JP2003192828A - Method for thermal decomposition treatment of organic resin material comprising inorganic component and facility therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To safely recover and reutilize an inorganic component contained in an organic resin material. <P>SOLUTION: A material for treatment which comprises the organic resin material containing the inorganic component is heat-treated in a low-oxygen atmosphere by external heating to decompose and remove the organic resin component. The inorganic component is recovered. The organic resin component is an epoxy resin composition and the inorganic component is silica. When the material for treatment contains a chlorine component, an agent subjected to a catalytic reaction with chlorine decomposed and separated by heating and producing a nontoxic chloride, together with the material for treatment, is added and heat-treated. Specifically, facilities are equipped with a heat-treating apparatus equipped with decomposition furnaces 1 and 2 for thermally decomposing the material for treatment comprising the organic resin material containing the inorganic material in the low-oxygen atmosphere by the external heating, a decomposed gas combustion furnace 3 fed with the gas produced by the thermal decomposition in the heat-treating apparatus and carrying out combustion treatment of the gas and a means 5 for recovering residues containing the inorganic component from the material for treatment fed from the heat-treating apparatus. A gas combustion treating furnace 6 is installed as a burning means for burning the residues containing the inorganic component, and burning and removing contained combustible components. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention removes organic components by subjecting an organic resin material containing inorganic particles such as silica (for example, epoxy resin molding residue, waste epoxy mold product, etc.) to thermal decomposition treatment. The present invention relates to a thermal decomposition treatment method and facility for recovering and reusing inorganic particles such as silica powder.

[0002]

Epoxy resin compositions are commonly used as electrical insulators or structural materials. As constituent components of this type of epoxy resin molded product, in addition to the epoxy resin and the curing agent, an inorganic agent such as silica (silicon dioxide) powder is mixed in order to lower the expansion coefficient of the cured product and reduce stress. There is.

Since the epoxy resin contains endocrine disrupting substances such as bisphenol A, it is important to treat it safely and surely.

On the other hand, silica powder has an average particle size of 10 μm.
It is a fine powder (having a particle size distribution of 1 to 200 μm), has a wide range of uses, and is useful as a precision instrument material or a building material.

[0005] Resin wastes such as epoxy resin products are generally crushed and granulated to be used as fuels for blast furnaces and the like, but they are also sources of dioxins and the aforementioned endocrine disrupting substances. Become.

By the way, as a technique for reusing the resin component of the epoxy resin molded product, JP-A-8-85736 is known as a technique for recovering an epoxy liquid material by thermal decomposition. According to this, the thermal decomposition of the resin is 340 to 9
It is preferable to heat within a temperature range of 00 ° C, particularly 350 to 450 ° C, and 510 to 5 when heated in an oxygen atmosphere.
Since the combustion reaction occurs at 40 ° C, it is desirable to heat at 500 ° C or lower.

Further, Japanese Patent Application Laid-Open No. 6-321521 is known as one in which a silicon compound such as silica powder is recovered from an epoxy resin molded product for recycling. According to this, the crushed epoxy resin composition is heat-treated at 1600 ° C. for 2 hours in a non-oxidizing atmosphere (argon atmosphere) to synthesize silicon carbide, which is a silicon compound having a high added value, and is collected.

[0008]

However, in order to recover silicon carbide as a silicon compound having a high added value from an epoxy resin molded article, the above-mentioned JP-A-6-321521 is used.
Like the means disclosed in the above publication, the reaction conditions are required to be a very high temperature atmosphere of 1600 ° C., and such means are not preferable because of high energy cost.

By the way, the epoxy resin molded product contains a large amount (50-80%) of inorganic components such as silica, which are rich in applications. Therefore, rather than spending energy costs to obtain high-value-added silicon carbide, recovering silica contained in epoxy resin molded products without spending energy costs, and adding material to epoxy resin or refractory ( For example, it is more preferable to reuse it as a raw material of castable material) and further as a construction material (eg fireproof panel).

However, a technique for recovering an inorganic component contained in an organic resin material such as an epoxy resin molded product has not been established yet, and in particular, the means disclosed in Japanese Patent Laid-Open No. 8-85736 mentioned above is used in an oxygen atmosphere. Since it is heated, it may generate dioxins, and endocrine disruptors may remain.

The present invention has been made in view of the above circumstances, and an object thereof is to safely recover and reuse an inorganic component such as silica contained in an organic resin material such as an organic resin molded product. Another object of the present invention is to provide a thermal decomposition treatment method and treatment facility for an organic resin material containing an inorganic component.

[0012]

The inventor decomposes and removes an organic resin component by subjecting an organic resin material such as an epoxy resin product crushed in a low oxygen atmosphere to thermal decomposition (dry distillation) by external heating. It was found that the inorganic component contained in the resin material is recovered.

