JPH07241475A - Photocatalyst body, its production and method for removing harmful substance using the same - Google Patents

Photocatalyst body, its production and method for removing harmful substance using the same

Info

Publication number
JPH07241475A
JPH07241475A JP6058227A JP5822794A JPH07241475A JP H07241475 A JPH07241475 A JP H07241475A JP 6058227 A JP6058227 A JP 6058227A JP 5822794 A JP5822794 A JP 5822794A JP H07241475 A JPH07241475 A JP H07241475A
Authority
JP
Japan
Prior art keywords
photocatalyst
particles
surface
polymer particles
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP6058227A
Other languages
Japanese (ja)
Inventor
Sadao Murasawa
Takeshi Zedo
猛 是洞
貞夫 村澤
Original Assignee
Ishihara Sangyo Kaisha Ltd
石原産業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ishihara Sangyo Kaisha Ltd, 石原産業株式会社 filed Critical Ishihara Sangyo Kaisha Ltd
Priority to JP6058227A priority Critical patent/JPH07241475A/en
Publication of JPH07241475A publication Critical patent/JPH07241475A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To rapidly and efficiently remove harmuful substances through using the photocatalyst bodies in an uniformly fluidized state to a fluid contg. the harmful substances to be treated by employing as the photocatalysf bodies polymer particles each of which contains photocatalyst particles on its surface and/or in the vicinity of its surface. CONSTITUTION:The photocatalyst bodies are produced by polymerizing a monomer in the presence of particles of a photocatalyst such as titanium oxide, etc., to form fluorine polymer and/or si1icon polymer particles, etc., each of which contains photocatalyst particles on its surface and/or in the vicinity of its surface. At this time, the photocatalyst particle content of each of the polymer particles is 0.1 to 80wt.% based on the weight of the polymer particle. The photocatalyst bodies are irradiated with light of a wavelength having higher energy than the band gap of the photocatalyst in the presence of the harmful substances to be treated. Accordingly, the photocatalyst bodies having small specific gravity can be uniformly fluidized with the fluid contg. the substances to be treated to remove organic halogen compounds, malodorous gases, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocatalyst having an excellent photocatalytic function and a method for producing the same. Furthermore, it relates to a method for removing harmful substances using the photocatalyst.

[0002]

2. Description of the Related Art When photocatalyst particles are irradiated with light having a wavelength greater than the band gap, photoexcitation produces electrons in the conduction band and holes in the valence band. The strong reducing power of electrons and the strong oxidizing power of holes generated by this photoexcitation are due to decomposition and purification of harmful substances, deodorization of malodorous gases such as ammonia, aldehydes and amines, and decomposition of water.
It is used for photocatalytic reactions such as sterilization, actinomycetes, fungi, and algae. For example, Japanese Patent Publication 2-985
Japanese Unexamined Patent Application Publication No. 0-202 describes that photocatalyst particles such as titanium oxide are used to remove and purify harmful substances in waste. Further, Japanese Patent Publication No. 4-78326 describes that photocatalyst particles such as titanium oxide are used to deodorize toilet urine odor, pet odor, cigarette odor, cooking odor, body odor, and the like. Further, Japanese Patent Publication No. 4-29393 describes that a predetermined voltage generated on photocatalyst particles such as titanium oxide by light irradiation is applied to cells to kill them.

[0003]

When photocatalyst particles are used in a photocatalytic reaction, the photocatalyst particles are prevented from scattering and flowing out from the reaction device during the photocatalytic reaction, and the photocatalyst particles are separated from the reaction device after the photocatalytic reaction is completed. Need to be easily collected. Therefore, the photocatalyst particles are generally used in a state of being carried or coated on a ceramic or metal support such as carrier particles having a high surface area or a structure having a honeycomb structure or a three-dimensional network structure. With such a photocatalyst body in which photocatalyst particles are carried on a support, scattering and outflow can be reduced, and separation / recovery can be facilitated. However, in the above-mentioned photocatalyst, the photocatalyst particles are difficult to be irradiated with light, so that the photocatalyst function of the photocatalyst particles is hard to be expressed, and a satisfactory photocatalyst function cannot be obtained. Moreover, there is a problem that the photocatalyst particles are separated from the support during the photocatalytic reaction.

