JP2006328123A - Method and apparatus for treating recovered spent halogen-containing plastic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for treating recovered spent halogen-containing plastics, which are capable of removing halogen atoms from the recovered spent halogen-containing plastics within a short time. <P>SOLUTION: The method for treating the recovered spent halogen-containing plastics comprises heating an alkylene glycol dispersion containing the halogen-containing plastics and an alkali to 125 to 196°C. The apparatus for treating the halogen-containing plastics comprises a frame having an opening; a lower cover member and an upper cover member attached to the frame; a reaction vessel body being capable of being transferred into the opening and provided with end openings respectively stopped by the lower and upper cover members in the opening; a flow guide means for vertically circulating contents and is formed in the inside of a reaction vessel constituted from the upper and lower members and the reaction vessel body; an agitation means for agitating the contents; and a heating means for heating the contents. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a processing method and a processing apparatus for a halogen-containing plastic recovered material, and more particularly to a processing method and a processing apparatus for a halogen-containing plastic recovered material that can remove halogen atoms from the halogen-containing plastic recovered material in a short time. .

  Various plastic products are easy to mold and excellent in properties such as strength, and are widely used in various applications. However, no matter how excellent in properties such as strength, plastic products will eventually be discarded and disposed of. Because of its excellent characteristics, there are a wide variety of waste plastic products that are discarded from plastic products used in a wide range of applications, and the amount of discarded plastic products is enormous. Therefore, disposal of recovered plastic products is a problem.

  At present, generally, the various plastic products collected are disposed of in landfills or incinerated.

  However, among various plastic products, when plastic products containing halogen atoms are simply disposed of in landfills or incinerated, there is a problem that there is a great adverse effect on people and the environment. In other words, when plastic products containing halogen atoms are simply disposed of in landfills, the plastic products are not easily decomposed in the soil, and additives contained therein are gradually leaked to contaminate the soil. . On the other hand, when plastic products containing halogen atoms are simply incinerated, halogen gas is generated by the thermal decomposition of plastic products containing halogen atoms, which not only damages the incinerator. Dioxins are easily generated.

  In particular, when a plastic product containing a halogen atom, such as a soft vinyl chloride resin product, contains a large amount of a phthalate plasticizer that is suspected of being an environmental hormone, it is simply When landfilled or incinerated, there is a serious problem that the adverse effects on people and the environment are extremely large.

  In order to avoid such problems, several methods are known as dehalogenation methods for removing halogen atoms from plastics containing halogen atoms. For example, a vinyl chloride polymer composition is dissolved in an organic solvent. The solution obtained by adding an alkaline agent to this solution is stirred and maintained in a temperature range from room temperature to the boiling point of the organic solvent under normal pressure while stirring, thereby chlorinating the vinyl chloride polymer composition. The method (patent document 1) characterized by dechlorinating a vinyl polymer can be mentioned.

  However, in the method described in Patent Document 1, in order to achieve a dechlorination rate of 97.2%, as described in the examples, the polarity for dissolving the vinyl chloride polymer composition is Using dimethyl sulfoxide as an aprotic solvent, a reaction time as long as 3 hours is required at a reaction temperature of 80 ° C.

JP 2003-253039 A

  An object of the present invention is to provide a processing method and a processing apparatus for a halogen-containing plastic recovered material capable of removing halogen atoms from the halogen-containing plastic recovered material in a short time.

  The inventor of the present invention, when dehalogenating a halogen-containing plastic recovered material, when using alkylene glycol, which has not been assumed as a solvent, the halogen-containing plastic recovered material is not dissolved in the solvent. However, it has been found that halogen atoms can be removed from a halogen-containing plastic recovered material in a short time.

That is, the present invention has been made on the basis of such knowledge, and as means for solving the above problems,
Claim 1 is a method for treating a halogen-containing plastic collection, characterized in that an alkylene glycol dispersion containing a halogen-containing plastic collection, an alkali and an alkylene glycol is heated to 125 to 196 ° C.
In one embodiment of the above means, the alkylene glycol dispersion has an alkali concentration of 0.25 to 1.5 mol / L,
In one aspect of the means, the alkylene glycol dispersion is heated for 5 to 35 minutes,
Claim 4 is a processing apparatus preferably used in this method, wherein the frame is formed in a frame shape, a closing member provided in the frame, and transportable into the frame. A reaction vessel body having an opening closed by the closure member, and a reaction vessel formed by the closure member and the reaction vessel body closing the opening of the reaction vessel body. And a flow guide means for circulating the contents up and down, a stirring means for stirring the contents in the reaction vessel, and a heating means for heating the contents in the reaction vessel. It is a processing equipment for the contained plastic recovered material,
In one aspect of the means, the closing member is a lower lid member and an upper lid member provided on the frame, and the reaction vessel main body is closed with the lower lid member and the upper lid member in the frame. With both ends opening
In another embodiment of the above means, the reaction vessel comprises a halogen-containing plastic recovered material insertion means and a discharge means for discharging the contents in the reaction container.

