KR101369021B1 - Low temperature oxidation catalyst improved water-stability for removal of toxic gases - Google Patents

Abstract

The present invention relates to a low temperature oxidation catalyst with improved water-stability for removing toxic gas and more specifically, to a low temperature oxidation catalyst for removing toxic gas which is used for the oxidation reaction for directly removing the toxic gas without a preprocessing step at a high temperature by putting water soluble salt of 8B class metal and copper metal used as an active component into a poly(styrene-vinyl benzene) copolymer carrier with moisture. The catalyst of the present invention has extended catalyst lifetime by not generating inactivation even in a condition with the moisture, and also the inactivated catalyst can be recycled after exposing to steam for one or two hours for the large scale processing of the toxic gas.

Description

Low temperature oxidation catalyst improved water-stability for removal of toxic gases}

The present invention relates to a low temperature oxidation catalyst having an effect of significantly extending the catalyst life by significantly reducing the catalyst deactivation even under conditions in which water coexists when applied to a low temperature oxidation reaction for removing toxic gases.

Exhaust gases emitted from industrial chimneys or automobiles contain harmful air, odor causing substances, carcinogenic substances, and the like, which are harmful to the environment and human body. Many countries around the world have established measures to regulate emissions and mandate the installation of control facilities. Exhaust gas purification techniques have been published in various ways, and among them, a method using an adsorbent and a catalyst is generally used. In the case of using the adsorbent as the exhaust gas purification method, since the adsorption capacity of the adsorbent such as activated carbon and zeolite is limited, no further adsorption effect can be obtained after a certain time, and it is not easy to reuse after use. There is a decisive disadvantage. On the other hand, the method of using a catalyst has been applied more commonly because it has a relatively long processing time and can be recycled several times.

The catalyst oxidation method is generally known as an exhaust gas purification method using a catalyst. Catalytic oxidation is a method of decomposing or deodorizing specific harmful components in exhaust gas by an oxidation reaction by a catalyst. In the catalytic oxidation method, precious metal catalysts such as platinum (Pt), palladium (Pd), and rhodium (Rh) are used, and cobalt (Co), chromium (Cr), copper (Cu), and manganese (Mn) as cocatalysts as necessary. , Transition metals such as iron (Fe), nickel (Ni) and tungsten (W) may be used.

Recently, a low temperature oxidation catalyst has been developed to remove specific toxic gases by oxidation under low temperature conditions of less than 200 ℃. European Patent No. 800,856 discloses a low temperature oxidation catalyst which performs oxidation at 140 ° C. to remove carbon monoxide (CO) and volatile organic compounds (VOC) in exhaust gas, and includes a platinum group metal and a metal oxide (eg, silicic acid) on a zeolite carrier. A catalyst in which aluminum, aluminum oxide, titanium oxide) is supported in a certain weight ratio is described. In addition, Korean Patent Publication Nos. 2005-0101689 and 2012-0096171 disclose oxidation of carbon monoxide (CO), sulfur dioxide (SO ₂ ), and acetaldehyde (CH ₃ ) in exhaust gas by performing an oxidation reaction at a low temperature of 20 ° C. to 80 ° C. A low temperature oxidation catalyst is described which simultaneously removes various harmful components such as COH), formaldehyde (HCOH), volatile organic compounds (VOC) and ammonia (NH ₃ ). Korean Patent Laid-Open Publication No. 2005-0101689 describes a low temperature oxidation catalyst in which palladium ions (Pd ²⁺ ), platinum ions (Pt ²⁺ ) and copper ions (Cu ²⁺ ) are supported on a activated carbon carrier in a molar ratio. In addition, Korean Patent Publication No. 2012-0096171 discloses palladium ions (Pd ²⁺ ) and platinum ions (Pt ²⁺ ) as active metal ions, and copper (Cu), manganese (Mn) and potassium (K) as promoters. Low temperature oxidation catalysts supported in a certain weight ratio are described.

