JP2002255669A - Porous body from non-pollutive remainder of waste fiber reinforced plastic material and producing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous body and a producing method thereof which utilizes both of a fiber part and a plastic part of waste FRP material at the same time, generates no harmful substance on the occasion of its usage, does not take in a harmful substance inside and is safe and secure. SOLUTION: By the mixed sintering of the remainder containing the fiber and carbides which is obtained by subjecting the waste FRP material to thermal decomposition treatment while adding a treating agent which generates harmless chloride by the contact reaction with an organic halogen compound included by the waste FRP material to the waste FRP material, the porous body in which the carbides are burned and removed and the pores are formed is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous body from detoxified waste fiber reinforced plastic material residue and a method for producing the same.

[0002]

2. Description of the Related Art Discarded fiber reinforced plastic materials (hereinafter referred to as waste FRP materials) contain softening materials such as glass fibers and combustible substances such as plastics. A switch to processing by use is conceivable, and various technologies for that purpose have been proposed.

[0003] First, as a thing using a glass component,
There is Japanese Patent Publication No. Hei 7-88237, which regenerates the crystallized glass by utilizing the glass component of the waste FRP material. The glass component obtained by pulverizing the residue obtained by thermally decomposing or burning the waste FRP material is used. Molding the main powder, 850-
Heat treatment is performed at 950 ° C. to obtain crystallized glass.
Japanese Patent Application Laid-Open No. 6-116057 discloses a method in which crushed glass fiber reinforced plastic or the like is added to fly ash as a main component, mixed and sintered at 700 to 1000 ° C. to obtain a porous ceramic. In this case, the added FRP is thermally decomposed at around 200 ° C. to generate gas and carbonize, and when the temperature further rises, this carbide also generates CO gas, and the ceramics become porous with pores formed. On the other hand, the glass fibers remain in a network, and toughness is generated.
As a result, a porous ceramic that can be reused as an adsorbent and a filtering material is obtained.

Japanese Patent Application Laid-Open No. Hei 10-87872 discloses a method of recovering fibers in the form of fibers, in which FRP is reacted in a supercritical or subcritical environment to obtain glass fibers without damage.
It separates and collects carbon fibers and reuses them.

[0005] Further, not only glass fiber reinforced plastics, but also Japanese Patent Application Laid-Open No. 2000-308864 discloses a method of forming a porous body by combining glass and carbide, which includes carbide powder, glass powder, and other inorganic materials. And heat-treated at a high temperature to obtain a porous material (granular, plate-like, etc.), which is reused as a roadbed material, a water purification material and the like. In Japanese Patent Application Laid-Open No. 2000-34179, various inorganic materials (for example, glass) are mixed with a flammable heating substance (for example, “char”), and 1000 to 1300 ° C.
By sintering, a granular sintered body having a porosity of 20% or more and having water retention is obtained, and is reused as a water-retentive ventilation material for agricultural soil and vegetation soil.

[0006]

In the above-mentioned prior art, Japanese Patent Publication No. Hei 7-88237 only uses glass fibers and does not use plastic components. Also, in Japanese Patent Application Laid-Open No. 6-116057,
The glass fiber members are used only as they are, and the plastic parts are used from the state of organic matter.Therefore, the organic halogen compounds contained may be taken into the sintered body, It has been difficult to apply it to a purification filter for use. In particular, many plastics contain organic halogen compounds (for example, chlorine). Heating without considering the treatment of these organic halogen compounds may result in the generation of dioxins and their attachment to fibers and carbides after heating. There is. Further, the gas generated by decomposition may corrode facility equipment such as a heat treatment furnace and a waste system.

In Japanese Patent Application Laid-Open No. 10-87872, only the plastic portion is decomposed and removed, and the fiber portion is recovered.
No. 000-34179 does not utilize discarded FRP material.

As described above, none of the conventional techniques effectively utilize both the fiber portion and the plastic portion of the discarded FRP material at the same time. In addition, no technical idea has been found for performing the treatment by focusing on the removal of the organic halogen compound contained in the plastic material, and the treatment without considering this leaves a problem in terms of safety and security.

On the other hand, soil containing an organic halogen compound such as dioxins is used as an object to be treated, and an alkali substance is added thereto and mixed therewith to react with, for example, chlorine constituting the organic halogen compound, thereby producing harmless chloride. The present inventors have proposed a technique for reducing the amount of an organic halogen compound by doing so (Japanese Patent Publication No. 11-19616). this is,
The dioxins are made by paying attention to the fact that they are composed of chlorine and that the removal of this chlorine suppresses the production of dioxins.

