KR100336821B1 - A method for manufacturing three direction-honeycomb module for solid catalyst support or dispersant and three direction-honeycomb module manufactured from this method - Google Patents

Abstract

The present invention is a new concept of three-way honeycomb (3D-honeycomb) used as a catalyst dispersion and a support in a low-pressure reactor to reduce the pressure loss in the reactor generated by the adsorption or chemical reaction using a solid catalyst Method for manufacturing a module and a three-way honeycomb module manufactured therefrom,

The honeycomb module manufactured by flattening the metal mesh plate and the corrugated plate that corrugates the plate, or by alternately arranging them, is washed with hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid or caustic soda, and calcined at high temperature to form an oxide film on the wire surface After forming, wash-coating with a catalyst slurry solution formed by adding a catalyst, an adhesive, and optionally an adhesion aid and a pore control agent to water, and when the catalyst is attached to the plate and the corrugated plate, they are alternated between the plate and the corrugated plate. The three-way honeycomb module

Compared with the conventional ceramic honeycomb, the surface area is larger and the flow direction is not only a channel, but also an irregular flow passage through the holes between the nets in the perpendicular direction to form a three-way turbulent flow to the reactant catalyst surface. Since the diffusion rate is improved, the reaction efficiency in the low pressure difference reactor can be greatly improved.

Description

METHODS FOR MANUFACTURING THREE DIRECTION-HONEYCOMB MODULE FOR SOLID CATALYST SUPPORT OR DISPERSANT AND THREE DIRECTION-HONEYCOMB MODULE MANUFACTURED FROM THIS METHOD}

The present invention relates to a method for producing a three-way honeycomb module for a solid catalyst support or a dispersion and a three-way honeycomb module prepared therefrom. More particularly, the present invention relates to a three-way honeycomb module prepared from the same. The present invention relates to a method for producing a three-way honeycomb module used as a catalyst dispersion and a support in a low-pressure reactor to reduce pressure loss in the reactor and a three-way honeycomb module prepared therefrom.

When solid particles are filled directly into the reactor by removing impurities such as hydrocarbons, NOx, VOC, dioxin, etc. present in the incinerator, the chimney or the exhaust gas discharged from automobiles using adsorbents or catalyst particles or in general chemical reactions using solid catalysts. In order to reduce the pressure loss in the reactor, it is necessary to use a special support capable of dispersing the catalyst particles.

The monolithic type module is widely used as a support for the dispersion coating of catalyst particles for such a low pressure difference reaction. For example, impurities such as hydrocarbons, NOx, VOC, etc. contained in the exhaust gas emitted from the chimney are used. It can be easily found in reactors used for removal by chemical reactions and honeycomb reactors for automobile exhaust treatment (see Catalyst Review-Sci. And Eng., 36 (2), 179-270, 1994).

Among them, honeycomb is an extrusion molded ceramic having a honeycomb-shaped cross section, and is widely used because of the same surface area per volume. The honeycomb fabricates a basic monolithic module of a predetermined size (for example, 100mmx100mmx2000mm) having regular passages parallel to the gas flow direction and fills the reactor with a catalyst or adsorbent applied on the surface of the module. .

Such honeycomb reactors have been widely used in research since the early 70's. R & D contents include US Pat. No. 3785781, US Pat. No. 4072471, US Pat. No. 4814146, US Pat. Patents and research results of optimization of honeycomb and catalyst materials of US Pat. No. 3991245, US Pat. No. 4824711, US Pat.

However, despite these findings, honeycomb reactors do not fundamentally overcome the following problems: First, the honeycomb reactors are enclosed with each other in a tunnel, so that they enter one passage. In this case, the fluids cannot be mixed with each other in a direction other than the flow direction, and flow distribution is not properly performed.

Second, the volume of the reactor should be increased more than necessary because the turbulence effect is small and the diffusion rate of the reactants moving from the fluid phase to the catalyst surface is low, resulting in poor reaction efficiency. For example, in the catalytic oxidation reaction of orthodichlorobenzene, we measured the same amount of particles as the packed-bed reactor filled with 10mesh vanadium / titania-based catalyst particles. ), The conversion rates of the bed-type and honeycomb reactors filled at the same flow rate were 34.6%, 23.5%, 57.7% at 250 ° C, 34.6%, and 95.3% at 300 ° C, respectively. The temperature difference was 47.6%, showing a larger difference as the temperature increased. As a result, it can be seen from the experimental results that the reaction rate of the honeycomb reactor with a slow material transfer rate decreases as the temperature increases.