That is, the present invention decomposes and removes an organic resin component by subjecting an object to be treated of an organic resin material containing an inorganic component to thermal decomposition (dry distillation) by external heating in a low oxygen atmosphere to remove the inorganic component. A method for thermally decomposing an organic resin material containing an inorganic component to be recovered, wherein the organic resin component is an epoxy resin composition and the inorganic component is silica.

Some organic resin materials such as epoxy resin moldings contain a chlorine component, which causes the generation of dioxins. Therefore, when the object to be treated contains a chlorine component, it is advisable to add, together with the object to be treated, a chemical which produces a harmless chloride by catalytically reacting with chlorine decomposed and deposited by heating. This dechlorinating agent is 1-100μ
It is effective that the average particle size of the powder is m or less and the average particle size is several μm or less.

The dechlorinating agent is an agent which is harmlessly substituted with chlorine to form a chloride by reacting with chlorine. For example, the inventors previously filed, alkali metals, alkali metal compounds,
It is effective to select at least one type of alkaline earth metal or alkaline earth metal compound or to mix two or more types.

Examples of the alkali metal compound include oxides, hydroxides, hydrogen carbonates, carbonates, silicates, aluminates, nitrates or sulfates of lithium, sodium, potassium, rubidium, cesium or francium. Etc.

Specific examples of the alkali metal compound treating agent include sodium hydrogen carbonate, sodium carbonate,
Examples thereof include sodium sesquicarbonate, natural soda, potassium carbonate, potassium hydrogen carbonate, sodium potassium carbonate, sodium hydroxide, potassium hydroxide and the like. In addition, sodium hydrogencarbonate is also referred to as sodium acid carbonate, sodium bicarbonate or sodium bicarbonate. Sodium carbonate is
It is also called sodium carbonate, soda, soda ash, laundry soda or crystalline soda. Sodium sesquicarbonate is also referred to as sodium monohydrogen dicarbonate, sodium hydrogen dicarbonate or sodium sesquicarbonate. Natural soda is also known as trona.

As the alkaline earth metal compound,
Examples thereof include oxides, hydroxides, hydrogen carbonates or carbonates of calcium, strontium, barium or radium.

Specific examples of the alkali metal compound treating agent include lime (CaO) and slaked lime (Ca (OH)).
₂ ), potassium carbonate (CaCO ₃ ) or dolomide (C
aCO ₃ · MgCO _3), and the like.

In order to carry out the thermal decomposition treatment method, the thermal decomposition treatment facility of the present invention uses an external heating to thermally decompose an object to be treated made of an organic resin material containing an inorganic component in a low oxygen atmosphere. The gas generated by the thermal decomposition in the heat treatment device is supplied, and the decomposition gas combustion furnace that combusts and processes this gas, and the residue containing inorganic components is recovered from the processed material supplied from the heat treatment device. Means to do
The organic resin component is an epoxy resin composition, and the inorganic component is silica.

Here, the gas containing the decomposed organic resin component is burned in the cracked gas combustion furnace.

The thermal decomposition treatment facility may be equipped with a combustion means for burning the residue containing the inorganic component to burn off the combustible component contained therein.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described with reference to the drawings.

1 and 2 are schematic views showing one form of a thermal decomposition treatment facility for carrying out the thermal decomposition treatment method of the present invention. The present invention is not limited to this form.

The thermal decomposition treatment facility comprises a first decomposition furnace 1, a second decomposition furnace 2 and a hot stove 3. In the present embodiment, a thermal decomposition treatment apparatus having a configuration in which the first decomposition furnace 1 and the second decomposition furnace 2 are arranged in upper and lower two stages and the material to be treated is subjected to carbonization treatment is provided. That is, as shown in FIG. 1, the first decomposition furnace 1 and the second decomposition furnace 2 are arranged in two stages so that the supply port side of the second decomposition furnace 2 communicates with the discharge port side of the first decomposition furnace 1. To be done.
A communication duct 13 is provided on the discharge side of the first decomposition furnace 1 and the supply side of the second decomposition furnace 2 to cover the discharge side and the supply side and to communicate with each other. The heat-treated object is supplied to the second decomposition furnace 2.

The first decomposition furnace 1 adopts a rotary kiln system, forms a rotatable rotary cylinder 11 and a gas duct on the outer periphery of the rotary cylinder 11, and introduces hot air gas into the rotary cylinder 11 to the outside. A heating jacket 12 as an external heating means for heating from above, a supporting roller (not shown) that rotatably supports the rotating cylindrical body 11 at both ends, and a rotation driving means (not shown) for rotationally driving the rotating cylindrical body 11. , Are provided. The hot air gas is introduced from the hot air stove 3 described later.

