JP2014122151A - Method for producing faujasite-type zeolite using alumino-borosilicate glass as raw material - Google Patents

Abstract

Provided is a method for producing a FAU-type zeolite in which an aluminoborosilicate glass which has become unnecessary is efficiently used effectively as a resource without consuming a great deal of energy, has excellent catalytic ability, and does not elute heavy metals. Provided is a method for producing an efficient and easily controllable FAU type zeolite.
A compounding step in which an aluminum borosilicate glass is used as a raw material and an aluminum compound and / or a silicon compound is added to the aluminoborosilicate glass so that the Si / Al molar ratio is 1.6 to 2.4; An alkali treatment step in which a mixture of an acid glass and an aluminum compound and / or a silicon compound is brought into contact with an alkali solution, and a hydrothermal synthesis treatment of the mixture of the alkali solution, glass, aluminum compound and / or silicon compound obtained in the alkali treatment step And a hydrothermal synthesis step for producing a FAU-type zeolite.
[Selection] Figure 1

Description

  The present invention relates to a method for producing faujasite (FAU) type zeolite using aluminoborosilicate 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.

  JP-A-59-35019 (Patent Document 1) discloses a method for producing zeolite using coal ash produced from a fluidized bed combustion furnace for coal as a raw material. The method described in Patent Document 1 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 Laid-Open No. 64-24014 (Patent Document 2) 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 2 is a method of producing a zeolite composition by blending and kneading a raw material with a 0.5N to 3N NaOH solution and autoclaving at a pressure of 3.0 kg / cm ² or more.

  Japanese Patent Application Laid-Open No. 58-120512 (Patent Document 3) discloses a method for producing a zeolite composition using a granulated slag powder as a raw material. In the method described in Patent Document 3, a granulated slag powder is dissolved in an inorganic acid aqueous solution, and then a precipitate obtained by adjusting the pH to 4 to 9 by blowing ammonia gas (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 4) discloses a method for producing FAU-type zeolite using ceramics, concrete, debris, glass and a mixture thereof as raw materials. In the method described in Patent Document 4, 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.

  Japanese Patent Application Laid-Open No. 2005-343765 (Patent Document 5) discloses a composite containing FAU-type zeolite, A-type zeolite, or FAU-type zeolite using incinerated ash (coal ash, etc.) discharged from a steel mill or the like as a raw material. A method of manufacturing a body is disclosed. In the method disclosed in Patent Document 5, the coal ash is heat-treated at 600 to 800 ° C. together with an alkali agent to activate the unburned carbon contained in the coal ash, and then water is further added to 50 to 110 ° C. Is a method for producing zeolite using silica and alumina contained in coal ash by hydrothermal treatment.

  Japanese Patent Laid-Open No. 2001-39740 (Patent Document 6) discloses a method for producing FAU-type zeolite using silica-alumina glass fiber and silica glass fiber as raw materials. The silica-alumina glass fiber and the silica glass fiber are immersed in a 0.5 to 3 mol / L sodium hydroxide solution. In this state, the sodium hydroxide solution is heated to 80 to 150 ° C. This is a method for precipitating zeolite.

JP 59-35019 A JP-A 64-24014 JP 58-120512 A JP 2007-131502 A JP 2005-343765 A JP 2001-39740 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.

  As the liquid crystal panel glass, glass called aluminoborosilicate glass is usually used. Aluminoborosilicate glass is a special glass made to be compatible with the manufacturing process of liquid crystal panels, 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 a heating facility to melt aluminoborosilicate 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 overall equipment. Also, it is disadvantageous from the viewpoint of energy consumption to use aluminoborosilicate 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. It becomes. 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 1 described above uses ash content from a fluidized bed combustion furnace for coal as a raw material. 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 1, 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 coal, In each case, it is necessary to prepare the composition.

  The method described in Patent Document 2 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 3 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 3, since slag contains a large amount of Ca that inhibits zeolitization, a treatment for removing Ca such as acid treatment is required, which is inefficient. Become.

  The method described in Patent Document 4 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 4 requires heating at a high temperature around 1000 ° C. and consumes a great deal of energy.

  The method described in Patent Document 5 described above is a method for producing FAU-type zeolite by heat-treating coal ash together with an alkali agent, and then adding water to perform hydrothermal treatment. However, since coal ash has a high melting point and is hard and stable, it requires heat treatment at a high temperature around 600 to 800 ° C. with an alkali agent in order to increase reactivity, which complicates the process and consumes a lot of energy. There is a problem to do.

