WO2000018686A1 - Method for production of amorphous titanium peroxide solution and anatase titanium oxide sol - Google Patents

Method for production of amorphous titanium peroxide solution and anatase titanium oxide sol

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Publication number
WO2000018686A1
WO2000018686A1 PCT/JP1999/005236 JP9905236W WO0018686A1 WO 2000018686 A1 WO2000018686 A1 WO 2000018686A1 JP 9905236 W JP9905236 W JP 9905236W WO 0018686 A1 WO0018686 A1 WO 0018686A1
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WO
Grant status
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Patent type
Prior art keywords
titanium
solution
peroxide
amorphous
hydroxide
Prior art date
Application number
PCT/JP1999/005236
Other languages
French (fr)
Japanese (ja)
Inventor
Shiro Ogata
Yoshimitsu Matsui
Original Assignee
Tao Inc.
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Filing date
Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/04Oxides; Hydroxides
    • C01G23/047Titanium dioxide
    • C01G23/053Producing by wet processes, e.g. hydrolysing titanium salts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/04Metal peroxides or peroxyhydrates thereof; Metal superoxides; Metal ozonides; Peroxyhydrates thereof
    • C01B15/047Metal peroxides or peroxyhydrates thereof; Metal superoxides; Metal ozonides; Peroxyhydrates thereof of heavy metals
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/02Amorphous compounds

Abstract

In the production of an amorphous titanium peroxide solution which comprising subjecting an aqueous solution containing titanium to a neutralization reaction with a basic substance, to form a titanium hydroxide gel, washing the gel followed by cooling, reacting the gel with a peroxide to form an amorphous titanium peroxide solution, allowing to stand for aging, concentrating and purifying, and, in the production of an anatase titanium oxide sol which comprises heating the solution after the aforementioned aging to thereby convert it to an anatase titanium oxide sol, and concentrating and purifying the resultant anatase titanium oxide sol, the improvement comprising adjusting the concentration of solids in the above titanium hydroxide gel after washing to 0.2 wt.% or more and less than 1.5 wt.%. The improvement provides a practical process for producing an amorphous titanium peroxide solution and an anatase titanium oxide sol which are homogeneous and have excellent quality.

Description

Specification -

Amorufasu titanium peroxide solution and Ana evening one peptidase type titanium oxide sol preparation -

Technical field

The present invention, excellent adhesion, high film forming properties, uniform can create flat thin film, and drying the coating has a property that does not dissolve in water, the protective coating of various materials, photocatalyst , ultraviolet cut film, novel process for producing colored Koti ring amorphous type known to be useful as etc. titanium peroxide soluble liquid, in particular to the preparation and manufacturing apparatus for an industrial level. Further the invention relates to a novel process for the preparation of excellent photocatalytic activity which is prepared from an amorphous titanium peroxide solution anatase titanium oxide sol, particularly a process for producing or manufacturing equipment at industrial level.

BACKGROUND

Recently, by using a photocatalyst, harmful substances, offensive odor components generated in daily living environment, or decompose and purify such oil, there is an attempt to or sterilized, Applicable range of photocatalysts is expanding rapidly. Accordingly, the photocatalyst particles any substrate on its photocatalytic function without compromising, and firmly, and the method for supporting is obtained over a long period of time. In particular, when using a high anatase titanium oxide sol photocatalytic function as a photocatalyst, since bar Inda one function to the substrate is weak, the adhesion improvement is particularly sought.

However, the in the prior art method, the adhesion strength is not sufficient, is less that can be carrying a long period of time, if you try to create what can be carrying a long period of time increases the bonding strength, the photocatalytic function is reversed there has been a problem that the decrease. In the case of using a substrate made of an organic polymer resin may be a rutile type titanium oxide in which the photocatalytic function than anatase is said to be weak, the photocatalytic reaction proceeds, photochemical organic polymer resin per se What reaction coupled with, there was a ^ entitled to deterioration and decomposition by long-term use. In the case of using an organic polymer resin as the substrate, which had been considered to be pre-co one tee ring with shea Rikazoru like, cracks and voids are generated in the process of coagulation and drying of the sheet Rikazoru , there is the performance function as a binder problems.

Then, the photocatalyst particles any substrate on without Rukoto impair its photocatalytic function, strongly, and as a result of searching for the method for supporting extended period of time, Hei 9 - 2 6 2 4 8 described in 1 JP as, when the amorphous titanium peroxide solution having no photocatalytic activity is used as a binder and foremost, the photocatalyst particles any substrate on without causing I of damaging the photocatalytic function, strongly, and the long it has been found by the inventors that as possible out be supported over a period.