Third, it is difficult to prepare various structures according to the reaction system because most of the ceramics are produced by extrusion molding.

Although low pressure differential modules of various shapes have been fabricated using corrugated plates and appropriately arranged using metal plates as materials, they still have low pressure differential monolithic modules that are superior to ceramic honeycombs in terms of surface area per unit volume and manufacturing cost. It cannot be developed (see Catal. Rev.-Sci. Eng., 36 (2), 179-270, 1994). For example, U.S. Patent No. 5,395,600 (1995) discloses 100 cell / in by alternately arranging wire mesh, metal ribbon or square frame supports to corrugate thin metal plates and place them at regular intervals. ^Although honeycomb module of less than ² is proposed, it is not improved in terms of surface area and performance per unit volume of existing honeycomb due to the characteristics of metal corrugated sheet.

In the example of using only a metal mesh instead of a metal sheet, US Pat. No. 5,026,273 (1991) manufactured a corrugated sheet using a special stainless steel mesh that withstands high temperatures, and paralleled them at regular intervals by bending them in a cylindrical reactor in parallel with a parallel passage reactor. Although the reactor is proposed in the form of (), it is also inferior to the ceramic honeycomb in terms of surface area. In addition, in order to use such a module as a catalyst for combustion of hydrocarbons, it is difficult to coat the catalyst on the metal network, and the plasma spraying method is introduced to coat the ceramic particles as a catalyst carrier. The coating method has a difficult disadvantage.

In order to improve the fabrication method, a method of fabricating a metal net with a corrugated plate, and extending the end thereof to fix the end edge in the reactor is proposed in US Pat. No. 5,527,756 (1996). The method of placement is difficult and is closer to PPR type than honeycomb type.

Therefore, while making up for these shortcomings, the surface area per unit volume of the module is higher and easier to manufacture than the existing honeycomb, and the development of more advanced honeycomb modules designed to enable flow between channels besides gas flow in the channel direction, which is a disadvantage of honeycomb, It is a desperate situation.

An object of the present invention is to improve all the problems of the existing ceramic honeycomb, and in manufacturing a honeycomb monolithic module using a metal mesh, the surface area per unit volume of the ceramic honeycomb is higher than that of the conventional ceramic honeycomb. The purpose is to provide a method of manufacturing a honeycomb module of the form (three directions).

Another object of the present invention is to provide a method for manufacturing a three-way honeycomb catalyst unit that can be coated by a conventional wash coating method at room temperature in coating the catalyst carrier and / or catalyst using the module. .

Another object of the present invention is to induce fluid flow in three directions (x, y, z axis), so that the flow distribution of the fluid is uniform and the flow is turbulent, so that the reaction efficiency in the low pressure differential reactor is improved. The purpose is to provide a comb module.

1 is a schematic diagram illustrating a metal mesh structure to be used basically in a three-way honeycomb module according to the present invention;

Figure 2 is an external perspective view schematically showing a box-shaped body forming the outline of the module to be filled in the reaction space of the reactor;

Fig. 3 is a schematic view showing a flat plate 3a and a corrugated plate 3b, respectively, to be used in the three-way honeycomb module of the present invention;

Figure 4 is a schematic diagram showing a three-way honeycomb module of the quadrangular form according to the present invention;

5 is a perspective view schematically showing a partial cutaway of a reactor employing a module according to the present invention; to be.