The method described in Patent Document 6 described above is a method for producing FAU-type zeolite by hydrothermally treating silica-alumina glass fiber and silica glass fiber as raw materials in a sodium hydroxide solution. However, the production method of FAU-type zeolite in the case where glass fiber consisting only of SiO ₂ and Al ₂ O ₃ is used as a raw material and there are various components such as aluminoborosilicate glass and components that inhibit zeolite formation is Not disclosed.

  A method for synthesizing zeolite from waste and a zeolite material synthesized from waste are disclosed, but a method for synthesizing FAU-type zeolite using aluminoborosilicate glass recovered from a liquid crystal panel as a raw material is not disclosed. Further, since zeolite synthesized from coal ash, incinerated ash, slag, and the like contains heavy metals derived from raw coal, ore, etc., elution of heavy metals becomes a problem when zeolite is synthesized.

  The present invention has been made to solve the above-mentioned problems, and the object of the present invention is to efficiently use the recovered aluminoborosilicate glass efficiently as a resource without consuming a great deal of energy. Another object of the present invention is to provide a method for producing a FAU-type zeolite which is excellent in catalytic ability, can be used as a builder agent, water quality / soil purification and separation agent, and has no elution of heavy metals. Another object of the present invention is to provide a method for producing an FAU type zeolite which is efficient and can be easily controlled.

  The faujasite (FAU) type zeolite production method of the present invention uses an aluminoborosilicate glass as a raw material, and an aluminum compound and / or an aluminoborosilicate glass so that the Si / Al molar ratio is 1.6 to 2.4. A compounding step of adding a silicon compound, an alkali treatment step of bringing a mixture of an aluminoborosilicate glass and an aluminum compound and / or a silicon compound and an alkali solution into contact, an alkali solution obtained in the alkali treatment step, glass and an aluminum compound, and And / or a hydrothermal synthesis step of hydrothermal synthesis of a mixture of silicon compounds.

  In the method for producing a FAU-type zeolite of the present invention, the concentration of the alkali solution used in the alkali treatment step is 2 to 5 N, and the contact between the aluminoborosilicate glass and the aluminum compound and / or silicon compound and the alkali solution is performed. It is preferably performed for 24 hours to 1000 hours.

In the method for producing a FAU-type zeolite of the present invention, the aluminoborosilicate glass preferably has a composition of SiO ₂ : 50% by weight or more and Al ₂ O ₃ : 10 to 20% by weight.

  In the method for producing the FAU type zeolite of the present invention, before the preparation step, the aluminoborosilicate glass is brought into contact with an acidic solution, and the surface layer of the aluminoborosilicate glass is compared with other regions of the aluminoborosilicate glass. It is preferable to include an acid treatment step for forming a region having a low content.

  The faujasite-type zeolite obtained in the method for producing a FAU-type zeolite of the present invention is preferably a Y-type zeolite.

  In the method for producing FAU type zeolite of the present invention, the hydrothermal synthesis step is preferably hydrothermal synthesis treatment at 60 to 150 ° C. for 10 hours to 1000 hours.

  The method for producing the FAU-type zeolite of the present invention preferably uses a material obtained by grinding the aluminoborosilicate glass to 1 to 1000 μm.

  In the method for producing FAU-type zeolite of the present invention, the concentration of the acidic solution used in the acid treatment step is 0.1 to 10 N, and the contact between the aluminoborosilicate glass and the acidic solution is performed for 1 minute to 100 hours. It is preferable that

  In the method for producing a FAU-type zeolite of the present invention, the acidic solution is preferably a solution containing at least one selected from hydrochloric acid and nitric acid.

  In the method for producing a FAU-type zeolite of the present invention, the aluminoborosilicate glass is preferably an aluminoborosilicate glass recovered from a liquid crystal panel.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to utilize effectively the alumino borosilicate glass collect | recovered from the liquid crystal panel etc. which became unnecessary to a high added value inorganic material. According to the present invention, since FAU type zeolite using aluminoborosilicate glass that has become unnecessary can be produced without performing high temperature melting or the like, a low environmental load and low cost production method is provided. Further, it becomes possible to produce FAU type zeolite by simple treatment, and an inexpensive zeolite material can be obtained. Furthermore, according to the present invention, it is possible to provide a method for producing FAU-type zeolite that can control the reaction through a predetermined treatment and can be used as a catalyst, a builder agent, water quality / soil purification, and a separation agent.

