KR101218871B1 - Photocatalyst-carrier and its manufacturing process - Google Patents

Abstract

 SUMMARY OF THE INVENTION The present invention provides a photocatalyst carrier having a strong photocatalytic effect due to the difficulty of peeling photocatalytic fine particles and a method of producing the same. More specifically, in the present invention, a titanium oxide first layer 5 is formed on the surface of a ceramic filter 3 which is an alumina ceramics porous body by using a dipcoater, and the temperature of 600 ° C. to 1100 ° C. The step of firing at temperature for 1 hour and the second layer of titanium oxide (7) were formed on the first layer of titanium oxide by using a dipcoater, and then baked at 200 ° C. for 2 hours. It relates to a photocatalyst carrier manufacturing method comprising the step of producing a photocatalyst carrier (1).

Photocatalyst

Description

Photocatalyst carrier and its manufacturing method {Photocatalyst-carrier and its manufacturing process}

1 is a cross-sectional view showing the configuration of the photocatalyst carrier 1.

2 is a photograph of the surface of the ceramic filter 3.

3 is a photograph of the surface of the photocatalyst carrier of Example 2. FIG.

4 is a photograph of the surface of the photocatalyst carrier of Example 3. FIG.

5 is a photograph of the surface of the photocatalyst carrier of Example 5 and Comparative Example 5.

6 is a cross-sectional photograph showing a titanium oxide layer formed on a glass thin plate.

[Description of Symbols]

One … Photocatalyst carrier

3…. Ceramics filter

5…. Titanium oxide first layer

7. Titanium oxide second layer

SUMMARY OF THE INVENTION The present invention provides a photocatalyst carrier having a strong photocatalytic effect due to the difficulty of peeling photocatalytic fine particles and a method of producing the same. More specifically, in the present invention, a titanium oxide first layer 5 is formed on the surface of a ceramic filter 3 which is an alumina ceramics porous body by using a dipcoater, and the temperature of 600 ° C. to 1100 ° C. The step of firing at temperature for 1 hour and the second layer of titanium oxide (7) were formed on the first layer of titanium oxide by using a dipcoater, and then baked at 200 ° C. for 2 hours. It relates to a photocatalyst carrier manufacturing method comprising the step of producing a photocatalyst carrier (1).

It has been known from the past that oxide photocatalysts such as titanium oxide have antifouling, deodorization and antibacterial functions by photocatalytic action. The expression structure of the photocatalytic action is as follows. In other words, when light having an energy equivalent to a band gap is irradiated onto the oxide photocatalyst, electrons are generated in the conduction band by photolithography, and holes are generated in the valence band. . The electrons thus produced show a strong reducing action, and the holes show a strong oxidation action. These redox reactions decompose organic matter and nitrogen compounds attached on the photocatalyst into water or carbon dioxide gas.

In recent years, the environmental purification method using the antifouling, deodorization, and antibacterial function of the oxide photocatalyst and the environmental purification device have attracted attention. However, since the oxide photocatalyst is usually in the form of a powder, it is necessary to immobilize the oxide photocatalyst on a substrate by a specific method in order to use it in an environmental purification apparatus. As the fixing method, the following methods (i) to (iii) are known.

(i) A powdered oxide photocatalyst is mixed with an organic binder and applied onto a substrate.

After (塗布), it is fixed by heating at room temperature. (See Patent Document 1)

(ii) Applying powdered oxide photocatalyst on inorganic substrate by mixing with inorganic binder

After (塗布), it is fixed by heating at room temperature. (See Patent Document 2)

(iii) Applying a coating agent prepared by mixing an oxide photocatalyst and a solvent on a substrate

After heating, the substrate is heated at a high temperature to fix the oxide photocatalyst on the substrate. (See Patent Document 3)

       [Patent Document 1] Publication No. 7-060132

       [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-38218

       [Patent Document 3] Japanese Patent Application Laid-Open No. 2001-259435

However, in the method of (i) and (ii), since the binder covers most of the surface of the oxide photocatalyst, the area of the exposed portion of the surface of the oxide photocatalyst is reduced, and the photocatalytic action is inactivated. have. In addition, in the method of (i), since the organic binder is decomposed by the photocatalytic action, there is also a problem in durability that the film strength decreases and the powder of the oxide photocatalyst gradually falls off.

In addition, in the method of (iii), the oxide photocatalyst is sintered due to heating at a high temperature, so that the surface area of the oxide photocatalyst decreases and the photocatalytic action is deteriorated. In addition, in the method of (iii) above, there is a problem in that the crystalline form of the oxide photocatalyst is phase-transformed into a low-active crystalline form by firing at a high temperature, thereby deactivating the photocatalytic action.

Accordingly, an object of the present invention is to provide a photocatalyst carrier having a large photocatalytic effect due to difficulty in peeling of photocatalytic fine particles and a method of producing the same.

The object of the present invention, i) attaching the photocatalytic fine particles to the substrate and calcined at a temperature of 500 ℃ to 1100 ℃ to form an A layer; And ii) attaching the photocatalytic fine particles on the A layer and baking at a temperature of 100 ° C. to 400 ° C. to form a B layer, wherein the substrate is a porous ceramics substrate. It is achieved by providing a photocatalyst carrier manufacturing method.

In the present invention, the layer A is firmly fixed to the substrate because the layer A is calcined at a temperature of 500 ° C to 1100 ° C (preferably 600 ° C to 1100 ° C, more preferably 600 ° C to 1000 ° C). . In addition, since both the A and B layers are made of photocatalytic fine particles, the bonding between the A and B layers is also robust. Therefore, the photocatalyst carrier produced by the present invention is excellent in durability since the A layer and the B layer are difficult to peel off.