Although the purpose of addition to the object to be treated is different, as a technique for adding an alkaline substance, ash is made symmetrical, as disclosed in JP-A-9-225431 and JP-A-2000-518.
No. 19 is known, and Japanese Patent Application Laid-Open No. 9-225431 discloses a technique of adding an alkali substance to lower the decomposition temperature of dioxins and performing heat treatment. or,
JP-A-2000-51819 discloses that an alkaline substance is added for pH adjustment.

Further, Japanese Patent Application Laid-Open No. 2000-246228 discloses a technique for purifying soil by adding an alkaline substance (NaOH, KOH) to the soil, and Japanese Patent Application Laid-Open No. 2000-246231 discloses a method for purifying soil using high-temperature and high-pressure water. Technology
Japanese Patent Application Laid-Open No. 2000-279942 discloses a technique for purifying soil by heat treatment.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and can effectively use both the fiber portion and the plastic portion of the waste FRP material at the same time. It is an object of the present invention to provide a safe and secure porous body and a method for producing the same without generating harmful substances and without taking harmful substances inside.

[0013]

The porous material from the detoxified waste FRP material residue according to claim 1 of the present invention is a waste FR material.
A residue containing fibers and carbide obtained by adding and mixing a treating agent that generates a harmless chloride by contacting and reacting with the organic halogen compound contained in the waste FRP material,
It is formed as a sintered body by mixed sintering with an inorganic material as a main component, and pores are formed by sintering and removing carbides from the sintered body.

According to a second aspect of the present invention, in the method for producing a porous body from the detoxified waste FRP material residue, the crushed waste FRP material is contacted with an organic halogen compound contained in the waste FRP material to cause harmless chloride. Pyrolysis treatment while adding and mixing a treating agent that produces a product to obtain a residue containing fibers and carbides, pulverized residue is added to and mixed with the main component inorganic material powder, and this mixture is dried and formed. Then, the compact is heated and sintered to sinter the carbide in the compact and evaporate and scatter outside the compact to form pores in the sintered compact.

The composition ratio of the main inorganic material is about 40%.
８０80% by weight, the fiber component is about 10-40% by weight, and the carbide is about 10-20% by weight. The particle size of the powder of the residue and the particle size of the inorganic material powder are both preferably about 30 to 200 μm. The porous body may be granular or plate-shaped. The heating temperature for the thermal decomposition is about 300 to 850 ° C., and the heating time is about 30 to 60 minutes depending on the quality of the object to be treated.
The object to be processed is stirred and heated while moving in the cylindrical container by external heating, and is performed in a low oxygen atmosphere. The treatment agent is added in an amount of about 3 to 20% by weight depending on the content of the organic halogen compound contained in the waste FRP material.

According to a third aspect of the present invention, in the porous body from the detoxified waste FRP material residue or the method for producing the same, the FRP material is a glass fiber FRP material.

The glass fiber is softened by heating and serves as a binder for the inorganic material as the main component. If glass fiber is insufficient, add waste glass.

According to a fourth aspect of the present invention, in the porous body or the method for producing the porous body from the detoxified waste FRP material residue, the inorganic material as a main component is an alumina-based material.

As the alumina type, aluminum oxide,
Aluminum hydroxide is used, but need not be alumina-based. For example, in addition to aluminum hydroxide buried as waste, magnetism and ceramics applied to various products (for example, glass) may be collected and used at present.

According to a fifth aspect of the present invention, there is provided a porous body from a detoxified waste FRP material residue or a method for producing the same, wherein glass is mixed as a binder for binding the inorganic material when mixing the residue with the inorganic material. is there.

In the case of a glass fiber FRP material, glass can be used as it is as a binder, but in the case of a carbon fiber FRP material, waste glass must be added and mixed. In addition, MgO, CaO, S
iO ₂ including adding and mixing, may attempt to decrease the sintering temperature.

The method for producing a porous body from the detoxified waste FRP material residue according to claim 6 is characterized in that:
As the solvent, at least one of pure water, an organic binder, and a dispersant is added.

As the organic binder, for example, polyvinyl alcohol is used, and as the dispersant, for example, ammonium polycarboxylate is used.