It is a flowchart which shows a preferable example of the manufacturing method of the FAU type zeolite of this invention. It is sectional drawing which shows typically the liquid crystal panel 1 of a typical example provided with the aluminoborosilicate glass used suitably for the manufacturing method of the FAU type zeolite of this invention. 2 is a graph showing an example of X-ray diffraction of the product obtained in Example 1. 4 is a graph showing an example of X-ray diffraction of the product obtained in Example 2. 4 is a graph showing an example of X-ray diffraction of the product obtained in Example 3. 4 is a graph showing an example of X-ray diffraction of the product obtained in Example 4. 6 is a graph showing an example of X-ray diffraction of the product obtained in Example 5. 6 is a graph showing an example of X-ray diffraction of the product obtained in Example 6. 6 is a graph showing an example of X-ray diffraction of the product obtained in Example 7. 6 is a graph showing an example of X-ray diffraction of the product obtained in Example 8. 6 is a graph showing an example of X-ray diffraction of the product obtained in Comparative Example 1. 6 is a graph showing an example of X-ray diffraction of a product obtained in Comparative Example 2. 6 is a graph showing an example of X-ray diffraction of a product obtained in Comparative Example 3. 6 is a graph showing an example of X-ray diffraction of a product obtained in Comparative Example 4. 6 is a graph showing an example of X-ray diffraction of a product obtained in Comparative Example 5. 7 is a graph showing an example of X-ray diffraction of a product obtained in Comparative Example 6. 10 is a graph showing an example of X-ray diffraction of the product obtained in Comparative Example 7.

  The FAU-type zeolite production method using the aluminoborosilicate glass of the present invention basically includes an alkali treatment step of mixing an aluminoborosilicate glass and an alkali solution, and a hydrothermal mixture of the aluminoborosilicate glass and the alkali solution. And a hydrothermal synthesis step of synthesizing.

  According to such a method for producing a FAU type zeolite of the present invention, a FAU type zeolite can be produced using aluminoborosilicate glass as a raw material without performing a melting treatment at a high temperature. This makes it possible to effectively use aluminoborosilicate glass used in liquid crystal panels and the like that are no longer necessary as a resource in a low environmental load process. In addition, since aluminoborosilicate glass which is essentially unnecessary is used as a raw material and the raw glass is not melted at a high temperature, the energy consumption is small, and an inexpensive zeolitic material can be obtained with low equipment cost and energy cost. In addition, by controlling the reaction precisely, it is possible to synthesize high-purity FAU-type zeolite, making it possible to produce zeolite that can be used for high-performance catalysts, builder agents, water / soil purification, separation agents, etc. Become.

Aluminoborosilicate glass according to the present _{invention, SiO} 2: 50 wt% or _more, Al ₂ O 3: have a composition of 10 to 20 wt%, preferably. Thereby, Si / Al is 1.6-2.4 in molar ratio, ie, Si / Al molar ratio exists in the range of 1.5 or more, FAU type zeolite, ie, Y type zeolite (Si / Al molar ratio) : 1.5 to 3) and X-type zeolite (Si / Al molar ratio: 1 to 1.5). The aluminoborosilicate glass having such a composition can be confirmed by, for example, composition analysis using fluorescent X-ray analysis.

In order to recycle the aluminoborosilicate glass used in the liquid crystal display device, the aluminoborosilicate glass used as a raw material in the present invention is an aluminoborosilicate glass used as a liquid crystal panel glass mounted on the liquid crystal display device. More preferably, the composition ranges are SiO ₂ : 50% by weight or more, Al ₂ O ₃ : 10 to 20% by weight, B ₂ O ₃ : 5 to 20% by weight, MgO + CaO + ZnO + SrO + BaO: 5 to 20% by weight. . From the viewpoint of the SiO ₂ and Al ₂ O ₃ composition, that is, the Si / Al molar ratio described above, the aluminoborosilicate glass having such a composition is suitably used as a raw material for the FAU-type zeolite.

