JP6593585B2 - Method of recovering glass from laminated glass and processing apparatus for recovery - Google Patents

Description

  The present invention relates to a method for recovering glass from laminated glass and a processing apparatus for recovering the glass.

One of the inventors of the present invention is a method for decomposing an object to be processed such as an organic substance, a polymer, a gas body, etc., by heating a semiconductor to a temperature that becomes an intrinsic electric conduction region to generate a large amount of electron / hole carriers, Is a treatment method (semiconductor thermal activation of semiconductor-conductors, hereinafter abbreviated TASC). (Patent Document 1, Non-Patent Document 1). A semiconductor that can be used in the TASC method may be a semiconductor that is stable in a high temperature and oxygen atmosphere. Therefore, an oxide semiconductor is preferably used. Examples of the oxide _{semiconductor, BeO, CaO, CuO, Cu} 2 O, SrO 2, BaO, MgO, NiO, CeO 2, MnO, GeO, PbO, TiO, VO, ZnO, FeO, PdO, Ag 2 O, TiO ₂ , MoO ₂ , PbO ₂ , IrO ₂ , RuO ₂ , Ti ₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , Cr ₂ O ₃ , ZrO ₂ , WO ₃ , MoO ₃ , WO ₂ , SnO ₂ , Co ₃ O ₄ , Sb ₂ O ₃ , Mn ₃ O ₄ , Ta ₂ O ₅ , V ₂ O ₅ , Nb ₂ O ₅ , MnO ₃ , Fe ₂ O ₃ , Y ₂ O ₂ S, MgFe ₂ O ₄ , NiFe ₂ O _{4 , ZnFe 2 O 4, ZnCo 2} O 4, MgCr 2 O 4, FeCrO 4, CoCrO 4, CoCrO 4, ZnCr 2 O 4, CoAl 2 O 4, NiAl 2 O 4 and the like That. Among these, chromium oxide (Cr ₂ O ₃ ) is excellent in high-temperature stability (melting point: about 2200 ° C.) and is a safe material used for dyeing glass bottles for beverages. In addition, iron oxide (α-Fe ₂ O ₃ : hematite) is a safe and inexpensive material and thus has high practicality.

An oxide semiconductor used in the TASC method exhibits an electrical resistance value close to that of an insulator at room temperature. However, an interband transition (intrinsic conduction) from a valence band to a conduction band becomes remarkable as the temperature rises, and 350-500 At ℃, a large number of holes (holes from which electrons have been released) and electrons are generated in the valence band and the conduction band, respectively. The holes generated in the valence band have a strong oxidizing power, take away the bonding electrons from the polymer or the like, and form unstable cation radicals in the polymer. Next, this radical propagates in the polymer that is the decomposition product, destabilizing the entire polymer, and the polymer is cut into small molecules such as ethylene (radical cleavage) in a form that self-destructs, and in the air Reacts with oxygen and completely decomposes into water and carbon dioxide. In other words, the decomposition process consists of the formation of radicals by the oxidizing power of holes, fragmentation by radical cleavage, and complete combustion of the cut molecules and oxygen. This technique is characterized in that radical propagation occurs even when the thickness of the polymer is 20 mm or more, and the decomposition effect reaches the inside of the decomposition target.
In addition, the same TASC method is used for fiber-reinforced plastics, and a method of completely disassembling the plastics and completely recovering the reinforcing fibers such as carbon fibers and glass fibers without damage is proposed (Patent Document 2, Non-Patent Document 2). ). This method is very useful for recycling high-cost carbon fibers and the like because it can be recovered as it is without cutting the long fibers that are the source of strength of the reinforcing fiber plastic material. Furthermore, it is a universal method capable of recovering not only the reinforcing fiber but also the inorganic material from the composite material composed of the inorganic material and the polymer.

  Laminated glass used for safety glass such as window glass of buildings and windshields of automobiles is formed by arranging an interlayer film for laminated glass between a plurality of glass plates, and in many cases two glass plates. As the intermediate film, a thermoplastic resin such as polyvinyl butyral resin, which has high adhesiveness and does not yellow even when irradiated with ultraviolet rays, is generally used.

  Laminated glass collected from the market after the expiration date, and laminated glass that is no longer needed due to defects in dimensions, appearance, etc. in the manufacturing process cannot be easily separated from the glass plate. Most are landfilled underground. Moreover, about the intermediate film to which the glass piece after grind | pulverizing a laminated glass adhered, disposal disposal by incineration etc. may be performed. However, as described above, if laminated glass that has become unnecessary is buried in the ground, a problem of environmental destruction is caused. In addition, when the intermediate film with the glass pieces attached is incinerated, there is a problem that unmelted glass becomes glass dust and pollutes the atmosphere. On the other hand, there is a problem that the molten glass accumulates on the combustion stoker and hinders the operation of the combustion apparatus.

