CN100582323C - Particulate titanium oxide, method and apparatus for manufacturing the same, and treatment methods using such titanium oxide - Google Patents

Abstract

Titanium oxide grains of large specific area and high crystallinity with reduced internal defects, whose high photocatalytic activity as a photocatalyst is promising; and titanium oxide grains which even when heated at high temperature, exhibits low tendency of transformation to rutile crystal structure and exhibits low rate of sintering. As titanium oxide grains for composing a photocatalyst, use is made of those of the shape of a boxy polyhedron. The polyhedron constituting the titanium oxide grains is composed of one or more titanium oxide single-crystal polyhedrons. The crystallinity can be enhanced by causing the flatness ratio of single-crystal polyhedrons to fall within the range of 0.33 to 3.0. It is preferred that the polyhedron be a hexa to decahedron. The rutile transformation ratio R (700 to 24) is to be 7.5% or less while the rutile transformation ratio R (500 to 24) is to be 2.0% or less. Titanium oxide grains of the above configuration are produced through a process comprising feeding titanium tetrachloride vapor and oxygen into a synthetic tube of quartz glass and heating them from the exterior of the synthetic tube by means of an oxyhydrogen flame burner so as to effect thermal oxidation.

Description

Titanium particles and manufacture method thereof, manufacturing installation and the treatment process of using this titanium oxide

Background technology

The present invention relates to be used for Titanium particles and manufacture method, manufacturing installation and the treatment process of photocatalyst etc., is by Titanium particles being made the particle of new shape, the photocatalytic activity in the time of can improving as photocatalyst greatly.

The photocatalyst of being made up of Titanium particles is well-known.The light-catalyzed reaction of Titanium particles is the chemical reaction that causes on the surface of Titanium particles, and the chemical substance of decomposing object is to begin its reaction from the surface that is adsorbed on Titanium particles.For this reason, the particle diameter of Titanium particles is more little shows high photocatalytic activity more.

In Japanese kokai publication hei 11-267519 communique, Japanese kokai publication hei 08-164334 communique, Japanese kokai publication hei 07-303835 communique, in the disclosed invention formerly, for this reason, wish the particle diameter miniaturization of Titanium particles is arrived the Titanium particles of number nm level., the Titanium particles for so several nm levels when making slurries, has problems on dispersiveness sometimes.

In addition, with commercially available Titanium particles, its particle shape all is a spheric, exists the specific surface area of per unit weight little, reactive inadequate problem as photocatalyst.

, the photocatalysis that it is found that titanium oxide be by with rayed on Titanium particles, excite the electronics that constitutes titanium oxide, produce electronics (e ^-) or hole (h ⁺), produce oxidizing power or reducing power thus.

, people know that also the electronics that has been excited or the part in hole carry out combination again with the defective of titanium oxide inside as recombination center, have so just reduced photocatalytic activity.

Therefore, wish to obtain the few Titanium particles of subsurface defect, in the TOHKEMY 2001-276615 communique in the disclosed invention formerly, proposed to show the Detitanium-ore-type monocrystalline of the big particle diameter of high catalytic activity.

, in manufacture method in the past, can not obtain the little Titanium particles of crystallinity height and particle diameter,, can only adopt the increasing particle diameter, sacrifice method for specific area in order to obtain the high particle of the few crystallinity of subsurface defect.For this reason, disclosed Titanium particles in the above-mentioned TOHKEMY 2001-276615 communique, few to the adsorptive capacity of the chemical substance of decomposing object, be disadvantageous as photocatalyst.

In addition, in Japanese kokai publication hei 10-081517 communique, Japanese kokai publication hei 10-095617 communique, proposed purposes, except spheroidal particle, also disclose the Titanium particles of needle-like, dendroid, starfish shape, shape such as tabular as pigment, masking material etc., for the Titanium particles of these shapes, break away from the original crystal form of titanium oxide and form, its crystallinity reduces greatly, becomes near amorphous structure, certainly exists a lot of problem of subsurface defect.

Therefore, do not know still that so far the specific surface area of unit weight is big, crystallinity is high and subsurface defect is few, suitable Titanium particles as photocatalyst.

In addition, as the manufacture method of Titanium particles, known have disclosed liquid phase synthesizing method of Japanese kokai publication hei 05-163022 communique and a disclosed gas phase synthesis method of TOHKEMY 2001-276615 communique., for these manufacture method, the specific surface area that can not synthesize above-mentioned unit weight is big, crystallinity is high and the few and suitable Titanium particles as photocatalyst of subsurface defect.

In addition, when making Titanium particles, Titanium particles need be carried and be held on the base material, it is contacted efficiently with the decomposition object as photocatalyst performance actual functional capability.As this Titanium particles is uploaded the method for holding to base material, as Japanese kokai publication hei 07-002522 communique is disclosed, the oriented method that contains the base material direct sintering of organic and/or inorganic materials.This method is that low melting glass etc. is used as jointing material, is heated to that this jointing material is softening, the fused temperature, is heated to usually about 700 ℃ and carries out sintering.

In addition, as No. 3279755 communiques of Japanese Patent are disclosed, there is organic system jointing materials such as using synthetic resins to be fixed on the method for base material.For this method, need select for use as the organic system jointing material to be difficult to oxidized titanium and to decompose, and the heating of a few hours through about 500 ℃ reaches solidified synthetic resins.

, for holding method these years since any all be the temperature that is heated to about 500 ℃～700 ℃, so variation has taken place in the crystalline texture of titanium oxide.

The titanium oxide that uses as photocatalyst is the material with Detitanium-ore-type crystalline texture, and this is because the photocatalytic activity cause better than rutile-type, the brookite type of other crystalline texture of this anatase-type titanium oxide.

, known to usually be, carrying when holding the Titanium particles of Detitanium-ore-type crystalline texture that as mentioned above, when being heated to 500 ℃～700 ℃ left and right sides, crystalline texture changes rutile-type into, photocatalytic activity reduces.

In addition, when carrying out this heating, the mutual sintering of Titanium particles, its surface-area reduces, because like this, photocatalytic activity also can reduce.

Therefore, problem of the present invention is to provide Titanium particles and manufacture method and manufacturing installation, and this Titanium particles can be expected high photocatalytic activity as photocatalyst, and specific surface area is big, and crystallinity height and subsurface defect are few.In addition, also provide Titanium particles, even this Titanium particles is heated to the also rare transformation to rutile-type crystalline texture of high temperature, in addition, even heating also is difficult to carry out sintering.And then, the method for utilizing of the decomposition method that uses such Titanium particles to handle objectionable impurities efficiently etc. also is provided.

Summary of the invention

In order to solve such problem, following scheme is proposed.

The 1st kind of embodiment of the present invention is Titanium particles, and its particle diameter is at 1nm～500nm, is the polyhedron of the box shape that is made of 1 or more a plurality of monocrystalline polyhedron or is that the polyhedron of box shape forms basically.Above-mentioned be basically the polyhedron of box shape comprise polyhedral angle have slightly the shape of disappearance polyhedron, have the polyhedron of circular shape and have concavo-convex etc. and make the polyhedron that shape changes a little.

The 2nd kind of embodiment of the present invention be, the Titanium particles of the 1st kind of embodiment, and the polyhedral flat ratio of its monocrystalline is 0.33～3.0.

The 3rd kind of embodiment of the present invention is that the Titanium particles of the 1st kind of embodiment, polyhedron wherein are any 1 kinds in 6 body～10 bodies.

The 4th kind of embodiment of the present invention be, the Titanium particles of any embodiment in the 1st～the 3rd, wherein, rutile number turnover R (700-24) be 7.5% or still less, rutile number turnover R (500-24) is 2.0% or still less.

The 5th kind of embodiment of the present invention be, the Titanium particles of any embodiment in the 1st～the 4th, and its particle diameter is 100～500nm.

The 6th kind of embodiment of the present invention be, the Titanium particles of any embodiment in the 1st～the 4th, and its particle diameter is 10～50nm.

The 7th kind of embodiment of the present invention be, the Titanium particles of any embodiment in the 1st～the 6th, and wherein, specific surface area is 3～40m ²/ g adds 5 milliliters of 5 volume % aqueous acetic acids and Titanium particles 50mg in the encloses container of internal diameter 15mm, under the state that suspends with 15mW/cm ²The UV-light of illumination irradiation 365nm, the amount of carbon dioxide that produced in its per 1 hour is positioned at that (x is a specific surface area, and unit is m with y=0.8x ²/ g; Y is the carbonic acid gas generating capacity, and unit is μ mol/hr.) upper area of line of expression.

The 8th kind of embodiment of the present invention be, the Titanium particles of any embodiment wherein, is doped with silicon in the 1st～the 6th, and specific surface area is 3～40m ²/ g adds 5 milliliters of 5 volume % aqueous acetic acids and Titanium particles 50mg in the encloses container of internal diameter 15mm, under the state that suspends with 15mW/cm ²The UV-light of illumination irradiation 365nm, the amount of carbon dioxide that produced in its per 1 hour is positioned at that (x is a specific surface area, and unit is m with y=0.8x ²/ g; Y is the carbon dioxide generating amount, and unit is μ mol/hr.) upper area of line of expression.

The 9th kind of embodiment of the present invention is the Titanium particles of the 7th kind of embodiment, wherein arbitrary element in Doping Phosphorus, nitrogen, silicon, the boron.

The 10th kind of embodiment of the present invention is a kind of titanium dioxide powder, is a plurality of titanium dioxide powders of having gathered of the Titanium particles of any embodiment in the 1st～the 8th, form this powder Titanium particles 80% or higher be the Detitanium-ore-type crystallization.

