KR100862272B1 - Catalyst for Removal of Carbon Monoxide and Preparation Method Thereof - Google Patents

Abstract

The present invention supports 0.1 to 1% by weight platinum group material based on 100% by weight of the metal oxide carrier, and the supported metal is dried for 1 to 3 hours at 100 to 200 ℃ and then fired for 1 to 3 hours at 400 to 550 ℃ Precious metal supporting step; 5 to 10% by weight of gallium was added to the supported platinum group catalyst, but the supported gallium was dried for 1 to 3 hours at 100 to 200 ° C and then composed of a transition metal supporting step of firing at 400 to 550 ° C for 1 to 3 hours. The present invention relates to a method for producing a catalyst for removing carbon monoxide.

Sintering Process, Sintering Furnace, Incinerator, Power Plant, Carbon Monoxide, Catalyst, Poisoning

Description

Catalyst for Removal of Carbon Monoxide and Manufacturing Method Thereof {Catalyst for Removal of Carbon Monoxide and Preparation Method Thereof}

1 is a diagram showing the carbon monoxide removal rate of the catalyst according to the present invention,

2 is a view showing the carbon monoxide removal rate of the conventional catalyst.

The present invention relates to a catalyst for removing carbon monoxide and a method of manufacturing the same, and more particularly, no deactivation occurs even at high concentrations of Cl ₂ , SO ₂ , HCl and HVOCs, which can cause catalyst poisoning, and the removal rate is reduced even in continuous operation. The present invention relates to a catalyst for removing endothelial carbon monoxide, and a method for preparing the same.

In general, flue gas generated from sintering furnaces, incinerators and power generation facilities contains carbon monoxide (CO), which is a toxic substance, and carbon monoxide is also generated by decomposition of carbon dioxide in places such as carbon dioxide (C0 ₂ ) laser devices. Since the carbon monoxide produced as described above is a toxic substance, a process for removing carbon monoxide is provided in the process of generating carbon monoxide. At this time, the method used to remove the carbon monoxide is a method of oxidizing and removing the carbon monoxide and oxygen present in the exhaust gas using most catalysts.

The catalyst most commonly used as a catalyst for removing carbon monoxide is a catalyst in which a noble metal such as platinum (Pt) or palladium (Pd) is supported on a metal oxide carrier such as alumina (Al ₂ O ₃ ) or titania (TiO ₂ ).

The catalyst is usually active at a high temperature of 150 ℃, and the recently developed catalyst for removing carbon monoxide at low temperatures is prepared by supporting a precious metal such as platinum or palladium on a variety of metal oxides, in this manufacturing method an expensive noble metal such as gold or platinum because it uses as a raw material and production cost-intensive, and in order to uniformly disperse the active metal ions such as catalyst manufacture of gold or platinum on the support, and requires a high level of skill, Cl ₂ There is a drawback of deactivation caused by waste gases containing catalytic poisons such as HCl, SOx and HVOCs.

As a catalyst for removing carbon monoxide at low temperatures, Hopcalite, which is composed of a mixture of tin oxide, manganese oxide, and copper oxide, is relatively economical and has a good effect of removing carbon monoxide, but its activity decreases in the presence of more than 10% moisture. There is a flaw.

Looking at the carbon monoxide removal catalyst and the prior art according to the manufacturing method as described above are as follows.

German Patent Nos. 4344981 and 4334983 disclose a patent for a carbon monoxide selective oxidation reaction process and a reactor using a platinum catalyst, but the activity of the catalyst is not high enough and the activity is not maintained for a long time. .

On the other hand, attempts have been made to change the components of catalysts, such as platinum catalysts supported by zeolites (US Pat. No. 5,955,395), iridium-based catalysts (US Pat. No. 6,162,558), palladium-based catalysts (US Pat. No. 5,162,012), and the like. Proposed. As such, studies have been made to develop a catalyst for carbon monoxide oxidation reaction in which the activity is high and the activity of the catalyst is maintained for a long time.

The present invention has been made to solve the above-mentioned problems, and a catalyst for removing endothelial carbon monoxide having no activity deterioration with respect to HCl, Cl ₂ , SOx and HVOCs, which are problematic for poisoning the catalyst, and a method for preparing the same There is a technical challenge to providing.