And for Ana evening one peptidase type titanium oxide sol having a photocatalytic activity made from the amorphous titanium peroxide solution or amorphous titanium peroxide solution, JP-A-9 one 7 1 4 1 8 No. their preparation in Japanese is disclosed ing. That is, in the publication, as a process for preparing amorphous peroxide titanium emissions solution according to the present invention, titanium tetrachloride 6 0% solution 5 cc with distilled water as a raw material 5 0 0 cc and solution in aqueous ammonia (1: 9) was added dropwise, to precipitate titanium hydroxide, washed with distilled water, hydrogen peroxide water 3 0% solution 1 0 cc added stirring, a yellow viscous solution (amorphous peroxide Ji Yun solution containing titanium) It discloses that to produce 7 0 cc. Also in this publication, this when amorphous titanium peroxide solution is heated at 8 0 ° C or anatase titanium oxide sol according to the present invention that can be obtained is described, also, the above-mentioned Japanese Laid by the present inventors 9 - 2 6 2 4 8 also 1 JP, as preparation of amorphous titanium peroxide solution of the present invention, the titanium salt aqueous solution such as a four inch chloride Tan, such as aqueous ammonia or sodium hydroxide alkali was added, pale bluish white occurring, hydroxyl amorphous -.. after washing 'separating the cation Tan, treated with hydrogen peroxide, p H 6 0~ 7 0, particle element size. 8 to 2 0 nm yellow transparent Amorufasu titanium peroxide solution which is a liquid is described to be obtained of. And in the publication, it is also described that can be produced Ana capacitor one peptidase type titanium oxide sol by heating Amorufa scan type titanium peroxide solution in 1 0 0 ° C or higher.

Disclosure of the Invention

However, production conditions of the amorphous titanium peroxide dissolved solution and anatase titanium oxide sol disclosed in the above publication are of a laboratory level, and not in the factory scale, can be applied in small-scale production and it'll production on a large scale, by the reaction heat generated in the process, the crystal grains is large or summer analyst evening one peptidase titanium peroxide sol, it was found that there are problems such as impurities come precipitated. Object of the present invention solves these problems, amorphous titanium peroxide solution and analysts evening is to provide a manufacturing method in the actual production level one peptidase type titanium oxide Nzoru.

The present inventors have made a keen study to solve the above problems, by reducing the solid content of the titanium hydroxide gel neutralization is the product of the reaction of titanium tetrachloride solution and ammonia water, the subsequent hydrogen peroxide by a this performing Peruokiso reaction with water found that the above problems can be solved, was Itaritsu completed the present invention.

That is, the present invention includes the steps of cooling and neutralization step Ru reacting the aqueous solution and a basic aqueous solution containing titanium, and a washing step of washing the resulting titanium hydroxide gel by neutralization reaction, the Chitangeru hydroxide after washing When the Peruokiso reduction step of reacting a peroxide with cooling water oxidation Chitangeru after cooling and curing step of curing the amorphous titanium peroxide solution produced by Bae Ruokiso reduction, Amorufasu peroxide after curing comprising a concentration and purification process, for example by ultrafiltration filtration treatment of titanium solutions, a process for the preparation of amorphous titanium peroxide solution, the solid concentration of the hydroxide of Chitangeru prior Peruokiso step after the washing step 0. 1 wt% or more 1.2 or preparation of amorphous titanium peroxide solution characterized in that less than weight percent, aqueous solution containing titanium and a base A neutralization step of reacting an aqueous solution, a cleaning step of cleaning the Chitangeru hydroxide generated Ri by the neutralization reaction, cooling the Chi hydroxide after washing evening Ringer's, over the post-cooling titanium hydroxide gel and Peruokiso reduction step of reacting the oxide with cold rejected, a curing step of curing the § Amorphous-type titanium peroxide solution produced by Peruokiso of the Amoru Fast titanium peroxide solution after curing to you one peptidase type titanium oxide sol a step pressurized heat converting, for example anatase titanium oxide sol produced by the heating step consists of the concentration and purification step by ultrafiltration treatment, a process for the preparation of anatase titanium oxide Tanzoru, Peruokiso step after the cleaning step 0 the solid content concentration of the titanium hydroxide gel before. 1 wt% or more 1. anatase, characterized in that less than 2 wt% Tanzoru relates to a process for the preparation of.

The present invention is an aqueous solution and the hydration reaction unit in which the basic aqueous solution are reacted, a cleaning means for cleaning the Chitangeru hydroxide produced by the neutralization reaction, the solid content concentration of the titanium hydroxide gel after washing comprising titanium a density adjustment means for adjusting, for example and means the concentration of solid contents consisting of heat exchanger (cooling) cools the conditioned water titanium oxide gel, for example a cooling device for applying a peracid compound to the cooled titanium hydroxide gel and Peruokiso means consisting of a reaction vessel equipped with a curing means for curing the amorphous titanium peroxide solution produced by Peruokiso reaction apparatus for producing an amorphous titanium peroxide solution and a ultrafiltration unit, in particular medium as the hydration means and Peruokiso means, it closed amorphous titanium peroxide dissolved, which comprises employing the system The manufacturing equipment and, an aqueous solution with a basic substance containing titanium - and a neutralization unit of reacting, and cleaning means for cleaning the Chitangeru hydroxide produced by the neutralization reaction, solid Chitangeru hydroxide after washing fraction a concentration adjusting means for the adjustment concentration, for example, means for heat exchanger solids concentration comprising a (cooling) cools the conditioned titanium hydroxide gel, for example, cooling the action of cooled peroxide hydroxide Chita Ringer's converting a Peruokiso means consisting of a reaction vessel equipped with a device, and a curing means for curing the amorphous titanium peroxide solution produced by Peruokiso reaction, the amorphous-type peroxy acid titanium solution after curing the anatase titanium oxide sol heating means, Ana evening one peptidase type titanium oxide sol manufacturing apparatus and a limited outer filtering means, in particular neutralize the reaction means and Peruokiso of As stage apparatus for producing Ana evening over peptidase type titanium oxide sol which is characterized that you adopt a closed system.