The 11st kind of embodiment of the present invention be, the titanium dioxide powder of the 10th kind of embodiment, and wherein the Detitanium-ore-type crystallization accounts for 90% or more.

The 12nd kind of manufacture method that embodiment is the Titanium particles of the 1st kind of embodiment of the present invention is characterized in that, supplies with titanium compound steam and oxygen in composite tube, from the composite tube indirect heating.

The 13rd kind of embodiment of the present invention is that the manufacture method of the Titanium particles of the 12nd kind of embodiment is characterized in that, uses oxyhydrogen flame lamp (plain scorching バ one Na of sour water) as heating source.

The 14th kind of embodiment of the present invention be, the 12nd or the manufacture method of the Titanium particles of the 13rd kind of embodiment, it is characterized in that rotating composite tube.

The 15th kind of embodiment of the present invention is that the manufacture method of the Titanium particles of the 12nd kind of embodiment is characterized in that in composite tube inside the columnar part that the mixed gas of titanium compound steam and oxygen is imported to the inwall side of composite tube being set, from indirect heating.

The 16th kind of embodiment of the present invention is that the manufacture method of the Titanium particles of the 15th kind of embodiment is characterized in that the interval of composite tube and columnar part is made 0.1～10mm.

The 17th kind of embodiment of the present invention is, the Titanium particles manufacture method of any embodiment in the 12nd～the 16th, it is characterized in that, the recovery method of the Titanium particles that generates is to utilize thermophoresis (サ one モ Off ォ レ シ ス) effect, and reclaim the downstream part that makes Titanium particles be deposited in composite tube.

The 18th kind of embodiment of the present invention be, the Titanium particles manufacture method of any embodiment is characterized in that the recovery method of the Titanium particles of generation is to use the method for the bag filter that is arranged on the composite tube downstream side in the 12nd～the 16th.

The 19th kind of embodiment of the present invention be, the Titanium particles manufacture method of any embodiment in the 12nd～the 16th, and the temperature that it is characterized in that the composite tube when synthetic is at 850～1500 ℃.

The 20th kind of manufacturing installation that embodiment is the Titanium particles of the 1st kind of embodiment of the present invention, it has composite tube, the heating source that composite tube is heated from the outside, make composite tube around the rotary driving part of its rotation with the raw material supplying portion of titanium compound steam and oxygen is provided in composite tube.

The 21st kind of embodiment of the present invention is that the manufacturing installation of the Titanium particles of the 20th kind of embodiment wherein, has the bag filter that the Titanium particles that generates in the composite tube is reclaimed.

The 22nd kind of embodiment of the present invention be, the 20th or the manufacturing installation of the Titanium particles of the 21st kind of embodiment, wherein, the columnar part that the mixed gas of titanium compound steam and oxygen is imported to composite tube inwall side is set in composite tube inside.

The 23rd kind of embodiment of the present invention is the photocatalyst that contains the Titanium particles of any embodiment in the 1st～the 8th.

The 24th kind of embodiment of the present invention is to contain the 10th or the photocatalyst of the titanium dioxide powder of the 11st kind of embodiment.

The 25th kind of embodiment of the present invention is the coating that contains the Titanium particles of any embodiment in the 1st～the 8th.

The 26th kind of embodiment of the present invention is to contain the 10th or the coating of the titanium dioxide powder of the 11st kind of embodiment.

The 27th kind of embodiment of the present invention is photocatalysis apparatus, wherein, has that Titanium particles with any embodiment in the 1st～the 8th carries the light-catalyzed reaction body that is held in the surface and the light source of irradiates light on this light-catalyzed reaction body.

The 28th kind of embodiment of the present invention is the method for decomposing harmful substances, wherein, uses the 10th or the titanium dioxide powder of the 11st kind of embodiment.

The 29th kind of embodiment of the present invention be, the method for the decomposing harmful substances of the 28th kind of embodiment, wherein, after processed object being contacted with Titanium particles decompose, with strainer separation of oxygenated titanium particle.

The 30th kind of method that embodiment is the decomposing harmful substances of the 29th kind of embodiment of the present invention, wherein, strainer is a glass fibre system, perforate is 2.0 μ m or bigger.

The 31st kind of embodiment of the present invention is deodour method, wherein, uses the 22nd or the photocatalyst of the 24th kind of embodiment.

The 32nd kind of embodiment of the present invention is method for disinfection, wherein, uses the 23rd or the photocatalyst of the 24th kind of embodiment.

The 33rd kind of embodiment of the present invention is the method for decomposing harmful substances, wherein, uses the 23rd or the photocatalyst of the 24th kind of embodiment.

Titanium particles of the present invention, owing to be the polyhedron formation of box shape, so the crystallinity height, subsurface defect and few surface defects, in addition, the specific surface area of per unit weight is big.Particularly preferably be the polyhedral flat ratio of crystallization and be 0.33～3.0 scope, its specific surface area is bigger, and crystallinity is also high.In addition, even heating, also rare from the transformation of highly active Detitanium-ore-type crystalline texture to SA rutile-type crystalline texture, sintering also is difficult to carry out.

For this reason, contain the photocatalyst of this Titanium particles, because the ratio of bonded again in the electronics that is excited, hole reduces, in addition, the adsorption area that decomposes the object material becomes big, so have high photocatalytic activity.In addition, the heat treated that is subjected to when being held in base material by Titanium particles is carried does not reduce photocatalytic activity yet.

In addition, the manufacture method of Titanium particles of the present invention and manufacturing installation can be made the Titanium particles of the polyhedron formation of above-mentioned box shape efficiently.

And then photocatalyst of the present invention, coating, photocatalysis apparatus have utilized above-mentioned titanium dioxide powder, so the decomposition efficiency height of objectionable impurities.In addition, deodorising effect, sterilization effect are also high.

Description of drawings

Fig. 1 is the approximate three-dimensional map of the example of the polyhedral Titanium particles of pattern ground expression box shape of the present invention.

Fig. 2 is the approximate three-dimensional map that the expression of pattern ground constitutes the polyhedral example of crystallization of Titanium particles of the present invention.

Fig. 3 is the chart of the relation of expression surface-area of Titanium particles of the present invention and acetic acid decomposition amount.

Fig. 4 is the summary pie graph of an example of the manufacturing installation of expression Titanium particles of the present invention.

Fig. 5 is the summary pie graph of another example of the manufacturing installation of expression Titanium particles of the present invention.

Fig. 6 is the summary pie graph of wanting portion of another example of the manufacturing installation of expression Titanium particles of the present invention.

Fig. 7 is the summary pie graph of an example of the device of the expression method that is used for decomposing harmful substances of the present invention.

Fig. 8 is the electron micrograph that shows the shape of the Titanium particles that is obtained by embodiment 1.

Fig. 9 is the result's of expression embodiment 2 a chart.

Figure 10 is the electron micrograph that shows the Titanium particles after the heating in the comparative example 3.

Figure 11 is the chart of the result among the expression embodiment 5.

Embodiment

(Titanium particles)

Below, explain Titanium particles of the present invention.

Fig. 1 is the mode chart of an example of expression Titanium particles of the present invention.The Titanium particles 1 of this example is the box shape, and is 10 bodies.

The present invention's said " polyhedron of box shape " is meant that the crystal plane that can infer tetragonal titanium oxide is reflected in the polyhedron on the profile of particle or is the polyhedron of box shape basically.

In addition, polyhedral Titanium particles of this box shape is to be made of the polyhedron of one or more titanium oxide monocrystalline (monocrystalline polyhedron) set, is varied to from 6 bodies to polyhedron-shaped more than hexad according to polyhedral set number of monocrystalline.For the present invention, these are included in the polyhedron of box shape of the present invention fully.In addition, even also there is the polyhedron that is no less than 6 bodies of 10 bodies for example etc. in the monocrystalline polyhedron, these are also included within the polyhedron of the present invention.

In these polyhedrons, 10 bodies as shown in Figure 1 most preferably.

In addition, when being example with 6 bodies as the polyhedron of box shape, the angle of 6 bodies has the shape of disappearance slightly or has circular shape a little, be originally completely 6 bodies but because heat or mechanical deformation, these also are counted as in 6 bodies that are included in here is the polyhedron of box shape basically.

And then, for example produce defective when being in crystalline growth, have concavo-convex etc. and make what shape changed a little in the part of 10 bodies, as long as have effect described later, all be included in 10 bodies of the present invention.As this polyhedron, 6 body～10 bodies are imbued with crystallinity, and are more better than the polyhedron of the more multiaspect number with other.

Generally, the crystal form of titanium oxide has 3 kinds of Detitanium-ore-types, rutile-type, brookite type, but polyhedral Titanium particles for box shape of the present invention, this Titanium particles is the pulverulence of a plurality of set, constitute this powder particle 80% or more, preferably 90% or mostly are Detitanium-ore-types, 20% or still less, preferably 10% or still less be to constitute by the rutile-type crystallization.

In addition, Detitanium-ore-type and rutile-type all are to belong to quadratic crystal, because a axle and the b axle of quadratic crystal are of equal value, so even also can determine the original a axle of titanium oxide, b axle and c axle in the polyhedron beyond 6 bodies.

Fig. 2 is the example of the monocrystalline polyhedron 2 of expression polyhedral Titanium particles of constituting box shape of the present invention.Will be from the center of this monocrystalline polyhedron 2 to the distance of face that intersects vertically with a axle or rib as X, the distance that will arrive the face that intersects vertically with the c axle or rib is as Z, when the polyhedral flat ratio H of monocrystalline is defined as H=X/Z, flat ratio H is the Titanium particles that 0.33～3.0, preferably 0.6～1.67 monocrystalline polyhedron constitutes, therefore the photocatalytic activity height is preferred.

