JPWO2014098229A1 - Separating and collecting plastic composite waste - Google Patents

Abstract

An object of the present invention is to provide a method that can be widely applied to a wide variety of plastic composite wastes and not only separates plastic components and non-plastic components, but also separates and recovers oil-suitable components from plastic components. In the treatment of plastic composite waste, particularly plastic composite waste made by combining various thermoplastics, thermosetting plastics and non-plastic components, and separating and recovering each component, ethylene glycols are used. The reaction resin is melted to obtain a reaction melt using the reaction initiator as a reaction initiator, and the plastic melt is separated from the plastic component and the non-plastic component using the reaction melt as a separation solvent. Provided is a method for separating and recovering plastic composite waste that is separated and recovered into components and sedimentation components.

Description

  The present invention relates to plastic composite waste, particularly various plastic composite waste, composite electrical products of metals and plastics and automobile products, medical waste, blended products of synthetic fibers and natural fibers, and composite plastics such as FRP. The present invention relates to a method for separating and collecting waste.

  As types of waste plastics, there are thermoplastic resins and thermosetting resins, and a method for separating them by specific gravity has been performed for a long time. However, thermoplastic resins are widely recycled. Since PVC discharges chlorine gas when it is subjected to thermal incineration, it is necessary to recover this chlorine gas (Patent Document 1). If these are liquefied, they cause equipment corrosion and increase the processing cost. . On the other hand, the decomposition reaction with diethylene glycol is difficult if PET resin does not use caustic soda as a catalyst (Patent Document 2). However, if caustic soda is used, it is depolymerized to produce terephthalate, etc., and recycled by washing with water. It is necessary and post-processing is troublesome. On the other hand, recycling of the thermosetting resin is difficult. For example, a cured epoxy resin is excellent in electrical characteristics, heat resistance, and adhesiveness, and thus is used in a wide range of fields such as insulating materials, adhesives, and paints. However, thermal decomposition is difficult and recycling is difficult. On the other hand, fiber reinforced plastics (hereinafter referred to as FRP) are generally widely used in automobiles, aircraft, sporting goods, and other fields because glass fibers are generally used as reinforcing fibers in terms of lightness and durability. However, recycling is difficult due to the reinforcing fiber. Therefore, FRP products using unsaturated polyester as the matrix resin and organic fibers other than glass fibers as the reinforcing fibers are decomposed using glycol, and the resulting decomposition products are condensed with dibasic acid and recycled. A method has been proposed (Patent Document 3). On the other hand, as a method for recycling FRP, an atmospheric pressure dissolution method using diethylene glycol monomethyl ether as a solvent and tripotassium phosphate hydrate as a catalyst has been proposed (Non-patent Documents 1 and 2).

  In addition, renal dialysis set and infusion set waste is highly infectious because it contains bodily fluids such as blood and injection needles, and the material contains a large amount of vinyl chloride resin and metal. , One of the most difficult waste to process. Therefore, the actual situation is that the waste from the renal dialysis set has been incinerated for the purpose of heat sterilization treatment, although there is a problem of generation of hydrogen chloride gas and dioxin.

