JP2001079511A - Method for recovering valuables from thermosetting- resin molding for electronic equipment and device therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To continuously recover inorganic valuables from a molding on an industrial scale at the time of recovering the valuables from the thermosetting- resin molding for electronic equipment used in a printed circuit board, etc., by crushing the molding, slurrying the crushed molding and continuously decomposing the slurry by supercritical hydroxidation. SOLUTION: The thermosetting-resin molding for electronic equipment is coarsely crushed by a crusher 1, then pulverized by a pulverizer 2, transferred to a slurrying device 3, slurried, increased in pressure by a pressurized feeder 4 and sent to a preheater 6. Meanwhile, an oxidizing agent pressurized by a pressurized feeder 5 and the pure water heated by a heat-exchanger type cooler 8 are introduced into the preheater 6. The materials are then heated by the preheater 6 and sent to a reactor 7, and the slurried molding is decomposed by the oxidizing agent by supercritical hydroxidation under a supercritical atmosphere. The treated fluid is cooled by the cooler 8, reduced in pressure by a pressure-reducing valve 13 and separated into solid and liquid by a centrifugal separator 14, and the solid inorganic valuables are stored in a tank 15.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for recovering valuable materials from thermosetting resin molded articles for electronic equipment used for resin sealing of electronic parts such as ICs and printed circuit boards on which electronic parts are mounted. It is about.

[0002]

2. Description of the Related Art A sealing resin used for sealing an electronic component such as an IC and a resin serving as a base of a printed circuit board are required to have excellent electrical insulation and heat resistance. As such a resin, a thermosetting resin such as an epoxy resin is used.

[0003] In general, thermosetting resins for electronic devices include, in addition to the base epoxy resin, a phenol resin as a curing agent, fused silica as an inorganic filler, an epoxy bromide resin as a flame retardant, and a flame retardant auxiliary agent. It is used as a thermosetting resin composition in combination with antimony trioxide and other trace additives.

In the step of sealing electronic parts such as ICs with resin, the electronic parts are sealed by molding a thermosetting resin composition. In the usual sealing process, it is inevitable that about 30 to 50 wt% of the thermosetting resin composition used for the molding is left as a waste such as culls or runners.

[0005] Further, discarded electronic devices such as computers are disassembled into housings, printed circuit boards and the like in order to collect plastics and metals. Electronic components such as mounted ICs are removed from the collected printed circuit boards.

[0006] Molding residue generated in the sealing process of electronic parts,
Since the printed circuit board recovered from the discarded electronic device is a molded body of a thermosetting resin, the resin cannot be recycled by heating and melting. Therefore, these thermosetting resin moldings had to be incinerated or landfilled.

On the other hand, as a method of recovering inorganic valuables contained in a thermosetting resin molded body, there is known a technique of burning a thermosetting resin molded body in air to recover inorganic valuables. (JP-A-8-108161).

[0008]

The method of burning a thermosetting resin molded article for electronic parts in air is a method capable of burning the thermosetting resin molded article and recovering inorganic valuables. When the thermosetting resin molded body is burned in the fire, the flame retardant is decomposed at the time of burning to generate harmful bromine compounds,
If the combustion temperature is low, harmful substances such as dioxin may be generated, and this is not a preferable method.

In addition, landfill treatment is not a preferable method in the present situation where landfill sites are narrowing, and is not a preferable method because inorganic valuables contained in thermosetting resin molded articles for electronic parts cannot be recycled. .

As a method of recovering inorganic valuables from thermosetting resin moldings such as culls and runners, there has been proposed a method of oxidatively decomposing thermosetting resin moldings for electronic parts using supercritical water ( JP-A-8-108161).

The above-mentioned supercritical hydroxylation decomposition treatment is an excellent method capable of recovering inorganic valuables from a thermoplastic resin molded article for electronic parts without generating harmful thermal decomposition exhaust gas.
The above method is a laboratory-level method in which a thermosetting resin molded body is pulverized to about 2 to 5 mm and subjected to supercritical hydroxyl decomposition by batch processing using an autoclave. It is not suitable for industrially processing a conductive resin molded article. In particular, in the case of industrial implementation, the thermosetting resin molded product pulverized to about 2 to 5 mm may be clogged in a pressurized feeder such as a plunger pump or a pipe.