In addition, in the present invention, since the photocatalytic fine particles can be immobilized without using a binder when forming the A layer and the B layer, the surface of the photocatalytic fine particles is not covered with the binder so that the effective surface area of the photocatalytic fine particles is large. Accordingly, the photocatalyst carrier produced by the present invention has a large photocatalytic action by the photocatalytic microparticles, thereby preventing fouling and deodorization.

(防臭) And excellent in antibacterial function.

In addition, the present invention can form the B layer on the outermost surface of the photocatalyst carrier. Since the baking temperature of this B layer is as low as 100 degreeC-400 degreeC, sintering does not occur and the effective surface area of the photocatalytic microparticles | fine-particles contained in B layer is large. Therefore, the photocatalyst carrier produced by the present invention has photocatalytic fine particles having a large effective surface area on the outermost surface, so that the photocatalytic action of the photocatalytic fine particles is large, and thus excellent in antifouling, deodorization, and antibacterial functions.

In addition, the present invention does not require the use of a binder for immobilizing the photocatalytic fine particles, thereby simplifying the manufacturing process.

For example, ceramics, metal, and glass are mentioned as a material of the said base material.

For example, the thickness of the film of the layer A is suitably in the range of 1 µm to 5 µm, and the thickness of the film of the layer B is in the range of 1 µm to 20 µm.

The particle size of the photocatalytic fine particles is preferably in the range of 5 µm to 100 nm.

(2) In the invention of claim 2, in the method of claim 1, the photocatalytic fine particles include titanium oxide, zinc oxide, zirconium oxide, strontium titanate, cadmium emulsification, and tungsten oxide. (Tungsten), iron oxide and silicon, any one selected from the group or a mixture thereof.

In the present invention, the photocatalytic fine particles are made of the above-mentioned material, so that the photocatalytic action is further increased.

The crystal forms of titanium oxide include rutile (Rutile), anatase and pantitanium (Brookite). In particular, anatase having a large photocatalytic action is preferable.

(3) The invention of claim 3 is the method of claim 1 or 2, wherein the photocatalytic fine particles constituting the layer A and the photocatalytic fine particles constituting the B layer are made of the same material. It relates to a manufacturing method.

In the present invention, since the photocatalytic fine particles constituting the A layer and the photocatalytic fine particles constituting the B layer are made of the same material, the adhesion between the A layer and the B layer is further enhanced. Therefore, the photocatalytic carrier manufactured by the present invention is more excellent in durability.

(4) The invention of claim 4 is the method according to any one of claims 1 to 3, wherein after applying the dispersion liquid in which the photocatalytic fine particles are dispersed in the steps i) and ii), A method for producing a photocatalyst carrier, wherein the photocatalytic fine particles are attached by evaporating a solvent of a dispersion.

The present invention can form an A layer, a B layer, or both of them by a method described above with a uniform thickness. Moreover, according to this invention, formation of A-layer, B-layer, or both is easy.

(5) The invention of claim 5 relates to the method of claim 4, wherein the photocatalytic fine particles are 5 to 30% by weight of the total weight of the dispersion.

In the present invention, the photocatalytic action is greater because the content of the photocatalytic fine particles is 5 to 30% by weight of the total weight of the dispersion.

(6) The invention of claim 6 relates to the method of producing a photocatalyst carrier according to any one of claims 1 to 5, wherein the porous ceramics substrate is a porous alumina substrate.

In the present invention, since the substrate is porous ceramics, the substrate is not damaged in the firing step. In addition, the photocatalyst carrier produced by the present invention has a large surface area and a large photocatalytic effect because the substrate is porous.

(7) The invention of claim 7 relates to a photocatalyst carrier produced by the method of any one of claims 1 to 6.

The photocatalyst carrier produced by the method of the present invention has the effect as described in claims 1 to 6.

Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples are only for explaining specific examples of the present invention, and the present invention is not limited to these Examples.

Example 1

a) The structure of the photocatalyst carrier of Example 1 is demonstrated using FIG. 1 and FIG. The photocatalyst carrier 1 is composed of a ceramic filter (porous ceramic substrate) 3 as a substrate and a first titanium oxide layer (A layer) 5 and a second titanium oxide layer (B layer) 7 which are sequentially laminated on the surface thereof. )

The ceramic filter (3) is made of alumina ceramics porous body (Al ₂ O ₃ : 76%, SiO ₂ : 19% -Porosity: 85%). The photograph which took the surface of this ceramic filter 3 with the electron microscope (scanning electron microscope S-4800 by Hitachi High-Technologies) is shown in FIG.

The titanium oxide first layer 5 and the titanium oxide second layer 7 are layers in which titanium oxide fine powders (photocatalytic fine particles) are respectively immobilized, and their thicknesses are all 1 µm to 2 µm.

b) Next, the manufacturing method of the photocatalyst carrier of Example 1 is demonstrated.

First, the titanium oxide first layer 5 was formed on the surface of the ceramic filter 3. Specifically, the ceramic filter 3 was immersed in a titanium oxide coating liquid (a dispersion in which photocatalytic fine particles were dispersed) using a dip coater (KD-5000 of SDI Co., Ltd.), and then lifted up. The titanium oxide coating liquid adhered to the surface of the ceramic filter 3 by this, and the solvent of the titanium oxide coating liquid evaporated after that, and the A layer which consists of titanium oxide on the surface of the ceramic filter 3 was formed.

