KR20010105537A - Ceramic catalyst for producing the radicals and method of prepartion for the same - Google Patents

Abstract

A bridge manager (bridge management device) is automatically determined. In a network, bridges (51-54) are formed by coupling portals (41-48) connected to buses (11-15) so that different buses (11-15) are connected together through the bridges (51-54). The portals (41-48) have registers that store the IDs, and the values indicative of the function, of the bridge managers corresponding to the respective portals. One bridge manager is selected from candidates (31, 34) according to the contents in the registers.

Description

CERAMIC CATALYST FOR PRODUCING THE RADICALS AND METHOD OF PREPARTION FOR THE SAME

The present invention relates to ceramic catalysts for converting ozone into radicals. More specifically, ozone is converted to radicals by using ceramic catalysts instead of ozone required for sterilization, deodorization, bleaching, wastewater, water purification and organic decomposition in the industrial environment. A ceramic catalyst for generating radicals from ozone and a method for producing the same.

Ozone has long been used for environmental purification, and has been used as a strong oxidizing agent, fungicide, and organic wastewater decomposer with superior oxidizing power (potential difference of 2.07 eV) than other oxidizing agents. However, despite the theoretical nature that all organics can be completely decomposed into CO ₂ and H ₂ O, ozone is often slow to react with organics or does not react selectively (eg, saturated hydrocarbons, pesticides). In particular, in the case of treating water with ozone, the reaction efficiency is inferior, so it is widely used throughout the industry. In addition, ozone was used for water and sewage treatment and disinfection and disinfection at home. However, it can cause discomfort due to the characteristic ozone smell caused by residual ozone.

Accordingly, in order to solve such a problem, Korean Patent Laid-Open Publication No. 99-45899 provides a radical generator comprising a platinum-titanium dioxide catalyst portion and an ultraviolet lamp, and irradiates titanium dioxide with ultraviolet rays as a principle of radical generation by the apparatus. Then, electrons of titanium dioxide are excited to react with water in the air where the holes are moist in the valence band generated to generate radicals, and electrons excited in the conduction band move to the surface of platinum. Reactions with oxygen and ozone produce O ^2- and O ^3- and these reactions have been described several times to produce hydroxyl radicals and other oxidants. Therefore, in the present invention, titanium dioxide, platinum, and ultraviolet lamps are essential for generating radicals from ozone. However, since the amount of ozone generated in ultraviolet lamps is small, the amount of radicals generated after decomposition is small, and radicals are deposited on the surface of titanium dioxide by ultraviolet irradiation. Because of the formation, the reaction rate of radicals is slow, and the effect is small. In addition, there is a problem that the use conditions are difficult because the ultraviolet lamp must be used.

In addition, Korean Utility Model Publication No. 2000-309 discloses that ozone generated in an air bubble ozone washer is decomposed into radicals with a catalyst composed of a ceramic catalyst, that is, SiO ₂ , Al ₂ O ₃ , TiO ₂ , MgO, ZrSiO, CaO. Disclosed is a bubble ozone washing machine equipped with a catalyst, and the present invention prevents ozone-specific odors and adverse effects on the human body as ozone generated in the washing machine is not dissolved in the washing water but is released into the atmosphere. It has the effect of increasing the washing effect so that the reaction is made quickly. However, as a constituent of the catalyst used for this, it is difficult to decompose a large amount of ozone, resulting in low radical generation rate, low reaction rate with ozone, and low radical effect. 30 or less). Therefore, it is necessary to add an active catalyst material to completely decompose ozone and increase the reaction rate.

Therefore, in order to overcome the problems of the conventional radical generators, there is an urgent need to provide a radical generator that generates a large amount of radicals by completely decomposing high concentration ozone with an ozone concentration of 100 ppm or more at a high reaction rate in a short time (99.9 or more).

In order to solve the problems of the prior art as described above, in order to obtain a ceramic catalyst having a high radical conversion rate without providing additional energy, the present invention uses a titanium silicon composite oxide made by firing titanium dioxide and silicon dioxide as an active ingredient, It is an object to provide a ceramic catalyst that converts ozone into radicals.

Still another object of the present invention is to provide a ceramic catalyst for converting ozone into radicals, using titanium dioxide composite oxide formed by calcining titanium dioxide and silicon dioxide further comprising manganese or manganese oxide as an active ingredient.