  Furthermore, plastic products including metal materials, such as various electrical products such as OA equipment, mobile terminals, mobile phones, TVs, vacuum cleaners, refrigerators, especially printed wiring boards used in these control units, and melting It is formed integrally with a metal material such as a pipe joint, a resin-coated electric wire, an optical cable, or a fiber reinforced plastic. In these metal-containing plastic products, it is required to cleanly and efficiently separate the metal material and the plastic material in the disposal process or the recycling process of the product that has become defective in the manufacturing process. Therefore, various treatment methods have been proposed as treatment methods in which a plastic material of a metal-containing plastic product is dissolved by heating and separated from the metal material or the like. For example, in Patent Document 4, edible waste oil is heated to 170 to 175 ° C., a metal-containing plastic product is introduced into the edible waste oil, the edible waste oil is stirred to melt the plastic, and the metal material is exposed. By the way, the metal material selection method of the plastic waste which stops the heating of edible waste oil, naturally cools, and takes out a metal material from edible waste oil after that is proposed. Patent Document 5 discloses that waste of electrical products such as OA equipment and home appliances is put into vegetable oil such as tempura oil heated to a temperature at which the plastic material is softened and melted, and then softened and melted to produce vegetable matter. The disposal method of the waste of the electrical product which takes out the melted plastic material which floated on the upper part of oil, and takes out the metal material which remains in an oil tank after that is proposed. However, when a metal-containing plastic product, such as a mobile phone, is introduced into oil as a heating medium, the plastic material is heated and dissolved as if the food is fried in oil and floats on the oil, while other metal materials However, if a plastic material is poured into the oil, it may ignite when the plastic material melts, which is dangerous. Therefore, in the treatment of metal-containing plastic products, there has been proposed a method for treating metal-containing plastic products capable of heating and dissolving a plastic material in an oil layer safely and efficiently (Patent Document 6). However, in recent years, electrical components such as a semiconductor circuit are often formed on a thermosetting resin substrate such as an epoxy resin in an electrical component, but in the case of such a thermosetting resin, an oil heating treatment is applied. However, it is difficult to separate and collect the metal material and the resin material effectively, and there is a problem that it cannot be applied to many electric products using a thermosetting resin such as an epoxy resin.

  In addition, various composite plastic wastes are currently appearing as waste that is difficult to recycle, but as products, aluminum / PP / PET three-layer sheets, PE / PET carpets, silver layer / PET sheet laminated X-ray films , Nylon / PET bottles, PET / cotton / nylon / acrylic blended clothing, FRP boats and bathtubs, carbon fiber piping and parts, leaded fishing nets, electric wires, PVC paper, etc. However, there are many materials that need to be separated and recovered so that the materials can be reused, but separation and recovery are difficult, so they are currently incinerated.

JP 2001-55583 A JP 2006-110531 A Japanese Patent No. 4096000 Japanese Patent Laid-Open No. 5-17041 JP-A-10-137734 JP 2008-213480 A

Hitachi Chemical Technical Report No. 42 (2004.4.1) Epoxy CFRP recycling by atmospheric pressure dissolution method

  As a result of intensive research to provide a method and apparatus capable of separating and recovering active ingredients such as plastics and metals and effectively using them without incineration of such composite plastic waste, including medical waste and FRP, the present invention One uses triethylene glycol (TEG) as a solvent, and when heated near the boiling point (286 ° C), it is possible to perform sterilization necessary for medical waste and sufficient temperature treatment to melt the thermoplastic resin, while thermosetting Since it functions as a reaction solvent for resin such as depolymerization, various processed materials are added as separation solvents to provide a universal separation and recovery method that can be widely applied to a wide variety of complex wastes. However, although the method using triethylene glycol is freed from chlorine-related corrosion in the vinyl chloride treatment and has an advantage that various composite plastics can be treated, there are problems that the solvent cost is high and the running cost is high. Therefore, the present invention provides a universal separation and recovery method that can be widely applied to a wide variety of plastic wastes, particularly composite wastes, and provides a very practical method that replaces the method using only triethylene glycol. For the purpose.

When the present inventors melt-processed resin such as PET, PU, PC, etc. to ethylene glycols, the melt reacting with ethylene glycols despite a decrease in the fraction of ethylene glycols. In the liquid, we found that the separation efficiency of plastic components and non-plastic components such as metals did not decrease. Focusing on this, as a result of earnest research using ester resin melt formed using ethylene glycol as a separation solvent, The present invention has been completed. That is, the present invention is a method for treating and recovering plastic composite waste by separating it into a floating system component, a dissolution system component and a sediment system component,
Using ethylene glycol as a reaction initiator, heating and melting a melted resin to form a reaction melt,
Separating the plastic composite waste into a plastic component and a non-plastic component using the reaction melt as a separation solvent A;
Separating the separated plastic component into a floating component, a dissolution component, and a sediment component using the reaction melt,
A method for separating and recovering plastic composite waste, wherein a non-plastic component, a precipitated plastic component, a dissolved plastic component and a floating plastic component are separated and recovered.