* Description of the simple symbols for the main parts of the drawings *

10 ... mesh structure 12 ... diameter of wire 14 ... wire hole

20 ... Main body 22 ... Support beam 30 ... Flatbed

40 ... corrugated plate 50 ... modular 60 ... reactor

According to one aspect of the invention,

(1) A flat plate of a metal mesh having a hole size of the wire mesh and a diameter ratio of the wire of 10 or less, and a corrugated plate corrugated with the flat plate selected from hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid, and caustic soda, respectively. Forming a oxide film on the surface of the wire by baking at a high temperature within a temperature range of 400-1000 ° C. after washing with;

(2) a catalyst for adsorbing the wire on which the oxide film is formed or performing a chemical reaction in water at a volume ratio of 1: 5-20, and then mixing 5-30% by weight of the adhesive based on the weight of the catalyst, and optionally an adhesive aid 1 Wash coating with a catalyst slurry solution comprising -10% by weight and no more than 30% by weight of pore control agent; And

There is provided a method for producing a three-way honeycomb module for a solid catalyst support or dispersion comprising a; (3) to prepare a honeycomb module by alternately closely contacting the catalyst plate and the corrugated plate.

According to the second aspect of the present invention,

(1) Hycomonic module produced by uniform volume by alternately arranging the flat plate of the metal net with the hole size of the wire mesh and the diameter ratio of the wire less than 10 and the corrugated plate corrugated with the plate. Washing with one selected from sulfuric acid, mixed acid of nitric acid and hydrofluoric acid, and caustic soda, followed by high temperature baking within a temperature range of 400-1000 ° C. to form an oxide film on the wire surface; And

(2) a catalyst for adsorbing the wire on which the oxide film is formed or performing a chemical reaction in water at a volume ratio of 1: 5-20, then mixing 5-30% by weight of the adhesive based on the weight of the catalyst, and optionally an adjuvant 1 Provided is a method for producing a three-way honeycomb module for a solid catalyst support or dispersion comprising a wash coating step of -10 wt% and a catalyst slurry solution formed by adding 30 wt% or less of the pore regulator.

According to a third aspect of the present invention, there is provided a three-way honeycomb module manufactured by the above methods.

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

As a technical configuration for achieving the above object, the present invention adopts a simple process assembling process using a metal mesh as a material instead of an extrusion method using a ceramic material.

That is, the material used in the production of three-way honeycomb devised in the present invention is processed to a crimp plate having a certain size of wrinkles by using a crimping machine of the metal mesh of the network structure, the plate and the corrugated plate of the mesh alternately Closely arranged and stacked to a certain thickness to produce a module.

The metal mesh used here can be any metal material, but in reality, the metal mesh, stainless mesh or aluminum mesh is convenient. In order to overcome the difficulty of coating the catalyst on the three-way honeycomb made of such a metal mesh, in the present invention, the metal mesh is baked at a high temperature for a certain period of time to form an oxide film having an appropriate thickness. Thus, the metal film on which the oxide film is formed is immersed in a catalyst slurry solution in which an adhesive and other additives are mixed, followed by drying and high temperature treatment to produce a 3-way honeycomb module coated with the final catalyst.

The three-way honeycomb module manufactured as described above shows much higher reaction efficiency per unit volume than the conventional catalyst module using ceramic honeycomb due to the high surface area and the formation and turbulence of the three-way flow path of the reaction gas.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

1 schematically illustrates a metal mesh structure 10 to be used basically in a three-way honeycomb and a module used therein according to the present invention. Here, the mesh structure 10 forms a mesh structure in which the wires 12 cross each other, and the shape of the holes 14 of the mesh wires formed while the wires 12 cross each other generally forms a square, but the wires 12 Depending on the shape of the intersections may form a square or rhombus.

The mesh structure 10 preferably has a strength that is not deformed by the influence of the high-pressure fluid flow generated in the reaction space of the reactor to be described later, for example, iron, stainless, aluminum, other metal alloys, etc. It can be used, and finally, the thickness needs to be a suitable level (eg 2 mm or less).

FIG. 2 is a perspective view schematically showing a rectangular outer shell box 20 forming an outer shape of a module to be filled in a reaction space of a reactor. Using a generally used flat plate or a flat plate of the net structure shown in Figure 1 is installed so that the upper and lower ends are opened and install a support beam 22 for fixing the plates to be filled therein.

3 schematically shows a plate 30 and a corrugated plate 40 which will be alternately filled in the outer box 20 or in the reaction space of the reactor. The flat plate 30 is manufactured by appropriately cutting the mesh structure 10 of FIG. 1 in consideration of the size of the outer box 20 or the reaction space of the reactor, and the corrugated plate 40 compresses the flat plate. It can be manufactured in any shape, such as zigzag cross section, sinusoidal cross section, or square cross section.