[0004]

The inventors of the present invention have conducted research to solve the above-mentioned problems, and as a result, (1) a photocatalyst body containing photocatalyst particles on the surface of polymer particles and / or in the vicinity thereof In addition, it is possible to reduce the scattering and outflow of photocatalyst particles from the reaction device during the photocatalytic reaction, and also to facilitate the separation and recovery of the photocatalyst particles from the reaction device after the photocatalytic reaction is completed, and Since the utilization efficiency can be increased, the catalyst has an excellent catalytic function, and since the polymer particles can be firmly adhered, the photocatalyst particles are less likely to be peeled from the polymer particles. (2) To obtain the photocatalyst body of the present invention The method of polymerizing a monomer in the presence of photocatalyst particles or the method of causing a mechanochemical reaction between polymer particles and photocatalyst particles is simple and efficient, (3) Photocatalyst of the present invention can be used for various photocatalytic reactions, in particular, it found such to be suitable for removal reaction of harmful substances, the present invention has been completed.
That is, the present invention provides a photocatalyst having an excellent photocatalytic function. Another object of the present invention is to provide a method for rapidly and efficiently removing harmful substances by using the photocatalyst of the present invention.

The present invention is a photocatalyst body comprising photocatalyst particles on the surface of polymer particles and / or in the vicinity thereof. The photocatalyst body of the present invention is different from a mere mixture of photocatalyst particles and polymer particles in that the photocatalyst particles are supported or coated on the surface of the polymer particles and / or
Alternatively, the photocatalyst particles are incorporated in the vicinity of the surface of the polymer particles, and the photocatalyst particles are partially exposed. The average particle diameter of the photocatalyst of the present invention can be appropriately set, but is 0.1 μm to 30 mm, preferably 0.5 μm to
It is 5 mm, more preferably 1 μm to 1 mm, and most preferably 3 μm to 0.5 mm. Further, the photocatalyst of the present invention preferably has a certain shape such as a spherical shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, or a hollow shape, and a spherical shape is particularly preferable. The specific gravity of the photocatalyst of the present invention is preferably 3.0.
Or less, more preferably 2.5 or less, and most preferably 2.0 or less.

In the present invention, polymer particles are particles made of a polymer. The material of the polymer particles is
Phenol type polymer, melamine type polymer, urea type polymer, urethane type polymer, polyester type polymer, styrene type polymer, acrylic type polymer, vinyl type polymer, silicone type polymer, polyethylene type polymer, polyamide type polymer, fluorine type polymer and those At least one such as a copolymer can be used. Particularly, a fluorine-based polymer, a silicon-based polymer or a copolymer thereof having excellent heat resistance and chemical resistance is preferable. Examples of the fluorine-based polymer include polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, ethylene-polytetrafluoroethylene copolymer, Crystalline polymers such as ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-
Amorphous polymers such as fluoroolefin copolymers and vinyl ester-fluoroolefin copolymers, various fluorine-based rubbers, and the like can be used. Further, as the silicon-based polymer, for example, a linear silicon-based polymer, an acrylic modified silicon-based polymer, various silicon-based rubbers, etc. can be used.

In the present invention, as the photocatalyst particles, for example, at least one known photocatalyst particle such as titanium oxide, strontium titanate, tungsten oxide, zinc oxide, tin oxide, and cadmium sulfide can be selected and used. In particular, it has an excellent photocatalytic function and is white,
Moreover, titanium oxide, which has high safety, is preferable. In the present invention, titanium oxide means various kinds of titanium oxide such as anatase type titanium oxide, rutile type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, and hydrous titanium oxide. In addition, a metal such as platinum or rhodium or a metal oxide such as an oxide or hydroxide of iron may be supported on the surface of the photocatalyst particles. The content of the photocatalyst particles contained in the polymer particles is preferably 0.1 to 8 based on the weight of the polymer particles.
0% by weight, more preferably 0.5-75% by weight, still more preferably 1-70% by weight, most preferably 3-6.
It is 0% by weight. If the content of the photocatalyst particles is less than the above range, it is difficult to obtain a sufficient photocatalytic function, which is not preferable, and if the content of the photocatalyst particles is more than the above range,
It is not preferable because the photocatalyst particles are easily separated from the polymer particles.

The photocatalyst of the present invention can be obtained by various methods, for example, a method of polymerizing a monomer in the presence of photocatalyst particles, a method in which photocatalyst particles are dissolved in a polymer, and then the solution is sprayed. And drying, a method of dissolving or wetting the surface of the polymer particles and then mixing the polymer particles with the photocatalyst particles, a method of causing the photocatalyst particles to collide with the surface of the polymer particles by a mechanochemical reaction, the polymer particles and the photocatalyst particles The method of kneading and and molding or crushing can be used. In the present invention, the above method or method is preferable because it is simple and efficient. In addition, the above
The surface of the photocatalyst obtained by the above method may be polished by a jet airflow stirrer or the like.