  According to the present invention, it is possible to provide a method for treating a halogen-containing plastic recovered material capable of removing halogen atoms from the halogen-containing plastic recovered material in a short time. Therefore, even if the treated product obtained by the method of the present invention is finally incinerated, halogen-containing materials such as halogen gas and hydrogen halide are not generated by thermal decomposition of the treated product. The incinerator is not damaged by halogen-containing substances such as gas, and dioxins are not generated.

  In addition, according to the present invention, there is provided a processing apparatus for a halogen-containing plastic recovered material capable of removing halogen atoms from the halogen-containing plastic recovered material in a short time compared to the same processing method as that of the present invention except that no alkylene glycol is used. it can.

  In other words, the halogen-containing plastic recovered material processing apparatus according to the present invention can close the opening of the reaction vessel body easily and in a short time with the closing member, and further, when the dehalogenation treatment is performed, Since the frame on which the closing member is mounted receives a pressure that increases in step 1, the bending moment is not applied to each member including the reaction vessel, and therefore the life of the apparatus is prevented from being shortened based on this bending moment.

  Furthermore, since the processing apparatus for the halogen-containing plastic recovered material of the present invention includes a flow guide means and a stirring means for circulating the contents up and down, the contents in the reaction vessel can be efficiently and uniformly stirred. It has become. Therefore, the reaction time of the method of the present invention can be further reduced by using the halogen-containing plastic recovered material processing apparatus of the present invention in the method of the present invention.

  The object to be treated by the method of the present invention is a halogen-containing plastic recovery. This recovered halogen-containing plastic is a halogen-containing plastic composition for molding containing at least one of a plastic containing a halogen atom in the molecule and an additive containing a halogen atom in the molecule, and is used as a product. Collected without using the above-mentioned halogen-containing plastic composition, and a half-product such as burrs and punching residue produced as a by-product upon molding using the halogen-containing plastic composition. Halogen-containing plastic products obtained, which are collected after use, and are assembled products that are a combination of the above-mentioned halogen-containing plastic products and resin products obtained using other resins. Halogen-containing plastic product collection separated from assembly product collection It can be mentioned.

  The halogen-containing plastic recovered material can be provided to the method of the present invention as it is when recovered, and the purpose is to remove halogen atoms from the halogen-containing plastic recovered material in a shorter time. If it is, it is good to use for the method of this invention as a pulverized material or a crushed material by grind | pulverizing or crushing a halogen-containing plastic recovery material. The size of the pulverized product or crushed product is not particularly limited, and may be, for example, several hundred μm to several cm.

  The plastic containing a halogen atom in the molecule in the halogen-containing plastic composition is not particularly limited as long as it has a halogen atom in the molecule. For example, a fluororesin, a vinyl chloride resin, Examples thereof include chloroprene resin, vinylidene fluoride resin, and chloroethylene trifluoride resin.

  Among these, a vinyl chloride resin is advantageous for applying the method of the present invention because a halogen atom can be removed in a short time. Examples of vinyl chloride resins include vinylidene chloride resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin, vinyl chloride vinylidene chloride copolymer resin, vinyl chloride acrylate ester, vinyl chloride methacrylate copolymer resin, vinyl chloride acrylonitrile copolymer. Examples thereof include a polymer, an ethylene vinyl chloride copolymer, and a propylene vinyl chloride copolymer.

  The additive containing a halogen atom in the molecule in the halogen-containing plastic composition is not particularly limited as long as it has a halogen atom in the molecule. For example, dimethyl pentachloride stearate, trichloro Plasticizers such as ethyl phosphate, trisdichloropropyl phosphate, trisdibromopropyl phosphate, antioxidants such as monoalkylene dibromophenol, tris (chloroethyl) phosphate, perchloropentacyclodecane, tetrabromobutane, tetrabromobisphenol A, tetrabromo Examples thereof include flame retardants such as ethane and decabromobiphenyl ether. In addition to the above, as additives containing halogen atoms in the molecule, various kinds of materials described in “New Edition / Plastic Compounding Agents—Basics and Applications” published on January 30, 1984, published by Taiseisha ” Additives can be mentioned.

  In the halogen-containing plastic composition, in addition to the plastic containing a halogen atom in the molecule and the additive containing a halogen atom in the molecule, for example, a plasticizer that does not contain a halogen atom in the molecule, Additives such as waxes, stabilizers, ultraviolet absorbers, reinforcing agents, flame retardants and antistatic agents may be contained.

  Alkylene glycol is used in the method of the present invention. The alkylene glycol is not particularly limited as long as it can achieve the object of the present invention. However, the alkylene glycol has high compatibility with the halogen-containing plastic recovered material, and deteriorates the halogen-containing plastic recovered material. From the standpoint of difficulty, it is preferably an alkylene glycol having 2 to 8 carbon atoms, more preferably an alkylene glycol having 2 to 4 carbon atoms, and particularly preferably ethylene glycol. Examples of the alkylene glycol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol and the like.