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The present invention is a precious metal supporting step for supporting 0.1 to 1% by weight of the platinum group material based on 100% by weight of the metal oxide carrier; It provides a method for producing a catalyst for removing carbon monoxide, characterized in that consisting of a transition metal supporting step of adding 5 to 10% by weight of 3B group material to the supported platinum group catalyst.

In this case, the supporting precious metal is dried for 1 to 3 hours at 100 to 200 ° C., and then baked at 400 to 550 ° C. for 1 to 3 hours, and the supporting transition metal is 100 to 200 ° C. It is dried for 1 to 3 hours and then calcined for 1 to 3 hours at 400 to 550 ℃.

The catalyst for removing carbon monoxide according to the present invention prepares an endothelial toxic catalyst by using a platinum group among precious metals as a main catalyst, a group 3B of transition metals as a cocatalyst, and a porous carrier having a large specific surface area as a metal oxide carrier.

The main catalysts according to the present invention are platinum (Pt), palladium (Pd), iridium (Ir), osmium (Os), rhodium (Rh), ruthenium (Pt) among elements belonging to the platinum group of the precious metal series, for example, Group 8 of the periodic table. Ru) or a mixture of one or more thereof may be used, and preferably platinum is used.

At this time, the main catalyst is preferably added in the form of a complex having nitrogen-containing ligands such as oxides, hydroxides, acids, halides, ammonium salts, halide complexes, nitrates, olefin complexes, phthalocyanine or acetylacetonate.

The promoter according to the present invention is boron (B), aluminum (Al), gallium (Ga), indium (In), titanium (Ti) or the like among the elements belonging to Group 3B of the transition metal series, such as Group 3B of the periodic table. One or more of these may be mixed and used, and preferably gallium is used.

The carrier according to the present invention may be one or more metal oxides selected from the group consisting of alumina, titania, zirconia, magnesia, ceria, silica, and tungsten oxides as the metal oxide supporting the main catalyst and the promoter. It is recommended to use titania or alumina. If necessary, silica or tungsten may be added to the titania.

In a particular embodiment, the carrier according to the present invention may be formed of Boehmite containing about 77% by weight of alumina.

The carrier has a specific surface area of 80 to 200 m ² / g, the shape can be arbitrarily selected according to the purpose of particulate, pellet, plate, honeycomb, etc., the flow path of the carrier is trapezoidal, rectangular, rectangular, It can be a thin wall channel that can have any suitable cross-sectional shape and size such as sinusoidal, hexagonal, elliptical or circular.

In a particular embodiment, the carrier according to the invention consists of titania, has a specific surface area of 180 to 200 m ² / g, and can be used by adding 10% by weight of silica to the titania carrier based on 100% by weight of titania.

In addition, the carrier consists of titania, has a specific surface area of 80 to 100 m ² / g, and may be used by adding 10 wt% silica and 10 wt% tungsten to the titania carrier based on 100 wt% titania. .

Since the catalyst for removing carbon monoxide according to the present invention is used as a catalyst for combustion of carbon monoxide to remove carbon monoxide generated in sintering furnaces, incinerators and power generation facilities, there is no need to provide a means for removing toxic components. Simplification is achieved. Furthermore, it is not necessary to keep the reaction temperature of the catalyst at a high temperature in order to suppress adsorption of the toxic component, thereby reducing the operating cost.

On the other hand, catalysts in which only precious metals are supported as active ingredients are deactivated under waste gas containing HCl, Cl ₂ , SOx, and HVOCs such as SO ₂ , thereby reducing the carbon monoxide removal rate. This is because the noble metal catalyst adsorbs SO ₂ and the catalytic activity is lowered.

On the other hand, catalysts containing noble metals and Group 3B as active ingredients on carriers with increased specific surface area are resistant to Group 3B, eg, acids, under waste gases containing toxic components such as HCl, Cl ₂ , SOx and HVOCs such as SO _2. Gallium may be used as a promoter to protect noble metal catalysts that are easily deactivated in halogenated compounds, and the removal rate of carbon monoxide may be maintained at a constant level by increasing the active site with a carrier having a large specific surface area.

Thus, a method for producing a carbon monoxide removal catalyst according to the present invention will be described as an example.