Another object of the present invention is by calcining titanium dioxide and silicon dioxide further comprising at least one compound of copper or Group 8 metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) An object of the present invention is to provide a ceramic catalyst which converts ozone into radicals using a titanium silicon composite oxide as an active ingredient.

Another object of the present invention is to provide a method for producing a ceramic catalyst comprising a step of mixing the titanium dioxide and silicon dioxide in a solution phase to hydrolyze and form a titanium silicon composite in the form of coprecipitation oxide, followed by drying and firing.

Still another object of the present invention is to prepare a ceramic catalyst which is deposited on a silicon dioxide and titanium dioxide ceramic catalyst in a manganese salt solution and calcined after drying or in an aqueous solution of copper metal or copper oxide or one or more Group 8 metal elements, It is to provide a method for producing a ceramic catalyst consisting of a step of drying and firing.

Still another object of the present invention is to provide a radical generator in ozone using a ceramic catalyst comprising an ozone portion having an ozone generator and a catalyst portion comprising a ceramic catalyst, wherein the ozone discharged from the ozone generator passes through the catalyst. It is.

1 is a view illustrating a principle of converting ozone into radicals using the ceramic catalyst of the present invention.

2 is an example of the radical generating device of the present invention.

Figure 3 relates to a method for producing a ceramic catalyst of the present invention, the first step relates to a method for producing a ceramic catalyst of a composite oxide of titanium dioxide and silicon dioxide, the second step is to a ceramic catalyst obtained in the first step When the process of coating and baking manganese or manganese oxide is shown, a 3rd process shows the process of coating and baking a copper, copper oxide, or group 8 metal element (or these oxides) on the ceramic catalyst obtained by the 2nd process.

Figure 4 illustrates an apparatus for initially supplying radicals to distilled water for the sterilization experiment of radicals produced by the ceramic catalyst in the present invention.

Figure 5 shows the sterilizing power of radicals generated from ozone using the ceramic catalyst of the present invention.

6 shows the results of examining the concentrations of ammonia and hydrogen sulfide before and after the passage of the ceramic catalyst in order to verify the deodorizing power of radicals generated by the ceramic catalyst of the present invention.

Figure 7 shows the decomposition efficiency of organic compounds by measuring the phenol concentration change before and after the passage of radicals produced by the ceramic catalyst of the present invention by gas chromatography.

The present invention relates to a ceramic catalyst for generating radicals for generating radicals from ozone. More specifically, ceramic catalyst for radical generation which increases the processing capacity of sterilization, deodorization, etc. by converting ozone into radicals by using a catalyst instead of ozone which requires sterilization, deodorization, waste water, water purification, and organic matter treatment in the whole industrial environment and its It relates to a manufacturing method.

Radical is the physicochemical properties of e is an odd number governing the chemically active species of the substance ^{(O -, O 2-, O} 2 -, OH -, HO 2 -) deulyimyeo, and these are prepared by contacting the reaction with ozone in a catalytic surface The radicals produced are highly oxidizing and therefore have functions such as sterilization, deodorization, organic matter decomposition, and bleaching. When the oxidative power of radicals is compared with ozone, chlorine and water, the radicals are (+3.00 eV)> ozone (+2.07 eV)> chlorine (+1.40 eV)> water (+1.23 eV). The ceramic catalyst of the present invention has the advantage of excellent ozone decomposing power at low temperature, excellent ozone decomposing power, high reaction rate, and arbitrarily adjustable ozone decomposing rate according to catalyst component adjustment.

As shown in FIG. 1, the principle of generating radicals from ozone by the ceramic catalyst of the present invention is as follows. First, ozone generated in ozone generator is decomposed into active species by ceramic catalyst, and the generated radicals are disinfected by contact with microorganisms and contaminants in water or gaseous phase, and decompose them. Will be displayed.

The ozone decomposition mechanism using the ceramic catalyst for generating radicals according to the present invention is as follows.

The present invention seeks to provide a ceramic catalyst for converting ozone into radicals using titanium titanium composite oxide formed by calcining titanium dioxide and silicon dioxide as an active ingredient.

In addition, the present invention is to provide a ceramic catalyst for converting ozone into radicals, using titanium dioxide composite oxide formed by calcining titanium dioxide and silicon dioxide further comprising manganese or manganese oxide as an active ingredient.