  By using alkylene glycol, especially ethylene glycol as a solvent, the dehalogenation reaction is significantly accelerated despite the relatively low processing temperature, and halogen atoms can be removed from the halogen-containing plastic collection in a very short time. Can do. In the method of the present invention, one or more alkylene glycols included in the category of alkylene glycol can be used as a solvent, but as a mixed solvent of alkylene glycol and polar aprotic solvent and / or cyclic ether or the like. It is not preferred to use alkylene glycol. When the mixed solvent is used, the relative amount of alkylene glycol used is reduced, so that the dehalogenation reaction is not promoted. Therefore, halogen atoms cannot be removed from the halogen-containing plastic recovered material in a short time.

  An alkali is used in the method of the present invention. If this alkali is a strong alkali, it will not specifically limit, For example, sodium hydroxide, potassium hydroxide, etc. can be mentioned.

  This alkali may be used as a solid or as a solution.

  Although the usage-amount of the said alkylene glycol is not specifically limited, For example, it is preferable that it is 50-500 mass parts with respect to 1 mass part of halogen-containing plastics recovered materials. If the amount of alkylene glycol used is less than 50 parts by mass, the compatibility with the halogen-containing plastic recovered product may be reduced, and the halogen atom removal rate may be reduced.

  The amount of alkali used is not particularly limited as long as the halogen atom can be removed from the halogen-containing plastic recovered material in a short time, but the alkali concentration in the alkylene glycol is 0.25 to 1.5 mol / mol. L is preferred. If the alkali concentration in the alkylene glycol is too high or too low, the halogen atom removal rate tends to decrease. If the alkali concentration is 0.25 to 1.5 mol / L, the high halogen atom concentration can be reduced in a short time. A removal rate is obtained. The alkali concentration is particularly preferably 0.5 to 1.0 mol / L in that a higher removal rate of dehalogenated atoms can be obtained in a short time.

  In the method of the present invention, first, a halogen-containing plastic recovered material and an alkali are dispersed in alkylene glycol. In the method of the present invention, the alkali may be dissolved in alkylene glycol.

  The alkylene glycol dispersion is then heated to 125-196 ° C. under normal pressure. If the heating temperature is lower than 125 ° C, halogen atoms may not be removed from the halogen-containing plastic recovered material in a short time. If the heating temperature exceeds 196 ° C, it is included in the halogen-containing plastic recovered material. A plastic containing a halogen atom in the molecule may thermally decompose.

  The heating temperature is preferably 125 to 155 ° C, particularly preferably 135 to 150 ° C, in that a high halogen atom removal rate can be obtained in a short time.

  Although the heating time depends on the alkali concentration and the like and cannot be determined unconditionally, in general, the object of the present invention can be achieved in a short time, for example, 5 to 35 minutes after reaching a predetermined heating temperature. Is preferable, and it is especially preferable that it is 5 to 25 minutes. On the other hand, if the alkali concentration or the like is adjusted to a preferable range, the object of the present invention can be sufficiently achieved in a very short heating time of 5 to 10 minutes.

  In the present invention, the heating time can be extended within a range in which a high halogen atom removal rate can be obtained.

  The heating means may be an electric heater, a heat medium, or the like, but microwave heating means such as a high-frequency heating device is preferable for efficient heating in a short time.

  In the method of the present invention, when the alkylene glycol dispersion is heated for a predetermined time, a mixture of a solid content and a liquid content is obtained. This mixture is separated into a solid content and a liquid part by solid-liquid separation means. The separation means is not particularly limited, and examples thereof include known means such as filtration means and centrifugal separation means.

  The liquid component thus separated contains an alkylene glycol, an alkali, an ester plasticizer or a decomposition product thereof, an additive, and optionally a halogen alkali salt. This liquid content or the alkylene glycol and alkali recovered from this liquid content can be used again in the method of the present invention.

  On the other hand, the separated solid content contains a plastic from which halogen atoms have been removed or a modified product thereof, and optionally an alkali salt of halogen. From this solid, the alkali salt of halogen can be easily removed according to a conventional method, and the residue from which the alkali salt of halogen has been removed contains no halogen atom. Thus, no halogen gas, hydrogen halide gas, or the like is generated by the thermal decomposition, and therefore, the incinerator is not damaged by the halogen gas, hydrogen halide gas, or the like, and dioxins are not generated.

  In the method of the present invention, the halogen-containing plastic recovered product may be washed in advance before the heat treatment, and additives contained in the halogen-containing plastic recovered product may be removed in advance.

