KR102067339B1 - High strength pellet composition containing a catalyst for removing harmful gas and preparation method thereof - Google Patents

Abstract

The present invention relates to a high-strength pellet composition containing a catalyst for removing harmful gases and a method for manufacturing the same, and more particularly, a high strength containing a catalyst for removing harmful gases, which is not easily broken due to improved strength and exhibits excellent gas removal characteristics. It relates to a pellet composition and a method for producing the same. The present invention is characterized in that it comprises a catalyst for removing harmful gases, silica microparticles, silica nanoparticles and clay.

Description

High strength pellet composition containing a catalyst for removing harmful gas and preparation method

The present invention relates to a high-strength pellet composition containing a catalyst for removing harmful gases and a method for manufacturing the same, and more particularly, a high strength containing a catalyst for removing harmful gases, which is not easily broken due to improved strength and exhibits excellent gas removal characteristics. It relates to a pellet composition and a method for producing the same.

Harmful or unpleasant hazards to humans such as carbon monoxide, nitrogen oxides, sulfur oxides and volatile organic compounds in everyday living spaces, markets, stores, automobiles, industrial sites, chemical plants, power plants, incinerators, boilers, underground roads, tunnels and underground parking lots The state contains harmful gas components, and adsorbents or catalyst materials are mainly used for selective removal of such harmful gases.

Activated carbon, zeolite, and the like are commonly used as the adsorbent. However, since the adsorbent has a limit in adsorption capacity, the adsorption capacity is considerably lowered or extinguished after a certain time, and there is a disadvantage in that it is not easy to reuse. In particular, activated carbon has a problem in that it does not adsorb various harmful gases.

As the catalyst material, precious metals such as platinum (Pt), gold (Au), and palladium (Pd) or transition metals such as manganese (Mn), cobalt (Co), iron (Fe), and the like, have a large surface area such as alumina, silica, and titania. Catalyst materials for oxidation reaction prepared by being supported on such carriers are mainly used.

On the other hand, the noble metal-containing catalyst shows an excellent removal performance compared to the transition metal-containing catalyst, but due to the cost of the precious metal material has a limitation in general-purpose applications. In recent years, catalysts using transition metals, which are more economical than precious metals, have been developed. Representatively, manganese oxides or copper-manganese oxides are used to remove harmful gases such as carbon monoxide, volatile organic compounds (VOCs), ammonia and hydrogen sulfide. A catalyst is being developed.

Such a catalyst may adhere to the filter media to physically or chemically capture or remove various harmful microparticles. Filter media is generally referred to collectively as filter media, and the filter media provided in the related art are composed of synthetic polymers, and a method of capturing fine particles by applying an electrostatic force to an ultrafine fiber layer has been mainly used. Recently, a method of fixing a deodorant such as porous activated carbon powder, activated carbon fiber or zeolite to a filter media using a predetermined binder mixture has been proposed.

However, catalysts are generally manufactured in powder form, in which case it is difficult to control the reaction of the catalyst in the reactor, pressure loss is large, and catalyst powder may cause contamination of the reactor and other devices, so You have to mold.

Recently, a catalyst in powder form has been used in a pellet form. However, when the pellet composition does not have sufficient mechanical strength, it breaks easily and generates a differential pressure in the reactor, which causes a decrease in activity and selectivity of the catalyst. Therefore, improving the strength of the pellet composition is a necessary requirement for industrial catalysts such as improving the performance of the catalyst. However, the conventional pellet composition does not have sufficient strength and is easily broken, and a phenomenon such as powder blowing occurs. Accordingly, the present inventors found that the strength of the pellets is significantly increased while maintaining the harmful gas removal performance when the pellets are manufactured by mixing two kinds of silica particles and clays having different particle sizes in the catalyst for removing harmful gases. It has been developed a high-strength pellet composition containing an optimized catalyst for removing harmful gases and a preparation method thereof.

Republic of Korea Patent Application Publication No. 10-2007-0028102 (Invention name: method for producing a copper-manganese oxide catalyst of the nanoparticles and the catalyst prepared according thereto, Applicant: Keimyung University Industry-Academic Cooperation Foundation, Publication Date: March 12, 2007) Republic of Korea Patent Publication No. 10-2016-0035224 (Invention name: Porous copper-manganese catalyst manufacturing method, Applicant: Sales F Co., Ltd., Publication Date: March 31, 2016) Republic of Korea Patent Application Publication No. 10-2011-0117301 (Name of the invention: nanometer sized copper-based catalyst production method, Applicant: SK Innovation Co., Ltd., Publication Date: October 27, 2011)

An object of the present invention is to provide a high-strength pellet composition containing a catalyst for removing harmful gases, and a method for producing the same, which is improved in strength to prevent damage to equipment by powder in the molding process, and is easy to move and store.

Another object of the present invention is to provide a high-strength pellet composition comprising a catalyst having excellent harmful gas removal performance.

The present invention relates to a high-strength pellet composition containing a catalyst for removing harmful gases, in order to achieve the above object, the present invention is characterized in that it comprises a catalyst for removing harmful gases, silica microparticles, silica nanoparticles and clay.

The harmful gas removal catalyst is preferably a manganese oxide catalyst or a copper-manganese oxide catalyst.

The silica microparticles preferably have an average particle size of 20 to 40 μm.