4 is a schematic view showing a module of a rectangular three-way honeycomb according to the present invention, in which the flat plate 30 and the corrugated plate shown in FIG. 3 in the box-shaped outer box 20 shown in FIG. 40 shows the state by which they alternately arrange | positioned alternately.

The three-way honeycomb module of the present invention can form a larger surface area per unit volume than the conventional ceramic honeycomb module by properly setting the ratio of the hole size of the mesh wire and the diameter of the wire, and thus considering the mesh area The ratio of the size of the wire hole 14 to the diameter of the wire 12 is 10 or less, preferably 3 or less, and more preferably 2.14 or less. The hole size of the mesh wire is the spacing D of the holes between the wires in the following equation. For example, when the three-way honeycomb is manufactured so that the spacing of the holes 14 of the mesh structure of the wire 12 having a diameter of 1.0 mm is 1.5 mm, the metal mesh devised in the present invention as compared to the general ceramic honeycomb. The three-way honeycomb of the surface area is more than doubled at the same cell density, contributing to improved reaction efficiency.

This can be expressed as a formula.

<Calculate Wire Mesh Surface Area>

Surface area of one crossed square wire (cylindrical)

Sp = 2 (D + dW) ² (where D is the spacing of the holes between the wires (mean value of width and length when the wire holes are rectangular) and dW is the wire diameter.

Wire cross-section area of one crossed rectangular wire (cylindrical)

Sw = (Where D and dW are as defined in Equation 1)

∴

Here, the condition Sw / Sp> 1 should be πdW> D + dW, so dW> D / 2.14, which is 2.14.

As a method of coating the catalyst on the module thus manufactured, both the method of coating the catalyst before inserting the plate and the corrugated plate into the module, or preparing the final module and then coating the catalyst.

To firmly coat the catalyst particles on the surface of the mesh, the metal mesh is washed with an acid (e.g. hydrochloric acid, sulfuric acid or other mixed acid) or an alkaline solution (e.g. The film is formed to a certain thickness, which is washed with a strong acid or strong alkali solution to roughen the surface, and then fired at a high temperature to prevent corrosion of the module during the reaction and more firmly adhere the catalyst particles by using the property that the catalyst particles are metal oxides. Let's go.

At this time, if the high-temperature firing temperature exceeds 1000 ℃ because the metal oxide film is all oxidized and broken (brittle) it is not preferable because it is in the range of 400-1000 ℃. For example, the metal oxide film formed on the surface of the wire through such a high temperature baking process is formed of Fe ₃ O _{4 in the} wire mesh wire and Al ₂ O _{3 in the} aluminum mesh.

The catalyst is then mixed with water in a ratio (a moderately dilutable range, for example 1: 5-20 volume ratios), with water, in an amount of 5-20% by weight, based on the weight of the catalyst, to aid adhesion of the catalyst particles. The catalyst slurry solution is prepared by adding an adhesive and then optionally adding 1-10 wt% of an adhesion aid and a pore regulator of 30 wt% or less based on the weight of the catalyst.

The catalyst is selected from Pt, Pd, Fe, Ni, V or metal oxides selected from FeOx, MoOx, VOx, CrOx, TiO ₂ alone or in combination with the active ingredient, silica, alumina, silica-alumina, titania, zeolite, It consists of high surface area carriers, such as activated carbon. In this case, the content of the catalytically active component supported on the surface of the carrier depends on the type of catalytically active component to be supported.

In addition, as the adhesive, an inorganic adhesive such as alumina sol, silica sol, water glass, etc. is used. When these adhesives are used at less than 5% by weight, the adhesive strength is insufficient. Therefore, the amount is preferably 5-20% by weight.

As an optional additive, the adhesion aid is selected from phosphate adhesion aids, limestone, magnesia, organic acids, etc., and the content thereof is preferably in the range of 1-10% based on the weight of the catalyst. If it is less than 1% by weight, the adhesive strength is lowered. If it exceeds 10% by weight, the catalytic activity may be lowered, which is not preferable.