In the present invention, since the raw material aluminoborosilicate glass has the above-mentioned composition, aluminoborosilicate glass recovered from a liquid crystal panel or the like that has become unnecessary can be suitably used as a raw material, so that effective use of resources becomes possible. . Unlike the case of using coal ash, fly ash, slag, etc., by using aluminoborosilicate glass for liquid crystal panels in this way, there is little variation in the raw material composition, so the reaction controllability is efficient and the FAU is efficient. Type zeolite can be produced.

  Furthermore, aluminoborosilicate glass has conventionally been processed at a high processing temperature and consumes a great deal of energy when remelted, so that it has hardly been recycled in terms of environmental load and energy cost. According to the present invention, there is an effect that it becomes possible to effectively use as a resource an aluminoborosilicate glass that has not been recycled in the past and is no longer needed and is expected to increase rapidly in the future.

  Here, FIG. 1 is a flowchart showing a preferred example of the method for producing the FAU-type zeolite of the present invention. As described above, the FAU-type zeolite production method of the present invention includes the preparation step (step S4 in FIG. 1), the alkali treatment step (step S5 in FIG. 1), and the hydrothermal synthesis step (step S6 in FIG. 1). However, in order to adjust the structure of the FAU-type zeolite to be synthesized, an acid treatment step (step S3 in FIG. 1) for treating the aluminoborosilicate glass with an acidic solution is further included. It is preferable. The flowchart of the example shown in FIG. 1 shows a case where the aluminoborosilicate glass recovery step (step S1 in FIG. 1) and the crushing step (step S2 in FIG. 1) are further included. Hereinafter, the method for producing the FAU-type zeolite of the present invention will be described in detail along the flowchart of the example shown in FIG.

[1] Aluminoborosilicate Glass Recovery Step In the example shown in FIG. 1, first, as the aluminoborosilicate glass recovery step (step S1), for example, aluminoborosilicate glass is recovered from a liquid crystal panel. Here, FIG. 2 is a cross-sectional view schematically showing a typical example of a liquid crystal panel. FIG. 2 shows a liquid crystal panel including an active element (not shown) such as a TFT (Thin Film Transistor). The liquid crystal panel 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 aluminoborosilicate glass from the liquid crystal panel of the example shown in FIG. 2 will be described. However, the procedure for recovering the aluminoborosilicate glass as a raw material in the present invention is not limited to this, and the liquid crystal It is not limited to those recovered from the panel.

  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.

  Aluminoborosilicate glass recovered from a liquid crystal panel or the like is usually attached with 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. In this way, aluminoborosilicate glass is recovered from the liquid crystal panel taken out from the used liquid crystal television.

[2] Pulverization Step In the example shown in FIG. 1, in the subsequent pulverization step (step S2), the aluminoborosilicate glass used as a raw material is pulverized. Here, the size of the pulverization of the aluminoborosilicate glass is preferably in the range of 1 to 1000 μm, and more preferably in the range of 1 to 500 μm. By using an aluminoborosilicate glass ground to 1 to 1000 μm 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 zeolite is efficient in the subsequent step. There is an advantage that can be generated automatically. In addition, the reaction proceeds to the inside of the aluminoborosilicate glass, the concentration fluctuation is reduced, and 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 liquid crystal panel screen-sized aluminoborosilicate glass recovered from the above-mentioned liquid crystal panel is processed with a hammer mill or the like and roughly crushed to a size of 5 mm or less, and further pulverized to 1000 μm or less using a ball mill, Used as a raw material for aluminoborosilicate glass.

[3] Acid Treatment Step In the example shown in FIG. 1, subsequently, in the acid treatment step (step S3), the above-mentioned aluminoborosilicate glass powder is brought into contact with an acidic solution. Thereby, the area | region with little calcium content is formed in the surface layer of alumino borosilicate glass compared with the other area | region of alumino borosilicate glass. The contact between the aluminoborosilicate glass powder and the acidic solution is performed, for example, using a known stirrer such as a magnetic stirrer, impeller stirrer, barrel stirrer and the like while mixing them with stirring. It is preferred that Thereby, the Ca content in the aluminoborosilicate 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 or longer. When the stirring time is less than 1 minute in the acid treatment step, a sufficient reaction between the acidic solution and the aluminoborosilicate glass cannot be obtained, and the Ca component in the aluminoborosilicate glass remains as it is, and the synthesis rate of zeolite becomes low. End up. Moreover, it is preferable that the stirring time in an acid treatment process is 100 hours or less. If stirring is performed for 100 hours in the acid treatment step, the Ca component in the aluminoborosilicate glass is sufficiently eluted, and the formation of zeolite is not inhibited. Therefore, if the stirring time exceeds 100 hours, the production efficiency deteriorates. End up.