In addition, when polyhedron is made up of a plurality of monocrystalline polyhedrons, can think to be divided into each monocrystalline polyhedron that similarly calculate its flat ratio for each monocrystalline polyhedron, the mean value of getting them is just passable.In addition, the practical measurement of this flat ratio is that the Titanium particles that has synthesized is observed with scanning electron microscope as object, measures this polyhedral size, calculates the value of X and Z, can calculate flat ratio from these.

In addition, the size of polyhedral Titanium particles of box shape of the present invention, median size makes 1～500nm, preferably 1～200nm, even more preferably 1～90nm, more preferably 10～70nm, 10～50nm preferably further, if when representing with size distribution, 85% the particle diameter that accounts for all particles is 10nm～100nm, preferably 10nm～40nm.

In addition, the median size of Titanium particles can be according to the suitable particle size range of use decision, from suitable selection of scope of 1～500nm.

In addition, Titanium particles of the present invention is very little to the transformation of rutile-type crystalline texture because of heating.In the present invention, use the transformation of rutile number turnover R (700-24) and rutile number turnover R (500-24) evaluation to rutile-type.

Said rutile number turnover R (700-24) is meant for the Titanium particles that is heated 24 hours under 700 ℃, the ratio of the Titanium particles of the Detitanium-ore-type crystalline texture before being heated is as A (preceding) %, with the ratio of Titanium particles of the Detitanium-ore-type crystalline texture after the heating as A (back) %

Define with [A (preceding)-A (back)]/A (preceding) * 100.

Said rutile number turnover R (500-24) is meant that with Titanium particles at 500 ℃ of following heating number turnovers in the time of 24 hours, other similarly defines with above-mentioned.

The ratio of the Titanium particles of Detitanium-ore-type crystalline texture is measured from its peak intensity with the X-ray diffraction method.

For Titanium particles of the present invention, rutile number turnover R (700-24) be 7.5% or still less, preferably 5.0% or still less, and rutile number turnover R (500-24) be 2.0% or still less, preferably 1.0% or still less.

In addition, Titanium particles of the present invention can suppress the sintering that causes because of heating significantly, can prevent because heat treated causes the reduction of its specific surface area.This can think because the effect that the crystallinity height of Titanium particles causes.

In such Titanium particles, because this polyhedron is to be made of 1 or more a plurality of monocrystalline polyhedrons, so excellent in crystallinity, subsurface defect and few surface defects.In addition, as shown in Figure 1, because particle shape is box or is box basically that so compare with spheric Titanium particles in the past, the specific surface area of per unit weight is big.

Particularly for flat ratio be 0.33～3.0, especially in 0.6～1.6 scope, can and then become the high material of crystallinity.For this reason, contain the photocatalyst of this Titanium particles,, can bring into play high photocatalytic activity with comparison in the past.

In addition, in such Titanium particles, because the rutile number turnover is little, minimum by heating to the transformation of rutile-type crystalline texture, and suppressed the mutual sintering of particle, so even, do not lose high catalytic activity by this Titanium particles being carried the heat treated when being held in base material yet.

In addition, the surface area ratio of Titanium particles of the present invention Titanium particles in the past is little, and has high crystalline, so have high photocatalytic activity.

That is, the specific surface area of measuring with the BET method is 3～40m ²The scope of/g adds 5 volume % aqueous acetic acid 5ml and Titanium particles 50mg in the encloses container of internal diameter 15mm, under the state that suspends with 15mW/cm ²The UV-light of illumination irradiation 365nm, the amount of carbon dioxide that produced in per 1 hour is positioned at as shown in Figure 3 y=0.8x, and (x is a specific surface area, and unit is m ²/ g; Y is the carbon dioxide generating amount, and unit is μ mol/hr.) the upper area of line, preferably have 40 μ mol or higher photocatalytic activity.In addition, to the Titanium particles of doped silicon, under identical test conditions, amount of carbon dioxide is positioned at as shown in Figure 3 y=0.8x, and (x is a specific surface area, and y is the carbon dioxide generating amount.) the upper area of line, preferably have the photocatalytic activity of 30 μ mol～45 μ mol.

For commercially available in the past Titanium particles, in order to obtain sufficient photocatalytic activity, its surface-area makes 50m ²/ g or more, but its manufacturing is difficult.Relative therewith, for Titanium particles of the present invention,, also demonstrate high catalytic activity although its surface-area is little, it is easy to manufacture.

In order to demarcate the acetic acid that above-mentioned photocatalytic activity uses as matrix, owing to resolving into carbonic acid gas, by quantitatively can estimate the degree of catalytic activity to the amount of carbon dioxide that produces by photocatalysis.As mentioned above, in the encloses container of internal diameter 15mm, add 5 volume % aqueous acetic acid 5ml and Titanium particles 50mg, under the state that suspends with 15mW/cm ²The UV-light of illumination irradiation 365nm, when comparing with the amount of carbon dioxide of generation in per 1 hour, as shown in Figure 3, the Titanium particles of commercially available product in the past and Titanium particles of the present invention have very big difference on photocatalytic activity.

Under this experiment condition, because the uviolizing area is certain, so the light quantity that excites that Titanium particles is subjected to is certain, decomposition amount depends on decomposing the sorptive power of object.Therefore, for the characteristic of in the past Titanium particles, the generation of carbonic acid gas is in direct ratio with the specific surface area of Titanium particles.

Titanium particles in the past, under current experiment condition, X-axis is specific surface area, when Y-axis is the carbon dioxide generating amount, on the line of y=0.8x or below mark and draw characteristic value.Show by this result,, can only make the characteristic particle that is positioned at this line below for method for making in the past.

, in phase diagram 3,, obtain being positioned at photocatalysis characteristic, at specific surface area 3～40m away from the top of this line for the Titanium particles of representing with sample A～D of the present invention ²In the scope of/g, the generation of per 1 hour carbonic acid gas is 40 μ mol or more for sample A～C.

Show that thus Titanium particles of the present invention has highlight catalytic active and high acetic acid degrading activity, this be not since due to the size of in the past specific surface area the difference of sorptive power cause, but other reasons, promptly since the reason of high crystalline cause.

In addition, Titanium particles of the present invention, other the element of also can mixing as required, the element of phosphorus, nitrogen, silicon, boron etc. for example carries out the adjustment of photocatalytic activity or the photocatalytic activity excitation wavelength feature change to long wavelength side skew etc.For example, among Fig. 3, the Titanium particles as sample D represents adds the silicon as hotchpotch, reduces the photocatalytic activity of Titanium particles.

(manufacturing of Titanium particles)

Below, at length describe for the manufacture method and the manufacturing installation of Titanium particles of the present invention.

The manufacturing of polyhedral Titanium particles of box shape of the present invention is by supplying with titanium compound steam and oxygen in composite tube, carrying out from the composite tube indirect heating basically.

Fig. 4 is an example of the manufacturing installation of expression Titanium particles of the present invention, symbol 11 expression composite tubes among the figure.This composite tube 11 is by the stable material of heat, the chemical property pipe that form, internal diameter 10～200mm of silica glass, aluminum oxide etc.These composite tube internal diameters are as if not enough 10mm, and the flow velocity of the raw material in composite tube 11 accelerates, and reaction efficiency is low; If when surpassing 200mm, it is big that the radial temperature distribution of composite tube 11 becomes, and it is big that the size distribution of Titanium particles becomes.

This composite tube 11 is fixed on the glass rotating disk that its two ends are not illustrated, and rotates with the rotating speed about 20～70rpm.In addition, below composite tube 11, configuration oxyhydrogen flame lamp 12 can be from indirect heating composite tube 11.This oxyhydrogen flame lamp 12 can be 1 or more, normally with 4～12 side by side configurations, but preferably with composite tube 11 even heating, size distribution is diminished.

In addition, pine for adding, preferably control the interval etc. of size, composite tube 11 and the oxyhydrogen flame lamp 12 of flame with this oxyhydrogen flame lamp 12 so that the periphery of composite tube 11 1/1 or manyly contact and be heated with flame, can carry out even heating thus.

In addition, symbol 13 expression bubblers, the inside of this bubbler 13 is full of the titanium compound liquid of titanium tetrachloride, titanium sulfate etc., is blown into (bubbling) the titanium compound liquid from managing 14 gases of supplying with such as argon gas, makes the gasification of titanium compound liquid.The temperature of the titanium compound liquid of this moment for example for titanium tetrachloride, from the size of vapour pressure, is 60 ℃ or higher.In order to make the titanium compound steam gasified not liquefy, need through being incubated the temperature of bubbler 13 or higher temperature, for example for titanium tetrachloride,, be fed to its inside from an end of composite tube 11 via the pipe arrangement 15 that is incubated 85 ℃ or higher temperature.

In addition, at an end of composite tube 11 by managing 16 oxygen of sending into from the oxygen supply source of not shown oxygen bottle etc.

At an end of the other end pipe connecting 17 of composite tube 11, the other end of this pipe 17 connects bag filter 18, is fed to bag filter 18 from the exhaust of composite tube 11.

This bag filter 18 is used for being synthesized in composite tube 11, along with part or all of the effusive Titanium particles of exhaust gas captures, can use the pressurized gas that has with air, nitrogen etc. to impact for strainer and remove plug-hole Titanium particles mechanism and mechanically shoot down the equipment of the mechanism of plug-hole thing.