(raw materials)

The raw material used in the manufacture of amorphous titanium peroxide solution of the present invention, include titanium salt aqueous solution, an alkali hydroxide, hydrogen peroxide, and pure water as diluent, cleaning, etc., preferably distilled water be able to. As titanium salt is a chloride of titanium tetrachloride is preferred. Although Examples of the water-oxidizing Al force Li can be exemplified aqueous ammonia or hydroxide Natoriumu, it is preferable to use aqueous ammonia. When using aqueous sodium hydroxide, which in the amorphous titanium peroxide dissolved solution and anatase in one peptidase type titanium oxide sol N a ions tend to remain prepared, titanate which inhibits a photocatalytic function when these have film forming the it is impure material that Soviet Ichida. - (dilution step)

Four highly concentrated solution of titanium chloride T i C 1 4 is distilled 2 0-2 0 0 times - be used by diluting with water. When used in lower concentration than 2 0 0-fold dilution, there is a problem that the volume of the line intends reaction vessel neutralization reaction is increased and costs, 1.5 wt% Yori high concentration when using a medium with ammonia water temperature of the liquid is increased by reaction heat at the time of the sum, there is a possibility that metatitanic acid insoluble in water is precipitated. Further, it is preferable to dilute with reduced heat due to heat generation at the time of dilution.

(Neutralization reaction)

Then to generate and precipitate a titanium hydroxide by hydration in a titanium tetrachloride solution and ammonia water which is adjusted to a predetermined concentration. The precipitated titanium hydroxide is in a gel state by polymerization or hydrogen bonds between the hydroxyl groups. Neutralization reaction is, p H is 6.0 to 7.5, preferably p H 6. 8-7. It is desirable to perform the cormorants by zero. p H 6. less than 0 in an amorphous titanium peroxide solution that is caused a problem that tends to one form jelly, but the production of Amoru Fast titanium peroxide viscosity 稠体 using this method. Also, PH 7. 5 exceeds repeatedly quickly become alkaline side when performing the cleaning at the time of pure water washing, the precipitated titanium hydroxide is problem that the yield was redissolved decreases occurs. Furthermore, the neutralization reaction, increases the film density at the time of the reacting the polymerization degree is deposited decreases at a low temperature of. 1 to 5 ° C. During the neutralization reaction, it is good preferable to add small portions with stirring ammonia water as salts titanium solution. (Wash) - from the product-precipitated titanium hydroxide gel, raw materials and C 1 unreacted - to remove chloride Anmoniumu an ion or NH 4 + ion product, wash the reaction with distilled water. First, some time after the neutralization reaction was left - Heck discarded by decantation to Rajo supernatant. Then, the remaining hydroxide Chita Ringer's (conductivity: about 4 0, 0 0 0 x S / cm) and allowed to stand about 4 to stir 1 0-fold amount of distilled water was added enough from, decantation of the supernatant discard Ri by the emissions. This washing operation, conductivity repeated until the following 8 / XSZ cm. Further, in the cleaning operation of the titanium hydroxide, it may be utilized centrifuged instead decantation one Chillon. And, in such cleaning operations, it is desirable to recover titanium hydroxide contained in the waste water after washing. As a method for recovering titanium hydroxide, hydroxide using the first or al centrifuge or decanter device of the washed separated titanium hydroxide gel collect wash effluent to one tank Risurari flows out mixed in the cleaning liquid it can be exemplified a method for recovering the solid-liquid separation titanium down.

(Solid-concentration control)

Finished titanium hydroxide of washing, the solid content by dehydrating 0.1 wt% or more 1. Less than 2% by weight, preferably 0.3 to 1.0 wt%, in particular rather preferably 0.4 wt% It is adjusted to. The concentration adjusting process is very important because it directly affects the physical properties such as the size of the desired product der Ru amorphous titanium peroxide solution and analysts evening grain terminal of over zero type titanium oxide sol. When the solid concentration is 1. 2% by weight or more, the temperature of the solution rises in Oite reaction heat to Peruokiso reaction the next step, the viscosity of the amorphous titanium peroxide solution is increased. Thus, the solid concentration is less than 1.2 wt%, especially 1.0 is not particularly a problem if the ANATA one peptidase type oxidic particles diameter of the sol point When the weight or less, the reaction efficiency in economic the lower limit of the target in a flat plane 0. 1% by weight or more, particularly 0.3 wt% or more.

(Cooling) - Chitangeru hydroxide was over a solid concentration adjustment is cooled to 1 ~ 5 ° C by a heat exchanger or the like. For example, 0 ° and cooled C below freezing is titanium hydroxide gel results in material that does not peroxidation reaction such as metatitanic acid, also the reaction rate in Peruokiso in accordance becomes more than 5 ° C temperature of the solution is increased faster, the temperature of the liquid coming raised by the heat of reaction. Therefore progresses polymerization degree of amorphous-type titanium peroxide, connexion a high viscosity of the solution, next manufactured amorphous titanium peroxide solution Koti Ngushi hard to be of, undesirable.

