WO2007097124A1 - Treatment method for converting waste asbestos into harmless products, process for production of zeolite, and intermediates for the production - Google Patents

Abstract

[PROBLEMS] To provide a process for producing zeolite at a low cost easily and safely by reutilizing waste asbestos in the form of a harmless product prepared therefrom; intermediates for the production; and methods for converting waste asbestos into harmless products. [MEANS FOR SOLVING PROBLEMS] A process for the production of zeolite, characterized by mixing asbestos with an aluminum -containing substance, heating the obtained mixture to form a solid solution containing silicon and aluminum, and treating the solid solution with an alkali.

Description

 Specification

 Method for detoxifying waste asbestos, method for producing zeoli cake, and production intermediate thereof

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a method for detoxifying waste asbestos, a method for producing zeoli cake using waste asbestos, and a silicon-containing solid solution and a key-aluminum-containing solid solution as intermediates for the production.

 Background art

 [0002] Asbestos is a mineral fiber having a needle-like crystal structure, and when a person inhales the dust, it causes serious diseases such as malignant mesothelioma. The asbestos consumed in Japan from 1930 to 2000 was 10 million tons, and about 90% of imported Aspes was used for building materials. As demolition of buildings that use Aspest-containing building materials will peak, the problems of Aspest exposure and disposal will become serious and become a social problem.

 [0003] Regarding the disposal of asbestos, the present situation is that most waste asbestos is packaged as it is and then landed in a final disposal site as specially managed waste. However, only by landfilling, it will not be possible to cope with the volume of Aspes dredging that is expected to increase in the future, and harmful waste asbestos will remain in the ground as it is. There was a risk of causing environmental problems. In order to solve this problem, recently, attempts have been made to make waste asbestos harmless and to recycle it as other waste.

[0004] For example, as a method for treating asbestos waste and calcium silicate waste, asbestos and calcium silicate or alumina are mixed and melted at a temperature around 1300 ° C to make them harmless (Patent Documents) 1) or as a method for treating waste asbestos materials, etc. A method that mixes waste asbestos and aluminum oxide, renders them harmless by treating them at 1 220 ° C or higher, and reuses them as raw materials for ceramic products (Patent Literature) 2) In addition, waste asbestos and aluminum loss, which is a by-product of aluminum smelting, are mixed and fired at 80 ° C or higher. There is known a method of reusing it as a raw material (see Patent Document 3).

 [0005] — On the other hand, zeolite is a general term for aluminosilicates with fine pores in the crystal, and has a structure (S i-0-AI-0-si) in which silicon and aluminum are bonded via oxygen. The basic skeleton is formed by three-dimensional combination. Zeolite is generally manufactured by mixing and firing sodium silicate and sodium aluminate solutions. ■ As part of recycling, incineration ash, waste waste sand, coal ash A method for producing zeolite using combustible wastes such as the above has been studied (see, for example, Patent Documents 4 and 5), and has recently been put into practical use.

 Patent Document 1: Japanese Patent Application Laid-Open No. 4 _ 1 8 8 7 9

 Patent Document 2: JP-A-5-1 3 8 1 4 7

 Patent Document 3: Japanese Patent Laid-Open No. 6-1 3 4 4 3 8

 Patent Document 4: Japanese Patent Laid-Open No. 1 1-1 9 9 2 2 5

 Patent Document 5: Japanese Patent Laid-Open No. 2 00 0 _ 1 5 9 5 1 7

 Disclosure of the invention

 Problems to be solved by the invention

 [0006] However, there is no known method for producing zeolite by reusing waste asbestos.

[0007] Further, in the method for detoxifying waste asbestos disclosed in Documents 1 and 2, even if calcium silicate waste material or aluminum oxide is added as a melting point depressant, the temperature is not lower than 120 ° C. Since melting is necessary, there has been a problem that the economic burden on the high-temperature melting furnace facilities and safety management increases. In addition, the product obtained by the above detoxification method is hard rock-like, so when using it as a raw material for zeolite, there is a problem in transportability, and if it is pulverized so that it can be transported more easily, the manufacturing process is reduced. Increased cost becomes a problem, so it is preferable Yes.

 [0008] Furthermore, in the method for recycling waste asbestos disclosed in Reference 3, aluminum dross, which is a by-product during the milling of aluminum, is used, and this aluminum loss contains metallic aluminum. In the alkaline treatment necessary for the production of Zeora, hydrogen gas was generated and caused an explosion, so it could not be used as a raw material for Zerai.

 [0009] Accordingly, an object of the present invention is to provide a method for producing zeolite using detoxified waste asbestos, and a production intermediate thereof.

 [0010] In addition, another object of the present invention is to provide a method for producing zeolite candy that can be easily and safely reused at low cost, and a production intermediate thereof.

 [001 1] Another object of the present invention is to provide a method for detoxifying harmful waste asbestos simply and at low cost.

 Means for solving the problem

 [0012] In view of the problems of the prior art, the inventor of the present application has conducted intensive research on the raw materials of Zeora coffee, and as a result, the waste asbestos solid solution obtained under the predetermined conditions is used as an alternative to the raw material of Zerai coffee. It was found that it was very useful to use, and the present invention was completed.

 [0013] (1) That is, in the present invention, waste asbestos and aluminate or a salt thereof are mixed and then heat-treated at 70 to 100 ° C. to obtain a carbon-aluminum-containing solid solution. This is a detoxification method for waste asbestos.

 [0014] (2) Further, the present invention is characterized in that waste asbestos and a silicon-containing substance are mixed and then heat-treated at 70 ° C to 100 ° C to obtain a silicon-containing solid solution. This is a detoxification method for waste Aspes.

 [0015] (3) Further, the present invention is characterized in that asbestos and an aluminum-containing substance are mixed and then heat-treated to form a carbon / aluminum-containing solid solution, and then the alkali / aluminum-containing solid solution is alkali-treated. This is a method for producing zeolite.

[001 6] (4) In the present invention, the aluminum-containing substance may be aluminate or The method for producing a zeolite according to (3), characterized in that it is a salt of

[0017] (5) Further, the present invention is the method for producing a zeolite according to (3), wherein the heat treatment is performed at 700 ° C or higher.

 [0018] (6) Moreover, the present invention is the method for producing a zeolite according to (3), wherein the heat treatment is performed at 700 to 1,000 ° C.