  As described above in detail, according to the method of the present invention, halogen atoms can be removed from a halogen-containing plastic recovered material in a short time. Furthermore, when a halogen-containing plastic recovered material containing an ester plasticizer is applied to the present invention, the ester plasticizer can be removed together with halogen atoms from the halogen-containing plastic recovered material.

  Therefore, a halogen-containing plastic recovered material containing an ester plasticizer may be applied to the present invention. The ester plasticizer that may be contained in the halogen-containing plastic recovered material is not particularly limited, and examples thereof include phthalate ester plasticizers, phosphate ester plasticizers, adipic acid ester plasticizers, and sebacic acid esters. Plasticizer, azelaic acid ester plasticizer, citric acid ester plasticizer, glycolic acid ester plasticizer, trimellitic acid ester plasticizer, phthalic acid isomer ester plasticizer, ricinol ester plasticizer, polyester type plasticizer, etc. it can. Among these plasticizers, the ester plasticizer is preferably a phthalate plasticizer if the purpose is to efficiently remove the plasticizer together with the halogen atom. Examples of the phthalate ester plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di (n-octyl) phthalate, di (2-ethylhexyl) phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, Diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, (n-hexyl) (n-decyl) ) Phthalate, (n-octyl) (n-decyl) phthalate, and the like.

  In particular, when a soft vinyl chloride resin composition comprising 100 parts by mass of the vinyl chloride resin and 30 to 100 parts by mass of the ester plasticizer is used as the halogen-containing plastic composition, the method of the present invention is used. This is advantageous because the above-mentioned purpose can be sufficiently achieved and the ester plasticizer can be removed together with chlorine atoms in a short time in a single treatment.

  In addition to the soft vinyl chloride resin and the ester plasticizer, for example, a wax, a stabilizer, an ultraviolet absorber, a reinforcing agent, a flame retardant, an antistatic agent, etc. are added to the soft vinyl chloride resin composition. An agent may be contained.

  When a soft vinyl chloride resin composition is applied to the method of the present invention, the residue obtained by removing the alkali salt of halogen from the solid content obtained after the heat treatment no longer contains halogen atoms, so that it is incinerated. However, the pyrolysis of this residue does not generate halogen gas, hydrogen halide gas, etc. Therefore, dioxins are generated without damaging the incinerator by halogen gas, hydrogen halide gas, etc. Nor. In addition, since this residue no longer contains an ester plasticizer, adverse effects on humans and the environment can be greatly reduced even when landfilled.

  Next, an example of a raw material recovery apparatus for a halogen-containing plastic recovered material (hereinafter sometimes simply referred to as “raw material recovery apparatus”) that can carry out the method of the present invention will be described with reference to the drawings. .

  As shown in FIG. 1, the raw material recovery apparatus 1 includes, as one element, the halogen-containing plastic recovered material processing apparatus 100 of the present invention (hereinafter, simply referred to as “processing apparatus 100”). It has been incorporated.

  The processing apparatus 100 will be described with reference to FIGS.

  As shown in FIG. 2, the processing apparatus 100 can be transferred to a frame 110 having an opening 116, a lower lid member 120 and an upper lid member 130 provided on the frame 110, and the opening 116 of the frame 110. The reaction vessel body 140 having both end openings 141 and 142 closed by the lower lid member 120 and the upper lid member 130 in the opening 116, and the upper lid member 130 closing the both end openings 141 and 142 of the reaction vessel body 140, and The flow guide means 160 through which the contents are circulated up and down, formed in the through hole 151 of the reaction vessel 150 (see FIG. 4) formed by the lower lid member 120 and the reaction vessel main body 140, and the reaction vessel 150 A stirring means 170 that stirs the contents inside and a heating means 145 that heats the contents inside the reaction vessel 150 are included. In this example, the lower lid member 120 and the upper lid member 130 correspond to an example of a closing member in the present invention. The opening 141 may be referred to as an upper opening, and the opening 142 may be referred to as a lower opening.

  As shown in FIG. 2, the frame 110 includes an upper horizontal member 111, a lower horizontal member 112, and a pair of vertical members 113 and 114 that connect and support them up and down, and has a rectangular opening 116. ing. In the opening 116, a reaction vessel 150 (see FIG. 4) formed by a lower lid member 120 and an upper lid member 130, which will be described later, and the reaction vessel main body 140 (see FIG. 4) is arranged, thereby increasing the internal pressure of the reaction vessel 150. Sometimes, since the frame 110 receives pressure applied to the lower lid member 120 and the upper lid member 130, which will be described later, the lower lid member 120 and the upper lid member 130 are prevented from being detached from the reaction vessel main body 140, and A bending moment due to pressure does not occur, and the life of the processing apparatus 1 based on this bending moment is prevented from being shortened.