(Peruokiso of)

Then, the solid content concentration of 0. 1% by weight or more 1. Less than 2 wt%, preferably 0. 3% by weight or more 1. 0 wt% or less, particularly preferably 0.4 Chitangeru hydroxide adjusted to wt% was added with aqueous hydrogen peroxide, it performs Peruokiso reaction by stirring reluctant 1 about 2 hours, such maintaining the temperature. 1 to 5 ° C. The addition amount of hydrogen peroxide water, the neutralization is determined by p H and a solid concentration of hydroxide Chita Ringer's after PH and washing after the reaction, for example, concentration 35 wt% peracetic acid hydrogen water used if, for complete reaction of the titanium hydroxide gel, about twice or more the amount of titanium tetrachloride solution are raw materials (stock basis), for example 1.2 5 be times added in several portions desirable. The amorphous titanium peroxide solution to produce the Peruokiso reaction is completed.

(Curing) Peruokiso amorphous titanium peroxide solution ends the reaction is subjected to then in curing process. Curing step is performed by a child stirred for several days while maintaining the amorphous titanium peroxide solution produced by Peruokiso reaction to room temperature. Curing is completed when the p H of the amorphous titanium peroxide solution became 6.0 or more. The curing process is a purpose of terminating the Peruokiso reaction completely, also desirable to neutralize the excess addition to that the aqueous hydrogen peroxide is decomposed in natural amorphous titanium peroxide solution during the reaction . (Concentration and purification of the amorphous titanium peroxide solution)

Next, an amorphous titanium peroxide solution passed through the curing process, as well as miscellaneous ions are removed by ultrafiltration and concentrated. Virtuous preferable to be treated with an ultrafilter temperature of the solution to a concentration treatment while cooling so increased. Such ultrafiltration, solid concentration from 1.6 to 1.7% by weight of amorphous titanium peroxide solution is obtained.

(Ana evening generation of over zero type titanium oxide sol)

On the other hand, the anatase-type titanium oxide sol had a solid content concentration 0 after the curing step first. 1% by weight or more 1. Less than 2 wt%, preferably 0. 3% by weight or more 1. 0 wt% or less, particularly preferably 0. 4 wt% Amorufu adjusted to § scan type titanium peroxide solution at the heating temperature 1 0 0~ 2 0 0 ° C, 1~ 2 0 hours of heat treatment, preferably a solution temperature 9 0 ° C over 1 0 0 ° It is prepared by performing 5 hours approximately pressurized heat treatment at C below. Moreover, the solid concentration of the concentrated production of amorphous peroxide titanium down solution from 1.6 to 1.7% by weight or more of those heat treatment, easy crystal grain size of the anatase type titanium oxide sol is large Ri name photocatalytic function there is likely to decrease. By this way the heat treatment at lower concentrations, the crystal grain size of the analysts evening over peptidase type titanium oxide sol becomes smaller, also up photocatalytic function. Further, heating for 8 hours at 1 0 0 ° C, pale those yellow slightly tinged suspended fluorescence is obtained, 1 0 0 ° C 1 but when heated 6 hours things very pale yellow is obtained, these are the drying degree of adhesion is reduced slightly as compared with those heated 1 0 0 C 5 hours. Until 2.4 wt% when di Pinguko one bets like viscosity low co one preparative liquid since this § Na evening one peptidase type titanium oxide sol viscosity than amorphous titanium peroxide solution is reduced It is used to increase the concentration.

Further, during the neutralization reaction, when adjusted p H is on the acidic side is not shortened heating time and progresses faster crystallization, for example 1 1 0 ° C shall may be performed 4-5 hours of heat treatment. On the other hand, when the neutralization reaction, when adjusted p H is on the alkaline side, the crystallization is slow, for example, 1 2 0 ° C, etc. performing heat treatment of about 6 hours, it is desirable to increase the heating temperature. (Concentration and purification of you one peptidase type titanium oxide sol)

Then, Ana evening one peptidase type titanium oxide sol produced by the heat treatment, ultrafiltration process is performed, along with miscellaneous ions are removed and concentrated. By either mow ultrafiltration treatment, a solid concentration from 2.3 to 2.4 wt%, p H 7. 5~ 9. 0 analyst evening one peptidase type titanium oxide sol is obtained.

(Manufacturing equipment)

The manufacturing apparatus of an amorphous titanium peroxide solution and anatase titanium oxide sol Ru can be exemplified by the Figures 1 and 2 wherein.