The silica nanoparticles preferably have an average particle size of 10 ~ 20nm.

The clay (montmorillonite), bentonite (bentonite), hectorite, heidite (beidellite), nontronite (satronite), saponite (laponite), laponite, dolomite, Talc, feldspar, vermiculite, kaolin, halosite, elite, greenite, brookite, vermicullite, synthetic mica, kanemite, magadiite and kenyaite It is preferably one or more selected from the group consisting of.

The pellet composition of the present invention is characterized in that 1 to 15 parts by weight of catalyst for removing harmful gases, 15 to 35 parts by weight of silica nanoparticles and 0.5 to 5 parts by weight of clay based on 100 parts by weight of silica microparticles.

The harmful gas removing a high-strength pellets containing the composition for a catalyst of the invention is preferable to have more than 5.0kg / m ² intensity and, more particularly, is characterized by having a strength of 5.0 ~ 6.5kg / m ^2.

In addition, the high-strength pellet composition containing the catalyst for removing harmful gas of the present invention preferably has a specific surface area of 200 m ² / g or more, and more specifically, has a specific surface area of 200-240 m ² / g. . In addition, it is characterized by having a mesopore volume of 0.65ml / g or more.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention relates to a high-strength pellet composition containing a catalyst for removing harmful gases, characterized in that it comprises a catalyst for removing harmful gases, silica microparticles, silica nanoparticles and clay.

That is, the present invention is characterized by producing a high-strength pellet composition by mixing two kinds of silica particles and clays having different sizes in the catalyst for removing harmful gases.

At this time, the harmful gas removal catalyst is preferably a manganese oxide catalyst or copper-manganese oxide catalyst. More preferably, the manganese oxide catalyst may be a manganese / silicon composite metal oxide catalyst, and the copper-manganese oxide catalyst may be a copper-manganese / silicon composite metal oxide catalyst.

The harmful gas removal catalyst is preferably included 1 to 15 parts by weight based on 100 parts by weight of silica microparticles. If the amount of the catalyst for removing the harmful gas is less than 1 part by weight based on 100 parts by weight of the silica microparticles, the effect of removing the harmful gas may not be sufficient. If the amount is more than 15 parts by weight, the excessive catalyst may deteriorate the harmful gas removal performance. It is not desirable.

The silica microparticles preferably have an average particle size of 20 to 40 μm. When the average particle size of the silica microparticles is less than 20 μm, the viscosity of the pellet composition becomes high, and thus, it is difficult to prepare a pellet composition of uniform physical properties due to poor mixing dispersibility when preparing pellets, and when the thickness exceeds 40 μm, the strength of the pellet composition decreases. It may be undesirable.

In addition, the silica microparticles more preferably have a specific surface area of 210 ~ 270m ² / g. If the specific surface area is less than 210m ² / g is not preferable because the harmful gas adsorption capacity of the pellet composition can be reduced. The larger the specific surface area of the silica microparticles, the better the catalyst performance, but sufficient strength and catalyst performance may be satisfied just by satisfying the above range.

In addition, the silica microparticles more preferably have a void volume of 0.6 ~ 0.9ml / g. If the void volume is out of the above range, the strength improvement effect is insignificant, which is not preferable.

The silica nanoparticles are preferably an average particle size of 10 ~ 20nm. When the average particle size of the silica nanoparticles is less than 10 nm, the dispersibility is poor due to agglomeration of the crystals with each other, and when the average particle size is more than 20 nm, the final specific surface area of the pellet composition may be lowered, which is not preferable.

In this case, the silica nanoparticles are more preferably colloidal silica in which 25 to 32 wt% of ultrafine silicon dioxide particles are dispersed in a solvent, and the solvent is selected from the group consisting of water or methyl ethyl ketone, methyl isobutyl ketone, methanol, and isopropanol. It may be one organic solvent.

In addition, the viscosity of the silica nanoparticles is more preferably less than 13cps at 25 ℃. When the viscosity of the silica nanoparticles exceeds 13 cps, the mixing dispersibility is poor when mixed with the catalyst for removing harmful gases, which makes it difficult to prepare a pellet composition having a uniform physical property.

In addition, the silica nanoparticles are preferably included 15 to 35 parts by weight based on 100 parts by weight of silica microparticles. When the content of the silica nanoparticles is less than 15 parts by weight based on 100 parts by weight of the silica microparticles, the effect of improving the strength of the pellet composition is not sufficient, and when the content of the silica nanoparticles exceeds 35 parts by weight, it is difficult to produce a pellet composition having a uniform physical property. Not.

The clay (montmorillonite), bentonite (bentonite), hectorite, heidite (beidellite), nontronite (satronite), saponite (laponite), laponite, dolomite, Talc, feldspar, vermiculite, kaolin, halosite, elite, greenite, brookite, vermicullite, synthetic mica, kanemite, magadiite and kenyaite It is preferably one or more selected from the group consisting of.

The clay preferably contains 0.5 to 5 parts by weight based on 100 parts by weight of the silica microparticles. If the content of clay is less than 0.5 parts by weight based on 100 parts by weight of the silica microparticles, there is a problem in controlling the physical properties of the catalyst, and if it exceeds 5 parts by weight, the catalyst activity may decrease, which is not preferable.