Exhaust from bag filter 18 is vented to outside the system by not shown gas barrier.

Use this device explanation to make the method for Titanium particles.

At first, to import in the composite tube 11 of rotation from the titanium compound steam of bubbler 13 with from the oxygen in oxygen supply source, with 12 heating of oxyhydrogen flame lamp, the titanium compound to titanium tetrachloride etc. composite tube 11 in carries out heated oxide, synthesizes Titanium particles from the outside.

The synthesis temperature of the conversion zone in the composite tube 11 in the time of should synthesizing is controlled at 850～1500 ℃, and as if 850 ℃ of less thaies, reactivity reduces; If at 850 ℃ or when higher, reach 90% or higher reactivity.In addition, when surpassing 1500 ℃, the Titanium particles of generation begins sintering mutually, and the specific surface area of the Titanium particles of generation reduces.

In addition, about the titanium compound steam in composite tube 11 and the flow velocity of oxygen, flow velocity is fast more, and the time by heating region is that the crystalline growth time is short more, can obtain the little Titanium particles of particle diameter., if flow velocity is too fast because reaction efficiency reduces significantly, thus industrial be unfavorable.Titanium tetrachloride as raw material, is used the composite tube 11 of the silica glass system of internal diameter 32mm, thickness 2.5mm, and when synthesis temperature was made 1230 ℃, preferred flow velocity was 150～1500mm/ minute.

In addition, use oxyhydrogen flame lamp 12 as being used for the synthetic heating source, the generation heat height of this oxyhydrogen flame lamp is compared and can be heated partly with electric heater.Therefore, can easily obtain generating the necessary heat energy of homogeneous nucleus, in addition, add that heating region narrows down, the crystalline growth of may command titanium oxide.In addition, can obtain atomic diffusion easily and move necessary high temperature, the Titanium particles that synthetic crystallization is high.

And then, supply to the titanium compound steam in the composite tube 11 and the ratio of oxygen, be based on the equivalent decision of oxidizing reaction, preferably supply with oxygen so that oxidizing reaction is fully carried out a little superfluously.For example, when using titanium tetrachloride, for 1 mole of titanium tetrachloride, preferably oxygen is about 1.05～1.2 moles.

The synthetic Titanium particles moves to the downstream side of composite tube 11 along with deflated flows in composite tube 11, but because the downstream side of not heating composite tube 11 so its temperature is low, is several 10 ℃.Therefore, the pyritous Titanium particles cools off hastily, is deposited in by the thermophoresis effect on the wall of downstream part of composite tube 11.The temperature of composite part is heated to about 1000 ℃ partly,,, can piles up Titanium particles efficiently so the thermophoresis effect acts on effectively because the downstream part is several 10 ℃.

In addition, if the downstream part of gas cooling composite tubes 11 such as water, nitrogen, the deposition efficiency of Titanium particles improves.And then if helium heat-conduction coefficient is big, that heat exchange action is high supplies in the composite tube 11, cooling, the thermophoresis effect that can more effectively carry out the downstream part improve, and deposition efficiency also improves thus.

On the other hand, be present in the remaining Titanium particles in the exhaust,, be sent in the bag filter 18, reclaim at this along with it flows.When this reclaims, because the synthetic Titanium particles is atomic fine particle, so easy blocking filter.Therefore, have with the pressurized gas of above-mentioned air, nitrogen etc. and impact with the mechanism of the Titanium particles of removing plug-hole to strainer and mechanically shoot down the equipment of the mechanism of plug-hole thing, suit for handling to stop up.

When this building-up reactions, can change the crystalline growth speed of polyhedral each crystal plane of crystallization, the above-mentioned flat ratio of may command thus by the reaction conditions of adjusting material concentration, temperature of reaction etc.In addition, also polyhedral number of may command.In addition, can make by flat ratio 0.33～3.0, preferably 0.6～1.67 crystallization polyhedron form, the high Titanium particles of photocatalyst effect.

And then, make the oxidation atmosphere by reacting atmosphere, Titanium particles with Detitanium-ore-type crystalline texture can be controlled to be 95% or more, suitably be varied to the reduction atmosphere by reacting atmosphere from the oxidation atmosphere, the ratio of its Detitanium-ore-type of may command and rutile-type.

Fig. 5 is another example of expression Titanium particles manufacturing installation of the present invention, for adding prosign with identical component part shown in Figure 4, omits its explanation.

The manufacturing installation that this is routine, be to use when in the Titanium particles that is synthesized, adding the hotchpotch of for example phosphorus, nitrogen, silicon, boron etc., increased the other bubbler 21 that is used for producing as the compound steam of hotchpotch, the compound steam as hotchpotch from this bubbler 21 collaborates through pipe 22 and pipe 15, is fed to then in the composite tube 11.

In addition,, also pipe 22 directly can be connected with composite tube 11, directly supply in the composite tube 11 in order to supply with the compound steam that becomes hotchpotch.And then, as heating source, be not limited to the oxyhydrogen flame lamp, can use parts such as electric heater to heat, but see more preferably oxyhydrogen flame lamp from above-mentioned reason.

In addition, the recovery of the Titanium particles of generation can only be to utilize the thermophoresis effect to make its mode that is deposited in the downstream part of composite tube, also can be not pile up the Titanium particles of generation and directly it is sent in the bag filter 18.In addition, also available method with raw material titanium compound heating and gasifying (baking) makes titanium compound steam.

Can make polyhedral Titanium particles of above-mentioned box shape efficiently according to the manufacture method of such Titanium particles.This manufacture method is classified as thermal oxidation method, but in the past at synthetic indoor titanium tetrachloride vapors and the heating oxygen sent into, in synthetic indoor method of carrying out the thermooxidizing of oxidizing reaction, only be to generate the globular Titanium particles, and only can obtain the big particle of particle diameter.

Relative therewith, above-mentioned manufacture method, the particle diameter that for example can obtain median size 20nm, accounts for 85% particle of all particles is the size-grade distribution of 10nm～40nm.

Fig. 6 is another example of manufacturing installation of expression Titanium particles of the present invention, and in this routine manufacturing installation, except the heating position in the inside of composite tube 11 is provided with the columnar part 31, other are identical with manufacturing installation shown in Figure 4.

This columnar part 31 is had round-ended cylinder shape or the bar-shaped parts of filled circles in vain in being, be by the material that forms composite tube 11 with silica glass etc. aspect the coefficient of thermal expansion near or identical materials constitute.As shown in the figure, this columnar part 31 leaves the inwall of composite tube 11, and disposes coaxially with composite tube 11, with the gap of inner-wall surface be 0.1～10mm.During this is at interval not enough 0.1mm, then the particle of Sheng Chenging stops up this gap, when surpassing 10mm, has increased the zone that temperature distributing disproportionation is spared, and the meaning that columnar part 31 is set has not just had.

In addition, the support of the columnar part 31 of this example is to be undertaken by the top ends that columnar part 31 is connected the pipe arrangement 15 that is used for base feed gas, rotatably supports pipe arrangement 15 with glass rotating disk 32.From the unstripped gas of pipe arrangement 15, be sent to the inside of composite tube 11 from the vertical hole 33 that is formed on pipe arrangement 15.

When describing,, be sent to the inwall side that composite tube 11 interior raw materials are directed to composite tube 11, flow along its inwall by such columnar part 31 is set for the method for using this routine manufacturing installation to make Titanium particles.Owing to the inner wall section of composite tube 11 can be heated to the highest temperature with oxyhydrogen flame lamp 12, the zone that the Heating temperature of unstripped gas in composite tube 11 is high is heated, and carries out oxidizing reaction.Thus, the Titanium particles of generation becomes the neat particle uniformly of particle diameter.In addition, can obtain the high particle of more crystallinity, reduce the inhomogeneous of crystal form, can make the high Titanium particles of catalytic activity thus.Use this manufacturing installation, for example can obtain median size 20nm, account for the particle diameter of 85% particle of all particles in the size-grade distribution of 10nm～40nm.

About creating conditions of this manufacture method, when the flow velocity of unstripped gas is fast, to lack by the needed time of heating region, though generate the little Titanium particles of particle diameter, reaction efficiency is low.Therefore, when 1100 ℃ of internal diameter 36mm, the external diameter 20mm of columnar part 31, the synthesis temperatures of composite tube 11, preferably with about flow rate control 150～1500mm/ minute of unstripped gas.

(application of Titanium particles)

Below, describe for the various application of using above-mentioned Titanium particles.

(photocatalyst)

Photocatalyst of the present invention comprises polyhedral Titanium particles of above-mentioned box shape or the titanium dioxide powder that a plurality of set of this Titanium particles form, with this Titanium particles or powder with suitable method apply, attached to bringing into play photocatalysis on the base material.For example, the dispersion agent that is dispersed in organic solvent etc. makes paste, with this cream be coated in glass, pottery, metal, timber, plastics, on the base material of filming etc., the heating back is held in the function that plays photocatalyst on the base material by carrying.In addition, add the jointing material of low melting glass or various polymkeric substance etc., it is coated on the base material, be fixed on the base material, also play the photocatalyst function by the heating and melting jointing material.

In addition, photocatalyst of the present invention also can make the responsive to visible light type.For example, with argon-dilution in the ammonia atmosphere of concentration of regulation, with the Titanium particles heating specified time of the present invention, can make responsive to visible light type photocatalyst.Even the visible light of responsive to visible light type photocatalyst 400nm or bigger wavelength is also brought into play photocatalytic activity, even, also can make full use of its photocatalytic activity from the visible light of the source of artificial light of the luminescent lamp of indoor grade, electric light etc.