Open type manufacturing apparatus shown in Figure 1, the titanium salt solution, such as titanium tetrachloride, hydroxide Al force Li hydroxide, etc. Anmoniumu, and each of the raw material tank 1 to 3 peroxides such as hydrogen peroxide solution , a titanium salt solution - a dilution tank 4, 5 of the hydroxide Al force Li, a hydration reaction means in comprised of neutralization vessel 6 of the alkali hydroxide and titanium salt solution, washing with Decant the neutralization reaction product a cleaning means consisting of bath 7, the heat exchanger and cooling means consisting of (cooling) 8, and Peruokiso means consisting Peruokiso reaction vessel 9 having a cooling mechanism, the amorphous-type titanium peroxide solution is Peruokiso reaction product and curing means comprising curing tank 1 0, and ultrafiltration unit consisting of ultrafiltration apparatus 1 1 for concentrating and removing miscellaneous I O emissions of amorphous titanium peroxide solution after curing, peroxide is the final product oxidation A storage tank 1 2 tan, heat exchanger and (heating) 1 3, a heating means comprising a heat treatment tank 1 4 for the Amorufasu titanium peroxide solution nourishment after birth Ana evening one peptidase type titanium oxide sol, heating process heat exchanger to stop the crystallization of the resulting anatase one peptidase type titanium oxide sol by (cooling) 1 and 5 made of the cooling means, concentrated to remove miscellaneous ions Ana evening in over peptidase type titanium oxide Nzoru produced by heat treatment ultrafiltration unit consisting of ultrafiltration device 1 6, and a storage tank 1 7 for a titanium oxide as a final product. It is also possible to have use of a centrifuge or ultrafiltration unit 1 8 instead of the above washing tank 7.

The apparatus for manufacturing a closed-type amorphous titanium peroxide solution and Ana evening one peptidase type titanium oxide sol shown in FIG. 2, the tubular mixing mixer, For example static take mixer (Noritake C o., Ltd.), raw material solution mixing tank Ya of, or washing Kiyoshiso, neutralization tank, which has a feature in that it employs a closed system to be used in place of Peruokiso reaction vessel, following, amorphous peroxide using the device showing an example of producing the titanium solution and anatase one peptidase type oxide Chitanzo Le.

A titanium salt aqueous solution from the raw material tank 2 1 titanium salt solution, and distilled water from the dilution water for the reservoir tank 2 3 equipped with a distillation water production equipment 2 2, is mixed and diluted by mixed-mixer 2 4. Me dilution concentration is adjusted by the flow rate control valve 2 5 provided on the lower stream of each tank. Similarly, hydroxide Al force Li from the raw material tank 2 6 hydroxide of an alkali, and distilled water from the dilution water for savings distillation tank 2 3, you mixed and diluted by a mixer 2 7. Similarly the concentration of dilution, the flow controller outlet provided downstream of the tank - adjusted by Rubarubu 2 5.

Then, a diluted aqueous titanium salt solution and diluted alkali hydroxide, and mixed in the desired proportions by the flow control device 2 8 were neutralized reaction by a mixer 2 9 provided on the downstream , and measured more p H in p H meter 3 0, feeds back the measured value to the flow rate control device 2 8.

Titanium hydroxide is neutralized reaction product is then washed water guide pipe and the drainage pipe in the middle is disposed thereon, introduced into the sheet Kkuna 3 1 having a liquid level water gauge and the solenoid valve is, decantation one Chillon cleaning is performed. Decantation - Chillon cleaning, by the discharge of the washing waste water from inlet and discharge pipe of the washing water via the washing water inlet pipe from the washing distilled water storage tank 3 3, a mixer 3, which is provided downstream of the thickener 3 1 after being stirred by 2, the value measured by conductivity meter 3 4 is automatically repeated until the specified value. Further, the washing waste water is collected in reslurry vessel 35 is configured to match the titanium hydroxide after washing the titanium hydroxide obtained by solid-liquid separation, hydroxide after washing the thus obtained titanium solids concentration is measured by the solids concentration (or specific gravity) instrument 3 6 provided downstream, that looks like distilled water is added the desired solids concentration in accordance with the measured values .

A peroxide from storage tank 3 7 peroxides such as hydrogen peroxide solution, the The desired titanium hydroxide became solid concentration, prior to mixing and mixed by a cooling mechanism with a mixer 3 8 Peruokiso carry out the reaction. Peruokiso of reactants are stirred aged at reaction aging tank 3 9. And such Peruokiso reduction reaction is preferably carried out in. 1 to 5 ° C. Amorphous titanium peroxide solution is Peruokiso reaction product ripening is over, then subjected to several days aging at room temperature in curing tank 4 0. Although curing may be carried out at low temperatures, because between time-consuming, preferably carried out at room temperature.

Amorphous titanium peroxide solution after curing is purified and concentrated by ultrafiltration unit 4 2 and a ultrafilter 4 1 and the cooling mechanism with a mixer 3 8. Simultaneously circulating the ultrafiltration device 4 to be treated was purified and concentrated by two dozens of times Z min to remove the effluent from the ultrafilter 4 1 in the circulation process, carried out Ho添 minute distilled water its to. Amorphous titanium peroxide solution having been subjected to the ultrafiltration process is filtered through a filter 4 3, after removal of the contaminants, for example, 1.7 as the weight percent of amorphous titanium peroxide solution in the product storage tank 4 within 4 It is stored in the following 1 5 ° C.