 [0019] (7) Further, in the present invention, asbestos and a silicon-containing substance are mixed and then heat-treated to obtain a silicon-containing solid solution, and then the alkali-containing substance is mixed with the silicon-containing solid solution and the alkali-containing substance. A method for producing zeolite.

 [0020] (8) Further, the present invention is characterized in that the above-mentioned key substance-containing substance is a key acid or a salt thereof, and the above-mentioned aluminum-containing substance is an aluminate or a salt thereof.

(7) A method for producing zeolite.

[0021] (9) Further, the present invention is the method for producing a zeolite according to (7), wherein the heat treatment is performed at 700 ° C or higher.

[0022] (10) Further, the present invention provides the method for producing a zeolite according to (7), wherein the heat treatment is performed at 700 to 1,000 ° C.

[0023] (11) Further, the present invention is characterized in that asbestos is heat-treated to form molten slag, and then the molten slag and the aluminum-containing material are mixed and then subjected to an al force treatment. It is a manufacturing method of a kite.

[0024] (12) The present invention is also characterized in that it is obtained by mixing asbestos and aluminate or a salt thereof, and then heat-treating at 700 to 1 000 ° C. It is a contained solid solution.

[0025] (1 3) Further, the present invention is characterized in that it is obtained by mixing asbestos and aluminate or a salt thereof and then heat-treating at 800 to 900 ° C. It is a solid solution.

[0026] (1 4) Further, in the present invention, after mixing the asbestos and the silicon-containing substance,

Contains silicon, obtained by heat treatment at 700 to 1 000 ° C It is a solid solution.

 [0027] (15) In the present invention, after mixing asbestos and a substance containing silicon,

 It is a silicon-containing solid solution obtained by heat treatment at 800-900 ° C.

 [0028] (16) Further, the present invention provides the silicon-containing solid solution as described in (14) or (15), wherein the key substance is a key acid or a salt thereof. Oh ^ ο

 [0029] According to the above means, the following operation is obtained.

 The invention's effect

 [0030] According to the method for producing zeoli cake of the present invention, the raw material mixture containing waste asbestos can be melted and solidified at an extremely low temperature compared to the conventional method, and the needle-like crystal structure of the asbestos cake can be eliminated and rendered harmless. As a result, it is possible to manufacture zeolite easily by effectively reusing it without imposing an economic burden.

 [0031] In addition, according to the method for producing zeoli rice cake of the present invention, waste asbestos can be rendered harmless at an extremely low temperature as compared with the conventional method, and the product is in powder form, so that it is easy to handle. Zeolite can be manufactured using raw materials with excellent transportability.

 [0032] Further, according to the method for producing zeoli rice cake of the present invention, waste asbestos can be rendered harmless at an extremely low temperature as compared with the conventional method, and it becomes a source of harmful gas in the raw material mixture containing waste asbestos. Because it does not contain any substances that can be obtained, zeolite can be manufactured using highly safe raw materials.

 BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described.

 [0034] In the first embodiment of the present invention, asbestos and an aluminum-containing substance are mixed and then heat-treated to form a carbon-aluminum-containing solid solution, and then the silicon-aluminum-containing solid solution is subjected to an aluminum force treatment. This is a method for producing zeoli rice cake.

[0035] The asbestos used in the production of the zeorai rice cake of the present embodiment is particularly limited. Serinolite chrysotile (spar asbestos ■ Mg ₆ S i ₄ O ₁₀ (OH) ₈ ), amphibolite crosilite (Ao Asbestos, Na ₂ (F e ^{2 +} > M g ) ₃ (F e ³⁺ ) ₂ Si ₈ 0 ₂₂ (OH) ₂ ), Amosite ((Mg <F e ^{2 +} ) ₇ Si ₈ 0 ₂₂ (OH) ₂ ), Anthophyllite ((Mg> F e ^{2 +} ) ₇ S i ₈ 0 ₂₂ (OH) ₂ ), tremolite (Ca ₂ Mg ₅ S i ₈ 0 ₂₂ (OH) ₂ ), actinolite (Ca ₂ (Mg, F e ² +) ₅ S i It is possible to detoxify waste containing various asbestos such as ₈ 0 ₂₂ (OH) ₂ ).

[0036] The aluminum-containing material used in the present embodiment is a material that can be used as a raw material for zeoli cake, and is not particularly limited as long as it does not generate hydrogen gas. Random, τ-alumina, aluminum oxide such as alumina, aluminum hydroxide, aluminate, sodium aluminate, potassium aluminate, calcium aluminate, cobalt aluminate, strontium aluminate, barium aluminate, beryllium aluminateア ル ミ, Aluminates such as magnesium aluminate can be used alone or in combination of two or more. Of these, aluminate or a salt thereof is preferable, and sodium aluminate is preferably used in the present invention.

 [0037] In the method for producing zeoli cake according to this embodiment, first, waste asbestos and aluminium-containing material are mixed well. The mixing ratio of the waste asbestos and the aluminum-containing substance is in a range in which the molar ratio of silicon to aluminum in the raw material is 10: 1 to 1: 4, preferably 2: 1 to 1: 2. Examples of the raw material mixing method include a method of directly pulverizing and mixing the raw material using a mixer, a pulverizer, etc., a method of dissolving and suspending the raw material using a solvent such as water, and stirring and mixing. There is no particular limitation.

[0038] Next, the obtained mixture of waste asbestos and aluminum-containing material is heat-treated. Examples of the heat treatment method include a method using an electric furnace, a method using microwave irradiation, a method using a microwave, a high frequency, a low frequency, a microplasma, a high frequency plasma, and the like. Among these, shortening of processing time The method using an electric furnace is particularly preferable from the viewpoint of downsizing the apparatus.

 [0039] The temperature of the heat treatment is 100 ° C or higher, preferably in the range of 700 ° C to 1 000 ° C, and more preferably in the range of 800 ° C to 900 ° C. If the processing temperature is less than 700 ° C, the needle-like crystal structure of Aspes 残存 remains and cannot be completely detoxified, and if it exceeds 1 000 ° C, detoxification is achieved and the processing temperature cannot be further increased. This is because the cost increases. Furthermore, since the formed silicon-aluminum-containing solid solution is hard and rocky, it needs to be pulverized, and the manufacturing process becomes complicated, which is not preferable. Here, the melting temperature of asbestos alone is about 1500 ° C. Therefore, compared to the conventional method in which waste asbestos is heat-treated and made harmless, according to the method of the present invention, the raw material mixture containing waste asbestos is melted and dissolved at an extremely low temperature, and the needle-like crystal structure of Aspes Can be eliminated and rendered harmless, so the cost of the harmless treatment can be reduced. The treatment time is a time sufficient for the raw material mixture to melt and dissolve at the treatment temperature, and is appropriately determined depending on the treatment temperature and the amount of the raw material mixture.

