WO2008081957A1

WO2008081957A1 - Method for producing metal-containing sulfur-introduced titanium oxide and metal-containing sulfur-introduced titanium oxide

Info

Publication number: WO2008081957A1
Application number: PCT/JP2007/075344
Authority: WO
Inventors: Daisuke Taki; Taichi Tanaka
Original assignee: Toho Titanium Co., Ltd
Priority date: 2006-12-26
Filing date: 2007-12-21
Publication date: 2008-07-10
Also published as: JP2008179530A; JP2008179529A

Abstract

Disclosed is a method for producing a metal-containing sulfur-introduced titanium oxide, which is characterized by comprising a firing step for obtaining a metal-containing sulfur-introduced titanium oxide by firing a mixture of a metal-containing raw material titanium oxide and a sulfur compound. This method for producing a metal-containing sulfur-introduced titanium oxide is further characterized in that the metal content in the metal-containing raw material titanium oxide is 0.03-0.15 part by mass as metal atoms, relative to 100 parts by mass of the metal-containing raw material titanium oxide in terms of TiO2. This method enables to produce a metal-introduced sulfur-containing titanium oxide which exhibits high photocatalytic activity under visible light. Also disclosed is a metal-containing sulfur-introduced titanium oxide.

Description

Specification

Method for producing metal-containing sulfur-introduced titanium oxide and metal-containing sulfur-introduced titanium oxide

The present invention relates to a method for producing a metal-containing sulfur-introduced titanium oxide used for a visible light photocatalyst, a photosensitized solar cell, or the like. Background art

Titanium oxide powder has long been used as a white pigment. In recent years, it has been used as an ultraviolet shielding material for cosmetics, photocatalysts, capacitors, thermistors, or sintered materials used in electronic materials such as raw materials for barium titanate. Recently, research and development of application of dye-sensitized titanium oxide to electrodes, etc. has been made. In particular, in recent years, the use as a photocatalyst has been actively attempted, and the use development of the photocatalytic reaction has been actively conducted. This titanium oxide photocatalyst has a wide variety of uses. Generation of hydrogen by water decomposition, synthesis of organic compounds using redox reaction, exhaust gas treatment, air purification, deodorization, sterilization, antibacterial, water treatment, lighting. Numerous applications have been developed, such as preventing contamination of equipment.

However, since titanium oxide shows a large refractive index in the wavelength region near visible light, light absorption hardly occurs in the visible light region. Considering the use under fluorescent lamps indoors, most of the spectrum of fluorescent lamps is 400 nm or more, so it is not possible to develop sufficient characteristics as a photocatalyst. In view of this, the development of more highly active photocatalysts that can exhibit catalytic activity in the visible light region is underway.

In recent years, the insufficient catalytic activity of photocatalysts doped with titanium oxide by conventional metals In order to improve the properties, a sulfur-containing titanium oxide powder in which a part of metal atoms is substituted with sulfur has been disclosed (Japanese Patent Laid-Open No. 2004-143032). In order to increase the decomposition efficiency of sulfur-containing titanium oxide toluene, metal cations (F e, Cu, In, W, Pb, V, Bi, Nb, Ti, Sr, Zn, Sulfur-containing titanium oxide into which at least one metal atom selected from the group consisting of Ba, Ca, K, Sn, and Zr is ionized is disclosed (Japanese Patent Laid-Open No. 2006-6-). 8 20 7 1).

(Patent Document 1) JP 2004-1 4 30 3 2 (Claims) (Patent Document 2) JP 2006-8 20 7 1 (Claims) According to the production method described in the examples of JP-A-2006-6-2071, there is a problem in that sulfur-containing titanium oxide having sufficient photocatalytic activity cannot be obtained.

Therefore, an object of the present invention is to describe a metal-containing sulfur-introduced titanium oxide (hereinafter referred to as a metal-containing sulfur-introduced titanium oxide) having a high photocatalytic activity under visible light. ) And a metal-containing sulfur-introduced titanium oxide. Disclosure of the invention

As a result of intensive research to solve the above-described problems in the prior art, the present inventors have obtained a metal-containing sulfur-introduced titanium oxide depending on the time when the metal compound used for introducing the metal is contained in the titanium oxide. A difference in the photocatalytic activity of the titanium salt. Specifically, before calcining the mixture of the hydrolyzate or alkali neutralized product of the titanium salt and the sulfur compound, the hydrolyzed product or alkali neutralized product of the titanium salt. It has been found that a metal-containing sulfur-introduced titanium oxide having high photocatalytic activity can be obtained by previously containing a metal in the product, and the present invention has been completed. That is, the present invention (1) has a firing step of firing a mixture of a metal-containing raw material titanium oxide and a sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and the metal content in the metal-containing material titanium oxide is , With respect to 10 parts by mass of the metal-containing raw material titanium oxide when converted to τ io ₂ , the metal atom is 0.03 to 0.15 parts by mass,

The present invention provides a method for producing a metal-containing sulfur-introduced titanium oxide characterized by the following.

In addition, the present invention (2) includes a baking raw material mixture preparation step for obtaining a mixture of a metal-containing titanium salt hydrolyzed Z alkali neutralized product and a sulfur compound, the metal-containing titanium salt hydrolyzed Z alkali neutralized product and the sulfur Calcining a mixture with the compound to obtain a metal-containing sulfur-introduced titanium oxide, and

The calcining raw material mixture preparation step comprises hydrolyzing Z-al strength re-neutralization treatment to prepare a slurry containing titanium salt hydrolyzed Z-al strength neutralized product by hydrolyzing or neutralizing titanium salt. A step of adding a metal compound to the slurry containing the hydrolyzed titanium salt hydrolyzed neutralized product and stirring to obtain a metal-containing titanium salt hydrolyzed / alternative neutralized product. In

• 9,

The amount of the metal compound added in the stirring and mixing treatment of the metal compound is from 0.03 to 0.5 parts by weight as a metal atom with respect to 100 parts by mass of the titanium salt hydrolyzed neutralized product when converted to Ti 0 ₂ . 0.15 in an amount of 5 parts by mass,

And mixing the sulfur compound between before the hydrolysis Z-al force neutralization treatment and after the metal compound stirring and mixing treatment,

Further, the present invention (3) includes a baking raw material mixture preparation step for obtaining a mixture of a heat-treated product of a metal-containing titanium salt hydrolyzed Z alkali neutralized product and a sulfur compound, Calcining the mixture of the heat-treated product and the sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and

The calcination raw material mixture preparation step comprises hydrolyzing / alkali neutralizing treatment to prepare a slurry containing titanium salt hydrolyzed / al strength neutralized product by hydrolyzing or neutralizing titanium salt. Metal compound is added to slurry containing salt hydrolysis / alkali neutralized product and stirred to obtain metal-containing titanium salt hydrolyzed metal compound stirring and mixing treatment to obtain alkali-neutralized product, and the metal-containing titanium salt in alkali Heat treatment of a Japanese product to obtain a heat-treated product, and

The amount of the metal compound added in the stirring and mixing treatment of the metal compound is from 0.03 to 0.5 parts by weight as the metal atom with respect to 100 parts by mass of the hydrolyzed alkali salt of the titanium salt when converted to Ti ₂ O ₂ . 0.1 5 parts by mass, and mixing the sulfur compound between before the hydrolysis and alkali neutralization treatment and after the heat treatment,

The present invention provides a method for producing metal-containing sulfur-introduced titanium oxide.

Further, the present invention (4) includes a calcining raw material mixture preparation step for obtaining a mixture of a metal-containing titanium salt hydrolyzed / alkali neutralized product and a sulfur compound, Calcining the mixture with the sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and

In the firing raw material mixture preparation step, hydrolysis and alkali neutralization treatment is performed by hydrolyzing or neutralizing titanium salt in the presence of a metal compound to obtain a metal-containing titanium salt hydrolyzed neutralized product. Process,

The amount of the metal compound be present in the hydrolysis Noarukari neutralization process, with respect to the titanium salt 1 0 0 parts by weight when T i O ₂ converted, 0 as the metal atom. 0 3 to 0.1 5 parts by weight The amount of In addition, a sulfur-containing compound is mixed between before the hydrolysis Z-al strength re-neutralization treatment and after the hydrolysis Z-al strength re-neutralization treatment. A method for producing titanium oxide is provided.

Further, the present invention (5) includes a baking raw material mixture preparation step for obtaining a mixture of a heat-treated product of metal-containing titanium salt hydrolyzed / alkali neutralized product and a sulfur compound, and a mixture of the heat-treated product and the sulfur compound. Firing step to obtain metal-containing sulfur-introduced titanium oxide, and

In the presence of the metal compound, the firing raw material mixture preparation step comprises hydrolyzing or alkali neutralizing the titanium salt to obtain a titanium salt hydrolyzed Z alkali neutralized product. Heat-treating the metal-containing titanium salt hydrolysis alkali neutralized product to obtain a heat-treated product, and

The amount of the metal compound be present in the titanium salt hydrolysis / Al Chikarari neutralization process, with respect to the titanium salt 1 0 0 parts by weight when T i O ₂ converted, 0.0 3 metal atom 0.15 in an amount of 5 parts by mass,

And mixing the sulfur compound between before the hydrolysis and the neutralization treatment until after the heat treatment,

In addition, the present invention (6) includes a firing raw material mixture preparation step for obtaining a mixture of a metal-containing titanium salt hydrolyzed Z alkali neutralized product and a sulfur compound, Calcining the mixture with the sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and

The firing raw material mixture preparation step includes hydrolyzing or neutralizing the titanium salt in the presence of a metal compound to hydrolyze the metal-containing titanium salt. Hydrolysis to prepare re-neutralized product-containing slurry Z metal strength neutralization treatment and metal-containing titanium salt hydrolysis Add alkali metal neutralized product-containing slurry, stir, metal-containing titanium A salt hydrolysis Z-alkali neutralized product to obtain a metal compound stirring and mixing process,

The total amount of the metal compound to be present in the hydrolysis and Z-force neutralization treatment and the metal compound to be added in the metal compound stirring and mixing treatment is 100 parts by mass with respect to 100 parts by mass of τ io ₂ The amount of metal atoms is 0.03 to 0.15 parts by mass,

Further, the present invention (7) includes a calcined raw material mixture preparation step for obtaining a mixture of a heat-treated product of metal-containing titanium salt hydrolyzed / alkali neutralized product and a sulfur compound, and a mixture of the heat-treated product and the sulfur compound. Firing step to obtain metal-containing sulfur-introduced titanium oxide, and

In the presence of the metal compound, the baking raw material mixture preparation step hydrolyzes or neutralizes the titanium salt to hydrolyze the metal-containing titanium salt hydrolyzed Z-alloy neutralized product-containing slurry. Metal alkali-containing neutralization treatment, metal-containing titanium salt hydrolysis, alkali-neutralized product-containing slurry, a metal compound is added and stirred to obtain a metal-containing titanium salt hydrolysis alkali-neutralized metal compound stirring and mixing treatment, Hydrolysis of the metal-containing titanium salt, heat treatment of an alkali neutral to obtain a heat-treated product, and the metal compound and the metal to be present in the hydrolysis / al force neutralization treatment. the total amount of the metal compound added in compound stirring and mixing process, with respect to the titanium salt 1 0 0 parts by weight when T i O ₂ converted, 0 as the metal atom. 0 3-0. 1 5 parts by mass

And mixing the sulfur compound between before the hydrolysis / al neutralization treatment and after the heat treatment,

Further, the present invention (8) has a metal content of 0.03 to 0.15 mass%, a sulfur content of 0.02 to 0.1 mass%, and a specific surface area of 60 to 1 2 Om ² Zg, the main component of the crystal structure is anatase-type titanium oxide, sulfur atoms in the titanium oxide are introduced into the titanium oxide titanium site, and the metal is contained on the surface and inside of the titanium oxide, A metal-containing sulfur-introduced titanium oxide is provided.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a metal containing sulfur introduction | transduction titanium oxide which has high photocatalytic activity in visible light, and a metal containing sulfur introduction | transduction titanium oxide can be provided. BEST MODE FOR CARRYING OUT THE INVENTION

The method for producing a metal-containing sulfur-introduced titanium oxide of the present invention includes a firing step of firing a mixture of a metal-containing raw material titanium oxide and a sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and the metal-containing raw material oxidation wherein the metal content in the titanium and with respect to the metal-containing raw material titanium oxide 1 00 parts by weight when T i O ₂ converted, 0. metal atom 0 3 to 0.1 5 it is parts by weight, the This is a method for producing a metal-containing sulfur-introduced titanium oxide. As for the content of the metal compound, the mass of the metal atom with respect to 100 parts by mass when converted to Ti 0 ₂ is preferably 0.03 to 0.15 parts by mass, particularly preferably 0.05 to 0. The mixing amount is 1 part by mass. When the mixing amount of the metal compound is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is visible. Becomes higher.

The method for producing a metal-containing sulfur-introduced titanium oxide according to the first aspect of the present invention (hereinafter also referred to as the production method (1) of the present invention) comprises a metal-containing titanium salt hydrolyzed alkali neutralized product A and a sulfur compound. Firing raw material mixture preparation step A to obtain a mixture A and the metal-containing titanium salt hydrolysis alkali neutralized product A and the sulfur compound A are calcined to obtain a metal-containing sulfur-introduced titanium oxide. A and

The calcination raw material mixture preparation step A is hydrolyzed or neutralized with a titanium salt to hydrolyze a titanium salt hydrolyzed Z-alkaline neutralized product A-containing slurry. And a metal compound stirring and mixing treatment A to obtain a metal-containing titanium salt hydrolyzed Z Al power re-neutralized product A by adding a metal compound to the titanium salt hydrolyzed Z alkali neutral A-containing slurry and stirring. Is the process of performing

0 amount in the metal compound stirred mixing process A is added the metal compound, relative to the titanium salt hydrolysis Z alkali neutralization product A 1 0 0 parts by weight when T i 0 ₂ terms, as the metal atom. 0 3 to 0.15 parts by mass, and before performing the hydrolysis Z-al force neutralization process A and after performing the metal compound stirring and mixing process A, a sulfur compound. Mixing,

It is a manufacturing method of a metal containing sulfur introduction | transduction titanium oxide. In the present invention, “hydrolysis or alkali neutralization” is also referred to as “hydrolysis alkali neutralization”.

In the calcining raw material mixture preparation step A, the metal-containing titanium salt hydrolyzed Z-al is obtained from the titanium salt by performing the hydrolysis Z-al strength neutralization treatment A and the metal compound stirring and mixing treatment A. Power neutralized product A is obtained.

In the baking raw material mixture preparation step A, first, the hydrolysis and alkali neutralization treatment A is performed. The hydrolysis and alkali neutralization treatment A hydrolyzes the titanium salt. The slurry containing the hydrolyzate A of the titanium salt or the neutral force neutralized product A of the titanium salt, ie, the titanium salt hydrolyzed Decomposition Alkali neutralized product A-containing slurry is prepared.

Examples of the titanium salt relating to the hydrolysis / alternative neutralization treatment A include, for example, organometallic compounds such as titanium alkoxide, titanium chlorides such as titanium tetrachloride and titanium trichloride, titanyl sulfate, and titanium sulfate. And inorganic salts such as sulfates. Of these, titanium tetrachloride, titanyl sulfate, and titanium sulfate are preferred from the viewpoint of handling and economy.

In the hydrolysis / alkali neutralization treatment A, the titanium salt may be hydrolyzed by preparing an aqueous solution in which the titanium salt is dissolved in water and heating the aqueous solution while stirring. . In this method, the hydrolysis temperature at the time of hydrolysis is preferably 20 ° C. to the boiling point of an aqueous solution, particularly preferably 40 to 80 ° C. When the hydrolysis temperature is less than 20 ° C, the hydrolysis rate tends to be slow. The hydrolysis time for the hydrolysis is usually 5 minutes to 10 hours, preferably 10 minutes to 5 hours, and particularly preferably 10 minutes to 1 hour. In the above description, the titanium salt is dissolved in water. However, the solvent for dissolving the titanium salt is not particularly limited as long as it dissolves the metal compound. And organic solvents such as alcohol. Among these, water is preferable from the viewpoint of easy handling and economical efficiency. Moreover, when hydrolyzing, you may mix this sulfur compound with water.

Hydrolysis In the alkali neutralization treatment A, hydrolysis is preferably performed in a low pH region because a hydrolyzate having a small particle size can be obtained. Therefore, when performing hydrolysis in the hydrolysis Z alkali neutralization treatment A, especially when the hydrolysis temperature is near the boiling point of the aqueous solution. In view of reducing the pH of the reaction system, it is preferable to install a reflux device or the like in the reaction tank to suppress the generated hydrogen chloride from being discharged out of the reaction system as hydrogen chloride gas.

In the hydrolysis / alkali neutralization treatment A, the titanium salt hydrolyzate is generated by hydrolyzing the titanium salt, and the titanium salt hydrolyzate is dispersed in an aqueous solvent. The titanium salt hydrolyzate A-containing slurry is obtained. The titanium salt hydrolyzate A is an intermediate in the process of changing from titanium oxide or the titanium salt to titanium oxide.