However, the low-temperature oxidation catalysts published to date have a problem of easily deactivating by water and shortening the catalyst life when the oxidation reaction is carried out in the condition of water coexistence, thus limiting the water content coexisting in the oxidation reaction system to 10% or less. Doing. In addition, an oxidation reaction, a reduction reaction or a redox reaction is carried out to regenerate the deactivated catalyst, and the regeneration process is generally performed using a special apparatus at a high temperature of 300 ° C. or higher.

It is an object of the present invention to provide a low temperature oxidation catalyst for removing toxic gases with improved water stability.

Another object of the present invention is to provide a method for removing toxic gas using the low temperature oxidation catalyst.

Another object of the present invention is to provide a method for easily regenerating the deactivated low temperature oxidation catalyst.

In order to solve the above problems, the present invention is a water-soluble salt of the Group 8B metal and copper metal is supported as an active ingredient in a porous vinyl polymer carrier having a water content of 20 to 60% by weight, 90 ℃ to 100 ℃ without high temperature firing process It is characterized by a low temperature oxidation catalyst for removing toxic gases used by drying at a temperature.

In addition, the present invention is a toxic gas selected from the group consisting of carbon monoxide (CO), sulfur dioxide (SO ₂ ), formaldehyde (HCOH), acetaldehyde (CH ₃ COH), and ammonia (NH ₃ ) in the presence of the low-temperature oxidation catalyst. It characterized by a method of removing by oxidizing to a temperature of 20 ℃ to 80 ℃.

The present invention also features a method of regenerating a low temperature oxidation catalyst which has been inactivated in an oxidation reaction by contacting with water vapor.

The low temperature oxidation catalyst of the present invention has excellent stability to moisture, and rather increases the catalytic activity under conditions where a certain amount of water coexists. Thus, the low temperature oxidation catalyst of the present invention has the effect of solving the problem that the conventional low temperature oxidation catalyst is inactivated by moisture.

The low temperature oxidation catalyst of the present invention is applied to an oxidation process for removing toxic gases directly without a high temperature firing process. In general, high temperature heat treatment of 400 ° C. or higher is performed as a pretreatment step for activating the catalyst prior to applying the catalyst to the process. However, the low temperature oxidation catalyst of the present invention has sufficient catalytic activity even when used directly by drying at 90 ° C. to 100 ° C. Have Thus, the low-temperature oxidation catalyst of the present invention is omitted because the heat treatment process for high temperature firing, there is an effect of simplifying the process and reducing the additional cost for the heat treatment.

The low temperature oxidation catalyst of the present invention maintains high catalytic activity even at low oxidation reaction temperatures of 20 ° C to 80 ° C. As a result, the process of removing the toxic gas using the low temperature oxidation catalyst of the present invention can be performed under mild conditions, thereby greatly reducing the cost of treating the toxic gas.

The low temperature oxidation catalyst of the present invention not only has excellent stability to moisture, but the deactivated catalyst can be regenerated by contacting water vapor for a certain time. As a result, the low-temperature oxidation catalyst of the present invention does not require additional costs such as equipment costs for regeneration, heat treatment costs, and the like, and thus it is possible to economically perform catalytic oxidation.

Therefore, the low temperature oxidation catalyst of the present invention has excellent stability to moisture to prolong the catalyst life, and does not require a separate heating device for activating and regenerating the catalyst, and thus, from indoor air purification systems to pollution-producing industrial sites. It can be used in a wide range of fields.

The present invention relates to a low temperature oxidation catalyst for removing toxic gases with improved water stability. The present invention achieves the object of improving the water stability of the catalyst by developing a technology for evenly supporting the active ingredient in the form of a water-soluble salt and a technology for preserving the supported water-soluble salt without being converted into a metal or a metal oxide. Could.