 [0040] In the manufacturing method of the present embodiment, zeolite is generated by subjecting a key alloy-containing solid solution obtained by cooling and solidification after heat treatment to an Al force treatment. Examples of the alkali used for the alkali treatment include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, but are not particularly limited thereto. Treatment conditions are as follows: At normal pressure, alkali concentration is 0.5 to 5 N, preferably 1.5 to 3.5 N, treatment temperature is 80 to 100 ° C, preferably 90 to 95 ° C, treatment time Is 0.5 to 48 hours, preferably 1 to 24 hours. In addition, the Al force treatment may be performed under a pressure of 1 to 5 atm, preferably 1.25 to 2 atm, in which case the alkali concentration is 0.5 to 51 \ 1, preferably <1. 5 to 3.5 N, treatment temperature is 120 to 230 ° C, preferably 130 to 150 ° C, and treatment time is 0.5 to 24 hours, preferably 1 to 10 hours. If these treatment conditions are less than the above lower limit, sufficient gelation cannot be obtained, and if the above upper limit is exceeded, excessive conditions will be caused, which may cause adverse effects such as damage to the container.

[0041] The product obtained by the above-described Al force treatment is obtained by filtration or centrifugation. By drying, the desired zeolite can be obtained.

 [0042] In the second embodiment of the present invention, after mixing asbestos and a silicon-containing material, heat treatment is performed to obtain a silicon-containing solid solution, and then, the above-mentioned silicon-containing solid solution and the aluminum-containing material are mixed. This is a method for producing zeoli rice cake, which is characterized in that it is treated with an al force.

 [0043] The key-containing substance used in the present embodiment is not particularly limited as long as it is a key-containing substance. For example, a sodium salt, a key salt such as sodium key acid, Examples thereof include silicate glass such as kainate glass, soda lime glass, potash lime glass, diatomaceous earth, kaolin, and metakaolin, and these can be used alone or in combination of two or more. Of these, kaic acid or a salt thereof is preferable, and sodium kaate is preferably used in the present invention.

 [0044] The raw material waste asbestos, the aluminum-containing material, the raw material mixing method, the heat treatment method, the temperature, the time, etc. used in the present embodiment are the same as those in the first embodiment. is there.

[0045] In the production method of the present embodiment, an aluminum-containing substance is mixed with the silicon-containing solid solution obtained by cooling and solidifying after the heat treatment, and the resulting mixture is subjected to al force retreatment to obtain a lysate. Generate. The mixing ratio of the silicon-containing solid solution and the aluminum-containing substance is such that the molar ratio of the silicon and the aluminum in the raw material is 10: 1 to 1: 4, preferably 2: 1 to 1: 2. The mixing method, alkali treatment method, conditions, and the like are the same as those in the first embodiment.

[0046] In a third embodiment of the present invention, the asbestos is produced by heat-treating asbestos into molten slag, then mixing the molten slag and the aluminum-containing substance, and then subjecting to asphalt treatment. Is the method.

[0047] The asbestos and aluminum-containing material used in the present embodiment is

 The same as in the first embodiment.

[0048] In the manufacturing method of the present embodiment, first, asbestos is heat-treated at about 150 ° C to obtain molten slag. The heat treatment method and conditions are the same as those in the first embodiment. It is the same as the case where it can be placed. Next, molten slag and an aluminum-containing material are mixed, and the resulting mixture is alkali-treated to obtain zeolite. The method of mixing the raw materials, the method and conditions of the power treatment, etc. are the same as those in the first embodiment.

 [0049] In the production method of the present invention, various zeolites such as sodalite, zeolite hA, zeolite p, and the like are adjusted by appropriately adjusting various conditions such as the ratio of silicon to aluminum in the raw material and the pressure of the alkali treatment. Can be manufactured.

 [0050] A fourth embodiment of the present invention is obtained by mixing asbestos and a silicon-containing substance and then heat-treating at 700 to 100 ° C. It is a solid solution.

 [0051] The method for producing the silicon-containing solid solution of the present embodiment is the same as that in the second embodiment.

 A fifth embodiment of the present invention is a silicon / aluminum-containing solid solution obtained by mixing asbestos and sodium aluminate, followed by heat treatment at 700 to 100 ° C.

 [0053] The method for producing the silicon-aluminum-containing solid solution of the present embodiment is the same as in the first embodiment.

[0054] By using the silicon-containing solid solution and the silicon-aluminum-containing solid solution of the present invention, the various zeolites can be produced. Example

 [0055] Next, the method for producing zeorai koji using the detoxification waste asbestos of the present invention and the production intermediate thereof will be described in more detail by way of examples, which illustrate the embodiment of the present invention. However, the present invention is not limited to these examples. Therefore, it goes without saying that various modifications can be made without departing from the scope of the present invention.

 [0056] The following experiments were performed using the following equipment, conditions, and reagents, except as otherwise specified.

(1) Measuring equipment (a) Powder X-ray diffractometer (RI NT 2200—V type, manufactured by Rigaku Corporation), magnification: 200 times

 (b) Electron microscope (Hitachi S_21 50 type or JEOL J SM-6330 F), magnification: 4000 times

 (2) Heating equipment

 (a) Non-oxidizing atmosphere quenching furnace (Thermal SAD 330 type), Operating temperature: 600-1060 ° C, Heating furnace effective dimension: 027 OXH 2 OO, Processing amount: 25 kg / gross (Jig ■ (Including tray) Oil tank: Approximately 250 liters, conducted under nitrogen flow

 (b) High-temperature electric furnace (Nems B4S— 1 Z 1 0_ 17 type), effective furnace dimensions: 300WX 300WX 350 H with temperature controller, heater: Supercantal 1 800 X 10 pieces, conducted in air

 (c) Desktop small-sized electric furnace (NHK-1 70 type, manufactured by Sakai Ceramics Co., Ltd.), operating temperature: 800-1 200 ° C

 (3) Reagent

 (a) Sodium aluminate (Wako Pure Chemical Industries, reagent grade 1)

 (b) Sodium hydroxide (Tosoh Pearl manufactured by Tosoh Corporation, 9% sodium hydroxide)

 (c) Calcium silicate (Reagent grade 1 manufactured by Wako Pure Chemical Industries)

 (d) Aluminum oxide (special grade reagent manufactured by Wako Pure Chemical Industries)

[0057] [Reference Example 1] Analysis of waste asbestos

 [0058] An optical microscope (simple incident polarization) photograph and an electron microscope photograph of the waste asbestos used are shown in FIGS. 1 and 2, respectively. Figure 3 shows the results of the identification of matching peaks with the J CPDS card chart of the used asbestos powder X-ray diffraction.

