JP2012116743A - Method for manufacturing inorganic material using alkali-free glass as raw material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for effectively using alkali-free glass which has been unnecessary and recovered as resources without consuming a large amount of energy and to provide a reaction controllable method for effectively and easily manufacturing an inorganic material having a zeolite structure which can be used for a water purification material and a catalytic material, etc.SOLUTION: The method for manufacturing the inorganic material using alkali-free glass as a raw material includes: an alkali treatment step of bringing the alkali-free glass into contact with an alkaline solution; and a hydrothermal synthesis step of hydrothermally synthesizing a hydrogel obtained by the alkali treatment step.

Description

  The present invention relates to a method for producing an inorganic material using alkali-free glass as a raw material.

  In recent years, home appliances such as a liquid crystal television using a liquid crystal panel, personal computers, portable terminals, and other products are rapidly spreading. Here, the above-mentioned “liquid crystal panel” refers to one in which a liquid crystal material is injected and sealed inside two bonded glass substrates, and a polarizing plate (resin) is bonded to the outside of each glass substrate. With the spread of products that use liquid crystal panels, the number of liquid crystal panel waste (waste liquid crystal panels) has also increased rapidly, but in the formation of a recycling society where coexistence with the environment is expected, waste liquid crystals Panels are also required to be recycled and effectively use resources.

  Currently, liquid crystal display devices and liquid crystal panels contained in waste such as home appliances and information equipment are small in amount of waste, and after being crushed for each product in a waste treatment facility, plastic Along with shredder dust containing a large amount of waste, it is landfilled or incinerated.

  Japanese Patent Application Laid-Open No. 2000-84531 (Patent Document) discloses a waste liquid crystal panel discharged from a liquid crystal panel manufacturing factory, a liquid crystal display device included in wastes such as home appliances and information equipment, and a method for treating the liquid crystal panel. 1) discloses a method in which products are crushed at a liquid crystal panel manufacturing plant or waste disposal facility, and then put into a non-ferrous smelting furnace and treated as an alternative material for silica. . In this method, the glass component in the liquid crystal panel enters the slag.

  JP 2000-351664 (Patent Document 2) discloses a method for producing ceramic products such as tiles, bricks and various blocks using glass waste, clay, and ceramic waste as raw materials. Yes. The method described in Patent Document 2 is a composition comprising a total of 100% by weight of 50 to 80% by weight of ground glass waste, 10 to 45% by weight of clay, and 5 to 40% by weight of ground ceramic waste. It is a method of adjusting, shaping and drying, followed by firing at 1000 to 1200 ° C.

Japanese Patent Application Laid-Open No. 2002-308646 (Patent Document 3) discloses low-temperature fired glass ceramics using soda-lime glass fine powder, fine powder of a compound containing CaO, and fine powder of a compound containing B ₂ O ₃ as raw materials. The manufacturing method is described. In the method described in Patent Document 3, the above compound is mixed, the mixture is press-molded into a required shape, and the molded product is fired at a temperature range of 825 to 900 ° C. It is a manufacturing method.

  Japanese Patent Application Laid-Open No. 59-35019 (Patent Document 4) discloses a method for producing zeolite using coal ash generated from a fluidized bed combustion furnace for coal as a raw material. The method described in Patent Document 4 was obtained by adding and blending an alumina source, an alkali source, and water as raw materials so that the silica / alumina, water / alkali, and alkali / alumina ratio was a predetermined molar ratio. This is a method for synthesizing zeolite synthesized using a raw material component mixture under hydrothermal conditions.

Japanese Patent Application Laid-Open No. 64-24014 (Patent Document 5) discloses a method for producing a zeolite composition using fly ash, which is a fuel residue of a coal-fired boiler, as a raw material. The method described in Patent Document 5 is a method for producing a zeolite composition by blending and kneading a raw material with a 0.5N to 3N NaOH solution and performing autoclave treatment at a pressure of 3.0 kg / cm ² or more.

  Japanese Patent Application Laid-Open No. 58-120512 (Patent Document 6) discloses a method for producing a zeolite composition using a granulated slag powder as a raw material. The method described in Patent Document 6 is a precipitate obtained by dissolving granulated slag powder in an inorganic acid aqueous solution and then blowing ammonia gas to adjust the pH to 4 to 9 (silica and alumina as main components, This is a method in which the calcium content is filtered off and the zeolite is synthesized by hydrothermal synthesis by adding an alkali metal hydroxide to the precipitate.

  Japanese Patent Application Laid-Open No. 2007-131502 (Patent Document 7) discloses a method for producing zeolite using ceramics, concrete, debris, glass and a mixture thereof as raw materials. In the method described in Patent Document 7, a mixture obtained by adding and mixing a solid base to a raw material is heated and melted to produce a powder in which Si and Al are readily soluble in water. This is a method for producing zeolite in which the obtained powder is added to water and reacted at a reaction temperature of 20 to 200 ° C.

JP 2000-84531 A JP 2000-351664 A JP 2002-308646 A JP 59-35019 A JP-A 64-24014 JP 58-120512 A JP 2007-131502 A

  Since the LCD panel is a display device that can contribute to power and resource savings, it is predicted that the production volume will increase rapidly and the display area will increase with the progress of the advanced information society. Along with this, the number and amount of waste liquid crystal panels are expected to increase rapidly in the future. Therefore, glass (liquid crystal panel glass) occupying most of the weight of the liquid crystal panel is preferably recycled from the viewpoint of reducing waste and valuing resources. However, since the method disclosed in Patent Document 1 is intended to be reused as a cement material, the liquid crystal panel glass becomes slag and cannot be recycled as the glass itself.

  From the viewpoint of effective use of resources, it is desirable to recycle the recovered liquid crystal panel glass as the liquid crystal panel glass itself. However, recycling to liquid crystal panel glass that requires strict specifications for optical and thermal characteristics due to the presence of impurities on the surface of the liquid crystal panel glass and the presence of many varieties with different glass compositions. Not technically established. Therefore, application development of the collected liquid crystal panel glass as a high value-added product other than the liquid crystal panel glass has been an issue.