The form of the pellet composition of the present invention can be prepared not only in a simple sphere but also in a three-dimensional form for increasing the contact area of contaminants.

Although the particle size of the pellet composition is not particularly limited, it is preferable that the particle size is such that the pressure loss can be minimized and the removal efficiency of the contaminants can be maximized, and the length of the cross section is usually 0.5 to 20 mm. For example, if it is a columnar pellet, the thing of about 0.5-10 mm in diameter and 0.5-15 mm in length can be easily obtained.

The harmful gas removing a high-strength pellets containing the composition for a catalyst of the invention is preferable to have more than 5.0kg / m ² intensity and, more particularly, is characterized by having a strength of 5.0 ~ 6.5kg / m ^2.

In addition, the high-strength pellet composition containing the catalyst for removing harmful gas of the present invention preferably has a specific surface area of 200 m ² / g or more, and more specifically, has a specific surface area of 200-240 m ² / g. . In addition, it is characterized by having a mesopore volume of 0.65ml / g or more.

In addition, the present invention (1 step) preparing a catalyst for removing harmful gas;

(Step 2) preparing a mixture by mixing the catalyst for removing harmful gases, silica microparticles, silica nanoparticles and clay;

(Step 3) extruding the mixture to prepare a molding composition; And

(Step 4) provides a method for producing a high-strength pellet composition containing a catalyst for removing harmful gases, characterized in that it comprises the step of heat-treating the molding composition.

The first step of removing the harmful gas catalyst is preferably a manganese oxide catalyst or a copper-manganese oxide catalyst, more preferably the manganese oxide catalyst is a manganese / silicon composite metal oxide catalyst, the copper-manganese oxide catalyst is copper It may be a manganese / silicon composite metal oxide catalyst.

At this time, if the catalyst for removing the harmful gas of the first step is a manganese oxide catalyst, (step a) preparing a manganese salt solution;

(b) adding a silicate aqueous solution to the aqueous solution of manganese salt and stirring to prepare a mixed solution;

(c) separating the mixed solution into a precipitate and a solution and washing the precipitate; And

(d step) characterized in that it further comprises the step of drying and heat-treating the precipitate washed above.

In the step a, the aqueous solution of manganese salt is preferably prepared by mixing 5 to 20 parts by weight of manganese salt based on 100 parts by weight of purified water. When the amount of manganese salt is less than 5 parts by weight based on 100 parts by weight of purified water, the amount of wastewater is increased, and when it exceeds 20 parts by weight, it is not preferable because it is not sufficiently dissolved or economical efficiency is lowered.

At this time, the manganese salt is preferably at least one selected from the group consisting of manganese acetate, manganese nitrate, manganese chloride, manganese iodide, manganese bromide, manganese sulfate and potassium manganate.

In the b step, the aqueous silicate solution is preferably mixed with a silicate at a concentration of 15 to 30% (w / v). If the concentration of the silicate is less than 15% (w / v) is not produced a catalyst for removing harmful gases, and if it exceeds 30% (w / v) it is undesirable because the catalyst properties may be lowered.

At this time, the silicate is to improve the reactivity when preparing the catalyst for removing harmful gases, to improve the porosity of the catalyst for removing harmful gases, sodium metasilicate (Na ₂ SiO ₃ ), potassium metasilicate (K ₂ SiO ₃ ) and It is preferably one kind selected from the group consisting of lithium metasilicate (Li ₂ SiO ₃ ).

The silicate aqueous solution in step b is preferably added so that the pH of the mixed solution is 6.5 ~ 7.5. If the pH is less than 6.5, the catalyst for removing harmful gas is not sufficiently produced, and if the pH exceeds 7.5, the performance of the generated catalyst for removing the harmful gas is deteriorated, which is not preferable.

In step c, the mixed solution may be separated into a precipitate and a solution through, for example, centrifugation, sedimentation, and bag filtration, but is not limited thereto.

In the d step, the heat treatment temperature is 200 ~ 300 ℃, heat treatment time is preferably 1 to 24 hours. When the heat treatment temperature and time is less than the above range, it is difficult to generate a catalyst. When the heat treatment temperature and time are above the above range, the density increases as the liquid phase sintering by the silicate proceeds, and thus the catalyst property may be degraded, which is not preferable.

Or when the catalyst for removing the noxious gas of step 1 is a copper-manganese oxide catalyst, step (a ') preparing an aqueous solution of manganese salt;

(b 'step) adding a copper salt and a manganese salt mixed aqueous solution to the manganese salt solution and stirring to prepare a first mixed solution;

(c 'step) adding a silicate aqueous solution to the first mixed solution and then stirring to prepare a second mixed solution;

(d 'step) separating the second mixed solution into a precipitate and a solution and washing the precipitate; And

(e 'step) characterized in that it further comprises the step of drying and heat-treating the precipitate washed above.

In the a 'step, the aqueous solution of manganese salt is preferably prepared by mixing 1 to 10 parts by weight of manganese salt based on 100 parts by weight of purified water. When the amount of manganese salt is less than 1 part by weight based on 100 parts by weight of purified water, the amount of wastewater is increased, and when it exceeds 10 parts by weight, it is not preferable because it is not sufficiently dissolved or economical efficiency is lowered.