According to a seventh aspect of the present invention, in the porous body from the detoxified waste FRP material residue or the method for producing the same, the treating agent is a powder having an average particle size of about 100 μm or less. However,
The average particle size of the treating agent is desirably 5 μm or less.
This is because the smaller the particle size, the more the contact surface area can be secured.
In addition, those provided with the vaporized components such as O, H, and CO evaporate during the heat treatment to become porous, and the contact surface area is further increased.

[0025] The porous body or the method for producing the porous body from the detoxified waste FRP material residue according to claim 8 is characterized in that the treating agent is one of an alkali metal, an alkali metal compound, an alkaline earth metal and an alkaline earth metal compound. Alternatively, it is formed by mixing two or more types.

As the alkali metal, Li, Na, K, R
b, Cs, and Fr are used. As the alkaline earth metal, for example, Ca, Sr, Ba, and Ra are used. As the alkali metal compound, lithium, sodium, potassium,
Each oxide of rubidium, each hydroxide, each hydrogen carbonate, each carbonate, each silicate, each phosphate, each aluminate, each nitrate, each sulfate gas is used, for example, as sodium hydrogen carbonate, Sodium acid carbonate, sodium bicarbonate, sodium bicarbonate, sodium carbonate, sodium carbonate, soda, soda ash, laundry soda, crystal soda, and sodium sesquicarbonate, sodium monohydrogen dicarbonate, sodium tricarbonate, sodium Sesquicarbonate, as natural soda, trona is used,
In addition, potassium carbonate, potassium hydrogen carbonate, sodium potassium carbonate, sodium hydroxide, and potassium hydroxide are used. Examples of the alkaline earth metal compound include lime (CaO), slaked lime (Ca (OH) ₂ ), and calcium carbonate (CaCO ₂ ). ₃ ), Dolomite (CaCO ₃ · MgC)
O ₃ ) is used.

[0027]

Embodiments of the present invention will be described below. In this embodiment, the crushed waste FRP
Is subjected to a thermal decomposition treatment while adding and mixing a treating agent that reacts with an organic halogen compound contained in the waste FRP material to produce harmless chloride, and obtains a residue containing fibers and carbide obtained by carbonization. The residue is pulverized and added to the main component inorganic material powder and mixed. The mixture is dried and molded, and the molded body is heated and sintered to burn the carbide in the molded body and evaporate to the outside of the molded body. Then, pores are formed in the sintered body to obtain a porous body. The porous body may be either granular or plate-like.

For example, crushed waste FRP material including glass fiber (waste FRP ship, waste FRP supplies, FRP waste material generated in the manufacturing process, etc.) is contacted with the organic halogen compound contained in the waste FRP material to react. Pyrolysis while adding and mixing a harmless chloride-forming treatment agent to obtain a residue containing glass fiber and a carbide of a resin, and pulverizing the residue and adding and mixing an inorganic material powder made of alumina. The mixture is dried and molded, and the molded body is heated to 850 to 1300 ° C.
By heating and sintering, the glass fibers are softened by heating and function as a binder for the inorganic material, and the carbides are burned and gasified to form pores, thereby obtaining a porous body.

On the other hand, the plastic portion of the waste FRP material often contains an organic halogen compound such as chlorine, and dioxin may be generated by simply carbonizing the plastic portion by thermal decomposition. Therefore, it is necessary to suppress the generation of dioxins by removing the organic halogen compound. Therefore, by adding and mixing a treating agent composed of an alkaline substance to the waste FRP material and heating it, an organic halogen compound (chlorine, dioxins) can be obtained.
Decomposes and reacts with the treating agent in contact with harmless chloride (Nac
1), and dioxins remain in the object to be treated and the exhaust gas, and the generation of dioxins is greatly suppressed.

In the above embodiment, a residue containing fibers and carbide is obtained by pyrolysis of the waste FRP material, and the carbide is removed from the sintered body by combustion gasification by mixing and sintering the residue and the inorganic material. Thus, the porous body having pores is obtained, and the organic halogen compound contained in the plastic is not contained in the sintered body. In addition, during the thermal decomposition treatment, a treatment agent that generates harmless chlorides by contact with the contained organic halogen compounds is added, and harmful to residual fibers, carbides and generated decomposition gas (exhaust gas). No organic halogen compounds remain, and the generation of dioxins is suppressed. Therefore, no harmful substances are generated in the treatment of the waste FRP and the production of the sintered body using the same as a raw material, and the treatment of the waste FRP material and the production of the sintered body can be performed safely and safely. A safe and secure sintered body can be obtained without harmful substances being taken into the sintered body, and can be applied to a purification filter for various uses. Further, the fiber portion and the carbide obtained by thermally decomposing the waste FRP material are used at the same time, so that a processing means capable of entirely reusing the waste FRP material that has been incinerated or buried exclusively can be obtained.