  As shown in FIGS. 2 and 4, the reaction vessel main body 140 has openings at both ends (hereinafter sometimes referred to as both-end openings. In FIG. 2, the opening located on the upper side is referred to as the upper opening 141. The opening located on the lower side is sometimes referred to as the lower opening 142). The upper opening 141 in the reaction vessel main body 140 is formed so as to be surrounded by an annular end 143 having an annular shape. The upper opening 141 has an annular bottom surface 141A and an opening of a through hole 151 having a cylindrical inner wall surface 144 whose end is the inner edge of the annular bottom 141A. Similarly to the upper opening 141, the lower opening 142 is surrounded and formed by an annular end portion 143. The lower opening 142 includes an annular bottom surface 142A and an annular bottom surface 142A. And an opening portion of a through-hole 151 having a cylindrical inner wall surface 144 with the inner edge of the inner wall as an end.

  The reaction vessel main body 140 is provided with a heating means 145 such as a heater, and the reaction vessel main body 140 itself can be heated to a predetermined temperature by energizing the heater. The heating means 145 is not limited to the heater as long as the inside of the reaction vessel can be heated, and may be a heating means by microwave irradiation.

  The reaction vessel main body 140 is placed outside the opening 116 of the frame 110 in the initial state, and the opening of the frame 110 in the processing state in which the dehalogenation process or the dehalogenation process and the deplasticizer process is performed. It can be arranged inside the part 116. For this purpose, the reaction vessel main body 140 is arranged to be able to be transferred to the opening 116 of the frame 110 by, for example, a transfer means (not shown) such as a robot arm, and is also provided on a frame moving means such as a frame. A frame moving device comprising a wheel (not shown), a rail (not shown) on which the wheel is mounted, and a driving means (not shown) for moving the frame 110 along the rail. The reaction container main body 140 outside the opening 116 of the 110 can be disposed inside the opening 116 of the frame 110.

  The lower lid member 120 is installed on the lower horizontal member 112 that forms the frame 110.

  The lower lid member 120 has a disc-shaped lower lid main body portion 120A and a disk shape having a diameter smaller than the diameter of the lower lid main body portion 120A, and is formed so as to protrude concentrically from the lower lid main body portion 120A. And a portion of the lower lid main body portion 120A that protrudes outward from the peripheral edge of the fitting convex portion 120B becomes a flange portion 121. The diameter and thickness of the fitting projection 120B are such that when the fitting projection 120B is fitted into the lower opening 142 of the reaction vessel main body 140, the upper surface of the fitting projection 120B is liquid-tight to the bottom portion 142A. It is determined that the outer peripheral surface of the fitting convex portion 120 </ b> B comes into liquid-tight contact with the inner peripheral surface of the opening 142. Further, the lower surface of the flange portion 121 is formed so as to come into liquid-tight contact with the end surface of the lower annular end portion 143 when the fitting convex portion 120A is fitted into the opening portion 142. In the case where the opening 142 is liquid-tightly closed by the lower lid member 120, it is preferable to use various packings, O-rings, and the like.

  The upper lid member 130 is formed in the same manner as the lower lid member 120. More specifically, the upper lid member 130 has a disc-shaped upper lid main body portion 130A, a disk having a diameter smaller than the diameter of the upper lid main body portion 130A, and is formed to protrude concentrically from the upper lid main body portion 130A. And is formed so that a portion of the upper lid main body portion 130A that protrudes outward from the peripheral edge of the fitting convex portion 130B becomes the flange portion 131. The diameter and thickness of the fitting convex portion 130B are such that when the fitting convex portion 130B is fitted into the upper opening 141 of the upper lid member 130, the lower surface of the fitting convex portion 130B contacts the bottom portion 141A in a liquid-tight manner. The outer peripheral surface of the fitting convex portion 130 </ b> B is determined so as to come into liquid-tight contact with the inner peripheral surface of the opening 141. The lower surface of the flange portion 131 is formed so as to come into liquid-tight contact with the end surface of the annular end portion 143 when the fitting convex portion 130B is fitted into the opening portion 141. In addition, when closing the said opening part 141 with the upper cover member 130 liquid-tightly, it is preferable to use various packings, O-rings, etc.

  The upper lid member 130 is provided on an upper horizontal member 111 that forms the frame 110 via an elevating means 180 described later so as to be movable up and down. In this respect, that is, the upper lid member 130 and the lower lid member 120 are different in that the upper lid member 130 is provided so as to be movable up and down with respect to the upper lateral member 111.

  The lifting / lowering means 180 includes a support member 182 that supports the central portion of the upper surface of the upper lid member 130, and a drive means 181 that raises and lowers the upper lid member 130 via the support member 182. In addition to the elevating means 180, in order to raise and lower the upper lid member 130 without tilting, in other words, to raise and lower the upper lid member 130 while holding the lower surface of the upper lid member 130 horizontally, a guide member (FIG. (Not shown) may be provided.