This photocatalyst and in the past the photocatalyst that contains Titanium particles similarly can be used for formation, surface antifouling etc. of the decomposition removal, sterilization, sterilization of decomposition removal, the repugnant substance of pollutent etc. or super-hydrophobicity tunicle, and its concrete use-pattern is identical with in the past the photocatalyst that contains Titanium particles.

(coating)

Coating of the present invention contains above-mentioned Titanium particles or titanium dioxide powder and is used to constitute the essential composition of resinous principle conduct of filming.

The use level of the Titanium particles of this photocatalyst coating forms for the branch total amount with respect to solid, is the scope of 0.1～80 quality %, the scope of 5～20 quality % preferably.If the use level of Titanium particles is lacked than above-mentioned scope, can not fully obtain the photocatalytic activity that this is filmed.In addition, if the use level of Titanium particles surpasses above-mentioned scope, the mobile variation of coating applies operational difficulty, in addition, because resinous principle tails off, might can not get firm filming.

Be engaged in the resinous principle in this coating, just be not particularly limited, can use the interior resinous principle that uses of paint field in the past, for example can use acrylic resin, Synolac, polyurethane series resin etc. as long as can form good filming as coating.In addition, can use the water-emulsifiable liquid of resinous principle 10～40 quality % of these resins.If use water-emulsifiable liquid, do not need to cooperate solvent, be favourable for environment.

The use level of this resinous principle forms for the branch total amount with respect to solid, is the scope of 20～99.9 quality %, the scope of 50～80 quality % preferably.

In addition,, all kinds of SOLVENTS that is suitable for dissolving used resinous principle can be used, for example, the ester class etc. of the ketone, vinyl acetic monomer etc. of the hydrocarbon system solvent, acetone etc. of water, ethanol, aromatic hydrocarbons or ring type hydrocarbon etc. can be made as the solvent that is engaged in this coating.The use level of this solvent for the total solid formation in the photocatalyst coating divides 100 mass parts, is about 80～99.5 mass parts.

In this coating, except above-mentioned necessary composition, in the scope of the rerum natura of not damaging this coating, photocatalytic activity, can add the additive of pigment, dispersion stabilizer, UV light absorber, antioxidant etc. as required.

For this coating, on the various base materials of the ceramic plate by it being coated in metal sheet, ceramic tile etc., glass, timber, concrete etc., can form by dry solidification and to have filming of photocatalytic activity.The method that applies to the base material of this photocatalyst coating, can be according to the shape of base material, material, size etc. from suitable selection the known various coating method in the past, for example, can use immersion coating, with brush coating, spraying, electrophoretic painting, spin coating method, scrape coatings such as the skill in using a kitchen knife in cookery.

For this coating, contain Titanium particles, so have filming more in the past than product was high photocatalytic activity by it being coated on the suitable base material, can forming with high photocatalytic activity.

In addition, in this coating, when the photocatalytic activity of Titanium particles is high, the interpolation material itself of resinous principle, solvent etc. is decomposed.For this reason, the preferred sometimes Titanium particles that photocatalytic activity is reduced a little by the element that adds silicon etc. that uses.

(photocatalysis apparatus)

Photocatalysis apparatus of the present invention has that there is the light-catalyzed reaction body of above-mentioned Titanium particles on its surface and the light source of irradiates light on this light-catalyzed reaction body.

Shape, structure for the light-catalyzed reaction body are not particularly limited, can be the state in powder shaped or the liquid that is suspended in water etc., the structure that obtains but the coating that preferably will contain above-mentioned Titanium particles or powder is coated in suitable substrate surface.

And then that this structure can make is tabular, the different shape of tubulose, cellular, particle shape etc., according to suitable selections such as the proterties of the object being treated that contains nuisance, supply methods.Above-mentioned tabular, tubulose, cellular etc. structure can be by making in the surface-coated above-mentioned coating of metal sheet or metal tube, metal system honeycomb material.In addition, emboliform structure can be made by apply above-mentioned coating on the particle of the suitable particle diameter of granulated glass sphere, synthetic resins pearl, porous ceramic etc.

The light source that is used for this photocatalysis apparatus, the preferably source of artificial light of high pressure mercury vapour lamp, xenon lamp, graphite etc.

The structure of this photocatalysis apparatus can be according to change aptly such as the proterties of the object being treated that contains nuisance or supply method.For example, when object being treated is the liquid of trade effluent etc., the above-mentioned light-catalyzed reaction body that can in groove, add tabular, tubulose, cellular, particle shape etc., and then in groove the configuration light source or use fiber optics from the light source of groove outside with rayed in groove and constitute, in groove, add processed liquid, by light-catalyzed reaction body decomposing harmful substances.

In addition, when object being treated is the gas of exhaust gas etc., also can in the stream of this processed gas, dispose above-mentioned light-catalyzed reaction body and light source, processed gas is contacted and decomposable harmful substances with the light-catalyzed reaction body, in the groove that has disposed light source, fill above-mentioned emboliform light-catalyzed reaction body, blow out processed gas from the groove below, form the thermopnore of light-catalyzed reaction body, handle processed gas.

According to photocatalysis apparatus of the present invention, have that there is the light-catalyzed reaction body of above-mentioned Titanium particles on its surface and the light source of irradiates light on this light-catalyzed reaction body.By such structure, can the high-level efficiency decomposing nitrogen oxide, the nuisance of pollution substance, odor pollutant etc.

(decomposition method of objectionable impurities)

Use in the method for decomposing harmful substances of titanium dioxide powder of the present invention, employed titanium dioxide powder is the powder that the Titanium particles set of particle diameter 100～500nm forms, constitute in all particles of this powder 90% or manyly form, and Titanium particles is formed by the polyhedron of 10 bodies of box-formed shape etc. by the Detitanium-ore-type crystallization.

This method is with this titanium dioxide powder and dissolving or has disperseed the fluid of the water, air etc. of objectionable impurities directly to contact, the light of irradiating ultraviolet light etc. thereon, after decomposing the objectionable impurities in the fluid, use the strainer filtered fluid, the method for Separation and Recovery titanium dioxide powder.

Usually, the Titanium particles that shows high photocatalytic activity is little particle diameter.For this reason, the Titanium particles from number nm to the particle diameter of tens of nm is used for such purposes.,, produce cohesion when being distributed in the water etc., form the aggregate about about 300nm if use the particle of such particle diameter.If aggregate that should size filters, can use the strainer about perforate 0.1 μ m, but can stop up immediately for the strainer of such pore, can not be practical.

Relative therewith, during Titanium particles in using the present invention, be big the using of 100～500nm although select its particle diameter, owing to improved original crystallinity, demonstrate excellent catalytic activity, bring into play high capacity of decomposition.In addition, the size of the aggregate after the cohesion is 2～5 μ m, so use the strainer of perforate 1～2 μ m, can filter rapidly, and strainer also is difficult to stop up the practicality height.

Fig. 7 is the example of treatment unit that expression is used for the decomposition method of objectionable impurities of the present invention, and the device of this example is with the objectionable impurities dissolving or is dispersed in liquid in the water as process object.

The treatment trough that symbol 51 is made up of stainless steel, plastics etc. among the figure, the vent pipe 53 of the liquid after connecting the inflow pipe 52 that flows into process object liquid on this groove 51 and flowing out disaggregating treatment.On the top of inflow pipe 52 prefilter 54 is set, removing thick rubbish that is dispersed in influent etc., at the cardinal extremity of vent pipe 53 separator-filter 55 is set, the titanium dioxide powder that is dispersed in process object liquid is filtered, Separation and Recovery.The strainer that this separator-filter 55 uses by making such as glass fibre.

In addition, accommodate ultra-violet lamp recess 56 in the formation of the top of treatment trough 51, the wall of this recess 56 is made of the UV-light perviousness glass of silica glass etc., become illumination window, from the process object liquid in the illumination window radiation treatment groove 51 such as the UV-light of the ultraviolet source 57 of accommodating high pressure mercury vapour lamp in the recess 56, xenon lamp, germicidal lamp, UV-lamp etc.Be distributed to the Titanium particles performance photocatalyst effect of process object liquid by this UV-light, dissolve or the objectionable impurities that is dispersed in the process object liquid is decomposed, by innoxious.

And then, in treatment trough 51, being formed for stirring the screwshaft 58 and the magnetic stirrer 59 of inner process object liquid, the magnetic stirrer 60 of the bottom of magnetic stirrer 59 by being arranged on treatment trough 51 is rotated.

In addition,, use when bringing into play active visible-light type, also can constitute all or part of of treatment trough 51 with materials such as glass by the visible light of sunlight etc. as Titanium particles.

Treatment process for the treatment unit that uses this example, the dispersion concentration of the Titanium particles in the process object liquid, for process object liquid 0.5～10 weight %, during less than 0.5 weight %, can not fully decompose, if when surpassing 10 weight %, even dispersion of particles difficulty, Titanium particles is entrained with harmful substances and sedimentation.

Along with the carrying out of disaggregating treatment, in separator-filter 55, catch Titanium particles, the dispersion concentration of the Titanium particles in the process object liquid reduces.At this moment, if carrying out known back washing washs, can eliminate the obstruction of separator-filter 55, and the dispersion concentration of the Titanium particles in the process object liquid is restored also.

In such decomposition method, in process object liquid, the Titanium particles cohesion, become 2 μ m or bigger aggregate, so use sieve aperture thicker, perforate 1 μ m or bigger separator-filter 55, can filter effectively, improve filtration velocity widely.For example, for useful area 500cm ², perforate 2 μ m glass fibre filter made device, can reach per 1 hour 10 liters or bigger filtration velocity.