As another optional additive, the pore control agent may be used as long as it is a water-soluble polymer such as cellulose, and the content thereof is preferably 30% by weight or less based on the weight of the catalyst. If it exceeds 30% by weight, It is undesirable because the adhesion to the wire surface of the catalyst is reduced.

The metallurgical net or pre-fabricated three-way honeycomb module was washed with the catalyst slurry solution prepared as described above, and then dried at room temperature and calcined. At this time, the wash coating method may first adhere the slurry solution containing only the carrier to prepare the final honeycomb module product, and then attach the catalyst active ingredient to the carrier adhered on the wire (impregnation), or the active ingredient may be attached to the carrier. The honeycomb module may be manufactured by wash coating the finished catalyst supported on the substrate.

The wash coating includes, but is not limited to, a process of spraying catalyst slurry on the surface of the wire mesh or immersing it in a slurry solution to dry the slurry. At this time, in order to increase the amount of catalyst supported, the supporting-drying process may be repeated.

In addition, when the pore regulator is used as an additive in the catalyst slurry solution, it may be subjected to a firing step after drying to volatilize the pore regulator, wherein the firing temperature is preferably 400 ° C. or higher. At lower temperatures, the pore modifier does not disappear even when fired, and as a result, the adhesive strength is lowered.

The reactor equipped with the three-way honeycomb module of the present invention manufactured in this manner has the following advantages over the reactor equipped with the general honeycomb module.

First, since the reactants are mixed freely not only in the flow direction of the fluid but also in a direction perpendicular to the flow of the fluid, the radial concentration gradient of the reactants at the reactor inlet, which may occur frequently in the existing honeycomb reactor, does not occur.

Second, the three-way honeycomb passages are connected by holes in the metal net than the conventional honeycomb reactors having flat surfaces and straight passages, so that the flow of the fluid becomes more turbulent and the diffusion rate of the reactants is faster. This reduces the material transfer resistance from the fluid phase to the surface of the solid catalyst, thereby increasing the overall reaction efficiency.

Third, due to the flow of the turbulent fluid and the characteristics of the metal wire mesh, heat transfer occurs rapidly, resulting in less thermal gradient even in a large reactor.

Fourth, the existing honeycomb reactor module manufactured in ceramic form is difficult and expensive to manufacture due to the difficulty of extrusion molding and high temperature firing, whereas the larger the reactor size, the simpler and easier to manufacture. It costs less to produce.

Fifth, the installed module is easy to be re-separated again, and after a long time of reaction, it is easy to remove dust, repair, and regenerate the catalyst, and its regeneration efficiency is also high.

Sixth, when solid matter or fine dust included in the reaction gas is attached to the reactor, passage blockage is improved as compared to the existing honeycomb reactor in which the passage is closed.

Seventh, the surface area per unit volume in the module, which is directly related to the reaction performance, is higher than that of the conventional ceramic honeycomb, thereby improving reactivity.

On the other hand, the application range of the honeycomb module manufactured by the present invention due to these characteristics is catalyzed for selective reduction of NOx, catalytic reaction for oxidative decomposition of VOC and hydrocarbon, catalytic reaction for automobile exhaust gas treatment, deodorization catalytic reaction And adsorption processes, steam reforming catalysis, catalytic combustion of fuel for steam turban, and the like.

The following examples show how to fabricate the three-way honeycomb described in the present invention using a specific metal mesh material and coat the catalyst, and the three-way honeycomb reactor prepared in this way and the conventional honeycomb reactor. It is presented to compare the activity of the flue gas treatment, but is not meant to be limited thereto.

<Example 1>

Fabrication of 3-way Honeycomb Catalyst Module of the Present Invention Using Corrugated Plate and Plate

A wire mesh having a hole size of 1.47 mm × 1.66 mm and a wire diameter of 0.8 mm was formed into a triangular corrugated plate having a depth of 5 mm and a width of 5 mm, and the flat plate and the corrugated plate were cut into 10 cm × 20 cm sizes, respectively. At this time, the corrugated plate was cut so that the wrinkled longitudinal direction was 20 cm.

The wire mesh plates were immersed in 5N hydrochloric acid solution for 5 hours to roughen the surface, and then fired at 600 ° C. for 5 hours to coat a protective film of Fe ₃ O ₄ on the wire.