Here, titanium oxide coating liquid is STS-01 (titanium oxide content of 30.1% of ISHIHARA IND.

(Weight ratio) and the average particle diameter of titanium oxide about 7 nm, pH 1.5) 4 times diluted (STS-01 and water mixed at the ratio of 1: 3). Since the content of titanium oxide in STS-01 is 30.1% by weight as described above, the content of used titanium oxide is 7.52% by weight of the total weight of the used titanium oxide coating liquid.

Next, the ceramic filter 3 and the titanium oxide first layer 5 were calcined for 2 hours using an electric furnace (KDF S-100 of DENKEN Co., Ltd.). The firing temperature was made into four types of 600 ° C, 800 ° C, 1000 ° C and 1100 ° C, and the one fired at 600 ° C was fired at Examples 1-1 and 800 ° C and the one fired at Examples 1-2 and 1000 ° C. Example 1-3 and what was baked at 1100 degreeC was made into Example 1-4.

Next, for each of Examples 1-1 to 1-4, a titanium oxide second layer 7 was formed on the titanium oxide first layer 5. The formation method used the method of immersing in a titanium oxide coating liquid using a dipcoater similarly to formation of the titanium oxide 1st layer 5. However, the titanium oxide coating liquid at this time was used by diluting STS-01 of ISHIHARA INDUSTRIES twice (mixing STS-01 and water in a ratio of 1: 1). Since the content of titanium oxide in STS-01 is 30.1% by weight, the content of used titanium oxide is 15.1% by weight of the total weight of the used titanium oxide coating liquid.

Next, the ceramic filter 3, the first titanium oxide layer 5 and the second titanium oxide layer 7 are calcined under conditions of 200 ° C. for 1 hour using an electric furnace (first Baking twice) The photocatalyst carrier 1 was completed. In addition, Table 1 shows a list of the manufacturing conditions of the photocatalyst carriers of Examples 1-1 to 1-4.

Example 1-1 Examples 1-2 Example 1-3 Example 1-4
Produce
Condition



Oxidation
titanium
The first layer Coating solution 4-fold dilution 4-fold dilution 4-fold dilution 4-fold dilution Plasticity
Temperature (℃) 600 800 1000 1100 Plasticity
Time (hr) 2 2 2 2
Oxidation
titanium
Second layer Coating solution 2-fold dilution 2-fold dilution 2-fold dilution 2-fold dilution Plasticity
Temperature (℃) 200 200 200 200 Plasticity
Time (hr) One One One One
Ammo
Nya
decomposition
Experiment

density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) Response time 0 minutes 200 0 200 0 200 0 200 0 Response time 2.5 minutes 35.1 84 39 80.5 44.2 77.9 46.3 76.9 5 minutes response time 15 92.5 18 91 17.8 91.1 20 90 Response time 7.5 minutes 10 95 11 94.5 11.5 94.3 12.5 93.8 Response time 10 minutes 6.3 96.9 8.5 95.8 8 96 10 95 Response time 15 minutes 4.8 97.6 6.2 96.9 6 95.5 6.5 96.8 Response time 30 minutes 2.2 98.9 3.5 98.3 3 98.5 3.7 98.2

In addition, the photocatalyst carriers of Comparative Examples 1-1 to 1-4 were prepared as follows.

[Comparative Example 1-1]

The formation of the titanium oxide first layer and the first firing were carried out in the same manner as in Example 1-1, but the formation of the titanium oxide second layer and the second firing were not performed.

Comparative Example 1-2

The formation of the titanium oxide first layer and the first firing were carried out in the same manner as in Example 1-2, but the formation of the titanium oxide second layer and the second firing were not performed.

Comparative Example 1-3

The formation of the titanium oxide first layer and the first firing were carried out in the same manner as in Example 1-3, but the formation of the titanium oxide second layer and the second firing were not performed.

[Comparative Example 1-4]

The formation of the first titanium oxide layer and the first firing were carried out in the same manner as in Example 1-4, but the formation of the second titanium oxide layer and the second firing were not performed.

In addition, Table 2 shows a list of the manufacturing conditions of the photocatalyst carrier in Comparative Examples 1-1 to 1-4.

Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Comparative Example 1-4
Produce
Condition



Oxidation
titanium
The first layer Coating solution 4-fold dilution 4-fold dilution 4-fold dilution 4-fold dilution Plasticity
Temperature (℃) 600 800 1000 1100 Plasticity
Time (hr) 2 2 2 2 Oxidation
titanium
Second layer Coating solution - - - - Plasticity
Temperature (℃) - - - - Plasticity
Time (hr) - - - -
Ammo
Nya
decomposition
Experiment


density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) Response time 0 minutes 200 0 200 0 200 0 200 0 Response time 2.5 minutes 105 47.5 127 36.5 105 47.5 170 15 5 minutes response time 88 56 110 45 100 50 150 25 Response time 7.5 minutes 82 59 115 42.5 90 55 135 32.5 Response time 10 minutes 75 62.5 100 50 78 61 125 37.5 Response time 15 minutes 70 65 88 56 76 62 110 45 Response time 30 minutes 55 72.5 73 63.5 60 70 90 55

c) Next, the effect which the photocatalyst carrier 1 of Example 1 brings is demonstrated. (i) In the photocatalyst carrier 1 of the first embodiment, the titanium oxide first layer 5 is firmly fixed to the ceramic filter 3 because it is calcined at a temperature of 600 ° C to 1100 ° C. It is. In addition, the bonding between the titanium oxide second layer 7 and the titanium oxide first layer 5 is also robust. Therefore, the photocatalyst carrier 1 of this Example 1 is hard to peel off the titanium oxide 1st layer 5 and the titanium oxide 2nd layer 7, and its durability is high.