In addition, dissolving or when being dispersed with harmful substances in the gas of air etc. imports to this gas in the treatment trough, when being arranged on fan in the treatment trough and stirring gas, titanium dioxide powder is swum becomes dispersion state, can adopt the method for irradiating ultraviolet light etc. under this state.In addition, also above-mentioned coating can be coated in suitable substrate surface and make the state of filming, make dissolving or the fluid that is dispersed with harmful substances film and contact, carry out the method for illumination with this.

With the objectionable impurities that the method for decomposing harmful substances of the present invention is decomposed, can enumerate oxynitride (NO _x), pollution substance, odor pollutant.As pollution substance and odor pollutant, for example can enumerate the sulfocompound etc. of nitrogenous compound, hydrogen sulfide or mercaptan etc. of carboxylic-acid, ketone, ammonia or amine etc. of the alcohols, acetic acid etc. of the aldehydes, butanols etc. of acetaldehyde etc.

According to the method for decomposable harmful substances of the present invention, contact with nuisance by to the Titanium particles irradiates light time and decompose this nuisance, efficiently decomposing nitrogen oxide (NO _x), nuisance such as pollution substance, odor pollutant.

Below, clearly state action effect of the present invention with embodiment.

Comparative example 1

, mix with the oxygen of heat tracing as raw material with titanium tetrachloride vapors, carry out the synthetic Titanium particles of thermooxidizing synthetic indoor.Titanium tetrachloride vapors is supplied with bubbler, and the bubbling temperature is 85 ℃.Bubbled gas uses argon gas, and its flow makes 200sccm.The reaction oxygen flow is 1000sccm, and reaction oxygen temperature is 1000 ℃.The shape of the Titanium particles that obtains is spherical.In addition, its median size is 90nm, and size distribution is, the particle diameter that accounts for 85% particle of all particles is 20nm～200nm.

Embodiment 1

The composite tube of the silica glass system of use, thermal source is the oxyhydrogen flame lamp, imports titanium tetrachloride vapors and oxygen in composite tube, makes Titanium particles by the thermal oxidation method from the composite tube indirect heating.Supply with titanium tetrachloride vapors with bubbling, bubbler temperature is made 85 ℃, the pipe arrangement holding temperature makes 140 ℃.Use argon gas for bubbled gas, its flow makes 180sccm.The reaction oxygen flow makes 1000sccm, and synthesis temperature makes 1230 ℃.Dispose 6 oxyhydrogen flame lamps.The internal diameter of quartz glass tube is that 32mm, thickness are 2.5mm, with its rotating speed rotation with 55rpm.

The shape of the Titanium particles that obtains is 10 bodies as shown in Figure 1.Its median size is 20nm, and size distribution is, the particle diameter that accounts for 85% particle of all particles is 10nm～40nm.In addition, flat ratio is 0.33～3.0.

Fig. 8 is the microphotograph of taking with scanning electron microscope of an example that is presented at the particle shape of this Titanium particles of making of creating conditions down.

In addition, measure carrying out X-ray diffraction, obtain the ratio (%) of the Titanium particles of Detitanium-ore-type crystalline texture from peak intensity, the result is 95%.

Then, this Titanium particles is carried out thermal treatment in 24 hours in nitrogen atmosphere, under 500 ℃.Titanium particles after the thermal treatment is carried out X-ray diffraction to be measured and electron microscope observation.The result of electron microscope observation is that particle does not carry out sintering, does not see interparticle necking phenomenon yet.In addition, the result who measures from X-ray diffraction can infer the ratio (%) of the Titanium particles of Detitanium-ore-type crystal structure as can be known from peak intensity.The Titanium particles of Detitanium-ore-type crystal structure accounts for and compares before all ratios of particle and the thermal treatment is not change.

This Titanium particles is carried out thermal treatment in 24 hours in nitrogen atmosphere, under 700 ℃.Carrying out X-ray diffraction for the Titanium particles after the thermal treatment measures and electron microscope observation.The result of electron microscope observation, particle does not carry out sintering, does not see interparticle necking phenomenon yet.

In addition, the result who measures from X-ray diffraction can infer the ratio (%) of the Titanium particles of Detitanium-ore-type crystal structure as can be known from peak intensity.The Titanium particles of Detitanium-ore-type crystal structure accounts for to compare before all ratios of particle and the thermal treatment small minimizing, but rutile number turnover R (700-24) is 5.0%.

Embodiment 2

The Titanium particles that embodiment 1 is obtained is coated on the quartz glass plate, uses the evaluation of the photocatalytic activity of uviolizing.

Evaluation is to carry out with the capacity of decomposition of the acetaldehyde under the same terms, measure to decompose the concentration of carbon dioxide that the back produces, and relatively with the relation of the polyhedral flat ratio H that constitutes Titanium particles.In Fig. 9 the expression have each flat ratio titanium oxide catalyst gas concentration lwevel over time.Its result, polyhedral flat ratio is that 1.01 and 1.58 sample has shown the highest activity, flat ratio is that 0.53 and 2.16 sample shows low slightly activity.

Comparative example 2

The Titanium particles that comparative example 1 is obtained is coated on the quartz glass plate, applies intestinal bacteria, to its irradiation invisible light, the investigation coliform count over time, the result is that time of no more than 1% of the coliform count that reaches initial is 60 minutes.

Embodiment 3

The Titanium particles that embodiment 1 is obtained is coated on the quartz glass plate, apply intestinal bacteria, to its irradiation ultraviolet radiation lamp, the investigation coliform count over time, the result is that no more than 1% or less time of the coliform count that reaches initial is 30 minutes.

Embodiment 4

Use the composite tube of silica glass system, thermal source is to use the oxyhydrogen flame lamp, imports titanium tetrachloride vapors and oxygen in composite tube, makes Titanium particles by the thermal oxidation method from the indirect heating of composite tube.Titanium tetrachloride vapors is to supply with the bubbling form, and the temperature of bubbling is 85 ℃, and bubbled gas is to use argon gas, and its flow is 180sccm.

The reaction oxygen flow is 1000sccm, and synthesis temperature is 1230 ℃.Quartz glass tube is that internal diameter 32mm, thickness are 2.5mm, makes its rotation with the rotating speed of 55rpm.

Carrying out X-ray diffraction for the synthetic Titanium particles measures and electron microscope observation.The result of electron microscope observation is, the shape of its particle is 10 bodies, and the median size of Titanium particles is 60nm, and the distribution of particle diameter is, the particle diameter that occupies 85% particle of all particles is 20～100nm.The result who measures from X-ray diffraction can infer the ratio (%) of the Titanium particles of Detitanium-ore-type crystal structure as can be known from peak intensity.Its result is illustrated in table 1.

Then this Titanium particles is carried out thermal treatment in 24 hours in nitrogen atmosphere, under 500 ℃.Carrying out X-ray diffraction for the Titanium particles after the thermal treatment measures and electron microscope observation.The result of electron microscope observation is that particle does not carry out sintering, does not see interparticle necking phenomenon yet.In addition, the result who measures from X-ray diffraction can infer the ratio (%) of the Titanium particles of Detitanium-ore-type crystal structure as can be known from peak intensity.The result is illustrated in table 1, and the Titanium particles of Detitanium-ore-type crystal structure relatively is not change before accounting for all ratios of particle and thermal treatment.

In addition, this Titanium particles is carried out thermal treatment in 24 hours in nitrogen atmosphere, under 700 ℃.Carrying out X-ray diffraction for the Titanium particles after the thermal treatment measures and electron microscope observation.The result of electron microscope observation is that particle does not carry out sintering, does not see interparticle necking phenomenon yet.

In addition, the result who measures from X-ray diffraction can infer the ratio (%) of the Titanium particles of Detitanium-ore-type crystal structure as can be known from peak intensity.The result is illustrated in table 1.The Titanium particles of Detitanium-ore-type crystal structure accounts for to compare before all ratios of particle and the thermal treatment small minimizing, but rutile number turnover R (700-24) is 4.2%.

Comparative example 3

Buying commercially available photocatalyst compares with Titanium particles.The Titanium particles that is used for comparison is with pyrohydrolytic method synthetic particle, and the result of electron microscope observation is, particle shape is a spheric, and its median size is 60nm, and size distribution is that the particle diameter that occupies the particle of all particles 85% is 20～100nm.The result who measures from X-ray diffraction can infer the ratio (%) of the Titanium particles of Detitanium-ore-type crystal structure as can be known from peak intensity.Its result is illustrated in table 1.

Then this Titanium particles is carried out thermal treatment in 24 hours in nitrogen atmosphere, under 700 ℃.Carrying out X-ray diffraction for the Titanium particles after the thermal treatment measures and electron microscope observation.The result of electron microscope observation is that particle is carrying out sintering, can see interparticle necking phenomenon.

The electron micrograph of the particle after this heating is illustrated in Figure 10.

From the result that X-ray diffraction is measured, can infer the ratio (%) of the Titanium particles of Detitanium-ore-type crystal structure from peak intensity.Its result is illustrated in table 1.Compared significantly before the ratio that the Titanium particles of Detitanium-ore-type crystal structure accounts for all particles and the thermal treatment and reduced, but rutile number turnover R (700-24) is 78.5%.

Table 1.