  As shown in FIG. 2 and FIG. 4, the flow guide means 160 is a reaction formed by the upper lid member 130 and the lower lid member 120 that close both end openings 141 and 142 of the reaction vessel main body 140 and the reaction vessel main body 140. Inside the container 150, the contents filled in the through-hole 151 are formed so as to be able to circulate up and down. As shown in FIG. 4, in the reaction container 150, the flow guide means 160 includes a groove 160 </ b> A formed on the upper surface of the fitting convex portion 120 </ b> B in the lower lid member 120 and a fitting convex portion 130 </ b> B in the upper lid member 130. It is formed as a groove 160A formed on the lower surface of the substrate. Since the groove 160A is formed in each of the upper lid member 130 and the lower lid member 120, the groove 160A in the upper lid member 130 will be described, and the description of the groove 160A in the lower lid member 120 will be omitted. The groove 160A in the upper lid member 130 is formed on the lower surface of the fitting convex portion 130B in the upper lid member 130 so that the longitudinal section is substantially hemispherical and becomes an annular concave portion when observed from the axial direction of the fitting convex portion 130B. . The groove 160A is preferably designed so that the outer edge of the groove 160A coincides with the edge of the through-hole 151. When such a groove 160A is formed, the contents of the reaction container rise along the inner wall surface 144 as shown in FIG. 4 when the fitting protrusion 130B is fitted into the opening 141. The raised contents are guided and circulated along the concave surface of the groove 160A, and then turn to a downward flow, so that the contents in the reaction vessel can be efficiently stirred. Therefore, when the processing apparatus 1 is used in the method of the present invention described above, the reaction time of the method of the present invention can be further shortened.

  As shown in FIG. 2, the stirring means 170 for stirring the contents in the reaction vessel 150 includes, for example, a stirring bar 171 and a canned motor 172 that outputs power for driving the stirring bar 171. The stirring rod 171 is provided through the lower horizontal member 112 and the lower lid member 120, and the canned motor 172 is provided on the outer wall surface of the lower horizontal member 112.

  As shown in FIG. 3, the processing apparatus 100 may be provided with a relief valve 138 as necessary so that the internal pressure can be adjusted when an abnormal reaction occurs and the internal pressure of the reaction vessel 150 rises. The relief valve 138 includes, for example, a pipe provided through the upper lid member 130 and a manual valve interposed in the middle thereof.

  Thus, the processing apparatus 100 includes the frame 110, the lower lid member 120, the upper lid member 130, the reaction vessel main body 140, the flow guide means 160, the stirring means 170, the heating means 145, and the relief valve 138 as necessary. However, when the processing apparatus 100 is configured as a continuous processing apparatus, the processing apparatus 100 further includes discharge means 135 and charging means 136 and 137 as shown in FIG. Preferably it is.

  The discharge means 135 is made of, for example, a pipe for discharging the content after the heat treatment from the through hole 151 of the reaction vessel 150, and is provided through the upper lid member 130.

  The charging means 136 and 137 are, for example, pipes for charging the halogen-containing plastic recovered material and the alkylene glycol having a predetermined alkali concentration into the through hole 151 of the reaction vessel 150, and are provided through the upper lid member 130. ing.

  Next, the raw material collection | recovery apparatus 1 incorporating the said processing apparatus 100 as one element is demonstrated with reference to FIG.

  The raw material recovery apparatus 1 includes the processing apparatus 100, a cutting machine 2, a storage tank 3, a storage tank 4, and a filtration device 7.

  As shown in FIG. 1, the cutting machine 2 is provided to cut a halogen-containing plastic recovered material into a pulverized product or a crushed product, and is installed above the processing apparatus 100. A suitable cutting machine 2 is provided with a cutting blade capable of crushing a halogen-containing plastic recovered material into, for example, a powder or a piece of several hundred μm to several cm.

  The storage tank 3 is provided to store the halogen-containing plastic recovered material cut by the cutting machine 2, and is installed between the cutting machine 2 and the processing apparatus 100.

  The storage tank 3 and the processing apparatus 100 are coupled via the charging means 137 of the processing apparatus 100. A manual valve (for example, a ball valve) 3B is interposed in the charging means 137, and the halogen-containing plastic recovered material cut from the storage tank 3 to the processing device 100 by opening and closing the manual valve 3B. Is to be inserted. The storage tank 3 can supply the cut halogen-containing plastic recovered material stored in the storage tank 3 to the processing apparatus 100 according to gravity. Therefore, even if the charging means 137 is not provided with a pump or the like. However, the halogen-containing plastic recovered material that is forcibly cut by providing these may be supplied to the processing apparatus 100. The storage tank 3 is connected to, for example, a storage tank for storing a solvent, and the recovered halogen-containing plastic recovered material and the solvent are mixed to prepare a slurry, and this slurry is charged into the processing apparatus 100. As such, it may be configured.