In the hydrolysis / alkaline neutralization treatment A, the titanium salt is neutralized by preparing an aqueous solution in which the titanium salt is dissolved in water. And the titanium salt and the alkali are brought into contact with each other. More specifically, for example,

(i) a method in which the aqueous alkali solution is dropped into the aqueous titanium salt solution and the two are brought into contact with each other;

(ii) a method of dropping the aqueous solution of titanium salt against the aqueous solution of alkali and bringing them into contact;

(ii) A method in which water is put in a reaction vessel, an aqueous solution of the titanium salt and an aqueous solution of the alkali are dropped therein, and both are brought into contact with each other,

Is mentioned.

The alkali related to the hydrolysis and alkali neutralization treatment A is not particularly limited, and examples thereof include ammonia and aqueous ammonia. Among these, ammonia or aqueous ammonia is contained in the metal-containing sulfur-introduced titanium oxide. Since a metal component derived from Al force is not contained, it is preferable for controlling the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light. In the methods (i) to (iii) described above, the alkali neutralization temperature during the alkali neutralization is preferably 10 to 80 ° C, particularly preferably 30 to 80 ° C, more preferably 4 0 ~ 70 ° C. When the alkali neutralization temperature is less than 10 ° C, the neutralization reaction hardly occurs. When the alkali neutralization temperature exceeds 80 ° C, the heat generation is intense and the generation of hydrogen chloride becomes significant, so the average particle size is small. Moreover, it is difficult to obtain an Al force neutralized compound having a large specific surface area. Further, the addition time of the alkali at the time of alkali neutralization is usually 1 minute to 10 hours, preferably 3 minutes to 5 hours, particularly preferably 5 minutes to 1 hour.

In the hydrolysis / alkali neutralization treatment A, the titanium salt alkali neutralized product is generated by neutralizing the titanium salt with an alkali force, and the titanium salt alkali force is neutralized in an aqueous medium. The titanium salt aluminum neutralized product A-containing slurry in which the product is dispersed is obtained. The titanium salt alkali neutralized product A is an intermediate in the process of changing from titanium oxide or the titanium salt to titanium oxide. Next, in the firing raw material mixture preparation step A, the metal compound stirring and mixing treatment A is performed. The metal compound stirring and mixing treatment A is carried out by adding the metal compound to the titanium salt hydrolyzed Z alkali neutralized product A-containing slurry, and stirring and mixing the metal containing titanium salt hydrolyzed Z alkali neutralized product A. It is a process to obtain. For example, in the metal compound stirring and mixing treatment A, the titanium salt hydrolysis neutralized product A prepared in the hydrolysis Z alkali neutralization treatment A is used in the titanium salt hydrolysis alkali. The metal compound is added to the slurry without separating the solvate A.

The metal compound related to the metal compound stirring and mixing treatment A may be any metal compound that dissolves uniformly in the slurry aqueous medium, and includes inorganic metal salts such as chlorides, sulfates and nitrates, or organic metal compounds. . Further, the metal species of the metal compound is preferably iron from the viewpoint that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased. The metal compound is preferably an inorganic metal salt, and is preferably an iron salt in that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased. concrete F e C l ₂ , F e C l ₃ , F e S 0 ₄ , F e ₂ (S 0 ₄ ) ₃ , F e (N 0 ₃ ) ₃ , F e I ₂ , F e I ₃ , Examples include iron citrate, fermented ammonium iron, ferric ammonium sulfate, ammonium citrate, iron sulfide, iron phosphate, and ammonium iron oxalate.

In the metal compound stirring and mixing treatment A, the mixing amount of the metal compound can be appropriately selected depending on the amount of metal introduced into the metal-containing sulfur-introduced titanium oxide. The mass of metal atoms with respect to 100 parts by mass in terms of T i O ₂ is preferably 0.03 to 0.15 parts by mass, particularly preferably 0.05 to 0.1 parts by mass. It is a mixing amount. When the mixing amount of the metal compound is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.

In the metal compound stirring and mixing treatment A, the stirring and mixing temperature at the time of stirring and mixing is preferably 20 to 80¾: particularly preferably 50 to 7, and the stirring and mixing time is preferably 1 to 2 hours.

In the metal compound stirring and mixing treatment A, the metal compound is dissolved in the solvent in the slurry by stirring and mixing in the slurry containing the titanium salt hydrolyzed alkali neutral A, and further stirred. By continuing the process, the metal compound is hydrolyzed, neutralized or reduced in the liquid content of the titanium salt hydrolyzed Z alkali neutralized product A-containing slurry, and converted into a hydroxide or an oxide. The produced hydroxide or oxide adheres to the surface of the titan salt hydrolyzed neutralized product A or is taken into the inside. Thereby, the metal-containing titanium salt hydrolyzed Z alkali neutralized product A is formed. Next, the produced metal-containing titanium salt hydrolyzed neutralized neutralized product A is separated from the slurry by a method such as filtration and centrifugation, or the solvent of the slurry is evaporated to remove the solvent, and the solid is removed. Product, and after washing as necessary, drying the metal-containing titanium salt Z alkali neutralized product A is obtained. At the time of the drying, the drying temperature is usually 90 to 1550 ^: the drying atmosphere is in an oxidizing atmosphere such as air or oxygen gas; inert such as nitrogen gas or argon gas Under gas atmosphere; under vacuum.

The metal-containing titanium salt hydrolyzed Z alkali neutralized product A after drying is mainly composed of anatase type crystal structure and has a specific surface area of 150 to 400 m ² Zg, preferably 200 to 30 m. ² / g, X-ray diffraction analysis shows that the half-value width of the (1 0 1) peak of anatase is 2 Θ = 1.2 to 1.5 °. It is preferable because of its high activity.

Then, as described above, in obtaining the metal-containing titanium salt hydrolyzed Z-al strength neutralized product A from the titanium salt in the baking raw material mixture preparing step, that is, the titanium salt hydrolyzed Z-alloy. By mixing the sulfur compound between before the metal re-neutralization treatment A and after the metal compound stirring and mixing treatment A, the titanium salt hydrolyzed neutral alkali A and the sulfur compound are mixed. A mixture A is obtained. More specifically, in the baking raw material mixture preparation step A, the sulfur compound is mixed, for example,

(A 1) Before performing the hydrolysis and alkali neutralization treatment A,

(A 2) While performing the hydrolysis / alkali neutralization treatment A,

(A3) Before the metal compound stirring and mixing treatment A,

(A4) While performing the metal compound stirring and mixing treatment A, or

(A5) After performing the metal compound stirring and mixing treatment A,

To do.

In the case of (A 1), for example, before heating the aqueous solution of the titanium salt, the sulfur compound is mixed with the aqueous solution of the titanium salt, or before dropping the Al force solution to the aqueous solution of the titanium salt. The sulfur compound is mixed with an aqueous solution of the titanium salt. For example.

In the case of (A 2), for example, when the alkaline aqueous solution is dropped into the titanium salt aqueous solution, the alkaline aqueous solution mixed with the sulfur compound is dropped into the titanium salt aqueous solution. When mixing the sulfur compound or performing dropwise addition of the titanium salt aqueous solution to the alkaline aqueous solution while carrying out the hydrolysis / alkaline neutralization treatment A, the aqueous solution of alkali By adding dropwise an aqueous solution of the titanium salt mixed with the sulfur compound, the sulfur compound is mixed while performing the hydrolysis and alkali neutralization treatment A.

In the case of (A 3), for example, before the metal compound stirring and mixing treatment A, the sulfur compound is mixed with the titanium salt hydrolyzed neutralized product A-containing slurry.

In the case of (A 4), for example, when the aqueous solution of the metal compound is added dropwise to the titanium salt hydrolyzed neutralized product A-containing slurry, Then, by adding dropwise an aqueous solution of the metal compound containing the sulfur compound, the sulfur compound is mixed while performing the metal compound stirring and mixing treatment A.

In the case of (A 5), for example, after the metal compound stirring and mixing treatment A is performed to obtain the metal-containing titanium salt hydrolyzed Z-al strength neutralized product A, the obtained metal-containing titanium salt hydrolyzed product is obtained. It is mentioned to mix the decomposition / alternative neutralized product A and the sulfur compound. In the case of (A 5), more specifically, for example, (A 5 _ 1) a solution in which the sulfur compound is dissolved in the metal-containing titanium salt hydrolyzed / al strength neutralized product A (A 5-2) Hydrolysis of the metal-containing titanium salt Z alkali neutral A and the sulfur compound in a dry process, A 5-3) Hydrolysis of the metal-containing titanium salt Z neutralized product A and the sulfur compound are dispersed in a dispersion medium. Among these mixing methods, the method (A 5 -2) is preferable from the viewpoint of operability.

The mixing of the sulfur compound may be performed at any time of the above (A 1), (A 2), (A 3), (A 4), or (A 5), or of these It can be divided into two or more periods.

The sulfur compound according to the firing raw material mixture preparation step A (the sulfur compound according to the method for producing the metal-containing sulfur-introduced titanium oxide of the present invention, the production of the metal-containing sulfur-introduced titanium oxide according to the first to seventh aspects of the present invention) The same applies to the sulfur compound according to the method.) Is a compound having a sulfur atom in the molecule, which is decomposed by heat in the firing step A described later, and so ₂ gas and SO ₃ gas are generated in the decomposition process. And sulfur-containing organic compounds, sulfur-containing inorganic compounds, metal sulfides, sulfur, etc., which are solid or liquid at room temperature, and more specifically, for example, thiourea, thiourea derivatives, Examples include sulfates. Of these, thiourea is particularly preferable because it completely decomposes at 400 to 500 ° C. and does not remain in the metal-containing sulfur-introduced titanium oxide.

Hydrolysis of the metal-containing titanium salt Alkaline neutralized product A and the sulfur compound In the mixture A, the amount of the sulfur compound is determined as follows. _The mass of sulfur atoms relative to 100 parts by mass when converted to ₂ is preferably 5 to 1500 parts by mass, particularly preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass. Is the amount. When the mixed amount of the sulfur compound in the mixture A of the metal-containing titanium salt hydrolyzed / alkaline neutralized product A and the sulfur compound is within the above range, the sulfur content is from 0.02 to It becomes easy to obtain 0.1% by mass of metal-containing sulfur-introduced titanium oxide. Further, the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.

In the firing step A, the metal-containing titanium salt hydrolyzed neutralized product A And a mixture A of the sulfur compound is calcined.

As a method for firing the mixture A of the metal-containing titanium salt hydrolyzed neutralized product A and the sulfur compound, the mixture A is put into a firing container and the lid is covered. At that time, if the system is completely open, the gas generated from the sulfur compound does not stay in the atmosphere, so a slight gap is left open. When the mixture is fired, the sulfur compound is decomposed by heat, and SO ₂ gas and S 0 ₃ gas are generated in the decomposition process, and sulfur in these gases is converted into the metal-containing titanium. Salt hydrolysis Z Incorporated into Z-force neutralized product A, some of the titanium atoms in the metal-containing titanium salt hydrolyzed neutralized product A are replaced with sulfur atoms.

That is, in the firing step A, the S 0 ₂ gas and SO ₃ gas generated by the decomposition of the sulfur compound are retained in the atmosphere while the metal-containing titanium salt hydrolyzed Al force re-neutralized product A and the sulfur compound And firing the mixture. The calcining temperature when calcining the mixture of the metal-containing titanium salt hydrolyzed neutralized product A and the sulfur compound is preferably 3500 to 800, particularly preferably 3500 to 600 ° C. The baking time is preferably 1 to 10 hours, particularly preferably 1 to 5 hours, and further preferably 2 to 5 hours. Hydrolysis of the metal-containing titanium salt Alkaline neutralized product A and the sulfur compound A When the firing temperature and firing time when firing the mixture A are within the above ranges, the metal-containing sulfur-introduced titanium oxide is visible. Increases photocatalytic activity with light.

The atmosphere at the time of firing the mixture of the metal-containing titanium salt hydrolyzed neutral alkali A and the sulfur compound is not particularly limited, and is in an oxidizing atmosphere such as in air or oxygen gas; in nitrogen gas, Under an inert atmosphere such as in argon gas; under vacuum.

In the firing step A, the metal-containing titanium salt hydrolyzed alkali neutralized product A The sulfur content in the metal-containing sulfur-introduced titanium oxide varies depending on the mixing amount of the sulfur compound in the mixture A and the calcination temperature. Therefore, in the firing step A, the metal-containing titanium salt hydrolyzed Z alkali neutralized product A and the mixture A of the sulfur compound, the amount of the sulfur compound in the mixture A, and the firing temperature are appropriately selected, and the metal The sulfur content in the contained sulfur-introduced titanium oxide can be adjusted, and the sulfur content in the metal-containing sulfur-introduced titanium oxide is preferably set to be from 0.02 to 0.1% by mass. .

Specifically, when the calcination temperature is 3500 to 400 ° C, the amount of the sulfur compound in the mixture A is changed to the amount of the metal-containing titanium salt hydrolyzed alkali hydrate A The amount of sulfur atoms relative to 100 parts by mass in terms of O ₂ is preferably 5 to 20 parts by mass, particularly preferably 5 to 10 parts by mass. It is. When the calcination temperature is 400 to 500 ° C., the amount of the sulfur compound in the mixture A is changed to the metal-containing titanium salt hydrolyzed Z Al force neutralized product A 0 _2-converted mass of a sulfur atom for 1 0 0 parts by weight of time is 1 0-5 0 it is preferred to a mass parts become mixed-weight, particularly preferably 2 0-4 0 weight parts to become mixed- It is to be a quantity. In addition, when the calcination temperature is 500 to 800 ° C., the amount of the sulfur compound in the mixture A is changed to the metal-containing titanium salt hydrolyzed Z-al strength neutralized product A It is preferable to set the mixing amount so that the mass of sulfur atoms with respect to 100 parts by mass when converted to O ₂ is 40 to 150 parts by mass, and particularly preferably 100 to 150 parts by mass. The mixing amount is a part.

In addition, in the firing step A, a mixture A of the metal-containing titanium salt hydrolyzed neutral alkali A and the sulfur compound is fired, and the total amount of mixing is predetermined for the obtained metal-containing sulfur-introduced titanium oxide. The sulfur compound can be mixed again and fired again within a range not exceeding the mixing amount of. The method for producing the metal-containing sulfur-introduced titanium oxide of the second aspect of the present invention (hereinafter also referred to as the production method (2) of the present invention) is a metal-containing titanium salt hydrolysis alkali-neutralized product B heat treatment A baking raw material mixture preparation step B to obtain a mixture B of the product B and a sulfur compound, and a baking step B to obtain a metal-containing sulfur-introduced titanium oxide by firing the mixture B of the heat-treated product B and the sulfur compound. Have

The calcining raw material mixture preparation step B comprises hydrolysis or alkali neutralization treatment B to hydrolyze or neutralize titanium salt to prepare titanium salt hydrolyzed Z aluminum force neutralized product B-containing slurry. A metal compound is added to the slurry containing the alkali salt B of the alkali salt hydrolysis B slurry and stirred to obtain a metal-containing titanium salt hydrolyzed Z-al strength neutralized product B. Heat treatment B to obtain a heat-treated product B by heat-treating the titanium salt hydrolyzed no-alkali neutralized product B, and

The amount of the metal compound added in the metal compound stirring and mixing treatment B is 0.003 as a metal atom with respect to 100 parts by mass of the titanium salt hydrolyzed alkali neutralized product B 10 when converted to Ti 0 ₂ . A sulfur compound is mixed between before the hydrolysis Al force re-neutralization treatment B and after the heat treatment B.

It is a manufacturing method of a metal containing sulfur introduction | transduction titanium oxide.

In the calcination raw material mixture preparation step B, the titanium salt hydrolysis Z alkali neutralization treatment B and the metal compound stirring and mixing treatment B are carried out to convert the metal-containing titanium salt hydrolysis Z alcohol from the titanium salt. Power neutralized product B is obtained. The hydrolysis / al strength neutralization treatment B according to the baking raw material mixture preparation step B, the titanium salt, the titanium salt hydrolysis hydroalkali neutralization product B, the titanium salt hydrolysis alkali neutralization product B-containing slurry, Metal compound stirring and mixing treatment B, the metal compound, the metal-containing titanium salt hydrolyzed neutralized product B, Firing raw material mixture preparation step A according to the hydrolysis Z al force neutralization treatment A, the titanium salt, the titanium salt hydrolysis alkali neutralized product A, the titanium salt hydrolysis Z alkali neutralized product A-containing slurry, This is the same as the metal compound stirring and mixing treatment A, the metal compound, and the metal-containing titanium salt hydrolyzed alkali neutralized product A.

In the firing raw material mixture preparation step B, the heat treatment B is performed after the metal compound stirring and mixing treatment B is performed.