Therefore, according to the present invention, not only the non-plastic component and the plastic component are separated, but also PP, PE, PS resin as a component floating in the separation solvent A, and PET, PU as a component dissolved in the separation solvent A. , PC and PA-based resins, PVC as a component that settles out from the separation solvent A, and plastic components can be separated and recovered into three types.
Further, according to the present invention, the ester resin melt formed by reaction with ethylene glycol has a higher boiling point than ethylene glycol used as a decomposition initiator. Separation of floating components such as PP, PE, PS, etc., not only maintaining the separation performance from plastic components but also suitable for oiling, while dissolving other plastic components and separating them by vacuum distillation PVC, epoxy resin, etc. can be recovered by sedimentation. That is, for example, the boiling point of ethylene glycol is 186 ° C., but the melt of 50:50 blend of ethylene glycol and PET has a boiling point of 220 ° C., and 288 ° C. of 5:95 blend is as follows. Moreover, the melt of triethylene glycol (TEG) and ester resin is as follows.
Compounding amount (vs. EG) 50% 95%
PET 221 ° C 288 ° C
PC 350 372
PU 360 370


Blending amount (vs TEG) 50% 75% 95%
PET 372 373 390
PC 352 358 384
PU 370 372 378
Here, the boiling point was defined as the liquid temperature when a drop dropped from the outlet during atmospheric distillation.
Therefore, not only the processing efficiency is improved by raising the boiling point of the solvent, but also the amount of ethylene glycol used can be reduced and recovered, which is extremely practical.
Therefore, in the present invention, the separation solvent A is one or more selected from the group consisting of ethylene glycol, ethylene glycol, diethylene glycol, and triethylene glycol, and the resin component that dissolves in the ethylene glycol to form a reaction melt. Is selected from one or more selected from PET resin (polyethylene terephthalate), PC resin (polycarbonate), PU resin (polyurethane), PA resin (nylon), component selection of ethylene glycols and soluble resins and both The boiling point of the separation solvent A used at a blending ratio of A decomposition solvent having a high boiling point of 300 ° C. or higher can shorten the processing time and is suitable for FRP and substrate processing.

  Plastic composite waste, medical waste, automobile waste, fishing nets, solar cells, mobile phones, home appliances, FRP and other plastic and non-plastic composites, with non-plastic components as metals and non-metals Inorganic substances such as semiconductors, glass fibers, and carbon fibers are included.

Before the step of heat separation in the separation solvent A, the plastic composite waste is immersed in the heating bath of the separation solvent B composed of cyclohexanone (or cyclohexane) or methyl isobutyl ketone and, if necessary, a xylene mixture thereof. In addition, it is possible to perform a pretreatment in which the plastic component is dissolved or swollen and separated from other non-plastic components in advance.
To dissolve PVC, immerse cyclohexanone (cyclohexane) or a mixture of xylene and xylene (xylene 80% or less) in a bath heated to 90-100 ° C under normal pressure and use it for pretreatment of wallpaper and automobile window frames. Can do. To swell PVC, immerse methyl isobutyl ketone (MIBK) or a mixture of xylene and xylene (MIBK 20-80%) in a bath heated to room temperature to 70 ° C. under normal pressure, swell and carry the circuit board from the solar panel. Can be used for pre-processing.

  In the present invention, FRP such as epoxy resin and unsaturated polyester resin can be separated and recovered from the reinforcing fibers. Also in the carbon fiber product, the carbon fiber and the matrix resin can be separated and recovered.

  The plastic composite waste contains PVC, and the PVC component is not dissolved in the separation solvent A, but separated from the other floating and dissolution system components and settled or heated in the separation solvent A with the addition of an alkaline agent. In addition to desalination treatment, it can be separated and collected from other floating and dissolution system components, and separated and recovered. In the range of 220 to 310 ° C., it can be desalted and separated by precipitation. In this case, it is preferable to neutralize the reaction system by adding an alkali agent to prevent the formation of dioxane. Further, at 220 ° C. or lower, PVC can be precipitated and collected separately without desalting.

  In the method of the present invention, when the waste plastic product is medical waste, it is preferable that the inside of the composite material separation tank is 220 ° C. or lower, and the plastic component and the metal component are separated and recovered at the temperature at which PVC does not decompose. .