The manganese salt of step a 'or b' is preferably at least one selected from the group consisting of manganese acetate, manganese nitrate, manganese chloride, manganese iodide, manganese bromide, manganese sulfate and potassium manganese, Manganese in stage b 'may be the same or different types.

The copper salt of step b 'is preferably at least one selected from the group consisting of copper acetate, copper nitrate, copper chloride, copper iodide, copper bromide and copper sulfate.

In the b 'step, the mixed copper salt and manganese salt solution is more preferably mixed with 1 to 10 parts by weight of copper salt and 5 to 20 parts by weight of manganese salt based on 100 parts by weight of purified water. When the content of copper salt and manganese salt is less than the above range based on 100 parts by weight of purified water, the amount of wastewater is increased, and if it exceeds the above range, it is not preferable because it is not sufficiently dissolved or economical efficiency is lowered.

In the step c ', the aqueous silicate solution is preferably a silicate is mixed at a concentration of 15 to 30% (w / v). When the concentration of silicate is less than 15% (w / v), the effect of improving the reactivity of copper salts and manganese salts is insignificant, and when it exceeds 30% (w / v), the catalytic properties may be lowered, which is not preferable.

In this case, the silicate is preferably one selected from the group consisting of sodium metasilicate (Na ₂ SiO ₃ ), potassium metasilicate (K ₂ SiO ₃ ) and lithium metasilicate (Li ₂ SiO ₃ ).

In the step c ', the silicate aqueous solution is preferably added so that the pH of the second mixed solution is 6.5 ~ 7.5. If the pH is less than 6.5, the catalyst for removing harmful gas is not sufficiently produced, and if the pH exceeds 7.5, the performance of the generated catalyst for removing the harmful gas is deteriorated, which is not preferable.

In the d 'step, the mixed solution may be separated into a precipitate and a solution through, for example, centrifugation, sedimentation, and bag filtration, but is not limited thereto.

In the step e ', the heat treatment temperature is 200 ~ 300 ℃, heat treatment time is preferably 1 to 24 hours. When the heat treatment temperature and time is less than the above range, it is difficult to generate a catalyst. When the heat treatment temperature and time are above the above range, the density increases as the liquid phase sintering by the silicate proceeds, and thus the catalyst property may be degraded, which is not preferable.

In the second step, the mixture is preferably mixed with 1 to 15 parts by weight of catalyst for removing harmful gases, 15 to 35 parts by weight of silica nanoparticles and 0.5 to 5 parts by weight of clay based on 100 parts by weight of silica microparticles.

At this time, the harmful gas removal catalyst may be mixed in a form dispersed in a solvent, the solvent is preferably water. The harmful gas removal catalyst is more preferably 10 to 25 parts by weight based on 100 parts by weight of the solvent. When the content of the catalyst for removing harmful gas is less than 10 parts by weight based on 100 parts by weight of the solvent, the effect of removing harmful gases is not sufficient, and when it exceeds 25 parts by weight, it is not preferable because it is not sufficiently dissolved or economical efficiency is lowered.

In addition, the silica nanoparticles may be mixed in the form of colloidal silica in which ultrafine silicon dioxide particles are dispersed in a solvent, and the solvent is selected from the group consisting of water or methyl ethyl ketone, methyl isobutyl ketone, methanol, and isopropanol 1 It is preferable that it is a seed organic solvent. More preferably, the silicon dioxide particles are mixed in an amount of 25 to 32 parts by weight based on 100 parts by weight of the solvent. When the content of the silicon dioxide particles is less than 25 parts by weight based on 100 parts by weight of the solvent, the strength improvement effect is not sufficient, and when it exceeds 32 parts by weight, it is not preferable because it is not sufficiently dissolved or economical efficiency is lowered.

In addition, the clay may be mixed in a form dispersed in a solvent, the solvent is preferably water. The clay is more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the solvent. If the content of clay is less than 0.5 parts by weight based on 100 parts by weight of the solvent, the effect of improving strength is not sufficient, and if it exceeds 5 parts by weight, it is not preferable because it is not sufficiently dissolved or economical efficiency is lowered.

In the second step, the catalyst for removing harmful gases, silica microparticles, silica nanoparticles and clay are preferably mixed by stirring for 0.5 to 5 hours. If the stirring time is less than 0.5 hours, each component is not sufficiently mixed, if it is more than 5 hours is not economical is not preferable.

In the third step, the mixture may be extruded through an extruder, and the extruder may be used without limitation as long as it is an extruder in the form of a slurry or a dough, for example, a screw extruder may be used.

In the fourth step, the heat treatment temperature is 200 to 300 ° C, and the heat treatment time is preferably 1 to 24 hours. If the heat treatment temperature and time is less than the above range, the strength of the pellet composition is not sufficient, and if it exceeds the above range, it is not economical and is not preferable.

Pellet composition for removing harmful gases provided by the present invention can be excellent in strength to prevent damage to the reactor during molding, and excellent in long-term molding holding properties that do not destroy the molded pellet composition is easy to move and store.

In addition, the pellet composition for removing harmful gases of the present invention includes a catalyst for removing harmful gases, and thus has excellent gas removal performance, so that industrial sites, automobiles, boilers, underground roads, tunnels, underground shopping centers, underground parking lots, and general home air conditioners are sold. It can be effectively applied where the purpose is to remove harmful gases.