The heat treatment B is a heat treatment of the metal-containing titanium salt hydrolyzed Z al force neutralized product B obtained by performing the hydrolysis / al strength neutralization treatment B and the metal compound stirring and mixing treatment B. This is a process for obtaining a processed product B. Then, by performing the heat treatment B, the specific surface area is 1 50 400 m ² / g, preferably 200 3 10 m ² Zg The half width of the (1 0 1) peak of anatase by X-ray diffraction analysis is reduced. 2 0 = 1. 2 1. 5 ° of the heat-treated product is obtained. In other words, the heat treatment B is a treatment for adjusting the specific surface area and the half width of the heat-treated product B to the above ranges.

In the heat treatment B, the heat treatment temperature when the metal-containing titanium salt hydrolyzed neutralized product B is heat-treated is 200 3550 ^< , preferably 250 300 ° C. When the heat treatment temperature is within the above range, the specific surface area is 150 500 m ² Zg, and the half-width of the (1 0 1) peak of anatase is 2 0 = 1. 2 1.5 ° It becomes easy to obtain a processed product. On the other hand, when the heat treatment temperature is less than 200 ° C, the specific surface area of the heat-treated product tends to be larger than 400 m ² Zg, or the half width of the (1 0 1) peak of anatase is 2 0 1.5 ° Prone to become wider. When the heat treatment temperature exceeds 350 ° C, the specific surface area of the heat-treated product tends to be smaller than 150 m ² g, or the half width of the anatase (1 0 1) peak is 2 0 = 1 It tends to be narrower than 2 °. The heat treatment temperature is If the temperature is lower than 2500 ° C, the specific surface area of the heat-treated product tends to be larger than 3 10 m ² Zg. If the temperature exceeds 300 ° C, the specific surface area of the heat-treated material is smaller than ²⁰⁰ m ² / g. easy.

In the heat treatment B, the heat treatment time when the metal-containing titanium salt hydrolyzed alkali neutralized product B is heat-treated is preferably 1 to 5 hours, particularly preferably 2 to 3 hours.

In the heat treatment B, the atmosphere for heat-treating the metal-containing titanium salt hydrolyzed / al strength neutralized product B is not particularly limited, and is in an oxidizing atmosphere such as in air or oxygen gas; nitrogen In an inert atmosphere such as in a gas or argon gas; in a vacuum, etc. In the air, the air is advantageous. Then, as described above, in obtaining the heat-treated product B from the titanium salt in the baking raw material mixture preparation step B, that is, before performing the titanium salt hydrolysis Z al force re-neutralization treatment B, Before the heat treatment B is performed, the sulfur compound is mixed to obtain a mixture B of the heat treated product B of the titanium salt hydrolyzed / al strength re-neutralized product B and the sulfur compound. More specifically, in the baking raw material mixture preparation step B, the sulfur compound is mixed, for example, before (B 1) hydrolysis and alkali neutralization treatment B,

(B 2) While performing the hydrolysis / alkali neutralization treatment B,

(B 3) Before the metal compound stirring and mixing treatment B,

(B 4) While performing the metal compound stirring and mixing treatment B,

(B 5) Before performing the heat treatment B, or

(B 6) After performing the heat treatment B

To do.

The (B 1), (B 2), (B 3), (B 4) related to the baking raw material mixture preparation step B are the (A 1), (B 4) related to the baking raw material mixture preparation step A The same as (A2), (A3) and (A4). In the case of (B 5), for example, the metal-containing titanium salt hydrolysis mixture B is obtained to obtain the metal-containing titanium salt hydrolyzed Al force neutralized product B, and then the metal-containing titanium salt hydrolyzed. Examples thereof include mixing the alkali neutralized product B and the sulfur compound. In the case of (B 5), more specifically, for example, (B 5-1) a solution in which the sulfur compound is dissolved in the metal-containing titanium salt hydrolyzed neutralized product B is added. (B 5-2) A method of evaporating the solvent containing the metal-containing titanium salt Alkaline hydrate B and the sulfur compound in a dry process, or (B 5-3 ) The metal-containing titanium salt hydrolyzed / alkaline neutralized product B and the sulfur compound may be mixed in a dispersion medium. Among these mixing methods, the (B 5-2) The method is preferable from the viewpoint of operability.

In the case of (B 6), for example, after the heat treatment B is performed to obtain the heat-treated product B, the obtained heat-treated product B and the sulfur compound are mixed. In the case of (B 6), more specifically, for example, (B 6-1) A solution in which the sulfur compound is dissolved is added to the heat-treated product B, mixed well, and then the solvent is added. A method of evaporating, (B 6-2) a method of mixing the heat-treated product B and the sulfur compound in a dry process, and (B 6-3) a method of mixing the heat-treated product B and the sulfur compound with a dispersion medium. Among these mixing methods, the method (B6-2) is preferable from the viewpoint of operability.

The sulfur compound may be mixed at any time of (B 1), (B 2), (B 3), (B 4), (A 5) or (B 6). Or it can be divided into two or more of these periods.

In the mixture B of the heat treatment B and the sulfur compound, the mixing amount of the sulfur compound, the mass of the sulfur atom with respect to 1 0 0 parts by weight when the heat treatment was B T i 0 ₂ converted, preferably 5 to 150 parts by weight, particularly preferably 10 ˜50 parts by mass, more preferably 20 to 40 parts by mass. Introducing metal-containing sulfur having a sulfur content of 0.02 to 0.1% by mass when the amount of the sulfur compound in the mixture B of the heat-treated product B and the sulfur compound is within the above range. Titanium oxide is easily obtained. Further, the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.

In addition, when the sulfur compound is mixed before the heat treatment B (B 5), the mixed amount of the sulfur compound is determined by adding the metal-containing titanium salt hydrolyzed Z alkali neutralized product B to T i O ₂ The amount of sulfur atoms with respect to 100 parts by mass when converted is preferably 5 to 20 parts by mass, particularly preferably 5 to 10 parts by mass. When the amount of the sulfur compound to be mixed before the heat treatment B is within the above range, the catalytic activity of the metal-containing sulfur-introduced titanium oxide is increased. Further, when the sulfur compound is mixed before the heat treatment B, the sulfur compound is further added to the heat-treated product B obtained by performing the heat treatment B within a range not exceeding a predetermined mixing amount. May be mixed.

In the firing step B, the mixture B of the heat-treated product B and the sulfur compound is fired.

Compared with the firing step A, the firing step B is mixed with the sulfur compound, and the former is a heat-treated product B of the metal-containing titanium salt hydrolyzed / al strength neutralized product B. On the other hand, the latter is the same as the calcination step A except that the metal-containing titanium salt hydrolyzed alkali neutral A. Therefore, the metal-containing titanium salt hydrolyzed / al strength neutralized product A in the description of the calcination step A may be read as the heat-treated product B and the mixture A as the mixture B.

In the production method (2) of the present invention, by performing the heat treatment B, the photocatalytic activity of the resulting metal-containing sulfur-introduced titanium oxide can be further increased. The method for producing a metal-containing sulfur-introduced titanium oxide according to the third aspect of the present invention (hereinafter also referred to as the production method (3) of the present invention) is a metal-containing titanium salt hydrolyzed / alternative neutralized product C Firing raw material mixture for obtaining a mixture C and sulfur compound C Preparation step C, the metal-containing titanium salt hydrolyzed / al strength re-neutralized product C and the sulfur compound C is calcined, and metal-containing sulfur is introduced. A firing step C for obtaining titanium oxide, and

The calcining raw material mixture preparation step C is hydrolyzed or alkalinized in the presence of a metal compound to hydrolyze or neutralize a titanium salt to obtain a metal-containing titanium salt hydrolyzed Z al force reneutralized product C. a step of performing sum process C, the amount of the metal compound be present in the hydrolysis Noarukari neutralization C is, with respect to the titanium salt 1 0 0 parts by weight when the T I_〇 ₂ terms, as a metal atom 0.03 to 0.15 is an amount of 5 parts by mass,

In addition, a method for producing a metal-containing sulfur-introduced titanium oxide, comprising mixing a sulfur compound before performing the hydrolysis Z-alkali neutralization treatment c and after performing the hydrolysis alkali-neutralization treatment C. It is.

In the calcining raw material preparation step C, by hydrolyzing the titanium salt in the presence of the metal compound, or by neutralizing the titanium salt in the presence of the metal compound. The metal-containing titanium salt hydrolyzed Z-al strength neutralized product c is obtained.

The titanium salt according to the hydrolysis Z alkali neutralization treatment C is the same as the titanium salt according to the titanium salt hydrolysis Z alkali neutralization treatment A. In addition, the metal compound according to the titanium salt hydrolysis Z-al force neutralization treatment c is the same as the metal compound according to the metal compound stirring and mixing treatment A.

In the hydrolysis / alternative neutralization treatment C, the titanium salt is hydrolyzed by preparing an aqueous solution in which the titanium salt and the metal compound are dissolved in water, and stirring the aqueous solution. The method of heating is mentioned. this In the method, the hydrolysis temperature during the hydrolysis is preferably 20 ° C. to the boiling point of the aqueous solution, particularly preferably 40 to 80 ° C. When the hydrolysis temperature is less than 20 ° C, the hydrolysis rate tends to be slow. The hydrolysis time for the hydrolysis is usually 5 minutes to 10 hours, preferably 10 minutes to 5 hours, and particularly preferably 10 minutes to 1 hour. In the above description, the titanium salt is dissolved in water, but the solvent for dissolving the titanium salt is not particularly limited as long as it dissolves the metal compound. Examples include organic solvents such as alcohol. Among these, water is preferable from the viewpoint of easy handling and economical efficiency.

When hydrolyzing in the hydrolysis Z alkali neutralization treatment C, hydrolysis is preferably performed in a low pH region because a hydrolyzate having a small particle size can be obtained. Therefore, when hydrolyzing in the hydrolysis Z alkali neutralization treatment c, particularly when the hydrolysis temperature is near the boiling point of the aqueous solution, a reflux apparatus is installed in the reaction tank, and the generated hydrogen chloride is chlorinated. It is preferable to suppress discharge from the reaction system as hydrogen gas because the pH of the reaction system can be lowered.

In the hydrolysis Z alkali neutralization treatment C, the titanium salt is hydrolyzed to produce the titanium salt hydrolyzate, and the metal compound is hydrolyzed or reduced. The metal-containing titanium salt hydrolyzate C is obtained by incorporating the hydroxide or the oxide into the surface adhesion or inside of the titanium salt hydrolyzate formed. . The metal-containing titanium salt hydrolyzate is titanium oxide or an intermediate in the process of changing from the titanium salt to titanium oxide.

In the hydrolysis Z-al strength neutralization treatment c, as a method for neutralizing the titanium salt, an aqueous solution in which the titanium salt and the metal compound are dissolved in water is prepared. While stirring, mix the alkali, A method of bringing the titanium salt into contact with the alkali, and more specifically, for example,

(ii) A method of dropping an aqueous solution of the titanium salt into the aqueous solution of the alkali and bringing them into contact;

Is mentioned. At this time, in the (i), (ii) and (iii), the metal compound can be added to the reaction vessel regardless of whether it is present in the aqueous solution of the titanium salt or in the aqueous solution of the alkali. The metal compound may be present in the added water, that is, the metal compound may be present in the dropped aqueous solution, or the metal compound may be present in the dropped aqueous solution.

The alkali related to the hydrolysis-no-alkali neutralization treatment C is not particularly limited, and examples thereof include ammonia and aqueous ammonia. Among these, ammonia or aqueous ammonia is contained in the metal-containing sulfur-introduced titanium oxide. Since a metal component derived from Al force is not contained, it is preferable for controlling the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light. In the above methods (i) to (iii), the alkali neutralization temperature during the alkali neutralization is preferably 10 to 80 ° C, particularly preferably 30 to 80, more preferably 40. ~ 70. When the alkali neutralization temperature is less than 10 ° C, the neutralization reaction hardly occurs. When the alkali neutralization temperature exceeds 80 ° C, heat generation is intense and generation of hydrogen chloride becomes remarkable. It is difficult to obtain Al strength intermediates with a large surface area. Further, the addition time of the alkali at the time of alkali neutralization is usually 1 minute to 10 hours, preferably 3 minutes to 5 hours, particularly preferably 5 minutes to 1 hour. Then, in the hydrolysis Z alkali neutralization treatment c, the titanium salt Al force re-neutralized product is formed by performing the Al force re-neutralization of the titanium salt, and the metal compound is hydrolyzed or reduced. Is converted into a hydroxide or an oxide, and the hydroxide or the oxide is taken into the surface of the alkali neutralized product of the produced titanium salt or is taken into the inside thereof, in the metal-containing titanium salt alkali. Japanese product C is obtained. The metal-containing titanium salt alkali neutralized product C is an intermediate in the process of changing from titanium oxide or the titanium salt to titanium oxide. In hydrolysis alkali neutralization process C, the mixing amount of the metal compound, 1 00 mass when can be appropriately selected by the introduction of the metal of the metal-containing sulfur introduced titanium oxide, which the titanium salt T io ₂ converted The mixing amount is such that the mass of the metal atom with respect to parts is preferably 0.03 to 0.15 parts by mass, particularly preferably 0.05 to 0.1 parts by mass. When the mixing amount of the metal compound is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.

The metal-containing titanium salt hydrolyzed alkali-neutralized product C after drying is mainly composed of anatase type crystal structure, and has a specific surface area of 150 to 400 m ² Zg, preferably 200 to 30 m ² / g. The half-width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 20 = 1.2 to 1.5 °, which indicates that the photocatalytic activity of metal-containing sulfur-introduced titanium oxide in visible light is high. This is preferable.

Then, as described above, when obtaining the metal-containing titanium salt hydrolyzed alkali neutralized product C from the titanium salt in the step of preparing the firing raw material mixture, that is, the hydrolysis / al force re-neutralization treatment. By mixing the sulfur compound between before the C and after the hydrolytic neutralization treatment C, the titanium salt hydrolyzed Z alkali neutralized product C and the sulfur compound are mixed. To obtain a mixture C. More specifically, in the baking raw material mixture preparation step C, the sulfur Mixing compounds, for example

(c i) The hydrolysis Z alkali neutralization treatment

(C 2) While performing the hydrolysis / alkali neutralization treatment C, or

(C 3) After the hydrolysis Z alkali neutralization treatment C

To do.

In the case of (C 1), for example, before heating the aqueous solution of the titanium salt, the sulfur compound is mixed with the aqueous solution of the titanium salt, or before the alkali is added dropwise to the aqueous solution of the titanium salt. And mixing the sulfur compound with an aqueous solution of the titanium salt.

In the case of (C 2), for example, when the alkaline aqueous solution is dropped into the titanium salt aqueous solution, the alkaline aqueous solution mixed with the sulfur compound is dropped into the titanium salt aqueous solution. When the sulfur compound is mixed while performing the hydrolysis-no-alkali neutralization treatment C, or when the titanium salt aqueous solution is dropped into the alkali aqueous solution, the sulfur aqueous solution is added to the alkali aqueous solution. By adding dropwise an aqueous solution of the titanium salt mixed with the compound, the sulfur compound is mixed while performing the hydrolysis-no-alkali neutralization treatment C.

In the case of (C 3), for example, the metal-containing titanium obtained is obtained by performing the hydrolysis Z-al strength neutralization treatment C to obtain the metal-containing titanium salt hydrolyzed al- strength neutralized product C. For example, the salt hydrolyzed neutralized product C and the sulfur compound may be mixed. In the case of (C 3), more specifically, for example, (C 3-1) A solution containing the sulfur compound dissolved in the metal-containing titanium salt hydrolyzed Z alkali neutralized product C is added. (C 3-2) Hydrolysis of the metal-containing titanium salt Z Al force re-neutralized product C and the sulfur compound in a dry process, (C 3-2) 3-3) Hydrolysis of the metal-containing titanium salt Z neutralized product C and the sulfur compound The method of mixing in a dispersion medium etc. is mentioned, Among these mixing methods, this (C3-2) method is preferable from the point of operativity.

The mixing of the sulfur compound can be performed at any one of the above (CI), (C2) or (C3), or can be performed at two or more of these times. .

Hydrolysis of the metal-containing titanium salt Z Al force neutralized product C and the mixture of the sulfur compound The amount of the sulfur compound in the mixture C is determined as follows. _The mass of sulfur atoms relative to 100 parts by mass when converted to ₂ is preferably 5 to 1500 parts by mass, particularly preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass. Is the amount. Hydrolysis of the metal-containing titanium salt Z Al force neutralized product c and the mixture c of the sulfur compound When the mixing amount of the sulfur compound is within the above range, the sulfur content is from 0.02 to It becomes easy to obtain 0.1% by mass of metal-containing sulfur-introduced titanium oxide. Further, the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.

In the firing step C, a mixture of the metal-containing titanium salt hydrolyzed / al strength re-neutralized product C and the sulfur compound. Is fired.