[0059] From Fig. 1 and Fig. 2, it was confirmed that the used asbestos had a needle-like crystal structure peculiar to harmful asbestos. In addition, according to Fig. 3, the waste asperities used were anisophyllite (melting point 1 468 ° C) and crosidite (melting point 1 1 9 It was found that the mixture at 3 ° C was slightly mixed with amosite (melting point 1 397 ° C).

 [Example 1] Clay from waste asbestos and sodium aluminate ■ Preparation of solid solution containing aluminum

 [0061] To 100 g of the waste asbestos of Reference Example 1 and 100 g of sodium aluminate, 250 ml of water was added and mixed well, and the water was evaporated to obtain a mixture of waste asbestos and sodium aluminate. The obtained mixture (10 g) was heated in a non-oxidizing atmosphere quenching furnace at 1 000 ° C. for 1 hour and then cooled to obtain 5.7 g of silicon / aluminum-containing solid solution. Fig. 4 shows an electron micrograph of the obtained solid solution, Fig. 6 (a) shows the result of powder X-ray diffraction, and Fig. 8 (a) shows an external view. For comparison, the result of powder X-ray diffraction of the waste asbestos of Reference Example 1 is shown in Fig. 6 (c).

 [0062] From Fig. 4 and Fig. 6, it was found that waste asbestos became a solid solution at a low temperature (1 000 ° C) when mixed with sodium aluminate, and the acicular crystal structure disappeared and became harmless. From Fig. 8, it was found that this solid solution was obtained in the form of powder.

 [0063] [Example 2] Preparation of zeolite from solid solution containing aluminum ■ [0064] 5 g of the solid solution obtained in Example 1 was added to 3.5 N sodium hydroxide solution 100 m

 In addition to I, heated at 100 ° C for 24 hours, washed several times with water, filtered through filter paper, dried at 100 ° C, and finished with ocher-colored sandy final product 2.3 g The yield was 46 <½). Fig. 5 shows an electron micrograph of the final product obtained, Fig. 6 (b) shows the result of powder X-ray diffraction, and Fig. 7 shows the identification result based on the matching peak with the J CP DS card chart by powder X-ray diffraction. Figure 8 (b) shows the external appearance and, respectively.

[0065] From FIG. 5 and FIG. 6, it was found that a crystal of lysozyme koji was produced by treating the solid solution of waste asbestos and sodium aluminate with alkali. From Fig. 7, it was found that the generated zeolite was mainly sodalite. Furthermore, from FIG. 8, this zeolite can be obtained in the form of powder as in the case of the above solid solution. I found out that

 [0066] [Example 3] Evaluation of adsorption capacity of zeorai

 [0067] In accordance with J I SK 1 474 activated carbon test method 5.1.2.2 (methylene blue adsorption capacity), an evaluation test of the adsorption capacity of Zeoli was performed. The final product obtained in Example 2 and, for comparison, zeolite derived from waste waste sand (Zeocast made by Nichimo) and zeolite derived from coal ash (Ca type artificial zeolite made by Kyuden Sangyo) Each 25 g was placed in a container with a stopper, and 25 mI of methylene blue solution was added and shaken for 30 minutes, followed by filtration. The results are shown in FIG.

 [0068] From Fig. 9, it was found that the zeolite obtained in Example 2 has the same excellent adsorbing ability as the waste waste-derived zeolite and the coal ash-derived zeolite.

 [0069] [Example 4] Preparation of zeolite from a solid solution containing aluminum prepared at various heat treatment temperatures

 [0070] The heat treatment was carried out in the same manner as in Example 1 except that the heat treatment temperatures were set to 700 ° C, 800 ° C, and 900 ° C, respectively. 6 g was obtained. Fig. 10 (a), Fig. 11 (a) and Fig. 12 (a) show the appearance photographs of the obtained solid solutions, and Fig. 13 to Fig. 15 show the electron micrographs of the obtained solid solutions. Shown respectively. From Fig. 10 to Fig. 12 these solid solutions are obtained in powder form, and from Fig. 13 to Fig. 15 the waste asbestos becomes a solid solution even at a low temperature of 700 to 900 ° C, and the acicular crystal structure disappears. I was able to make it harmless. At a heat treatment temperature of 700 ° C, a slight asbestos needle-like crystal structure is observed, but it is thought that it is almost harmless.

 [0071] The same treatment as in Example 2 was carried out except that 5.5 g of the solid solution obtained above was used to obtain final products of 3.8 g, 3.7 g, and 3.6 g, respectively. . The electron micrographs of the final product obtained are shown in Figs. 16 to 18, the results of powder X-ray diffraction are shown in Figs. 19 (a), (b), and (c), and the appearance photo is shown in Fig. 1. This is shown in Fig. 1 (b), Fig. 1 1 (b) and Fig. 1 2 (b), respectively.

[0072] Instead of the solid solution, water was added to the waste asbestos and sodium aluminate of Reference Example 1 and mixed well, and the mixture obtained by evaporating the water was used. Was treated in the same manner as in Example 2 to obtain the final product. The electron micrograph of the final product obtained (unheated) is shown in Fig. 20, and the results of powder X-ray diffraction are shown in Fig. 19 (d). For comparison, the powder X-ray diffraction results of the final product of Example 2 (1 000 ° C) and the waste asbestos of Reference Example 1 are shown in Figs. 19 (e) and (f), respectively. .

 [0073] From FIG. 16 to FIG. 19, it was found that the acicular crystal structure disappeared and became completely harmless to produce zeolite. Also, from FIG. 10 to FIG. 12, it was found that these zeolites can be obtained in the form of powder as with the above solid solutions.