The pretreated plates were mixed with a catalyst slurry solution in which water and TiO ₂ powder were mixed (wherein the solution composition was water: TiO ₂ (catalyst active ingredient) in a 1: 0.2 volume ratio, and the alumina sol (carrier) was based on the TiO ₂ weight. 10% by weight, 5% by weight of phosphoric acid (adhesive aid) and 10% by weight of PVA (pore control agent), after wash coating, dried at room temperature for 10 hours and calcined at 450 ° C. for 10 hours to coat the catalyst. Plates were prepared.

At this time, the wash coating was selected to be immersed in the catalyst slurry solution.

This loading-drying-firing process was repeated to coat 5.9% TiO ₂ . Then, the plate and the corrugated plate were alternately stacked to prepare a three-way honeycomb catalyst module having a total thickness of 10 cm, a cross-sectional area of 10 x 10 cm, and a channel length of 20 cm.

<Example 2>

3-way Honeycomb Module Fabrication Using Cylindrical Module

An aluminum mesh having an aluminum wire diameter of 0.8 mm and a width of 1.5 mm between wires was fabricated using a crimp plate with an uneven corrugated plate having a height of 5.0 mm and a width of 5.0 mm. The aluminum flat plate and the corrugated plate were cut to a width of 30 cm, and the two sheets were overlapped, and rolled until the diameter became 10 cm, thereby preparing a cylindrical three-way honeycomb having a final diameter of 10 cm x length of 30 cm.

The honeycomb module was added with 3N caustic soda solution for 1 hour to roughen the surface, and then calcined in air at 500 ° C. for 10 hours to form an alumina layer on the wire surface.

The honeycomb module thus pretreated was subjected to a supporting-drying-firing process in the same manner as in Example 1 to prepare a honeycomb module coated with 6.2% TiO ₂ based on the weight of the module.

<Example 3>

NOx reduction reaction according to reaction temperature

Prepared in the same manner as in Example 1, the passage size is 49 cells / in ² , the module outer size of 5cmx5cmx10cm after the three-way honeycomb module is immersed in a solution of vanadium precursor (NH ₄ VO ₂ ) dissolved After drying at room temperature and baking at a high temperature of 450 ° C., 10% of V ₂ O ₅ was supported compared to TiO ₂ .

For comparison, TiO ₂ and V ₂ O ₅ were supported on the same ceramic honeycomb having the same passage and outer size in the same manner as described above. For the selective reduction of NO, reactants consisting of 500 ppm NO, 500 ppm ammonia, 8% water and other air were tested for NOx reduction under a total flow rate of 90,000 cc / min and a reaction temperature of 250-400 ° C.

The generated gas was analyzed by the NO analyzer and the conversion ratio of NO is shown in Table 1 below. The NO conversion rate refers to the amount selectively reduced and removed by the reaction among the total amount of NO introduced into the reactor.

NOx conversion rate (%) according to reactor type Temperature (℃) 250 300 350 400 3-way honeycomb 40 72 95 83 General Honeycomb 37 61 85 79

As shown in Table 1, it was confirmed that the selective reduction of NO in the three-way honeycomb of the present invention maintains a high conversion rate in all temperature ranges compared with the case of using a general honeycomb reactor.

<Example 4>

VOC oxidation according to reaction temperature

5.0x5.0x10cm obtained by adhesively coating a solution in which a vanadium precursor (NH ₄ VO ₃ ) and a titania (TiO ₂ ) powder are mixed at a ratio of 1:10 on a wire mesh having a hole size of 1.27 mm x 1.66 mm and a wire diameter of 0.4 mm. VOC oxidation was carried out using a three-way honeycomb of size. The reactants used were 900 ppm of dichlorobenzene and the remainder of which was injected with air, with a total flow rate of 8,000 cc / min and a reaction temperature of 200-300 ° C.

For comparison, a general honeycomb reactor obtained by coating the same catalyst system solution with a passage size of 49 cells / in ² was used.

The resulting gas was analyzed using gas chromatography to show the conversion of dichlorobenzene in Table 2 below. The conversion rate of the dichlorobenzene means the amount oxidized to CO ₂ by the reaction of the total amount of dichlorobenzene introduced into the reactor.