  Therefore, various methods for recovering glass from laminated glass have been proposed. In JP-A-6-345499, heating to 150 to 200 ° C., which is not higher than the glass softening temperature, is first performed, and then a heating wire such as nichrome wire is applied to the intermediate film layer between two glass plates of laminated glass at 500 ° C. The method of heating and pressing the above, moving the laminated glass to melt and cut, and separating the glass plate and the intermediate film is described. Since the processing speed cannot be increased, it is not suitable for processing in large quantities. Japanese Patent Application Laid-Open No. 2002-79209 discloses that a laminated glass is depressurized to 10 Pa after being crushed and heated in an oven in a substantially oxygen-free state at 400 ° C., and an intermediate film component is separated from the separated silicate glass. A method of liquefying and recovering with a vacuum distillation apparatus is described. Depending on the degree of vacuum, carbonization of the intermediate film occurs, and it is difficult to completely recover the intermediate film after separation. In JP 2007-260566 A, a glass product that has been cut and crushed is heated by a heat treatment apparatus in a temperature atmosphere above the glass softening point, and the organic compound or polymer compound adhering to the glass product is thermally decomposed, A method is described in which the glass product is removed from the heat treatment apparatus before the glass product reaches the glass softening point. First, it is cut into strips of about 5 x 15 cm by a cutting and crushing machine, then the glass is crushed by the shearing force of the rotating cutter, and the glass cullet of about 1 to 2 cm square size is bonded to the intermediate film. It is said that the process of cullet is taken and is a very time-consuming processing method.

  Therefore, if the “thermal activation technology of semiconductor (TASC)” which is the method of the present application is applied as a method for removing the polymer interlayer from the laminated glass, the TASC method is a clean solution that completely decomposes the polymer into water and carbon dioxide. Therefore, it is possible to construct a system that easily and inexpensively collects glass from laminated glass.

Japanese Patent No. 4517146 JP 2013-146649 A JP-A-6-345499 JP 2002-79209 A JP 2007-260566 A

T.A. Shinbara, T .; Makino, K .; Matsumoto, and J.M. Mizuguchi: Complete decomposition of polymerics by partially generated holes at high temperatures in titanium dioxide and its decompositions. Appl. Phys. 98, 044909 1-5 (2005) Hitoshi Mizuguchi: Complete decomposition, recycling technology and processing technology of FRP by thermal activation of semiconductors 47, 37-47 (2012)

  As described above, in the recycling of laminated glass, it is difficult to recover the glass because it is not easy to remove the intermediate film by separating the glass plate and the intermediate film, which hinders the practical application of recovery. It was. It is an object of the present invention to solve this problem and provide a method for completely decomposing a polymer in a laminated glass and recovering the glass.

  In the present invention, the semiconductor thermal activation technology (TASC) is applied to the dismantling of the laminated glass, the oxide semiconductor is brought into contact with the side surface of the laminated glass that is the object to be processed, that is, the portion where the intermediate film is exposed, In the presence of oxygen, the object to be processed is heated at a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region, whereby the polymer is completely decomposed to recover the glass.

Laminated glass has a structure in which a polymer sheet is sandwiched between two tempered glasses. The present inventor has conducted extensive experiments in order to completely decompose and remove the polymer from such a laminated glass and recover the glass, and has reached the present invention through the following process.
Degradation of polymer by TASC method is

As described above, the radical generated by the oxidation of holes takes the bonding electrons from the polymer, destabilizes the polymer, and is cut into small molecules. At that time, it was stated that radicals propagate even over 20 mm. The key to solving this problem is how far the radicals can propagate in the interlayer film.

  Even if an oxide semiconductor is brought into contact with the upper or bottom glass surface from the structure of the laminated glass described above, the thermal activation effect of the semiconductor does not work on glass which is an inorganic substance. The only way to decompose the polymer is to bring the oxide semiconductor into contact with the side surface of a piece of laminated glass (120 × 120 × 5 mm). Therefore, an experiment was performed in which a dispersion film of an oxide semiconductor was applied to four sides in the lateral direction of the laminated glass so as to be in contact with the intermediate film, and the laminated glass was run horizontally in a lateral direction. Initially, radicals could not be expected to run far beyond 20 mm, for example 60 mm or more. However, as a result of the actual TASC treatment, surprisingly, the interlayer film of the laminated glass was completely decomposed, the glass was separated and recovered, and the inorganic substance contained in the polymer could be recovered as a residue.