[0031]

Embodiments of the present invention will be described below. First,
A waste FRP ship reinforced with glass fiber is roughly crushed by a heavy machine, and then crushed to a predetermined size (for example, 1 to 3 cm) by a rotary crusher having a two-wheel blade or a one-wheel blade. Next, the crushed product is put into a pyrolysis furnace by external heating,
By performing a thermal decomposition treatment at 0 ° C., organic substances such as plastics are thermally decomposed to obtain a residue containing glass fibers and carbide. In the thermal decomposition treatment, a treatment agent is added to the crushed object to be treated. As a treating agent, for example, sodium hydrogen carbonate is used, and 5% by weight is added to and mixed with the object to be treated.
Drying at 400 ° C. for 30 minutes and dechlorination (to produce harmless chloride by contacting with decomposed chlorine), and then heat-treating at 500 to 600 ° C. for 30 minutes to perform carbonization. .

The organic halogen compound contained in the object is decomposed by heating. The decomposed chlorine component and the precipitated chlorine component react with the added treating agent to produce harmless chloride (for example, inorganic sodium chloride). For this reason, harmful organic halogen compounds are not contained in the residual fibers, carbides, and generated decomposition gas, and it is safe in the subsequent process,
Residues that can be used safely can be obtained.

The residue obtained as described above is pulverized to a predetermined size by a pulverizer (for example, about 30 to 200 μm).
m). In the residue, the treating agent (sodium bicarbonate) and the generated chloride (the product of the reaction between the organic halogen compound and the treating agent) remain, but they may be sintered as they are. Of course, you may wash and remove by water washing etc. On the other hand, an inorganic material powder (for example, aluminum oxide), which is a main component and has a particle size similar to that of the residue, is prepared.
40 to 80% by weight of inorganic material powder, 20 to 60 residue
% By weight (10 to 40% by weight of fiber component, 10 to 40% by weight of carbide)
20% by weight).

Next, pure water is added and mixed and pulverized for 3 hours by a ball mill. An organic binder such as polyvinyl alcohol and a polycarboxylic acid ammonium salt as a dispersant are added to the raw material slurry thus obtained to obtain a slurry-like raw material, and this raw material is spray-dried at a drying temperature of 150 ° C. Perform spray granulation. The granules thus obtained are subjected to a hydrostatic pressing machine (commonly known as CIP) to obtain 0.3 to
It is molded at a pressure of 0.6 KPa. After the molding, the temperature is gradually increased by a batch type gas furnace (sintering furnace). First, the contained carbide is burned, gasified and discharged to form pores, and the temperature is further raised to a firing holding temperature of 1100. The mixture is fired at a temperature of 100 ° C. for 2 hours and cooled at a temperature reduction rate of 100 ° C./h to obtain a porous sintered body. Alternatively, the slurry-like raw material obtained as described above is defoamed while being stirred under reduced pressure, poured into a mold, dried, and fired under the same temperature conditions as described above. The former, which is stamped by a hydrostatic press, has better handling.

Here, the content of aluminum oxide as the main component is in the range of about 40 to 80% by weight, but if it is less than this, the strength becomes insufficient and it becomes difficult to maintain the shape. Above this, the porosity decreases. I do. Also, when the contents of the residue, the fiber component and the carbide are in the above and below ranges, the strength and the porosity are similarly unfavorable. If Mgo, Sio ₂ , or Cao is added as a sintering aid, the firing temperature is reduced, and a reduction in energy cost is expected.