  A melt system component selected from the group consisting of PET resin, PC resin, PU resin, and PA resin is reacted with ethylene glycol heated near the boiling point under pressure or normal pressure, and the resulting melt or its solidified powder is the main component. At least 5 parts by weight of ethylene glycol is added to 50 parts by weight of a polyester resin component selected from the group consisting of PET resin, PC resin, and PU resin. A separation solvent which is a melt obtained by reacting with each other or a coagulated powder thereof is preferable.

  In the present invention, the melt containing the reacted plastic component can be distilled under reduced pressure to recover ethylene glycol as an unreacted volatile component and reused.

  In the present invention, when the waste plastic contains PVC, it can be desalted without using a catalyst by melting in an ester resin melt that can be heated to 220 ° C. or higher and 350 ° C. under pressure or atmospheric pressure. In addition, unlike conventional oil refiners, low-temperature corrosion is less likely to occur, and the dechlorination effect is excellent, and the residual chlorine concentration of pyrolysis oil is well below the national limit of 100 ppm.

  In the present invention, an ester resin melt having a boiling point of 220 ° C. to 390 ° C. obtained by reacting with ethylene glycols as a reaction initiator can be used as a separation solvent for treating composite plastics.

  The boiling point of ethylene glycol is 186 ° C., but the melt of ethylene glycol and PET at 50:50 has a boiling point of 220 ° C., and the melt of ethylene glycol and PET at 5:95 has a boiling point of 288 ° C. In the melt of triethylene glycol and ester resin, ethylene glycol has a boiling point of 286 ° C., but it has a 50:50 distribution ratio with PC (polycarbonate) at 350 ° C. and a 5:95 distribution ratio at 384, PET (polyethylene). 50:50 distribution ratio with terephthalate) reaches 3720 ° C. and 5:95 distribution ratio reaches 390 ° C. Therefore, the boiling point of the separation solvent that can be substituted for triethylene glycol can be increased, and the processing efficiency can be improved.

  Therefore, the separation solvent according to the present invention is extremely practical because it not only improves the treatment efficiency in the plastic composite waste treatment method but also reduces the amount of triethylene glycol used.

    Furthermore, according to the present invention, medical waste is not a thermal incineration method, and can be sterilized without any problem of exhaust gas treatment by high-temperature heat treatment in a melt. Can be separated and recovered. That is, according to the present invention, medical waste containing chlorine-containing and metal-containing plastics can be sterilized (detoxified) and plastics can be collected separately.

  Furthermore, according to the present invention, when disassembling a FRP product using a thermosetting resin as a matrix resin, the waste FRP product is not separated or pulverized without using an alkali metal hydroxide. The resin and the reinforcing fiber can be separated.

It is a schematic diagram which shows the processing process of the composite type plastics of this invention. It is a schematic diagram of the processing facility of aluminum / PET / PE / PVC composite waste. It is a schematic diagram of the processing facility of CFRP. It is a schematic diagram of the processing equipment of wallpaper (PVC / paper). It is a schematic diagram of the processing equipment of a mobile phone. It is a schematic diagram of the continuous processing facility of aluminum / PET / PE / PVC composite waste. It is a schematic diagram of the continuous processing equipment of a mobile phone.

  Embodiments of the present invention will be described below based on examples. The plastic composite waste of the present invention is a composite material of plastic and non-plastic such as medical waste, automobile waste, fishing net, solar cell, mobile phone, home appliance, FRP, etc. Inorganic materials such as metals, non-metals, semiconductors, glass fibers, and carbon fibers are included. Depending on the type of waste, it is preferable to perform pretreatment using the separation solvent B in advance. For wallpaper and automobile window frames, it may be preferable to dissolve PVC at a normal pressure and a temperature of 90 to 100 ° C. using cyclohexanone or a mixture of xylene and xylene (second stone: equivalent to kerosene). In addition, in the case of solar panels including circuit boards and parts for mobile phones and semiconductors, metal frames, etc., methyl isobutyl ketone or a mixture thereof with xylene (second stone: equivalent to kerosene), normal pressure, normal temperature to 70 It is preferable to swell PVC at a temperature of 0 ° C. to separate the substrate from the metal frame, the semiconductor, and the like.