  Although the density | concentration of an acidic solution can be suitably selected according to the kind of acid, the kind of zeolite, etc., 0.1-10N are preferable and 0.1-5N are more preferable. This is because when the concentration of the acidic solution is less than 0.1 N, the reaction between the aluminoborosilicate 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) of the aluminoborosilicate glass powder and the acidic solution is preferably aluminoborosilicate glass powder / acidic solution = 1/1000 to 1/1. If the acidic solution exceeds 1000 with respect to the aluminoborosilicate glass powder 1, the required acidic solution becomes too much and the processing efficiency is deteriorated. When the acidic solution is less than 1 with respect to the aluminoborosilicate glass powder 1, the contact area between the aluminoborosilicate glass powder and the acidic solution becomes small, and the dissolution reaction does not proceed sufficiently.

  The obtained mixture of aluminoborosilicate glass powder and acidic solution is filtered to separate the aluminoborosilicate glass powder and acidic solution.

  In addition, when synthesizing a zeolite structure that can be synthesized even if the Ca concentration in the aluminoborosilicate glass powder 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, and the SiO ₂ / Al ₂ O ₃ molar ratio in the powder is adjusted. For example, the SiO ₂ contained in an aluminum borosilicate glass,, _Al 2 _{O 3,} based on contained in an aluminum borosilicate glass,, _Al 2 _{O 3,} based on contained in the aluminum compounds added, SiO ₂ contained in the silicon compound added By adding an aluminum compound and / or a silicon compound so that the Si / Al molar ratio is in the range of 1.6 to 2.4, the Si ₂ / Al ₂ O ₃ molar ratio is considered. This makes it possible to synthesize a FAU type zeolite that is a metastable phase having a chemical composition with a molar ratio in the range of 1-3. Here, when the Si / Al molar ratio is less than 1.6, A type zeolite which is a low Si zeolite species is predominantly produced, and there is a problem that FAU type zeolite is not produced, If it exceeds 2.4, Na-P1 zeolite, which is a stable phase among the high Si zeolite species, is predominantly produced, and FAU-type zeolite is not produced.

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

  As the silicon compound to be added, for example, sodium metasilicate can be used. By using sodium metasilicate as the silicon compound, it is easily soluble in an alkaline solution, and the effect that the solution reaction proceeds quickly is achieved.

  As the form of the aluminum compound or silicon compound, powder is preferable. 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 the FAU-type zeolite of the present invention, the above-mentioned aluminoborosilicate glass, aluminum compound, and The mixture of silicon compounds is contacted with an alkaline solution. The contact between the aluminoborosilicate glass and the mixture of the aluminum compound and / or silicon compound and the alkali solution is performed using a conventionally known stirrer such as a magnetic stirrer, impeller stirrer, barrel stirrer, or the like. It is preferable to carry out mixing while stirring. As a result, the aluminoborosilicate glass is dissolved in the alkaline solution.

  As for the stirring temperature in an alkali treatment process, 5-60 degreeC is preferable. When the stirring temperature exceeds 60 ° C. in the alkali treatment step, aging (aging) is lost and the hydrothermal reaction described later proceeds. In addition, 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.

  Aging (aging) is preferably performed by setting the alkali treatment time to preferably 24 hours to 1000 hours. As a result, excessive Si is taken into the aluminosilicate formed from Si and Al dissolved in the solution from the glass, and crystal nuclei of Si-rich aluminosilicate are generated. The FAU-type zeolite is a zeolite having a high Si / Al ratio, and it is possible to promote the generation of the FAU-type zeolite by performing aging. When the alkali treatment time is less than 24 hours, the above-mentioned crystal nuclei are not sufficiently generated. Since an aging effect can be obtained also in the hydrothermal synthesis step, aging can be omitted.

  The alkali solution used in the alkali treatment step is not particularly limited, but sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, carbonate from the viewpoint of reactivity, waste liquid treatment, and ease of handling. A solution containing an alkaline substance such as potassium hydrogen is preferred. The solution may contain two or more of these alkaline substances. In addition, since it is a strong alkali solution, has extremely high reactivity and is inexpensive, and Na-type zeolite is produced, among these, sodium hydroxide is preferably used as the alkaline solution.