The pressing force when embossing with a hydrostatic molding machine depends on the desired strength of the sintered body, the porosity, the mixing ratio of the raw materials, the raw materials, the workability of handling, and the like. Is determined as appropriate. Firing is performed in a gas atmosphere at 11
The firing was performed at a firing holding temperature of 00 ° C. for 2 hours, and cooling was performed at a cooling rate of 100 ° C./h. However, firing may be performed in an air atmosphere. The firing holding temperature is about 850 to 1300 ° C., and the cooling rate is the firing holding temperature. From about 50 to 200 in the range from
C / h may be used. If the firing temperature is lower than this, the release of the contained carbides due to gasification decreases, and the porosity decreases. If the rate of cooling (cooling rate) is lower than this, the strength is reduced, and if it is higher than this, cracks or the like occur.

The particle size of the raw material is about 30 to 200 μm, but if it is less than this, the structure becomes dense, and the release of the internal carbide by gasification decreases, and if it is more than this, the strength decreases.

FIG. 1 shows the composition of a porous body produced by the above-mentioned production method, wherein 1 is alumina as a main component, 2 is glass serving as a binder for alumina 1, and 3 is formed when carbide is gasified. Pores.

[0039]

As described above, according to the present invention, waste FR
A residue containing fibers and carbides is obtained by the thermal decomposition of the P material, and carbides are removed from the sintered body by combustion gasification by mixing and sintering the residue and the inorganic material to obtain a porous body having pores. The organic halogen compound contained in the plastic is not contained in the sintered body. In addition, a treating agent that forms harmless chloride upon contact with the organic halogen compound contained during thermal decomposition is added, and the harmful organic halogen compound remains in the residual fiber carbide and the generated decomposition gas. And the generation of dioxins is suppressed. Therefore, no harmful substances are generated in the processing of the waste FRP material and the generation of the sintered body, and these processings can be performed safely and safely. In addition, no harmful substances are taken into the sintered body, and a safe and secure sintered body can be obtained, which can be applied to a purification filter for various uses. Further, the fiber portion and the carbide obtained by thermally decomposing the waste FRP material are used at the same time, so that a processing means capable of entirely reusing the waste FRP material that has been incinerated or buried exclusively can be obtained.

[Brief description of the drawings]

FIG. 1 is a composition diagram of a porous body according to the present invention.

[Explanation of symbols]

 1. Aluminum oxide 2. Glass 3. Pores

Claims (8)

[Claims] 1. A waste fiber-reinforced plastic material is mixed with a treating agent that produces a harmless chloride by contacting and reacting with an organic halogen compound contained in the waste fiber-reinforced plastic material.
Residue containing fiber and carbide obtained by thermal decomposition treatment,
Detoxified waste fiber reinforced plastic material residue characterized by being formed as a sintered body by mixed sintering with an inorganic material as a main component, and having pores formed by burning and removing carbides from the sintered body. From the porous body. 2. A crushed waste fiber reinforced plastic material,
Thermal decomposition treatment is performed while adding and mixing a treating agent that generates a harmless chloride by contacting and reacting with the organic halogen compound contained in the waste fiber reinforced plastic material to obtain a residue containing fiber and carbide, and pulverize the residue. The mixture is added to and mixed with the inorganic material powder of the main component, and the mixture is dried and formed, and the formed body is heated and sintered to burn the carbide in the formed body and evaporate to the outside of the formed body to form a sintered body. A method for producing a porous body from detoxified waste fiber reinforced plastic material residue, characterized by forming pores. 3. The porous body from detoxified waste fiber reinforced plastic material residue or the method for producing the same according to claim 1, wherein the fiber reinforced plastic material is a glass fiber reinforced plastic material. 4. The porous body from a detoxified waste fiber reinforced plastic material residue or a method for producing the same according to claim 1, wherein the inorganic material as a main component is an alumina-based material. . 5. The detoxified waste fiber reinforced plastic according to claim 1, wherein glass is mixed as a binder for binding the inorganic material when the residue and the inorganic material are mixed. A porous body from a material residue or a method for producing the same. 6. The detoxified waste fiber according to claim 2, wherein at least one of pure water, an organic binder, and a dispersant is added as a solvent during dry molding of the mixture. A method for producing a porous body from a reinforced plastic material residue. 7. The treatment agent is a powder having an average particle size of 100 μm or less, and the porous body from the detoxified waste fiber reinforced plastic material residue according to any one of claims 1 to 6, or Its manufacturing method. 8. The method according to claim 1, wherein the treating agent is formed by mixing one or more of an alkali metal, an alkali metal compound, an alkaline earth metal and an alkaline earth metal compound. A porous body from the detoxified waste fiber reinforced plastic material residue according to any of the above, or a method for producing the same.