(Ii) In the photocatalyst carrier 1 of the first embodiment, since titanium oxide is immobilized without using a binder, the surface of titanium oxide is not covered with a binder, and the effective surface area of titanium oxide is large. Therefore, the photocatalyst carrier 1 of the first embodiment has a large photocatalytic action by titanium oxide.

(Iii) In the photocatalyst carrier 1 of the first embodiment, the titanium oxide second layer 7 is exposed to the outermost surface. Since the firing temperature of this titanium oxide second layer 7 is as low as 200 ° C, no sintering occurs and the effective surface area of titanium oxide is large. Accordingly, the photocatalyst carrier 1 of the first embodiment has a titanium oxide second layer 7 having a large effective surface area on the outermost surface, thereby having a large photocatalytic effect of titanium oxide.

(Iii) Since the photocatalyst carrier 1 of the first embodiment does not need to use a binder for immobilizing titanium oxide, the manufacturing process can be simplified.

d) Next, the experiment conducted to confirm the photocatalytic action produced by the photocatalyst carrier 1 of the first embodiment will be described. The following experiment was carried out for each of the photocatalyst carriers of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4.

(Iii) Experimental method

In a container of a volume of 67 L, an invisible light (Black Light) as a light source for illuminating the photocatalyst carrier and the photocatalyst and a fan for stirring the air inside the vessel were installed. The illumination degree of an invisible light was 30 W, and the stirring speed by a blower was 0.4 m <3> / min.

Next, the vessel was sealed and ammonia was injected so as to have an initial concentration of 200 ppm. And when the time (reaction time) from the injection of ammonia was 0 minutes, 2.5 minutes, 5 minutes, 7.5 minutes, 10 minutes, 15 minutes and 30 minutes, respectively, the ammonia concentration meter (3L (0.5-78 ppm of detector tubes of GASTEC) ), 3La (2.5 ~ 200ppm)) was used to measure the ammonia concentration.

(Ii) experimental results

Ammonia concentrations and removal rates for each reaction time are shown in Tables 1 and 2 above. Here, the removal rate refers to the initial concentration of ammonia as C ₀ and the measured concentration as C _n . When it does, it means what is represented by following General formula (I).

% Removal = ((C ₀ -C _n ) / C ₀ ) × 100 (I)

As shown in Table 1, the photocatalyst carriers 1 of Examples 1-1 to 1-4 were all very high, with removal rates of 98% or more in 30 minutes of reaction time. As a result, it was confirmed that the photocatalyst carrier 1 of Example 1 had a high ammonia decomposition effect (deodorization effect) due to the photocatalytic action.

In addition, since the ammonia decomposition effect of the photocatalyst carrier 1 of Examples 1-1 to 1-4 was all high, the baking temperature of the titanium oxide 1st layer 5 was 600 degreeC-1100 degreeC. It was confirmed that the range was appropriate.

In contrast, as shown in Table 2, the photocatalyst carriers of Comparative Examples 1-1 to 1-4 had a very low removal rate of 55% to 72.5% in 30 minutes of reaction time.

The reason why the ammonia removal rate of the photocatalyst carriers of Comparative Examples 1-1 to 1-4 is low is as follows. That is, the photocatalyst carriers of Comparative Examples 1-1 to 1-4 are not provided with the titanium oxide second layer 7, but are provided with only the titanium oxide first layer 5. Since the titanium oxide first layer 5 is calcined at a high temperature of 600 ° C to 1100 ° C, sintering occurs and the surface area of titanium oxide is reduced. As a result, the ammonia removal rate of the photocatalyst carriers of Comparative Examples 1-1 to 1-4 was lowered.

[Example 2]

Basically, the photocatalyst carrier 1 of Examples 2-1 to 2-4 was produced similarly to the said Examples 1-1 to 1-4. In the present Example 2, however, the titanium oxide coating liquid used for forming the titanium oxide first layer 5 was prepared by diluting STS-01 by six times (mixing STS-01 and water in a ratio of 1: 5). I did. Since the content of titanium oxide in STS-01 is 30.1% by weight, the content of used titanium oxide is 5.02% by weight of the total weight of the used titanium oxide coating liquid. In addition, Table 3 shows a list of methods for producing the photocatalyst carrier 1 in Examples 2-1 to 2-4.

Example 2-1 Example 2-2 Example 2-3 Examples 2-4
Produce
Condition



Oxidation
titanium
The first layer Coating solution 6-fold dilution 6-fold dilution 6-fold dilution 6-fold dilution Plasticity
Temperature (℃) 600 800 1000 1100 Plasticity
Time (hr) 2 2 2 2
Oxidation
titanium
Second layer Coating solution 2-fold dilution 2-fold dilution 2-fold dilution 2-fold dilution Plasticity
Temperature (℃) 200 200 200 200 Plasticity
Time (hr) One One One One
Ammo
Nya
decomposition
Experiment


density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) Response time 0 minutes 200 0 200 0 200 0 200 0 Response time 2.5 minutes 46.8 76.6 36.4 81.8 39 80.5 41.6 79.2 5 minutes response time 15 92.5 17 91.5 18.2 90.9 24.5 87.8 Response time 7.5 minutes 10.5 94.8 11.5 94.3 10.5 94.8 15 92.5 Response time 10 minutes 7.5 96.3 7.5 96.3 8 96 12.5 93.8 Response time 15 minutes 5 97.5 5.5 97.3 6 97 7.8 96.1 Response time 30 minutes 2.8 98.6 3 98.5 3.3 98.4 3.8 98.1

In addition, the photocatalyst carriers of Comparative Examples 2-1 to 2-4 were prepared as follows.