In the present invention, in order to evenly carry the active ingredient in the form of a water-soluble salt, a porous vinyl polymer having a water content of 20 to 60% by weight is used as the catalyst carrier. Porous vinyl-based polymer is a hydrophobic polymer with excellent water resistance to water may be suitable for achieving the object of the present invention to develop a catalyst for improved water stability, but affinity for the water-soluble salt used as an active ingredient is rather catalytic activity It may cause you to drop. Therefore, in the present invention, by adjusting the water content of the hydrophobic vinyl polymer used as a carrier in the range of 20 to 60% by weight, more preferably 20 to 55% by weight to increase the affinity for the water-soluble salts to increase the amount of active ingredients supported It was also possible to disperse evenly in the carrier. In order to increase the carrying amount of the active ingredient, the specific surface area of the porous vinyl polymer carrier is 200 m 2 / g or more, and more preferably, the specific surface area is in the range of 300 to 500 m 2 / g. In addition, in consideration of the convenience and porosity of the catalytic reaction, the specific gravity of the porous vinyl polymer carrier is preferably less than 0.5 cc / g, more preferably the specific gravity of the carrier is 0.2 to 0.3 cc / g. The carrier for preparing the low temperature oxidation catalyst of the present invention is particularly preferably a specific surface area of 300 to 500 m 2 / g, specific gravity of 0.2 to 0.3 cc / g, and thermal decomposition temperature measured by a thermal analyzer (TG) of 150 to 200 ° C. Poly (styrene-vinylbenzene) copolymer. Porous vinyl-based polymer used as a carrier in the present invention may further increase the amount of the active ingredient by introducing a functional group such as sulfonate group, carboxylic acid group, trimethylammonium group, dimethylammonium group in the main chain or side chain portion.

The low temperature oxidation catalyst of the present invention is used by supporting a Group 8B metal and a copper metal in the form of a water-soluble salt as an active ingredient. It is well known in the art to use Group 8B metals and copper metals as active ingredients of low temperature oxidation catalysts. According to the conventional low temperature oxidation catalyst production method, the metal salt is supported on the carrier by a conventional supporting method, and then heat treatment is performed at 400 ° C. or higher to activate the catalyst. The metal salt is sintered and converted into metal or metal oxide by such heat treatment. Or the active ingredient may be entangled to form a lump. However, in the present invention, since a separate heat treatment is not performed after supporting the metal salt on the carrier, the water-soluble salt used as the active ingredient is preserved as it is, without being converted to metal or metal oxide, so that it acts as a catalyst. have. As a result, the low temperature oxidation catalyst of the present invention was able to exhibit excellent catalytic activity for a long time in the oxidation reaction for removing toxic gases, and it is easy to reproduce the initial performance through a simple regeneration process even if the catalyst activity is reduced and regenerated.

The water-soluble salt used for the preparation of the low temperature oxidation catalyst is a water-soluble compound containing a group 8B metal or a copper (II) metal such as palladium (II), platinum (II), and rhodium (II). There is no particular restriction on the choice of water soluble salts. The water soluble salt may specifically include a halide compound or an acid salt compound. More specifically, it may be a halide compound such as chloride, or at least one organic acid or inorganic acid salt compound selected from acetate, sulfate, nitrate and phosphate. In addition, the present invention places no particular limitation on the amount of the water-soluble salt supported as the active ingredient, and the amount of the supported amount can be adjusted as appropriate within the usual range commonly used in the art. Specifically, the water-soluble salt of the Group 8B metal may be supported by 0.01 to 10% by weight, preferably 0.1 to 5% by weight, and particularly preferably 0.1 to 2% by weight, based on the weight of the carrier. . Specifically, the water-soluble salt of copper metal may be supported by 10 to 50% by weight based on the weight of the carrier, preferably 10 to 30% by weight, and particularly preferably 10 to 20% by weight.