  What is more surprising is that the same results were obtained even when the coating on the four sides of the laminated glass was three sides, two sides and one side. That is, it was confirmed that radicals were sufficiently propagated even in a 120 mm square surface of the laminated glass. This was expected that radicals would cover the entire laminated glass of a predetermined size as long as the temperature of the interlayer film was sufficient. When one side of the laminated glass having a long side of 330 mm is coated with an oxide semiconductor and subjected to TASC treatment in the horizontal direction, the interlayer film of the laminated glass is completely decomposed as expected, and the glass is separated and recovered. It was. Based on the above results and discussion, the present invention has been completed.

The method of recovering glass from laminated glass includes a step of attaching an oxide semiconductor to at least one side surface of the object to be processed using a laminated glass having a length of 120 mm or more in any of two directions as the object to be processed; In a state where the oxide semiconductor is in contact with the side surface of the object to be processed, in the presence of oxygen, the object to be processed is heated at a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region, and the polymer that adheres the laminated glass to each other is decomposed. The method includes a step of removing, and a step of recovering glass from the dismantled product.

  In addition, as a method for recovering the glass from the laminated glass, a step of attaching an oxide semiconductor to at least one side surface of the laminated glass that is an object to be processed, and the laminated glass is installed so that the laminated glass is in a vertical direction. In a state where the oxide semiconductor is in contact with the side surface of the object to be processed, in the presence of oxygen, the object to be processed is heated at a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region, The method includes a step of decomposing and removing polymers that adhere to each other, and a step of recovering glass from the dismantled product.

The processing apparatus for recovering glass from the laminated glass according to the present invention uses a laminated glass having a length of 120 mm or more in any of the two directions as an object to be processed, and an oxide semiconductor on at least one side surface of the object to be processed. A dispersion apparatus is formed by coating, and a transport device that transports the object to be processed at a constant speed in a state where the oxide semiconductor is in contact with a side surface of the object to be processed; Obtained by decomposing and removing the polymer in the object to be treated in the heat treatment unit for heating to a temperature higher than the temperature of the intrinsic electric conduction region, an air supply mechanism for supplying air into the heat treatment unit, and the heat treatment unit And a collection unit for collecting glass from the dismantled product.

In addition, as a processing apparatus for recovering glass from laminated glass, an oxide semiconductor dispersion film is applied to at least one side surface of laminated glass that is an object to be processed, and the oxide semiconductor is brought into contact with the side surface of the object to be processed In this state, the laminated glass has a heat treatment chamber in which the laminated glass is placed so that the laminated glass is in a vertical direction. In the heat treatment chamber, the object to be processed has the oxide semiconductor as an intrinsic electric conduction region. Heated to a temperature above, the heat treatment unit has an air introduction port for supplying air from the outside and an exhaust port for discharging gas generated by the heat treatment, and the polymer in the object to be treated in the heat treatment chamber Glass is recovered from a dismantled product obtained by decomposition and removal.

    In the present invention, the air-permeable structure means a porous or honeycomb structure having good air permeability. In the TASC method, sufficient oxygen is required to completely decompose the cut molecules into water and carbon dioxide, and a method of purifying the gas to be processed through a highly breathable structure is effective.

  According to the present invention, since the polymer can be completely decomposed and removed by treating the laminated glass with the semiconductor thermal activation method (TASC), the glass can be recovered from the disassembled material at a low cost in a short time. Can do. Further, by completely decomposing and removing the polymer, the effect of reducing the waste size can be obtained.

2 is a cross-sectional photograph of a laminated glass 1 composed of a top glass 2, a bottom glass 3, and an intermediate film 4. It is a photograph which shows the upper surface glass 2 and the lower surface glass 3 which were demolished on the solid honeycomb 5 after the intermediate film 4 was decomposed and removed. It is sectional drawing of the electric furnace 6 for a laminated glass process. 1 is a top view illustrating an example in which an oxide semiconductor 10 is applied to at least one side surface of a laminated glass 1. FIG. It is a figure which shows the state in which the laminated glass 1 which apply | coated the oxide semiconductor 10 is surrounded by the semiconductor oxide carrying honeycomb 12. FIG. It is a photograph which shows the mode before (a) and after a process (b) which arrange | positions a laminated glass to a perpendicular direction, and performs a TASC process. It is a top view of the TASC continuous processing apparatus 13 for laminated glass. It is an apparatus figure for processing a laminated glass by vertical arrangement.

  As shown in FIG. 1, the laminated glass 1 has a structure in which a polymer sheet is sandwiched between two tempered glasses of an upper glass 2 and a lower glass 3 as an intermediate film 4.