Comparative Example 2-1

The formation of the titanium oxide first layer and the first firing were carried out in the same manner as in Example 2-1, but the formation of the titanium oxide second layer and the second firing were not performed.

Comparative Example 2-2

The formation of the titanium oxide first layer and the first firing were carried out in the same manner as in Example 2-2, but the formation of the titanium oxide second layer and the second firing were not performed.

Comparative Example 2-3

The formation of the titanium oxide first layer and the first firing were carried out in the same manner as in Example 2-3, but the formation of the titanium oxide second layer and the second firing were not performed.

Comparative Example 2-4

The formation of the first layer of titanium oxide and the first firing were carried out in the same manner as in Example 2-4, but the formation of the second layer of titanium oxide and the second firing were not performed. In addition, Table 4 shows a list of production conditions of the photocatalyst carrier in Comparative Examples 2-1 to 2-4.

Comparative Example 2-1 Comparative Example 2-2 Comparative Example 2-3 Comparative Example 2-4
Produce
Condition



Oxidation
titanium
The first layer Coating solution 6-fold dilution 6-fold dilution 6-fold dilution 6-fold dilution Plasticity
Temperature (℃) 600 800 1000 1100 Plasticity
Time (hr) 2 2 2 2
Oxidation
titanium
Second layer Coating solution - - - - Plasticity
Temperature (℃) - - - - Plasticity
Time (hr) - - - -
Ammo
Nya
decomposition
Experiment


density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) Response time 0 minutes 200 0 200 0 200 0 200 0 Response time 2.5 minutes 100 50 113 43.5 165 17.5 160 20 5 minutes response time 90 55 102 49 160 20 155 22.5 Response time 7.5 minutes 85 57.5 100 50 145 27.5 142 29 Response time 10 minutes 77 61.5 90 55 140 30 135 32.5 Response time 15 minutes 75 62.5 85 57.5 135 32.5 120 40 Response time 30 minutes 60 70 73 63.5 98 51 105 47.5

The photocatalyst carrier 1 of Examples 2-1 to 2-4 may have the same effect as in Example 1. The photocatalyst carriers of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4 were subjected to the decomposition test of ammonia in the same manner as in Example 1. The results are shown in Table 3 and Table 4 above.

As shown in Table 3, the photocatalyst carriers 1 of Examples 2-1 to 2-4 were all very high, with removal rates of 98% or more in 30 minutes of reaction time. As a result, it was confirmed that the photocatalyst carrier 1 of Example 2 had a high ammonia decomposition effect (deodorization effect) due to the photocatalytic action.

In addition, since the ammonia decomposition effect of the photocatalyst carrier 1 of Examples 2-1 to 2-4 was all high, the baking temperature of the titanium oxide 1st layer 5 was 600 degreeC-1100 degreeC. It was confirmed that the range was appropriate.

On the other hand, as shown in Table 4, the photocatalyst carriers of Comparative Examples 2-1 to 2-4 which did not have the titanium oxide second layer had a very low removal rate of 47.5% to 70% in 30 minutes of reaction time. The reason for this is that the photocatalyst carriers of Comparative Examples 2-1 to 2-4 do not include the titanium oxide second layer 7, but are calcined at a high temperature of 600 ° C to 1100 ° C to cause sintering. This is because only the titanium first layer 5 is provided.

In addition, the surface of the photocatalyst carrier 1 of Examples 2-1 to 2-4 was image | photographed with the electron microscope (scan type electron microscope S-4800 by Hitachi High-Technologies). This photo is shown in FIG. 3 (a) is a photograph of Example 2-1;

FIG. 3B is a photograph of Example 2-2, FIG. 3C is a photograph of Example 2-3, and FIG. 3D is a photograph of Example 2-4.

As shown in FIG. 3, in Examples 2-1 to 2-3 where the firing temperature of the titanium oxide first layer 5 is 600 ° C to 1000 ° C, the titanium oxide first layer 5 is sintered ( Although generation | occurrence | production of a large particle does not occur, Sintering of the titanium oxide 1st layer 5 starts to arise in part in Example 2-4 whose baking temperature is 1100 degreeC.

When sintering of the titanium oxide first layer 5 proceeds, a portion of the surface of the ceramic filter 3 not covered with the titanium oxide first layer 5 is formed, and the titanium oxide second layer 7 is formed therein. By being fixed directly to this ceramic filter 3, the adhesiveness of the titanium oxide 2nd layer 7 falls. Accordingly, it can be seen from FIG. 3 that the firing temperature of the titanium oxide first layer 5 is more preferably 1000 ° C or lower.

[Example 3]

Basically, the photocatalyst carrier 1 of Examples 3-1 to 3-4 was produced similarly to Example 1 above. However, in the present Example 3, the titanium oxide coating liquid used for formation of the titanium oxide 1st layer 5 was used as the stock solution of STS-01. In addition, the baking conditions of the titanium oxide 1st layer 5 were all 500 degreeC and 4 hours.

