KR101952314B1 - Method of stacked hexagonal type catalyst cartridge for selective catalytic reduction and catalyst carrier using the same - Google Patents

Abstract

A method for manufacturing a catalyst module element according to the present invention comprises the steps of: a) coating a ceramic fiber sheet with a slurry containing a carrier raw material, a catalyst raw material and an inorganic process additive; And b) drying the coated ceramic fiber sheet.

Description

[0001] The present invention relates to a method of manufacturing a hexagonal stacked hexagonal selective catalytic reduction catalyst,

The present invention relates to a process for producing a stacked hexagonal selective catalyst reduction catalyst cartridge and a catalyst carrier using the same, and more particularly to a process for producing a stacked hexagonal selective catalytic reduction catalyst cartridge by stacking sheet- A hexagonal selective catalyst reduction catalyst cartridge, and a catalyst support using the same.

According to the Kyoto Protocol, greenhouse gas emission regulations are being implemented in favor of currently advanced countries, and greenhouse gas emission regulations are being implemented in various fields such as energy, transportation, and agriculture. In particular, emission gas regulations for fixed and mobile pollutants using high temperature combustion systems are constantly being strengthened.

Nitrogen oxides (NOx) in the exhaust gas generated from combustion reactors at high temperatures, such as thermal power plants, cogeneration plants, and chemical plants, are a direct cause of air pollution such as acid rain and smog generation. The emission of nitrogen oxides is regulated, and the regulation value becomes increasingly severe.

As a method for removing such NOx, there is a method of improving the combustion condition on the generation mechanism by using the combustion technique and the burner technique such as the low-excess air combustion method, the exhaust gas recirculation method, the low NOx burner utilization method, and the generation of NOx (SCR), Selective Non-Catalytic Reduction (SNCR), plasma process, and wet process are methods of post-treatment of nitrogen oxides discharged from combustion.

Although the pretreatment method is fundamentally an ideal method for suppressing the formation of nitrogen oxides, the energy efficiency and the removal efficiency of nitrogen oxides are much lower than those of the post-treatment methods. Therefore, since most of the nitrogen oxides can not be completely removed, (NOx) is mixed with a reducing agent at a relatively low temperature by using a reducing agent such as ammonia (NH3), urea or hydrocarbon (HC), and nitrogen oxides (NOx) (Selective Catalytic Reduction (SCR)) which reduces harmful nitrogen (N ₂ ) and water vapor.

The catalyst used in this selective catalytic reduction technique may be classified into a honeycomb structure type monolithic catalyst produced by an extrusion molding process, a metal plate catalyst produced using a metal plate, a pellet catalyst, Body type monolytic catalyst and plate catalyst are mainly used. Such a catalyst is a catalyst prepared by carrying one or more active metal oxides such as vanadium oxide, tungsten oxide, molybdenum oxide, and iron oxide in a titanium dioxide, alumina, zirconia, silica, zeolite, etc., which are large in specific surface area and chemically stable carrier raw materials Is prepared by using a catalyst raw material powder. Particularly, the honeycomb structure type monolithic catalyst is produced by extruding the clay made by adding various organic and inorganic additives to the above catalyst raw material through a mold having a desired shape, extruding it into a honeycomb structure, drying it, and calcining it.

The honeycomb structure type monolithic catalyst is advantageous in that it can easily control the specific surface area and the pore size and is effective in reducing the nitrogen oxide by supporting the active metal oxide. On the other hand, when the catalyst itself contains the expensive active metal oxide, Gamma-alumina, zeolite, and the like, it consumes a large amount of expensive raw material, and in addition to a large amount of various organic and inorganic process additives to overcome the problem of titanium dioxide which is not easily formed and the low strength due to low temperature calcination The production yield is low and the production cost is high due to the long baking process due to the effect of the organic additive.

Korean Patent No. 10-1308496

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a method for manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge having excellent moldability.

Another object of the present invention is to provide a method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge, which can be easily optimized for each process by simplifying the manufacturing process, and is excellent in moldability so as to shorten production time and cost.

Another object of the present invention is to provide a catalyst carrier using a stacked hexagonal selective catalyst reduction catalyst cartridge manufacturing method.

On the other hand, other unspecified purposes of the present invention will be further considered within the scope of the following detailed description and easily deduced from the effects thereof.