In order to recover the glass from the laminated glass 1, first, from the laminated glass, about 120 × 1
Cut out a 20 × 5 mm piece of laminated glass. The side surface of the laminated glass piece is brought into contact with the oxide semiconductor 10 such as Cr 2 O 3 and held in an electric furnace at 500 ° C. for 20 to 30 minutes in the air to completely decompose the polymer component, and the polymer in the laminated glass piece is completely removed. Dismantle. Laminated glass 1
In order to bring the oxide semiconductor into contact with the oxide semiconductor 10, the side surface of the laminated glass 1 (FIG. 1)
The dispersed film is formed by coating. As a method of coating, a method of dip-coating the side surface with a suspension of an oxide semiconductor, a method of spraying a dispersion of an oxide semiconductor on the side surface, or a method of coating with a brush or the like may be used.

By the TASC treatment, the intermediate film (polymer such as polyvinyl butyral, polyurethane, ethylene vinyl acetate copolymer) is completely decomposed, and the two glasses are separated.
In this way, the top glass 2 and the bottom glass 3 are easily recovered as shown in FIG. 2 from the dismantled product after the TASC treatment is performed on the laminated glass 1.

As a practical method for recovering the upper glass 2 and the lower glass 3 from the laminated glass 1,
It is preferable to use a continuous processing apparatus. This is provided with a carry-in unit, a preheating unit, a TASC processing unit, a cooling unit, a carry-out unit, and a sorting and collecting unit on a conveyor that is conveyed at a constant speed. The object to be processed in a state in which the dispersion film of the oxide semiconductor 10 is formed on the side surface of the laminated glass piece is placed on the honeycomb, loaded from the transport unit, subjected to TASC processing in the TASC processing unit, and from the unloading unit. It is unloaded and the glass is separated and collected at the sorting and collecting section.

Moreover, what is called a batch type processing apparatus can also be employ | adopted as a cheap and simple method of collect | recovering the upper surface glass 2 and the lower surface glass 3 from the laminated glass 1. FIG. In this method, one or a plurality of laminated glasses are arranged in the vertical direction, and TASC treatment is performed in the heat treatment chamber.
Considering that TASC treatment is effective regardless of the type of organic matter, this treatment equipment removes polymers by TASC treatment of any plastic and plastic composite material, and efficiently recovers valuable resources if they remain. Can be used as a device for

Example 1
An experiment was conducted using a laminated glass of a crown model of Toyota Motor Corporation. First, a piece of laminated glass 1 of 120 × 120 × 5 mm was cut out from a laminated glass having a size of about 800 × 1600 × 5 mm with a diamond cutter, and used as a dismantled sample for TASC treatment. The upper surface of the laminated glass 1 is a glass plate 2 having a thickness of about 2 mm, the lower surface is a glass 3 having a thickness of about 2 mm, and a transparent intermediate film 4 having a thickness of 0.75 mm is provided between the glass 2 and the glass 3. there were.

As shown in FIG. 4A, the four side surfaces of the laminated glass piece were dipped and coated in a suspension of Cr ₂ O _{3 as} the oxide semiconductor 10 in order. This was placed on the honeycomb 5 of a cordierite (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ) composition of solid (not coated with Cr ₂ O ₃ ). The honeycomb 5 on which the laminated glass 1 was placed was placed in the electric furnace 6 shown in FIG. 3, the heater 7 was energized while air was introduced from the air inlet 8, the temperature was raised to 500 ° C., and the temperature was controlled at 500 ° C. for 30 minutes. Thereafter, the temperature control power supply was turned off to cool. By the above series of TASC treatments, the polymer of the laminated glass pieces was completely decomposed, and two glasses were obtained as shown in FIG. The decomposed polymer becomes water and carbon dioxide gas and is discharged from the air exhaust port 9. The oxide semiconductor 10 (Cr ₂ O ₃ ) and the laminated glass 1 are in contact only on the side surface, but due to the oxidizing power that appears in the oxide semiconductor 10, the side surface deprives the polymer of bonding electrons and is unstable in the polymer. Cation radicals are formed. This radical propagates in the polymer, which is the decomposition target, destabilizes the whole polymer, and the polymer is cut into small molecules such as ethylene (radical cleavage) in such a way that it self-destructs. Reacts and decomposes completely into water and carbon dioxide. This is a feature of the TASC method. That is, once the radicals are formed on the side surfaces, the decomposition reaction continues in the in-plane direction, so that complete decomposition of the polymer is realized. Note that although a honeycomb in which an oxide semiconductor is not supported is used, a honeycomb in which an oxide semiconductor is supported may be used. In the present invention, since the decomposition of the polymer proceeds only from the side surface of the laminated glass, the stage on which the laminated glass is placed does not have to be a honeycomb, and does not necessarily need to be a porous material with high air permeability.
When the intermediate film is decomposed, a strange odor of acetaldehydes is generated, but it is not brominated by a VOC (volatile organic compound) purification device using TASC technology. Also, (although there is a range by manufacturers, the melting point is about 150-200 ° C.) butyral resin by TASC process, it is possible to ignite, _Cr 2 _{O 3} supporting honeycomb in an electric furnace as shown in FIG. 5 12 When the laminated glass 1 was surrounded, no ignition occurred. That is, the generated combustible gas is completely decomposed into carbon dioxide gas and water when passing through the box carrying Cr ₂ O ₃ .