The rotary cylinder 11 has a supply port side (not shown) for carrying in the object to be processed at one end side and a discharge port side (not shown) at the other end side, and a rotary cylinder (not shown) inside the cylinder body. A plurality of feed blades inclined with respect to the axis of the body 11 are provided. Then, the object to be treated supplied from the supply-side duct 10 is introduced into the rotary cylinder 11 from the side of the supply port, and the rotation of the rotary cylinder 11 causes the object to be treated to be transferred to the outlet side while stirring. Is possible. still,
The supply-side duct 10 is provided with a hopper (not shown) for introducing a mixture in which an object to be treated and a dechlorinating agent are mixed.

The second decomposition furnace 2 is a furnace for decomposing and precipitating the resin component remaining in the treated material supplied from the first decomposition furnace 1, and adopts a rotary kiln system to It has the same structure and includes a rotating cylinder 21 and a heating jacket 22. A detailed description of the configuration of the second decomposition furnace 2 will be given to the above description of the first decomposition furnace 1.

The hot-air stove 3 has a hot-air gas (for example, a temperature of 450).
It is a facility for generating and supplying (.about.600 ° C.) and is provided with a combustion burner 31 for generating hot air. The generated hot gas is supplied to the heating jacket 22 of the second decomposition furnace 2 to heat the rotating cylindrical body 21 of the second decomposition furnace 2, and then the connecting pipe 23
It is supplied into the heating jacket 12 of the first decomposition furnace 1 via. At this time, temperature adjustment air is sent in to adjust the temperature of the hot air gas. In this way, the first decomposition furnace 1 and the second decomposition furnace 2 are indirectly heated by the hot air gas from the outside, and the object to be treated inside is subjected to carbonization treatment.

The residue generated in the second decomposition furnace 2 is a mixture of inorganic silica and carbide. In the present embodiment, the separating device 5 separates the inorganic material (silica) from the carbide and recovers the inorganic material. The separation device 5 employs a specific gravity difference separation method as a separation means.
The separating device 5 is equipped with a conveying means 4 such as a screw or a spiral in order to introduce the mixture.

Further, as in the thermal decomposition treatment facility disclosed in FIG. 2, a carbide combustion device 7 may be provided instead of the separation device 5.

The carbide combustion device 7 is equipment for burning the treated material (carbide) whose volume has been reduced in the second decomposition furnace 2 to ash it. The processed material is introduced by a conveying means such as a pipe conveyor provided in the discharge side duct 24.

The carbide combustion device 7 is composed of a rotary furnace 71. The rotary furnace 71 is made of a tubular steel material, and a fireproof / heatproof layer (not shown) made of castable material is provided inside the tubular steel material. Has been. The rotary furnace 71 is supported on both sides in the axial direction by rotary rollers 72 and 73, and is provided with a means for rotating it by a drive source 74 composed of a motor M at the center.

The rotary furnace 71 is constructed so as to be inclined by 2 to 3 degrees in the traveling direction so that natural conveyance is possible. Further, inside the rotary furnace 71, there is provided a rotary transfer means (not shown) extending in the axial direction and projecting in the radial direction.

On the upstream side of the rotary furnace 71, that is, on the carbide charging side, a box-shaped charging jacket 75 seals 7.
7, which is provided via a means for conveying carbide (screw,
(Spiral) 4 and a combustion burner 76 for igniting and burning carbides.

Further, on the downstream side of the rotary furnace 71, that is,
On the ash discharge side, fireproof castable material inside
Box-shaped discharge jacket 7 with a heat-resistant layer (not shown)
8 is provided via a seal 79. The ash discharged from the discharge jacket 78 is collected in an ash collection box (not shown). The exhaust gas from the exhaust jacket 78 is supplied to the gas combustion processing furnace 6 via the pipe 80.

The gas combustion treatment furnace 6 burns the dry distillation gas generated in the first decomposition furnace 1 and the second decomposition furnace 2. Here, the dry distillation gas is introduced from the dry distillation gas conduit 60 through the ejector 61. At this time, in the gas combustion processing furnace 6,
Exhaust hot air gas from the heating jacket 12 is circulated blower 6
3 and an ejector blower 64 or other transfer means, and is introduced through the ejector 61. The dry distillation gas conduit 60 is kept warm by hot gas to prevent floating substances from adhering to the inner wall of the conduit.

The gas combustion processing furnace 6 has a gas combustion chamber for combusting the introduced gas. In the gas combustion chamber, the dry distillation gas and the exhaust gas generated in the carbide combustion device 7 are mixed and burned by the combustion burner 62. When the dry distillation gas is sufficiently generated, the combustion by the combustion burner 62 is appropriately limited by restricting the fuel supply. The gas that has been subjected to the high temperature combustion treatment is used in the heat exchanger 65 and the bag filter 6.
6, exhausted through the exhaust blower 67 and chimney 68 to the outside of the system.