An object of the present invention is to provide a method for recovering valuable materials from a thermosetting resin molded article for electronic parts on an industrial level, and an apparatus therefor.

[0013]

That is, according to the present invention, after a thermosetting resin molded article for electronic equipment is finely pulverized, the finely pulverized thermosetting resin molded article for electronic equipment is continuously crushed with supercritical water. The present invention relates to a method and an apparatus for recovering inorganic valuables such as fused silica and antimony trioxide by performing critical hydroxylation decomposition or supercritical water decomposition.

The thermosetting resin molded article for electronic equipment to be treated in the present invention is a molding residue such as a cull or a runner generated in a sealing step of an electronic part such as an IC, or a discarded electronic part such as a computer. Printed circuit boards collected from equipment.

These thermosetting resin molded articles for electronic devices are obtained by molding a thermosetting resin composition. The thermosetting resin composition may be a thermosetting resin such as an epoxy resin or a phenol novolak resin, usually a curing accelerator such as diazabicycloundecene, a fused silica, a glass fiber, an inorganic filler such as calcium carbonate, or a odorant. And a flame retardant such as antimony trioxide and the like.

The means for pulverizing the thermoplastic resin molded article for electronic equipment should have a particle size (for example, 0.1 to 10 mm) that can supply the thermosetting resin composition for electronic equipment to the reactor without blocking it.
The degree is not particularly limited as long as it can be crushed below, and examples thereof include a meal type crusher.

In the present invention, in order to efficiently perform the pulverization, the heat-exchangeable resin molded article for electronic equipment is first coarsely pulverized.
Then, it is preferable to pulverize. Examples of the pulverizing means include, for example, jaw crushers, gyre crushers, cone crushers, mills such as rod mills, ball mills, and vibrating rod mills, twin-screw mills, and dry mills such as vertical mills, or, for example, Wet pulverization such as a toothed roll, a ban mill, and a stirring mill may be used.

The pulverized thermosetting resin molded article for electronic equipment may be continuously supplied to the reactor as a slurry of water or the like. In order to form a slurry, the pulverized thermosetting resin molded article for electronic equipment and a solvent such as water may be vigorously stirred.
By using the slurry, a pressurizing supply device such as a plunger pump, a pipe, and the like are not blocked, and the slurry can be continuously fed into the reactor.

The reactor used for the supercritical water decomposition or supercritical water oxidation in the method of the present invention is a high-pressure gas target facility, and may be a pipe type or a vessel type. The reaction conditions for the supercritical water splitting or supercritical water oxidation in the present invention are such that the reaction temperature is generally 375 ° C to 700 ° C, preferably 600 to 700 ° C.
The temperature is around 650 ° C., and the reaction pressure is 22 to 50 MPa, preferably 22 to 25 MPa. Reaction time is 1 second ~
One hour, preferably 1-2 minutes.

The treated fluid after the supercritical water splitting or the supercritical water decomposition may be cooled, decompressed and discharged. In addition, since the energy for preheating the supply water can be reduced by using the supply water as the cooling solvent as the cooling means, it is preferable to use heat exchange type cooling.

In the case of performing supercritical water oxidation, the pulverized thermoplastic resin molded article for electronic equipment may be subjected to supercritical water oxidation in the presence of an oxidizing agent. As the oxidizing agent, for example, air, oxygen, hydrogen peroxide and the like can be used. In supercritical water, the thermoplastic resin or the like dissolves and has excellent diffusibility of an oxidizing agent such as oxygen, so that the thermoplastic resin and the like are oxidatively decomposed in a very short time. The thermosetting resin such as an epoxy resin or a phenol resin constituting the thermosetting resin molded article for electronic equipment is completely oxidatively decomposed into carbon dioxide and water by the supercritical hydroxylation decomposition. In addition, halogen-containing polymers such as brominated epoxy resins are produced by decomposition of halogens such as bromine in addition to carbon dioxide and water.By adding an alkali such as sodium hydroxide to the supply fluid,
Bromine or the like can be converted to an inorganic salt such as sodium bromide. Further, inorganic valuables such as fused silica and antimony trioxide contained in the thermoplastic resin molded article for electronic equipment are recovered from the processing fluid after the supercritical hydroxylation decomposition. The recovery means is not particularly limited, but a centrifugal separator or a solid-liquid separation means such as filter filtration from the processing fluid cooled under reduced pressure,
What is necessary is just to collect inorganic valuables.