In addition, the firing temperature of the titanium oxide second layer 7 was set to four types of 100 ° C, 200 ° C, 300 ° C, and 400 ° C, and was calcined at 100 ° C in Examples 3-1 and 200 ° C. The thing baked at 3-2 and 300 degreeC and the thing baked at Example 3-3 and 400 degreeC was set to Example 3-4. In addition, Table 5 shows a list of the manufacturing conditions of the photocatalyst carrier 1 in Examples 3-1 to 3-4.

Example 3-1 Example 3-2 Example 3-3 Example 3-4
Produce
Condition


Oxidation
titanium
The first layer Coating solution Undiluted solution Undiluted solution Undiluted solution Undiluted solution Plasticity
Temperature (℃) 500 500 500 500 Plasticity
Time (hr) 4 4 4 4 Oxidation
titanium
Second layer Coating solution 2-fold dilution 2-fold dilution 2-fold dilution 2-fold dilution Plasticity
Temperature (℃) 100 200 300 400 Plasticity
Time (hr) One One One One
Ammo
Nya
decomposition
Experiment


density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) Response time 0 minutes 200 0 200 0 200 0 200 0 Response time 2.5 minutes 16.7 91.7 9 95.5 32.24 83.9 38.74 80.6 5 minutes response time 7 96.5 4 98 10 95 17.8 91.1 Response time 7.5 minutes 4 98 2 99 6.2 96.9 13.8 93.1 Response time 10 minutes 3 98.5 1.5 99.3 5 97.5 11.3 94.4 Response time 15 minutes 2 99 One 99.5 3.4 98.3 9.5 95.3 Response time 30 minutes 1.6 99.2 0.1 99.95 2 99 6 97

The photocatalyst carrier 1 of Examples 3-1 to 3-4 may have the same effect as in Example 1. The ammonia decomposition test was carried out to the photocatalyst carriers 1 of Examples 3-1 to 3-4 in the same manner as in Example 1. The results are shown in Table 5 above.

As shown in Table 5, in the photocatalyst carrier 1 of Examples 3-1 to 3-4, the removal rate was very high, at 97% or more in 30 minutes of reaction time. In particular, Examples 3-1 to 3-3, in which the firing temperature of the titanium oxide second layer 7 was 100 ° C to 300 ° C, had a higher removal rate of 99% or more. In addition, Example 3-2 having the sintering temperature of the second titanium oxide layer 7 at 200 ° C. had the highest removal rate of 99.95%.

As a result, it was confirmed that the photocatalyst carrier 1 of Example 3 had a high ammonia decomposition effect (deodorization effect) due to the photocatalytic action. Moreover, since the ammonia decomposition effect of the photocatalyst carrier 1 of Examples 3-1 to 3-4 was all high, it was confirmed that the range of 100 degreeC-400 degreeC is suitable as the baking temperature of the titanium oxide 2nd layer 7. .

Next, the surface of the photocatalyst carrier 1 of Examples 3-1 to 3-4 was image | photographed with the electron microscope (scan type electron microscope S-4800 by Hitachi High-Technologies). This photo is shown in FIG. Figure 4 (a) is a photograph of Example 3-1,

FIG. 4B is a photograph of Example 3-2, FIG. 4C is a photograph of Example 3-3, and FIG. 4D is a photograph of Example 3-4.

In FIG. 4, in Examples 3-1 to 3-3, in which the sintering temperature of the second titanium oxide layer 7 is 100 ° C to 300 ° C, a wave shape of several tens of micrometers cycles appears in the second titanium oxide layer 7 have. On the other hand, in Example 3-4, where the firing temperature is 400 ° C, such a wave shape does not appear.

    If there was a wave shape as shown in Examples 3-1 to 3-4, the surface area of the titanium oxide second layer 7 was increased to improve the photocatalytic action. Accordingly, it can be seen from FIG. 4 that the baking temperature of the second titanium oxide layer 7 is more suitable in the range of 100 ° C to 300 ° C.

Example 4

Basically, the photocatalyst carrier 1 of Examples 4-1 to 4-4 was produced similarly to Example 1 above. However, in Example 4, the titanium oxide coating liquid used for forming the titanium oxide first layer 5 was used as the stock solution of STS-01. In addition, all the baking conditions of the titanium oxide 1st layer 5 were 500 degreeC and 4 hours.

In addition, the titanium oxide coating liquid used for the formation of the second titanium oxide layer 7 was prepared by the stock solution of STS-01, 2-fold dilution (mixing STS-01 and water 1: 1), and 3-fold dilution (STS-01 and water). To 1: 2) and 4-fold dilution (STS-01 and water to 1: 3), and using the stock solution in Example 4-1, using 2-fold dilution Example 4- Example 4-3 and Example 4-4 were used for the 2- and 3-fold dilutions.

Since the titanium oxide content of the STS-01 stock solution is 30.1% by weight as described above, the titanium oxide content used in the formation of the titanium oxide second layer 7 in Example 4-1 is 30.1 of the total weight of the titanium oxide coating solution. It is weight%, the titanium oxide content rate used in Example 4-2 is 15.1 weight% of the total weight of the titanium oxide coating liquid, and the titanium oxide content rate used in Example 4-3 is 10.0 weight% of the total weight of the titanium oxide coating liquid, The titanium oxide content used in 4-4 is 7.52 weight% of the total weight of the titanium oxide coating liquid. In addition, Table 6 shows a list of production conditions of the photocatalyst carrier in Examples 4-1 to 4-4.