Hereinafter, a preferred embodiment of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, it is provided to fully convey the spirit of the present invention to those skilled in the art so that the contents introduced herein are thoroughly and completely.

Preparation Examples 1 and 2. Preparation of Catalysts for Removing Hazardous Gases

Preparation Example 1 Preparation of Manganese Oxide Catalyst

63.85 g of potassium permanganate (KMnO ₄ ) and 643.67 g of manganese acetate tetrahydrate (Mn (CH ₃ COO) ₂ .4H ₂ O) were added to 6 kg of purified water to prepare a mixed solution. Subsequently, precipitation of manganese dioxide (MnO ₂ ) was induced by a redox precipitation reaction while stirring at 16.9 ° C. for 4 hours. At this time, the pH of the solution was 5.02. Thereafter, sodium metasilicate aqueous solution (Na ₂ SiO ₃ , 23.5 w / v%) was added to the manganese dioxide precipitation solution to pH 7.0, and stirred at 17.4 ° C. for 4 hours. After the reaction was completed, the precipitate and the solution were separated using a centrifuge, and the precipitate was washed three times with distilled water to remove impurities. Subsequently, the precipitate was dried at 120 ° C. for 1 hour and then heat treated at 250 ° C. for 4 hours to prepare manganese oxide (IV) manganese (II) catalyst (Mn ₃ O ₄ catalyst), and the components of the catalyst were analyzed by X-ray fluorescence. As a result, it was confirmed that the chemical formula of (Mn ₃ O ₄ ) _0.183 (SiO ₂ ) _0.817 .

Preparation Example 2 Preparation of Copper-Manganese Oxide Catalyst

An aqueous potassium permanganate solution was prepared by dissolving 153.24 g of potassium permanganate (KMnO ₄ ) in 3 kg of purified water. Subsequently, 121.09 g of copper acetate monohydrate (Cu (CH ₃ COO) ₂ .H ₂ O) and 356.49 g of manganese acetate tetrahydrate (Mn (CH ₃ COO) ₂ .4H ₂ O) were dissolved in ₃ kg of purified water to dissolve copper-manganese acetate. An aqueous solution was prepared and the copper-manganese acetate aqueous solution was added to the aqueous potassium permanganate solution and mixed. After stirring at 17.5 ° C. for 4 hours, precipitation of CuO: MnO ₂ was induced by a redox precipitation reaction. At this time the pH of the solution was 4.38. Next, an aqueous sodium metasilicate solution (Na ₂ SiO ₃ , 23.5 w / v%) was added to the CuO: MnO ₂ precipitation solution so as to have a pH of 7.0, and stirred at 19.8 ° C. for 4 hours. After the reaction was completed, the precipitate and the solution were separated using a centrifuge, and the precipitate was washed three times with distilled water to remove impurities. The precipitate was then dried for one hour at 120 ℃, copper and heat-treated at 250 ℃ 4 hours - After a manganese oxide catalysts were prepared through the X- ray fluorescence spectrometry analysis of the components of the catalyst (K ₂ O) _0.020 (Na ₂ O) _0.013 (CuO) _0.099 (MnO ₂ ) _0.327 (SiO ₂ ) It was confirmed to have a chemical formula of _0.572 .

Examples 1 to 3 and Comparative Examples 1 to 11. Preparation of a pellet composition comprising a manganese oxide catalyst

Example 1. Preparation of pellet composition according to the production method of the present invention

2.0 kg of manganese oxide catalyst dispersion (19 wt%) prepared in Preparation Example 1, silica powder (average particle diameter 35 μm, specific surface area 217 m ² / g, pore volume 0.8 ml / g) 5.0 kg, colloidal silica (solid content 30.2 wt%) %, Particle size 12nm, 4.0kg of viscosity 9.17cps (@ 25 ℃) and 4.0kg of montmorillonite dispersion (2wt%) in a kneader and mixed for 1 hour. Subsequently, the mixed mixture was extruded into pellet granules having a diameter of 3.5 mm and a length of about 10 mm by using an extrusion type pellet granulation apparatus. Thereafter, hot air dried at 70 ° C. for 20 hours, and then heat treated at 250 ° C. for 4 hours to prepare a pellet composition including a manganese oxide catalyst.

Examples 2 to 3. Preparation of pellet composition according to the production method of the present invention

To prepare a pellet composition in the same manner as in Example 1, the weight of each composition was referred to the values in Table 1 below.

Comparative Example 1. Preparation of pellet composition using silica powder having an average particle diameter of less than 20 mu m

A pellet composition was prepared in the same manner as in Example 1, except that an average particle diameter of 18 μm and a specific surface area of 220 m ² / g were used for silica powder.

Comparative Example 2. Preparation of Pellet Composition Using Silica Powder with an Average Particle Size Over 40 µm

A pellet composition was prepared in the same manner as in Example 1, except that silica powder having an average particle diameter of 45 μm and a specific surface area of 261 m ² / g was used.

Comparative Example 3. Specific Surface Area 210m ² pellet composition using silica powder less than / g

A pellet composition was prepared in the same manner as in Example 1, except that silica powder having an average particle diameter of 35 μm and a specific surface area of 204 m ² / g was used.

Comparative Example 4 Preparation of Pellet Composition Using Colloidal Silica with Particle Size of Less Than 10nm

A pellet composition was prepared in the same manner as in Example 1, except that colloidal silica having a particle size of 8 nm was used.