  Note that glass called non-alkali glass is usually used for the liquid crystal panel glass. The alkali-free glass is a special glass made so as to be compatible with the manufacturing process of the liquid crystal panel, and has a strain point of 650 ° C. or higher. On the other hand, the strain point of soda lime glass widely used for glass products such as bottle glass, architectural window glass, glass fiber, and tableware glass is 550 ° C. or lower. As described above, since the strain points are different by 100 ° C. or more, it is possible to perform melting processing of alkali-free glass for recycling in a soda lime glass melting processing facility generally used for glass products. It is very difficult in terms of performance and heat resistance of the entire equipment. In addition, it is disadvantageous from the viewpoint of energy consumption to use alkali-free glass with a high melting temperature for general-purpose products such as architectural window glass, glass fiber, and tableware glass that usually uses soda-lime glass as a raw material. Become. Thus, the present condition is that the method used for the use as a raw material of a normal soda-lime glass product is not technically established. For this reason, as a use of liquid crystal panel glass that has become unnecessary, there is a demand for a recycling method that is used for applications in which the processing temperature does not increase compared to the temperature of the current manufacturing process.

  The method described in Patent Document 2 described above is a method in which pulverized glass waste is used as a main raw material, and ceramic waste pulverized in this is used as a raw material, followed by heating and baking at a high temperature of 1000 to 1200 ° C. However, since the method disclosed in Patent Document 2 undergoes a high-temperature firing step, there is a problem that a great amount of energy is consumed as a recycling method. Therefore, energy cost and equipment cost increase, and the obtained ceramic product becomes expensive.

  The method described in Patent Document 3 described above is a method of firing a mixture of compounds using pulverized soda-lime glass waste as a main raw material at 825 to 900 ° C. However, the method disclosed in Patent Document 3 is a method of preparing a ceramic material by preparing and crystallizing soda-lime glass waste to a composition corresponding to the soda-lime glass waste. Application to non-alkali glass is described. Has not been.

The method described in Patent Document 4 described above uses ashes raw material from a fluidized bed combustion furnace for coal. The ash produced by the combustion of coal is the one in which the inorganic components contained in the coal remain in a baked state, and are mainly composed of Al ₂ O ₃ and SiO ₂ , and the Al ₂ O ₃ / SiO ₂ ratio is , In the range of 2-5. For this reason, in the method disclosed in Patent Document 4, since the raw material coal ash contains many impurities, the synthesis rate of zeolite is low, and the synthesis rate varies due to variations in the raw material composition depending on the origin of the raw material coal. It is necessary to prepare the composition each time.

  The method described in Patent Document 5 described above is a method for producing a zeolite composition using fly ash, which is a fuel residue of a coal-fired boiler, as a raw material. However, fly ash is coal ash that has been quenched and vitrified after melting in a boiler, has a high melting point, is hard and stable, and thus has a problem that it is difficult to react. A pretreatment such as melting at a high temperature is required, resulting in poor efficiency.

  The method described in Patent Document 6 described above is a method of generating zeolite using granulated slag as a raw material. However, when slag is used as a raw material as in the method disclosed in Patent Document 6, since the slag contains a large amount of Ca that inhibits zeolitization, a treatment for removing Ca, such as acid treatment, is required, resulting in poor efficiency. Become.

  The method described in Patent Document 7 described above is a zeolite in which a raw material is mixed with a solid base, heated and dissolved at 200 to 1000 ° C., easily dissolved in water, and subjected to hydrothermal synthesis at 20 to 200 ° C. It is a manufacturing method. However, the method disclosed in Patent Document 7 requires heating at a high temperature around 1000 ° C. and consumes a great deal of energy.

  The present invention has been made in order to solve the above-mentioned problems, and the object of the present invention is to provide a method for efficiently using the recovered alkali-free glass as a resource without consuming a great deal of energy. Furthermore, an object of the present invention is to provide an efficient and easily controllable production method of an inorganic material having a zeolite structure that can be used as a water purification material, a catalyst material or the like.

  The present invention relates to a method for producing an inorganic material using alkali-free glass as a raw material, an alkali treatment step in which the alkali-free glass is brought into contact with an alkali solution, and hydrothermal treatment for hydrothermal synthesis treatment of the hydrogel obtained in the alkali treatment step And a synthesis step.

The method for producing an inorganic material of the present invention includes an acid treatment step of treating an alkali-free glass with an acidic solution, and a preparation step of adding an aluminum compound so as to have a predetermined Al ₂ O ₃ / SiO ₂ ratio. It is preferable to further include before the treatment step.

In the present invention, the alkali-free glass, _SiO 2: 50 wt% or _more, Al ₂ O 3: It is preferable to have a composition of 10 to 20 wt%.

  The alkali-free glass in the present invention is preferably alkali-free glass recovered from a liquid crystal display device.

  In the method for producing an inorganic material of the present invention, it is preferable to use a material obtained by pulverizing non-alkali glass to 0.001 to 1 mm.

  The inorganic material obtained in the present invention is preferably zeolite, more preferably A-type zeolite and / or P1-type zeolite and / or ANA-type zeolite.

The alkaline solution in the present invention preferably has a concentration of 0.1 to 10N.
The alkali treatment step in the present invention is preferably stirred for 1 second to 100 hours.

  In the hydrothermal synthesis step of the present invention, hydrothermal synthesis treatment is preferably performed at 70 to 250 ° C.

  The hydrothermal synthesis step in the present invention is preferably hydrothermal synthesis treatment under a pressure of 1 to 10 atm.

  The alkaline solution in the present invention is preferably a solution containing at least one selected from sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate and potassium hydrogen carbonate.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to utilize effectively the alkali free glass collect | recovered from the liquid crystal panel etc. which became unnecessary to a high added value inorganic material. According to the present invention, an inorganic material using an alkali-free glass that has become unnecessary can be produced without performing high-temperature melting or the like, and therefore, a low environmental load and low-cost production method is provided. In addition, an inorganic material can be produced by a simple treatment, and an inexpensive zeolite material can be obtained. Furthermore, according to the present invention, there is provided an inorganic material production method capable of controlling the reaction through a predetermined treatment and synthesizing a zeolite material having a desired structure.