	The ratio (%) of Detitanium-ore-type before the thermal treatment	The ratio (%) of the Detitanium-ore-type after the thermal treatment in 500 ℃, 24 hours	The ratio (%) of the Detitanium-ore-type after the thermal treatment in 700 ℃, 24 hours	Rutile number turnover (%) R (500-24)	Rutile number turnover (%) R (700-24)
						Embodiment 4	95.0	95.0	91.0	0.0	4.2
Comparative example 3	70.0	-	15.0	-	78.5

Embodiment 5

Titanium particles that embodiment 4 is made and low melting glass and tackiness agent, solvent obtain the titanium oxide slurries.These titanium oxide slurries are coated on the quartz glass plate equably, and 700 ℃ were heated 2 hours down in atmosphere, carried out sintering, made the sheet glass that is loaded with Titanium particles.This sheet glass is utilized uviolizing and carries out the evaluation of photocatalytic activity.Evaluation is to carry out with the capacity of decomposition of acetaldehyde, measures and decomposes the concentration of carbon dioxide that the back produces.

For relatively, make the sheet glass that is loaded with same Titanium particles with the Titanium particles (commercially available product) of comparative example 3, carry out same evaluation.Represented gas concentration lwevel among Figure 11 over time.In addition, apply under the state that (does not have thermal treatment) behind the slurries before sintering and carry out same experiment, its result is also illustrated in Figure 11.

Its result is, is used for the sheet glass that the commercially available Titanium particles of comparison is made, and activity descends widely before and after agglomerating, but the characteristic of the sheet glass of making of the Titanium particles of embodiment 4 does not change, and has shown high acetaldehyde decomposition ability.

Embodiment 6

Use the Titanium particles manufacturing installation of Fig. 4, carry out the manufacturing of Titanium particles.The reaction composite tube of the silica glass system of external diameter 40mm is set on the glass rotating disk, rotates with 45rpm.In this pipe, import titanium tetrachloride vapors 50sccm and oxygen 1200sccm, be heated to 1300 ℃ with the oxyhydrogen flame lamp, synthetic Titanium particles in the reaction composite tube from the outside of reacting composite tube.The Titanium particles that has synthesized reclaims with bag filter.

The Titanium particles that has reclaimed is a decahedron, and from the result of X-ray diffraction analysis (XRD) peak identification as can be known, 96% of all particles in the powder are the Detitanium-ore-type crystallizations, use BET method measurement the specific area in addition, and the result is 10.2m ²/ g.

The Titanium particles 50mg that obtains is joined the encloses container of internal diameter 15mm, it is suspended in 5 milliliters of 5 volume % aqueous acetic acids, under the state that suspends, use 15mW/cm ²The ultraviolet of illumination irradiation 365nm, during the amount of carbon dioxide that per hour produces with quantitative analysis by gas chromatography, the result is 54 μ mol.

Embodiment 7

The reaction composite tube of the silica glass system of external diameter 40mm is set on the glass capstan, rotates with 45rpm.In this pipe, import titanium tetrachloride vapors 20sccm and oxygen 1200sccm, be heated to 1300 ℃ with the oxyhydrogen flame lamp, synthetic Titanium particles in the reaction composite tube from the outside of reacting composite tube.The Titanium particles that has synthesized reclaims with bag filter.

The Titanium particles that has reclaimed is a decahedron, and from the result of X-ray diffraction analysis (XRD) peak identification as can be known, 96% of all particles in the powder are the Detitanium-ore-type crystallizations, use BET method measurement the specific area in addition, and the result is 32.4m ²/ g.

The Titanium particles 50mg that obtains is joined the encloses container of internal diameter 15mm, it is suspended in 5 milliliters of 5 volume % aqueous acetic acids, under the state that suspends, use 15mW/cm ²The UV-light of illumination irradiation 365nm, with the amount of carbon dioxide that quantitative analysis by gas chromatography per hour produces, the result is 52 μ mol.

Embodiment 8

The reaction composite tube of the silica glass system of external diameter 40mm is set on the glass capstan, rotates with 45rpm.In this pipe, import titanium tetrachloride vapors 30sccm and oxygen 1200sccm, be heated to 1300 ℃ with the oxyhydrogen flame lamp, synthetic Titanium particles in the reaction composite tube from the outside of reacting composite tube.The Titanium particles that has synthesized reclaims with bag filter.

The Titanium particles that has reclaimed is a decahedron, and from the result of X-ray diffraction analysis (XRD) peak identification as can be known, 96% of all particles in the powder are the Detitanium-ore-type crystallizations, use BET method measurement the specific area in addition, and the result is 21.8m ²/ g.

The Titanium particles 50mg that obtains is joined the encloses container of internal diameter 15mm, it is suspended in 5 milliliters of 5 volume % aqueous acetic acids, under the state that suspends, use 15mW/cm ²The UV-light of illumination irradiation 365nm, with the amount of carbon dioxide that quantitative analysis by gas chromatography per hour produces, the result is 51 μ mol.

Embodiment 9

The reaction composite tube of the silica glass system of external diameter 40mm is set on the glass capstan, rotates with 45rpm.In this pipe, import titanium tetrachloride vapors 40sccm and silicon tetrachloride vapor 2sccm and oxygen 1200sccm, be heated to 1300 ℃ with the oxyhydrogen flame lamp, synthetic Titanium particles in the reaction composite tube from the outside of reacting composite tube.The synthetic Titanium particles reclaims with bag filter.

The Titanium particles that reclaims is a decahedron, and from the result of X-ray diffraction analysis (XRD) peak identification as can be known, 96% of all particles in the powder are the Detitanium-ore-type crystallizations, use BET method measurement the specific area in addition, and the result is 30.1m ²/ g.

The Titanium particles 50mg that obtains is joined the encloses container of internal diameter 15mm, it is suspended in 5 milliliters of the 5 volume % aqueous acetic acids, under the state that suspends, use 15mW/cm ²The UV-light of illumination irradiation 365nm, with the amount of carbon dioxide that quantitative analysis by gas chromatography per hour produces, the result is 36 μ mol.In raw material, add the silicon capacity of decomposition of controlled oxidation titanium particle wittingly.The comparison of product and product of the present invention in the past

Buy 4 kinds of commercially available Titanium particles (below, be called commercially available powder A～D), carry out XRD respectively.From the qualification result at XRD peak as can be known, 4 kinds all is that the Detitanium-ore-type crystallization accounts for 95% or more titanium dioxide powder.Measure the specific surface area of these particles with BET.

These Titanium particles 50mg is joined the encloses container of internal diameter 15mm respectively, it is suspended in 5 milliliters of the 5 volume % aqueous acetic acids, under the state that suspends, use 15mW/cm ²The UV-light of illumination irradiation 365nm, the amount of carbon dioxide that per hour produces with quantitative analysis by gas chromatography.As the y axle, specific surface area obtains result shown in Figure 3 as the x axle with the amount of carbon dioxide that obtains.

To in the foregoing description 6～9, mark and draw in Fig. 3 together respectively as sample A～D by Titanium particles that make, that measured specific surface area and photocatalytic activity.

From the result of Fig. 3 as can be seen,, X-axis is being taken as specific surface area as the commercially available powder A～D of product in the past, when Y-axis is taken as the carbon dioxide generating amount, characteristic value be mark and draw on the line of y=0.8x or below.Can find out significantly from this result, when using technology in the past, be merely able to make the characteristic particle that is positioned at this line below.

On the other hand, as the represented Titanium particles of the present invention of sample A～D, can obtain the photocatalysis characteristic above this line far away, specific surface area is at 10～40m ²The scope of/g, the generation of carbonic acid gas hourly is 40 μ mol or more for sample A～C.

In addition, in Fig. 3, as the represented Titanium particles of sample D, by adding silicon as hotchpotch, can be so that the photocatalytic activity of Titanium particles descends.

Embodiment 10

Use the manufacturing installation of Fig. 6, make Titanium particles.The composite tube of the silica glass system of use as thermal source, imports titanium tetrachloride vapors and oxygen with the oxyhydrogen flame lamp in composite tube, utilize from the thermal oxidation method of composite tube indirect heating and make Titanium particles.Titanium tetrachloride vapors is to supply with in the bubbling mode, and the bubbling temperature is 85 ℃, and the pipe arrangement holding temperature is 140 ℃.Bubbled gas uses argon gas, and its flow is 200sccm.The reaction oxygen flow is 1000sccm, and synthesis temperature is 1100 ℃.The silica glass external diameter of pipe is that 40mm, thickness are 2mm, and the external diameter of columnar part is 20mm, and the gap of quartz glass tube and columnar part is 8mm.Rotating speed with 55rpm makes its rotation.

The shape of the Titanium particles that obtains is 10 bodies as shown in Figure 1.Its median size is 20nm, and size distribution is, the particle diameter that occupies 85% all particle of particle is 10nm～40nm.Flat ratio is 0.33～3.0 in addition.

In addition, carry out X-ray diffraction and measure the ratio (%) of obtaining the Titanium particles of Detitanium-ore-type crystal structure from peak intensity, the result is 95%.

Embodiment 11

Change creating conditions among the embodiment 1, make particle diameter 200～350nm, have the decahedron shape, particle is all 97% is Detitanium-ore-type crystalline titanium dioxide powder.

In the treatment trough of silica glass system, add 1.5 liters of the aqueous solution of methylene blue of 10 μ mol/L,, stir the aqueous solution to wherein dropping into above-mentioned titanium dioxide powder 15g.To the UV-light of this treatment trough by UV-lamp illumination wavelength 365nm.The ultraviolet light-receiving area of treatment trough is 300cm ², use 2.5mW/cm ²Illumination shine.