Comparative Example 5. Preparation of Pellet Composition Using Colloidal Silica with Viscosity> 13 cps (@ 25 ° C)

A pellet composition was prepared in the same manner as in Example 1, but using colloidal silica having a viscosity of 15 cps (@ 25 ° C.).

Comparative example  6 to 11.Preparation of pellet compositions by varying the weight of each composition

To prepare a pellet composition in the same manner as in Example 1, the weight of each composition was referred to the values in Table 1 below.

Silica
Micro
particle
(kg) Manganese oxide
Catalyst Dispersion
(Catalyst content in dispersion)
(kg) Colloidal silica
(Silica nanoparticle content)
(kg) Clay dispersion
(In dispersion
Clay content)
(kg) Remarks Example 1 5 2 (0.38) 4 (1.208) 4 (0.08) Example 2 5 3.5 (0.665) 4 (1.208) 3.5 (0.07) Example 3 5 2 (0.38) 5.5 (1.661) 2.5 (0.05) Comparative Example 1 5 2 (0.38) 4 (1.208) 4 (0.08) Silica Microparticles Below Average Particle Size Comparative Example 2 5 2 (0.38) 4 (1.208) 4 (0.08) Silica Microparticles Above Average Particle Size Comparative Example 3 5 2 (0.38) 4 (1.208) 4 (0.08) Less than silica microparticle specific surface area Comparative Example 4 5 2 (0.38) 4 (1.208) 4 (0.08) Silica Nanoparticles Below Average Particle Size Comparative Example 5 5 2 (0.38) 4 (1.208) 4 (0.08) Silica Nanoparticle Viscosity Exceeded Comparative Example 6 - 3.5 (0.665) 5.5 (1.661) 6 (0.12) Comparative Example 7 5 3.5 (0.665) - 6.5 (0.13) Comparative Example 8 5 5 (0.95) 5 (1.51) - Comparative Example 9 5 5 (0.95) 3 (0.906) 2 (0.04) Comparative Example 10 5 2 (0.38) 6 (1.812) 2 (0.04) Comparative Example 11 5 2 (0.38) 4 (1.208) 15 (0.3)

Evaluation example  1. Characterization of Pellet Compositions Comprising Manganese Oxide Catalysts

Evaluation example  1-1. Strength of the pellet composition, Specific surface area  And pore volume measurement

The strength of the pellet composition including the manganese oxide catalyst obtained in Examples 1 to 3 and Comparative Examples 1 to 11 was measured using a strength tablet (Campbell Tablet).

In addition, the specific surface area and pore volume were measured by nitrogen adsorption-desorption isotherm analysis of the manganese oxide catalysts obtained through Examples 1 to 3 and Comparative Examples 1 to 11, and BJH (Barrett-Joyner). -Halenda) The pore diameter was calculated by the pore size model, and the results are shown in Table 2 below.

burglar
(kg / m ² ) Packing density
(g / ml) Specific surface area (S _BET )
(m ² / g) Pore volume Pore diameter (BJH)
(nm) V _total
(ml / g) V _meso
(ml / g) Example 1 5.2 0.408 232.2 0.781 0.757 45.4 Example 2 5.2 0.407 232.0 0.781 0.755 45.5 Example 3 5.4 0.413 232.6 0.784 0.759 45.1 Comparative Example 1 3.7 0.327 231.9 0.772 0.750 46.9 Comparative Example 2 3.1 0.316 231.5 0.770 0.749 46.8 Comparative Example 3 4.5 0.344 232.1 0.779 0.755 45.5 Comparative Example 4 3.4 0.321 231.8 0.770 0.747 46.9 Comparative Example 5 3.6 0.324 220.0 0.775 0.751 45.7 Comparative Example 6 2.1 0.278 251.4 0.809 0.781 41.3 Comparative Example 7 2.5 0.284 222.1 0.778 0.755 50.5 Comparative Example 8 2.7 0.297 215.3 0.765 0.741 51.2 Comparative Example 9 3.0 0.302 211.8 0.764 0.739 52.6 Comparative Example 10 4.8 0.390 231.9 0.773 0.750 46.9 Comparative Example 11 4.9 0.394 231.7 0.768 0.754 47.0

Referring to Table 2, it was confirmed that the pellet compositions of Examples 1 to 3 have improved strength compared to Comparative Examples 1, 2, 4 to 9.

Evaluation Example 1-2. Ammonia (NH ₃ ) Removal efficiency evaluation

Ammonia removal efficiency of the pellet compositions obtained through Examples 1 to 3 and Comparative Examples 1 to 11 was evaluated.

First, 1 g of the pellet composition of Examples 1 to 3 and Comparative Examples 1 to 11 was pretreated at 120 ° C. for 1 hour. Subsequently, it was encapsulated in a 10L Tedlar bag, vacuumed, a 52 ppm ammonia standard gas was injected, and a change in concentration of ammonia over time was measured using a test tube, and the results are shown in Table 3 below. It was.