In the case of performing the supercritical water decomposition, the pulverized thermoplastic resin molded article for electronic equipment which has been pulverized in the absence of an oxidizing agent may be subjected to the supercritical water decomposition. By the supercritical water decomposition, the thermosetting resin such as the epoxy resin and the phenol resin constituting the thermosetting resin molded article for electronic equipment is decomposed into phenol compounds such as phenol and isopropylphenol. Therefore, organic valuables such as phenols and inorganic valuables such as fused silica and antimony trioxide can be recovered by subjecting the thermoplastic resin molded article for electronic equipment to supercritical water splitting.

In order to recover the organic valuables from the processing fluid after the supercritical water decomposition, the inorganic valuables may be recovered from the processing fluid cooled under reduced pressure and then adsorbed with activated carbon, a synthetic adsorbent or the like.

The treated fluid after the recovery of the valuables may be subjected to a discharge treatment as it is. However, when a small amount of phenols is contained, a biological treatment, a physical oxidation treatment such as ozone, ultraviolet rays, etc. And the like.

When the thermosetting resin molded article for electronic equipment to be processed includes metal parts such as lead wires and copper foil such as printed circuit boards, these metal parts are subjected to supercritical hydroxylation decomposition or supercritical decomposition. Therefore, it is preferable to remove in advance. By removing metal parts in advance, the required volume of the reactor can be minimized,
Further, it is possible to avoid a blockage trouble and a wear problem of the valuable resource recovery device.

For example, after a metal part is removed from the coarsely pulverized thermosetting resin molded article for electronic equipment by a metal separation / removal means, it may be finely pulverized and then subjected to subsequent processing. As means for separating and removing the metal component, for example, means such as specific gravity separation means such as a hydrocyclone or magnetic separation means can be mentioned.

[0027]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of an apparatus for recovering valuable materials from a thermosetting resin molded article for electronic equipment according to the present invention will be described below with reference to the drawings.

Embodiment 1 FIG. 1 is a block flow diagram showing an embodiment of an apparatus for recovering inorganic valuables from a thermosetting resin molded article for electronic equipment by supercritical hydroxylation decomposition. .

The thermosetting resin molded product for electronic equipment is roughly pulverized by the coarse pulverizer 1 to a particle size of about 1 to 10 mm.
The coarsely pulverized thermosetting resin molded body is pulverized by the pulverizer 2 to a particle size of about 100 to 500 μm. The finely pulverized thermosetting resin molded body is transferred to a slurrying device 3 and is vigorously stirred in a solvent such as water to form a slurry. The slurried thermosetting resin molded body is subjected to a predetermined pressure (22M) by a pressure supply device 4 such as a plunger pump.
(Pa or more) and send it to the preheater 6. On the other hand, the oxidizing agent is also pressurized by the pressurizing supply device 5 and sent to the preheater 6. The heated pure water sent from the heat exchange type cooler 8 is also sent to the preheater 6.

The feed fluid comprising the slurry, the oxidizing agent and the pure water is heated by the preheater 6 to a temperature above the critical point of water (above 375 ° C.) and is continuously sent to the reactor 7. In the reactor 7, the thermosetting resin molded body slurried in a supercritical atmosphere of water is supercritically hydrolyzed and decomposed by an oxidizing agent. The organic matter such as the epoxy resin constituting the thermosetting resin molded body is oxidatively decomposed into carbon dioxide and water by the supercritical hydroxylation decomposition reaction. Inorganic compounds such as fused silica and antimony trioxide contained in the thermosetting resin molded body are directly contained in the processing fluid.