Referring to the method for producing a low temperature oxidation catalyst of the present invention in more detail as follows. Although the present invention specifically illustrates a catalyst production method based on impregnation, the present invention is not limited to the catalyst production method, and any method may be used as long as it is a conventional production method used in the art. This desired catalyst can be readily prepared.

First, the water-soluble salt of Group 8B metal and the water-soluble salt of copper metal supported as active ingredients are weighed, and then dissolved in distilled water to obtain a metal salt solution. At this time, a small amount of an organic solvent such as alcohols, acetone, or the like may be added to dissolve the metal salt more quickly. The prepared vinyl salt solution is immersed in the porous vinyl polymer used as the carrier, and the metal salt is supported on the carrier. And the solvent is evaporated while stirring at a temperature of 60 to 80 ℃ to obtain a solid product. The solid product is dried in an air at 90 ° C to 100 ° C to obtain a low temperature oxidation catalyst for which the present invention is desired.

On the other hand, the present invention is characterized by a method for removing toxic gases using the low temperature oxidation catalyst prepared above. As described above, the low temperature oxidation catalyst of the present invention is to be applied directly to the toxic gas removal process without the heat treatment process for the catalyst activation. That is, under the condition that the low temperature oxidation catalyst of the present invention is present and the temperature inside the reactor is maintained at 20 ° C. to 80 ° C., the exhaust gas is introduced into the reactor. The low temperature oxidation catalyst of the present invention oxidizes and removes various toxic gases such as carbon monoxide (CO), sulfur dioxide (SO ₂ ), formaldehyde (HCOH), acetaldehyde (CH ₃ COH), and ammonia (NH ₃ ). It is possible. In addition, the low temperature oxidation catalyst of the present invention exhibits excellent catalytic efficacy with a removal rate of 90% or more of these toxic gases. In addition, the low temperature oxidation catalyst of the present invention does not significantly reduce the catalytic activity even after long-term operation.

On the other hand, the present invention is characterized by a regeneration method of the low temperature oxidation catalyst used in the above toxic gas removal process. In the catalyst regeneration method proposed by the present invention, the low-temperature oxidation catalyst having reduced activity may be brought into contact with water vapor for about 1 to 3 hours. While conventional low temperature oxidation catalysts use complicated equipment for regeneration, the present invention can maintain its initial activity by a simple method of contact with water vapor and within a short time.

The present invention will now be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Example]

Example 1.

As a conventional catalyst preparation method, a low temperature oxidation catalyst was prepared by impregnation. That is, 25 g of CuCl ₂ , 0.1 g of Pt (NO ₃ ) ₂ , 3.0 g of PdCl ₂ , and 93 g of Cu (NO ₃ ) ₂ · 3H ₂ O were added to 5 L of distilled water and stirred to prepare an aqueous metal salt solution. . 1 kg of a poly (styrene-vinylbenzene) copolymer was immersed here. And the solvent was evaporated while stirring, maintaining 80 degreeC temperature, and the solid product was obtained. The solid product was dried in the air at 100 ° C. for about 5 hours to prepare a low temperature oxidation catalyst. The prepared low temperature oxidation catalyst was used immediately for the toxic gas removal process without a separate heat treatment process.

In order to evaluate the performance of the prepared low temperature oxidation catalyst, 20 g of the catalyst was placed inside a fixed bed reactor, and then the reactor internal temperature was maintained at 60 ° C., and then toxic gas was introduced at 350 cc / min flow rate through the bomb. In this experiment, 700 ppm of carbon monoxide (CO), 550 ppm of sulfur dioxide (SO ₂ ), 250 ppm of formaldehyde (HCOH), 250 ppm of acetaldehyde (CH ₃ COH), and 1.2% by volume of ammonia (NH ₃ ) were used. Toxic gas contains 0.1% moisture. The oxidation reaction was carried out for 10 hours, and the efficiency of the catalyst was compared and evaluated by measuring the concentration of toxic gas in the reactor when the oxidation reaction time was 1 hour, 5 hours, 10 hours.