Example 1
The separation and recovery device used in the present invention includes a composite material separation device 10 containing ethylene glycols as a solvent. Waste A that can be introduced here includes dissolved plasticizer, dissolved residue, Al / PET / PE composite material, carpet, X-ray film, medical infectious plastic, GFRP (glass fiber FRP), CFRP (carbon fiber FRP), Includes substrate, automobile plastic, and used clothing. Waste A is separated in the separator 10 by floating plastic P1 (PE: polyethylene, PP: polypropylene, PS: polystyrene), sediment (metal, glass fiber, carbon fiber), and reaction plastic P2 (PET: polyethylene terephthalate, PC: polycarbonate, PU: polyurethane, PA: polyamide) and thermosetting plastic P3 (PVC: thermosetting plastic such as polyvinylidene chloride and epoxy resin). PVC should be recovered at 220 ° C. or lower without being decomposed, but it is dechlorinated by raising the temperature to 270 to 280 ° C., and reacted with ethylene glycols such as TEG through a gas cleaning device 80 and recovered as acids (dioxane). May be.

  A receiving tank 20 is connected to the bottom of the separation device 10, and the dissolved plastics P2 and P3 are recovered together with the separation solvent A (S). An evaporating tank 30 is connected to the receiving tank 20 via a filter (not shown), and the unreacted solid is heated to a boiling point or higher under reduced pressure to evaporate ethylene glycol and circulate to the separator 10 while the residue is removed. Collect as reactant. When the dissolved resin is a PET resin, it is used as it is as an extender of the PET resin, and when it contains other resins, it is used as a mixed resin.

  On the other hand, molten floating plastic (PE, PP, PS, etc.) P1 is sent from the reaction separation tank 10 to the thermal decomposition apparatus 40, and if necessary, it is thermally decomposed together with waste B (waste edible oil, waste tire, waste lubricant oil). The distillation apparatus 50 fractionates into cracked gas (in-house fuel), light oil (in-house fuel), and heavy oil (in-house fuel), and a part thereof is described in the quality improvement apparatus 60 (for example, Japanese Patent No. 5144020) It is recovered as boiler fuel via a quality improvement device that uses alcohol, and is used for power generation by the generator 70. Further, it is recovered as a partial residue.

  On the other hand, sediment (metal, non-metal, glass fiber, carbon fiber (filament), filler, cotton, hemp, acrylic, etc.) is recovered as a recycled product after heated ethylene glycol, steam cleaning and hot air drying, for example. . The washing water can be used by evaporating the water to recover the solvent and circulating it to the decomposition apparatus 10.

(Adjustment of separation solvent)
In the present invention, it is important that the solvent composition in the separation apparatus is adjusted so that the composition ratio of polyester resin such as PET, PC, PU, etc. with respect to TEG is 95% by weight or less and 50% by weight or more. When 95, 50 parts by weight of TEG (triethylene glycol) 50, 25, 5 parts by weight are added and heated to melt, separation solvents I having boiling points of 372 ° C., 373 ° C. and 390 ° C. are obtained, respectively. When the solvent composition is a composition ratio of polyester resin such as PET, PC, PU, etc. with respect to EG, 50 parts by weight of EG (ethylene glycol) is added to 50 parts by weight of PET, and when heated and melted, the boiling point is 221 respectively. Separation solvent I at 288 ° C. is obtained.
On the other hand, when TEG (triethylene glycol) 5, 25, and 50 parts by weight are added to PC 95, 75, and 50 parts by weight and heated to melt, separation solvent II having boiling points of 352 ° C., 358 ° C., and 384 ° C. is obtained. When 50 parts by weight of EG (ethylene glycol) 50 and 95 parts by weight of PC are added and heated to melt, separation solvent II having boiling points of 350 ° C. and 372 ° C. is obtained.
Further, when 50 parts by weight of TEG (triethylene glycol) 50 and 75 parts by weight are added to 50, 75 and 95 parts by weight of PU and heated to melt, separation solvent III having boiling points of 350 ° C. and 372 ° C. is obtained. When 50 parts by weight of EG (ethylene glycol) 50 and 95 parts by weight of PU are added and heated to melt, separation solvent III having boiling points of 360 ° C. and 370 ° C. is obtained.