The processing fluid subjected to the supercritical hydroxylation decomposition is discharged by a discharge processing system. That is, the processing fluid is cooled by the heat exchange type cooler 8 and passes through the pipe 12 to the pressure reducing valve 1.
The pressure is reduced by 3 and a discharge process is performed. Heat exchange type cooler 8
The pure water used as a refrigerant is sent from the pure water tank 11 to the heat exchange type cooler 8 by the pressurized supply device 10 and exchanges heat with the heat exchange type cooling 8 processing fluid. The pure water heated by the heat exchange is sent to the preheater 6 via the pipe 9. By performing heat recovery by the heat exchange type cooler 8,
The heat energy cost for heating the supply water can be reduced.

The cooled and decompressed processing fluid is separated into solid and liquid by a centrifugal separator 14, and the solid inorganic valuables are stored in an inorganic valuables tank 15. Since the inorganic valuables separated by the centrifugal separator 14 are hardened to some extent, they may be finely pulverized and stored in the inorganic valuables tank 15.

The liquid separated into solid and liquid by the centrifuge 14 is
The antimony may be directly discharged as it is, or antimony may be removed by the antimony treatment device 16 and discharged in order to further remove a trace amount of antimony contained in the fluid. Examples of the antimony treatment device 16 include a device in which an oxidation unit such as ultraviolet-ozone oxidation and ultraviolet-hydrogen peroxide is combined with a filtration unit using a filtration membrane or the like, and further oxidizes antimony trioxide. The antimony oxide is made more insoluble and highly filtered, and the antimony is removed by filtration.

Embodiment 2 FIG. 2 is a block flow diagram showing one embodiment of an apparatus for recovering inorganic valuables from a thermosetting resin molded body including a metal part such as a printed board by supercritical hydroxylation decomposition. It is.

In FIG. 2, the same components as those in the apparatus of FIG. 1 are denoted by the same reference numerals.

The apparatus shown in FIG. 2 differs from the apparatus shown in FIG. 1 in that a metal remover 17 is provided between the coarse crusher 1 and the fine crusher 2.

That is, after the thermosetting resin molded body including the metal parts is roughly pulverized by the coarse pulverizer 1, the metal remover 17 is used.
Removes metal parts. The thermosetting resin molded body from which the metal parts have been removed is finely pulverized by the fine pulverizer 2. The processing steps after the fine pulverization are the same as those of the collecting apparatus shown in FIG. By removing the metal parts, the reactor 7 can be made more compact.

Embodiment 3 FIG. 3 is a block flow diagram showing an embodiment of an apparatus for recovering organic and inorganic valuables from a thermosetting resin molded article for electronic equipment by supercritical water decomposition. Things.

The thermosetting resin molded article for electronic equipment is roughly pulverized by the coarse pulverizer 1 to a particle size of about 1 to 10 mm.
The coarsely pulverized thermosetting resin molded body is pulverized by the pulverizer 2 to a particle size of about 100 to 500 μm. The finely pulverized thermosetting resin molded body is transferred to a slurrying device 3 and is vigorously stirred in a solvent such as water to form a slurry. The slurried thermosetting resin molded body is sent to the preheater 6 while being raised to a predetermined pressure by the plunger pump 4. The heated pure water sent from the heat exchange type cooler 8 is also sent to the preheater 6. The supply fluid composed of the slurry of the thermosetting resin molded body and pure water is heated to a predetermined temperature by the preheater 6 and is injected into the reactor 7.

In the supply fluid, a supercritical water decomposition reaction proceeds in a supercritical atmosphere of water in the reactor 7, and the thermosetting resin molded body is decomposed. By the supercritical water decomposition reaction, the thermosetting resin is decomposed into phenols such as phenol and isopropylphenol. The processing fluid after the supercritical water decomposition reaction contains organic valuables of phenols and inorganic valuables such as fused silica and antimony trioxide.

The processing fluid decomposed by the supercritical water is cooled by the heat-exchange type cooler 8, decompressed by the pressure reducing valve 13 through the pipe 12, and is subjected to a discharge treatment. Pure water used as a refrigerant in the heat exchange cooler 8 is subjected to heat exchange with the processing fluid in the heat exchange cooler 8 from the pure water tank 11 by the pressurized supply device 10. Through the preheater 6 and used as supply water.