First, a platinum group material is supported on a metal oxide carrier. The precursor of the platinum group is not particularly limited, and the method of supporting the platinum group material is also not limited. After supporting the platinum group material is subjected to a heat treatment process, dried for 1 to 3 hours at 100 to 200 ℃ in an air atmosphere and then fired for 1 to 3 hours at 400 to 550 ℃.

Next, a group 3B material of the transition metal series is added to the supported platinum catalyst. In this case, a commercial platinum supported catalyst may be used as it is. As the precursor of the Group 3B material, any compound may be used. Group 3B materials are supported by impregnation, which can be either dry or wet. The catalyst on which the group 3B is supported is dried at 100 to 200 ° C. for 1 to 3 hours in an air atmosphere, and then calcined at 400 to 550 ° C. for 1 to 3 hours. At this time, the catalyst prepared based on 100% by weight of the metal oxide carrier contains 0.1 to 1% by weight of the platinum group material and 5 to 10% by weight of the Group 3B material.

The catalyst prepared by the above-mentioned method oxidizes carbon monoxide in a gas in which catalytic toxic components are present. At this time, using a conventional fixed bed atmospheric flow reactor, the catalyst is first charged, then pretreated at 300 to 500 ° C. while flowing hydrogen, and then a carbon mixture containing carbon monoxide is supplied to continuously oxidize carbon monoxide. During the pretreatment and reaction, the space velocity of the gas is 5,000 to 60,000 h ⁻¹ , and the composition of the reactants is 0.1 to 1% by volume carbon monoxide, 1 to 75% hydrogen, 10 to 15% oxygen, 0 to 30% water vapor, o-DCB 0.05 Nav 0.1%, HCl 0.8-1.2%, Cl2 0.3-0.5%, SO2 1-1.2%.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention by these examples.

<Example 1>

81.9 g of Titania [Hombikat UV-100, Rockwood, Germany] was dissolved in 116.5 g of secondary distilled water and 25.7 g of colloidal silica [AS-40, Nissan Chemical, Japan], followed by diaamium dinitro platinum [Pt (NH ₃ ) ₂ (NO ₂ ) ₂ , Hangeol Gold, Korea] 33.8g was added and wet impregnated.

Then, the platinum-supported catalyst was dried at 120 ° C. for 2 hours and then calcined at 500 ° C. for 2 hours. The prepared catalyst contains 1 weight percent platinum.

Then, 145.4 g of gallium nitrate [Ga (NO ₃ ) ₃ , Hanjin Gold, Korea] was added to the platinum-supported catalyst, wet impregnated, dried at 120 ° C. for 2 hours, and then calcined at 500 ° C. for 2 hours. It was. The prepared catalyst contained 1 weight percent platinum, 10 weight percent silica and 5 weight percent gallium based on 100 weight percent metal oxide carrier.

Then, the prepared catalyst was dispersed in distilled water, ball milled to a suitable particle size, coated on cordierite honeycomb [100 CPSI cordierite honeycomb, Cocat China, China], dried at 120 ° C. for 2 hours, and then dried at 500 ° C. for 2 hours. It was calcined during to prepare a honeycomb type Pt-Ga / TiO ₂ -SiO ₂ catalyst.

Then, in order to measure the oxidation performance of carbon monoxide, a 22.5cc volume catalyst was inserted into a fixed bed reactor [CO oxidation tester, Samson Hitech, South Korea], followed by a space velocity of 40,000 hr ^-1 , nitrogen 82.65% by volume, and carbon monoxide by one volume. Gas was simulated at%, 13% by volume, 1% by volume of water, 0.05% by volume of o-DCB, 0.8% by volume of HCl, 0.3% by volume of Cl ₂ , and 1.2% by volume of SO ₂ for 500 minutes at 350 ° C.

The composition of the catalyst is shown in Table 1, the results are shown in FIG.

Example 2

In the same manner as in Example 1, 81.9 g of titania [Hombikat UV-100, Rockwood, Germany] and 25.7 g of colloidal silica [AS-40, Nissan Chemical, Japan] instead of 25.7 g of titania [DT51, Milleium, France] 81.9 g Honeycomb type Pt-Ga / TiO ₂ -using a carrier prepared by mixing 11.9 g of ammonium paratungsten [ WO ₃ , Duksan Chemical, Korea] and 25.7 g of colloidal silica [AS-40, Nissan Chemical, Japan] WO ₃ -SiO ₂ catalyst was prepared. The prepared catalyst contained 1% by weight of platinum, 5% by weight of gallium, 10% by weight of tungsten, and 10% by weight of silica based on 100% by weight of the metal oxide carrier.