Compared with the calcination step A, the calcination step C is mixed with the sulfur compound. The former is the metal-containing titanium salt hydrolyzed / al strength neutralized product C, whereas the latter is the metal-containing Titanium salt hydrolysis Z Similar to the calcination step A except that it is a neutralized alkali A. Therefore, the metal-containing titanium salt hydrolyzed / al strength neutralized product A in the description of the calcination step A, the metal-containing titan salt hydrolyzed / al strength neutralized product C, and the mixture A It should be read as Mixture C.

The method for producing the metal-containing sulfur-introduced titanium oxide of the fourth aspect of the present invention (hereinafter also referred to as the production method (4) of the present invention) is a method for hydrolyzing metal-containing titanium salt Solution Z-strength neutralized product D Heat-treated product D and sulfur compound D are obtained D Preparation process D for calcining raw material and hydrolysis of the metal-containing titanium salt Z-strength neutralized product D A mixture D of D and the sulfur compound is calcined to obtain a metal-containing sulfur-introduced titanium oxide; and

In the presence of the metal compound, the firing raw material mixture preparation step D hydrolyzes or neutralizes the titanium salt to obtain a titanium salt hydrolyzed neutralized neutralized product D. Heat-treating D and the metal-containing titanium salt hydrolyzed Al force neutralized product D to obtain a heat-treated product D.

The amount of the metal compound be present in the hydrolysis Z Al Chikarari neutralization D is, with respect to the titanium salt 1 0 0 parts by weight when T i O ₂ converted, by a metal atom 0.0 3-0 1 The amount is 5 parts by mass,

In addition, a sulfur compound is mixed between before the hydrolysis Z al force re-neutralization treatment D and after the heat treatment D.

In the firing raw material mixture preparation step D, the titanium; ^ hydrolysis Z neutralization treatment D and the heat treatment D are carried out, whereby the metal-containing titanium salt hydrolysis in alkali Heat D of Japanese product D is obtained. The calcination raw material mixture preparation step D The hydrolysis Z al force neutralization treatment D, the titanium salt, the metal compound, the metal-containing titanium salt hydrolysis Z alkali neutralization product D is the calcination raw material mixture preparation step C. This is the same as the hydrolysis / alkaline neutralization treatment C, the titanium salt, the metal compound, and the metal-containing titanium salt hydrolyzed Z alkali neutralized product C.

In the firing raw material mixture preparation step D, the heat treatment D is performed after the hydrolysis / al strength neutralization treatment D is performed.

The heat treatment D may be performed by performing the hydrolysis Z-al force neutralization treatment D. Hydrolysis of metal-containing titanium salt Z Al force re-neutralized product D is heat-treated to obtain heat-treated product D. Then, by performing the heat treatment D, the specific surface area is 150 to 400 m ² / g, preferably ^{200 to} 3 10 m ² / g, and the (1 0 1) peak of anatase by X-ray diffraction analysis The heat-treated product having a half-value width of 2 0 = 1. 2 to 1.5 ° is obtained. In other words, the heat treatment D is a treatment for adjusting the specific surface area and the half-value width of the heat-treated product D to the above ranges.

The heat treatment D is heat-treated compared to the heat treatment B. The former is the metal-containing titanium salt hydrolyzed / alkaline neutralized product D, whereas the latter is the metal-containing titanium. Salt hydrolysis The same as heat treatment B except that it is an alkali neutralized product B. Therefore, the metal-containing titanium salt hydrolyzed Z-alkaline neutralized product B in the explanation of the heat-treated B is converted into the metal-containing titanium salt hydrolyzed Z alkali-neutralized product D and the heat-treated product B. The heat-treated product D may be replaced with this.

Then, as described above, in obtaining the heat-treated product D from the titanium salt in the baking raw material mixture preparation step D, that is, before performing the titanium salt hydrolysis Z-al force re-neutralization treatment D, Before the heat treatment D is performed, the sulfur compound is mixed to obtain a mixture D of the heat-treated product D of the titanium salt hydrolysis neutralized product D and the sulfur compound. More specifically, in the baking raw material mixture preparation step D, the sulfur compound is mixed, for example, before (D 1) hydrolysis Z alkali neutralization treatment D,

(D 2) While performing the hydrolysis Z alkali neutralization treatment D,

(D 3) Before performing the heat treatment D, or

(D 4) After performing the heat treatment D

To do.

The (D 1) and (D 2) relating to the baking raw material mixture preparation step D This is the same as (C 1) and (C 2) in the raw material mixture preparation step C. In the case of the (D 3), for example, the hydrolysis-alkali neutralization treatment D is performed to obtain the metal-containing titanium salt hydrolyzed Z-al strength neutralized product D, and then the obtained metal-containing titanium salt hydrolyzed. An example of this is to mix the decomposed Z-al strength neutralized product D with the sulfur compound. In the case of (D3), more specifically, for example, (D3-1) hydrolysis of the metal-containing titanium salt alkali neutralized product D is added with a solution in which the sulfur compound is dissolved, (D 3-2) Hydrolysis of the metal-containing titanium salt Z Al force re-neutralized product D and the sulfur compound, or (D 3 — 3) Hydrolysis of metal-containing titanium salt Z Alkali neutralized product D and sulfur compound are mixed in a dispersion medium. Among these mixing methods, (D 3 -2) The method is preferable from the viewpoint of operability.

In the case of (D4), for example, after the heat treatment D is performed to obtain the heat-treated product D, the obtained heat-treated product D and the sulfur compound are mixed. In the case of (D 4), more specifically, for example, (D 4-1) A solution in which the sulfur compound is dissolved is added to the heat-treated product D, and after sufficiently mixing, the solvent is added. A method of evaporating, (D 4-2) a method of mixing the heat-treated product D and the sulfur compound in a dry process, and (D 4-3) a method of mixing the heat-treated product D and the sulfur compound with a dispersion medium. Among these mixing methods, the method (D4-2) is preferred from the viewpoint of operability.

The mixing of the sulfur compound may be performed at any one of the times (D 1), (D 2), (D 3) or (D 4), or two or more of these times. It can also be divided into two.

In the mixture D of the heat treatment D and sulfur compounds, mixtures of sulfur compounds, for 1 00 parts by weight when the heat treatment was D T i O ₂ converted The amount of the sulfur atom is preferably 5 to 1550 parts by mass, particularly preferably 10 to 50 parts by mass, and still more preferably 20 to 40 parts by mass. Introduction of metal-containing sulfur having a sulfur content of 0.02 to 0.1% by mass when the amount of the sulfur compound in the mixture D of the heat-treated product D and the sulfur compound is within the above range. Titanium oxide is easily obtained. Further, the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.

In addition, when the sulfur compound is mixed before the heat treatment D (D 3), the amount of the sulfur compound is determined by converting the metal-containing titanium salt hydrolyzed alkali neutralized product D to Ti 0 ₂ In this case, the mass of sulfur atoms with respect to 100 parts by mass is preferably 5 to 20 parts by mass, particularly preferably 5 to 10 parts by mass. When the amount of the sulfur compound to be mixed in the heat-treated product D is within the above range, the catalytic activity of the metal-containing sulfur-introduced titanium oxide is increased.

In the firing step D, the mixture D of the heat-treated product D and the sulfur compound is fired.

Compared with the firing step A, the firing step D is mixed with the sulfur compound, and the former is a heat-treated product D of the metal-containing titanium salt hydrolyzed / al strength neutralized product D. On the other hand, the latter is the same as the calcination step A except that the metal-containing titanium salt hydrolyzed Z-alkaline intermediate A. Therefore, the metal-containing titanium salt hydrolyzed Z al force neutralized product A in the description of the firing step A may be read as the heat-treated product D, and the mixture A as the mixture D.

In the production method (4) of the present invention, by performing the heat treatment D, the photocatalytic activity of the resulting metal-containing sulfur-introduced titanium oxide can be further increased.

The fifth metal-containing sulfur-introduced titanium oxide production method of the present invention (hereinafter referred to as the present invention) Also described as Ming's manufacturing method (5). ) Is a calcined raw material mixture preparation step E to obtain a mixture E of a metal-containing titanium salt hydrolyzed / alkali neutralized product E (2) and a sulfur compound, and the metal-containing titanium salt hydrolyzed / alkaline neutralized product A mixture E of E (2) and the sulfur compound is calcined to obtain a metal-containing sulfur-introduced titanium oxide, and

In the firing raw material mixture preparation step E, in the presence of a metal compound, the titanium salt is hydrolyzed or alkali neutralized to obtain a metal-containing titanium salt hydrolyzed / alkali neutralized product E (1) -containing slurry. Hydrolysis to be prepared Z alkali neutralization treatment E and the metal-containing titanium salt hydrolyzed Z alkali-neutralized product E (1) Add the metal compound to the slurry and stir to obtain the metal-containing titanium salt hydrolyzed Z The metal compound stirring and mixing treatment E to obtain the alkali neutralized product E (2), and

Titanium salt 1 00 mass when the total amount of the hydrolyzed Z Al Chikarari neutralized the metal compound be present in E or gold group compound stirred mixing process the metal compound added in E is obtained by T i 0 ₂ conversion calculation Is an amount of 0.03 to 0.15 parts by mass as a metal atom,

And before performing this hydrolysis Al force re-neutralization process E until after performing this metal compound stirring mixing process E, a sulfur compound is mixed.

In the firing raw material mixture preparation step E, the hydrolysis / alkali neutralization treatment E and the metal compound stirring and mixing treatment E are performed.

In the hydrolysis / alkali neutralization treatment E, by hydrolyzing the titanium salt in the presence of the metal compound, or by neutralizing the titanium salt in the presence of the metal compound. A slurry containing the metal-containing titanium salt hydrolyzed alkali neutralized product E (1), that is, a metal-containing titanium salt hydrolyzed / alkali neutralized product E (1) -containing slurry is obtained. The hydrolysis Z-al strength re-neutralization treatment E is the same as the hydrolysis Z-al strength re-neutralization treatment C. The titanium salt according to the hydrolysis Z-al strength re-neutralization treatment E, the metal compound, The titanium salt hydrolyzed Z alkali neutralized product E (1) is the same as the titanium salt, the metal compound, and the titanium salt hydrolyzed neutralized product C of the hydrolyzed alkali neutralized treatment C. .

And, in the hydrolysis / alkali neutralization treatment E, the metal-containing titanium salt hydrolyzed neutralized product E (1) is produced. The metal-containing titanium salt hydrolyzed alkali-neutralized product E (1) is It is an intermediate in the process of changing from titanium oxide or the titanium salt to titanium oxide.

Next, in the metal compound stirring / mixing treatment E, the metal compound is added to the slurry containing the metal-containing titanium salt hydrolyzed / alkali neutralized product E (1), stirred and mixed, and the metal-containing titanium salt hydrolyzed / This is a treatment for obtaining the metal-containing titanium salt hydrolyzed Z-alkaline intermediate E (2) in which the metal is further introduced into the alkali neutralized product E (1). In addition, in this invention, the thing before processing by this metal compound stirring mixing process E is described as this metal containing titanium salt hydrolysis alkali neutralized product E (1), The treated product was described as the metal-containing titanium salt hydrolyzed neutralized product E (2).

The metal-containing titanium salt hydrolyzed Z alkali neutralized product E (2) after drying is mainly composed of anatase type crystal structure and has a specific surface area of 150 to 400 m ² / g, preferably 200 to 3 1 Om ² / g, X-ray diffraction analysis shows that the half width of the (1 0 1) peak of the anatase is 2 Θ = 1.2 to 1.5 ° force Photocatalyst of metal-containing sulfur-introduced titanium oxide with visible light It is preferable in terms of high activity.

Compared with the metal compound stirring and mixing treatment A, the metal compound stirring and mixing treatment E is contained in a slurry. / Alkali neutralized product E (1), while the latter is the same as the metal compound stirring and mixing treatment A except that the latter is the titanium salt hydrolyzed neutral force neutralized product A. Accordingly, the titanium salt hydrolysis Z alkali power neutralized product A in the description of the metal compound stirring and mixing treatment A is used as the metal-containing titanium salt hydrolyzed / alkali neutralized product E (1) and the metal-containing product. The titanium salt hydrolyzed neutralized product A may be read as the metal-containing titanium salt hydrolyzed Z alkali neutralized product E (2).

The total amount of the metal compound to be present in the hydrolysis / al neutralization treatment E and the metal compound stirring and mixing treatment E depends on the amount of metal introduced into the metal-containing sulfur-introduced titanium oxide. Although it can be appropriately selected, the mass of the metal atom with respect to 100 parts by mass when the titanium salt is converted to TiO ₂ is preferably 0.03 to 0.15 parts by mass, particularly preferably 0.05 to 0.1 Mixing amount to be 1 part by mass. When the mixing amount of the metal compound is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.

Then, as described above, in obtaining the metal-containing titanium salt hydrolyzed Z Al force re-neutralized product E (2) from the titanium salt in the firing raw material mixture preparation step E, that is, the titanium salt hydrolyzed By mixing the sulfur compound between before the Z-alternative neutralization treatment E and after the metal compound stirring and mixing treatment E, the titanium salt hydrolysis alkali neutralized product E (2) And a mixture E of the sulfur compound is obtained. More specifically, in the baking raw material mixture preparation step E, the sulfur compound is mixed, for example,

(E 1)

(E 2) While performing the hydrolysis Z Al force re-neutralization treatment E,

(E 3) Before the metal compound stirring and mixing treatment E,

(E 4) While performing the metal compound stirring and mixing treatment E, or (E 5) After performing the metal compound stirring and mixing treatment E

To do.

The (E 1) and (E 2) related to the baking raw material mixture preparation step E are the same as the (C 1) and (C 2) related to the baking raw material mixture preparation step C, and The (E 3), (E 4), and (E 5) related to the baking raw material mixture preparation step E are the (A 3), (A4), and (( Same as A5).

The mixing of the sulfur compound may be performed at any time of the above (E 1), (E 2), (E 3), (E 4) or (E 5), or these It can be divided into two or more of them.

The amount of the sulfur compound in the mixture E of the metal-containing titanium salt hydrolyzed Z alkali neutralized product E (2) and the sulfur compound is determined by the metal-containing titanium salt hydrolyzed Z alkali neutralized product E The mass of sulfur atoms with respect to 100 parts by mass when (2) is converted to Ti 0 ₂ is preferably 5 to 150 parts by mass, particularly preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass. It is an amount that becomes a part. Hydrolysis of the metal-containing titanium salt Z Alkali neutralized product E (2) and the sulfur compound In the mixture E of the sulfur compound within the above range, the sulfur content is 0.02 ˜0.1% by mass of metal-containing sulfur-introduced titanium oxide is easily obtained. Further, the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods. In the firing step E, a mixture E of the metal-containing titanium salt hydrolyzed Z-al strength neutralized product E (2) and the sulfur compound is fired.

Compared with the calcination step A, the calcination step E is mixed with the sulfur compound. The former is the metal-containing titanium salt hydrolyzed alkali neutralized product E (2), whereas the latter is the metal It is the same as the calcination step A except that the titanium salt is hydrolyzed with an alkali neutralized product A. Therefore, in the firing step A In the description, the metal-containing titanium salt hydrolyzed Z-alkaline neutralized product A can be read as the metal-containing titanium salt hydrolyzed Z-alkali neutralized product E (2), and the mixture A can be read as the mixture E. That's fine.

The sixth metal-containing sulfur-introduced titanium oxide production method of the present invention (hereinafter also referred to as the production method (6) of the present invention) is a metal-containing titanium salt hydrolyzed Z alkali neutralized product F (2). Heat-processed product F and sulfur compound mixture F Preparation step F for obtaining a raw material mixture F, Metal-containing titanium salt hydrolysis Z Al force re-neutralized product F (2) Heat-processed product F and the sulfur compound And firing step F to obtain a metal-containing sulfur-introduced titanium oxide, and a mixture F of

In the firing raw material mixture preparation step F, in the presence of a metal compound, the titanium salt is hydrolyzed or alkali-neutralized to obtain a metal-containing titanium salt hydrolyzed alkali neutralized product F (1) -containing slurry. Hydrolysis-no alkali neutralization treatment F to be prepared and the metal-containing titanium salt hydrolysis Z alkali-neutralized product F (1) Add the metal compound to the slurry and stir to hydrolyze the metal-containing titanium salt in alkali. The metal compound stirring and mixing treatment F to obtain a hydrate F (2), the metal-containing titanium salt hydrolysis / alkali neutralized product F (2), and the heat treatment F to obtain the heat treatment product F, Is a process to perform,

The total amount of the metal compound to be present in the hydrolysis and the neutralization treatment F and the metal compound to be mixed in the metal compound stirring and mixing treatment F is the titanium salt when converted to Ti 0 ₂ 1 0 0 It is an amount of 0.03 to 0.15 parts by mass with respect to parts by mass as metal atoms,

In addition, a sulfur compound is mixed between before the hydrolysis-no-alkali neutralization treatment F and after the heat treatment F.