 [0074] [Example 5] Preparation of various types of zeolite ■ Clay prepared with aluminum ratio ■ Preparation of zeolite from solid solution containing aluminum

 [0075] 5.0 g of sodium aluminate (weight ratio of waste asbestos to sodium aluminate 2: 1), 2.5 g (weight ratio of waste asbestos to sodium aluminate 4: 1) and 1. O g ( Treated as in Example 1 except that the weight ratio of waste asbestos to sodium aluminate was set to 10: 1). 5 g was obtained. Electron micrographs of the obtained solid solution are shown in Figs. 21 to 23, and the results of powder X-ray diffraction are shown in Fig. 24, respectively.

 [0076] The same procedures as in Example 2 were performed except that 10 g of the solid solution obtained above was used, respectively, to obtain final products of 4.57 g, 4.11 g, and 3.36 g, respectively. The Electron micrographs of the final product obtained are shown in FIGS. 25 to 27, respectively.

[0077] From FIG. 21 to FIG. 24, in the solid solution, the weight ratio of waste asbestos to sodium aluminate is 4: 1 to 10: 1 (the molar ratio of silicon to aluminum is 4: 1 to 10: 1). In the weight ratio of waste asbestos to sodium aluminate 2: 1 to 1: 1 (the molar ratio of key to aluminum 2: 1 to 1: 1), the acicular crystal structure is It was found that it disappeared and became completely harmless.

[0078] From Fig. 25 to Fig. 27, the final product is waste asbestos and aluminate. In all of the sodium weight ratios of 1: 1 to 10: 1 (the molar ratio of kaen to aluminum of 1: 1 to 10: 1), the needle-like crystal structure of Aspes was not observed, and it was completely detoxified. I was able to generate.

 [0079] [Example 6] Preparation of silicon from waste asbestos and aluminum hydroxide ■ Preparation of solid solution containing aluminum

 [0080] 20 g of aluminum hydroxide and 1 O g of sodium hydroxide were well ground in a mortar, and 30 g of waste asbestos of Reference Example 1 was further added and mixed well. 20 g of the obtained mixture was heated at 100 ° C. for 1 hour in a non-oxidizing atmosphere quenching furnace and then cooled to obtain 17 g of a solid aluminum-containing solid solution. An electron micrograph of the obtained solid solution is shown in FIG. The results of powder X-ray diffraction are shown in Fig. 29.

 [0081] From Fig. 28 and Fig. 29, in the obtained solid solution, the needle-like crystal structure of Aspes was completely lost, and even if aluminum hydroxide or sodium hydroxide was used instead of sodium aluminate, It was found that the same result as in Example 1 was obtained.

 [Example 7] Cyanide from waste asbestos and waste aluminum ■ Preparation of solid solution containing aluminum

 [0083] 3 g of waste aluminum and 4 g of sodium hydroxide were thoroughly ground in a mortar, and the waste asbestos g of Reference Example 1 was further added and mixed well. The obtained mixture (10 g) was heated in a non-oxidizing atmosphere quenching furnace at 100 ° C. for 1 hour and then cooled to obtain 7.1 g of silicon / aluminum-containing solid solution. An electron micrograph of the obtained solid solution is shown in FIG. The results of powder X-ray diffraction are shown in Fig. 31.

 [0084] From FIG. 30 and FIG. 31, in the obtained solid solution, the needle-like crystal structure of Aspes was completely disappeared, and even when waste aluminum and sodium hydroxide were used instead of sodium aluminate, the examples were obtained. It was found that the same result as 1 was obtained.

[0085] [Example 8] Preparation of other types of zeolite from solid solution containing aluminum [0086] 29 g of sodium aluminate was dissolved in 2 OOm I of water to obtain a sodium aluminate solution. Further, 112 g of sodium hydroxide was dissolved in 268 g of water, and 420 g of sodium silicate was added to obtain a sodium silicate solution. The obtained sodium aluminate solution and sodium silicate solution were mixed and aged at 15 ° C. for 16 hours to form a slurry.

 [0087] 34 g of sodium silicate and 12.3 g of sodium hydroxide were dissolved in 1 12.2 g of water to obtain a sodium silicate solution. The sodium kainate solution 10.6 g obtained was mixed in the same manner as in Example 1 with the silicon-aluminum-containing solid solution 3.3 g, aged for 24 hours, heated to 100 ° C, 35 g of caic acid, 2 g of sodium hydroxide, 35 g of water and 4 ml of slurry were added and heated at 105 ° C. for 36 hours, followed by filtration and drying to obtain an ocher sandy final product. Fig. 32 shows the electron micrograph of the final product obtained, Fig. 33 shows the result of powder X-ray diffraction, and Fig. 34 shows the result of identification by the matching peak with the JCPDS card chart by powder X-ray diffraction. .

 [0088] From FIG. 32 and FIG. 33, it was found that the needle-like crystal structure of Aspes was disappeared and detoxified to produce zeolite crystals. Also, from Fig. 34, it was found that the generated zeolite was mainly a mixed type of soda rai and zeolite Z.

 [0089] [Example 9] Preparation of other types of zeolite from solid solution containing aluminum

[0090] 29 g of sodium aluminate was dissolved in 2 OOm I of water to obtain a sodium aluminate solution. Further, 112 g of sodium hydroxide was dissolved in 268 g of water, and 420 g of sodium silicate was added to obtain a sodium silicate solution. The obtained sodium aluminate solution and sodium silicate solution were mixed and aged at 15 ° C. for 16 hours to form a slurry. Obtained in the same manner as in Example 1 ■ Algium-containing solid solution 4.5 g and asbestos molten slag 3.3 g were mixed well, and then Key ■ Aluminum-containing solid solution 4.69 g, water 47 ml After adding 2 ml of slurry and heating at 100 ° C for 40 hours under 1.5 atm pressure After filtration, washing to 1 to 1 << 10 or less, and drying at 105 °° for 16 hours, 9.6 g of an ocher sandy final product was obtained. The electron micrograph of the final product obtained is shown in Fig. 35, the result of powder X-ray diffraction is shown in Fig. 36, and the result of identification by matching peak with JCP DS card chart by powder X-ray diffraction is shown in Fig. 37. I showed them.

 [0091] From FIG. 35 and FIG. 36, it was found that the needle-like crystal structure of Aspes was lost and made harmless, and a zeolite crystal was formed. In addition, from Fig. 37, it was found that the generated zeolite was mainly a mixed type of soda light and zeolite A.