Another object of the present invention further comprises at least one compound selected from the group consisting of copper, or copper oxides, and Group 8 metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) or oxides The present invention provides a ceramic catalyst which converts ozone into radicals using titanium titanium composite oxide formed by calcining titanium dioxide and silicon dioxide as an active ingredient.

The catalyst adsorbs ozone on the surface of the catalyst to maintain the decomposition time, decomposes the ozone into oxygen active species, and serves to separate the decomposed oxygen active species from the catalyst.

The ceramic catalyst of the present invention has the advantage of excellent ozone decomposing power at low temperature, excellent ozone decomposing power, high reaction rate, and arbitrarily adjustable ozone decomposing rate according to catalyst component adjustment.

Still another object of the present invention is to prepare a ceramic catalyst which is deposited on a silicon dioxide and titanium dioxide ceramic catalyst in a manganese salt solution, followed by drying and sintering in an aqueous solution of copper metal or copper oxide, or one or more Group 8 elements, and dried. And it provides a method for producing a ceramic catalyst consisting of the step of firing.

In one example of the present invention, the method for producing a ceramic catalyst is composed of a first step, namely, mixing, hydrolysis, filtration, washing, drying, calcining, mixing, molding, and firing steps of raw materials. More preferably, a second process may be added, which is a step of coating at least one active catalyst material on the catalyst product produced by the first process.

The catalyst production process is roughly divided into a catalyst carrier production process and a catalyst material production process. The catalyst carrier production process is performed by quantifying a titanium alkoxide solution and a silicon alkoxide solution in a TiO ₂ : SiO ₂ = 1-5: 1 weight ratio. After mixing and stirring for 3 hours, a predetermined amount of ammonia and distilled water are added to hydrolyze to form co-precipitation oxides of titanium and silicon.

The co-precipitated oxide produced is precipitated and filtered, washed with water 3-4 times, filtered and then low-water at 80-150 ° C. for 1-10 hours. The dried raw material is calcined at 300-800 ° C. at high temperature to produce microcrystalline titanium silicon composite oxide which is the main raw material of the catalyst carrier.

Since the prepared composite oxide is powdery, in order to catalytically decompose gaseous ozone, it must be made of a carrier having a certain form of breathability (eg spherical, pellet, honeycomb, etc.). The catalyst carrier is manufactured by high temperature firing at 500-12000 ° C. in order to form an extruder and to have a stable crystal phase.

In order to impart excellent ozone decomposition and radical change characteristics to the calcined carrier at low temperature, the manganese salt solution is impregnated with a first washing coating evenly over the entire ceramic catalyst. The manganese-coated ceramic catalyst contains a large amount of moisture and is dried in 50-150 ° C. for 5-10 hours and calcined at 300-800 ° C., followed by a second wash coating. The secondary coating is obtained by impregnating and coating the primary coated product with a copper salt or Group 8 metal salt (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) solution to double the activity of the catalyst. It is prepared by drying at -150 ° C for 5-10 hours and calcining at high temperature at 500-1200 ° C.

In one example of the present invention, the ozone section 1 having an air inlet 5 and the ozone generator 3, the ozone outlet 7 are connected to the ozone section, and the radical outlet 15 and the ceramic catalyst 13 are connected. It is made of a catalyst unit 11 including, and relates to a radical generator in ozone using a ceramic catalyst made so that ozone discharged from the ozone generator passes through the catalyst. Referring to the generator using the radical generator of the present invention, as shown in Fig. 2, the generator comprises an ozone generator 1 and a catalyst 11, and the ozone generator applies a high voltage to both electrodes in air. It is composed of a structure that generates ozone by discharging (silent discharge), and the catalyst part has a structure that generates radicals by passing the generated ozone through a filter (sphere, pellet, honeycomb structure, etc.) made of a catalyst material. The structure is composed of a system, the catalyst unit may be a box-shaped as shown in Figure 2, by installing a diaphragm may maximize the contact time and the contact area of the ozone gas and the ceramic catalyst.

Radical generators of the present invention are applied to environmental and chemical treatment fields such as home appliances, sterilization and deodorization devices in industrial fields, water purification and wastewater treatment devices in water treatment fields, air purification and gas treatment devices in air conditioning fields, and chemical oxidation devices for each application. It can be used extensively.

The invention will be described in more detail with reference to the following examples, but the following examples are merely illustrative and are not intended to limit the scope of the invention to the examples.