In the firing raw material mixture preparation step F, the hydrolysis Z al force neutralization treatment F, the metal compound stirring and mixing treatment F, and the heating treatment F are performed. The hydrolysis raw alkali neutralization treatment F according to the firing raw material mixture preparation step F, the metal compound stirring and mixing treatment F, the titanium salt, the metal compound, the metal-containing titanium salt hydrolysis Z alkali neutralized product F (1) The metal-containing titanium salt hydrolysis / alkali neutralized product F (2) is the hydrolysis / alkali neutralization treatment E, the metal compound stirring / mixing treatment E, the titanium salt according to the baking raw material mixture preparation step E. These metal compounds, the metal-containing titanium salt hydrolyzed neutralized product E (1), and the metal-containing titanium salt hydrolyzed neutralized product E (2) are the same.

In the firing raw material mixture preparation step F, the hydrolysis Z alkali neutralization treatment F is performed to obtain the metal-containing titanium salt hydrolysis neutral alkali treatment product F (1) -containing slurry, and then the metal By carrying out compound stirring treatment F, the metal-containing titanium salt hydrolyzed neutralized neutralized product F (2) is obtained.

In the firing raw material mixture preparation step F, the heat treatment F is performed after the metal compound stirring and mixing treatment F is performed.

The heat treatment F is a treatment for obtaining a heat-treated product F by heat-treating the metal-containing titanium salt hydrolysis neutralized neutralized product F (2) obtained by performing the metal compound stirring and mixing treatment F. Then, by performing the heat treatment F, the specific surface area is 150 to 400 m ² Zg, and the half width of the (1 0 1) peak of the anatase by X-ray diffraction analysis is 2 0 = 1.2 to I. The heat-treated product of 5 ° is obtained. In other words, the heat treatment F is a treatment for adjusting the specific surface area and the half-value width of the heat-treated product F to the above ranges.

The heat treatment F is heat-treated compared to the heat treatment B. The former is the metal-containing titanium salt hydrolyzed Z-alkaline neutralized product F (2), whereas the latter is the metal Containing titanium salt hydrolysis It is the same as the heat treatment B except that it is an alkali neutralized product B. Therefore, the gold in the description of the heat treatment B Metal-containing titanium salt hydrolysis Z Al force neutralized product B can be read as the metal-containing titanium salt hydrolyzed Z alkali neutralized product F (2), and the heat-treated product B can be read as the heat-treated product F. That's fine.

Then, as described above, when the heat-treated product F is obtained from the titanium salt in the baking raw material mixture preparation step F, that is, before the titanium salt hydrolyzing neutralization treatment F is performed, the heat treatment is performed. By mixing the sulfur compound until after F is performed, a mixture F of the heat-treated product F of the titanium salt hydrolyzed alkali neutralized product F (2) and the sulfur compound is obtained. More specifically, in the baking raw material mixture preparation step F, the sulfur compound is mixed, for example,

(F 1) before hydrolysis Z alkali neutralization treatment F,

(F 2) While performing the hydrolysis-no-alkali neutralization treatment F,

(F 3) Before the metal compound stirring and mixing treatment F,

(F 4) While performing the metal compound stirring and mixing treatment F,

(F 5) Before performing the heat treatment F, or

(F 6) After performing the heat treatment F

To do.

(F 1) and (F 2) relating to the firing raw material mixture preparation step F are the same as the (C 1) and (C 2) relating to the firing raw material mixture preparation step C, and The (F 3) and (F 4) relating to the firing raw material mixture preparation step F are the same as the (A 3) and (A4) relating to the firing raw material mixture preparation step A, and the firing raw material mixture The preparation steps (F 5) and (F 6) are the same as the (B 5) and (B 6) according to the baking raw material mixture preparation step B.

The sulfur compound may be mixed at any time of the above (F 1), (F 2), (F 3), (F 4), (F 5) or (F 6). Or it can be divided into two or more of these periods. In the mixture F of the heat treatment F and sulfur compounds, mixtures of sulfur compounds, the mass of the sulfur atom with respect to 1 0 0 parts by weight when the heat treatment was F T i O ₂ converted, preferably Is in an amount of 5 to 1500 parts by mass, particularly preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass. Introducing metal-containing sulfur having a sulfur content of 0.02 to 0.1% by mass when the amount of the sulfur compound in the mixture F of the heat-treated product F and the sulfur compound is within the above range. Titanium oxide is easily obtained. Further, the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.

Moreover, before the heat treatment F (F 5), if mixing the sulfur compound, the mixing amount of the sulfur compound, 1 0 0 mass when the heat treatment was F T i 0 ₂ converted The amount of sulfur atoms with respect to parts is preferably 5 to 20 parts by weight, particularly preferably 5 to 10 parts by weight. When the amount of the sulfur compound to be mixed in the heat-treated product F is within the above range, the catalytic activity of the metal-containing sulfur-introduced titanium oxide is increased.

In the firing step F, the mixture F of the heat-treated product F and the sulfur compound is fired.

Compared with the firing step A, the firing step F is mixed with the sulfur compound, whereas the former is a heat-treated product F of the metal-containing titanium salt hydrolyzed Z alkali neutralized product F (2). The latter is the same as the calcination step A except that the metal-containing titanium salt hydrolyzed / alkali neutralized product A. Therefore, the metal-containing titanium salt hydrolyzed Z-al strength neutralized product A in the description of the firing step A may be read as the heat-treated product F, and the mixture A as the mixture F. In the production method (6) of the present invention, by performing the heat treatment F, the photocatalytic activity of the obtained metal-containing sulfur-introduced titanium oxide can be further increased. In the production methods (1) to (6) of the present invention, the metal-containing titanium salt hydrolyzed alkali neutralized product A, the metal-containing titanium salt hydrolyzed / al strength neutralized product B heat-treated product B, the metal Hydrolyzed titanium salt hydrolyzed alkali neutralized product C, metal-containing titanium salt hydrolyzed alkali neutralized product D, heat-treated product D of the metal-containing titanium salt hydrolyzed / alkali neutralized product E (2), and the metal The heat-treated product F of the titanium salt hydrolyzed neutralized product F (2) containing the main component of the crystal structure is anatase type and has the following physical properties (i), (ii), and (iii) It is preferable in that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.

(I) a specific surface area of 1 50 to 400 m ² Zg, preferably ^{200~ 3 1 0 m 2 Z g} .

(ii) The half width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 0 = 1.2 to 1.5 °.

(iiii) The metal content is 0.03 to 0.15 mass%.

In addition, the main component of the crystal structure is anatase type, and the metal-containing titanium salt hydrolyzed neutralized product A having the physical properties (i) to (iii), the metal-containing titanium salt hydrolyzed Z-al strength neutralized product B heat-treated product B, metal-containing titanium salt hydrolyzed alkali neutralized product C, metal-containing titanium salt hydrolyzed neutral force neutralized product D heat-treated product D, metal-containing titanium salt hydrolyzed / alloy Potassium neutralized product E (2) and the heat-treated product F of the metal-containing titanium salt hydrolyzed / alkali neutralized product F (2) are mixed amount of metal compound, hydrolysis condition, alkaline neutralized condition, slurry Separation of solids from the liquid or by appropriately selecting conditions such as washing and drying as necessary to obtain the solids, or by performing heat treatment and appropriately selecting the heat treatment conditions Can be obtained.

A method for producing a metal-containing sulfur-introduced titanium oxide according to the seventh aspect of the present invention (hereinafter, This is also referred to as the production method (7) of the present invention. ) Has a firing step G for firing a mixture of a metal-containing raw material titanium oxide and a sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide,

The metal content in the metal-containing raw material titanium oxide is 0.03 to 0.15 parts by mass as metal atoms with respect to 100 parts by mass of the metal-containing raw material titanium oxide when converted to Tio ₂ .

The metal-containing raw material titanium oxide according to the production method (7) of the present invention, metal-containing organic weight, relative to the metal-containing raw material titanium oxide 1 00 parts by weight when T i 0 ₂ terms, 0 as a metal atom 03 to 0.1 1 Titanium oxide in 5 parts by mass. And, the metal-containing raw material titanium oxide according to the production method (7) of the present invention is mainly composed of anatase type crystal structure, and has the following physical properties (i),

Titanium oxide having (ii) and (iiii) is preferred in that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.

(i) The specific surface area is 150 to 400 m ² / g, preferably 2000 to 3 10 m ² Z g.

(ii) The half-width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 0 = 1.2 to 1.5. It is.

(iiii) The metal content is 0.03 to 0.15 mass%.

In the firing step G according to the production method (7) of the present invention, the mixture G of the metal-containing raw material titanium oxide and the sulfur compound is fired.

Compared with the firing step A according to the production method (1) of the present invention, the firing step G according to the production method (7) of the present invention is mixed with the sulfur compound. In contrast to titanium, the latter is the same as calcination step A except that the metal-containing titanium salt hydrolyzed Z alkali neutralized product A. Therefore, the metal-containing titanium salt hydrolyzed Z The neutralized product A may be read as the metal-containing raw material titanium oxide, and the mixture A as the mixture G.

In the production methods (1) to (7) of the present invention, the obtained metal-containing sulfur-introduced titanium oxide is further metal-introduced to obtain metal-containing sulfur-introduced titanium oxide in which the metal is reintroduced. An introduction process may be performed. For example, the metal-containing sulfur-introduced titanium oxide obtained by the firing step is immersed in a solution of the metal compound, hydrolyzed, alkali neutralized, irradiated with light, or the solvent is evaporated, and then heated as necessary. Processing may be performed. In addition, the metal-containing sulfur-introduced titanium oxide obtained by performing the firing step and the metal compound can be obtained by CVD, PVD (sputtering method, vacuum deposition method, ion plating method, etc.), plating method, etc. A metal may be contained on the surface of the sulfur-introduced titanium oxide. Furthermore, the metal re-introduced metal-containing sulfur-introduced titanium oxide in which the metal is re-introduced and the sulfur compound are mixed and fired to re-introduce the metal. A sulfur re-introduction step may be performed in which the metal-containing sulfur-introduced titanium oxide further contains sulfur. Further, the metal reintroduction step and the sulfur reintroduction step may be repeated.

The metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention is a compound in which a sulfur atom is introduced into the skeleton structure of titanium oxide, and is one of anatase-type titanium oxide titanium sites (cation sites). Part has a structure substituted with a sulfur atom. That is, the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention is a sulfur cation-substituted titanium oxide.

The confirmation that the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention has a structure in which a part of the titanium site is substituted with a sulfur atom is confirmed by X-ray photoelectron spectroscopy (XPS). Done by analysis. Sulfur-containing acid When titanium fluoride is sulfur-containing titanium oxide in which part of the titanium site is replaced with sulfur atoms, a characteristic peak around 1 69 eV derived from S ^{4 +} is observed. In other words, if a characteristic peak around 1 69 eV is seen, it is assumed that a part of the titanium site (force thione site) is replaced with sulfur atoms. On the other hand, when the sulfur-containing titanium oxide is not sulfur-containing titanium oxide in which part of the titanium site is substituted with sulfur atoms, but sulfur-containing titanium oxide in which some oxygen atoms are substituted with sulfur atoms, S ² _ characteristic peak around 1 6 0 e V derived is observed, the characteristic peaks in the vicinity of 1 6 9 e V derived from the S ⁴ + is not observed. In addition, when the sulfur-containing titanium oxide is not a compound in which some of the atoms in the titanium oxide are substituted with sulfur atoms, but a simple mixture of titanium oxide and sulfur, There is no characteristic peak in any of the vicinity of eV.

In the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention, the metal compound is present in the form of metal ions or oxides on the surface and inside of the metal-containing sulfur-introduced titanium oxide particles. Ratio of the amount of metal present in titanium oxide to the total amount of metal contained (%) ((Amount of metal present in titanium oxide Z Total amount of metal contained in titanium oxide) X

1 0 0) is 15% or more and 90% or less, preferably 20% or more and 85% or less, and particularly preferably 50% or more and 75% or less. Since the metal compound is present not only on the sulfur-containing titanium oxide surface but also inside thereof, the decomposition performance into carbon dioxide is particularly good. Here, the amount of metal present on the surface is a value obtained by boiling the metal-containing sulfur-introduced titanium oxide in a 9% hydrochloric acid aqueous solution and analyzing the weight composition. On the other hand, the amount of metal present inside is the total amount of metal minus the amount of metal present on the surface. The total amount of metal is a value obtained by analyzing the amount of metal from a product obtained by boiling and melting the metal-containing sulfur-introduced titanium oxide with hydrofluoric acid. As the metal species, photocatalyst with visible light From the viewpoint of high activity, iron is preferable.

The metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention has a metal content of 0.03 to 0.15% by mass, a sulfur content of 0.02 to 0.1% by mass, The surface area is 60 to 120 m ² Z g, and the main crystal structure is the anatase type.

That is, the metal-containing sulfur-introduced titanium oxide of the present invention has a metal content of 0.03 to 0.15 mass%, a sulfur content of 0.02 to 0.1 mass%, and a specific surface area of 60 to 1. 20m ² Zg,

The main part of the crystal structure is the anatase type,

Sulfur atoms in titanium oxide are introduced into the titanium oxide titanium site.

This is a metal-containing sulfur-introduced titanium oxide in which a metal is contained in and on the surface of titanium oxide.

The metal content of the metal-containing sulfur-introduced titanium oxide of the present invention is 0.03 to 0.15% by mass, preferably 0.05 to 0.1% by mass. When the metal content is within the above range, the photocatalytic activity of visible light of the metal-containing sulfur-introduced titanium oxide is increased.

The sulfur content of the metal-containing sulfur-introduced titanium oxide of the present invention is 0.02 to 0.1% by mass, preferably 0.03 to 0.1% by mass. When the sulfur content is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.

The specific surface area of the metal-containing sulfur introduced titanium oxide of the present ^{invention, 6 0~ 1 20 m 2 /} g, preferably ^{6 5~ 1 0 5m 2 / g} , particularly preferably 80: is I 00 m ² / g . When the specific surface area is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.

The crystal structure of the metal-containing sulfur-introduced titanium oxide of the present invention is suitable for X-ray diffraction analysis. According to this, it is a phase mainly composed of anatase. In the present invention, the fact that the crystal structure is mainly anatase type means that the rutile ratio defined by the following formula is 1% or less (AS TM D 3 7 2 0-8 4 ). In addition, the metal-containing sulfur-introduced titanium oxide of the present invention may contain wurtzite. For example, in the X-ray diffraction pattern, “Both the peak area of the anatase-type crystalline titanium oxide and the peak area of the surface index of 120 and the surface index of the wurtzite-type titanium oxide” The ratio of the “peak area of the plane index 1 2 1 of lucite-type crystalline titanium oxide” is 10% or less. When the main body of the crystal structure is the anatase type, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.

Rutile ratio (mass%) = 1 0 0-1 0 0 / (1 + 1. 2 X 1 τ / I d) I r: strongest interference line of rutile crystalline titanium oxide in the X-ray diffraction pattern (face index 1 1 0) peak area,

I d: Peak area of the strongest interference line (surface index 1 0 1) of anatase-type titanium oxide powder in the X-ray diffraction pattern

In the metal-containing sulfur-introduced titanium oxide of the present invention, the metal is present in the form of metal ions or oxides on the particle surface and inside of the metal-containing sulfur-introduced titanium oxide, and the titanium oxide with respect to the total amount of metal contained in the titanium oxide. The ratio of the amount of metal present in the interior (%) ((the amount of metal present in the titanium oxide and the total amount of metal contained in the titanium oxide) XI 0 0) is 15% or more and 90% or less. The ratio (%) of the amount of metal present in the titanium oxide to the total amount of metal contained in the titanium oxide is within the above range, so that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide in visible light, particularly to carbon dioxide gas The decomposition performance of becomes higher. Moreover, the ratio (%) of the amount of metal present in the titanium oxide to the total amount of metal contained in the titanium oxide is the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide under visible light, decomposition characteristics of organic matter, and carbon dioxide. The decomposition performance of From the standpoint of higher, it is preferably 20% or more and 85% or less, particularly preferably 50% or more and 75% or less.

The metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention and the metal-containing sulfur-introduced titanium oxide of the present invention have excellent visible light absorption characteristics and photocatalytic activity in visible light. Compared with the metal-containing sulfur-introduced titanium oxide obtained by the production method, the photocatalytic activity under visible light is high. In addition, since the metal compound is present not only on the surface of the sulfur-containing titanium oxide but also inside thereof, the decomposition performance into carbon dioxide gas is particularly good. Therefore, the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention and the metal-containing sulfur-introduced titanium oxide of the present invention are useful as photocatalysts that exhibit catalytic activity by irradiation with visible light.

Further, the production method of the present invention is simpler than the conventional method for producing metal-containing sulfur-introduced titanium oxide because the introduction of metal is performed before obtaining sulfur-containing titanium oxide, that is, before introducing sulfur. It is.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

(Example)

(1) Measurement of sulfur content in titanium oxide

It was measured by an infra-red gas combustion one-infrared absorption method (measuring device: EMIA-520 from Horiba, Ltd.).