The composition of the catalyst is shown in Table 1, the results are shown in FIG.

Example 3

In the same manner as in Example 1, 81.9 g of titania [Hombikat UV-100, Rockwood, Germany] and colloidal silica [AS-40, Nissan Chemical, Japan] 25.7 g instead of alumina [Pural NF, Sasol, South Africa] A honeycomb type Pt-Ga / Al ₂ O ₃ catalyst was prepared using 81.9 g. The prepared catalyst contained 1 wt% platinum and 5 wt% gallium based on 100 wt% of the metal oxide carrier.

The composition of the catalyst is shown in Table 1, the results are shown in FIG.

Example 4

Performed in the same manner as in Example 2, but omitting the step of mixing the ammonium paratungsten [ WO ₃ , Duksan Chemical, Korea] and colloidal silica [AS-40, Nissan Chemical, Japan] honeycomb-type Pt-Ga / TiO ₂ Catalyst was prepared. The prepared catalyst contained 1 wt% platinum and 5 wt% gallium based on 100 wt% of the metal oxide carrier.

The composition of the catalyst is shown in Table 1, the results are shown in FIG.

As shown in FIG. 1, the carbon monoxide removal rate of the catalyst in which gallium was further supported as a promoter on the platinum-supported catalyst was increased at the same time as that of the catalyst supporting only platinum.

However, when the specific surface area of the metal oxide support was small as in Example 4, it was confirmed that the added gallium reduced the catalytic activity point and the initial carbon monoxide removal rate was reduced.

Example 1 Example 2 Example 3 Example 4 Pt 1wt% 1wt% 1wt% 1wt% WoO ₃ 10wt% Ga 5wt% 5wt% 5wt% 5wt% SiO ₂ 10wt% 10wt% Specific surface area 190m ² / g 95 m ² / g 170m ² / g 90m ² / g Master TiO ₂ TiO ₂ Al ₂ O ₃ TiO ₂

Comparative Example 1

In the same manner as in Example 1, 81.9 g of titania [Hombikat UV-100, Rockwood, Germany] and 25.7 g of colloidal silica [AS-40, Nissan Chemical, Japan] were substituted with 81.9 g of titania [DT51, Millenium, France]. Honeycomb-type Pt / TiO ₂ catalyst was prepared by omitting the use of g and impregnating 145.4 g of gallium nitrate [Ga (NO ₃ ) ₃ , Seong Gold, Korea]. The prepared catalyst contained 1% by weight platinum based on 100% by weight metal oxide carrier.

The composition of the catalyst is shown in Table 2, the results are shown in FIG.

Comparative Example 2

In the same manner as in Example 1, 81.9 g of titania [Hombikat UV-100, Rockwood, Germany] and 81.9 g of titania [DT51, Milleium, France] instead of 25.7 g of colloidal silica [AS-40, Nissan Chemical, Japan] Ammonium molybdate [(NH ₄ ) 6 Mo ₇ O ₂₄ , Duksan Pharm., Korea] using a carrier prepared by mixing 15.1 g, gallium nitrate [Ga (NO ₃ ) ₃ , jung gold, South Korea] 145.4 g The honeycomb-type Pt / TiO ₂ -MoO ₃ catalyst was prepared by omitting the impregnation process. The prepared catalyst contained 1 wt% platinum and 10 wt% molybdenum based on 100 wt% of the metal oxide carrier.

The composition of the catalyst is shown in Table 2, the results are shown in FIG.

Comparative Example 3

In the same manner as in Example 1, 81.9 g of titania [Hombikat UV-100, Rockwood, Germany] and 81.9 g of titania [DT51, Millenium, France] instead of 25.7 g of colloidal silica [AS-40, Nissan Chemical, Japan] Elanthania [La ₂ O ₃ , Deoksan Pharmaceutical, Korea] using a carrier prepared by mixing 8.19g, the process of impregnating 145.4g of gallium nitrate [Ga (NO ₃ ) ₃ , grain gold, South Korea] To prepare a honeycomb-type Pt / TiO ₂ -La ₂ O ₃ catalyst. The prepared catalyst contained 1% by weight platinum and 10% by weight lantania based on 100% by weight metal oxide carrier.