In order to achieve the above object, a method of manufacturing a catalyst module element having a hexagonal cell according to an embodiment of the present invention comprises the steps of: a) providing 20 to 60% by weight of a carrier raw material, 0.1 to 10% 25 to 65% by weight of silica, and 0.1 to 10% by weight of a silane-based compound; b) drying the coated ceramic fiber sheet; c) forming a semi-hexagonal pattern on the side surface of the dried ceramic fiber sheet to produce a sheet-like cartridge; And d) laminating the sheet-like cartridge, wherein the catalyst material comprises one or more precursors selected from a vanadium precursor, a tungsten precursor, a molybdenum precursor, a ceria precursor, an iron precursor, and a manganese precursor, Based compound is any one selected from the group consisting of trimethoxysilylpropyl aniline (TMSPA), tetramethylorthosilicate, tetraethylorthosilicate (TEOS), tetrapropyl orthosilicate, tetrabutylorthosilicate, and mixtures thereof.

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In the method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention, after the step d), e) heat treating the stacked sheet-like cartridges.

In the method for manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention, the carrier raw material may be one or more selected from titanium dioxide, alumina, silica, alumina-silica, zirconia, zeolite and cordierite Oxide. ≪ / RTI >

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In the method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention, the slurry includes an inorganic filler containing at least one of clay and alumina (Al ₂ O ₃ ) 1 to 20% by weight based on the total weight of the slurry.

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In the method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention, the ceramic fiber sheet is immersed in the slurry for 10 seconds, and the weight is measured to find that the immersion rate defined by the following formula 1 is 200% .

[Formula 1]

(Wherein, W _m (%) is a needle supporting ratio, W ₁ (g) before immersion is the weight, W ₂ (g) after immersion is no game)

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The stacked hexagonal selective catalytic reduction catalyst cartridge according to the technical idea of the present invention can reduce the amount of expensive catalyst raw material and exhibit excellent catalytic activity.

The catalyst carrier having a hexagonal-shaped cell has a wide contact area and a porosity, and is also excellent in vibration resistance characteristics.

The method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to the technical idea of the present invention simplifies the manufacturing process, facilitates optimization for each process, and shortens production time and cost.

On the other hand, even if the effects are not explicitly mentioned here, the effect described in the following specification, which is expected by the technical features of the present invention, and its potential effects are treated as described in the specification of the present invention.

1 is a process flow diagram of a method for manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention.
2 is a process flow diagram of a method for manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention.
3 is a process flow diagram of a method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to another embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The following embodiments and drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. In addition, unless otherwise defined in the technical and scientific terms used herein, unless otherwise defined, the meaning of what is commonly understood by one of ordinary skill in the art to which this invention belongs is as follows, A description of known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted.

In describing the present invention, the terms first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

Furthermore, the terms used in the present invention are used only to describe specific embodiments, and are not intended to limit the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present invention, the terms "comprising" or "having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

A method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention comprises the steps of: a) coating a ceramic fiber sheet with a slurry containing a carrier raw material, a catalyst raw material, and an inorganic process additive; And b) drying the coated ceramic fiber sheet.

In describing the present invention, the term "carrier" means a structure for supporting and supporting a catalyst, and ceramic materials can be used as an example thereof.

1 is a process flow diagram of a method for manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention. 2 is a process flow diagram of a method for manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention. 3 is a process flow diagram of a method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to another embodiment of the present invention.

1, a method for manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention includes a step S100 of manufacturing a ceramic fiber sheet, a step S200 of coating a slurry, a step S300 of manufacturing a sheet- , And a catalyst module device manufacturing step (S400).

The ceramic fiber sheet manufacturing step (S100) is silica (SiO _2), alumina (Al ₂ O _3), calcium (CaO), and dried to furnish comprising magnesium (MgO), and organic oxidation for producing a ceramic fiber sheet oxide .

The ceramic fiber sheet may include 40 to 60 wt% of the silica (SiO ₂ ), 10 to 30 wt% of the alumina (Al ₂ O ₃ ), 10 to 30 wt% of the calcium oxide (CaO) ) 1 to 5 wt%.

In detail, the ceramic fiber sheet may include 40 to 60 wt% of silica (SiO ₂ ) so as to basically form and stabilize the network of the ceramic fiber sheet.

In detail, the ceramic fiber sheet may contain 10 to 30 wt% of calcium oxide (CaO) so as to reduce viscosity while having a filling function.