 [0092] [Example 10] Preparation of zeoli candy by microwave irradiation

[0093] To 250 g of waste aspest of Reference Example 1 and 100 g of sodium aluminate, 250 mI of water was added and mixed well, and the water was evaporated to obtain a mixture of waste asbestos and sodium aluminate. Add the same amount of carbon and water to 1.0 g of the resulting mixture, and put it in a microwave oven (Iwatani Sangyo I M575, AC 100 V, rated power consumption 900 W, rated high-frequency output 50 OW). The wave was irradiated for 10 minutes to obtain 0.78 g of solid aluminum-containing solid solution. An electron micrograph of the obtained solid solution is shown in FIG. From this, a slightly needle-like crystal structure of Asbestos is recognized, but it is presumed that it is almost harmless.

 [0094] The same treatment as in Example 2 was carried out except that the solid solution obtained above was used to obtain 0.42 g of the final product. The electron micrograph of the final product obtained is shown in Fig. 39, and the results of powder X-ray diffraction are shown in Fig. 40 (a). For comparison, the result of powder X-ray diffraction of the final product of Example 2 (heat treatment in a non-oxidizing atmosphere quenching furnace) is shown in FIG. 40 (b).

[0095] From FIG. 39 and FIG. 40, in the obtained final product, the needle-like crystal structure disappeared completely, and soot was formed, and the embodiment was carried out in a very short time by heat treatment by microwave irradiation. It was found that the same zeolite as 2 can be produced. [0096] [Example 1 1] Preparation of zeoli soot from a solid solution containing silicon

[0097] Treatment was performed in the same manner as in Example 1 except that sodium silicate (5 g of sodium silicate, 5 g of waste asbestos) was used instead of sodium aluminate to obtain 7.4 g of potassium solid solution. An electron micrograph of the obtained solid solution is shown in FIG. As a result, it was found that the needle-like crystal structure of asbestos disappeared and became harmless.

 [0098] 0.5 g of the obtained solid solution and 0.25 g of sodium aluminate were mixed, added to 100 ml of 3.5 N sodium hydroxide solution, heated at 100 ° C for 24 hours, and then several times with water. It was washed, filtered through filter paper, and dried at 1 oo ° C to obtain 0.49 g of an ocher sandy final product. The electron micrograph of the final product obtained is shown in Fig. 42, and the results of powder X-ray diffraction are shown in Fig. 43 (a). For comparison, the result of powder X-ray diffraction of the final product of Example 2 (preparation from a silicon / aluminum-containing solid solution) is shown in FIG. 43 (b).

 [0099] From FIG. 42 and FIG. 43, in the final product obtained, the needle-like crystal structure disappeared completely, and soot crystals were formed, and the same zeolite as in Example 2 was also obtained from the silicon-containing solid solution. It was found that can be manufactured.

 [0100] [Example 2] Preparation of molten slag from waste asbestos

 [0101] 40 g of the waste asbestos of Reference Example 1 was heated and melted in a high-temperature electric furnace at an average temperature of 1 500 ° C for 4 hours and then cooled to room temperature to obtain 26.Og of molten asbestos molten slag. Fig. 44 shows an electron micrograph of the molten slag obtained, and Fig. 46 (a) shows the results of powder X-ray diffraction. For comparison, Fig. 46 (c) shows the results of powder X-ray diffraction of the waste gas best in Reference Example 1.

 [0102] From Fig. 44 and Fig. 46, it was found that waste asbestos became a massive molten slag by heating, and the acicular crystal structure disappeared and became harmless.

 [0103] [Example 1 2] Preparation of zeoli cake from waste asbestos molten slag and sodium aluminate

 [0104] The molten slag 10 g obtained in Reference Example 2 and sodium aluminate 1 O g were used.

3. Add 5N sodium hydroxide solution to 60ml and heat at 100 ° C for 24 hours After washing with water several times, separating with a centrifuge and drying at 1 oo ° C to obtain 13.9 g of ocher sandy final product (yield to key source 1 39%) . FIG. 45 shows an electron micrograph of the final product obtained, and FIG. 46 (b) shows the result of powder X-ray diffraction.

[0105] From Fig. 45 and Fig. 46, it was found that lysoleite crystals were produced by alkali treatment of molten asbestos molten slag and sodium aluminate.

 [0106] [Comparative Example 1] Preparation of zeoli cake from waste aspest and sodium aluminate

 [0107] The same processing as in Example 1 2 except that 10 g of waste asbestos was used instead of molten slag was carried out to obtain 7.7 g of oval needle-like fibrous final product (concentration on the key source). The rate was 76.9%). An electron micrograph of the final product obtained is shown in FIG.

 [0108] From FIG. 47, it was found that even when waste asbestos and sodium aluminate were treated with alkali, a needle-like crystal structure remained and was not detoxified, and no zeolite was produced.

 [0109] [Comparative Example 2] Preparation of zeolite from molten asbestos molten slag

 [0110] The same treatment as in Example 12 was conducted except that 20 g of molten slag was used instead of molten slag and sodium aluminate. 1 04. 2 <½) was obtained. An electron micrograph of the final product obtained is shown in FIG.

[0111] From Fig. 48, it was found that even when the molten slag was alkali-treated without adding sodium aluminate, the shape of the waste asbestos remained amorphous and no zeolite was formed.

[0112] [Example 1 3] Preparation of zeolite slag from molten asbestos slag and waste aluminum

[0113] In the same manner as in Example 1 except that waste aluminum collected from the lid of a commercial soft drink is used instead of sodium aluminate, the ocher-colored sandy final product is obtained. 17.6 g of the product (yield 1 76.7% based on the key source) was obtained. An electron micrograph of the final product obtained is shown in FIG.

[0114] From Fig. 49, it was found that the same results as in Example 1 2 were obtained when waste aluminum was used as the aluminum source.

[0115] [Example 14] Appearance evaluation after heat treatment of detoxified waste asbestos melt and melting point depressant

 [0116] Due to the revision of the Waste Disposal and Cleaning Law (Waste Treatment Law), etc., it became difficult to handle Aspes-Sardine at facilities in general offices. An experiment was conducted using 1 waste asbestos heat-treated at 1500 ° C and detoxified rock-like waste asbestos melt. Fig. 50 (a) shows an external view of the detoxified rock-like waste asbestos melt, and Fig. 50 (b) shows an external view of the crushed powder.