The cooled and decompressed processing fluid is separated into a solid and a liquid by a centrifugal separator 14, and a solid composed of inorganic valuables such as fused silica and antimony trioxide is sent to an inorganic valuables tank 15. The liquid separated by the centrifugal separator is sent to an organic valuables recovery device 18, organic phenols are recovered, and the organic valuables are sent to an organic valuables tank 19. The processing fluid from which the inorganic and organic valuables have been recovered may be discharged if the release standard is satisfied.If the processing fluid contains a trace amount of antimony, it is further oxidized to make the antimony more insoluble and filtered. Another processing may be performed.

Fourth Embodiment FIG. 4 is a block flow diagram showing one embodiment of an apparatus for recovering inorganic and organic valuables from a thermosetting resin molded body including metal parts such as a printed circuit board. .

The apparatus shown in FIG. 4 differs from the apparatus shown in FIG. 3 in that a metal remover 17 is provided between the coarse crusher 1 and the fine crusher 2.

That is, after the thermosetting resin molded body including the metal parts is roughly pulverized by the coarse pulverizer 1, the metal remover 17 is used.
Removes metal parts. The thermosetting resin molded body from which the metal parts have been removed is finely pulverized by the fine pulverizer 2. The processing steps after the pulverization are the same as those of the recovery apparatus shown in FIG.

[0046]

According to the present invention as described in claim 1 or 2, inorganic valuables can be continuously recovered from a thermosetting resin molded article for electronic equipment on an industrial scale.

According to the third aspect of the present invention, inorganic valuables can be continuously recovered on an industrial scale from thermosetting resin molded products for electronic devices including metal parts, and the required volume of the reactor is reduced. It can be minimized, and it is also possible to avoid a blockage trouble and a wear problem of the valuable resource recovery device.

According to the present invention, inorganic valuables and organic valuables can be continuously recovered from a thermosetting resin molded article for electronic equipment on an industrial scale.

According to the present invention, inorganic and organic valuables can be continuously recovered on an industrial scale from a thermosetting resin molded article for electronic equipment including metal parts. Can be minimized, and a blockage trouble and a wear problem of the valuable resource recovery device can be avoided.

According to the present invention, it is possible to provide an apparatus for continuously recovering inorganic valuables from a thermosetting resin molded article for electronic equipment on an industrial scale.

According to the present invention, an apparatus for continuously recovering inorganic and organic valuables from a thermosetting resin molded article for electronic equipment on an industrial scale can be provided.

According to the present invention, it is possible to provide an apparatus for continuously recovering valuable materials from a thermosetting resin molded article for electronic equipment including metal parts on an industrial scale. It is possible to minimize the volume, and it is possible to avoid a blockage trouble and a wear problem of the valuable resource recovery device.

[Brief description of the drawings]

FIG. 1 is a block flow diagram of an apparatus for recovering inorganic valuables from a thermosetting resin molded article for electronic equipment by supercritical hydroxylation decomposition.

FIG. 2 is a block flow diagram of an apparatus for recovering inorganic valuables from a thermosetting resin molded body including metal parts by supercritical hydroxylation decomposition.

FIG. 3 is a block flow diagram of an apparatus for recovering organic valuables and inorganic valuables from a thermosetting resin molded article for electronic equipment by supercritical water splitting.

FIG. 4 is a block flow diagram of an apparatus for recovering inorganic valuables and organic valuables from a thermosetting resin molded article containing metal parts.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Coarse crusher 2 Fine crusher 3 Slurry apparatus 4 Pressurized supply apparatus 5 Pressurized supply apparatus 6 Preheater 7 Reactor 8 Heat exchange type cooler 9 Piping 10 Pressurized supply apparatus 11 Pure water tank 12 Piping 13 Pressure reducing valve 14 Centrifuge 15 Inorganic valuables tank 16 Antimony treatment equipment 17 Metal separation and removal equipment 18 Organic valuables recovery equipment 19 Organic valuables tank