Example 2
A piece of the same laminated glass 1 was cut out from the laminated glass used in Example 1. As the oxide semiconductor 13, α-Fe ₂ O ₃ (iron oxide: hematite) was used instead of Cr ₂ O ₃ used in Example 1, and the same TASC treatment as in Example 1 was performed. As a result, as in Example 1, the polymer of the laminated glass pieces was completely decomposed, and two glasses were obtained.

Example 3
In Example 3, instead of the four side surfaces of one piece of the laminated glass 1, three sides are immersed in a suspension of Cr ₂ O ₃ that is the oxide semiconductor 10 sequentially as shown in FIG. Dip coated. This was placed on a solid honeycomb 5 and subjected to TASC treatment in air at 500 ° C. for 30 minutes. As a result, as in Example 1, the polymer of the laminated glass pieces was completely decomposed, and two glasses were obtained.

Example 4
As shown in FIG. 4 (c), two opposite edges of the four side surfaces of one piece of the laminated glass 1 are sequentially immersed in a suspension of Cr ₂ O ₃ that is the oxide semiconductor 10 to dip the This was coated and placed on the solid honeycomb 5 and subjected to TASC treatment in air at 500 ° C. for 30 minutes. As a result, as in Example 1, the polymer of the laminated glass pieces was completely decomposed, and two glasses were obtained.

Example 5
As shown in FIG. 4 (d), one edge of the four side surfaces of the laminated glass 5 is immersed in a suspension of Cr ₂ O ₃ which is an oxide semiconductor 13, and is dip coated. Was placed on the solid honeycomb 5 and subjected to TASC treatment in air at 500 ° C. for 30 minutes. As a result, as in Example 3, the polymer of the laminated glass pieces was completely decomposed and two glasses were obtained.
Thus, it has been demonstrated that the complete decomposition of the polymer automatically proceeds to the end 120 mm away by the feature of the TASC method if the oxide semiconductor is brought into contact only on the surface of the polymer.

Example 6
A piece of the same laminated glass 1 was cut out from the laminated glass used in Example 1. The four side surfaces of the laminated glass pieces were sequentially dipped and coated in a suspension of Cr ₂ O _{3 as} the oxide semiconductor 10. As shown in FIG. 6 (a), the laminated glass is arranged in the vertical direction so as to be placed on the honeycomb 5 of the solid cordierite composition and sandwiched between the two honeycombs 5 of the solid cordierite composition. . When the treatment was performed under the same conditions as in Example 1, the polymer of the laminated glass piece was completely decomposed, and two glasses were obtained as shown in FIG. 6B.
In Examples 1 to 5, the laminated glass was disposed horizontally (sideways) for processing. In the case of the horizontal placement, when the polymer intermediate film is in a molten state, the intermediate film is crushed by the weight of the upper glass, and air (oxygen) tends to be difficult to enter between the glass surfaces. In other words, the cut and gasified molecules are released from the end face, react with oxygen in the air near the end face, and change into carbon dioxide and water. Even so, the polymer intermediate film could be completely separated into two sheets of glass by the TASC effect. In the present example in which the laminated glass was arranged in the vertical direction (vertical placement), the following improvements were observed with respect to the horizontal placement.
When the temperature rises and the TASC process starts, the two sheets (or two or more glasses) bonded together with the intermediate film are automatically separated by their own weight.
When separated, the molten polymer film on which the radicals on the two pieces of glass are propagated is exposed. As a result, due to the TASC effect, the cut and gasified molecules quickly react with oxygen in the air to become carbon dioxide and water. That is, the processing speed is increased.
The glass separated after the TASC treatment is easy to take out (compared to horizontally stacked glasses).
Compared to horizontal (stacked) processing equipment, vertical processing equipment is simple.