Example

Example 1: TiO ₂ : SiO ₂ Method for producing a ceramic catalyst having a weight ratio of 4: 1

As a main raw material, a titanium alkoxide and silicon alkoxide solution was mixed and stirred for 3 hours at a weight ratio of TiO ₂ : SiO ₂ of 4: 1, and then hydrolyzed with ammonia and distilled water, and washed with water three times and filtered. After drying for 5 hours at 120 ℃ calcined at 500 ℃ to produce a microcrystalline titanium silicon oxide. The molding aid was added to the resultant in an amount of 20 parts by weight to form a sphere having an average particle diameter of 3 mm, and then calcined at 1000 ° C. to prepare a ceramic carrier.

Example 2: TiO ₂ : SiO ₂ Method for producing a ceramic catalyst with a weight ratio of 3: 1

A ceramic carrier was prepared in the same manner as in Example 1 except that the titanium alkoxide and silicon alkoxide solution as the main raw material were mixed at a weight ratio of TiO ₂ : SiO ₂ of 3: 1.

Example 3: TiO ₂ : SiO ₂ Method for producing a ceramic catalyst with a weight ratio of 5: 1

A ceramic carrier was prepared in the same manner as in Example 1 except that the titanium alkoxide and silicon alkoxide solution, which were the main raw materials, were mixed at a weight ratio of TiO ₂ : SiO ₂ of 5: 1.

Example 4-6 Manganese Coated Ceramic Catalyst

The ceramic carrier obtained in Example 1-3 was first impregnated with a mixed solution of manganese salt, dried at 100 ° C. for 5 hours, and then calcined at 700 ° C. to prepare a manganese-coated ceramic catalyst.

Example 7 Ceramic Catalysts Coated with Group VIII Metal Salts, Copper Salts and Manganese Salts

The TiO ₂ : SiO ₂ weight ratio of 4: 1 obtained in the above-mentioned ceramic catalyst was secondaryly impregnated with a mixed solution of copper salt, platinum salt and palladium salt, dried at 80 ° C. for 10 hours, and calcined at 1000 ° C. at high temperature. A catalyst coated with manganese salt, copper salt and group 8 metal salt was prepared.

Example 8: Measurement of Radical Generation

After filling 20 g of the catalyst prepared in Examples 1 to 7 with the radical generator as shown in FIG. 2, the ozone decomposition rate, that is, the radical generation rate was verified by measuring the ozone concentration before and after passing after passing 100 ppm of ozone air through the catalyst. . Since the half-life of radicals is extremely short, it is impossible to measure the concentration. Thus, the ozone decomposition rate was determined by measuring the ozone concentration before and after passing through the ceramic catalyst, and this was set as the test standard for radicals. This is because only ozone and air are contained in the radical generator, and since the air component is very stable and does not participate in the reaction, only ozone is converted into radicals by the ceramic catalyst. The experimental results are shown in Table 1 below, and the ozone decomposition rate was calculated by the following equation.

Example TiO ₂ : Weight ratio of SiO ₂ Presence or absence of manganese coating Copper or Group 8 metals coated Ozone decomposition rate One 4: 1 x x 53.3 2 3: 1 x x 38.5 3 5: 1 x x 51.8 4 4: 1 O x 95.3 5 3: 1 O x 88.5 6 5: 1 O x 89.7 7 4: 1 O O 99.9

Example 9: Sterilization Test

Experimental method, as shown in Figure 5, in order to verify the sterilizing power of radicals generated from ozone using a ceramic catalyst, the initial ozone generated in the ozone generator as a catalyst of the radical generator as shown in Figure 2 having the ceramic catalyst of Example 7 After converting to 100 radicals by passing ozone gas having a concentration of 100 ppm (shown in FIG. 4), 10 ^3-4 cells of Staphylococcus aureus and E. coli were respectively added to 1000 cc of distilled water, and then slowly stirred, and the radical gas was fed into 1000 cc / After generating bubbles for 20 minutes in the amount of minutes, the number of bacteria remaining in distilled water was observed under a microscope. The experimental results are shown in Table 2 and FIG. 5, and the highest bactericidal power of 96.6 was verified.

