,
NOx adsorbent manufacturing method, characterized in that the molar ratio of the potassium permanganate and the manganese acetate is set to 0 to 0.6:1. 3. The method of claim 2,
The particle maker 10,
Copper acetate (Cu(CH ₃ COO) ₂ ) or copper nitrate (Cu(NO ₃ ) ₂ ) to the prepared solution is further titrated to produce manganese dioxide particles. 4. The method of claim 3,
The particle maker 10,
NOx adsorbent manufacturing method, characterized in that the copper acetate is titrated to the preparation solution by 10-15 wt% of the preparation solution. 3. The method of claim 2,
The particle maker 10,
The preparation solution is produced by titrating copper nitrate with the manganese acetate solution to the potassium permanganate solution, and potassium hydroxide (KOH) is further titrated to the preparation solution, and after stirring the preparation solution, copper hydroxide (Cu(OH)) ₂ ) A method for producing a NOx adsorbent, characterized in that the manganese dioxide particles are produced by co-precipitation. 6. The method of claim 5,
The particle maker 10,
NOx adsorbent manufacturing method, characterized in that the copper nitrate is titrated to the potassium permanganate solution by 12-20 wt% of the preparation solution. 6. The method of claim 5,
The particle maker 10,
NOx adsorbent manufacturing method, characterized in that the potassium hydroxide is titrated to the preparation solution so that the pH of the preparation solution becomes pH 10 or less. 6. The method of claim 5,
The washing machine 20,
NOx, characterized in that the volume ratio of the manganese dioxide particles and the distilled water is set to 1.6:2, and the washing process is performed once to prevent dissolution of surface OH functional groups of the NOx adsorbent while removing the residual ions. Adsorbent manufacturing method. According to claim 1,
The first dryer 30,
A method for producing a NOx adsorbent, characterized in that the wet cake state of the manganese dioxide particles are dried at 100° C. or higher for 20 hours or more. According to claim 1,
The crusher 40,
NOx adsorbent manufacturing method, characterized in that crushing the dried manganese dioxide particles to 1 ~ 1.4 mm. According to claim 1,
The stirrer 50,
The NOx adsorbent manufacturing method, characterized in that the content of the organic-inorganic binder is set to 1 to 3%. According to claim 1,
The second dryer 70,
A method for producing a NOx adsorbent, characterized in that the NOx adsorbent is dried at 100° C. or higher for 20 hours or more.

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