It is a flowchart which shows a preferable example of the manufacturing method of the inorganic material of this invention. It is sectional drawing which shows typically the liquid crystal panel 1 of a typical example provided with the alkali free glass used suitably for the manufacturing method of the inorganic material of this invention. 4 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 2. 6 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 3. 6 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 4. 6 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 5. 6 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 6. 6 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 7. 10 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 8. 10 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 9. 10 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 10. 10 is a graph showing an example of X-ray diffraction of the inorganic material obtained in Example 11. 10 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 12. 10 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 13. 14 is a graph showing an example of X-ray diffraction of the inorganic material obtained in Example 14. 16 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 15. 10 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 16. 10 is a graph showing an example of X-ray diffraction of an inorganic material obtained in Example 17.

  The method for producing an inorganic material using an alkali-free glass of the present invention basically includes an alkali treatment step in which an alkali-free glass is brought into contact with an alkali solution, and a hydrothermal process for hydrothermal synthesis treatment of the hydrogel obtained in the alkali treatment step. And a synthesis step. According to such a method for producing an inorganic material of the present invention, an inorganic material can be produced using alkali-free glass as a raw material without performing a melting treatment at a high temperature. Thereby, the alkali-free glass used for the liquid crystal panel etc. which became unnecessary can be effectively utilized as a resource in a low environmental load process. In addition, since it is made from alkali-free glass, which is no longer necessary, and it does not melt at high temperature, it consumes less energy and has low equipment and energy costs. Inorganic materials that can be used for molecular sieves, catalysts, etc. can be produced.

The alkali-free glass in the present invention preferably has a composition of SiO ₂ : 50% by weight or more and Al ₂ O ₃ : 10 to 20% by weight. Thereby, SiO ₂ / Al ₂ O ₃ is 4.24 or more in molar ratio, that is, Si / Al molar ratio is in the range of 1 or more, Y-type zeolite (Si / Al molar ratio of 3 or more) and A-type It is suitable as a raw material for zeolite (Si / Al molar ratio 1 to 3). In addition, it can be confirmed that the alkali-free glass has such a composition by, for example, composition analysis using fluorescent X-ray analysis.

In order to recycle the alkali-free glass used in the liquid crystal display device, the alkali-free glass in the present invention is an alkali-free glass composition range used as a liquid crystal panel glass mounted on the liquid crystal display device, SiO. _2:50 wt% or _more, Al ₂ O 3: _{10~20 wt%, B} 2 O 3: _5~20 wt%, MgO + CaO + ZnO + SrO + BaO: and more preferably in the range of 5 to 20 wt%. From the viewpoint of the SiO ₂ and Al ₂ O ₃ composition, that is, the Si / Al molar ratio described above, the alkali-free glass having such a composition is suitably used as a raw material for zeolite.

  In the present invention, since the alkali-free glass as a raw material has the above-described composition, the alkali-free glass recovered from a liquid crystal panel or the like that has become unnecessary can be suitably used as a raw material, so that resources can be effectively used. Unlike the case of using coal ash, fly ash, slag, etc., by using alkali-free glass for liquid crystal panels in this way, since there is little variation in the raw material composition, the reaction controllability is efficient and the zeolite is It can be manufactured.

  Furthermore, alkali-free glass has conventionally been processed at a high processing temperature, and consumes a great deal of energy when remelted. Therefore, it has hardly been recycled from the viewpoint of environmental load and energy cost. According to the present invention, there is an effect that it is possible to effectively use as a resource non-alkali glass that has not been recycled in the past and is no longer required and is expected to increase rapidly in the future.

  Here, FIG. 1 is a flowchart showing a preferred example of the method for producing an inorganic material of the present invention. As described above, the method for producing an inorganic material of the present invention only needs to have an alkali treatment step (step S5 in FIG. 1) and a hydrothermal synthesis step (step S6 in FIG. 1). In order to adjust the structure of the zeolite, before that, an acid treatment step (step S3 in FIG. 1) for treating the alkali-free glass with an acidic solution, and a preparation for adding an aluminum compound so as to have a predetermined Si / Al ratio It is preferable to further include a process (step S4 in FIG. 1). The flowchart of the example shown in FIG. 1 shows a case where a non-alkali glass recovery step (step S1) and a crushing step (step S2) are further included. Hereafter, the manufacturing method of the inorganic material of this invention is demonstrated in detail along the flowchart of the example shown in FIG.

[1] Alkali-free Glass Recovery Step In the example shown in FIG. 1, first, as the alkali-free glass recovery step (step S1), for example, alkali-free glass is recovered from a liquid crystal panel. Here, FIG. 2 is a cross-sectional view schematically showing a typical example of the liquid crystal panel 1. FIG. 2 shows a liquid crystal panel including an active element (not shown) such as a TFT (Thin Film Transistor). The liquid crystal panel 1 of the example shown in FIG. 2 includes, for example, two panel glasses (color filter side panel glass 2a and TFT side panel glass 2b) arranged to face each other. These panel glasses (glass substrates) 2a and 2b are provided with a sealing resin body (seal material) 3 along the peripheral edge on the oppositely disposed side (inner surface side) and bonded together. Further, in a region sealed by the panel glasses 2a and 2b and the sealing resin body 3, liquid crystal is sealed and a liquid crystal layer 4 is formed.

  Further, in a typical liquid crystal panel, as shown in FIG. 2, a polarizing plate 5 is adhered to the opposite side (outer surface side) of each panel glass 2a, 2b with an adhesive. Yes. In a typical liquid crystal panel, as shown in FIG. 2, an antireflection film 6, a color filter 7, a transparent conductive film 8 and an alignment film 9 are formed on the inner surface side of the color filter side panel glass 2a. Further, in a typical liquid crystal panel, as shown in FIG. 2, a pixel electrode 10, a bus electrode 11, an insulating film 12, a transparent conductive film 8 and an alignment film 9 are formed on the inner surface side of the TFT side panel glass 2b. Yes. The film thicknesses of the antireflection film 6, the color filter 7, the transparent conductive film 8, the alignment film 9, the pixel electrode 10, the bus electrode 11 and the insulating film 12 are compared with the thicknesses of the two panel glasses 2a and 2b. Thin enough. Hereinafter, the procedure for obtaining the alkali-free glass from the liquid crystal panel of the example shown in FIG. 2 will be described, but the procedure for recovering the alkali-free glass as a raw material in the present invention is not limited to this, and from the liquid crystal panel It is not limited to those recovered.