Type of bacteria Bactericidal power Remarks Staphylococcus aureus 96.6 Escherichia coli 97.4

Example 10: Deodorization Experiment

In order to verify the deodorizing power of the radicals, ammonia and hydrogen sulfide were adjusted to 450 ppm and 95 ppm concentrations in a sealed 1M ³ space, respectively, and 100 ppm of ozone was converted into radicals through the 20 g catalyst prepared in Example 7 in a convection using a fan. After maintaining for a certain time, the concentration of residual ammonia and hydrogen sulfide was measured with a gas detector to verify the deodorization efficiency. An overview of the experimental method is shown in FIG. 6. The results obtained are shown in Table 3 below.

Reagent Types Deodorization Efficiency () Remarks 15 minutes 60 minutes ammonia 95 95 Hydrogen sulfide 63.6 96.4

Example 11: Decomposition of Organic Compound

In order to verify the decomposition performance of the organic compound of the radical, as shown in Figure 7 added a phenol to a concentration of 50ppm in 1000cc distilled water and stirred for a certain time, after complete dissolution, the 20g catalyst prepared in Example 7 with a gas of ozone concentration 100ppm By converting into radical through to generate bubbles for a certain time in the amount of 1000cc per minute, the change of phenol concentration was measured by gas chromatography to determine the decomposition efficiency of organic compounds.

The results are shown in the following Table 4, and since the phenol decomposition efficiency is excellent at 95.4, it can be used for wastewater treatment and water purification treatment.

Bubble occurrence time (hours) Early One 3 5 10 Phenol Residue (ppm) 50 12.5 3.4 5.2 2.3 Decomposition Efficiency 0 75 83.2 89.6 95.4

Example 12: Bleaching Experiment

In order to verify the bleaching effect of the radicals produced by the ceramic catalyst of the present invention, 100L distilled water was injected into the washing machine and 2 kg of contaminated washing test cloth was put in. Then, 100 ppm of ozone was passed through 20 g of the catalyst prepared in Example 7 into a washing machine. After washing for 10 minutes while converting into radicals and blowing into a washing tank, the bleaching effect was tested by measuring the whiteness of the test cloth before and after washing. Washing bleaching power is calculated from the following formula.

Experimental results showed a laundry bleaching power of 33, which is better than using an oxygen-based bleach.

The present invention provides a ceramic catalyst, that is, a ceramic catalyst comprising a titanium silicon composite oxide composed of titanium dioxide and silicon dioxide as an active ingredient, and preferably at least one additional component selected from the group consisting of manganese, copper, or group 8 elements. It relates to a ceramic catalyst for converting ozone into a radical comprising a and a method for producing the same. The ceramic catalyst of the present invention has the advantage of excellent ozone degrading power at room temperature without extra energy source, excellent mass ozone degrading power, high reaction rate, and arbitrarily adjustable ozone decomposing rate according to the adjustment of catalyst components. It can be used for systems, deodorizers, wastes and water treatment systems. In addition, the ceramic catalyst of the present invention can prevent human pollution caused by secondary pollution or ozone use due to the use of conventional chemicals, and reacts quickly because it decomposes organisms of bacteria, odors and contaminants into the gas phase. It can handle a lot of capacity in a short time, and it can be widely used in future industrial development by supplementing the problem of using ozone or chemicals.

Claims (8)

A ceramic catalyst which generates radicals from ozone, using as an active ingredient a titanium silicon composite oxide composed of titanium dioxide and silicon dioxide. The ceramic catalyst of claim 1, wherein the catalyst further comprises manganese or manganese oxide. The ceramic catalyst of claim 1, wherein the catalyst comprises at least one compound selected from Group 8 compounds consisting of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt, copper, and copper oxide. 3. The ceramic catalyst according to claim 2, wherein the catalyst comprises at least one compound selected from Group 8 compounds consisting of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt, copper, and copper oxide. A method of preparing the ceramic catalyst according to claim 1, wherein the titanium compound and the silicon compound are mixed in a solution to hydrolyze to form a titanium silicon composite in the form of a coprecipitation oxide, and then dried and calcined. The method of claim 4, wherein the ceramic catalyst is added to the manganese salt solution, followed by drying and calcining. The method of claim 5, wherein the ceramic catalyst is added to an aqueous solution of one or more Group 8 elements, followed by drying and calcining. An ozone unit having an air inlet and an ozone generator, an ozone outlet, connected to the ozone unit, comprising a catalyst outlet including a radical outlet and a catalyst according to any one of claims 1 to 3, wherein the ozone discharged from the ozone generator is Radical generator using the ceramic catalyst of any one of claims 1 to 4, which is to pass through the catalyst.