JP4248288B2 - Recycling method of titanium metal-containing waste, titanium oxide coating liquid and manufacturing method thereof, titanium oxide member - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for recycling a titanium metal-containing waste, a titanium oxide coating solution, a method for producing the same, and a production apparatus therefor, and more specifically, ammonia water and hydrogen peroxide in a titanium metal-containing waste. And a method of recycling a titanium metal-containing waste, a method of manufacturing a titanium oxide coating solution, and a product thereof, wherein a titanium metal complex is formed by adding an acid and recycled as a titanium oxide coating solution, etc. is there.
[0002]
[Prior art]
Titanium is light, strong and durable, so it is used in various applications such as aircraft and golf shafts. When forming titanium, since titanium is a high melting point metal, cutting is usually performed, and cutting waste of several tons to several tens of tons is generated annually. Titanium cutting waste and other wastes have been landfilled so far, but the landfill suitable land area has been steadily decreasing, and as a result, the processing costs have risen, so titanium metal such as titanium cutting waste has increased. The development of an effective utilization method of contained waste has been eagerly desired.
[0003]
On the other hand, a titanium oxide coating solution has a great demand because it can form a titanium oxide film useful as a photocatalyst or a protective film. Until now, titanium oxide coating liquid is made by reacting titanium raw materials such as ilmenite ore with hydrochloric acid or sulfuric acid, etc., then hydrolyzing to make titanium hydroxide, and then baking it to titanium oxide and pulverizing In addition, a complicated process of mixing with a binder is necessary, and it is very expensive, from several thousand yen to several hundred thousand yen per liter (see Non-Patent Documents 1 to 3).
[0004]
[Non-Patent Document 1]
Titanium oxide properties and applied technology, Manabu Kiyono, p. 13-33 (1991), Gihodo Publishing Co., Ltd. [Non Patent Literature 2]
The world of photocatalyst, Hiroshi Takeuchi, Sadao Murazawa, Satoshi Ibusuki, p. 24-25 (1998), Industrial Research Committee, Inc. [Non-Patent Document 3]
Chemical Handbook Application, Chemical Society of Japan, p. 153 (1980), Maruzen Co., Ltd.
[Problems to be solved by the invention]
In such a situation, the present inventors, in view of the above prior art, as a result of earnestly researching with the goal of developing a method for recycling titanium metal-containing waste such as titanium cutting waste, Found that titanium oxide coating liquid, inorganic binder, deodorant, etc. can be recycled by adding ammonia water and hydrogen peroxide water to titanium cutting scrap of titanium metal-containing waste to form titanium metal complex, creating the present invention It came to do.
The present invention is a titanium down switching cutting scrap titanium metal-containing waste, for Useful photocatalysts as such photocatalyst or a protective film titanium oxide film or titanium oxide coating liquid, an inorganic binder, inexpensive recycling methods and their as deodorants An object of the present invention is to provide a manufacturing method and an efficient environment-friendly manufacturing apparatus.
[0006]
[Means for Solving the Problems]
The present invention for solving the above-described problems comprises the following technical means.
(1) a titanium metal shavings of titanium metal-containing waste, such rapid temperature rise does not occur, after the addition of aqueous ammonia little by little, with the addition of hydrogen peroxide little by little to form a titanium metal complex A process for producing a yellow titanium oxide coating liquid by forming a sol or allowing it to stand as a gel and a supernatant , and adding aqueous ammonia and hydrogen peroxide to the titanium metal-containing waste A method for producing a titanium oxide coating liquid for photocatalyst , comprising the step of liquefying and recovering ammonia gas generated at the time and recycling it to a raw material .
(2) to the titanium metal-containing waste, after it added portionwise with stirring ammonia water, an after added portionwise with stirring hydrogen peroxide to produce a sol, separating the supernatant liquid gel The manufacturing method of the titanium oxide coating liquid as described in said (1) obtained.