Examples 2-4 and Comparative Examples 1-2.

A low-temperature oxidation catalyst was prepared in the same manner as in Example 1, but a poly (styrene-vinylbenzene) copolymer having different water contents, specific surface area, specific gravity, and pyrolysis temperature was used as a carrier.

In addition, the prepared low temperature oxidation catalyst was used directly in the toxic gas removal process illustrated in Example 1 without further heat treatment to evaluate the efficacy of the catalyst. The results are shown in Table 1 below.

division Toxic gas density 0 hours 1 hours 5 hours 10 hours
Example 1 CO (ppm) 700 100 0 0 SO ₂ (ppm) 550 80 20 0 HCOH (ppm) 250 30 15 0 CH ₃ COH (ppm) 250 33 10 0 NH ₃ (% by volume) 1.2 0.4 0.05 0
Example 2 CO (ppm) 700 120 5 0 SO ₂ (ppm) 550 80 23 0 HCOH (ppm) 250 50 15 0 CH ₃ COH (ppm) 250 33 20 0 NH ₃ (% by volume) 1.2 0.5 0.03 0
Example 3 CO (ppm) 700 100 10 0 SO ₂ (ppm) 550 80 20 0 HCOH (ppm) 250 30 24 0 CH ₃ COH (ppm) 250 33 20 0 NH ₃ (% by volume) 1.2 0.4 0.06 0
Comparative Example 1 CO (ppm) 700 400 500 700 SO ₂ (ppm) 550 300 180 550 HCOH (ppm) 250 180 150 250 CH ₃ COH (ppm) 250 150 150 250 NH ₃ (% by volume) 1.2 0.8 1.0 1.2
Comparative Example 2 CO (ppm) 700 410 520 700 SO ₂ (ppm) 550 320 180 550 HCOH (ppm) 250 140 160 250 CH ₃ COH (ppm) 250 140 150 250 NH ₃ (% by volume) 1.2 0.7 1.1 1.2 Properties of Poly (Styrene-Vinylbenzene)
Example 1: 45% water content, specific surface area 340 m 2 / g, specific gravity 0.2 cc / g, pyrolysis temperature 160 ° C
Example 2: 50% water content, specific surface area 330 m 2 / g, specific gravity 0.2 cc / g, pyrolysis temperature 165 ° C
Example 3: 55% water content, specific surface area 320 m 2 / g, specific gravity 0.2 cc / g, pyrolysis temperature 170 ° C
Comparative Example 1: Water content 10%, specific surface area 250 m 2 / g, specific gravity 0.3 cc / g, pyrolysis temperature 180 ° C
Comparative Example 2: 5% water content, specific surface area 300 m 2 / g, specific gravity 0.3 cc / g, pyrolysis temperature 170 ° C

According to Table 1, it can be seen that the water content of the polymer acts as a major factor in determining the catalytic activity in using the poly (styrene-vinylbenzene) copolymer as a carrier. As suggested by the present invention, the catalysts of Examples 1 to 3 were able to maintain high catalytic activity without deactivation of the catalyst even when used continuously for 10 hours under the condition of coexistence of moisture. Could be removed. However, the catalysts shown as Comparative Example 1 or Comparative Example 2 were prepared using a poly (styrene-vinylbenzene) copolymer having a low water content of 10% or 5% as a carrier, and the toxic gas removal efficiency was remarkably low. In addition, it was confirmed that the catalyst deactivation phenomenon tends to increase significantly as the operation time increases.

Comparative Examples 3 to 7.

A low-temperature oxidation catalyst was prepared in the same manner as in Example 1, except that polyethylene (Comparative Example 3), polystyrene (Comparative Example 4), polyvinyl alcohol (Comparative Example 5), or zeolite of H-ZSM-5 (Comparative Example) was used as a carrier. 6) and activated carbon (Comparative Example 7) were used respectively.