In detail, the ceramic fiber sheet may include 10 to 30 wt% of aluminum oxide (Al ₂ O ₃ ) so as to function as a network forming agent.

In detail, the ceramic fiber sheet may contain 1 to 5 wt% of magnesium oxide (MgO) so as to control the liquidus temperature.

On the other hand, the ceramic fiber sheet may be dipped in the slurry for 10 seconds and measured for its weight, so that the dipping rate defined by the following formula 1 may be 200% or more.

[Formula 1]

(Wherein, W _m (%) is a needle supporting ratio, W ₁ (g) before immersion is the weight, W ₂ (g) after immersion is no game)

In detail, the ceramic fiber sheet having a dipping rate of 200% or more is impregnated with the slurry described above, thereby imparting moldability to the slurry-coated ceramic fiber sheet and maintaining the shape thereof. When the dipping rate is 200% or less, sufficient slurry can not be impregnated into the ceramic fiber sheet, and this effect can not be obtained.

Next, the slurry coating step (S200) will be described.

The slurry coating step (S200) may mean coating the slurry containing the carrier raw material, the catalyst raw material, and the inorganic process additive described above on the ceramic fiber sheet produced in the above-described ceramic fiber sheet manufacturing step (S100).

In detail, the carrier raw material may be any one that serves as the above-mentioned carrier. The kind of the carrier raw material may be those conventionally used in this field. As a specific example, the carrier raw material may include one or two or more oxides selected from silica, alumina, silica-alumina, titanium dioxide, zirconia, and zeolite. Any one or two or more of them may be used as the carrier raw material, but titanium dioxide is preferable in terms of cost competitiveness and sulfur durability improvement.

The carrier raw material may be included in an amount of 20 to 60% by weight based on the total weight of the slurry. The slurry satisfying the above-mentioned categories is preferable for improving the dispersibility with other mixtures and improving the performance of the catalyst itself. If the carrier raw material is less than 20% by weight, the performance of the catalyst itself may be deteriorated. Also, when the carrier raw material is more than 60% by weight, the viscosity of the slurry is not only rapidly increased but also can be nonuniformly coated on the surface of the fiber sheet.

The catalyst raw material is supported on the carrier raw material described above, and serves to reduce the nitrogen oxides by generating acid sites at the carrier raw material or carrier interface. In addition, the catalyst raw material can suppress the conversion of sulfur dioxide present in the exhaust gas discharged from ships, automobiles, etc. to sulfur trioxide or other sulfur compounds.

In the method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention, the catalyst raw material may include one or more precursors selected from vanadium precursor, tungsten precursor, molybdenum precursor, ceria precursor, iron precursor, and manganese precursor . ≪ / RTI >

In detail, the catalyst material may be contained in an amount of 0.1 to 10% by weight based on the total weight of the slurry. The content of the catalyst raw material may vary depending on the environment to which the catalyst according to the present invention or the catalyst carrier is applied, so that the present invention is not limited to the content of the catalyst raw material. However, when the content of the catalyst raw material is less than 0.1 wt%, it is difficult to realize the desired denitration performance of the present invention. When the content of the catalyst raw material is more than 10 wt%, the catalyst content is excessively carried The conversion rate from the dialysis term to the triple termination term is increased and the durability of the catalyst due to the formation of by-products may be lowered.

The inorganic process additive serves to improve the dispersibility, viscosity, coating property, and the like of the slurry, and also improves moldability, strength, durability, etc. of the catalyst cartridge according to the present invention.

In particular, the inorganic processing additive may comprise colloidal silica. The slurry according to the present invention can improve the viscosity, gelling property, compatibility, etc. of the slurry by including the colloidal silica.

In the context of the present invention, the term "colloid " refers to fine particles dispersed in a solution, the particles having a particle size of up to about 1 μm, such as from about 20 nm to about 800 nm, 500 nm. Here, the solution may mean a medium containing water.

In describing the present invention, the term "colloidal silica" may refer to a material containing silicon dispersed in a solution. For example, the colloidal silica may be a silicon oxide in a sol or jelly state, and may be a silica mixed solution dispersed in a specific solution.

As a specific, non-limiting example, the colloidal silica may be prepared from sodium silicate by ion exchange and acid-neutralization methods, and then growing the produced particles to have particles of uniform size distribution.