An operation example of the thermal decomposition treatment facility of the present invention will be outlined.

First, in the first decomposition furnace 1, an object to be treated (a resin molded body is crushed, and the size is, for example, 10 to 2).
Dechlorinating agent mixed with 0 mm square under) (for example,
Sodium hydrogen carbonate (amount added: 10% by weight) is added, and dry distillation treatment is performed under an atmosphere of 300 to 400 ° C. and a constant residence time (for example, about 30 minutes). At this time, a resin-forming component such as chlorine contained in the object to be treated is decomposed and deposited from the object to be treated. In addition, the chlorine component reacts with the dechlorinating agent that is added and mixed to generate a harmless chloride by substitution. Further, other decomposed and precipitated resin components are subjected to combustion treatment in the gas combustion treatment furnace 6 via the carbonization gas conduit 60, and under a constant atmosphere and residence time (for example, in an atmosphere of about 850 ° C., A residence time of 2 seconds or more), detoxification treatment is performed.

Next, in the second decomposition furnace 2, the first decomposition furnace 1
The treated product supplied from the above is subjected to dry distillation treatment at 450 to 550 ° C., whereby the resin component remaining in the treated product is further decomposed and deposited, and the resin component is removed. The decomposed and deposited component is supplied to the gas combustion treatment furnace 6 and is detoxified.

The decomposed gas (dry distillation gas) generated by the thermal decomposition treatment in the first and second decomposition furnaces 1 and 2 is transferred through the dry distillation gas conduit 60 together with a part of the hot air gas and fresh air by the transfer means. It is introduced into the gas combustion processing furnace 6 through the above and is subjected to combustion processing.

The residue generated by the thermal decomposition treatment in the second decomposition furnace 2 is a mixture of inorganic substances (such as silica) and carbide. The mixture is supplied to the separation device 5 or the carbide combustion device 7 by the conveying means 4, and the inorganic component such as silica is recovered.

[0044]

As is apparent from the above description, the thermal decomposition treatment method and its facility according to the present invention have the following effects.

(1) Since the resin constituent components of the resin body are decomposed and removed by heating, the contained inorganic components can be reliably separated and recovered and can be reused.

(2) Bisphenol A contained in the resin body
Since harmful components such as are decomposed and deposited and burned, safe and reliable detoxification can be performed.

(3) By adding a dechlorinating agent for treatment, the generation of dioxins can be effectively suppressed.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an embodiment of the present invention.

FIG. 2 is a schematic view showing another exemplary embodiment of the present invention.

[Explanation of symbols]

1 ... First decomposition furnace 2nd second decomposition furnace 3 ... hot stove 4 ... Transport means 5 ... Separation device 6 ... Gas combustion treatment furnace 7 ... Carbide combustion furnace

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) F23G 5/16 F23G 5/16 B 7/12 ZAB 7/12 ZABZ // C08L 63:00 C08L 63:00 F-term (reference) 3K061 AA08 AB01 AB02 AC13 BA05 BA10 CA01 CA07 FA03 FA10 FA21 3K078 AA05 AA10 BA08 BA21 CA02 CA07 CA21 CA24 4F301 AA24 AB02 CA09 CA25 CA52 CA67 4G072 AA25 BB05 GG03 MM28 QQ13 4J002 GT001 016JFD016001

Claims (5)

[Claims] 1. An inorganic component for decomposing and removing an organic resin component to recover an inorganic component by subjecting an object to be treated made of an organic resin material containing an inorganic component to heat treatment by external heating in a low oxygen atmosphere. A method for thermally decomposing an organic resin material containing an inorganic resin, wherein the organic resin component is an epoxy resin and the inorganic component is silica. 2. When the substance to be treated contains a chlorine component, a chemical agent which produces a harmless chloride by reacting with the chlorine which has been analyzed by heating is added together with the substance to be treated for heat treatment. The method for thermally decomposing an organic resin material containing an inorganic component according to claim 2. 3. The method for thermally decomposing an organic resin material containing an inorganic component according to claim 1, wherein the gas generated by heating the object to be treated is further burned. 4. A heat treatment apparatus for thermally decomposing an object to be treated made of an organic resin material containing an inorganic component by external heating in a low oxygen atmosphere, and a gas generated by the heat decomposition in the heat treatment apparatus are supplied. A pyrolysis treatment facility provided with a decomposition gas combustion furnace that combusts and treats this gas, and means for recovering a residue containing an inorganic component from a treated material supplied from a heat treatment apparatus, wherein the organic resin component is an epoxy resin. Pyrolysis treatment facility that is a resin and the inorganic component is silica. 5. The thermal decomposition treatment facility according to claim 4, further comprising a combustion unit that burns and removes the combustible component contained by burning the residue containing the inorganic component.