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C22B 7/00 B09B 5/00 ZABC C08L 101: 00 (72) Inventor Tomoyuki Iwamori Shinsuna, Koto-ku, Tokyo 1-2-8, Organo Co., Ltd. (72) Inventor's position: New Year 5-7-1, Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Yuji Ikuta Shibago, Minato-ku, Tokyo 7-1-1 F-term in NEC Corporation (Reference) 4D004 AA07 AA22 BA05 BA06 CA04 CA13 CA22 CA32 CA36 CA39 CB13 CB31 4F073 AA27 AA31 AA32 BA21 BA22 DA01 DA09 DA11 EA02 EA11 EA63 EA79 HA02 HA04 HA09 4F301 AB22 CA04 CA09 CA23 CA24 CA32 CA41 CA51 CA65 CA72 CA73 4K001 AA00 BA22 CA00 CA01 CA02 CA03 CA04 DB00

Claims (8)

[Claims] 1. A thermosetting resin molded article for electronic equipment is supercritically hydrolyzed and decomposed in the presence of water and an oxidizing agent at a supercritical temperature / pressure or higher to be included in the thermosetting resin molded article for electronic equipment. The method for recovering inorganic valuables is characterized in that a thermosetting resin molded article for electronic equipment is pulverized, and the pulverized thermosetting resin molded article for electronic equipment is continuously subjected to supercritical hydroxylation decomposition as a slurry. Of recovering inorganic valuables from thermosetting resin molded articles for electronic equipment. 2. The inorganic material from a thermosetting resin molded article for an electric device according to claim 1, wherein the oxidizing agent is at least one selected from the group consisting of air, oxygen and hydrogen peroxide. How to collect valuables. 3. When the thermosetting resin molded article for an electronic device includes a metal component, after the thermosetting resin molded product for an electronic device is pulverized, the metal component is separated and removed. The method for recovering inorganic valuables from a thermosetting resin molded article for electric equipment according to claim 1 or 2, wherein the thermosetting resin molded article is continuously subjected to a supercritical hydroxylation decomposition treatment as a slurry. 4. A thermosetting resin molded article for electronic equipment is subjected to supercritical water decomposition with water at a supercritical temperature and pressure or higher in the absence of an oxidizing agent, and is included in the thermosetting resin molded article for electronic equipment. In the method of recovering organic and inorganic valuables, the thermosetting resin molded body for electronic equipment is pulverized, and the pulverized thermosetting resin molded body for electronic equipment is continuously subjected to supercritical water decomposition as a slurry. A method for recovering organic valuables and inorganic valuables from a thermosetting resin molded article for electronic equipment, characterized by the following. 5. When the thermosetting resin molded article for an electronic device includes a metal component, after the thermosetting resin molded product for an electronic device is pulverized, the metal component is separated and removed. 5. The thermosetting resin molded body is continuously subjected to supercritical water splitting treatment as a slurry.
3. A method for recovering organic and inorganic valuables from a thermosetting resin molded article for an electric device according to the item 1. 6. A pulverizing means for pulverizing a thermosetting resin molded article for electronic equipment, a slurrying means for making a pulverized thermosetting resin molded article for electronic equipment into a slurry, and a supply containing the slurry and an oxidizing agent. Pressurized supply means for pressurizing and supplying a fluid to the reactor, heating means for heating the supplied fluid, a reactor for performing a supercritical hydroxylation decomposition reaction of the supplied fluid in a supercritical water atmosphere, and a processing fluid from the reactor. A discharge processing system for discharging
An apparatus for recovering valuable resources from a thermosetting resin molded article for electronic equipment, comprising: a valuable resource recovery system for recovering inorganic valuable resources from the discharged processing fluid. 7. A pulverizing means for pulverizing a thermosetting resin molded article for electronic equipment, a slurrying means for making the pulverized thermosetting resin molded article for electronic equipment into a slurry, and reacting a supply fluid containing the slurry with the slurry. Pressure supply means for pressurizing the supply fluid to the vessel, heating means for heating the supply fluid, a reactor for performing a supercritical water decomposition reaction of the supply fluid in a supercritical water atmosphere, and discharging the processing fluid from the reactor An apparatus for recovering valuable resources from a thermosetting resin molded article for electronic equipment, comprising: a discharge processing system; and a recovery system for recovering organic and inorganic valuables from the discharged processing fluid. 8. The recovery of a valuable material from a thermosetting resin molded article for electronic equipment according to claim 6, wherein a metal separation and removal means is added between the pulverization means and the slurrying means. apparatus.