Example 7
A piece of the same laminated glass 1 was cut out from the laminated glass used in Example 1. As the oxide semiconductor 13, α-Fe ₂ O ₃ (iron oxide: hematite) was used instead of Cr ₂ O ₃ used in Example 6, and the laminated glass was arranged in the vertical direction in the same manner as in Example 6 to achieve TASC. Processed. As a result, as in Example 6, the polymer of the laminated glass pieces was completely decomposed, and two glasses were obtained.

(Configuration example of processing equipment)
Example 8
In order to perform the TASC process of the laminated glass 1 continuously, it is preferable to use the TASC continuous processing apparatus 13 for laminated glass shown in FIG. On the honeycomb, a workpiece to be treated with dip coating of an oxide semiconductor is placed on the side surface of a piece of laminated glass 1 and placed in the carrying-in portion 14 on the apparatus inlet side. Instead of a honeycomb, a base having an arbitrary shape and material for supporting a glass piece may be used. One piece of the laminated glass 1 placed on the honeycomb is continuously transported at a transport speed of about 100 mm / min by a conveyor installed from the carry-in section 14 to the carry-out section 18. Air is introduced into the preheating unit 15, the TASC processing unit 16, and the cooling unit 17 from the outside. One piece of the honeycomb and the laminated glass 1 is heated to 500 ° C. while passing through the preheating unit 15. TASC processing is performed when passing through the TASC processing section 16 which is a heat processing section controlled to 500 ° C. over about 1000 mm, and the organic component in the laminated glass piece is completely decomposed and removed. Since the gas discarded from the heat treatment unit 16 is not completely carbon dioxide and water and may contain low molecular weight organic matter, a VOC purifying apparatus based on the TASC method is provided outside the exhaust port. Good to place. This is an apparatus in which multiple honeycomb semiconductor wafers with heaters embedded are arranged in series. By heating to 500 ° C with the heater, the low-molecular organic substances that pass through are completely decomposed into carbon dioxide and water. And released into the atmosphere as a harmless gas. As shown in FIG. 5, when the laminated glass piece as the object to be processed is surrounded by the honeycomb structure 12 supporting the oxide semiconductor 10 in the heat treatment section, the honeycomb structure 12 heated to 500 ° C. It is even better because the low molecular weight organic gas passing through the gas is decomposed into carbon dioxide and water. The honeycomb can be replaced with other breathable structures. In addition, in order that the object to be processed is surrounded by the honeycomb structure 12 in the heat treatment unit 16, the object to be treated may be placed in the box of the honeycomb structure 12 and placed in the carry-in part. The honeycomb structure 12 may be incorporated so as to cover the workpiece. Cooling is performed while passing through the cooling unit 17. Note that it is not necessary to cool to room temperature, and the temperature to be cooled may be appropriate. Organic matter is completely decomposed and removed from the disassembled material on the honeycomb that has come out of the cooling unit 17 by the TASC treatment. When the organic matter is sent to the separation and recovery unit 19 through the carry-out unit 20, the separation and recovery unit 19 separates the glass. Collected. As described in Japanese Patent Application Laid-Open No. 2006-206654, there is a case where an inorganic valuable material that gives a specific function to the intermediate film is included and it is desired to collect this. In such a case, since only the organic substance is decomposed and removed by the TASC treatment, the inorganic particles remain, and are separated and collected as valuables together with the glass in the separation and collection unit.

  In the continuous processing apparatus, it has been described that all paths from the carry-in unit 14 to the carry-out unit 18 are conveyed at a constant speed. In the TASC processing chamber in which the preliminary heating unit 15, the TASC processing unit 16, and the cooling unit 17 are integrated, the TASC processing may be performed in a stopped state. In this case, an electric furnace with an entrance / exit door is placed in the center in the TASC processing chamber, and when the honeycomb with laminated glass is loaded, the entrance door opens and the furnace is treated. Things are carried and the entrance is closed. After the treatment, the door on the outlet side is opened, and the dismantled material on the honeycomb subjected to the TASC treatment is carried out. This system, which is based on the batch method, is slightly complicated in transport control, but the advantages are that it is easy to manage temperature and that it can control the necessary oxygen, so that steady TASC processing is possible.