NH ₃ Concentration (ppm) / removal rate (%) 30 minutes 60 minutes Example 1 20/62 12/77 Example 2 19/64 10/81 Example 3 21/60 12/77 Comparative Example 1 32/39 19/64 Comparative Example 2 27/48 17/67 Comparative Example 3 41/21 35/33 Comparative Example 4 37/29 23/56 Comparative Example 5 34/35 24/54 Comparative Example 6 30/42 25/52 Comparative Example 7 35/33 30/42 Comparative Example 8 34/35 30/42 Comparative Example 9 40/23 35/33 Comparative Example 10 40/23 34/35 Comparative Example 11 43/17 38/27

Referring to Table 3, the pellet composition of Examples 1 to 3 was excellent in the harmful gas removal effect. On the other hand, in Comparative Examples 3, 10 and 11, although the strength of the pellet composition is excellent, the catalyst performance is significantly reduced compared to Examples 1 to 3, which is not suitable for practical use.

Evaluation example  1-3. Acetaldehyde ( CH ₃ CHO ) Removal efficiency evaluation

Acetaldehyde removal efficiency of the pellet compositions obtained through Examples 1 to 3 and Comparative Examples 1 to 11 was evaluated.

First, 1 g of the pellet composition of Examples 1 to 3 and Comparative Examples 1 to 11 was pretreated at 120 ° C. for 1 hour. Subsequently, it was encapsulated in a 10L tedlar bag, vacuumed, 50 ppm concentration of acetaldehyde standard gas was injected, and a change of acetaldehyde concentration over time was measured using a test tube. Shown in

CH ₃ CHO Concentration (ppm) / removal rate (%) 30 minutes 60 minutes Example 1 27/46 20/60 Example 2 25/50 19/62 Example 3 28/44 21/58 Comparative Example 1 33/34 24/52 Comparative Example 2 31/38 23/54 Comparative Example 3 39/22 33/34 Comparative Example 4 32/36 26/48 Comparative Example 5 33/34 25/50 Comparative Example 6 38/32 30/40 Comparative Example 7 41/18 31/38 Comparative Example 8 40/20 31/38 Comparative Example 9 45/10 38/24 Comparative Example 10 45/10 39/22 Comparative Example 11 48/4 40/20

Referring to Table 4, the pellet composition of Examples 1 to 3 was excellent in the harmful gas removal effect. On the other hand, in the case of Comparative Examples 3, 10 and 11, although the strength of the pellet composition is excellent, the catalyst performance is significantly reduced compared to Examples 1 to 3, which is not suitable for practical use.

Evaluation example  1-4. Nitrogen Dioxide (NO ₂ ) Removal efficiency evaluation

Nitrogen dioxide removal efficiency for the pellet compositions obtained through Examples 1 to 3 and Comparative Examples 1 to 11 was evaluated.

First, 20 g of the pellet compositions of Examples 1 to 3 and Comparative Examples 1 to 11 were pretreated at 120 ° C. for 1 hour. Subsequently, it was encapsulated in a 10L Tedlar bag and vacuum-treated, and nitrogen dioxide at a concentration of 55 ppm was injected, and a change in concentration of nitrogen dioxide over time was measured using a test tube, and the results are shown in Table 5 below.

NO ₂ Concentration (ppm) / removal rate (%) 30 minutes 60 minutes Example 1 28/49 15/73 Example 2 25/56 12/78 Example 3 29/47 16/71 Comparative Example 1 37/33 31/44 Comparative Example 2 35/36 29/47 Comparative Example 3 46/16 40/27 Comparative Example 4 39/29 32/42 Comparative Example 5 38/31 32/42 Comparative Example 6 33/40 28/49 Comparative Example 7 38/31 31/44 Comparative Example 8 37/33 31/44 Comparative Example 9 40/27 33/40 Comparative Example 10 45/18 39/29 Comparative Example 11 47/15 41/26

Referring to Table 5, the pellet composition of Examples 1 to 3 was excellent in the harmful gas removal effect. On the other hand, in the case of Comparative Examples 3, 10 and 11, although the strength of the pellet composition is excellent, the catalyst performance is significantly reduced compared to Examples 1 to 3, which is not suitable for practical use.

Example 4 and Comparative Examples 12 to 14. Preparation of a Pellet Composition Comprising a Copper-Manganese Oxide Catalyst

Example 4 Preparation of a Pellet Composition According to the Manufacturing Method of the Present Invention

2.0 kg of copper-manganese oxide catalyst dispersion (16 wt%) prepared in Preparation Example 2, silica powder (average particle diameter 35 μm, specific surface area 217 m ² / g, pore volume 0.8 ml / g) 5.0 kg, colloidal silica (solid content) 30.2 wt%, particle size 12 nm, 4.0 kg of viscosity 9.17 cps (@ 25 ° C.) and 4.0 kg of montmorillonite dispersion (2 wt%) were added to a kneader and mixed for 1 hour. Subsequently, the mixed mixture was extruded into pellet granules having a diameter of 3.5 mm and a length of about 10 mm by using an extrusion type pellet granulation apparatus. Thereafter, hot air dried at 70 ° C. for 20 hours, and then heat treated at 250 ° C. for 4 hours to prepare a pellet composition including a copper-manganese oxide catalyst.

Comparative Examples 12 to 14. Preparation of pellet composition by varying the weight of each composition

To prepare a pellet composition in the same manner as in Example 4, the weight of each composition was referenced to the values in Table 6.