Dichlorobenzene Conversion Rate (%) by Reactor Type Temperature (℃) 210 240 270 300 3-way honeycomb 67 88 96 98 General honeycomb reactor 15 50 71 85

As shown in Table 2, as a result of the oxidation reaction of dichlorobenzene in the three-way honeycomb according to the present invention, the conversion rate is maintained significantly in all temperature ranges compared to the case of using a conventional honeycomb reactor as a comparative reactor. It was.

Example 5

VOC oxidation according to the reaction gas concentration

The three-way honeycomb and the general honeycomb reactor used in Example 2 were used to perform VOC oxidation according to the concentration of the reaction gas.

The concentration of the reactant dichlorobenzene was changed to 100-1500ppm, the total flow rate was 8,000cc / min, the reaction temperature was fixed at 270 ℃. The generated gas was analyzed by gas chromatography, and the conversion ratio of the obtained dichlorobenzene is shown in Table 3 below.

Dichlorobenzene Conversion Rate (%) by Reactor Type Concentration (ppm) 100 300 900 1500 3-way honeycomb 98 98 96 94 General honeycomb reactor 94 83 80 62

As shown in Table 3, as a result of performing oxidation reaction of dichlorobenzene in the three-way honeycomb according to the present invention, a high conversion rate was maintained at all concentration ranges compared to the case of using a conventional honeycomb reactor, which is a comparative reactor. In particular, the greater the concentration of the reactant, the greater the difference can be seen.

This is believed to be because the reactant oxidation rate of the 3-way honeycomb was accelerated due to the large surface area and the turbulent flow of the fluid.

<Example 6>

VOC Oxidation with Total Flow Rate Variation

The VOC oxidation was carried out with varying total flow rates using the three-way honeycomb and the general honeycomb reactor used in Example 2. As the reactant used, 300 ppm of dichlorobenzene was used, and the rest was injected with air.

The total flow rate of the reaction gas was changed to 8,000-20,000cc / min, and the reaction temperature was fixed at 270 ° C. The generated gas was analyzed by gas chromatography, and the conversion ratio of dichlorobenzene is shown in Table 4 below.

Dichlorobenzene Conversion Rate (%) by Reactor Type Total flow rate (cc / min) 2000 3000 4000 5000 3-way honeycomb 98 97 94 92 General honeycomb reactor 83 77 71 69

As shown in the table, in the three-way honeycomb according to the present invention it can be seen that the larger the flow rate than the case of using a conventional honeycomb reactor as a comparison reactor, the greater the difference in conversion rate.

This is because the higher the flow rate in the three-way honeycomb, the greater the flow resistance caused by the holes and wires, the more turbulent the flow of the fluid, and thus the overall reaction efficiency is improved by the faster the diffusion rate of the reactants.

<Example 7>

Oxidation of Benzene with Reaction Temperature

Benzene oxidation reaction was carried out using a 3.5x3.5x5.0cm three-way honeycomb obtained by adhesively coating 6.0 wt% of 0.3 wt% Pt-loaded titania powder on a wire mesh having a hole size of 1.27 mm x 1.66 mm and a wire diameter of 0.2 mm. Was performed. Benzene concentration was used at 1,000ppm, the rest was injected with air, the total flow rate was 2,000cc / min, the reaction temperature was 160-220 ℃.

The comparative reactor was a 49 honeycomb reactor, obtained by coating the same catalyst solution, at 49 cells / in ² , and the size and amount of catalyst used were the same as the three-way honeycomb. The composition and the total flow rate of the reactants were also the same as those of the 3-way honeycomb.

The generated gas was analyzed by gas chromatography, and the benzene conversion rate is shown in Table 5 below. The benzene conversion rate refers to the amount oxidized and removed by the reaction among the total amount of benzene introduced into the reactor.

Benzene conversion rate (%) according to reactor type Temperature (℃) 160 180 200 220 3-way honeycomb 6 54 96 100 General honeycomb reactor 7 13 40 69

As shown in the table, as a result of performing the oxidation reaction of benzene in the three-way honeycomb according to the present invention, it was confirmed that the conversion rate is maintained significantly higher than when using a conventional honeycomb reactor as a comparative reactor.