In the method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention, the colloidal silica may include 35 to 350 parts by weight of the colloidal silica relative to 100 parts by weight of the carrier raw material. Accordingly, the slurry according to the present invention not only improves the physical strength not dissolved or softened under acidic conditions, but also chemically stable at a high temperature and can have a high surface area.

In detail, when the amount of the colloidal silica is less than 35 parts by weight based on 100 parts by weight of the carrier raw material, the viscosity may increase rapidly and the mixing property of the slurry may be deteriorated. When the amount of the colloidal silica is more than 350 parts by weight based on 100 parts by weight of the carrier raw material, the coating property of the slurry on the ceramic fiber sheet may be a problem, and the content of the carrier raw material may be relatively decreased The function of the catalyst itself may be deteriorated.

On the other hand, the silica content (solid content) of the colloidal silica may include 20 to 50% by weight. Colloidal silica having a high concentration of 50% by weight or more has a problem of being liable to gel or precipitation of silica. In addition, the colloidal silica may contain 50 to 70% by weight of polyethylene glycol and may be stably dispersed and stored and transported. Can be obtained by polymerizing ethylene oxide, and can be a solvent excellent in molecular structure.

In addition, in the method for manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention, the above inorganic processing additive may include colloidal silica, an inorganic filler, and a silane compound.

In detail, the inorganic filler serves to prevent cracks between the ceramic fiber sheet and the slurry in the step S300 of producing a sheet-like cartridge to be described later. In one example, the inorganic filler may include at least one of clay, alumina (Al ₂ O ₃ ), and the like. Accordingly, the catalyst cartridge or the catalyst carrier according to the present invention can have an effect of improving the strength thereof. At this time, the inorganic filler may be included in an amount of 1 to 20 wt% based on the total weight of the slurry.

As a specific example, when the inorganic filler includes the clay, the clay may be 1 to 10% by weight based on the total weight of the slurry.

In another specific example, when the inorganic filler includes the alumina, the alumina may be 1 to 10 wt% based on the total weight of the slurry.

On the other hand, the silane-based compound has a role of imparting moldability and strength by bonding with the amorphous silica contained in the above-mentioned colloidal silica. At this time, the silane compound may be contained in an amount of 0.1 to 10% by weight based on the total weight of the slurry. When the content of the silane compound is less than 0.1 wt%, the effect of addition of the silane compound is insignificant. When the content of the silane compound exceeds 10 wt%, the addition of the silane compound causes crystallization, Problems can arise.

In a specific, non-limiting example, the silane-based compound is selected from the group consisting of trimethoxysilylpropyl aniline (TMSPA), tetramethylorthosilicate, tetraethylorthosilicate (TEOS), tetrapropylorthosilicate, tetrabutylorthosilicate, And may be any one selected from the group consisting of

In addition, in the method of manufacturing a stacked hexagonal selective catalytic reduction catalyst cartridge according to an embodiment of the present invention, the slurry may further include at least one of a binder, a dispersant, a surfactant, and a release agent.

In detail, it is sufficient that the binder improves the formability of the ceramic fiber sheet coated with the slurry. For example, the binder may be selected from the group consisting of polyvinyl alcohol (PVA), polyvinyl butyral (PVB), hydroxyethyl cellulose (HEC), polymethyl cellulose (PMC), polymethylmethacrylate (PMMA), paraffin , Wax emulsion, microcrystalline wax, and the like. As a specific, non-limiting example, the binder may comprise from 1 to 10% by weight based on the total weight of the slurry.

Specifically, the dispersant may be one used for dispersion stabilization of the carrier raw materials described above. As a specific and non-limiting example, the dispersant may be included in an amount of 1 to 10 parts by weight based on the total weight of the slurry.

Specifically, the dispersant may be an anionic dispersant. For example, the anionic dispersant may be an anionic dispersant having a phosphoric acid functional group. For example, the anionic dispersing agent having a phosphoric acid functional group is selected from the group consisting of BYK-W903, BYK-W9010, BYK 110, BYK 180, Darvan-C, α-terpineol, SN dispersant 9228, Rhodamine- Any one or more can be used.