( 3 ) Ammonia water is added little by little to titanium metal-containing waste while stirring, hydrogen peroxide water is added little by little with stirring to form a sol, and then the gel is separated to obtain a supernatant. The manufacturing method of the titanium oxide coating liquid as described in said (1) .
( 4 ) Ammonia water and hydrogen peroxide water are added to the titanium metal cutting waste of the titanium metal-containing waste while suppressing evaporation and decomposition of the ammonia water and hydrogen peroxide water to form a titanium metal complex to form a sol. or generate further by on standing gel and supernatant, yellow prepared as titanium oxide coating liquid, photocatalytic titanium oxide coating which comprises a sol or gel of the titanium metal complex liquid.
(5) the coated substrate to an acid titanium coating solution according to (4), the manufacturing method of the titanium oxide layer, characterized by heating or drying.
( 6 ) A titanium oxide member, characterized in that the substrate is coated with the titanium oxide coating liquid according to (4) .
(7) a titanium metal shavings of titanium metal-containing wastes as raw materials, an apparatus for producing photocatalytic titanium oxide coating solution, anti reacting a titanium shavings, aqueous ammonia, and hydrogen peroxide 応器, Raw material titanium metal cutting waste, ammonia water, hydrogen peroxide raw material inlet installed at the top of the reactor, and condensate for liquefying ammonia gas generated when ammonia water and hydrogen peroxide water are added vessel, the reaction solution stirring means for stirring and the reactor apparatus for producing a photocatalytic titanium oxide coating solution is characterized that you include a titanium oxide coating solution outlet of the installed product in the lower part of the.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail.
The titanium metal-containing waste used in the present invention is not limited to any kind as long as it is titanium cutting waste of waste containing titanium metal, but a titanium metal-containing waste having a large titanium metal content is desirable.
[0008]
The shape of the titanium metal-containing waste used in the present invention is various, such as powder, granular, plate, foil, tubular, cylindrical, prismatic, conical, spherical, bowl-shaped, and rugby ball type. Although it is mentioned, the thing with a large surface area such as powder is desirable.
[0009]
The aqueous ammonia used in the present invention is an aqueous ammonia solution and may be ammonia-containing waste water. The hydrogen peroxide solution used in the present invention is an aqueous solution of hydrogen peroxide, and may be waste water containing hydrogen peroxide solution. In this way, by using wastewater, it is possible to further contribute to the use of waste.
[0010]
Examples of acids used in the reference examples of the present invention include carbonic acid, formic acid, acetic acid, propionic acid, succinic acid, uric acid, phosphoric acid, citric acid, malic acid, succinic acid, folic acid, amino acids, linoleic acid, linolenic acid, salicylic acid, phthalic acid. Acid, stearic acid, nitric acid and the like are particularly preferable, and a mixture thereof may be used. Moreover, the waste water containing them may be sufficient. As such, the use of waste water can further contribute to the use of waste.
[0011]
In the titanium metal-containing waste recycling method of the present invention, a titanium oxide coating solution is obtained by adding ammonia water and hydrogen peroxide water to such a titanium metal-containing waste to form a titanium metal complex. And a titanium oxide coating liquid can be manufactured by this method. In addition, when an acid is added, not a dispersion liquid but a water-soluble uniform titanium oxide coating liquid is obtained.
[0012]
At this time, it is necessary to add ammonia water and hydrogen peroxide water to the titanium metal-containing waste in this order. At this time, after the titanium metal-containing waste is loosened or pulverized, the production rate of the titanium oxide coating solution is greatly increased by adding ammonia water or hydrogen peroxide water and stirring. Can be made. Further, at this time, it is preferable to add them little by little so as not to cause a rapid temperature rise, so that evaporation and decomposition of aqueous ammonia and hydrogen peroxide can be suppressed. It is desirable to cool in the case of a sudden temperature rise. In the present invention, it is desirable to recover evaporated ammonia water and reuse it as a raw material.