 [0117] Sodium aluminate and detoxified waste aspaste melt powder in weight ratio 1

 : Mixed at 1, and heat-treated at 800 ° C and 1 200 ° C using a small desktop electric furnace. The appearance photographs of the obtained product are shown in FIGS. 51 and 52, respectively. From FIG. 51, it was found that the appearance of the product heat-treated at 800 ° C. was powdery, and from FIG. 52, the appearance of the product heat-treated at 1 200 ° C. was massive.

 [0118] In addition, calcium silicate or calcium silicate mixed with 15% aluminum oxide and detoxified waste asbestos melt powder were mixed at a weight ratio of 1: 1, and then a tabletop small electric furnace was used. Heat treatment was performed at 200 ° C. The appearance photographs of the obtained product are shown in FIGS. 53 and 54, respectively. Further, 15% of aluminum oxide was mixed with the harmless waste gas best melt powder, and heat treatment was performed under the same conditions as described above. An appearance photograph of each product obtained is shown in FIG. From Fig. 53 to Fig. 55, it was found that the appearance of each product heat-treated at 1 200 ° C was agglomerated.

[0119] From the results of Examples 1, 4 and 14, the optimum heat treatment temperature in the production process of the zeolite cake of the present invention is that the appearance of the product after the heat treatment is 1 000 ° C. I found out that:

 Industrial applicability

 [0120] According to the method for producing Zeoli rice cake of the present invention, the raw material mixture containing waste Aspest is melted and dissolved at an extremely low temperature as compared with the conventional method, and the needle-like crystal structure of Asbestos rice cake is eliminated and rendered harmless. As a result, it is possible to manufacture zeolite easily by effectively reusing it without imposing an economic burden. In addition, since the product is in powder form, zeolite can be produced using raw materials that are easy to handle and have excellent transportability. Furthermore, since the raw material mixture containing waste asbestos does not contain substances that can be a source of harmful gases, zeolite can be manufactured using raw materials with excellent safety.

 [0121] Therefore, the zeolite obtained by the method for producing the zeolite cake of the present invention has an extremely excellent adsorption ability, and has the ability to adsorb formaldehyde and the like, which are the cause of sick house syndrome, and the moisture conditioning ability and moisture absorption ability. Application to building materials used, application to museums, application to soil improvers using the adsorption capacity of harmful substances, adsorption of environmental hormones, use in sewage treatment and water treatment plants, smell, and adsorption capacity of ammonia It is extremely useful when used as a deodorant for pets, cars, households, etc. Brief Description of Drawings

 [0122] [Fig. 1] Photo of the used asbestos optical microscope (simple incident polarized light) (Reference Example 1).

 [Fig. 2] An electron micrograph of the used asbestos (Reference Example 1).

 [Fig. 3] The result of identification by matching peak with the JCPDS card chart by powder X-ray diffraction of the waste asbestos used (Reference Example 1).

 FIG. 4 is an electron micrograph of a solid aluminum-containing solid solution obtained from waste asbestos and sodium aluminate (Example 1).

 FIG. 5 is an electron micrograph of the final product obtained from the solid aluminum-containing solid solution of Example 1 (Example 2).

[Fig. 6] Solid solution of Example 1, final product of Example 2, and waste asbestos of Reference Example 1. It is the result of powder X-ray diffraction.

 FIG. 7 is an identification result by a matching peak with a J CPDS card chart by powder X-ray diffraction of the final product of Example 2.

 FIG. 8 is an appearance photograph of the silicon / aluminum-containing solid solution of Example 1 and the final product of Example 2.

 FIG. 9 shows the results of an evaluation test of the adsorption capacity of the final product of Example 2 (Example 3).

FIG. 10 is an appearance photograph of a silicon / aluminum-containing solid solution obtained at a heat treatment temperature of 700 ° C. (Example 4) and its final product.

 FIG. 11 is a photograph of the appearance of a silicon / aluminum-containing solid solution (Example 4) obtained at a heat treatment temperature of 800 ° C. and its final product.

FIG. 12 is an appearance photograph of a silicon / aluminum-containing solid solution obtained at a heat treatment temperature of 900 ° C. (Example 4) and its final product.

 FIG. 13 is an electron micrograph of a silicon / aluminum solid solution obtained at a heat treatment temperature of 700 ° C. (Example 4).

 FIG. 14 is an electron micrograph of a silicon / aluminum solid solution obtained at a heat treatment temperature of 800 ° C. (Example 4).

 FIG. 15 is an electron micrograph of a silicon / aluminum solid solution obtained at a heat treatment temperature of 900 ° C. (Example 4).

 FIG. 16 is an electron micrograph of the final product obtained at a heat treatment temperature of 700 ° C. (Example 4).

 FIG. 17 is an electron micrograph of the final product obtained at a heat treatment temperature of 800 ° C. (Example 4).

 FIG. 18 is an electron micrograph of the final product obtained at a heat treatment temperature of 900 ° C. (Example 4).

 [Figure 19] Heat treatment temperatures 700 ° C, 800 ° C, 900 ° C, unheated (Example 4) and 1 000 ° C (Example 2) final product and waste asbestos (reference) It is the result of powder X-ray diffraction of Example 1).

FIG. 20 is an electron micrograph of the final product obtained without heating (Example 4). FIG. 21 is an electron micrograph of a solid solution obtained with a weight ratio of waste asbestos to sodium aluminate of 2: 1 (Example 5).

 FIG. 22 is an electron micrograph of a solid solution obtained at a weight ratio of waste asbestos to sodium aluminate of 4: 1 (Example 5).

 FIG. 23 is an electron micrograph of a solid solution obtained with a weight ratio of waste asbestos to sodium aluminate of 10: 1 (Example 5).

 FIG. 24 is a result of powder X-ray diffraction of a solid solution obtained at a weight ratio of waste asbestos to sodium aluminate of 2: 1, 4: 1 and 10: 1 (Example 5).

FIG. 25 is an electron micrograph of the final product obtained with a weight ratio of waste asbestos to sodium aluminate of 2: 1 (Example 5).

 FIG. 26 is an electron micrograph of the final product obtained at a weight ratio of waste asbestos to sodium aluminate of 4: 1 (Example 5).

 FIG. 27 is an electron micrograph of the final product obtained with a weight ratio of waste asbestos to sodium aluminate of 10: 1 (Example 5).