Further, the dispersant may further include a solvent. The solvent includes, for example, hexane, toluene, cyclohexanone, ethyl cellosolve, butyl cellosolve, butyl carbitol (diethylene glycol monobutyl ether), dibutyl carbitol (diethylene glycol dibutyl ether) , Propylene glycol monomethyl ether and the like; a solvent such as butyl carbitol acetate (diethylene glycol monobutyl ether acetate), hexylene glycol, alpha-terpineol, methyl ethyl ketone, benzyl alcohol, Gamma-butyrolactone, ethyl lactate, 3-pentanediol, 2,2,4-trimethyl-monoisobutyrate (Texanol) may be used alone or in combination of two or more.

Specifically, the surfactant may have a function of stabilizing uneven particle charges, and more specifically, it may prevent the amorphous silica particles in the colloidal silica from being synthesized on the surface of the carrier raw material. As a specific, non-limiting example, the surfactant may be included in an amount of 1 to 5 wt% based on the total weight of the slurry.

At this time, the surfactant may be a silicone surfactant. The silicone surfactant may comprise a polyether modified polydimethylsiloxane. Specific examples of the nonionic surfactant include BYK-301, BYK-306, BYK-307, BYK-320, BYK-325, BYK-331, BYK-333, BYK- At least one selected from the group consisting of -337, BYK-341, BYK-344, BYK-346, BYK-347, BYK-348, BYK-349, BYK-370, BYK- Can be used.

In addition, the surfactant may include any one of a nonionic surfactant, a cationic surfactant, and an anionic surfactant. Examples of such surfactants include ethoxylate nonylphenol, ethoxylated tridecyl alcohol, sodium stearate, sodium disopropynaphthalene sulfonate, And may include any one or two or more selected from potassium pyrophosphate, sodium hexametaphosphate, and Dodecyltrimethlyammoium chloride.

Specifically, the mold release agent can prevent the ceramic fiber sheet coated with the slurry from adhering to the mold for pattern formation when shaping the mold. As a specific, non-limiting example, the release agent may be included in an amount of 1 to 5% by weight based on the total weight of the slurry 100. If the content of the releasing agent is less than 1% by weight, the effect on addition of the releasing agent is insignificant. If the content of the releasing agent is more than 5 parts by weight, a large amount of organic materials may be produced. Therefore, a further heat treatment process may be required to remove such organic materials.

At this time, the releasing agent may be glycerin, mineral oil, ferrous, and the like, but the present invention is not limited to the type of the releasing agent.

Next, the sheet-like cartridge manufacturing step (S300) will be described.

In the method of manufacturing a catalyst module element having a hexagonal cell according to an embodiment of the present invention, the sheet-type cartridge manufacturing step S300 includes a step S310 of drying the coated ceramic fiber sheet in the slurry coating step S200 ), And a semi-hexagonal pattern forming step (S320) by processing the dried ceramic fiber sheet.

More specifically, the step of drying the ceramic fiber sheet (S310) may be a step of drying the ceramic fiber sheet coated with the slurry so that the moisture content thereof is controlled. That is, if the moisture content in the ceramic fiber sheet becomes too high, the ceramic fiber sheet becomes stuck to the metal mold during the shaping process, and molding breakage can occur. On the other hand, when the moisture content of the ceramic fiber sheet is low, the moldability of the ceramic fiber sheet is lowered, so that the moisture content in the fiber sheet is suitably adjusted. In order to control the moisture content, the drying temperature may be about 100 ° C or higher and the drying may be performed for 1 to 100 seconds in the step of drying the ceramic fiber sheet (S310). However, But is not limited to. Further, in the step of drying the ceramic fiber sheet (S310), hot air drying, infrared drying, or the like may be used as the drying method, but the present invention is not limited to the drying method.

In more detail, the semi-hexagonal pattern forming step S320 may include forming a semi-hexagonal pattern on the side surface of the dried ceramic fiber sheet in step S310 of drying the ceramic fiber sheet.

In describing the present invention, the term "semi-hexagonal pattern" may mean a shape in which hexagonal shapes are symmetrically split in half. In one embodiment of the present invention, in the semi-hexagonal pattern forming step S320, a sheet-like cartridge protruding or recessed in a semi-hexagonal shape along one side of the ceramic fiber sheet may be manufactured.

More specifically, the semi-hexagonal pattern forming step (S320) may be a step of forming a continuous semi-hexagonal pattern using a roll press on the side surface of the dried ceramic fiber sheet. That is, in the semi-hexagonal pattern forming step (S320), the ceramic fiber sheet is moved to a bending roll press that generates heat at 150 to 400 ° C, so that a bent half-hexagonal pattern can be continuously formed. At this time, when the temperature of the roll press is raised to 150 to 400 ° C., the organic matter in the ceramic fiber sheet is removed, and at the same time, the formed mixture is dried and bonded, thereby maximizing the formability.