(2) X-ray diffraction analysis

The following X-ray diffraction measurement conditions were used. As for the half-value width, the width (angle) at which the height of the anatase (1 0 1) peak is 1 to 2 was measured.

(X-ray diffraction measurement conditions)

Diffraction device RAD— 1 C (manufactured by Rigaku Corporation) X-ray tube

Tube voltage and tube current 40 kV, 3 O mA

Slit D S-S S: 1 degree, R S: 0.15 mm

Monochromator graph item

Measurement interval 0.0 0 2 degrees

Counting method Constant clock method

The rutile ratio depends on the peak area (I r) of the strongest interference line (plane index 1 1 0) of rutile crystalline titanium oxide in the X-ray diffraction pattern according to AS TM D 3 7 2 0— 8 4 and the anatase The peak area (Id) of the strongest interference line (surface index 10 1) of the type titanium oxide powder was obtained, and obtained from the following calculation formula. Rutile ratio (mass%) = 1 0 0-1 0 0 / (1 + 1.2 X 1 τ / I d)

(3) Measurement of specific surface area

Measured by BET method. The sample was degassed at 110 ° C.

(4) Photocatalytic performance measurement test 1

The degradation performance of isopropyl alcohol (IPA) was evaluated. Prepare 5 ml of a petrolonitrile solution with an initial IPA concentration of 50 mm o 1/1 in a 10 ml test tube. 0.1 g of the metal-containing sulfur-introduced titanium oxide powder obtained is mixed. Prepare two such test tubes (test tube X I and test tube Y 1). One test tube (test tube X I) is irradiated with light excluding wavelengths below 3500 nm for 2 hours while stirring with a stir bar. The other test tube (test tube Y 1) is stirred for 2 hours in a safe place so as not to be exposed to light.

After a predetermined time, the solution in each test tube was centrifuged, the supernatant was separated, and the concentration of I PA was measured using gas chromatography. I P A decomposition performance was determined by the following equation.

Degradation performance A (%) = (I PA concentration of Y 1 after 2 hours-X 1 after 2 hours IPA concentration) X 1 00 Z (IPA concentration of Y 1 after 2 hours)

(5) Photocatalytic performance measurement test 2

The concentration of carbon dioxide produced as a result of the decomposition of acetonitrile and the decomposition of acetonitrile was measured.

Place 0.1 g of metal-containing sulfur-introduced titanium oxide powder in a petri dish of 60 mm and irradiate with ultraviolet light for 16 hours or longer. Place this sample in a 3 L tedlar bag and enclose 1 L of gas adjusted in the air so that the initial concentration of acetonitrile gas is 100 ppm. Let this stand in the dark for 5 hours, and measure the aldehyde concentration and carbon dioxide concentration.

Furthermore, light is irradiated for 18 hours, and the acetonitrile and carbon dioxide concentrations are measured with a gas monitor device (INNOVA photoacoustic gas monitor). A fluorescent lamp is used as the light source. The decomposition performance was evaluated by the following two formulas. Decomposition performance B (ppm) = 1 8 h CO ₂ concentration after the irradiation - CO ₂ concentration after 5 hours left without irradiating

Decomposition performance C (%) = (Acetaldehyde concentration after standing for 5 hours without irradiation) 1 1 0 (Acetaldehyde concentration after 5 hours without irradiation) X 1 00 (Acetaldehyde concentration after 5 hours without irradiation)

(6) X P S measurement

The measurement was performed under the following measurement conditions. No pretreatment of the sample such as etching was performed.

(X P S measurement conditions)

XPS system: XP S-5 700 manufactured by PH I

X-ray source: Monochrome A l Kct (1 4 8 6. 6 e V) 200 W Measurement area: 800 μm diameter

Detection angle: 45 ° (From sample normal)

Neutralizing electron gun: used (7) Measurement of iron content in titanium oxide (total iron content in titanium oxide) 2 g of titanium oxide, 15 m 1 hydrofluoric acid with a concentration of 50%, nitric acid with a concentration of 60%

Boil and dissolve in 10 ml of mixed acid (fluoric nitric acid), dilute the solution with pure water to a total volume of 250 ml, and then use ICP emission spectroscopy (emission analysis using high frequency inductively coupled plasma as the light source) ) To measure the iron concentration.

(8) Measurement of iron content on titanium oxide surface

After boiling 2 g of titanium oxide in 5 Om 1 of hydrochloric acid with a concentration of 9% and diluting with pure water so that the total amount becomes 10 Om 1, ICP emission spectroscopy analysis (using high frequency inductively coupled plasma as the light source) The iron concentration was measured by an emission analysis method.

[Example 1]

(Production of iron-containing titanium salt alkali neutralized product)

In a round bottom flask equipped with a stirrer and having a capacity of 1 000 ml, 297 g of titanium tetrachloride aqueous solution (titanium concentration: 4% by mass) was placed, and then heated to 60 ° C. Next, aqueous ammonia was added all at once, and neutralization was performed at 60 ° C. for 1 hour so that the pH of the reaction system was maintained at 7.4 to obtain a slurry. Then, this slurry one, iron chloride _{(F e C 1 3 · H} 2 O ( KK Wako Pure Chemical)) aqueous solution, when the titanium salt alkali neutralized product in slurries and T io ₂ conversion calculation It added so that it might become 0.05 mass part as an iron atom with respect to 100 mass parts, and it stirred and mixed at 60 degreeC for 1 hour, and obtained the liquid mixture. Next, this mixed solution was heated at 110 ° C. for 24 hours to evaporate and remove water to obtain a solid. The obtained solid was washed twice with pure water and filtered twice, and the filtered solid was It was dried at 110 ° C. for 24 hours to obtain an iron-containing titanium salt alkali neutralized product a1.

(Additional heat treatment) The iron-containing titanium salt alkali neutralized product a 1 was heat-treated at 25 ° C. for 3 hours under atmospheric pressure to obtain a heat-treated product b 1. The ratio of the heat-treated product b 1 is 2 80 m ² / g, the half-width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 Θ = 1.4 2 °, iron content Was 0.05 mass%.

(Baking)

The heat-treated product b 1 and thiourea pulverized in a mortar so that the mass of sulfur atoms is 40 parts by mass with respect to 100 parts by mass when the heat-treated product b 1 is converted to T i O ₂ To obtain a mixture. The mixture was then fired at 400 for 2.5 hours in a firing furnace. The fired product thus obtained was pulverized with a ball mill, washed with pure water, and then dried with 110 to obtain yellow to yellow-orange iron-containing sulfur-introduced titanium oxide c 1. Table 1 shows the characteristics of the iron-containing sulfur-introduced titanium oxide c 1 and the photocatalytic performance measurement results.

[Example 2]

(Production of iron-containing titanium salt alkali neutralized product)

In the slurry after neutralization treatment, iron chloride (Fe C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) aqueous solution, titanium oxide in the slurry converted to Ti O ₂ 100 mass Instead of adding 0.05 parts by mass as iron atoms to the part, iron chloride (Fe C 1 ₃ · H ₂ O (Wako Pure Example 1) Except that the aqueous solution is added so that the titanium oxide in the slurry is 0.03 parts by mass as iron atoms with respect to 100 parts by mass when converted to Ti 0 _2. The same procedure was followed to obtain an iron-containing titanium salt aluminum neutralized product a2.

(Heat treatment)

A heat treatment is performed in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a 1 is used instead of the iron-containing titanium salt alkaline neutralized product a 2. Object b 2 was obtained. The heat-treated product b 2 has a specific surface area of 17 Om ² / g, an anatase (1 0 1) peak half-width of 2 Θ = 1.25 ° by X-ray diffraction analysis, and an iron content of 0. 0 3% by mass.

(Baking)

An iron-containing sulfur-introduced titanium oxide c 2 was obtained in the same manner as in Example 1 except that the heat-treated product b 2 was used instead of the heat-treated product b 1. Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c 2 and the measurement results of its photocatalytic performance. [Example 3]

(Manufacture of iron-containing titanium salt Al neutralized product)

The slurry after neutralization, iron chloride _{(F e C 1 3 · H} 2 0 ( Ltd. Wako Pure Chemical)) solution, the titanium oxide in the slurry to 1 00 parts by weight when the T io ₂ terms Instead of adding 0.05 parts by mass as iron atoms, iron chloride (Fe C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) was added to the neutralized slurry. ) The same method as in Example 1, except that the aqueous solution was added so that the amount of iron atoms was 0.06 parts by mass with respect to 100 parts by mass when titanium oxide in the slurry was converted to TiO _2. To obtain an iron-containing titanium salt aluminum neutralized product a3.

(Heat treatment)

A heat-treated product b3 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a3 was used instead of the iron-containing titanium salt alkaline neutralized product a1. The specific surface area of the heat-treated product b 3 is 270 m ² Zg, the half width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 Θ = 1.4 3 °, and the iron content is 0.06 mass% Met.

(Baking) An iron-containing sulfur-introduced titanium oxide c3 was obtained in the same manner as in Example 1 except that the heat-treated product b3 was used instead of the heat-treated product b1. Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c3 and the photocatalytic performance measurement results.

[Example 4]

(Manufacture of iron-containing titanium salt Al neutralized product)

In the slurry after neutralization treatment, an aqueous solution of iron chloride (Fe C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) and titanium oxide in the slurry converted to Ti ₂ O 1 0 0 Instead of adding 0.5 mass parts as iron atoms with respect to mass parts, the slurry after the neutralization treatment was mixed with iron chloride (Fe C 1 ₃ · H ₂ O (WA light Junyaku Co.)) solution, except that the addition of titanium oxide in the slurry as zero. 0 7 parts by iron atoms relative to 1 0 0 parts by weight when T i 0 ₂ terms is performed In the same manner as in Example 1, an iron-containing titanium salt alkali neutralized product a4 was obtained.

(Heat treatment)

A heat-treated product b4 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a4 was used instead of the iron-containing titanium salt alkaline neutralized product a1. The heat-treated product b 4 has a specific surface area of 2900 m ² Z g, an anatase (1 0 1) peak half-value of 2 0 = 1.40 ° by X-ray diffraction analysis, and an iron content of 0 0 7% by mass.

(Baking)

An iron-containing sulfur-introduced titanium oxide c 4 was obtained in the same manner as in Example 1 except that the heat-treated product b 4 was used instead of the heat-treated product b 1. Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c4 and the photocatalytic performance measurement results. [Example 5]

(Manufacture of iron-containing titanium salt Al neutralized product)

When the slurry after neutralization treatment is converted to T i O ₂ with an aqueous solution of iron chloride (F e C 1 ₃ · H ₂ 0 (manufactured by Wako Pure Chemical Industries, Ltd.)) and neutralized titanium salt alkali in the slurry. Instead of adding 0.05 parts by mass of iron atoms to 100 parts by mass of iron, the neutralized slurry is mixed with iron chloride (F e C 1 3 · H ₂ 0 (stock the company manufactured by Wako pure Chemical Industries, Ltd.)) aqueous solution, and 0.1 parts by iron atoms relative to 1 0 0 parts by weight when the titanium emission salt Al Chikarari neutralized product of the slurry in one T i O ₂ converted The iron-containing titanium salt alkali neutralized product a5 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a5 was obtained.

(Heat treatment)

A heat-treated product b5 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a1 was used instead of the iron-containing titanium salt alkaline neutralized product a1. The heat-treated product b 5 has a specific surface area of 300 m ² Zg, and the half width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 0 = 1.4 3. The iron content was 0.10% by mass.

(Baking)

An iron-containing sulfur-introduced titanium oxide c5 was obtained in the same manner as in Example 1 except that the heat-treated product b5 was used instead of the heat-treated product b1. Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c5 and the photocatalytic performance measurement results.

[Comparative Example 1]

(Production of neutralized titanium salt alkali)

Titanium tetrachloride in a 1 000 ml round bottom flask equipped with a stirrer A solution (titanium concentration: 4% by mass) 29 7 g was added, and then heated to 60 ° C. Next, aqueous ammonia was added all at once, and neutralization was performed at 60 ° C. for 1 hour so that the pH of the reaction system was maintained at 7.4 to obtain a slurry. Next, this slurry was heated at 110 ° C. for 45 hours to evaporate and remove water to obtain a solid, and the obtained solid was washed twice with pure water and filtered twice. The solid was dried at 110 ° C. for 12 hours to obtain a titanium salt alkali neutralized product d1.

(Heat treatment)

A heat-treated product e1 was obtained in the same manner as in Example 1 except that the titanium salt alkali neutralized product dl was used instead of the iron-containing titanium salt alkali neutralized product a1. The heat-treated product e 1 has a specific surface area of 300 m ² Z g, an anatase (1 0 1) peak half-width of 2 0 = 1.4 1 ° by X-ray diffraction, and an iron content of 0% by mass. there were.

(Baking)

A sulfur-containing titanium oxide f 1 was obtained in the same manner as in Example 1 except that the heat-treated product b 1 was used instead of the heat-treated product b 1. Table 1 shows the characteristics of this sulfur-containing titanium oxide f1 and the photocatalytic performance measurement results.

[Comparative Example 2]

(Production of iron-containing titanium salt alkali neutralized product)

In the slurry after neutralization treatment, an aqueous solution of iron chloride (F e C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) and neutralized titanium salt alkali in the slurry when converted to T io ₂ Instead of adding 0.5 mass parts as iron atoms to 100 mass parts, iron chloride (F e C 1 3 'H ₂ 0 (stock) (Wako Pure Chemicals Co., Ltd.))) An aqueous solution is made of iron with respect to 100 parts by mass when converted to Ti 0 _{2 of the} neutralized titanate in the slurry. Except for adding 0.1 part by mass as an atom, the same procedure as in Example 1 was performed to obtain an iron-containing titanium salt aluminum force neutralized product d2.

(Heat treatment)

A heat-treated product e2 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkaline neutralized product a1 was used instead of the iron-containing titanium salt alkaline neutralized product d2. The heat-treated product e 2 has a specific surface area of 1 3 5 ni ² Z g, X-ray diffraction analysis reveals that the half width of the (1 0 1) peak of anatase is 2 Θ = 1.18 °, and the iron content is 0 0 1% by mass.

(Baking)

An iron-containing sulfur-introduced titanium oxide f 2 was obtained in the same manner as in Example 1 except that the heat-treated product b 2 was used instead of the heat-treated product b 1. Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide f 2 and the photocatalytic performance measurement results.

Table 1

In Examples 1 to 5, when a raw material titanium oxide was produced, a predetermined amount of an iron compound was added to a slurry containing a titanium salt Al force neutralized product, so that the iron content was 0.03 to 0.15% by mass of iron-containing sulfur-introduced titanium oxide was obtained, and the iron-containing sulfur-introduced titanium oxide was compared with iron-containing sulfur-introduced titanium oxide of Comparative Example 2 having an iron content of 0.1% by mass. In comparison, although the specific surface area was slightly smaller, the photocatalytic performance was high. Further, from Examples 1 to 5 and Comparative Examples 1 and 2, in the production of the iron-containing titanium salt alkali neutralized product, the amount of the iron compound added to the slurry containing the titanium salt alkali neutralized product is It can be seen that the specific surface area of the iron-containing titanium salt aluminum neutralized product decreases as the number increases. Therefore, in the production of the iron-containing titanium salt alkali neutralized product, the specific surface area of the iron-containing titanium salt alkaline neutralized product depends on the amount of iron compound added to the slurry containing the titanium salt alkaline neutralized product. Can be adjusted. As a result of XPS spectral analysis of the iron-containing sulfur-introduced titanium oxides cl to c 5 of Examples 1 to 5, a characteristic peak around 1 6 9 e V derived from S ^{4 +} was observed. ^No characteristic peak around 1600 eV derived from 2_ was observed. In addition, from the results of X-ray diffraction analysis of iron-containing sulfur-introduced titanium oxide cl to c5, no peak of brookite phase was observed.

[Example 6]

(Manufacture of iron-containing titanium salt Al neutralized product)

In a 1 000 ml round bottom flask equipped with a stirrer, titanium tetrachloride aqueous solution (titanium concentration: 4% by mass) 2 9 7 g and iron chloride (FeC 1 ₃ · H ₂ o (Made by Mitsuru Pure Chemical Co., Ltd.)) The aqueous solution was added so that the amount of iron atom was 0.05 parts by mass with respect to 100 parts by mass of titanium tetrachloride when converted to Tio ₂ , and then heated to 60 ° C. Next, aqueous ammonia was added all at once, and neutralized at 60 ° C. for 1 hour so that the pH of the reaction system was maintained at 7.4 to obtain a slurry. This slurry was heated at 110 for 24 hours to evaporate and remove water to obtain a solid. The obtained solid was washed with pure water twice and filtered twice. It was dried at 10 hours for 24 hours to obtain an iron-containing titanium salt aluminum neutralized product a6.

(Heat treatment)

A heat-treated product b 6 was prepared in the same manner as in Example 1, except that the iron-containing titanium salt alkaline neutralized product a 1 was used instead of the iron-containing titanium salt alkaline neutralized product a 6. Got. The specific surface area of the heat-treated product b 6 is 29 Om ² Zg, the half width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 0 = 1.4 4 °, and the iron content is 0.05. It was mass%.