(Example 2)
The plastic composite waste is treated as follows using the facility shown in FIG. Add 50 parts by weight of TEG (triethylene glycol) to 50 parts by weight of PET and heat and melt it in the batch-type dissolution tank 100, and then add aluminum / PET / PE / PVC composite waste to 220 A while stirring and stirring. Heat and hold at ˜250 ° C. for 0.5 to 1 hour to separate the resin and aluminum components. Next, since the resin component PE that floats is suitable for oiling, it is once taken out into a washing tank, washed with TEG at 220 ° C., sent to a thermal decomposition apparatus, and oil is recovered. The TEG used for washing is collected in the separating agent receiving tank 101. On the other hand, the separation solvent containing the dissolved resin component is transferred to the separating agent receiving tank 101 and sent to the vacuum distillation apparatus 102 to separate the TEG and the PET mixed resin, and the TEG is recovered via the condenser 103, and the separating agent receiving tank. Return to 102. Since undissolved aluminum and precipitated PVC remain in the dissolution tank, these are taken out, dried, and separated into aluminum and PVC. In the upper part of the dissolution tank 100, the solvent to be vaporized is condensed by the condenser 104, recovered and returned to the dissolution tank.
In this embodiment, 1) PE, PP, and PS do not react in the separation solvent, but float upward and are separated from other resins.
2) Since PVC does not dissolve in the separation solvent and is separated together with the metal or the like, it is not necessary to separate the PVC in advance.
3) PE resin can be recovered as an oily raw material, aluminum as a material, PET resin as a filler, and PVC resin as a raw material. Therefore, it is suitable for separating and collecting carpets (PET / PE), elution residues (PET / aluminum / other resins), fishing nets, medical waste, automobile waste, used clothes, and the like.

(Example 3)
The CFRP, which is a plastic composite waste, is processed by the equipment shown in FIG. A 7-mm thick CFRP tube is added to a separation solvent A prepared by adding 25 parts by weight of TEG (triethylene glycol) to 75 parts by weight of PET and melted by heating in a batch-type dissolution tank 100. Hold for a while to separate the defibrated FRP (68% by weight) and the resin content (32%). Unwinding is taken out after washing with TEG, etc., dried and reused, while the resin content is collected in the solvent receiving tank 101 together with the separation solvent and sent to the vacuum distillation apparatus 102 to separate the resin content such as TEG and epoxy, TEG is recovered via the condenser 103 and returned to the separating agent receiving tank 101. Resin such as epoxy is reused as a binder. Others are the same as in the second embodiment.
In addition, this embodiment is suitable for processing GFRP, substrates, and the like.
・ The substrate is separated into epoxy resin and metal with a separation solvent and separated.
5) FRP is divided into a glass fiber and a resin component, the glass fiber remains in the dissolution tank, and the resin component is dissolved and recovered in the separation solvent.

Example 4
FIG. 4 shows a facility for processing wallpaper (PVC / paper), which is a plastic composite waste. Mixing 30 parts by weight of xylene with 70 parts by weight of cyclohexanone, and adding the wallpaper to the separation solvent B prepared by heating to 80-100 ° C. in a batch-type dissolution tank 100, maintaining the pressure at normal pressure for 20 minutes while stirring, PVC (70% by weight) and paper (30%) are separated. The paper is dried and collected. The resin content is recovered in the solvent receiving tank 101 together with the separation solvent B, cooled by the cooler 110 and sent to the methanol distribution tank 111 to separate the cyclohexanenon and methanol content from the cyclohexanenon and PVC resin content, and cyclohexanenon and methanol. The methanol evaporator 112 separates the cyclohexanone and methanol, the methanol is returned to the methanol evaporator 112 and the cyclohexanone is returned to the solvent receiving tank 101, while the cyclohexanone and the PVC resin are separated from each other by the cyclohexanone evaporator 113. Recover.
In addition, this embodiment is suitable for the processing of automobile window frames made of iron and PVC, distribution lines made of copper and PVC, and the like.