  As shown in FIG. 1, the storage tank 4 is provided for preparing and storing alkylene glycol having a predetermined alkali concentration. The storage tank 4 includes a storage tank 5 for storing alkylene glycol provided above the storage tank 4 and a storage tank 6 for storing alkali provided above the storage tank 4. . The storage tank 4 and the storage tank 5 are coupled via a fluid transfer means such as a pipe 5A. A manual valve 5B is interposed in the middle of the pipe 5A, and alkylene glycol is transferred from the storage tank 5 to the storage tank 4 according to gravity by opening and closing the manual valve 5B. In addition, the storage tank 4 and the storage tank 6 are coupled via a transfer means such as a pipe 6A. A manual valve (for example, a ball valve) 6B is provided in the middle of the pipe 6A, and alkali is introduced from the storage tank 6 to the storage tank 4 according to gravity by opening and closing the manual valve 6B. The alkylene glycol and alkali may be forcibly transferred to the storage tank 4 through a pump or the like in the middle of the pipe 5A and the pipe 6A. In addition, when an alkaline solution is used as the alkali, a storage tank may be used instead of the storage tank 6.

  The said processing apparatus 100 and the storage tank 4 are couple | bonded through the charging means 136 of the said processing apparatus 100. FIG. The charging means 136 is provided with a manual valve 4B in the middle thereof, so that alkylene glycol having a predetermined alkali concentration is transferred from the storage tank 4 to the processing apparatus 100 by opening and closing the manual valve 4B. It has become. In the raw material recovery apparatus 1 shown in FIG. 1, the storage tank 4 is located above the processing apparatus 100, so that alkylene glycol having a predetermined alkali concentration can be transferred to the processing apparatus 100 according to gravity. The alkylene glycol having a predetermined alkali concentration can be forcibly transferred to the processing apparatus 100 by inserting a pump or the like in the middle of the charging means 136.

  The filtration device 7 includes, for example, a filter 7A installed downstream of the discharge means 135 and a storage tank 7B for storing the filtrate separated by the filter 7A. A manual valve 7C is provided in the middle of the discharge means 135 of the processing device 100 so that the processed content is transferred from the processing device 100 to the filtration device 7 by opening and closing the manual valve 7C. It has become. Although not shown, in order to transfer the contents after the heat treatment, transfer means such as a pump may be provided in the middle of the discharge means 135 to transfer the contents to the filtration device 7. A transfer means based on a pressure difference such as a means may be further provided to transfer the contents to the filtration device 7.

  The storage tank 7B and the storage tank 4 are coupled via a fluid transfer means 8 such as a pipe. The fluid transfer means 8 is provided with a pump 8A and a manual valve 8B in the middle, and contains alkali after heat treatment from the storage tank 7B to the storage tank 4 by starting the pump 8A and opening / closing the manual valve 8B. The alkylene glycol is transferred.

  The raw material recovery apparatus 1 and the processing apparatus 100 for the halogen-containing plastic recovery product operate as follows.

  First, the halogen-containing plastic recovered material is put into the cutting machine 2, and the halogen-containing plastic recovered material is stored in the storage tank 3.

  On the other hand, the reaction container body 140 is transferred to the opening 116 of the frame 110, and the lower opening 142 is moved by the lower lid member 120 so that the fitting protrusion 120A is fitted to the lower opening 142 of the reaction container body 140. Close.

  Next, the driving means 181 is activated, and the upper lid member 130 is lowered toward the reaction vessel main body 140 by the support member 182 with the upper lid member 130 held at the tip, and the annular end 143 of the reaction vessel main body 140 and the upper lid member The upper opening 141 of the reaction vessel main body 140 is closed so that the fitting protrusion 130B is fitted to the upper flange 141, and the flange portion 131 of the frame 110 is closed. The reaction vessel 150 whose through-hole 151 is in a liquid-tight state is installed and fixed.

  As described above, the reaction vessel 150 is formed in which the inside is liquid-tight only by fitting the upper lid member 130 and the lower lid member 120 to the opening portions 141 and 142 at both ends of the reaction vessel main body 140, and the lid member is bolted. Therefore, the attachment and detachment between the opening portions 141 and 142 and the upper lid member 130 and the lower lid member 120 in the reaction vessel main body 140 can be performed in a short time. In addition, since the reaction vessel 150 formed in this manner is disposed in the opening 116 of the frame 110, even when the internal pressure of the reaction vessel 150 rises, the reaction vessel 150 is loaded on the lower lid member and the upper lid member. Therefore, the lower lid member 120 and the upper lid member 130 are not detached from the reaction vessel main body 140.

  Next, the manual valve 3B is opened, and a predetermined amount of the halogen-containing plastic recovered material is charged into the through hole 151 of the reaction vessel 150 via the charging means 137.

  On the other hand, the manual valve 5B and the manual valve 6B are opened by a predetermined amount, and a predetermined amount of alkylene glycol and alkali are transferred from the storage tank 5 and the storage tank 6 to the storage tank 4 to prepare alkylene glycol having a predetermined alkali concentration. The The prepared alkylene glycol having a predetermined alkali concentration is stored in the storage tank 4.