Silica Micro Particles (kg) Copper-Manganese Oxide Catalyst Dispersion
(Catalyst content in dispersion)
(kg) Silica nanoparticles
(kg) Clay dispersion
(Clay content in dispersion)
(kg) Example 4 5 2 (0.32) 4 4 (0.08) Comparative Example 12 - 4.5 (0.72) 5.5 5 (0.1) Comparative Example 13 5 4.5 (0.72) - 5.5 (0.11) Comparative Example 14 5 4.5 (0.72) 5.5 -

Evaluation example  2. Characterization of Pellet Compositions Containing Copper-Manganese Oxide Catalysts

Evaluation Example 2-1. Determination of strength, specific surface area and pore volume of pellet composition

The strength of the pellet composition comprising the copper-manganese oxide catalyst obtained in Example 4 and Comparative Examples 12-14 was measured using a strength tablet (Campbell Tablet).

In addition, the specific surface area and the pore volume were measured by nitrogen adsorption-desorption isotherm analysis of the copper-manganese oxide catalysts obtained in Example 4 and Comparative Examples 12 to 14, and BJH (Barrett-Joyner). -Halenda) The pore diameter was calculated by the pore size model, and the results are shown in Table 7 below.

burglar
(kg / m ² ) Filling density (g / ml) Specific surface area (S _BET )
(m ² / g) Pore volume Pore diameter (BJH)
(nm) V _total
(ml / g) V _meso
(ml / g) Example 4 6.2 0.388 200.9 0.676 0.655 49.6 Comparative Example 12 3.4 0.206 228.6 0.728 0.721 32.4 Comparative Example 13 3.7 0.213 181.2 0.624 0.619 50.8 Comparative Example 14 3.6 0.210 204.4 0.679 0.653 44.7

Referring to Table 7, it was confirmed that the pellet composition of Example 4 has a significantly improved strength compared to Comparative Examples 12 to 14.

Therefore, the present invention can satisfy both excellent strength and catalyst performance by limiting the properties and content of each component in the preparation of the pellet composition.

Claims (10)

1 to 15 parts by weight of catalyst for removing harmful gases, 15 to 35 parts by weight of silica nanoparticles and 0.5 to 5 parts by weight of clay, based on 100 parts by weight of silica microparticles,
The silica microparticles have an average particle size of 20 to 40㎛, specific surface area of 210 to 270m ² / g, void volume of 0.6 ~ 0.9ml / g,
The silica nanoparticles have an average particle size of 10 ~ 20nm, the viscosity is a high-strength pellet composition containing a catalyst for removing harmful gases, characterized in that less than 13cps at 25 ℃. The method of claim 1,
The hazardous gas removal catalyst is a high-strength pellet composition containing a catalyst for removing harmful gases, characterized in that the manganese oxide catalyst or copper-manganese oxide catalyst. delete delete The method of claim 1,
The clay is montmorillonite, bentonite, hectorite, beadelite, nontronite, saponite, laponite, dolomite, talc, leadstone, vermiculite, kaolin, halosite, illite, green stone, brookite, vermiculite, synthetic A high-strength pellet composition containing a catalyst for removing noxious gas, characterized in that at least one selected from the group consisting of mica, canneite, margotite, and kenyanite. delete (Step 1) preparing a catalyst for removing harmful gas;
(Step 2) preparing a mixture by mixing the catalyst for removing harmful gases, silica microparticles, silica nanoparticles and clay;
(Step 3) extruding the mixture to prepare a molding composition; And
(Step 4) heat-treating the molding composition; including;
In the second step, the mixture includes 1 to 15 parts by weight of a catalyst for removing harmful gas, 15 to 35 parts by weight of silica nanoparticles, and 0.5 to 5 parts by weight of clay based on 100 parts by weight of silica microparticles,
The silica microparticles have an average particle size of 20 to 40㎛, specific surface area of 210 to 270m ² / g, void volume of 0.6 ~ 0.9ml / g,
The silica nanoparticles have an average particle size of 10 ~ 20nm, the viscosity is a method for producing a high-strength pellet composition containing a catalyst for removing harmful gases, characterized in that less than 13cps at 25 ℃. The method of claim 7, wherein
The first step of the noxious gas removal catalyst is a manganese oxide catalyst or a copper-manganese oxide catalyst, the method for producing a high-strength pellet composition containing a noxious gas removal catalyst, characterized in that. The method of claim 8,
The manganese oxide catalyst (step a) to prepare a manganese salt solution;
(b) adding a silicate aqueous solution to the aqueous solution of manganese salt and stirring to prepare a mixed solution;
(c) separating the mixed solution into a precipitate and a solution and washing the precipitate; And
(d) a method for producing a high-strength pellet composition containing a catalyst for removing harmful gases, characterized in that it comprises the step of drying and heat-treating the washed precipitate. The method of claim 8,
The copper-manganese oxide catalyst (a 'step) to prepare a solution of manganese salt;
(b 'step) adding a copper salt and a manganese salt mixed aqueous solution to the manganese salt solution and stirring to prepare a first mixed solution;
(c 'step) adding a silicate aqueous solution to the first mixed solution and then stirring to prepare a second mixed solution;
(d 'step) separating the second mixed solution into a precipitate and a solution and washing the precipitate; And
(e 'step) method for producing a high-strength pellet composition containing a catalyst for removing harmful gases, characterized in that it comprises the step of drying and heat treatment the precipitate washed.