In order to use the photocatalyst of the present invention for various photocatalytic reactions, the photocatalyst is irradiated with light having a wavelength having an energy equal to or higher than its band gap in the presence of a substance to be treated. In order to increase the light utilization efficiency, the photocatalyst of the present invention is
It is preferably used by flowing it into a fluid containing the substance to be treated. In order to make the photocatalyst flow, various methods can be used, such as introducing a fluid from the lower part of the reactor containing the photocatalyst particles, or stirring the fluid containing the photocatalyst with a stirrer. . INDUSTRIAL APPLICABILITY The photocatalyst of the present invention is suitable for a reaction to remove harmful substances, and particularly suitable for a reaction to remove harmful substances contained in water to be treated. Hazardous substances that are decomposed or oxidized by photocatalytic reactions and removed are substances that have a potential adverse effect on the human body and living environment, such as herbicides, fungicides, insecticides, nematicides, etc. Various agricultural chemicals, various surfactants, various biological oxygen demand substances such as proteins and amino acids, hydrocarbons, organic halogen compounds, organic substances such as organic phosphorus compounds, nitrogen compounds, sulfur compounds, cyan compounds, chromium Examples thereof include inorganic compounds such as compounds, microorganisms such as bacteria, actinomycetes, fungi, algae, and molds. Specific examples of the hydrocarbon include aldehydes, amines, mercaptans, oils and alcohols. Specific examples of the organic halogen compound include polychlorinated biphenyl, freon, trihalomethane, trichloroethylene, and tetrachloroethylene. Specific examples of the nitrogen compound include ammonia and nitrogen oxides. The photocatalyst of the present invention can efficiently decompose and remove organic halogen compounds such as polychlorinated biphenyls, trihalomethanes, trichloroethylene, and tetrachloroethylene. As the light having a wavelength having an energy equal to or more than the band gap, light containing ultraviolet rays is preferable, and for example, light of sunlight, fluorescent lamp, black light, halogen lamp, xenon flash lamp, mercury lamp or the like can be used. Particularly, light containing near-ultraviolet rays of 300 to 400 nm is preferable. The irradiation amount and irradiation time of light can be appropriately set depending on the amount of the substance to be treated.

[0010]

Example 1 Sodium hydroxide was added to an acidic titanium oxide sol (CS-N manufactured by Ishihara Sangyo Co., Ltd.) obtained by heating and hydrolyzing titanyl sulfate so that the pH was 7, and then filtered. Washed,
It was dried at a temperature of 110 ° C., and then the obtained dried product was crushed by a thunder crusher to obtain a titanium oxide powder. Next, the titanium oxide powder and beads made of polymethylmethacrylate (manufactured by Soken Chemical Industry Co., Ltd., MR-7GS, average particle size 7.2 μm)
Are mixed at a weight ratio of 2: 1 and then put into a hybridizer system (NHS-O type manufactured by Nara Machinery Co., Ltd.) to carry out a mechanochemical reaction to oxidize the surface of the polymer particles and the vicinity thereof. A spherical photocatalyst (sample A) carrying titanium photocatalyst particles was obtained. The titanium oxide content of this sample A was 56% by weight, and the specific gravity of this sample A was 2.0. The average particle size of this sample A was 7.7 μm.

Example 2 70% by weight of butyl acrylate monomer, 20% by weight of 1,3-butylene glycol dimethacrylate monomer and 10% by weight of titanium oxide powder of Example 1 were subjected to suspension polymerization at a temperature of 60 ° C. for 1 hour. Thus, a spherical photocatalyst body (Sample B) was obtained in which titanium oxide photocatalyst particles were carried on the surface of the acrylic copolymer particles and in the vicinity thereof. The titanium oxide content of this sample B was 9% by weight, and the specific gravity of this sample B was 1.3. The average particle size of this sample B is 1
It was 0.3 μm.

The photocatalytic function of the samples (A, B) obtained in the examples was investigated as follows. 0.2 g of sample A and 1.2 g of sample B were dispersed in 25 ml of pure water. Next, 25 ml of 2-propanol was added to 25 ml of these suspensions.
After the addition of 1 liter, a 150 W xenon lamp was irradiated for 2 hours under stirring and flow to perform a photocatalytic reaction of 2-propanol. The concentration of 2-propanol before the reaction and 2 after the reaction
-The decomposition rate of each sample was calculated from the concentration of propanol. The results are shown in Table 1. As is clear from this table, the photocatalyst of the present invention was excellent in the photocatalytic function.
Since the photocatalyst of the present invention has a small specific gravity, it can be used in a state in which it uniformly flows in a fluid containing a substance to be treated, so that the substance to be treated is well contacted and the light utilization efficiency is improved. Therefore, it is considered to have an excellent photocatalytic function. Moreover, the photocatalyst of the present invention can reduce the scattering and outflow of the photocatalyst particles from the reaction device during the photocatalytic reaction, and also facilitates the separation and recovery of the photocatalyst particles from the reaction device after the photocatalytic reaction is completed. We were able to. It was also confirmed that the photocatalyst particles were not peeled off from the polymer particles.