  Although the density | concentration of the alkaline solution used for an alkali treatment process can be suitably selected according to the kind of alkali, the kind of zeolite, etc., 2-5N are preferable. This is because when the concentration of the alkaline solution is less than 2N, FAU-type zeolite may not be generated. When an alkaline solution exceeding 5N is used, more materials are used and a high-concentration alkaline solution is used. There is a problem of safety and waste liquid treatment due to the use of.

  The mixing ratio (volume ratio) of the mixture of the aluminoborosilicate glass and the aluminum compound and / or silicon compound and the alkaline solution is a mixture of the aluminoborosilicate glass and the aluminum compound and / or silicon compound / alkaline solution = 1 / 1000-1. / 10 is preferred. When the alkaline solution exceeds 1000 with respect to the mixture 1 of the aluminoborosilicate glass and the aluminum compound and / or the silicon compound, the necessary alkaline solution becomes too much, and the processing efficiency may deteriorate. When the alkali solution is less than 10 with respect to the mixture 1 of the aluminoborosilicate glass and the aluminum compound and / or silicon compound, the contact area between the mixture of the aluminoborosilicate glass and the aluminum compound and / or silicon compound and the alkali solution is small. Therefore, the dissolution reaction may not proceed sufficiently.

[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 the FAU-type zeolite of the present invention, is hydrothermally synthesized. Process and synthesize zeolite. The hydrothermal synthesis treatment can be performed either batchwise or continuously. For example, a hydrogel is introduced into a pressure vessel or a reactor, and preferably heated to 60 to 150 ° C, more preferably 60 to 120 ° C. Thus, a hydrothermal state is obtained. This makes it possible to synthesize zeolite 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, thereby contributing to energy saving. When the temperature in the hydrothermal synthesis process is less than 60 ° C., the synthesis reaction rate is extremely slow, the efficiency is deteriorated, the production of zeolite is slow, and the glass phase tends to remain. Moreover, when it exceeds 150 degreeC, it is because phases other than FAU type zeolites, such as Na-P1 type | mold zeolite, will produce | generate and the purity of FAU type zeolite may become low.

  The hydrothermal synthesis pressure is the saturated vapor pressure at that temperature, the amount 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 of hydrothermal synthesis is preferably 10 hours to 1000 hours, more preferably 10 hours to 200 hours. When the synthesis time is less than 10 hours, the glass phase may remain and the zeolite may not be sufficiently formed. On the other hand, if the synthesis time exceeds 1000 hours, phases other than FAU-type zeolite are produced, and high-purity FAU-type zeolite cannot be obtained.

  According to the FAU-type zeolite production method of the present invention as described above, the FAU-type zeolite can be obtained directly from the above-described raw materials. That is, by appropriately selecting the conditions for hydrothermal synthesis, it is possible to directly obtain a high-purity FAU-type zeolite without requiring an expensive synthesizer.

  In the method for producing FAU-type zeolite of the present invention, hydrothermal synthesis is preferably performed in a temperature range of 110 ° C. or lower, and in this case, the temperature at which waste heat of the boiler can be used. Can contribute to energy conservation.

  By the method for producing FAU-type zeolite of the present invention, high-purity FAU-type zeolite can be obtained from the waste material of the liquid crystal panel. FAU-type zeolite is excellent in catalytic ability among many zeolites, and can be used for industrially important applications such as fluid catalytic cracking (FCC) process of petroleum.

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

<Reference Example 1>
A commercially available glass for liquid crystal panel was ball milled to prepare a glass powder sample. As for the particle size distribution, the center diameter D50 was 8 μm. As a result of obtaining the composition of SiO ₂ and Al ₂ O ₃ of the glass by wavelength dispersion type fluorescent X-ray analysis, SiO ₂ was 62 mass% and Al ₂ O ₃ was 18 mass%.

<Example 1>
10 g of aluminoborosilicate glass pulverized to a center diameter of 8 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. To 14 mL of 2.0 M NaOH aqueous solution, 0.91 g of waste glass treated with nitric acid was added, and 0.38 g of NaAlO ₂ was further added. As the NaOH raw material, special grade sodium hydroxide pellets manufactured by Kishida Chemical were used, and as the NaAlO ₂ raw material, deer primary sodium aluminate manufactured by Kanto Chemical Co., Ltd. was used. At this time, the Si / Al molar ratio was 1.6. The mixed solution was stirred for 24 hours at room temperature, and hydrothermal synthesis was performed at 95 ° C. for 12 hours to 96 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample.