On the other hand, the amorphous titanium peroxide solution after curing undergoes a mixing mixer 4 5 with heating mechanism, is converted to be heated in the heating device with the container 4 6 anatase oxidation sol. The analyst evening can also be used O one Tokurebu conversion to one peptidase type titanium oxide sol, etc. When performing in 1 0 0 ° C or higher, as a container with a heating device as required. The analyst evening one peptidase type titanium oxide sol is then subjected to ultrafiltration with an ultrafilter apparatus 4 7 similarly to the above amorphous titanium peroxide solution. Ultrafiltration finished Ana evening one peptidase type oxidation sol is stored for example, 2.4 as the weight percent of you one peptidase type titanium oxide sol in the product storage tank 4 within 8 below 1 5 ° C. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic illustration of an open-type amorphous titanium peroxide solution and analysts evening one peptidase type oxidation sol of the manufacturing apparatus.

FIG. 2 is a schematic illustration of a closed-type amorphous titanium peroxide solution and analysts evening one peptidase type oxidation sol of the manufacturing apparatus. - BEST MODE FOR CARRYING OUT THE INVENTION

Below, but by way of examples to explain the present invention more specifically, this inventions the scope is not limited to these examples. Example 1 [open type manufacturing apparatus]

(Preparation of an amorphous titanium peroxide solution)

Raw material tank 1 of titanium tetrachloride T i C 1 4 5 0% solution to a solution prepared by diluting (Sumitomo Shichi' Box Co., Ltd.) in dilution tank 4 to 7 0-fold with distilled water, the raw material tank 2 was diluted in dilution tank 5 2 5% solution hydroxide Anmoniumu NH 4 OH (manufactured by Takasugi pharmaceutical Co., Ltd.) to 1 0-fold with distilled water solution, volume ratio 7 in neutralizing anti応槽6: 1 mixed and subjected to neutralization reaction. Hands upon neutralization reaction, Nozomiyon continue the addition of dilute hydroxide Anmoniumu solution 1 7 0 L titanium chloride solution 1 2 0 0 L portionwise with stirring, a neutralization reaction after p H is 6.8 to 7 . was adjusted to 1. Neutralization reaction after a while was left to dehydration-concentration tank 7, the supernatant discarded, and the remaining approximately four times distilled water gel of titanium hydroxide T i (OH) 4 was added and thoroughly stirred allowed , it was discarded and the supernatant. To remove material and salt of Anmoniumu unreacted repeating such an operation 7 times, where the conductivity of the supernatant became 8 S / cm, leaving only titanium hydroxide gel discarded the supernatant It was. Distilled water used in this washing was 1 6 7 6 0 Mr.

1 having a solid concentration by dehydration or the like. 0 and adjusted to wt%, those that cooling the titanium hydroxide gel 6 1 0 L of bluish white color after washing 3 ° C, 3 5% hydrogen peroxide water ( Japan Paokisai manufactured preparative Ltd.) was added in a 2 4 L 3 0 minutes every 2 times, about 5 ° C overnight stirring and aged for the yellow transparent amorphous titanium peroxide solution to about 6 4 0 L is obtained obtained. The Amorufasu peroxide titanium down solution was aged under stirring in 4 days aging tank 9 at room temperature, solids concentration 1. 0 wt% of amorphous titanium peroxide solution was prepared.

Then, an amorphous titanium peroxide solution after curing, in order to concentrate and air removed by the miscellaneous ions, using Nippon Nerisui Co. ultrafilter 1 0, so that the temperature of the solution does not rise 2 0 ° while cooling and C, also by adding distilled water was carried out until the conductivity of the effluent from the ultrafilter is 2 S / cm. The ultrafiltration process, solids concentration of 1. 7 wt%, p H 6. 5 purposes that amorphous titanium peroxide solution 2 5 0 L were obtained.

(Production of anatase titanium oxide sol from amorphous titanium peroxide solution)

Solid concentration 1 after the curing. 0 wt% of the amorphous titanium peroxide solution, the bath in the heat treatment vessel 1 2 is heated for 6 hours at 1 0 0 ° C, Ana after heating evening one peptidase type oxide sol was obtained. Ana evening over peptidase type titanium oxide sol produced by the heat treatment, ultrafiltration with an ultrafilter apparatus 1 3 until the conductivity is less than 2 SZ cm is applied, is concentrated together with miscellaneous ions are removed, solids concentration from 2.3 to 2.4 wt%, p H 7. 8, the particle size. 8 to 2 0 nm Ana evening one peptidase type titanium oxide sol of interest were obtained, example 2 [closed manufacturing apparatus ]

(Production of Amorufasu titanium peroxide solution)

Distillation with four titanium tetrachloride aqueous solution from the raw material tank 2 1 of 50% solution of titanium tetrachloride (manufactured by Sumitomo Sitix Ltd.) is accommodated 1. O m 3, the production capacity of 3. 2 m 3 / h of distilled water from 2 O m 3 dilution of distilled water storage tank 2 3 equipped with a water producing apparatus 2 2, by a mixer 24 and mixed-diluted and diluted adjusted to 7 0 times. Similarly, the hydroxide Anmoniumu solution from the raw material tank 2 6 1. O m 3 to 2-5% solution of hydroxide Anmoniumu (manufactured by Takasugi Pharmaceutical Co., Ltd.) is housed, from dilute water for the storage tank 24 of distilled water, were mixed and diluted with a mixer 2 7 was diluted adjusted to 1 0-fold. Dilution was adjusted by controlling the solenoid valve by the liquid quantity value of Oparu fluid meter. In addition, as the mixing mixer scan evening using a take mixer (Roh Ritake C o., Ltd.) (hereinafter the same).