In addition, the prepared low temperature oxidation catalyst was used directly in the toxic gas removal process illustrated in Example 1 without further heat treatment to evaluate the efficacy of the catalyst. The results are shown in Table 2 below.

division carrier Toxic
gas density 0 hours 1 hours 5 hours 10 hours
Example 1
Poly (styrene-vinylbenzene) CO (ppm) 700 100 0 0 SO ₂ (ppm) 550 80 20 0 HCOH (ppm) 250 30 15 0 CH ₃ COH (ppm) 250 33 10 0 NH ₃ (% by volume) 1.2 0.4 0.05 0
Comparative Example 3
Polyethylene CO (ppm) 700 500 600 700 SO ₂ (ppm) 550 300 450 550 HCOH (ppm) 250 220 250 250 CH ₃ COH (ppm) 250 200 250 250 NH ₃ (% by volume) 1.2 0.9 0.8 1.2
Comparative Example 4
polystyrene CO (ppm) 700 500 600 700 SO ₂ (ppm) 550 450 450 550 HCOH (ppm) 250 220 200 250 CH ₃ COH (ppm) 250 200 200 250 NH ₃ (% by volume) 1.2 0.9 0.8 1.2
Comparative Example 5
Polyvinyl alcohol CO (ppm) 700 500 600 700 SO ₂ (ppm) 550 300 450 550 HCOH (ppm) 250 220 250 250 CH ₃ COH (ppm) 250 200 250 250 NH ₃ (% by volume) 1.2 0.9 0.8 1.2
Comparative Example 6
H-ZSM-5 CO (ppm) 700 300 200 100 SO ₂ (ppm) 550 350 150 100 HCOH (ppm) 250 120 90 100 CH ₃ COH (ppm) 250 100 80 100 NH ₃ (% by volume) 1.2 0.8 0.7 0.5
Comparative Example 7
Activated carbon CO (ppm) 700 300 230 110 SO ₂ (ppm) 550 350 110 100 HCOH (ppm) 250 120 80 70 CH ₃ COH (ppm) 250 100 70 70 NH ₃ (% by volume) 1.2 0.7 0.6 0.4 Poly (styrene-vinylbenzene): water content 45%, specific surface area 340 m 2 / g, specific gravity 0.2 cc / g, pyrolysis temperature 160 ° C
Polyethylene: Water content 2%, Specific surface area 2㎡ / g, Specific gravity 1.5 cc / g, Pyrolysis temperature 120 ℃
Polystyrene: moisture content 5%, specific surface area 20 ㎡ / g, specific gravity 0.1 cc / g, pyrolysis temperature 100 ℃
Polyvinyl alcohol: water content 5%, specific surface area 2 ㎡ / g, specific gravity 3.0 cc / g, pyrolysis temperature 120 ℃
H-ZSM-5: water content 10%, specific surface area 400 m 2 / g, specific gravity 1.2 cc / g, pyrolysis temperature 900 ° C

Table 2 is a result of comparing the activity of the catalyst prepared by using a polymer material other than the porous vinyl copolymer as a carrier. Polyethylene, polystyrene, polyvinyl alcohol has a low specific surface area and high density due to the characteristics of the material, and thus has a limit in increasing the amount of metal salt supported, and thus the catalytic activity is very low. In addition, the catalysts of Comparative Examples 3 to 7 showed a tendency of markedly increased deactivation under the condition in which water coexisted, but after 6 hours of operation, the catalyst could no longer be expressed as a catalyst.

Comparative Examples 8 to 9.

A low-temperature oxidation catalyst is prepared in the same manner as in Example 1, but the carrier of the poly (styrene-vinylbenzene) copolymer is supported by a metal oxide (e.g., CuO, PdO), which is a non-aqueous metal salt compound, as an active ingredient. An oxidation catalyst was prepared.