Finally, the catalyst module element manufacturing step (S400) will be described.

In the method of manufacturing a catalyst module element in which a hexagonal cell is formed according to an embodiment of the present invention, the catalyst module element manufacturing step (S400) includes a step of stacking the sheet type cartridge manufactured in the above-described sheet type cartridge manufacturing step (S300) S410), and heat treating the stacked sheet-like cartridges (S420).

In more detail, the step S410 of stacking the sheet-type cartridges may be a step of cross-stacking the unit bodies in the stacking direction using the sheet-like cartridges as one unit. That is, the adjacent unit pieces of the unit body cross each other to form a hexagonal cell between the unit bodies.

Specifically, the step S420 of heat-treating the sheet-like cartridge may be a step of heating the stacked sheet-like cartridges to remove the organic additive in the slurry described above, and oxidizing and activating the catalyst raw material added in the form of a precursor.

More specifically, the step of heat-treating the sheet-type cartridge (S420) may perform firing at a temperature of 300 to 650 ° C. for about 1 to 3 hours by using a firing furnace of a tunnel type structure in the stacked sheet type cartridge, But is not limited to the firing temperature and the holding time.

According to another aspect of the present invention, there is provided a method of manufacturing a ceramic fiber sheet, comprising the steps of: a) first coating the ceramic fiber sheet with the inorganic process additive described above; b) second coating a first coated ceramic fiber sheet with a slurry containing the carrier material and the catalyst material as described above; And c) drying the second coated ceramic fiber sheet.

Referring to FIG. 2, the method for fabricating a stacked hexagonal selective catalytic reduction catalyst cartridge according to another embodiment of the present invention includes a step S100 of manufacturing a ceramic fiber sheet, an inorganic process additive coating step S150, a slurry coating step S201, , A sheet-like cartridge manufacturing step (S300), and a catalyst module element manufacturing step (S400).

The ceramic fiber sheet manufacturing step (S100), the sheet-like cartridge manufacturing step (S300), and the catalyst module element manufacturing step (S400) are the same as described above.

The inorganic process additive coating step (S150) may mean a first coating of the inorganic process additive on the ceramic fiber sheet produced in the ceramic fiber sheet production step (S100).

The slurry coating step (S201) may refer to the second coating of the slurry containing the carrier raw material and the above-mentioned catalyst raw material in the first coated ceramic fiber sheet in the inorganic process additive coating step (S150) .

Further, the present invention includes a catalyst module element using the above-described method of manufacturing a catalyst module element having a hexagonal cell.

A catalyst module element having a hexagonal cell according to an embodiment of the present invention may be a stacked sheet-type cartridge having a semi-hexagonal pattern. Accordingly, the present invention can improve the moldability by coating the above-mentioned slurry on the above-mentioned ceramic fiber sheet to maintain a stable structure after forming the semi-hexagonal pattern. In particular, a continuous semi-hexagonal pattern is formed to have a stable geometrical structure, so that the vibration resistance and pressure loss characteristics of the catalyst module element can be improved.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.

Examples 1-5

Manufacture of ceramic fiber sheet

Wherein 10 to 30 parts by weight of an organic material is prepared in an amount of 10 to 15 wt% of Al ₂ O ₃ , 30 to 50 wt% of SiO _2, 30 to 50 wt% of CaO, 1 to 5 wt% of MgO, . Mixing the inorganic material and the organic material raw material and agitating the raw material, forming a raw material with the raw raw material, improving the surface smoothness of the raw material, and drying the raw material having improved smoothness, A ceramic fiber sheet having a thickness of 500 mm and a thickness of 0.35 mm was produced.

Preparation of titanium dioxide mixed slurry

Titanium dioxide on anatase crystal (TiO ₂₎ powder, colloidal silica, clay (NCMA-40, Mizusawa Industrial Chemicals ), alumina (Al ₂ O ₃₎ powder, silanes, dispersing agents, binders, surface active agent, mineral oil, and vanadium precursors (Ammonium metavanadate) were stirred and ultrasonically dispersed to prepare a titanium dioxide mixed slurry.