Example 4-1 Example 4-2 Example 4-3 Example 4-4
Produce
Condition


Oxidation
titanium
The first layer Coating solution Undiluted solution Undiluted solution Undiluted solution Undiluted solution Plasticity
Temperature (℃) 500 500 500 500 Plasticity
Time (hr) 4 4 4 4 Oxidation
titanium
Second layer Coating solution Undiluted solution 2-fold dilution 3-fold dilution 4-fold dilution Plasticity
Temperature (℃) 200 200 200 200 Plasticity
Time (hr) One One One One
Ammo
Nya
decomposition
Experiment


density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) Response time 0 minutes 200 0 200 0 200 0 200 0 Response time 2.5 minutes 10 95 9 95.5 12 94 12.5 93.8 5 minutes response time 4.5 97.8 4 98 6 97 5 97.5 Response time 7.5 minutes 3 98.5 2 99 3.5 98.3 2.5 98.8 Response time 10 minutes 2 99 1.5 99.3 2 99 2 99 Response time 15 minutes One 99.5 One 99.5 One 99.5 1.2 99.4 Response time 30 minutes 0.5 99.8 0.1 99.95 0.8 99.6 0.5 99.8

The photocatalyst carrier 1 of Examples 4-1 to 4-4 can bring about the same effects as in Example 1 above. The photocatalyst carriers 1 of Examples 4-1 to 4-4 were subjected to the decomposition test of ammonia in the same manner as in Example 1. The results are shown in Table 6 above.

As shown in Table 6, in the photocatalyst carrier 1 of Examples 4-1 to 4-4, the removal rate was very high, 99.6% or more, in 30 minutes of reaction time. In particular, in Examples 4-1 to 4-2 using a stock solution (titanium oxide content of 30.1 wt%) or 2-fold dilution (titanium oxide content of 15.1 wt%) of STS-01 as the titanium oxide coating agent, the removal rate was more than 99.8%. High.

As a result, it was confirmed that the photocatalyst carrier 1 of Example 4 had a high ammonia decomposition effect (deodorization effect) due to the photocatalytic action. Further, since the ammonia decomposition effects of the photocatalyst carriers 1 of Examples 4-1 to 4-4 were all high, the titanium oxide content used for the formation of the second titanium oxide layer 7 was 7.52 of the total weight of the titanium oxide coating liquid. It was confirmed that the range of% to 30.1% by weight is appropriate.

[Example 5]

Basically, the photocatalyst carrier 1 of Example 5 was manufactured similarly to the said Example 1. However, in Example 5, the titanium oxide coating liquid used for forming the titanium oxide first layer 5 was used as a stock solution of STS-01, and the firing conditions of the titanium oxide first layer 5 were 500 ° C and 4 hours.

In addition, the photocatalyst carrier of Comparative Example 5 was prepared as follows.

[Comparative Example 5]

The formation and the first firing of the titanium oxide first layer 5 were not performed, and the formation and the second firing of the titanium oxide second layer 7 were performed in the same manner as in Example 5. Therefore, the structure of the photocatalyst carrier of the comparative example 5 remove | eliminates the titanium oxide 1st layer 5 from the photocatalyst carrier 1 of Example 5. FIG.

In addition, Table 7 shows a list of the manufacturing conditions of the photocatalyst carrier in Example 5 and Comparative Example 5.

Example 5 Comparative Example 5
Manufacture conditions



Titanium oxide
The first layer
Coating solution Undiluted solution - Firing temperature (캜) 500 - Firing time (hr) 4 - Titanium oxide
Second layer
Coating solution 2-fold dilution 2-fold dilution Firing temperature (캜) 200 200 Firing time (hr) One One
ammonia
Decomposition




density
(ppm) Removal rate
(%) density
(ppm) Removal rate
(%) Response time 0 minutes 200 0 200 0 Response time 2.5 minutes 20 90 9 95.5 5 minutes response time 10 95 4 98 Response time 7.5 minutes 7 96.5 2 99 Response time 10 minutes 4.5 97.8 1.5 99.3 Response time 15 minutes 3 98.5 One 99.5 Response time 30 minutes 1.5 99.3 0.1 99.95

The photocatalyst carriers of Example 5 and Comparative Example 5 were subjected to the decomposition test of ammonia in the same manner as in Example 1. The results are shown in Table 7 above.

As shown in Table 7, the photocatalyst carrier 1 of Example 5 had a very high removal rate of 99.95% in 30 minutes of reaction time. As a result, it was confirmed that the photocatalyst carrier 1 of Example 5 had a high ammonia decomposition effect (deodorization effect) due to the photocatalytic action.

Moreover, the test for confirming the adhesiveness of the titanium oxide 2nd layer 7 was performed about the photocatalyst carrier of Example 5 and the comparative example 5. As shown in FIG. Specifically, the photocatalyst carriers of Example 5 and Comparative Example 5 were washed, and the surface state before and after the cleaning was examined by electron microscopy (scanning electron microscope S-4800 by Hitachi High-Technologies, Inc.). Observed using. Here, the washing | cleaning conditions were made into the flowing-water process for 5 minutes using the constant water.

The results are shown in Fig. 5 (a) is a photograph of the surface of the photocatalyst carrier of Comparative Example 5 before cleaning, and FIG. 5 (b) is a photograph of the surface of the photocatalyst carrier 1 of Example 5 before cleaning, and FIG. c) is a photograph of the surface of the photocatalyst carrier of Comparative Example 5 after washing, and FIG. 5 (d) is a photograph of the surface of the photocatalyst carrier 1 of Example 5 after washing.