[0013]
Amount of ammonia water and hydrogen peroxide at this time, ammonia water is 10 to 20 mol relative to a titanium metal 1 mole of titanium metal-containing waste, it hydrogen peroxide solution is 25 to 40 molar Is preferred. When the concentration of aqueous ammonia or hydrogen peroxide is low, a low-concentration titanium oxide coating solution is obtained, and when these concentrations are high, a high-concentration titanium oxide coating solution is obtained. The concentration of ammonia water or hydrogen peroxide water is preferably about 30% from the viewpoint of cost and availability, but waste water containing them can also be used.
[0014]
In this case, in the case of the reference example to which an acid was added, an aqueous solution was obtained, whereas in the case of the present invention in which no acid was added, a sol was obtained, and when it was allowed to stand, a gel and a supernatant were obtained. It is done. Any of these can be used as a titanium oxide coating solution for producing a titanium oxide film useful as a photocatalyst or a protective film, and a titanium oxide powder can be obtained by heating and drying as it is. In addition, it can be used as a flocculant by diluting it, or it can be used as a deodorant by spraying it directly in a room or garbage. Furthermore, the supernatant obtained when no acid is added can also be used as a deodorant by spraying it into a room or garbage as it is. And since a gel becomes a hard film | membrane when dried, it can be utilized also as a normal temperature hardening type inorganic binder.
[0015]
When producing this titanium oxide coating solution, a titanium metal-containing waste, ammonia water, hydrogen peroxide water inlet and condenser are installed in the upper part of the reaction vessel, have a stirring means, and take out the product in the lower part. Using the manufacturing equipment provided with a mouth, first throw in the waste containing titanium metal , add hydrogen peroxide water while stirring and adding ammonia water, liquefy and recover the ammonia gas generated at that time By recycling to raw materials, efficient production can be performed.
[0016]
As an apparatus used in the method of the present invention, for example, a stirrer 2 and a condenser 3 are preferably installed in a reactor 1 having a raw material inlet and a product outlet, and the remaining ammonia gas is reacted. A titanium oxide coating liquid production apparatus provided with a fan 4 that is returned to the container is exemplified. The apparatus of the present invention is not limited to the above-described means, and can be used in the same manner as long as they are effective.
Next, the operation of the apparatus of the present invention will be described. Titanium metal-containing waste is charged into the reactor 1 from the raw material inlet, then ammonia water is added, and the mixture is thoroughly stirred with the stirrer 2, and then hydrogen peroxide is added with stirring. The ammonia gas generated at this time is liquefied by the condenser 3 and returned to the reactor 1, and the ammonia gas remaining in the reactor 1 is returned to the reactor 1 by the fan 4 and reused as a raw material. When hydrogen peroxide is added to the reactor 1 with stirring, a yellow titanium oxide coating solution sol is obtained, and when left standing for a while, it is separated into a gel and a supernatant. In addition , when hydrogen peroxide and an acid are added to the reactor 1 with stirring, a yellow water-soluble uniform titanium oxide coating solution is obtained. It is possible to appropriately add other arbitrary means to the apparatus of the present invention according to the purpose of use.
[0017]
The titanium oxide coating liquid of the present invention thus obtained can be coated on a substrate and heated or dried to produce a titanium oxide film. At this time, the higher the heating temperature, the harder the film. Further, when heated and dried at a low temperature, an amorphous titanium oxide film is obtained, and when heated at about 300 to 600 ° C., a titanium oxide film having a high-performance crystal form of anatase as a photocatalyst is obtained. Further, when heated at a temperature higher than that, a titanium oxide film having a rutile crystal form can be obtained.
[0018]
The titanium oxide coating solution of the present invention thus obtained can be produced as it is or by adding photocatalyst particles to the resulting dispersion and coating on various substrates, and heating or drying to produce a titanium oxide member. it can. When this titanium oxide member is irradiated with artificial light from sunlight, fluorescent lamps, incandescent lamps, black lights, UV lamps, mercury lamps, xenon lamps, xenon lamps, halogen lamps, metal halide lamps, etc., electrons and holes are generated. By virtue of its oxidizing power, harmful chemical substances are quickly and efficiently oxidized and decomposed into carbon dioxide and the like to be harmless.