Then, the diluted hydroxide Al force Li and dilute aqueous titanium salt solution, were mixed in equal amounts by the flow rate control device 2 8 were neutralized reaction by mixed-mixer 2 9 provided on the downstream . At that time, the flow rate of definitive to a mixer 2 9 was approximately 1 8 0 k gZh. The mixing ratio by the flow controller outlet Ichiru apparatus 2 8 controls the respective inflow by measurement of pH meter 3 0, was set to p H 6. 9 ± 0. 2.

Chitangeru hydroxide is neutralized reaction product having at thickener 3 1 which is automated liquid level water gauge and solenoid valve assembly seen combined with a mixer 3 2 and washing distilled water storage tank 3 3 It was washed by the cleaning mechanism. Washing, until the measured value by the conductivity meter 3 4 becomes a value of 8 SZC m, row by adding the washing water for the 9-fold amount to the titanium hydroxide gel in thickener 3 1 ivy. The cleaning waste water in thickener 3 1 is collected in reslurry vessel 35, combined with titanium hydroxide after washing the titanium hydroxide obtained by solid-liquid separation. Chitangeru hydroxide finishing the washing, with more distilled water to a solids concentration measuring instrument 3 6, concentration of the solid content was adjusted to 0.7 wt%.

35% aqueous hydrogen peroxide and hydrogen peroxide from storage tank 3 7 (Japan Pas made one Okisai preparative Ltd.), and the hydroxide titanium down adjusted to a solid concentration of 0.9 wt%, the cooling mechanism mixed by biasing a mixer 3 8 was Peruokiso reaction. Peruokiso reaction was, 3 ° C. 1 8 hours and stirred aged at reaction aging tank 3 9 with a cooling device. Aging is ended Peruokiso reaction product § mode Rufasu titanium peroxide solution, then subjected to room temperature during 9 about 6 hours curing in curing tank 4 0.

Amorphous titanium peroxide solution after curing was purified and concentrated by ultrafiltration unit 4 2 with ultrafilter 4 1. Purification and concentration by ultrafiltration unit 4 2 0. Circulates 8 3 m 3 / h of processing speed, and at the same time to remove waste water from the ultrafilter 4 1 in the circulation process, and Ho添the amount of distilled water It was carried out until the conductivity of the effluent from the ultrafilter 4 1 becomes 2 / cm. Amorphous titanium peroxide solution having been subjected to the ultrafiltration process is filtered through a filter 4 3, after removal of the contaminants, solids concentration 1.7 wt%, p H 6. 2 of § mode Rufasu peroxide titanium solution was obtained. The amorphous peroxide titanium solution is stored below 1 5 ° C in the product storage tank 4 inside 4.

(Production of Ana evening over peptidase type titanium oxide sol from amorphous titanium peroxide solution)

On the other hand, the amorphous titanium peroxide solution after curing undergoes a mixing mixer 4 5 with a heating mechanism heating 1 0 0 ° C 5 hours in a heating device with a container 4 6 converts the analysts data one peptidase type titanium oxide sol filtered, ANATA one peptidase type titanium oxide sol after the filtration, and then subjected to ultrafiltration with an ultrafilter apparatus 4 7 above amorphous titanium peroxide solution the same way. ANATA one peptidase type titanium oxide sol to ultrafiltration treatment example end is filtered, after removal of the contaminants, solids concentration 2.4 wt%, p H 8. 2, particle size. 8 to 2 0 nm analyst evening one peptidase product storage tank 4 within 8 is stored in the following 1 5 ° C as the type oxidation sol. Industrial Applicability

According to the present invention, may become crystals with large amorphous titanium peroxide solution and anatase one peptidase type oxidation sol, there is no danger due to heat generation, without the yield loss, amorphous titanium peroxide solution and analysts evening can be produced by actual production level over zero type titanium oxide sol.