 FIG. 28 is an electron micrograph of a solid aluminum-containing solid solution obtained from waste asbestos and aluminum hydroxide (Example 6).

FIG. 29 is a result of powder X-ray diffraction of a solid solution containing silicon / aluminum soot obtained from waste asbestos and aluminum hydroxide.

 FIG. 30 is an electron micrograph of a solid aluminum-containing solid solution obtained from waste asbestos and waste aluminum (Example 7).

 [Fig. 31] Results of powder X-ray diffraction of solid aluminum-containing solid solution obtained from waste aspaste and waste aluminum.

 FIG. 32 is an electron micrograph of another type of final product obtained from the solid aluminum-containing solid solution (Example 8).

 FIG. 33 shows the result of powder X-ray diffraction of the final product of Example 8.

 FIG. 34 shows the result of identification of the final product of Example 8 by a matching peak with a powdery X-ray diffraction pattern of a JC PDS card.

[Fig.35] Key types of other types of final products obtained from aluminum-containing solid solutions It is an electron micrograph (Example 9).

 FIG. 36 is the result of powder X-ray diffraction of the final product of Example 9.

 FIG. 37 shows the result of identification of the final product of Example 9 by a matching peak with a powdery X-ray diffraction pattern of a JCPDS card.

 FIG. 38 is an electron micrograph of a carbon solid aluminum solution obtained by heat treatment by microwave irradiation (Example 10).

FIG. 39 is an electron micrograph of the final product obtained by heat treatment using microwave irradiation (Example 10).

 FIG. 40 is a result of powder X-ray diffraction of the final product of Example 10 and Example 2.

FIG. 41 is an electron micrograph of a silicon-containing solid solution (Example 11).

FIG. 42 is an electron micrograph of the final product obtained from the silicon-containing solid solution (Example 11).

 FIG. 43 shows the results of powder X-ray diffraction of the final products of Example 1 and Example 2.

[Fig.44] An electron micrograph of molten asbestos molten slag (Reference Example 2).

FIG. 45 is an electron micrograph of the final product obtained from the molten slag of Reference Example 2 (Example 12).

 FIG. 46 shows the results of powder X-ray diffraction of the molten slag of Reference Example 2, the final product of Example 12 and the waste base of Reference Example 1.

 FIG. 47 is an electron micrograph of the final product from waste asbestos and sodium aluminate (Comparative Example 1).

 FIG. 48 is an electron micrograph of the final product from the molten slag of waste asbestos (Comparative Example 2).

 FIG. 49 is an electron micrograph of the final product from the molten slag of waste asbestos and waste aluminum (Example 13).

 FIG. 50 is a photograph of the appearance of a detoxified rock-like waste aspaste melt and a powder of this as ground (Example 14).

[FIG. 51] An appearance photograph of a product obtained by mixing sodium aluminate and detoxified waste aspaste melt powder at a weight ratio of 1: 1 and heat-treating at 800 ° C. ( Example 1 4).

 FIG. 52 is an appearance photograph of a product obtained by mixing sodium aluminate and detoxified waste aspaste melt powder at a weight ratio of 1: 1 and heat-treating at 1 200 ° C. (Example 1) Four) .

 [Fig. 53] An appearance photograph of a product obtained by mixing calcium silicate and detoxified waste asbestos melt powder at a weight ratio of 1: 1 and heat-treating at 1 200 ° C (Example 1) Four) .

 [Fig.54] Obtained by mixing 15% of aluminum oxide with calcium silicate and detoxified waste asbestos melt powder at a weight ratio of 1: 1, and heat treatment at 1 200 ° C It is the external appearance photograph of a product (Example 14).

FIG. 55 is an external appearance photograph of a product obtained by mixing 15% of aluminum oxide with detoxified waste aspaste melt powder and heat-treating it at 1 200 ° C. (Example 14)

Claims

The scope of the claims  [I] It is characterized by mixing waste asbestos and aluminate or a salt thereof, followed by heat treatment at 70 to 100 ° C. to form a solid aluminum-containing solid solution. Detoxification method for waste Aspes.  [2] Waste asbestos detoxification treatment method, characterized by mixing waste asbestos and a substance containing silicon and then heat-treating it at 70 ° C to 100 ° C to form a solid solution containing keyen .  [3] A method for producing zeoli rice cake, comprising mixing asbestos and an aluminum-containing substance, followed by heat treatment to obtain a carbon / aluminum-containing solid solution, and then subjecting the carbon / aluminum-containing solid solution to an alkali treatment.  [4] The method for producing zeoli cake according to claim 3, wherein the aluminum-containing substance is aluminate or a salt thereof.  [5] The method for producing zeoli cake according to claim 3, wherein the heat treatment is performed at 700 ° C or higher.  [6] The method for producing a zeoli cake according to claim 3, wherein the heat treatment is performed at 700 to 100 ° C.  [7] It is characterized in that asbestos and a silicon-containing substance are mixed and then heat-treated to form a silicon-containing solid solution, and then the above-mentioned silicon-containing solid solution and the aluminum-containing substance are mixed and then subjected to an alkali treatment. A method for producing Zeora.  [8] The method for producing a zeolite cake according to [7], wherein the silicon-containing substance is a key acid or a salt thereof, and the aluminum-containing substance is an aluminate or a salt thereof.  [9] The method for producing a zeoli cake according to claim 7, wherein the heat treatment is performed at 700 ° C or higher. [10] The method for producing a zeoli cake according to claim 7, wherein the heat treatment is performed at 700 to 100 ° C. [II] The asbestos is heat-treated to form molten slag, and then the molten slag and the aluminum-containing material are mixed and then subjected to an aluminum force treatment. A method of manufacturing rai rice cake.  [12] A solid aluminum-containing solid solution obtained by mixing asbestos with aluminate or a salt thereof and then heat-treating at 700 to 1 000 ° C.  [13] A solid aluminum-containing solution obtained by mixing asbestos and aluminate or a salt thereof and then heat-treating at 800 to 900 ° C. [14] A silicon-containing solid solution obtained by mixing asbestos and a silicon-containing substance and then heat-treating at 700 to 1 000 ° C.  [15] A silicon-containing solid solution obtained by mixing asbestos and a silicon-containing substance and then heat-treating at 800 to 900 ° C.  [16] The silicon-containing solid solution according to [14] or [15], wherein the key-containing substance is a key acid or a salt thereof.