  First, the polarizing plate 5 is removed from the liquid crystal panel 1 having a structure as shown in FIG. 2, for example, taken out from a display device having a liquid crystal panel such as a liquid crystal television. The removal of the polarizing plate 5 utilizes a known mechanical method. Next, the bonded glass substrates 2a and 2b are separated into two. Specifically, the four sides inside the sealing resin body 3 in the glass substrate are cut into a rectangular shape along the sealing resin body 3 using a cutting tool such as a diamond saw or a glass cutter. Thereafter, by applying an external force as necessary, the glass substrate having a size slightly smaller than the original size is cut and removed from the liquid crystal panel. When the glass substrate is removed, the sealed liquid crystal layer 4 is opened, and the liquid crystal is exposed in a state of being attached to the glass substrate. Next, the liquid crystal is removed by scraping off the exposed glass substrate using a resin squeegee.

  The alkali-free glass recovered from a liquid crystal panel or the like usually has impurities such as an organic thin film used for a color filter, a metal thin film used for a TFT (Thin Film Transistor), and an inorganic thin film. Such impurities can be removed by appropriately combining conventionally known mechanical methods such as sand blasting and rotational polishing, and conventionally known chemical methods such as etching with an acidic solution and an organic solvent. Thus, alkali-free glass is collected from the liquid crystal panel taken out from the used liquid crystal television.

[2] Pulverization Step In the example shown in FIG. 1, the alkali-free glass used as a raw material is pulverized in the subsequent pulverization step (step S2). Here, the size of the alkali-free glass is preferably in the range of 0.001 to 1 mm, and more preferably in the range of 0.001 to 0.5 mm. By using an alkali-free glass pulverized to 0.001 to 1 mm as a raw material, the contact area with the alkali solution is increased in the alkali treatment step described later, and the reaction efficiency is increased, so that the hydrogel is efficiently There is an advantage that it can be generated. Further, the reaction proceeds to the inside of the alkali-free glass, the concentration fluctuation is reduced, and an inorganic material having a uniform zeolite structure with little variation in structure can be obtained.

  As a pulverization method, pulverization can be performed using a conventionally known shearing type crusher, hammer mill, roll mill, cutter mill, ball mill, jet mill or the like. Further, it can be pulverized by performing a multi-stage process. After roughly crushing using a hammer mill or the like, fine crushing with a ball mill or the like enables efficient crushing. For example, a non-alkali glass with a screen size recovered from the above-mentioned liquid crystal panel is treated with a hammer mill or the like and roughly crushed to a size of 5 mm or less, and further pulverized to 1 mm or less using a ball mill. Used as a raw material for alkali glass.

[3] Acid Treatment Step In the example shown in FIG. 1, subsequently, in the acid treatment step (step S3), the above alkali-free glass powder and an acidic solution are mixed and subjected to an acid treatment for stirring. As a specific method of mixing and stirring, a conventionally known stirrer can be used. For example, a magnetic stirrer, impeller stirrer, barrel stirrer, or the like can be used. Thereby, the Ca content in the alkali-free glass is dissolved in the acidic solution and separated and removed.

  As the acidic solution, for example, a solution containing an acidic substance such as hydrochloric acid or nitric acid can be used. The solution may contain two or more of these acidic substances. By using a solution containing hydrochloric acid and nitric acid, Ca can be efficiently removed at low cost.

  The stirring temperature in the acid treatment step is preferably 5 to 100 ° C. When the stirring temperature exceeds 100 ° C. in the acid treatment step, the acidic substance is vaporized, which causes a safety problem and may cause corrosion of the equipment. When the stirring temperature is less than 5 ° C. in the acid treatment step, the dissolution reaction becomes extremely slow and the efficiency is deteriorated.

  The stirring time in the acid treatment step is preferably 1 minute to 10 hours, and more preferably 10 minutes to 5 hours. When the stirring time is less than 1 minute in the acid treatment step, a sufficient reaction between the acidic solution and the alkali-free glass cannot be obtained, and the Ca component in the alkali-free glass remains as it is, and the synthesis rate of zeolite is lowered. Further, when the stirring time is 10 hours or longer in the acid treatment step, the progress of the reaction becomes extremely slow, and the production efficiency is deteriorated.

  Although the density | concentration of an acidic solution can be suitably selected according to the kind of acid, the kind of zeolite, etc., 0.01-10N are preferable and 0.1-5N are more preferable. This is because when the concentration of the acidic solution is less than 0.01 N, the reaction between the alkali-free glass and the acidic solution becomes small, and efficient zeolite synthesis is lost. Moreover, when the density | concentration of an acidic solution exceeds 10N, a waste liquid process becomes difficult and there exists a possibility that efficiency may worsen.

  The mixing ratio (volume ratio) between the alkali-free glass powder and the acidic solution is preferably alkali-free glass powder / acidic solution = 1 / 1000-1. If the mixing ratio (volume ratio) is smaller than 1/1000, the necessary acidic solution becomes too much, and the processing efficiency is deteriorated. When the mixing ratio (volume ratio) is greater than 1, the contact area between the alkali-free glass powder and the acidic solution becomes small, and the dissolution reaction does not proceed sufficiently.

  The obtained mixture of the alkali-free glass powder and the acidic solution is filtered to separate the alkali-free glass powder and the acidic solution.

  In addition, when synthesizing sodalite, Laumontite, etc. that can be synthesized even if the Ca concentration is high, the acid treatment step can be omitted.