(Example 5)
FIG. 5 shows a facility for processing a mobile phone (PVC / substrate) which is a plastic composite waste. Mixing 80 parts by weight of methyl isobutyl ketone with 20 parts by weight of xylene and heating to 70 ° C. in the pre-dissolving tank 120 and putting the mobile phone into the prepared separation solvent B, and holding at normal pressure for 20 minutes while stirring, PVC (70% by weight) is swollen and separated from the substrate (30%). The separation solvent B is collected in the preliminary solvent receiving tank 121 and circulated. The substrate is put into the processing facility of FIG. The same number is attached to the same member, and the description is omitted. Thereafter, the substrate is treated in the same manner as in Example 3, and the substrate is separated into glass fibers and noble metals that do not dissolve in the separation solvent A, and resins such as epoxy that dissolve in the separation solvent A. As the separation solvent B, methyl isobutyl ketone or methyl ethyl ketone may be used instead of cyclohexanone.
In addition, this embodiment is suitable for processing of electrical equipment including a substrate.

(Example 6)
Example 2 Aluminum / PET / PE / PVC Composite Waste and Example 3 CFRP
The processing equipment for continuously performing the process is as shown in FIGS. The continuous processing equipment is a continuous dissolution tank 200 into which raw materials such as aluminum / PET / PE / PVC composite waste and CFRP are added, and the vertical tank 201 and the subsequent horizontal tank 202 are L-shaped. And an inclined discharge tank 204 extending obliquely upward from the end thereof and a dryer 205 horizontally provided from the upper end thereof. The horizontal tank 202 is provided with a horizontal rotary transfer machine 206 from the beginning to the end, and the discharge tank 203 is provided with an oblique rotary transfer machine 207 to feed the raw material forward and obliquely upward. When the dissolved liquid level L of the vertical tank 201 and the inclined discharge tank 203 is the same, and the level L is exceeded from the inclined discharge tank 203, the dissolved liquid overflows and is discharged to the vacuum distillation apparatus 208, where the decomposition solvent A Dissolve TEG and dissolved resin dissolved in a dissolved solution such as PET. The distilled TEG is returned to the vertical tank 201 as a decomposing agent via the aggregator 209. Aluminum, PE resin, and PVC are discharged up the inclined discharge tank 204, but are TEG washed from above in the inclined discharge tank 204, dried by the dryer 205, and discharged. Other conditions are the same as those in the first embodiment, and the description is omitted.

  In FIG. 7, since the raw material charged into the vertical tank 201 is CFRP, the separation material from the dryer 205 is the defibrating CFRP, and the separation resin from the vacuum distillation unit 208 is a resin such as epoxy. Since other conditions are the same as those in the third embodiment, description thereof is omitted.

In particular, advantages of using the present invention include the following points.
1) PVC treatment of the present invention
In the present invention, the PVC resin can be separated and recovered by precipitating the PVC from the separation solvent A by treating the PVC resin at a decomposition temperature of 220 ° C. or lower. The dechlorination treatment can be performed at a temperature of 270 to 280 ° C. When it becomes acidic due to the influence of chlorine gas, it is preferably neutralized by adding an alkali agent.
2) Conventional plastic waste needs to be collected separately and processed, but according to the present invention, a boiling point solvent of 300 ° C. or higher is obtained without using a large amount of expensive triethylene glycol (TEG). By using this, the processing efficiency can be improved. Decomposition at a high temperature of 300 ° C. or higher is suitable for separating and collecting CFRP, GFRP reinforced with glass fiber or graphite fiber, and reinforced fiber and matrix resin in a carbon resin molded product. Therefore, the separation solvent can be selectively formed so that the composition of the separation solvent A and the mixing ratio thereof are 220 ° C. or lower, 220 to 280 ° C., 300 ° C. or higher and the temperature of the decomposition treatment.
3) Further, the resin component can be separated and recovered without separating the resin component floating without reacting with the solvent and the PET resin reacting with the solvent. While PE, PP, and PS that float on the solvent can be recovered as an effective oil component, the resin component that dissolves and reacts in the solvent is recovered as a reactant and can be used as a useful material.
4) Since valuable metals can be effectively separated and recovered from medical waste and substrates containing metals that have been incinerated in the past, it is highly practical.
5) In a solar panel, a cellular phone, etc., it is pretreated by immersing it in a warming bath of a separation solvent B made of methyl isobutyl ketone or a mixture of xylene and xylene (preferably methyl isobutyl ketone 20 to 80%) that swells the PVC resin. It is efficient to take out the semiconductor, the substrate, etc. and leave it to the decomposition treatment with the separation solvent A. Wallpapers, automobile window frames, etc. are treated by immersing them in a heating bath of cyclohexanone that dissolves PVC resin or xylene and xylene (preferably cyclohexanone 20 to 80%) separation solvent B to separate the resin from paper, metal, etc. It is preferable to keep it.
Therefore, the present invention includes a composite plastic waste separation process consisting of a two-stage process of pretreatment and composite material separation process.
6) In particular, when the batch-type dissolution tank is a continuous processing facility as shown in FIGS. 6 and 7, continuous processing of composite waste is possible and the efficiency is excellent.