  The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized product was identified. An XRD measurement result is shown in FIG. As can be seen from FIG. 3, a diffraction peak of FAU type zeolite was observed at a synthesis time of 12 to 96 hours.

<Example 2>
A sample was obtained in the same manner as in Example 1 except that the amount of NaAlO ₂ added was changed to 0.16 g (Si / Al molar ratio: 2.1). Similarly, as a result of XRD measurement, a diffraction peak of FAU type zeolite was observed at a synthesis time of 12 hours to 96 hours. The result of XRD measurement of the product when the synthesis time is 48 hours is shown in FIG.

<Example 3>
A sample was obtained in the same manner as in Example 1 except that the amount of NaAlO ₂ added was changed to 0.10 g (Si / Al molar ratio: 2.4). Similarly, as a result of XRD measurement, a diffraction peak of FAU type zeolite was observed at a synthesis time of 12 hours to 96 hours. The result of XRD measurement of the product when the synthesis time is 48 hours is shown in FIG.

<Examples 4 to 6>
Samples were obtained in the same manner as in Examples 1 to 3, except that the NaOH concentration was changed to 3.0M. X-ray diffraction was performed in the same manner as in Examples 1 to 3, and the phases of the synthesized products were identified. At any Si / Al ratio, a diffraction peak of FAU type zeolite was observed at a synthesis time of 48 hours to 96 hours. FIG. 6 (Example 4), FIG. 7 (Example 5), and FIG. 8 (Example 6) show the XRD measurement results of the product when the synthesis time is 48 hours, respectively.

<Example 7>
10 g of aluminoborosilicate glass pulverized to a center diameter of 8 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. To 14 mL of 2.0 M NaOH aqueous solution, 0.91 g of waste glass treated with nitric acid was added, and further 0.16 g of NaAlO ₂ was added. At this time, the Si / Al molar ratio is 2.1. The mixed solution was stirred for 48 hours and 480 hours at room temperature, and hydrothermal synthesis was performed at 75 ° C. for 96 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample.

  The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized product was identified. The XRD measurement results are shown in FIG. As can be seen from FIG. 9, FAU type zeolite diffraction peaks were observed at aging times of 48 hours and 480 hours.

<Example 8>
10 g of aluminoborosilicate glass pulverized to a center diameter of 8 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. To 14 mL of 2.0 M NaOH aqueous solution, 0.91 g of waste glass treated with nitric acid was added, and further 0.16 g of NaAlO ₂ was added. At this time, the Si / Al molar ratio is 2.1. The mixed solution was stirred for 96 hours at room temperature, and hydrothermal synthesis was performed at 65 ° C. and 95 ° C. for 96 hours. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample.

  The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized product was identified. The XRD measurement results are shown in FIG. As can be seen from FIG. 10, diffraction peaks of FAU type zeolite were observed at synthesis temperatures of 65 ° C. and 95 ° C.

<Comparative Examples 1-3>
10 g of aluminoborosilicate glass pulverized to a center diameter of 8 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. To each 14 mL of 1.0 M (Comparative Example 1), 2.0 M (Comparative Example 2), and 3.0 M (Comparative Example 3) NaOH aqueous solution, 0.91 g of waste glass treated with nitric acid was added, and NaAlO ₂ 0. 77 g was added. At this time, the Si / Al molar ratio is 1.1. The mixed solution was aged for 24 hours at room temperature, and hydrothermal synthesis was performed 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.

  The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized product was identified. A diffraction peak of A-type zeolite was observed at NaOH concentrations of 1.0M, 2.0M, and 3.0M. No FAU type zeolite was obtained. The XRD measurement results are shown in FIG. 11 (Comparative Example 1), FIG. 12 (Comparative Example 2), and FIG. 13 (Comparative Example 3), respectively.

<Comparative Examples 4-6>
10 g of aluminoborosilicate glass pulverized to a center diameter of 8 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. To each 14 mL of 1.0 M (Comparative Example 4), 2.0 M (Comparative Example 5), and 3.0 M (Comparative Example 6) NaOH aqueous solution, 0.91 g of waste glass treated with nitric acid was added, and NaAlO ₂ was further reduced to 0. 0.06 g was added. At this time, the Si / Al molar ratio is 2.6. The mixed solution was aged for 24 hours at room temperature, and hydrothermal synthesis was performed 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.