[0019]
【Example】
Next, the present invention will be specifically described based on reference examples and examples, but the present invention is not limited to the following examples.
Reference example 1
(1) Manufacture of titanium oxide coating solution Dissolve 1 mol of titanium metal cutting waste and put it in a beaker, add 20 mol of ammonia water to 1 mol of titanium metal cutting waste while stirring, then add 35 mol of hydrogen peroxide solution. While stirring, 1 mol of acetic acid was further added with stirring. As a result, a yellow titanium oxide coating solution was obtained. This was coated on a glass substrate and heated at 500 ° C. to form a titanium oxide film on the glass substrate. As a result of examining the crystal form of the titanium oxide film with an X-ray diffractometer, it was a high-performance anatase as a photocatalyst.
[0020]
(2) Photocatalytic activity of titanium oxide member Using this titanium oxide member, it was widely used as a solvent and cleaning agent in high-tech industry and cleaning industry, and decomposed trichlorethylene, which is a problem by contaminating groundwater and soil. . 18 ml of an aqueous solution of trichlorethylene having a concentration of 10 ppm was put in a quartz glass test tube, 0.1 g of the obtained titanium oxide member was put therein, and then irradiated with light from a 500 W high-pressure mercury lamp. After 1 hour, the amount of trichlorethylene contained in the reaction solution was measured using a gas chromatograph. As a result, trichlorethylene was decomposed and not detected.
[0021]
Example 1
1 mol of titanium metal cutting waste was loosened and placed in a beaker, and after adding 18 mol of ammonia water to 1 mol of titanium metal cutting waste, hydrogen peroxide was added with 38 mol of stirring. As a result, a yellow titanium oxide coating solution sol was obtained. This was left for a while and separated into a gel and a supernatant. After adding 0.1 mol of anatase-type titanium oxide powder to this gel and dispersing well, it was coated on a polyester plate and dried at 200 ° C. to obtain a titanium oxide member with a titanium oxide film.
[0022]
Using this titanium oxide member, the dyeing effluent was decolorized. As a model effluent, 0.1 ml of an aqueous solution of 10 ppm of eosin was placed in a quartz cell and then dropped on the obtained titanium oxide member, and irradiated with a 300 W xenon lamp. As a result, after 1 hour, it was completely decolored and became colorless and transparent. Furthermore, when the supernatant liquid was put into a spray bottle and sprayed on garbage, a remarkable deodorizing effect was obtained.
[0023]
Example 3
In FIG. 1, one Example of the manufacturing apparatus of the titanium oxide coating liquid of this invention is shown. A titanium metal-containing waste, ammonia water, hydrogen peroxide water, acid inlet and condenser 3 are installed in the upper part of the reactor 1, a stirrer 2 is provided, and a product outlet is provided in the lower part. . First, the titanium metal-containing waste is put into the reactor 1, then ammonia water is added, and the mixture is thoroughly stirred with the stirrer 2. Thereafter, hydrogen peroxide or further an acid (reference example) is added while stirring. added. The ammonia gas generated at this time was liquefied by the condenser 3 and returned to the reactor 1. The ammonia gas remaining in the reactor 1 was also returned to the reactor 1 by the fan 4 and recovered, and recycled as a raw material, whereby the raw material could be effectively used and efficient production could be performed. In addition, it was possible to suppress the discharge of ammonia and hydrogen peroxide into the environment, and to suppress odors and environmental pollution caused by ammonia and hydrogen peroxide.