DESCRIPTION OF SYMBOLS 10 Separation apparatus 20 Solvent receiving tank 30 Solvent evaporation tank 40 Thermal decomposition apparatus 50 Distillation apparatus 60 Quality improvement apparatus 70 Generator 80 Gas cleaning apparatus 100 Batch type dissolution tank 101 Separating agent reception tank 102 Vacuum evaporator 200 Continuous dissolution tank 208 Vacuum evaporation vessel

Claims (10)

It is a method of treating and recovering plastic composite waste by separating it into a floating system component, a dissolution system component and a sedimentation system component,
Using ethylene glycol as a reaction initiator, heating and melting a melted resin to form a reaction melt,
Separating the plastic composite waste into a plastic component and a non-plastic component using the reaction melt as a separation solvent A;
Separating the plastic component separated by the reaction melt into a flotation component, a dissolution component, and a precipitation component,
A method for separating and collecting plastic composite waste, which is separated into non-plastic components, precipitated plastic components, dissolved plastic components and floating plastic components and collected.  PP, PE, PS resin is included as a component that floats in the separation solvent A, PET, PU, PC, and PA resin is included as a component that dissolves in the separation solvent A, and PVC resin is used as a component that precipitates from the separation solvent A. The method of claim 1 comprising.   One or more selected from the group consisting of ethylene glycol, diethylene glycol, and triethylene glycol as ethylene glycols, and a resin component that dissolves in the ethylene glycols to form a reaction melt is PET resin, PC resin, PU resin, PA The method according to claim 1, wherein the separation solvent A is composed of at least one selected from the resin positions, and the boiling point of the separation solvent A to be used is determined by selecting components of ethylene glycols and ester resins and the blending ratio of both. .   Plastic composite waste is a composite material of plastic and non-plastic such as medical waste, automobile waste, fishing net, solar cell, mobile phone, home appliance, FRP, elution residue, etc. The method of Claim 1 containing inorganic substances, such as a metal, a semiconductor, glass fiber, and carbon fiber.  Before the step of heating and separating in the separation solvent A, the plastic composite waste is immersed in the heating bath of the separation solvent B composed of cyclohexanone, silohexane, methyl isobutyl ketone or their xylene mixed solution to dissolve the plastic components. The method according to claim 1, wherein a pretreatment is performed by swelling and pre-separating from other non-plastic components.   The method according to claim 1, wherein the plastic composite waste is FRP or carbon fiber product such as epoxy resin and unsaturated polyester resin, and includes a step of separating the matrix resin and the reinforcing fiber.   The method according to claim 1, wherein the plastic composite waste contains PVC, and the PVC component is precipitated from the separation solvent A and separated from other flotation and dissolution system components.   The method according to claim 1, wherein the waste plastic product is medical waste, and the metal component and the resin component are separated together with the sterilization treatment.   A melt system component selected from the group consisting of PET resin, PC resin, PU resin, and PA resin is reacted with ethylene glycol heated near the boiling point under pressure or normal pressure, and the resulting melt or its solidified powder is the main component. A separation solvent for separating and recovering plastic composite waste, characterized in that: A melt obtained by adding at least 5 parts by weight of ethylene glycol and reacting with 50 parts by weight of a dissolved resin component selected from the group consisting of PET resin, PC resin, PU resin, and PA resin, or a coagulated powder thereof. The separation solvent according to claim 9, wherein the boiling point is in the range of 220 ° C to 390 ° C.

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