Example 9
If the laminated glass is placed vertically and processing is to be performed by a continuous processing apparatus, it is inevitable that the apparatus becomes large. Therefore, it is preferable to perform the processing by the so-called batch furnace method shown in FIG. Cr ₄ O ₃ was dip-coated on four sides of the laminated glass piece cut out to 130 mm × 130 mm, and the laminated glass piece was placed vertically in the heat treatment chamber 6 which is an electric furnace. The heat treatment chamber 6 has an air introduction port 8 and an exhaust port 9. When the heat treatment chamber 6 is heated to 500 ° C., the organic substance that is the interlayer film of the laminated glass is decomposed by the TASC treatment, and the generated high-temperature gas rises. Is good. Since the gas discarded from the heat treatment chamber 6 is not completely carbon dioxide and water and may contain low molecular weight organic matter, VOC purification by the TASC method is performed outside the exhaust port 9. The device 20 may be arranged. Low molecular organic substances passing through the VOC purification device 20 in which a plurality of honeycomb heaters 12 in which the oxide semiconductor 10 is supported and in which heaters are embedded are arranged in series are completely decomposed into carbon dioxide gas and water and released into the atmosphere as harmless gases. Is done. When the honeycomb structure 12 supporting the oxide semiconductor 10 is disposed in the vicinity of the ceiling exhaust port 9 in the heat treatment chamber, the low molecular organic gas that passes through the honeycomb structure 12 heated to 500 ° C. is converted into carbon dioxide gas and water. Better because it is decomposed. When the TASC treatment is performed with such an apparatus, the interlayer film of the laminated glass is completely decomposed and removed, and the two glasses separated from the dismantled product in the electric furnace can be easily recovered. It is possible to arrange a plurality of, for example, about 5 laminated glasses side by side in an electric furnace, and it is possible to increase the processing speed per sheet. The batch processing system shown in FIG. 8 is characterized by small size, low cost, and low power consumption compared to a continuous processing furnace. Therefore, even when the laminated glass is placed horizontally, there is an advantage if a small amount is processed.

Example 10
The batch furnace system shown in FIG. 8 is not limited to laminated glass, and plastics and plastic composite materials can be applied to a wide range of materials to completely decompose and remove the polymer contained therein. When valuables are contained in the residue, it can be efficiently recovered. First, the object to be processed is placed in the heat treatment chamber 6 with the oxide semiconductor 10 being in contact only with the surface of the plastic or plastic composite material that is the object to be processed. Plastic composite materials include fiber reinforced plastics, bonded magnets, solar cell panels, laminated glass and the like. As a method of bringing the oxide semiconductor 10 into contact only with the surface of the plastic or the plastic composite material, a method of placing the object to be processed on the honeycomb 12 supporting the oxide semiconductor 10, There are a dip coating method, a method in which a solution containing the oxide semiconductor 10 is sprayed on the object to be processed, a method in which a solution containing the oxide semiconductor 10 is applied to the object to be processed, and the like. Air is supplied to the heat treatment chamber 6 from the outside through an air introduction port 8, and gas generated by the heat treatment is discharged from the exhaust port 9. In the heat treatment chamber 6, when the oxide semiconductor 10 that is in contact with the object to be processed is heated to a temperature at which the oxide semiconductor 10 becomes an intrinsic electric conduction region or higher, the polymer in the object to be processed is decomposed by the TASC treatment. It goes to the discharge port 9 in the molecular gas state. Since the honeycomb 12 carrying the oxide semiconductor 10 is disposed near the exhaust port 9 in the heat treatment chamber 6, the gas passing through the honeycomb is purified by the TASC effect. Further, a VOC purification device 20 including a honeycomb 12 supporting the oxide semiconductor 10 is connected to an exhaust port of the heat treatment chamber, and is discharged from the heat treatment chamber 6 and passes through the VOC purification device 20 by the TASC effect. The gas is broken down into water and carbon dioxide, and only harmless gases are released to the atmosphere.

  According to the present invention, glass can be recovered from laminated glass at a low cost in a short time using a semiconductor thermal activation (TASC) method, so that a large amount of processing demand is expected in the future. For waste, recycling that has not been realized in the past can be established as a practical business, and industrial applicability is great.

1 Laminated glass 2 Top glass
3 Bottom glass
4 Intermediate Film 5 Solid Honeycomb 6 Electric Furnace 7 Heater 8 Air Inlet 9 Exhaust Port 10 Oxide Semiconductor 11 Stand 12 Oxide Semiconductor-Supporting Honeycomb 13 TASC Continuous Processing Device 14 for Laminated Glass Carry-in Unit 15 Preheating Unit 16 TASC Treatment Unit 17 Cooling unit 18 Unloading unit 19 Sorting and collecting unit 20 VOC purification device

Claims (12)