That is, in Comparative Example 8, 25 g of CuCl ₂ , 0.1 g of Pt (NO ₃ ) ₂ , 3.0 g of PdCl ₂ , and 31.9 g of CuO were added to 5 L of distilled water and stirred to prepare a metal salt mixture. 1 kg of vinyl copolymer) was immersed and the solvent was evaporated while stirring while maintaining the temperature of 80 ° C. to obtain a solid product.

In Comparative Example 9, 25 g of CuCl ₂ , 0.1 g of Pt (NO ₃ ) ₂ , 2.07 g of PdO and 93 g of Cu (NO ₃ ) ₂ .xH ₂ O were added to 5 L of distilled water and stirred, followed by stirring. After the preparation, 1 kg of poly (styrene-vinylbenzene) copolymer was immersed and the solvent was evaporated while stirring while maintaining the temperature of 80 ° C. to obtain a solid product.

Each solid product prepared above was dried in an air at 100 ° C. for about 5 hours to prepare a low temperature oxidation catalyst. The prepared low temperature oxidation catalyst was used immediately for the toxic gas removal process without a separate heat treatment process. In addition, the prepared low temperature oxidation catalyst was used directly in the toxic gas removal process illustrated in Example 1 without further heat treatment to evaluate the efficacy of the catalyst. The results are shown in Table 3 below.

division Toxic gas density 0 hours 1 hours 5 hours 10 hours
Example 1 CO (ppm) 700 100 0 0 SO ₂ (ppm) 550 80 20 0 HCOH (ppm) 250 30 15 0 CH ₃ COH (ppm) 250 33 10 0 NH ₃ (% by volume) 1.2 0.4 0.05 0
Comparative Example 8 CO (ppm) 700 500 400 400 SO ₂ (ppm) 550 350 300 300 HCOH (ppm) 250 200 180 170 CH ₃ COH (ppm) 250 210 200 190 NH ₃ (% by volume) 1.2 1.0 0.9 0.8
Comparative Example 9 CO (ppm) 700 400 300 250 SO ₂ (ppm) 550 300 250 240 HCOH (ppm) 250 280 220 220 CH ₃ COH (ppm) 250 290 230 230 NH ₃ (% by volume) 1.2 1.0 0.7 0.5

Table 3 is a result of comparing the activity for the catalyst prepared by changing the metal salt compound supported on the porous vinyl copolymer as the active ingredient. Comparative Example 8 and Comparative Example 9 are catalysts prepared by supporting non-aqueous metal salts such as CuO and PdO as active ingredients, and due to low solubility of the metal salts, it is difficult to evenly disperse in the carrier and have very limited loading, and the prepared surface is not smooth. It was bumpy without. In addition, the catalysts of Comparative Example 8 and Comparative Example 9 not only produced activity, but also operated for 5 hours, and thus the catalyst was inactivated, and thus the catalysts could not be expressed.

Experimental example. Catalyst Regeneration Capability Assessment

In order to evaluate the regeneration ability of the low-temperature oxidation catalyst according to the present invention, after the toxic gas removal reaction according to Example 1 for 10 hours was carried out to contact the steam from 90 ℃ to 100 ℃ steam discharged from the steam generator for 3 hours . In addition, after the regenerated catalyst was placed in the reactor, the toxic gas removal reaction was performed, and the results are shown in Table 4 below.

division Toxic gas density 0 hours 1 hours 5 hours 10 hours
Initial catalyst CO (ppm) 700 100 0 0 SO ₂ (ppm) 550 80 20 0 HCOH (ppm) 250 30 15 0 CH ₃ COH (ppm) 250 33 10 0 NH ₃ (% by volume) 1.2 0.4 0.05 0
Regenerated catalyst CO (ppm) 700 110 8 0 SO ₂ (ppm) 550 80 40 0 HCOH (ppm) 250 30 20 0 CH ₃ COH (ppm) 250 33 10 0 NH ₃ (% by volume) 1.2 0.4 0.05 0.1

According to Table 4, the low-temperature oxidation catalyst of the present invention can be regenerated by a simple method of contacting with water vapor without using complicated equipment for regeneration, and the regenerated catalyst can maintain almost the same activity as the initial catalyst. there was.