[0013]

[Table 1]

[0014]

The present invention relates to the surface of polymer particles and / or
Or a photocatalyst body containing photocatalyst particles in the vicinity of its surface, which can reduce the scattering and outflow of photocatalyst particles from the reaction device during the photocatalytic reaction, and from the reaction device after the end of the photocatalytic reaction. The separation / collection of photocatalyst particles can be facilitated. Moreover, since it has an excellent photocatalytic function, organic halogen compounds, malodorous gas, oil, bacteria,
Since it is possible to quickly and efficiently remove substances that may adversely affect the human body or living environment, such as fungi and algae, and substances that have the potential to do so, not only for industrial use but also for general household use, deodorant, It is extremely useful as a sterilizer. The method of the present invention is a method of polymerizing a monomer in the presence of photocatalyst particles or a method of performing a mechanochemical reaction between polymer particles and photocatalyst particles, and is useful in that the photocatalyst of the present invention can be obtained simply and efficiently. That's the method. Furthermore, the method for removing harmful substances of the present invention is a method of irradiating the photocatalyst of the present invention with light having a wavelength having an energy equal to or higher than the band gap, and it is possible to remove harmful substances quickly and efficiently. This is a useful method.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Office reference number FI technical display area // A62D 3/00 ZAB

Claims (8)

[Claims]
1. A photocatalyst body comprising photocatalyst particles on the surface of polymer particles and / or near the surface thereof.
2. The catalyst body according to claim 1, wherein the photocatalyst particles are titanium oxide.
3. The photocatalyst body according to claim 1, wherein the photocatalyst particles are contained in an amount of 0.1 to 80% by weight based on the weight of the polymer particles.
4. The photocatalyst body according to claim 1, wherein the polymer particles are fluorine-based polymer particles and / or silicon-based polymer particles.
5. A method for producing a photocatalyst body, which comprises polymerizing a monomer in the presence of photocatalyst particles to contain the photocatalyst particles on the surface of the polymer particles and / or in the vicinity of the surface.
6. A method for producing a photocatalyst, characterized in that the polymer particles and the photocatalyst particles are subjected to a mechanochemical reaction to contain the photocatalyst particles on the surface of the polymer particles and / or in the vicinity of the surface.
7. A method for removing a harmful substance, which comprises irradiating the photocatalyst according to claim 1 with light having a wavelength having an energy larger than the band gap in the presence of the harmful substance.
8. A toxic substance characterized in that the photocatalyst according to claim 1 is made to flow into the water to be treated containing the toxic substance, and then the photocatalyst is irradiated with light having a wavelength having an energy not less than the band gap. Removal method.
JP6058227A 1994-03-02 1994-03-02 Photocatalyst body, its production and method for removing harmful substance using the same Pending JPH07241475A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6058227A JPH07241475A (en) 1994-03-02 1994-03-02 Photocatalyst body, its production and method for removing harmful substance using the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6058227A JPH07241475A (en) 1994-03-02 1994-03-02 Photocatalyst body, its production and method for removing harmful substance using the same

Publications (1)

Publication Number Publication Date
JPH07241475A true JPH07241475A (en) 1995-09-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
JP6058227A Pending JPH07241475A (en) 1994-03-02 1994-03-02 Photocatalyst body, its production and method for removing harmful substance using the same

Country Status (1)

Country Link
JP (1) JPH07241475A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997041069A1 (en) * 1996-04-30 1997-11-06 Tao Inc. Sink-and-float body for purification and purificator
US6090736A (en) * 1997-12-25 2000-07-18 Agency Of Industrial Science And Technology Photocatalytic powder for environmental clarification and process for producing same, said powder-containing polymer composition, and shaped article of said composition and process for producing same
JP2008036465A (en) * 2006-08-01 2008-02-21 Fujitsu Ltd Photocatalytic composite material and its manufacturing method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997041069A1 (en) * 1996-04-30 1997-11-06 Tao Inc. Sink-and-float body for purification and purificator
US6090736A (en) * 1997-12-25 2000-07-18 Agency Of Industrial Science And Technology Photocatalytic powder for environmental clarification and process for producing same, said powder-containing polymer composition, and shaped article of said composition and process for producing same
US6291067B1 (en) 1997-12-25 2001-09-18 Japan As Represented By Director General Of The Agency Of Industrial Science And Technology Photocatalytic powder for environmental clarification and powder-containing polymer composition thereof
JP2008036465A (en) * 2006-08-01 2008-02-21 Fujitsu Ltd Photocatalytic composite material and its manufacturing method

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