In the photocatalyst carrier 1 of Example 5, as shown in FIG. 5 (b), before cleaning, a scale shape of about 10 μm is observed over the entire surface. This scaly shape indicates that it is covered with the titanium oxide second layer 7. Therefore, the photocatalyst carrier 1 of the comparative example 5 was covered with the titanium oxide 2nd layer 7 over the whole surface before washing | cleaning.

In addition, even after washing the photocatalyst carrier 1 of Example 5, as shown in FIG. 5 (d), the surface of the photocatalyst carrier 1 was covered with scaly shape over the entire surface as before the washing. As a result, it was confirmed that the photocatalyst carrier 1 of Example 5 did not peel off of the titanium oxide second layer 7 even if it was washed, and the durability was high.

Next, before the cleaning, the photocatalyst carrier of Comparative Example 5 showed a scale shape of about 10 μm over the entire surface as shown in FIG. 5 (a) and was uniformly covered with the titanium oxide second layer 7. However, after cleaning the photocatalyst carrier of Comparative Example 5, as shown in Fig. 5 (c), the scale remains only in the upper right area of the photograph, and the other part of the surface of the ceramic filter 3 It was exposed. (See Figure 2)

As a result, it was found that the photocatalyst carrier of Comparative Example 5 had a low titanium oxide first layer 5 and thus had low adhesiveness of the second titanium oxide layer 7, resulting in poor durability.

Experimental Example

The experiment for confirming the thickness of the titanium oxide 1st layer 5 and the titanium oxide 2nd layer 7 in the photocatalyst support body 1 of Examples 1-5 was performed. Specifically, the cross section was observed with an electron microscope after the titanium oxide coating liquid was applied to the glass thin plate in the same manner as in Examples 1 to 5 and baked. The titanium oxide coating liquid was prepared by diluting STS-01 twice. In addition, the experiment was performed about the case where baking temperature is 100 degreeC, 150 degreeC, 200 degreeC, 250 degreeC, 300 degreeC, and 400 degreeC, respectively.

The results are shown in FIG. FIG. 6 (a) shows the case where the firing temperature is 100 ° C., FIG. 6 (b) shows the case where the firing temperature is 150 ° C., and FIG. 6 (c) shows the case where the firing temperature is 200 ° C.,

Fig. 6 (d) shows the case where the firing temperature is 250 ° C, Fig. 6 (e) shows the case where the firing temperature is 300 ° C, and Fig. 6 (f) shows the case where the firing temperature is 400 ° C. In the photographs of Figs. 6 (a) to 6 (f), the lower layer is a glass thin layer and the upper layer is a layer made of titanium oxide.

6 (c) and 6 (e), in which the layer made of titanium oxide can be clearly identified in the photograph shown in FIG. 6, the thicknesses of the layer made of titanium oxide were 1.3 μm and 1.6 μm, respectively. Therefore, it is estimated that the thickness of the titanium oxide 1st layer 5 and the titanium oxide 2nd layer 7 in Examples 1-5 is also a value close to this.

In addition, this invention is not limited to the said Example, It can implement in various aspects in the range which does not deviate from this invention. For example, in Examples 1 to 5, instead of titanium oxide, other photocatalytic materials such as zinc oxide, zirconium oxide, strontium titanate, cadmium emulsion, tungsten oxide ( Tungsten), iron oxide, and silicon can be used.

As the titanium oxide coating liquid, for example, a solution diluted with STS-21 (titanium oxide content rate 38.8% (weight ratio) of titanium oxide, average particle diameter of about 100 nm, pH 8.3) of ISHIHARA INDUSTRY or water can be used.

As described above, the present invention provides a photocatalyst carrier having a strong photocatalytic action and a method of manufacturing the same, which can be easily and adhesively fixed on a substrate without using a binder. Therefore, the photocatalyst carrier produced by the method of the present invention is excellent in antifouling, deodorization and antibacterial function due to the large photocatalytic action of the photocatalytic fine particles.

Claims (7)

i) attaching the photocatalytic fine particles to the substrate and baking at a temperature of 500 ° C. to 1100 ° C. to form an A layer; And ii) attaching the photocatalytic fine particles on the A layer and baking at a temperature of 100 ° C. to 400 ° C. to form a B layer, wherein the substrate is a porous ceramics substrate. Photocatalyst carrier manufacturing method. The method of claim 1, wherein the photocatalytic microparticles are composed of titanium oxide, zinc oxide, zirconium oxide, strontium titanate, cadmium emulsion, tungsten oxide, tungsten oxide, iron oxide and silicon. The method of producing a photocatalyst carrier, characterized in that any one or a mixture thereof selected from the group. The method for producing a photocatalyst carrier according to claim 1, wherein the photocatalytic fine particles constituting said A layer and the photocatalytic fine particles constituting said B layer are made of the same material. The method of claim 1, wherein after applying the dispersion in which the photocatalytic fine particles are dispersed in step i) or ii), the photocatalytic fine particles are attached by evaporating the solvent of the dispersion. Photocatalyst carrier manufacturing method.  The method for producing a photocatalyst carrier according to claim 4, wherein the content rate of the photocatalytic fine particles is 5 to 30% by weight of the total weight of the dispersion. The method according to claim 1, wherein the porous ceramic substrate is a porous alumina substrate. The photocatalyst carrier manufactured by the method of any one of Claims 1-6.

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