The composition of the catalyst is shown in Table 2, the results are shown in FIG.

Comparative Example 4

A honeycomb-type Pt / TiO _2- SiO ₂ catalyst was prepared by performing the same method as Example 1, but omitting a process of impregnating 145.4 g of gallium nitrate [Ga (NO ₃ ) ₃ , Hangeol Gold, Korea]. The prepared catalyst contained 1% by weight of platinum and 10% by weight of silica based on 100% by weight of the metal oxide carrier.

The composition of the catalyst is shown in Table 2, the results are shown in FIG.

Comparative Example 5

Prepared in the same manner as in Example 2, but omitting a process of impregnating 145.4 g of gallium nitrate [Ga (NO ₃ ) ₃ , Hangeol Gold, Korea] to prepare a honeycomb Pt / TiO ₂ -WO ₃ -SiO ₂ catalyst. It was. The prepared catalyst contained 1% by weight of platinum, 10% by weight of tungsten and 10% by weight of silica based on 100% by weight of the metal oxide carrier.

The composition of the catalyst is shown in Table 2, the results are shown in FIG.

      Comparative Example 6

The process was carried out in the same manner as in Example 3, except that 81.9 g of alumina [Spherite 501, Axens, France] was used instead of 81.9 g of alumina [Pural NF, Sasol, South Africa], and 145.4 g of gallium nitrate was impregnated. Omitted, the honeycomb Pt / Al ₂ O ₃ catalyst was prepared. The prepared catalyst contained 1% by weight platinum based on 100% by weight metal oxide carrier.

The composition of the catalyst is shown in Table 2, the results are shown in FIG.

      Comparative Example 7

The honeycomb Pt / Al ₂ O ₃ catalyst was prepared by the same method as Example 3, but omitting the process of impregnating 145.4 g of gallium nitrate. The prepared catalyst contained 1 weight percent platinum.

The composition of the catalyst is shown in Table 2, the results are shown in FIG.

As shown in FIG. 2, the carbon monoxide removal rate was increased at the same time when the platinum was formed by adding silica to titania, the silica and tungsten were added to titania, or formed of alumina.

Item / Feature Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Pt 1wt% 1wt% 1wt% 1wt% 1wt% 1wt% 1wt% WoO ₃ 10wt% MoO ₃ 10wt% La ₂ O ₃ 10wt% SiO ₂ 10wt% 10wt% Specific surface area 90m ² / g 95 m ² / g 105m ² / g 190m ² / g 100m ² / g 180 m ² / g 170m ² / g Master TiO ₂ TiO ₂ TiO ₂ TiO ₂ TiO ₂ Al ₂ O ₃ Al ₂ O ₃

As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. Therefore, it should be understood that the embodiments described above are all illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention all changes or modifications derived from the meaning and scope of the claims to be described later rather than the detailed description and equivalent concepts thereof.

The platinum group catalyst to which the Group 3B material added according to the present invention is not deactivated under waste gas containing catalyst poisoning components such as HCl, Cl ₂ , SOx, and HVOCs, which are problematic for catalyst poisoning. In addition to the excellent removal efficiency, there is a wide range of catalytic activity effect.

Claims (11)

delete delete delete delete delete delete delete A precious metal supporting step of supporting 0.1 to 1% by weight platinum group material based on 100% by weight of the metal oxide carrier, drying the supported metal at 100 to 200 ° C. for 1 to 3 hours, and then firing at 400 to 550 ° C. for 1 to 3 hours. ; 5 to 10% by weight of gallium was added to the supported platinum group catalyst, but the supported gallium was dried for 1 to 3 hours at 100 to 200 ° C and then composed of a transition metal supporting step of firing at 400 to 550 ° C for 1 to 3 hours. Method for producing a catalyst for removing carbon monoxide, characterized in that. delete delete The method of claim 8, The platinum group material is platinum, palladium, iridium, osmium, rhodium, ruthenium or a method for producing a catalyst for removing carbon monoxide, characterized in that at least one of them.

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