(Baking)

Example except that the heat-treated product b 6 is used instead of the heat-treated product b 1 In the same manner as in Example 1, iron-containing sulfur-introduced titanium oxide c6 was obtained. Table 2 shows the measurement results of the characteristics and photocatalytic performance of the iron-containing sulfur-introduced titanium oxide c6. [Example 7]

(Manufacture of iron-containing titanium salt Al neutralized product)

Iron chloride (Fe C 1 ₃ · H ₂ 0 (Wako Pure Chemical Industries, Ltd.)) Aqueous solution of iron tetrachloride relative to 100 parts by mass of titanium tetrachloride when converted to TiO ₂ Instead of putting it in mass parts, the iron chloride (Fe C 1 ₃ · H ₂ 0 (manufactured by Wako Pure Chemical Industries, Ltd.)) aqueous solution was used to convert titanium tetrachloride into Ti O ₂ at 1 00 An iron-containing titanium salt alkali neutralized product a7 was obtained in the same manner as in Example 6 except that the iron atom was added in an amount of 0.1 part by mass with respect to part by mass.

(Heat treatment)

A heat-treated product b7 was obtained in the same manner as in Example 1, except that the iron-containing titanium salt alkali neutralized product a1 was used instead of the iron-containing titanium salt alkaline neutralized product a7. It was. The specific surface area of the heat-treated product b 7 was 3 10 m ² Zg, the half-value width of the (1 0 1) peak of anatase by X-ray diffraction analysis 2 0 = 1.48 °, and the iron content was 0.10% by mass. It was.

(Baking)

An iron-containing sulfur-introduced titanium oxide c7 was obtained in the same manner as in Example 1 except that the heat-treated product b1 was used instead of the heat-treated product b1. Table 2 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c7.

[Comparative Example 3] Put the sulfur-containing titanium oxide f 1 obtained in Comparative Example 1 in pure water, stir it, and then add an aqueous solution of iron chloride (Fe C 1 ₃ · H ₂ 0 (manufactured by Wako Pure Chemical Industries, Ltd.)) The titanium oxide fl contained was added so as to be 0.05 parts by mass of iron atoms with respect to 100 parts by mass when converted to Ti 0 ₂ and stirred for 30 minutes to obtain a suspension. After stirring, the obtained suspension was filtered, and the filtered powder was dried at 110 ° C. for 12 hours to obtain a copper-colored sulfur-containing titanium oxide g 3. Table 2 shows the measurement results of the characteristics and photocatalytic performance of this sulfur-containing titanium oxide powder g3.

[Comparative Example 4]

Iron chloride (Fe C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) Sulfur-containing ^ "Titanium oxide f 1 when converted to TiO ₂ , iron atoms with respect to 100 parts by mass Instead of adding 0.05 parts by mass, iron chloride (Fe C 1 3 'H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) aqueous solution, sulfur-containing titanium oxide f 1 T i O ₂ A bronze sulfur-containing titanium oxide g 4 was obtained in the same manner as in Comparative Example 3 except that the iron atom was added in an amount of 0.1 part by mass with respect to 100 parts by mass when converted. Table 2 shows the measurement results of characteristics and photocatalytic performance of this sulfur-containing titanium oxide g4.

Table 2

As a result of XPS spectrum analysis of iron-containing sulfur-introduced titanium oxide c6 of Example 6 and iron-containing sulfur-introduced titanium oxide c7 of Example 7, both were derived from S ^{4 +} around 1 6 9 e V The characteristic peak in the vicinity of 1600 eV derived from S ² _ was not observed. From the results of X-ray diffraction analysis of iron-containing sulfur-introduced titanium oxides c6 and c7, no peak of brookite phase was observed.

As a result of measuring the photocatalyst performance, the iron-containing titanium salt Al force neutralization obtained by adding an iron compound to the slurry containing the neutralized titanium salt alkali obtained by neutralizing the titanium salt with Al force The iron-containing sulfur-introduced titanium oxide obtained by reacting the product with the sulfur compound has the best decomposition performance into carbon dioxide gas, and then the titanium salt in the titanium salt solution containing the iron compound. The iron-containing titanium salt alkali neutralized product obtained by neutralization with Al is reacted with the sulfur compound. The iron-containing sulfur-introduced titanium oxide obtained in this way had good decomposition performance into carbon dioxide. On the other hand, compared with the iron-containing sulfur-introduced titanium oxide obtained by these methods, first, the aluminum salt neutralized product of the titanium salt and the sulfur compound were calcined to obtain the sulfur-containing titanium oxide, and the iron compound was The sulfur-containing titanium oxide with iron introduced was poor in its ability to decompose into carbon dioxide. [Example 8]

(Production and heat treatment of iron-containing titanium salt Al neutralized product)

A heat-treated product b8 was obtained in the same manner as in Example 4 except that the heat treatment temperature in the heat treatment was changed to 350 ° C instead of 250 ° C. The specific surface area of the heat-treated product b 8 is 180 m ² Zg, the half-width of the (101) peak of anatase by X-ray diffraction analysis is 20 = 1.35 °, and the iron content is 0.07% by mass. there were.

(Baking)

An iron-containing sulfur-introduced titanium oxide c8 was obtained in the same manner as in Example 4 except that the heat-treated product b4 was used instead of the heat-treated product b4. Table 3 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c8. [Example 9]

A heat-treated product b9 was obtained in the same manner as in Example 4 except that the heat treatment temperature in the heat treatment was changed to 300 ° C instead of 250 ° C. The specific surface area of the heat-treated product b9 is 220 m ² Zg, the half-width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 20 = 1.35 °, and the iron content is 0.07% by mass. there were. (Baking)

An iron-containing sulfur-introduced titanium oxide c9 was obtained in the same manner as in Example 4 except that the heat-treated product b9 was used instead of the heat-treated product b4. Table 3 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c9.

[Example 1 0]

A heat-treated product b 10 was obtained in the same manner as in Example 4 except that the heat treatment temperature in the heat treatment was changed to 200 ° C. instead of 250 ° C. The heat-treated product b 10 has a specific surface area of 340 m ² / g, an anatase (1 0 1) peak half-width of 2 6 = 1. 48 ° by X-ray diffraction analysis, and an iron content of 0.0 7 It was mass%.

(Baking)

An iron-containing sulfur-introduced titanium oxide c 10 was obtained in the same manner as in Example 4 except that the heat-treated product b 4 was used instead of the heat-treated product b 4. Table 3 shows the measurement results of the characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c10. [Example 1 1]

(Manufacture of iron-containing titanium salt aluminum neutralized product, heat treatment and calcination) Example 4 except that the calcination temperature in the calcination was set to 4-50 ° C instead of 400 ° C. In the same manner, iron-containing sulfur-introduced titanium oxide c 1 1 was obtained. Table 3 shows the measurement results of the characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c 11. Table 3

[Example 1 2]

(Manufacture of iron-containing titanium salt Al neutralized product)

The same procedure as in Example 4 was performed to obtain an iron-containing titanium salt aluminum neutralized product a 1 2.

(Heat treatment)

When the iron-containing titanium salt aluminum strength neutralized product a 1 2 and thiourea pulverized in a mortar are converted to Ti 0 ₂ of the iron-containing titanium salt aluminum strength neutralized product a 12 It mixed so that the mass of a sulfur atom might be 5 mass parts with respect to a mass part, and the mixture was obtained. Next, the mixture was heat-treated at 300 ° C. for 3 hours under atmospheric pressure, and the fired product obtained was pulverized with a ball mill to obtain the heat-treated product b 12. The heat-treated product b 1 2 has a specific surface area of 2 20 ni ² Z g, and the half width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 Θ = 1. The iron content was 36 ° C. and 36 ° C.

(Baking)

The mass of sulfur atoms is 40 parts by mass with respect to 100 parts by mass of the heat-treated product b 1 2 and thiourea pulverized in a mortar when the heat-treated product b 1 2 is converted to Ti 0 ₂ So that a mixture was obtained. Next, the mixture was baked at 400 ° C. for 2.5 hours in a baking furnace. The obtained fired product was pulverized with a ball mill, washed with pure water, and dried at 110 ° C. to obtain yellow to yellow-orange iron-containing sulfur-introduced titanium oxide c 12.

Table 4 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c12.

[Example 1 3]

(Manufacture of iron-containing titanium salt Al neutralized product)

This was carried out in the same manner as in Example 4 to obtain an iron-containing titanium salt aluminum neutralized product a 1 3.

(Heat treatment)

The heating was carried out in the same manner as in Example 12 except that the iron-containing titanium salt aluminum strength neutralized product a 1 2 was used instead of the iron-containing titanium salt aluminum strength neutralized product a 1 3. The treated product b 1 3 was obtained. The heat-treated product b 1 3 has a specific surface area of 2 20 m ² Zg, an anatase (1 0 1) peak half width of 2 6 = 1. 3 6 ° by X-ray diffraction analysis, and an iron content of 0.0 7 It was mass%.

(Baking)

The mass of sulfur atoms is 40 parts by mass with respect to 100 parts by mass of the heat-treated product b 1 2 and thiourea pulverized in a mortar when the heat-treated product b 1 2 is converted to Ti 0 ₂ Thus, instead of mixing the heat-treated product b 1 3 and thiourea crushed in a mortar, the heat-treated product b 1 3 is converted to TiO ₂ Except for mixing, so that the mass of sulfur atoms is 20 parts by mass with respect to 100 parts by mass of the obtained iron, the iron-containing sulfur-introduced titanium oxide c 1 3 is obtained. It was.

Table 4 shows the measurement results of the characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c13.

[Example 1 4]

(Manufacture of iron-containing titanium salt Al neutralized product)

The same procedure as in Example 4 was performed to obtain an iron-containing titanium salt aluminum neutralized product a 1 4.

(Heat treatment) '

The heating was carried out in the same manner as in Example 12 except that the iron-containing titanium salt aluminum strength neutralized product a 1 2 was used instead of the iron-containing titanium salt aluminum strength neutralized product a 1 4. The treated product b 1 4 was obtained. The heat-treated product b 14 has a specific surface area of 2 20 m ² Zg, an anatase (1 0 1) peak half-width of 2 0 = 1. 3 6 ° by X-ray diffraction analysis, and an iron content of 0.0 7 mass. /. Met.

(Baking)

The iron-containing sulfur-introduced titanium oxide c 14 was obtained in the same manner as in Example 13 except that the firing temperature in the firing was changed to 400 ° C. instead of 450 ° C.

Table 4 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c14.

[Example 1 5]

(Production of iron-containing titanium salt alkali neutralized product)

Performed in the same manner as in Example 4, neutralized iron-containing titanium salt Al power a 1 5 Got.

(Heat treatment)

In place of the iron-containing titanium salt alkali neutralized product a 1 2, the iron-containing titanium salt alkaline product a 15 is used, and thiourea is added to the iron-containing titanium salt alkaline product a 1 2. the so mass of sulfur atom relative to 1 00 parts by weight when T i O ₂ converted is 5 parts by weight, instead of mixing, the Chio urea, iron-containing titanium salts Al Chikarari neutralization Except for mixing so that the mass of sulfur atoms is 10 parts by mass with respect to 100 parts by mass of product a 15 converted to Ti O ₂ , the same procedure as in Example 12 was performed. And the heat-treated product b 15 was obtained. The heat-treated product b 15 has a specific surface area of 220 m ² / g, an anatase (1 0 1) peak half-value of 2 0 = 1. 36 °, and an iron content of 0 by X-ray diffraction analysis. 0 7% by mass.

(Baking)

An iron-containing sulfur-introduced titanium oxide c 15 was obtained in the same manner as in Example 14 except that the heat-treated product b 15 was used instead of the heat-treated product b 14. Table 4 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c 15.

[Comparative Example 5]

(Production of iron-containing titanium salt alkali neutralized product)

When the slurry after neutralization treatment is converted to TiO ₂ with an aqueous solution of iron chloride (F e C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) and neutralized titanium salt alkali in the slurry. Instead of adding 0.07 parts by mass of iron atoms with respect to 100 parts by mass of iron, iron chloride (Fe C 1 3 'H ₂ 0 ( Ltd. Wako Junyaku Co.)) aqueous solution of iron per 1 00 parts by mass when the titanium emission salt Al Chikarari neutralized product in slurry T i O ₂ converted Except for adding 0.3 parts by mass as an atom, the same procedure as in Example 4 was performed to obtain an iron-containing titanium salt aluminum neutralized product d5.

(Heat treatment)

In place of the iron-containing titanium salt alkali neutralized product a 1 2, heat treatment was carried out in the same manner as in Example 12 except that the iron-containing titanium salt Al neutralized product d 5 was used. 5 was obtained. The heat-treated product e 5 has a specific surface area of 250 m ² Zg, an anatase half-width of 2 1 = 1.45 ° by X-ray diffraction analysis, and an iron content of 0.3% by mass. there were.

(Baking)

A treatment was performed in the same manner as in Example 14 except that the heating compound e 5 was used instead of the heating compound b 14 to obtain iron-containing sulfur-introduced titanium oxide f 5. Table 4 shows the measurement results of the characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide f5. [Comparative Example 6]

(Manufacture of iron-containing titanium salt Al neutralized product)

When the slurry after neutralization treatment is converted to T i O ₂ with an aqueous solution of iron chloride (F e C 1 ₃ · H ₂ 0 (manufactured by Wako Pure Chemical Industries, Ltd.)) and neutralized titanium salt alkali in the slurry. Instead of adding 0.07 parts by mass of iron atoms to 100 parts by mass of iron, the slurry after neutralization treatment was added with iron chloride (F e C 1 3 · H ₂ O ( Ltd. Wako Junyaku Co.)) solution, so as to be 0.5 parts by mass as an iron atom with respect to 1 00 parts by mass when the titanium emission salt Al Chikarari neutralized product in slurry T i O ₂ converted The iron-containing titanium salt Al power re-neutralized product d6 was obtained in the same manner as in Example 4 except that it was added to the product.

(Heat treatment)

In place of the iron-containing titanium salt aluminum neutralized product a 1 2, the iron-containing titanium salt A heat-treated product e6 was obtained in the same manner as in Example 12 except that the neutralized product d6 was used. The heat-treated product e 6 has a specific surface area of 2 60 ni ² Z g, an anatase (1 0 1) peak half-value of 2 Θ == 1.46 °, and an iron content of 0 by X-ray diffraction analysis. It was 5% by mass.

(Baking)

An iron-containing sulfur-introduced titanium oxide f6 was obtained in the same manner as in Example 14 except that the heat-treated product e6 was used instead of the heat-treated product b14. Table 4 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide f6. Table 4

[Example 1 6]

(Manufacture of iron-containing titanium salt Al neutralized product) The same procedure as in Example 1 was performed to obtain an iron-containing titanium salt aluminum neutralized product a 1 6.

(Heat treatment)

The heat-treated product b 1 was prepared in the same manner as in Example 12 except that the iron-containing titanium salt alkaline neutralized product a 1 6 was used instead of the iron-containing titanium salt alkaline neutralized product a 1 2. 6 was obtained. The heat-treated product b 1 6 has a specific surface area of 2 2 Om ² Zg, an anatase half-width of 2 θ = 1.36 ° by X-ray diffraction analysis, and an iron content of 0.05 mass %Met.

(Baking)

An iron-containing sulfur-introduced titanium oxide h 16 was obtained in the same manner as in Example 12 except that the heat-treated product b 1 6 was used instead of the heat-treated product b 1 2. The obtained iron-containing sulfur-introduced titanium oxide h 1 6 was put into pure water, stirred, and an aqueous solution of iron chloride (Fe C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) The sulfur-introduced titanium oxide h 16 is added to 100 parts by mass when converted to Ti 0 ₂ so that it becomes 0.05 parts by mass as iron atoms, and stirred for 30 minutes to obtain a suspension. It was. After stirring, the resulting suspension was filtered, and the filtered powder was dried at 110 ° C. for 12 hours to obtain a copper-colored iron-containing sulfur-introduced titanium oxide c 16. Table 5 shows the measurement results of characteristics and photocatalytic performance of the iron-containing sulfur-introduced titanium oxide c 16.

[Example 1 7]

In the same manner as in Example 16, heat-treated product b 17 was obtained.

(Baking)

An iron-containing sulfur-introduced titanium oxide h 1 7 was obtained in the same manner as in Example 13 except that the heat-treated product b 1 7 was used instead of the heat-treated product b 1 3. The iron-containing sulfur-introduced titanium oxide h 1 7 is put into pure water, stirred, and an aqueous solution of iron chloride (FeC 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) Sulfur-introduced titanium oxide h 17 was added to 100 parts by mass when converted to Ti O ₂ so that the amount was 0.1 parts by mass as iron atoms, and stirred for 30 minutes to obtain a suspension. . After stirring, the resulting suspension was filtered, and the filtered powder was dried at 110 ° C. for 12 hours to obtain a copper-colored iron-containing sulfur-introduced titanium oxide c 17. Table 5 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c 17. [Example 1 8]

The same procedure as in Example 4 was performed to obtain an iron-containing titanium salt aluminum neutralized product a 1 8.