As described above, by using the three-way honeycomb and the catalyst module using the same according to the present invention, the reaction rate per unit volume is improved by using a mesh-like flat plate and a corrugated plate body, so that the selective reduction of NOx or the oxidation of VOC and hydrocarbon, etc. As shown in FIG. 1, the present invention has an effect of showing higher efficiency than a conventional honeycomb type reactor in a pressure load due to a high flow rate.

In addition, the flow of the fluid is turbulent and has the effect that the radial gradient of the reactants does not occur. The fast heat transfer of turbulent fluids is also very effective for systems that require fast response, such as automotive exhaust treatment.

In addition, it is simple and easy to manufacture such a flat plate and a corrugated plate, or a module filled therein, which is very effective in terms of manufacturability, and in the presence of solids or fine dust in the reaction gas, compared to a honeycomb reactor in which channels are closed. Channel blockage has been greatly improved.

Claims (9)

(1) After washing the plate of the metal mesh with the pore size of the wire mesh and the diameter ratio of the wire of 10 or less and the corrugated plate corrugated with the plate, respectively, selected from hydrochloric acid, sulfuric acid, mixed acid of nitric acid and hydrofluoric acid, and caustic soda. Forming an oxide film on the surface of the wire by baking at a high temperature within a temperature range of 400-1000 ° C .; (2) a catalyst for adsorption or chemical reaction of the wire on which the oxide film is formed is mixed in a catalyst: water 1: 5-20 volume ratio, and then 5-30% by weight of the adhesive based on the weight of the catalyst, and optionally Washing coating with a catalyst slurry solution comprising 1-10 wt% of an adhesion aid and 30 wt% or less of a pore regulator; And (3) a method of manufacturing a three-way honeycomb module for a solid catalyst support or dispersion comprising a; preparing a honeycomb module by alternately arranging a catalyst-attached plate and a corrugated plate in close contact. (1) Hycombine module, hydrochloric acid, sulfuric acid, nitric acid, made of uniform volume size by alternately arranging the plate of the metal net with the hole size of the wire mesh and the diameter ratio of the wire less than 10 Washing with one selected from a mixture of hydrofluoric acid and caustic soda and baking at a high temperature within a temperature range of 400-1000 ° C. to form an oxide film on the wire surface; And (2) a catalyst for adsorption or chemical reaction of the wire on which the oxide film is formed is mixed in a catalyst: water 1: 5-20 volume ratio, and then 5-30% by weight of the adhesive based on the weight of the catalyst, and optionally Washing coating with a catalyst slurry solution comprising 1-10% by weight of the adhesion aid, 30% by weight or less of the pore control agent, and a three-way honeycomb module manufacturing method for a solid catalyst support or dispersion. The method for manufacturing a three-way honeycomb module according to claim 1 or 2, wherein the mesh uses a metal mesh such as iron, stainless steel, aluminum, or the like. The method according to claim 1 or 2, wherein the corrugation of the corrugated plate is triangular, square, rhombic, or sinusoidal. The method of claim 1 or 2, wherein the ratio of the hole size of the mesh wire to the diameter ratio of the wire is 3 or less. The catalyst according to claim 1 or 2, wherein the catalyst is selected from the group consisting of Pt, Pd, Fe, Ni, V or metal oxides selected from FeOx, MoOx, VOx, CrOx, TiO ₂ , or a composite active ingredient, and silica, Characterized by consisting of a high surface area carrier selected from alumina, silica-alumina, titania, zeolite, activated carbon The method according to claim 6, wherein the carrier is first bonded to the catalyst component on the wire on which the oxide film is formed, and then the active component is supported on the carrier that is previously bonded after the three-dimensional honeycomb module is manufactured. According to claim 1 or 2, wherein the adhesive used in the catalyst slurry solution is selected from alumina sol, silica sol, water glass, the adhesion aid is selected from phosphate, limestone, magnesia, organic acid, the pore control agent is cellulose Method for using a water-soluble polymer such as Three-way honeycomb module for solid catalyst support or dispersion prepared by the method of claim 1 or 2.