Any length in two directions also the laminated glass is 120mm or more as an object to be treated, a step of depositing an oxide semiconductor in at least one side of the object to be treated, the oxide semiconductor on the side surface of the object to be processed A step of heating the object to be processed at a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region in the presence of oxygen in the contact state, and decomposing and removing the polymer that adheres the laminated glass to each other; Recovering the glass from the glass, and a method of recovering the glass from the laminated glass.   A step of attaching an oxide semiconductor to at least one side surface of a laminated glass that is an object to be treated; a step of installing the laminated glass so that the laminated glass is in a vertical direction; and an oxide on the side surface of the object to be treated Heating the object to be processed at a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region in the presence of oxygen in a state where the semiconductor is brought into contact, and decomposing and removing the polymer that adheres the laminated glass to each other; A step of recovering the glass from the dismantled product, and a method of recovering the glass from the laminated glass.   From the laminated glass according to claim 1 or 2, wherein the oxide semiconductor is adhered to the side surface of the laminated glass by a method of dip coating the side surface of the laminated glass on the suspension of the oxide semiconductor. A method of collecting glass. The object to be treated is enclosed in a structure having gas permeability carrying the oxide semiconductor, wherein the structure in the presence of oxygen, wherein the oxide semiconductor is heated to a temperature at which the intrinsic conductive region A method for recovering glass from the laminated glass according to claim 1. The step of decomposing and removing the polymer in the object to be processed by heating the object to be processed in the presence of oxygen is introduced into a continuous processing apparatus that conveys the object to be processed at a constant speed, and the continuous processing apparatus In the period during which the oxide semiconductor stays in a temperature region that becomes an intrinsic electric conduction region,
Recovering glass from the dismantling thereof is described in separate collection portion in the continuous processing apparatus, by recovering the glass, to claim 1 or claims 3 to 4, characterized in that it is separated and recovered To recover glass from laminated glass. Using a laminated glass having a length of 120 mm or more in any of the two directions as an object to be processed, a dispersion film of an oxide semiconductor is formed by coating on at least one side surface of the object to be processed, and the oxidation is performed on the side surface of the object to be processed. A transport device that transports the object to be processed at a constant speed in a state in which a physical semiconductor is in contact;
A heat treatment unit that heats the object to be processed to a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region;
An air supply mechanism for supplying air into the heat treatment unit;
A processing apparatus for recovering glass from laminated glass, comprising: a recovery unit that recovers glass from a dismantled product obtained by decomposing and removing the polymer in the object to be processed in the heat treatment unit. In a state where the oxide semiconductor is in contact with at least one side surface of the laminated glass that is the object to be processed, the laminated glass has a heat treatment chamber in which the laminated glass is placed so that the laminated glass is in a vertical direction.
In the heat treatment chamber, the object to be processed is heated to a temperature higher than the temperature at which the oxide semiconductor becomes an intrinsic electric conduction region,
The heat treatment chamber has an air introduction port for supplying air from the outside and an exhaust port for discharging gas generated by the heat treatment,
A processing apparatus for recovering glass from laminated glass, wherein the glass is recovered from a dismantled product obtained by decomposing and removing the polymer in the object to be processed in the heat treatment chamber.   A VOC purifying apparatus including a gas-permeable structure supporting the oxide semiconductor is connected to an exhaust port of the heat treatment unit or the heat treatment chamber, and the structure is configured so that the oxide semiconductor is intrinsically electric. The gas discharged from the heat treatment unit or the heat treatment chamber and passing through the VOC purification device is purified to a harmless gas by being heated to a temperature that is a conduction region or higher. The processing apparatus for collect | recovering glass from the laminated glass of 7. The object to be processed is surrounded by a gas permeable structure supporting the oxide semiconductor, and the structure is a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region in the heat treatment portion or the heat treatment chamber. The processing apparatus for recovering glass from the laminated glass according to claim 6, wherein the glass is recovered by heating.   The heat treatment section or the heat treatment chamber is a treatment chamber having an inlet and an outlet for air and an inlet door and an outlet door through which the object to be processed passes, and after the object to be processed is introduced from the inlet door, The entrance door is closed, the entrance door and the exit door are closed, and the polymer in the object to be processed is decomposed and removed in a state where the object to be processed is stopped, and the dismantled product obtained is carried out from the exit door. The processing apparatus for collect | recovering glass from the laminated glass of Claim 6 thru | or 9 characterized by the above-mentioned. An air-permeable structure supporting the oxide semiconductor is disposed near the exhaust port in the heat treatment chamber, and the structure is heated to a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region. The processing apparatus for recovering glass from laminated glass according to claim 7 or 8, wherein the gas guided to the exhaust port is purified. 9. The plurality of laminated glasses in which the oxide semiconductor dispersion film is formed on one side surface by coating are disposed in the heat treatment chamber so as to be in a vertical direction. The processing apparatus for collect | recovering glass from the laminated glass of 11.