(Heat treatment)

The heat-treated product b 1 was prepared in the same manner as in Example 12 except that the iron-containing titanium salt alkaline neutralized product a 1 8 was used instead of the iron-containing titanium salt alkaline neutralized product a 1 2. 8 got. The heat-treated product b 1 8 has a specific surface area of 260 m ² / g, the half-width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 Θ = 1.40 °, and the iron content is 0.0 7 It was mass%.

(Baking)

An iron-containing sulfur-introduced titanium oxide h 1 8 was obtained in the same manner as in Example 13 except that the heat-treated product b 1 8 was used instead of the heat-treated product b 1 3. The iron-containing sulfur-introduced titanium oxide h 1 8 is put into pure water, stirred, and an aqueous solution of iron chloride (Fe C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)) and 0.0 3 parts by weight of iron atoms of sulfur introduced titanium oxide h 1 8 and against the 1 0 0 parts by weight when T i O ₂ converted - so as to put, stirred for 30 minutes, A suspension was obtained. After stirring, the resulting suspension was filtered, and the filtered powder was dried at 110 ° C. for 12 hours to obtain a copper-colored iron-containing sulfur-introduced titanium oxide c 18. Table 5 shows the measurement results of the properties and photocatalytic performance of this iron-introduced sulfur-containing titanium oxide c 18.

[Example 1 9]

In a 1 000 ml round bottom flask equipped with a stirrer, titanium tetrachloride aqueous solution (titanium concentration: 4% by mass) 2 9 7 g, iron chloride (Fe C 1 ₃ · H ₂ O (Made by Mitsuru Pure Chemical Co., Ltd.))) Aqueous solution was put in an amount of 0.05 parts by mass as iron atoms with respect to 100 parts by mass of titanium tetrachloride when converted to Ti O ₂ , and then heated to 60 ° C. Heated. Next, ammonia water was added all at once, and the mixture was neutralized at 60 for 1 hour so that the pH of the reaction system was maintained at 7.4 to obtain a slurry. This slurry was heated at 110 ° C. for 24 hours to evaporate and remove water to obtain a solid, and the obtained solid was washed twice with pure water and filtered twice. It was dried at 110 ° C for 24 hours to obtain a neutralized iron-containing titanium salt.

Next, 800 g of pure water was added to the iron-containing titanium salt aluminum neutralized product to prepare a slurry. In this slurry, an aqueous solution of iron chloride (Fe C 1 ₃ · H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.)), 100 mass when the neutralized titanium salt alkali in the slurry is converted to TiO ₂ The mixture was added in an amount of 0.05 mass parts as iron atoms, and stirred and mixed at 60 ° C for 1 hour to obtain a mixed solution. Next, this mixed solution was heated at 110 ° C. for 24 hours to evaporate and remove water to obtain a solid. The obtained solid was washed with pure water and filtered twice, and filtered. The subsequent solid matter was dried at 110 ° C. for 24 hours to obtain an iron-containing titanium salt neutralized product a 19. (Heat treatment)

The heat-treated product was obtained in the same manner as in Example 13 except that the iron-containing titanium salt aluminum strength neutralized product a 1 3 was used instead of the iron-containing titanium salt aluminum strength neutralized product a 19. b 1 9 was obtained. The heat-treated product b 19 has a specific surface area of 2700 m ² Zg, an anatase (1 0 1) peak half-width of 2 Θ = 1.43 ° by X-ray diffraction analysis, and an iron content of 0.07 It was mass%.

(Baking)

An iron-containing sulfur-introduced titanium oxide c 19 was obtained in the same manner as in Example 13 except that the heat-treated product b 19 was used instead of the heat-treated product b 13. Table 5 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c 19 and the measurement results of its photocatalytic performance. Table 5

[Example 20]

A round bottom flask equipped with a stirrer was charged with 1 000 g of pure water and then heated to 60 ° C. Titanium tetrachloride aqueous solution (titanium concentration: 6% by mass) 2 00 g and ammonia water (28%) diluted 5 times with pure water 2 05 7 g Over time, dripping and neutralization were performed. Next, in this slurry, an aqueous solution of iron chloride (Fe C 1 ₃ · H ₂ 0 (manufactured by Wako Pure Chemical Industries, Ltd.)) is used, and the titanium salt alkali neutralized product in the slurry is converted to TiO 2 1 It added so that it might be set to 0.07 mass part as an iron atom with respect to 00 mass part, 60 degreeC and stirring mixing were performed for 1 hour, and the liquid mixture was obtained. Next, this mixed solution was heated at 110 ° C. for 24 hours to evaporate and remove water to obtain a solid, and the obtained solid was washed twice with pure water and filtered twice. The solid was dried at 110 ° C. for 24 hours to obtain an iron-containing titanium salt aluminum neutralized product a20.

(Heat treatment)

'In the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a 20 was used instead of the iron-containing titanium salt alkali neutralized product a 1, and the heat-treated product b 20 was Obtained. The heat-treated product b 20 has a specific surface area of 300 m ² / g, an anatase (1 0 1) peak half-width of 2 0 = 1.45 ° by X-ray diffraction analysis, and an iron content of 0. 0 7% by mass.

(Baking)

An iron-containing sulfur-introduced titanium oxide c20 was obtained in the same manner as in Example 1 except that the heat-treated product b1 was used instead of the heat-treated product b1. Table 6 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c 20 and the measurement results of its photocatalytic performance.

[Example 2 1] A round bottom flask equipped with a stirrer was charged with 1 000 g of pure water and then heated to 60 ° C. Titanium tetrachloride aqueous solution (titanium concentration: 6% by mass) 20 00 g and ammonia water (28%) diluted 5 times with pure water 2057 g, both of which take 3 hours to neutralize Then, dripping and neutralization were performed. This liquid was heated at 110 ° C. for 24 hours to evaporate and remove water, and then the obtained solid was washed with pure water and filtered twice. The filtered powder was dried at 110 ° C. for 24 hours.

Next, an aqueous solution of iron chloride (Fe C 1 ₃ · H ₂ 0 (manufactured by Wako Pure Chemical Industries, Ltd.)) was added to a slurry in which 100 g of this powder was dispersed in 5000 g of pure water. was added Chikarari neutralized product such that 0.07 parts by iron atoms per 1 00 parts by weight when T i 0 ₂ converted, subjected to stirring and mixing 60 ° C, 1 hour, the mixture Obtained. The mixture is then heated to 1 10 ° C. for 24 hours to evaporate and remove water to obtain a solid, and the resulting solid is washed twice with pure water and filtered twice. Was dried at 110 ° C. for 24 hours to obtain an iron-containing titanium salt alkali neutralized product a 2 1.

(Heat treatment)

The same procedure as in Example 1 was conducted except that the iron-containing titanium salt alkali neutralized product a 2 1 was used instead of the iron-containing titanium salt alkali neutralized product a 1, and the heat-treated product b 2 1 was used. Obtained. The specific surface area of the heat-treated product b 2 1 is 300 m ² / g, and the half width of the (10 1) peak of anatase by X-ray diffraction analysis is 20 = 1.42. The iron content was 0.07% by mass.

(Baking)

An iron-containing sulfur-introduced titanium oxide c 2 1 was obtained in the same manner as in Example 1 except that the heat-treated product b 2 1 was used instead of the heat-treated product b 1. Table 6 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c 21 and the photocatalytic performance measurement results. Table 6

Industrial applicability

According to the present invention, titanium oxide having high photocatalytic activity with visible light can be produced.

Claims

The scope of the claims

1. having a firing step of firing a mixture of a metal-containing raw material titanium oxide and a sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide;

The metal content in the metal-containing raw material titanium oxide is 0.3 to 0.15 parts by mass as metal atoms with respect to 100 parts by mass of the metal-containing raw material titanium oxide when converted to Ti 0 ₂ thing,

The manufacturing method of the metal containing sulfur introduction | transduction titanium oxide characterized by these.

2. A step of preparing a calcined raw material mixture to obtain a mixture of a metal-containing titanium salt hydrolyzed / alkaline neutralized product and a sulfur compound, and a mixture of the metal-containing titanium salt hydrolyzed neutral potassium neutralized product and the sulfur compound. Firing step to obtain metal-containing sulfur-introduced titanium oxide, and

The firing raw material mixture preparation step includes hydrolysis or alkali neutralization of a titanium salt to prepare a slurry containing a titanium salt hydrolysis-no-alkali neutralized product, an alkali neutralization treatment, and the titanium salt hydrolysis Z-al force. A metal compound is added to the slurry containing the re-neutralized product and stirred to obtain a metal-containing titanium salt hydrolyzed Z-al force re-neutralized product and a metal compound stirring and mixing process.

The amount of addition of the metal compound with the metal compound stirred mixing process is, in respect to the titanium salt hydrolysis alkali neutralization product 1 0 0 parts by weight when T i 0 ₂ conversion calculation, 0.0 3 metal atom 0.1 5 parts by mass, and mixing the sulfur compound between before the hydrolysis and Z-force neutralization treatment and after the metal compound stirring and mixing treatment, The manufacturing method of the metal containing sulfur introduction | transduction titanium oxide characterized by these.

3. a baking raw material mixture preparation step for obtaining a mixture of a metal-containing titanium salt hydrolyzed / alkali neutralized heat-treated product and a sulfur compound; Calcining a mixture with a yellow compound to obtain a metal-containing sulfur-introduced titanium oxide, and

The calcination raw material mixture preparation step includes hydrolyzing Z alkali neutralization treatment, wherein the titanium salt is hydrolyzed or neutralized to prepare a slurry containing the titanium salt hydrolyzed z al force neutralized product. Titanium salt hydrolysis Z metal alkali added to the slurry containing a neutralized product, stirring to obtain a metal-containing titanium salt hydrolyzed / Al force neutralized product, and the metal-containing titanium Heat treatment of the neutralized alkali salt product to obtain a heat-treated product, and

The amount of addition of the metal compound with the metal compound stirred mixing process is, in respect to the titanium salt hydrolysis alkali neutralization product 1 0 0 parts by weight when the T1 〇 ₂ conversion calculation, 0.0 3 metal atom 0.15 parts by mass, and mixing the sulfur compound between before the hydrolysis and Z neutralization treatment and after the heat treatment,

A process for producing a metal-containing sulfur-introduced titanium oxide characterized by

4. Metal-containing titanium salt hydrolyzed Z-alkali neutralized product and sulfur compound to obtain a mixture of the calcined raw material, and a mixture of the metal-containing titanium salt hydrolyzed alkali neutralized product and the sulfur compound Firing step to obtain metal-containing sulfur-introduced titanium oxide, and

The amount of the metal compound to be present in the hydrolysis Z-al force neutralization treatment is from 0.03 to 0.1 as a metal atom with respect to 100 parts by mass of the titanium salt when converted to τ i O ₂ . 5 parts by mass

And before the hydrolysis and alkali neutralization treatment, A method for producing a metal-containing sulfur-introduced titanium oxide, comprising mixing a sulfur compound before and after performing a force neutralization treatment.

5. Hydrolysis of metal-containing titanium salt A calcined raw material mixture preparation step for obtaining a mixture of a heat-treated product of alkali neutralized product and a sulfur compound, and a mixture of the heat-treated product and the sulfur compound are calcined, A sintering step for obtaining a metal-containing sulfur-introduced titanium oxide,

The firing raw material mixture preparation step includes hydrolyzing or neutralizing titanium salt in the presence of a metal compound to obtain a titanium salt hydrolyzed Z-alloy neutralized product. A heat treatment to obtain a heat-treated product by heat-treating the metal-containing titanium salt hydrolyzed / alkali neutralized product,

0 The amount of the metal compound be present in the titanium salt hydrolysis / Al Chikarari neutralization process, with respect to the titanium salt 1 0 0 parts by weight when T io ₂ terms, as the metal atom. 0 3-0 1 The amount is 5 parts by mass,

And mixing the sulfur compound between before the hydrolysis Z alkali neutralization treatment and after the heat treatment,

6. Metal-containing titanium salt hydrolysis Firing raw material mixture preparation step for obtaining a mixture of alkali neutralized product and sulfur compound, and metal-containing titanium salt hydrolyzed alkali neutralized product and sulfur compound mixture are calcined. And a metal-containing sulfur-introduced titanium oxide obtaining step,

The calcining raw material mixture preparation step comprises hydrolyzing or neutralizing the titanium salt in the presence of a metal compound to prepare a metal-containing titanium salt hydrolyzed neutralized product-containing slurry. Metal neutralization treatment and metal-containing titanium salt hydrolyzed alkali neutralized product-containing slurry Add a metal compound and stir to obtain a metal-containing titanium salt hydrolyzed neutralized product And a metal compound stirring and mixing process,

The total amount of the metal compound to be present in the hydrolysis-no-alkali neutralization treatment and the metal compound to be added in the metal compound stirring and mixing treatment is 100 parts by mass of titanium salt when converted to Tio _2. The amount is 0.03 to 0.15 parts by mass as an atom,

A method for producing a metal-containing sulfur-introduced titanium oxide, comprising mixing a sulfur compound before performing the hydrolysis-no-alkali neutralization treatment and after performing the metal compound stirring and mixing treatment.

7. Hydrolysis of metal-containing titanium salt Z-alkaline neutralized heat-treated product and sulfur compound to obtain a mixture of a calcined raw material mixture, a mixture of the heat-treated product and the sulfur compound, Calcining to obtain a metal-containing sulfur-introduced titanium oxide, and

The firing raw material mixture preparation step includes hydrolyzing the titanium salt in the presence of a metal compound or neutralizing the aluminum salt to prepare a metal-containing titanium salt hydrolyzed / alteric acid neutralized material-containing slurry. Decomposition Z alkali neutralization treatment and metal-containing titanium salt hydrolyzed neutralized neutralized product-containing slurry Add metal compound and stir to obtain metal-containing titanium salt hydrolyzed Z alkali neutralized product Metal compound stirrer And a heat treatment for obtaining a heat-treated product by subjecting the metal-containing titanium salt hydrolyzed Z-alkaline neutral product to a heat treatment, wherein the metal is present in the hydrolysis-no-alkali neutralization treatment. the total amount of the compound及Pi the metal compound stirred mixture is added in the process the metal compound, relative to titanium salt 1 0 0 parts by weight when T i O ₂ converted, 0 as the metal atom. 0 3 to 0.1 5 parts by mass

8. After performing the firing step, further performing a metal reintroduction step of introducing metal into the metal-containing sulfur-introduced titanium oxide obtained in the calcining step to obtain a metal-containing sulfur-introduced titanium oxide. The method for producing a metal-containing sulfur-introduced titanium oxide according to any one of claims 1 to 7.

9. After performing the metal reintroduction step, the metal-containing sulfur-introduced titanium oxide obtained in the metal reintroduction step and the sulfur compound are mixed, calcined, sulfur is introduced, and the metal-containing sulfur 9. The method for producing a metal-containing sulfur-introduced titanium oxide according to claim 8, wherein a sulfur reintroduction step for obtaining the introduced titanium oxide is performed, or the metal reintroduction step and the sulfur reintroduction step are repeated.

10. The method for producing a metal-containing sulfur-introduced titanium oxide according to claim 3, wherein the heat treatment temperature of the heat treatment is 200 to 350 ° C. 10.

1 1. The method for producing a metal-containing sulfur-introduced titanium oxide according to any one of claims 2 to 7, wherein the titanium salt is titanium tetrachloride.

1 2. The method for producing a metal-containing sulfur-introduced titanium oxide according to any one of claims 2 to 11, wherein the metal compound is a metal compound containing an iron element.

1 3. Iron content of the metal-containing raw material titanium oxide, the titanium salt hydrolyzed / alkali neutralized product or the heat-treated product is 0.03 to 0.15% by mass, and the crystal structure is mainly anatase type The specific surface area is 150 to 400 m ² Z g, and the half width of the (1 0 1) peak of anatase by X-ray diffraction analysis is 2 Θ = 1 · 2 to 1.5 ° Item 1 A method for producing a metal-containing sulfur-introduced titanium oxide according to any one of Items 1 to 12.

1 4. Metal content is 0.03 ~ 0.15 mass%, sulfur content is 0.02 ~ 0.1 mass%, specific surface area is 60 ~: I 20 m ² Z g, crystal structure The main component is an anatase type titanium oxide, and the sulfur atom in the titanium oxide is A metal-containing sulfur-introduced titanium oxide, which is introduced into a titanium oxide titanium site and contains metal inside the titanium oxide.

15. The metal-containing sulfur according to claim 14, wherein the ratio of the amount of metal present in the titanium oxide to the total amount of metal contained in the titanium oxide is 15% or more and 90% or less. Introduced titanium oxide.

16. The metal-containing sulfur-introduced titanium oxide according to any one of claims 14 and 15, wherein the metal is iron.