[0024]
【The invention's effect】
As described above, the present invention is a method for recycling titanium metal-containing waste such as cutting chips of titanium useful titanium oxide film or titanium oxide coating solution as such photocatalyst or a protective film, no machine binder, deodorant Is to provide. A titanium metal complex can be formed and recycled to a titanium oxide coating solution by a simple method of adding ammonia water and hydrogen peroxide water to titanium metal-containing waste such as titanium cutting waste. Then, a titanium metal-containing waste and aqueous ammonia and hydrogen peroxide water inlet and condenser was placed on top of the reaction vessel, a stirring means, by manufacturing device product outlet is provided in the lower part An efficient titanium oxide coating solution can be produced. Moreover, it can isolate | separate into a gel and a supernatant liquid and can recycle to an inorganic binder and a deodorizer . And a titanium oxide film can be easily manufactured by coating the substrate with the titanium oxide coating solution and heating or drying. In addition, titanium oxide members made by coating a substrate with a titanium oxide film can receive artificial light from sunlight, fluorescent lamps, incandescent lamps, black lights, UV lamps, mercury lamps, xenon lamps, halogen lamps, metal halide lamps, etc. Irradiation generates electrons and holes. Due to their strong oxidizing power, harmful chemical substances are rapidly and efficiently oxidized and decomposed into carbon dioxide and the like to be rendered harmless. Therefore, it is economical because it can be used as an environmental purification material that can effectively perform antibacterial fungi, deodorization, water treatment, air purification, etc. with low cost, energy saving and maintenance-free just by irradiating light. Great effect.
[Brief description of the drawings]
FIG. 1 shows an embodiment of an apparatus for producing a titanium oxide coating solution of the present invention.

Claims (7)

Titanium metal shavings of titanium metal-containing waste, so as not occur abrupt temperature rise, after the addition of aqueous ammonia little by little, with the addition of hydrogen peroxide little by little to form a titanium metal complexing sol Or a step of producing a yellow titanium oxide coating solution by leaving it as a gel and a supernatant , and when ammonia water and hydrogen peroxide solution are added to the titanium metal-containing waste. A process for producing a titanium oxide coating solution for photocatalyst , comprising the step of liquefying, recovering, and recycling the ammonia gas to be a raw material . In the titanium metal-containing waste, after added portionwise with stirring ammonia water, after stirring the aqueous hydrogen peroxide was added portionwise to generate a sol to obtain a gel to separate the supernatant, wherein Item 2. A method for producing a titanium oxide coating solution according to Item 1 . Titanium metal-containing waste, after added portionwise with stirring ammonia water, after addition in portions with stirring hydrogen peroxide to produce a sol, to obtain a supernatant liquid was separated gel, claim A method for producing a titanium oxide coating solution according to 1 . Is it possible to add ammonia water and hydrogen peroxide water to the titanium metal cutting waste of the titanium metal-containing waste while suppressing evaporation and decomposition of the ammonia water and hydrogen peroxide water to form a titanium metal complex to generate a sol? Furthermore, the titanium oxide coating liquid for photocatalysts containing the sol or gel of the said titanium metal complex manufactured as a yellow titanium oxide coating liquid by leaving it as a gel and a supernatant liquid further . It was coated on a substrate an acid titanium coating solution according to claim 4, the manufacturing method of the titanium oxide layer, characterized by heating or drying. A titanium oxide member, wherein the substrate is coated with the titanium oxide coating liquid according to claim 4 . Titanium metal shavings of titanium metal-containing wastes as raw materials, an apparatus for producing photocatalytic titanium oxide coating solution, anti 応器, the reactor is reacted with the titanium shavings, aqueous ammonia, and hydrogen peroxide Raw material titanium metal scrap, ammonia water and hydrogen peroxide installed at the top of the material inlet , condenser for liquefying ammonia gas generated when adding ammonia water and hydrogen peroxide water , reaction stirring means, the reactor apparatus for producing a photocatalytic titanium oxide coating solution is characterized that you include a titanium oxide coating solution outlet of the installed product in the lower part of for agitating the liquid.

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