Claims (15)

Water-soluble salts of Group 8B metals and copper metals are supported as active ingredients on porous vinyl-based polymer carriers having a water content of 20 to 60% by weight, and are used for removing toxic gases by drying at 90 ° C to 100 ° C without high temperature firing. Low temperature oxidation catalyst.
The method of claim 1,
The porous vinyl polymer has a specific surface area of 300 to 500 m 2 / g, specific gravity of 0.2 to 0.3 cc / g low temperature oxidation catalyst for removing toxic gases.
3. The method of claim 2,
The porous vinyl polymer is a low-temperature oxidation catalyst for toxic gas removal, characterized in that the thermal decomposition temperature measured by a thermal analyzer (TG) is 150 to 200 ℃.
The method of claim 3, wherein
The porous vinyl polymer is a low-temperature oxidation catalyst for toxic gas removal, characterized in that the poly (styrene-vinylbenzene) copolymer.
5. The method of claim 4,
The styrene-vinylbenzene copolymer is a low temperature oxidation catalyst for removing toxic gases, characterized in that a functional group selected from a sulfonate group, a carboxylic acid group, a trimethylammonium group, and a dimethylammonium group is further combined.
The method of claim 1,
The water-soluble salt is a metal halide compound, or a low temperature oxidation catalyst for removing toxic gases, characterized in that the organic acid or inorganic acid salt compound.
The method of claim 1,
The low-temperature oxidation catalyst for removing toxic gases, characterized in that the Group 8B metal is at least one selected from palladium (II), platinum (II) and rhodium (II).
The method of claim 1,
The water-soluble salt of the Group 8B metal is at least one selected from the group consisting of chlorides, acetates, sulfates, nitrates and phosphates of metals selected from palladium (II), platinum (II) and rhodium (II). Oxidation catalyst.
The method of claim 1,
The water-soluble salt of the copper metal is a low-temperature oxidation catalyst for toxic gas removal, characterized in that at least one selected from chloride, acetate, sulfate, nitrate and phosphate of copper (II) metal.
The method of claim 1,
The low-temperature oxidation catalyst for removing toxic gases, characterized in that the water-soluble salt of the 8B metal is supported by 0.1 to 10% by weight based on the weight of the carrier.
The method of claim 1,
The water-soluble salt of the copper metal is a low-temperature oxidation catalyst for removing toxic gases, characterized in that supported by 10 to 50% by weight based on the weight of the carrier.
The method according to any one of claims 1 to 11,
The toxic gas is a low-temperature oxidation catalyst for toxic gas removal, characterized in that selected from the group consisting of carbon monoxide (CO), sulfur dioxide (SO ₂ ), formaldehyde (HCOH), acetaldehyde (CH ₃ COH) and ammonia (NH ₃ ). .
The method according to any one of claims 1 to 11,
The catalyst is a low temperature oxidation catalyst for removing toxic gases, characterized in that the regeneration in contact with water vapor.
The group consisting of carbon monoxide (CO), sulfur dioxide (SO ₂ ), formaldehyde (HCOH), acetaldehyde (CH ₃ COH) and ammonia (NH ₃ ) in the presence of the low temperature oxidation catalyst of any one of claims 1 to 11. Toxic gas removal method, characterized in that to remove the toxic gas selected from the oxidizing reaction at a temperature of 20 ℃ to 80 ℃.
The low temperature oxidation catalyst regeneration method of claim 1, wherein the low temperature oxidation catalyst of any one of claims 1 to 11 is contacted with water vapor to regenerate the low temperature oxidation catalyst.