[4] Preparation Step In the example shown in FIG. 1, in the subsequent preparation step (step S4), an aluminum compound and / or a silicon compound is added to adjust the Si / Al molar ratio in the powder. For example, the Si / Al molar ratio in consideration of Si contained in the alkali-free glass, Al contained in the alkali-free glass, and Al and / or Si contained in the added aluminum compound and / or silicon compound is 0. . By adding an aluminum compound and / or a silicon compound so as to be in the range of 4 to 9, by treating at a predetermined temperature by hydrothermal synthesis described later, the A type and / or Na-P1 type zeolite Synthesis is possible. When the Si / Al molar ratio in the original composition of the alkali-free glass is in the range of 0.4 to 9, A-type and / or Na-P1-type zeolite can be synthesized even if the preparation step is omitted.

  Further, regarding the Si / Al molar ratio in consideration of Si contained in the alkali-free glass, Al contained in the alkali-free glass, and Al contained in the added aluminum compound and / or silicon compound, Si / Al mole By adding an aluminum compound so that the ratio is in the range of 9 to 20, ANA type zeolite can be synthesized. If the Si / Al molar ratio in the original composition of the alkali-free glass is in the range of 9 to 20, ANA type zeolite can be synthesized even if the preparation step is omitted.

As an aluminum compound to be added, for example, NaAlO ₂ , Al (OH) ₃ , AlCl ₃ or the like can be used. By using NaAlO ₂ , Al (OH) ₃ , and AlCl ₃ , the reactivity is high and the reaction can proceed efficiently.

As the silicon compound to be added, for _example, it can be used as _{Na 2 SiO 3 · 9H 2 O} . By using Na ₂ SiO ₃ · 9H ₂ O, the reactivity is high and the reaction can be efficiently advanced.

  The form of the aluminum compound and / or silicon compound to be added is preferably powder. Thereby, it becomes possible to uniformly mix and stir in the alkali treatment step described later.

[5] Alkali Treatment Step In the example shown in FIG. 1, next, in the alkali treatment step (step S5), which is an essential step in the method for producing an inorganic material of the present invention, the alkali-free glass powder and the alkali solution described above. And stir. As a specific method of mixing and stirring, a conventionally known stirrer is used. For example, a magnetic stirrer, impeller stirrer, barrel stirrer, or the like can be used. Thereby, an alkali free glass melt | dissolves in an alkaline solution and will be in the state of a hydrogel.

  The stirring temperature in the alkali treatment step is preferably 5 to 80 ° C. When the stirring temperature exceeds 80 ° C. in the alkali treatment step, the alkaline solution is vaporized, which may cause a safety problem. Moreover, when the stirring temperature in an alkali treatment process will be less than 5 degreeC, a dissolution reaction will become very slow and efficiency may worsen.

  The stirring time in the alkali treatment step is preferably 1 second to 100 hours. If the stirring time is less than 1 second in the alkali treatment step, a sufficient reaction between the alkali solution and the alkali-free glass cannot be obtained, and the alkali-free glass remains as it is, and the synthesis ratio of zeolite may be lowered. In addition, when the stirring time is 100 hours or longer in the alkali treatment step, the progress of the reaction may become extremely slow and the efficiency may deteriorate.

  Although it does not restrict | limit especially as an alkaline solution used for an alkali treatment process, From a viewpoint of waste liquid treatment and a viewpoint of the ease of handling, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, potassium carbonate, potassium hydrogencarbonate etc. A solution containing the alkaline substance is preferred. The solution may contain two or more of these alkaline substances. Of these, sodium hydroxide is preferably used as the alkaline solution because it is a strong alkaline solution, extremely reactive, and inexpensive.

  Although the density | concentration of the alkali solution used for an alkali treatment process can be suitably selected according to the kind of alkali, the kind of zeolite, etc., 0.1-10N are preferable and 0.2-5N are more preferable. This is because when the concentration of the alkaline solution is less than 0.1 N, the reaction between the alkali-free glass and the alkaline solution becomes small, and efficient zeolite synthesis is lost. Further, when an alkaline solution exceeding 10 N is used, there is a possibility that the waste liquid treatment becomes difficult.

  The mixing ratio (volume ratio) between the alkali-free glass powder and the alkali solution is preferably alkali-free glass powder / alkali solution = 1/1000 to 1/10. If the mixing ratio (volume ratio) is less than 1/1000, the required alkaline solution becomes too much, and the processing efficiency may deteriorate. When the mixing ratio (volume ratio) is larger than 1/10, the contact area between the alkali-free glass powder and the alkaline solution is decreased, and the dissolution reaction may not sufficiently proceed.

[6] Hydrothermal synthesis step In the example shown in FIG. 1, next, the hydrogel obtained in the hydrothermal synthesis step (step S6), which is an essential step in the method for producing an inorganic material of the present invention, is subjected to a hydrothermal synthesis treatment. And synthesize zeolite. The hydrothermal synthesis treatment can be carried out either batchwise or continuously. For example, the hydrogel is introduced into a pressure vessel or a reactor, and preferably heated to 70 to 250 ° C, more preferably 100 to 200 ° C. Thus, a hydrothermal state is obtained. This makes it possible to synthesize inorganic materials at a lower temperature, unlike the method of firing as a conventional ceramic material, and is a temperature range in which waste heat from a boiler or the like can be used, which contributes to energy saving. When the temperature in the hydrothermal synthesis step is less than 70 ° C., the synthesis reaction rate tends to be extremely slow and the efficiency tends to deteriorate, and when it exceeds 250 ° C., other compounds are formed. This is because there is a case where it is done.

  For example, it is possible to synthesize A-type zeolite by preparing the Si / Al molar ratio in the range of 0.4 to 9 in the above-described preparation step and hydrothermally synthesizing at 95 ° C. in the hydrothermal synthesis step. It is possible to synthesize Na-P1-type zeolite by hydrothermal synthesis at 150 ° C.

  Moreover, in the above-mentioned preparation process, it prepared so that Si / Al molar ratio might be in the range of 9-20, added a silicon compound, and hydrothermally synthesized at 150 ° C. in the hydrothermal synthesis process, the ANA type zeolite was obtained. Can be synthesized.

  The hydrothermal synthesis pressure is the saturated vapor pressure at that temperature, and the volume of liquid and solid introduced into the reaction vessel is set so as to be 1 to 10 atm, and the volume of the space in the reaction vessel is adjusted. .