The titanium dioxide mixed slurry prepared in the following Table 1 was subjected to viscosity evaluation, gelation evaluation and mixing evaluation. The viscosity was evaluated at 25 ° C using a Brookfield viscometer (using a Spindle 60 series, adjusted within a range of 50 ± 10%). Excellent: ⊚, good: ◯, poor: Δ, poor: X The gelation was performed by coating the above-mentioned titanium dioxide mixed slurry on glass and then leaving it at 25 캜 and 50% relative humidity for 100 hours, and then, on the glass surface, on the basis of the presence or absence of an oil film: Excellent: : X. < / RTI > The blendability of the titanium dioxide mixed slurry was expressed as zeta potential according to KS Q ISO 24153: excellent: ⊚, good: ◯, insufficient: Δ, poor: X through viscosity measurement.

As shown in Table 1, the viscosity increases in proportion to the increase of the contents of titanium dioxide and silane, and also the viscosity decreases in inverse proportion to the increase of the colloidal silica content. The gelation was confirmed to be directly affected by the amount of silane. If the amount of silane exceeds 10% by weight, the gelation progresses at a short time at room temperature. It was confirmed that the mixing property was affected by the content of colloidal silica. When the content of the colloidal silica is less than 25% by weight, the powdery phase is contained in the titanium dioxide mixed slurry and mixing is impossible. It was also confirmed that the mixing property was influenced by the silane content. That is, when the amount of the silane exceeds 10% by weight, the titanium dioxide mixed slurry is gelled and is incapable of mixing.

In addition, the titanium dioxide mixed slurry may contain 20 to 60% by weight of the titanium dioxide, 25 to 65% by weight of the colloidal silica and 1 to 10% by weight of the silane, and the silanized colloidal silica particles may be precipitated or precipitated without gelation Dispersed in a stable manner, excellent in mixing properties of various particles, and confirmed to have an appropriate viscosity for producing a sheet type cartridge.

As described above, the sheet-like cartridge according to the present invention is characterized in that a ceramic fiber sheet containing silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), calcium oxide (CaO) and magnesium oxide (MgO) is coated with titanium dioxide, colloidal silica, , A titanium dioxide slurry containing alumina, silane, a dispersant, a binder, a surfactant, a mineral oil, and a vanadium precursor is impregnated and can have excellent moldability.

The catalyst module device according to the present invention is advantageous in that the sheet-like cartridges having excellent moldability are stacked to form hexagonal cells, the geometric contact area is high, the deposition of particulate matter is prevented, and the mechanical impact is strong. In addition, a sheet-type cartridge is laminated and produced, thereby simplifying the process and facilitating optimization for each process.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (17)

a) coating a slurry containing 20 to 60% by weight of carrier raw material, 0.1 to 10% by weight of catalyst raw material, 25 to 65% by weight of colloidal silica, and 0.1 to 10% by weight of silane based compound in a ceramic fiber sheet;
b) drying the coated ceramic fiber sheet;
c) forming a semi-hexagonal pattern on the side surface of the dried ceramic fiber sheet to produce a sheet-like cartridge; And
d) stacking the sheet-like cartridges,
Wherein the catalyst material comprises one or more precursors selected from a vanadium precursor, a tungsten precursor, a molybdenum precursor, a ceria precursor, an iron precursor, and a manganese precursor,
The silane-based compound is any one selected from the group consisting of trimethoxysilylpropyl aniline (TMSPA), tetramethyl orthosilicate, tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate, tetrabutyl orthosilicate, A method of manufacturing a stacked hexagonal selective catalyst reduction catalyst cartridge.
delete delete The method according to claim 1,
After the step d)
and e) heat treating the stacked sheet-like cartridges.
The method according to claim 1,
Wherein the carrier raw material comprises one or two or more oxides selected from titanium dioxide, alumina, silica, alumina-silica, zirconia, zeolite and cordierite.
delete delete delete The method according to claim 1,
The slurry
Clay, and alumina (Al ₂ O ₃ )
Wherein the inorganic filler is contained in an amount of 1 to 20 wt% based on the total weight of the slurry.
delete delete The method according to claim 1,
Wherein the ceramic fiber sheet is immersed in the slurry for 10 seconds and the weight is measured to determine a deposition rate of 200% or more as defined by the following formula (1).
[Formula 1]

(Wherein, W _m (%) is a needle supporting ratio, W ₁ (g) before immersion is the weight, W ₂ (g) after immersion is no game)
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