After 30 minutes, usable floor area 500cm ², perforate 2.0 μ m the round tube type strainer of glass fibre sieve aperture system, use from heavy filtration, can in 25 minutes, full dose filter.The strainer after the filtration is washed in the water back washing, and dry washings can reclaim 13.5g and be equivalent to drop into 90% of titanium dioxide powder.

With the concentration of the methylenum coeruleum in the quantitative filtering solution of spectrophotometer, 0.8 μ mol/L consequently, it is water white detecting by an unaided eye.

Comparative example 4

Prepare commercially available titanium dioxide powder.This powder is particle diameter 10～40nm, spheric shape, and all 90% of particle is the Detitanium-ore-type crystallization.

Use this commercially available titanium dioxide powder, under the condition identical, carry out the decomposition of aqueous solution of methylene blue with embodiment 11.

But the filtration after the processing is to use area 500cm ², perforate 0.1 μ m the round tube type strainer of glass fibre sieve aperture system carry out.By 120 minutes from heavy filtration, have only 20ml to pass through to filter.In case stop to filter carry out back washing and wash after, during test-filtration, then the oxidized titanium particle of filter pore stops up once more, filtration velocity does not improve.

With the concentration of the methylenum coeruleum in the quantitative filtering solution of spectrophotometer, 0.8 μ mol/L consequently, it is water white detecting by an unaided eye.

Comparative example 5

Preparation is loaded with the photocatalyst of the commercially available glass pearl of Titanium particles.With this photocatalyst of electron microscope observation, can distinguish that its pearl directly is 1mm, the surface attachment of pearl has the Titanium particles of particle diameter 10～40nm.In addition, with the crystal form of X-ray diffraction analysis and observation Titanium particles, because the peak that influences of granulated glass sphere is very wide, but the peak of observing Detitanium-ore-type and rutile-type is equal intensity.

Use this photocatalyst 150g, under the condition identical, carry out the disaggregating treatment of aqueous solution of methylene blue with embodiment 11.

After 30 minutes, usable floor area 500cm ², perforate 2.0 μ m the round tube type strainer of glass fibre sieve aperture system carry out from heavy filtration, the result be in 15 minutes full dose by filtering.The strainer after the filtration is washed in the water back washing, dry washings, and the almost full dose of the photocatalyst of input can reclaim, but can see the Titanium particles that comes off from granulated glass sphere, when reusing, is envisioned that the decline of disaggregating treatment ability.

With the concentration of the methylenum coeruleum in the quantitative filtering solution of spectrophotometer, 4.6 μ mol/L consequently, it is blue transparent detecting by an unaided eye.

Embodiment 12

The treatment trough of the silica glass system of making, its capacity is 1.5 liters, and top is provided with the axle of band paddle, and inside can be stirred, and can flow into and discharge a certain amount of aqueous solution with pump.Inflow pipe and vent pipe are set on treatment trough, and inflow pipe is installed prefilter, erection space 500cm on the vent pipe ², perforate 2.0 μ m the cylindric separator-filter of glass fibre sieve aperture system.

Be full of water in the treatment trough, and then the identical powder 15g of titanium dioxide powder of input and embodiment 11 uses, from the aqueous solution of methylene blue of inflow pipe with 0.5 liter/hour flow inflow concentration 10 μ mol/L.

The aqueous solution of methylene blue that sufficient time flows in the methylenum coeruleum concentration moment identical with the concentration of the aqueous solution of methylene blue of inflow of the aqueous solution of discharging from vent pipe, begins the UV-light of treatment trough irradiation from the 365nm of UV-lamp.The ultraviolet light-receiving area of treatment trough is 300cm ², use 2.5mW/cm ²Illumination shine.In order to prevent the obstruction of separator-filter, stopped pump in per 45 minutes in carrying out, after the contrary direction running of pump, the back washing of carrying out 5 minutes with 0.5 liter/hour flow is washed.

Every aqueous solution of taking to discharge from vent pipe is at regular intervals measured methylenum coeruleum concentration, and the result is that its concentration becomes steady state after shining 1 hour, is 3.6 μ mol/L.

Utilize the field on the industry

Titanium particles of the present invention can be used as photochemical catalyst, is used in the purposes such as decomposition to harmful substance, deodorization, sterilization.

Claims (31)

1. Titanium particles, its particle diameter is 1nm～500nm, the polyhedron of the box shape that is constituted by 1 or more a plurality of monocrystalline polyhedron or be that the polyhedron of box shape forms basically, above-mentioned be basically the polyhedron of box shape comprise polyhedral angle have slightly the shape of disappearance polyhedron, have the polyhedron of circular shape and have concavo-convex etc. and make the polyhedron that shape changes a little; Described polyhedron is any a kind in 6 body～10 bodies; Rutile number turnover R (700-24) is 7.5% or lower, and rutile number turnover R (500-24) is 2.0% or lower.

2. the described Titanium particles of claim 1, the polyhedral flat ratio of its monocrystalline is 0.33～3.0.

3. the described Titanium particles of claim 1, its particle diameter is 100～500nm.

4. the described Titanium particles of claim 1, its particle diameter is 10～50nm.

5. the described Titanium particles of claim 1, wherein, specific surface area is 3～40m ²/ g adds 5 milliliters of 5 volume % aqueous acetic acids and Titanium particles 50mg in the encloses container of internal diameter 15mm, make its under the state that suspends with 15mW/cm ²The UV-light of illumination irradiation 365nm, the amount of carbon dioxide that produced in per 1 hour is positioned at the zone of the top of the line of representing with y=0.8x, wherein, x is a specific surface area, unit is m ²/ g; Y is the carbon dioxide generating amount, and unit is μ mol/hr.

6. the described Titanium particles of claim 1 wherein, is doped with silicon, and specific surface area is 3～40m ²/ g adds 5 milliliters of 5 volume % aqueous acetic acids and Titanium particles 50mg in the encloses container of internal diameter 15mm, under the state that suspends with 15mW/cm ²The UV-light of illumination irradiation 365nm, the amount of carbon dioxide that produced in per 1 hour is positioned at the zone of the top of the line of representing with y=0.8x, wherein, x is a specific surface area, unit is m ²/ g; Y is the carbon dioxide generating amount, and unit is μ mol/hr.

7. the described Titanium particles of claim 5, wherein arbitrary element in Doping Phosphorus, nitrogen, silicon, the boron.

8. a titanium dioxide powder is the titanium dioxide powder that a plurality of set of the described Titanium particles of claim 1 form, constitute the Titanium particles of this powder all 80% or mostly are Detitanium-ore-type crystallizations.

9. the described titanium dioxide powder of claim 8, wherein the Detitanium-ore-type crystallization occupies 90% or more.

10. a method of making the described Titanium particles of claim 1 is characterized in that, supplies with titanium compound steam and oxygen in composite tube, from the composite tube indirect heating.

11. the manufacture method of the described Titanium particles of claim 10 is characterized in that, uses the oxyhydrogen flame lamp as heating source.

12. the manufacture method of the described Titanium particles of claim 10 is characterized in that, the rotation composite tube.

13. the manufacture method of the described Titanium particles of claim 10 is characterized in that, the columnar part that the mixed gas of titanium compound steam and oxygen is imported to the inwall side of composite tube is set, from indirect heating in composite tube inside.

14. the manufacture method of the described Titanium particles of claim 13 is characterized in that, the interval of composite tube and columnar part is made 0.1～10mm.

15. the manufacture method of the described Titanium particles of claim 10 is characterized in that, the recovery method of the Titanium particles of generation is to utilize the thermophoresis effect, piles up Titanium particles in the downstream part of composite tube and reclaims.

16. the manufacture method of the described Titanium particles of claim 10 is characterized in that, the recovery method of the Titanium particles of generation is to use the method for the bag filter in the downstream side that is arranged on composite tube.

17. the manufacture method of the described Titanium particles of claim 10 is characterized in that, the temperature of the composite tube when synthetic is at 850～1500 ℃.

18. device of making the described Titanium particles of claim 1, wherein, have composite tube, from the heating source of its this composite tube of indirect heating, make composite tube around the rotary driving part of its rotation and the raw material supplying portion that to composite tube, supplies with titanium compound steam and oxygen.

19. the manufacturing installation of the described Titanium particles of claim 18 wherein, has the bag filter that the Titanium particles that generates is reclaimed in composite tube.

20. the manufacturing installation of claim 18 or 19 described Titanium particles wherein is provided with the columnar part that the mixed gas of titanium compound steam and oxygen is imported to the inwall side of composite tube in composite tube inside.

21. a photocatalyst wherein, contains the described Titanium particles of claim 1.

22. a photocatalyst wherein, contains the described titanium dioxide powder of claim 8.

23. a coating wherein, contains the described Titanium particles of claim 1.

24. a coating wherein, contains the described titanium dioxide powder of claim 8.

25. a photocatalysis apparatus wherein, has the described Titanium particles of claim 1 is carried the light-catalyzed reaction body that is held in the surface and the light source of irradiates light on this light-catalyzed reaction body.

26. the method for a decomposing harmful substances wherein, is used the described titanium dioxide powder of claim 8.

27. the method for the described decomposing harmful substances of claim 26, wherein, after Titanium particles being contacted with processed object decompose, with strainer separation of oxygenated titanium particle.

28. the decomposition method of the described objectionable impurities of claim 27, wherein, strainer is a glass fibre system, and perforate is 2.0 μ m or bigger.

29. a deodour method wherein, uses the described photocatalyst of claim 21.

30. a method for disinfection wherein, uses the described photocatalyst of claim 21.

31. the method for a decomposing harmful substances wherein, is used the described photocatalyst of claim 21.

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