  The synthesis time for hydrothermal synthesis is 1 hour to 100 hours. If the synthesis time is less than 1 hour, the zeolite may not be sufficiently produced. If the synthesis time exceeds 100 hours, the synthesis speed becomes extremely slow, and the efficiency may be deteriorated.

  For example, when the A-type zeolite is synthesized by hydrothermal synthesis at 150 ° C., the hydrothermal synthesis time is preferably 24 to 72 hours.

  Thus, various zeolites can be synthesized by appropriately selecting the Si / Al ratio, the heating temperature in the hydrothermal synthesis process, and the treatment time in the hydrothermal synthesis process.

  According to the method for producing an inorganic material of the present invention as described above, an inorganic material having a zeolite structure can be obtained directly from the above-described raw materials. In other words, by applying an acid treatment step or appropriately selecting the preparation in the preparation step, an inorganic compound having a zeolite structure composed of the above-described raw material compound having a desired structure without requiring an expensive synthesis apparatus or the like. The material can be obtained directly.

  In addition, the manufacturing method of the inorganic material is preferably a hydrothermal synthesis and production in a temperature range of 250 ° C. or less, and in this case, the temperature range in which the waste heat of the boiler can be used, and energy saving Can contribute.

  The inorganic material obtained by the method of the present invention can be obtained in various zeolite structures depending on conditions. Such inorganic materials can be used for water purification agents, catalyst materials, and the like.

  The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

<Example 1>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 250 mL of 1M, 3M, and 5M HCl and stirred at room temperature for 3 hours, followed by suction filtration and drying to obtain hydrochloric acid-treated waste glass. Further, 10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 250 mL of 1M, 3M, and 5M HNO ₃ and stirred at room temperature for 3 hours, followed by suction filtration and drying to obtain nitric acid-treated waste glass.

  Under each acid treatment condition, the filtrate subjected to suction filtration was quantitatively analyzed, and the elution rate of each component in the glass component (ratio of the amount of the eluted component to the amount of each component contained in the glass) was evaluated. The results are shown in Table 1. It was confirmed that Ca was preferentially eluted in the solution by the acid treatment.

<Example 2>
2 g of alkali-free glass pulverized to a center diameter of 10 μm was weighed, 15 mL of 10 M NaOH was added thereto, and mixed and stirred in a polytetrafluoroethylene container. At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 2.1 to 6.8. After stirring for 24 hours, hydrothermal synthesis was performed in a hot air heater at 150 ° C. under conditions of 1, 3, 4, and 5 days. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized inorganic material was identified. The results are shown in FIG. As can be seen from FIG. 3, it was confirmed that sodalite, which is a kind of zeolite, was synthesized.

<Example 3>
2 g of alkali-free glass pulverized to a center diameter of 10 μm was weighed, 15 mL of 1M NaOH was added thereto, and mixed and stirred in a polytetrafluoroethylene container. At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 2.1 to 6.8. After stirring for 24 hours, hydrothermal synthesis was performed at 150 ° C. in a warm air heater under the conditions of 1, 2, 3, 4, and 5 days. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized inorganic material was identified. The results are shown in FIG. As can be seen from FIG. 4, it was confirmed that sodalite, which is a kind of zeolite, was synthesized.

<Example 4>
2.6 g of alkali-free glass pulverized to a center diameter of 10 μm was weighed, 40 mL of 0.2 M NaOH was added thereto, and the mixture was stirred in a polytetrafluoroethylene container. Further mixed with 3.362 g NaAlO ₂ . At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 0.4 to 0.8. After stirring for 10 minutes, hydrothermal synthesis was performed in a hot air heater at 95 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized inorganic material was identified. The results are shown in FIG. As can be seen from FIG. 5, it was confirmed that a Ca—Al—Si—O-based compound, Laumontite (Ca ₄ Al ₈ Si ₁₆ O ₄₈ ) and the like were synthesized.

<Example 5>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 250 mL of HCl of 1M, 3M, and 5M in each concentration and stirred at room temperature for 3 hours, and then filtered through suction and dried to obtain hydrochloric acid-treated waste glass. 2.6 g of waste glass treated with hydrochloric acid at each concentration was separately added to 40 mL of 0.2 M NaOH, and further mixed with 3.362 g of NaAlO ₂ . At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 0.4 to 0.8. After stirring for 10 minutes, hydrothermal synthesis was carried out at 95 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The results for 1M, 3M and 5M concentrations of HCl treatment are shown in FIG. As can be seen from FIG. 6, it was confirmed that type A zeolite and chabazite were synthesized under any hydrochloric acid treatment conditions.

<Example 6>
After adding 10 g of alkali-free glass pulverized to a center diameter of 10 μm to 250 mL of 1M, 3M, 5M HNO ₃ and stirring at room temperature for 3 hours, nitric acid treatment waste glass was obtained through suction filtration and drying. 2.6 g of waste glass treated with nitric acid at each concentration was separately added to 40 mL of 0.2 M NaOH, and further mixed with 3.362 g of NaAlO ₂ . Similar to Example 5, the Si / Al molar ratio is 0.4 to 0.8 in the case of the alkali-free glass having the above-mentioned preferred composition. After stirring for 10 minutes, hydrothermal synthesis was carried out at 95 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The results for the 1M, 3M, and 5M concentrations of HNO ₃ treatment are shown in FIG. As can be seen from FIG. 7, it was confirmed that A-type zeolite and Chabazite were synthesized under any nitric acid treatment conditions.

<Example 7>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 200 mL of 1M HCl and stirred at 100 ° C. for 2 hours, followed by suction filtration and drying to obtain hydrochloric acid-treated waste glass. 2.6 g of waste glass treated with hydrochloric acid was added to 40 mL of 0.2 M NaOH and further mixed with 3.362 g of NaAlO ₂ . At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 0.4 to 0.8. After stirring for 10 minutes and 24 hours, hydrothermal synthesis was carried out at 95 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The results are shown in FIG. As can be seen from FIG. 8, it was confirmed that A-type zeolite and Chabazite were synthesized for any stirring time.