  The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized product was identified. A diffraction peak of Na-P1 type zeolite was observed at any of NaOH concentrations of 1.0M, 2.0M, and 3.0M. No FAU type zeolite was obtained. The XRD measurement results are shown in FIG. 14 (Comparative Example 4), FIG. 15 (Comparative Example 5), and FIG. 16 (Comparative Example 6), respectively.

  Table 1 shows the results of the presence or absence of production of FAU-type zeolite in Examples 1 to 6 and Comparative Examples 1 to 6.

  In Table 1, o indicates the result when FAU-type zeolite is produced, and x indicates the result when FAU-type zeolite is not produced.

<Comparative Example 7>
10 g of aluminoborosilicate glass pulverized to a center diameter of 8 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. To 14 mL of 2.0 M NaOH aqueous solution, 0.91 g of waste glass treated with nitric acid was added, and further 0.16 g of NaAlO ₂ was added. At this time, the Si / Al molar ratio is 2.1. Hydrothermal synthesis was carried out under the conditions of 96 hours at 75 ° C. without aging (aging time 0 hour) while stirring the mixed solution. After completion of the hydrothermal synthesis, the synthesized product was filtered off by suction filtration, and dried to obtain a sample.

  The obtained sample was subjected to X-ray diffraction, and the phase of the synthesized product was identified. The XRD measurement results are shown in FIG. As can be seen from FIG. 17, a diffraction peak of P-type zeolite was observed, and no FAU-type zeolite was produced.

  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 (10)

A method for producing faujasite-type zeolite using aluminoborosilicate glass as a raw material,
A compounding step of adding an aluminum compound and / or a silicon compound to the aluminoborosilicate glass so that the Si / Al molar ratio is 1.6 to 2.4;
An alkali treatment step in which an aluminoborosilicate glass and a mixture of an aluminum compound and / or a silicon compound and an alkali solution are contacted;
A method for producing faujasite-type zeolite, comprising a hydrothermal synthesis step of hydrothermal synthesis treatment of a mixture of an alkali solution obtained in the alkali treatment step, glass, an aluminum compound and / or a silicon compound.   The concentration of the alkali solution used in the alkali treatment step is 2 to 5 N, and the contact between the aluminoborosilicate glass and the mixture of aluminum compound and / or silicon compound and the alkali solution is performed for 24 to 1000 hours. The method for producing a faujasite type zeolite according to claim 1. _3. The faujasite type according to claim 1, wherein the aluminoborosilicate glass has a composition of SiO ₂ : 50 wt% or more and Al ₂ O ₃ : 10 to 20 wt%. A method for producing zeolite.   Before the blending step, an acid treatment step is performed in which the aluminoborosilicate glass is brought into contact with an acidic solution, and the surface layer of the aluminoborosilicate glass is formed with a region having a lower calcium content than other regions of the aluminoborosilicate glass. The method for producing a faujasite type zeolite according to any one of claims 1 to 3, wherein the zeolite is contained.   The method for producing a faujasite type zeolite according to any one of claims 1 to 4, wherein the obtained faujasite type zeolite is a Y type zeolite.   The said hydrothermal synthesis process performs hydrothermal synthesis processing at 60-150 degreeC for 10 hours-1000 hours, The manufacturing method of the faujasite type zeolite of any one of Claims 1-5 characterized by the above-mentioned.   The method for producing a faujasite type zeolite according to any one of claims 1 to 6, wherein the aluminoborosilicate glass is pulverized to 1 to 1000 µm.   The concentration of the acidic solution used in the acid treatment step is 0.1 to 10 N, and the contact between the aluminoborosilicate glass and the acidic solution is performed for 1 minute to 100 hours. 8. A method for producing a faujasite type zeolite according to any one of items 7 to 9.   The method for producing a faujasite type zeolite according to any one of claims 4 to 8, wherein the acidic solution is a solution containing at least one selected from hydrochloric acid and nitric acid.   The method for producing a faujasite type zeolite according to any one of claims 1 to 9, wherein the aluminoborosilicate glass is an aluminoborosilicate glass recovered from a liquid crystal panel.

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