Claims

The scope of the claims -
1. A neutralization step of reacting an aqueous solution and a basic aqueous solution containing titanium, and a cleaning step of cleaning the Chitangeru hydroxide produced by the Neutralization reaction, cooling the Chitangeru hydroxide after washing, after cooling and Peruokiso reduction step of reacting a peroxide with cooling to titanium hydroxide gel, and curing step of curing the amorphous titanium peroxide solution produced by Peruokiso reduction, concentration and purification of amorphous titanium peroxide solution after the curing process consisting of, a process for the preparation of § Amorphous-type titanium peroxide solution, 0 solids concentration of Chitangeru hydroxide prior Peruokiso step after the washing step. 1 wt% or more 1. be less than 2 wt% preparation of amorphous peroxide titanium down solution characterized in.
2. Concentration and purification steps, the preparation of amorphous titanium peroxide solution of claim 1, wherein a carried out by ultrafiltration treatment.
3. A neutralization step of reacting an aqueous solution and a basic aqueous solution containing titanium, and a cleaning step of cleaning the Chitangeru hydroxide produced by the Neutralization reaction, cooling the Chitangeru hydroxide after washing, after cooling and Peruokiso reduction step of reacting a peroxide with cooling to titanium hydroxide gel, and curing step of curing the amorphous titanium peroxide solution produced by Peruokiso reduction, Ana evening one peptidase amorphous titanium peroxide solution after curing a heating step of converting the type titanium oxide sol, consisting generated Ana evening and concentrated and purification steps one peptidase type titanium oxide sol by heating process, Ana evening in a method of manufacturing an peptidase type titanium oxide sol, after Arai诤 step Peruokiso step 0 having a solid concentration of hydroxide Chitange Le before. 1 wt% or more 1. anatase, characterized in that less than 2 wt% The process of reduction sol.
4. Concentration and purification steps, Ana evening preparation one peptidase type titanium oxide sol according to claim 3, characterized in that it is carried out by ultrafiltration treatment.
5. Adjust the neutralization reaction means for reacting an aqueous solution and a basic aqueous solution containing titanium, and a cleaning means for cleaning the Chitangeru hydroxide produced by the neutralization reaction, the solid content of the titanium hydroxide gel of after rinsing a concentration adjusting means for the means for cooling the Chitangeru hydroxide surface solid content concentration is adjusted, a Peruokiso means for applying a peroxide to the cooling water titanium oxide gel, amorphous form produced by Peruoki Seo reaction and Nutrient raw means for curing the titanium peroxide solution, an amorphous titanium peroxide solution of a manufacturing apparatus that includes a ultrafiltration unit.
6. A means for cooling the heat exchanger (cooling), the manufacturing apparatus of Amorufa scan type titanium peroxide solution of claim 5, wherein the Peruokiso means is a reaction vessel equipped with a cooling device.
7. Neutralization as a reaction means and Peruokiso means, closed apparatus for manufacturing amorphous titanium peroxide solution of claim 5 or 6, wherein adopting system.
8. Adjust the neutralization reaction means for reacting an aqueous solution and a basic aqueous solution containing titanium, and a cleaning means for cleaning the Chitangeru hydroxide produced by the neutralization reaction, the solid content of the titanium hydroxide gel of after rinsing a concentration adjusting means for the means for cooling the Chitangeru hydroxide solids concentration is adjusted, a Peruokiso means for applying a peroxide to the cooling water titanium oxide gel, over amorphous-type produced by Peruoki Seo reaction and Nutrient raw means for curing the titanium oxide solution, the heating means and, Ana evening one peptidase type titanium oxide sol having a ultrafiltration means for converting the amorphous titanium peroxide solution after curing to you one peptidase type oxidation sol of manufacturing equipment.
9. A means for cooling the heat exchanger (cooling), anatase titanium oxide sol of a manufacturing apparatus according to claim 8, wherein the Peruokiso means is a reaction vessel equipped with a cooling device. -
1 0. Neutralization as a reaction means and Peruokiso means, Ana evening one peptidase type oxidation sol production apparatus according to claim 8 or 9, wherein the employing a closed system. -
PCT/JP1999/005236 1998-09-28 1999-09-27 Method for production of amorphous titanium peroxide solution and anatase titanium oxide sol WO2000018686A1 (en)

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CN101747453B (en) 2008-12-02 2011-08-03 中国石油天然气股份有限公司 Aging process of multiple-catalytic agent in solution polymerization system and device
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US9267868B2 (en) 2008-08-29 2016-02-23 Lee H. Angros In Situ heat induced antigen recovery and staining apparatus and method
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US8092742B2 (en) 1999-07-08 2012-01-10 Lee Angros In situ heat induced antigen recovery and staining apparatus and method
US8007721B2 (en) 1999-07-08 2011-08-30 Lee Angros In Situ heat induced antigen recovery and staining apparatus and method
US8071023B2 (en) 1999-07-08 2011-12-06 Lee Angros In situ heat induced antigen recovery and staining apparatus and method
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US8518174B2 (en) 2002-11-07 2013-08-27 Sustainable Titania Technology Incorporated Titania-metal composite and method for preparation thereof, and film forming method using dispersion comprising the composite
CN1729145B (en) 2002-11-07 2010-04-28 萨斯提那普尔科技股份有限公 Titania-metal composite and method for preparation thereof, and film forming method using dispersion comprising the composite
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WO2004041723A1 (en) * 2002-11-07 2004-05-21 Sustainable Titania Technology Incorporated Titania-metal composite and method for preparation thereof, and film forming method using dispersion comprising the composite
US7303738B2 (en) 2002-12-20 2007-12-04 Sumitomo Chemical Company, Limited Method for producing titanium oxide
EP1742788A4 (en) * 2004-04-16 2016-04-13 Tioxoclean Inc Metal peroxide films
US9267868B2 (en) 2008-08-29 2016-02-23 Lee H. Angros In Situ heat induced antigen recovery and staining apparatus and method
US9766165B2 (en) 2008-08-29 2017-09-19 Lee H. Angros In situ heat induced antigen recovery and staining apparatus and method
CN101747453B (en) 2008-12-02 2011-08-03 中国石油天然气股份有限公司 Aging process of multiple-catalytic agent in solution polymerization system and device

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