<Example 8>
After adding 10 g of alkali-free glass pulverized to a center diameter of 10 μm to 250 mL of 3M HNO ₃ and stirring at room temperature for 3 hours, a nitric acid-treated waste glass was obtained through suction filtration and drying. 2.6 g of waste glass treated with nitric acid was separately added to 40 mL of 0.2 M NaOH, and further mixed with 3.362 g of NaAlO ₂ . In the same manner as in Example 7, the non-alkali glass having the above preferred composition has a Si / Al molar ratio of 0.4 to 0.8. After stirring for 10 minutes and 24 hours, hydrothermal synthesis was carried out at 95 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The results are shown in FIG. As can be seen from FIG. 9, it was confirmed that A-type zeolite and Chabazite were synthesized for any stirring time.

<Example 9>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 250 mL of 5M HCl and stirred at room temperature for 3 hours, followed by suction filtration and drying to obtain hydrochloric acid-treated waste glass. 2.6 g of waste glass treated with hydrochloric acid was added to 40 mL of 0.2 M NaOH and further mixed with 0.16 g of NaAlO ₂ . At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 1.8 to 4.9. After stirring for 1 hour, the mixture was allowed to stand for 24 hours, and then hydrothermal synthesis was performed at 150 ° C. for 24, 48, and 72 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The result about the hydrothermal synthesis process for 24, 48, 72 hours is shown in FIG. As can be seen from FIG. 10, it was confirmed that Na-P1-type zeolite was synthesized for any hydrothermal synthesis time.

<Example 10>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 250 mL of 5M HNO ₃ and stirred at room temperature for 3 hours, followed by suction filtration and drying to obtain nitric acid-treated waste glass. 2.6 g of nitric acid-treated waste glass was added to 40 mL of 0.2 M NaOH and further mixed with 0.16 g of NaAlO ₂ . As in Example 9, the Si / Al molar ratio is 1.8 to 4.9 in the case of the alkali-free glass having the above-mentioned preferred composition. After stirring for 1 hour, the mixture was allowed to stand for 24 hours, and then hydrothermal synthesis was performed at 150 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The results of the hydrothermal synthesis treatment for 24, 48 and 72 hours are shown in FIG. As can be seen from FIG. 11, it was confirmed that Na-P1-type zeolite was synthesized for any hydrothermal synthesis time.

<Example 11>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 200 mL of 1M HCl and stirred at 100 ° C. for 2 hours, followed by suction filtration and drying to obtain hydrochloric acid-treated waste glass. 0.5 g, 1.0 g, and 2.0 g of waste glass treated with hydrochloric acid were added to 40 mL of 10 M NaOH in separate containers. This corresponds to the mixing ratio (volume ratio) between the glass powder and the alkali solution in the alkali treatment step, that is, alkali-free glass powder / alkali solution = 1/200, 1/100, and 1/50. At this time, the alkali-free glass of the preferred composition described above _(SiO 2: 50 wt% or _more, Al ₂ O 3: _{10~20 wt%, B} 2 O 3: _5~20 wt%, MgO + CaO + ZnO + SrO + BaO: 5~20 weight If the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight, and 5% by weight, respectively, the upper limit of SiO ₂ is 80% by weight. ), The Si / Al molar ratio is 2.1 to 6.8. After stirring for 1 hour, hydrothermal synthesis was performed in separate containers at 150 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The results for 0.5 g, 1.0 g, and 2.0 g are shown in FIG. As can be seen from FIG. 12, it was confirmed that sodalite, which is a kind of zeolite, was synthesized for any amount of waste glass.

<Example 12>
After adding 10 g of alkali-free glass pulverized to a center diameter of 10 μm to 250 mL of 3M HNO ₃ and stirring at room temperature for 3 hours, a nitric acid-treated waste glass was obtained through suction filtration and drying. Nitric acid-treated waste glass (0.5 g, 1.0 g, and 2.0 g) was added to 40 mL of 10 M NaOH in a separate container. As in Example 11, the Si / Al molar ratio is 2.1 to 6.8 in the case of the alkali-free glass having the preferred composition described above. After stirring for 1 hour, hydrothermal synthesis was performed in separate containers at 150 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The results for 0.5 g, 1.0 g, and 2.0 g are shown in FIG. As can be seen from FIG. 13, it was confirmed that sodalite, which is a kind of zeolite, was synthesized for any amount of waste glass.

<Example 13>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 250 mL of 3M HCl and stirred at room temperature for 3 hours, followed by suction filtration and drying to obtain hydrochloric acid-treated waste glass. 0.5 g, 1.0 g, and 2.0 g of waste glass treated with hydrochloric acid were added to 40 mL of 10 M NaOH in separate containers. This corresponds to the mixing ratio (volume ratio) between the glass powder and the alkali solution in the alkali treatment step, that is, non-alkali glass powder / alkaline solution = 1/200, 1/100, and 1/50. Furthermore, it mixed with 1.01 g, 2.02 g, and 4.04 g of Na ₂ SiO ₃ .9H ₂ O, respectively. At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 3.0 to 8.6. After stirring for 1 hour, hydrothermal synthesis was performed in separate containers at 150 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The result about 0.5 g of waste glass, 1.0 g, and 2.0 g is shown in FIG. As can be seen from FIG. 14, it was confirmed that Na-P1-type zeolite was synthesized for any amount of waste glass.

<Example 14>
After adding 10 g of alkali-free glass pulverized to a center diameter of 10 μm to 250 mL of 3M HNO ₃ and stirring at room temperature for 3 hours, a nitric acid-treated waste glass was obtained through suction filtration and drying. Nitric acid-treated waste glass (0.5 g, 1.0 g, and 2.0 g) was added to 40 mL of 10 M NaOH in a separate container. Furthermore, it mixed with 1.01 g, 2.02 g, and 4.04 g of Na ₂ SiO ₃ .9H ₂ O, respectively. Similar to Example 13, the non-alkali glass having the preferred composition described above has a Si / Al molar ratio of 1.8 to 4.9. After stirring for 1 hour, hydrothermal synthesis was performed in separate containers at 150 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The result about waste glass 0.5g, 1.0g, and 2.0g is shown in FIG. As can be seen from FIG. 15, it was confirmed that Na-P1 type zeolite was synthesized for any amount of waste glass.

<Example 15>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 250 mL of 5M HCl and 5M HNO ₃ and stirred at room temperature for 3 hours, followed by suction filtration and drying to obtain hydrochloric acid-treated waste glass and nitric acid-treated waste glass. Hydrochloric acid and nitric acid treated waste glass 2.6g was added to 0.2 M NaOH in 40mL each, was further mixed with _{Na 2 SiO} 3 · 9H 2 O in 19.98 g. At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 9-20. After stirring for 1 hour, hydrothermal synthesis was performed at 150 ° C. for 24, 48 and 72 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The result about the hydrothermal synthesis process for 24, 48, and 72 hours is shown in FIG. As can be seen from FIG. 16, it was confirmed that any of the ANA zeolite also hydrothermal synthesis time _{(Na 16 Si 32 Al 16 O} 96 · 16H 2 O) was synthesized.

<Example 16>
10 g of alkali-free glass pulverized to a center diameter of 10 μm was added to 250 mL of 5M HNO ₃ and stirred at room temperature for 3 hours, followed by suction filtration and drying to obtain nitric acid-treated waste glass. Add 1.0 g of waste glass treated with nitric acid to 14 mL of 0.05 M, 0.1 M, 0.2 M, 0.5 M, 1.0 M, 2.0 M, 5.0 M, 10.0 M NaOH, respectively. It was mixed with NaAlO ₂ of 1.287g. At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 0.4 to 0.8. After stirring for 10 minutes, hydrothermal synthesis was carried out at 95 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. The results for 0.05M, 0.1M, 0.2M, 0.5M, 1.0M, 2.0M, 5.0M, 10.0M NaOH are shown in FIG. As can be seen from FIG. 17, minute peaks of A-type zeolite were observed for 0.05M and 0.1M. It was confirmed that A-type zeolite was synthesized for 0.2M, 0.5M, 1M and 2M. For 5M and 10M, it was confirmed that sodalite was synthesized.

<Example 17>
Adding alkali-free glass 10g pulverized to a central diameter 10μm in 5M HNO ₃ in 250 mL, 10 min at 55 ° C., 1 hour, After stirring for 3 types of conditions for 3 hours, nitrated waste via suction filtration, dried Glass was obtained.

1.0 g of waste glass treated with nitric acid at each time was separately added to 14 mL of 0.2 M NaOH, and further mixed with 1.287 g of NaAlO ₂ . At this time, alkali-free glass (SiO ₂ : 50 wt% or more, Al ₂ O ₃ : 10 to 20 wt%, B ₂ O ₃ : 5 to 20 wt%, MgO + CaO + ZnO + SrO + BaO: 5 to 20 wt% of the above preferred composition. Range, provided that the composition of Al ₂ O ₃ , B ₂ O ₃ , MgO + CaO + ZnO + SrO + BaO is 10% by weight, 5% by weight and 5% by weight, respectively), the upper limit of SiO ₂ is 80% by weight) If present, the Si / Al molar ratio is 0.4 to 0.8. After stirring for 10 minutes, hydrothermal synthesis was carried out at 95 ° C. for 48 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample of an inorganic material.

  Each sample obtained was subjected to X-ray diffraction to identify the synthetic substance. FIG. 18 shows the results of three types of nitric acid treatment in which the acid treatment step is 10 minutes, 1 hour (60 minutes), and 3 hours (180 minutes). As can be seen from FIG. 18, it was confirmed that A-type zeolite and Chabazite were synthesized for any nitric acid treatment time.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  DESCRIPTION OF SYMBOLS 1 Liquid crystal panel, 2a Color filter side panel glass, 2b TFT side panel glass, 3 Seal resin body, 4 Liquid crystal layer, 5 Optical film, 6 Antireflection film, 7 Color filter, 8 Transparent conductive film, 9 Orientation film, 10 Pixel Electrode, 11 bus electrode, 12 insulating film.

Claims (12)

  A method for producing an inorganic material using alkali-free glass as a raw material, comprising: an alkali treatment step in which the alkali-free glass is brought into contact with an alkali solution; and a hydrothermal synthesis step in which a hydrogel obtained in the alkali treatment step is hydrothermally synthesized. A method for producing an inorganic material, comprising: The method further includes an acid treatment step of treating the alkali-free glass with an acidic solution, and a preparation step of adding an aluminum compound so as to have a predetermined Al ₂ O ₃ / SiO ₂ ratio, before the alkali treatment step. The manufacturing method of the inorganic material of Claim 1. The alkali-free glass, _SiO 2: 50 wt% or _more, Al ₂ O 3: 10 to 20 having a weight percent of the composition, method of producing an inorganic material according to claim 1 or 2.   The said alkali free glass is the alkali free glass collect | recovered from the liquid crystal display device, The manufacturing method of the inorganic material in any one of Claims 1-3 characterized by the above-mentioned.   The method for producing an inorganic material according to any one of claims 1 to 4, wherein an alkali-free glass is ground to 0.001 to 1 mm.   The method for producing an inorganic material according to any one of claims 1 to 5, wherein the obtained inorganic material is zeolite.   The method for producing an inorganic material according to claim 6, wherein the obtained inorganic material is A-type zeolite and / or P1-type zeolite and / or ANA-type zeolite.   The method for producing an inorganic material according to claim 1, wherein the alkaline solution has a concentration of 0.1 to 10N.   The said alkali treatment process is stirred for 1 second-100 hours, The manufacturing method of the inorganic material in any one of Claims 1-8 characterized by the above-mentioned.   The method for producing an inorganic material according to claim 1, wherein the hydrothermal synthesis step performs a hydrothermal synthesis process at 70 to 250 ° C. 10.   The method for producing an inorganic material according to claim 1, wherein the hydrothermal synthesis step is a hydrothermal synthesis process under a pressure of 1 to 10 atm.   The inorganic solution according to any one of claims 1 to 11, wherein the alkaline solution is a solution containing at least one selected from sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, and potassium hydrogen carbonate. Material manufacturing method.

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