  Subsequently, the manual valve 4B is opened, and an alkylene glycol having a predetermined alkali concentration is charged into the through hole 151 of the reaction vessel 150 through the charging means 136, and the halogen-containing plastic recovered material and the predetermined product are stored in the through hole 151. The contents containing an alkylene glycol having an alkali concentration are filled.

  Next, the stirring means 170 of the heat treatment tank 100 is activated. When the stirring means 170 is activated, as shown in FIG. 4, the contents filled in the through hole 151 of the reaction vessel 150 circulate up and down and flow like convection.

  Specifically, as shown by the arrow in FIG. 4, first, the propelling force generated by the rotating stirring rod 171 gives a force to flow to the contents filled in the through hole 151 of the reaction vessel 150. The contents flow toward the lower lid member 120. Next, the contents flow along the groove 160A formed on the upper surface of the fitting convex portion 120B in the lower lid member 120, and the flowing direction is changed to a direction against gravity. Subsequently, the content in which the flowing direction is in the direction opposite to gravity rises along the inner wall surface 144 of the reaction vessel main body 140. When the contents rise to the upper end of the inner wall surface 144, this time, the fluid flows along the groove 160A formed on the lower surface of the fitting convex portion 130B in the upper lid member 130, and the flowing direction is changed to a direction according to gravity. Further, the contents whose flowing direction is directed to the direction according to gravity descend toward the vicinity of the center of the lower lid member 120. The contents descending to the vicinity of the stirring bar 171 are again given a force to flow by the propulsive force generated by the stirring bar 171, and the contents flow toward the lower lid member 120 in the same manner. By repeating such a flow, as shown by the arrow in FIG. 4, the contents filled in the through hole 151 circulate up and down and flow.

  Next, the heating means 145 is activated, and the contents filled in the through hole 151 of the reaction vessel 150 are heated to a predetermined temperature for a predetermined time under normal pressure while continuously circulating and flowing up and down.

  When the contents filled in the through-hole 151 are continuously circulated up and down and heated while flowing, the contact frequency between the halogen-containing plastic recovered material and the alkylene glycol having a predetermined alkali concentration, particularly alkali, increases. Therefore, the dehalogenation reaction is remarkably accelerated, and the halogen atoms can be removed from the halogen-containing plastic recovered material in a very short time.

  When the heat treatment is finished, the manual valve 7C is opened, and the contents after the heat treatment are transferred to the filtration device 7 from the through hole 151 of the reaction vessel 150 through the discharge means 135, and separated into a solid content and a liquid content. The

  The liquid component stored in the storage tank 7B is transferred to the storage tank 4 via the fluid transfer means 8 by the pump 4C. On the other hand, the solid content is separated on the filter 7A, and the recovery process of the halogen-containing plastic recovery product is completed.

  The operation of the raw material recovery apparatus 1 and the processing apparatus 100 has been described as an example of batch operation. However, the raw material recovery apparatus 1 and the processing apparatus 100 can be operated continuously. In the case of continuous operation, the halogen-containing plastic recovered material that is cut while the contents filled in the through-hole 151 are heated up to a predetermined temperature for a predetermined time under normal pressure while circulating and flowing up and down. The alkylene glycol having a predetermined alkali concentration is charged into the through-hole 151 of the reaction vessel 150 through the charging means 137 and 136 at a certain ratio, respectively, and the amount of the halogen-containing plastic recovered and the predetermined amount The content after the heat treatment corresponding to the amount of alkylene glycol having an alkali concentration is discharged through the discharge means 135.

  As described above, an example of the raw material recovery apparatus 1 and the processing apparatus 100 has been described with reference to the drawings. However, the raw material recovery apparatus 1 and the processing apparatus 100 are not limited to the apparatuses shown in the drawings, and the method of the present invention can be used. The design may be changed as appropriate within the range that can be implemented.

  For example, as shown in FIG. 2, the heating unit 145 of the processing apparatus 100 is provided so as to cover the outer peripheral surface of the reaction vessel main body 140, but the heating unit 145 covers the outer peripheral surface of the reaction vessel main body 140. For example, as shown in FIG. 5, the heating means 145 may be provided inside the reaction vessel main body 140.

  As shown in FIGS. 2 to 4, the upper lid member 130 of the processing apparatus 100 is formed in a disk shape having the flange 131, but the upper lid member 130 opens the opening 141 of the reaction vessel main body 140. It is not always necessary to have the flange portion 131 if it can be closed. For example, as shown in FIG. 6, the upper lid member 139 may be formed in a disk shape. In this case, as shown in FIG. 6, the reaction vessel main body 140 does not need to have the annular end 143 at the opening 141. Further, the lower lid member 120 does not need to have the flange portion 121 as well.

  Further, as shown in FIG. 2, the lifting means 180 of the processing apparatus 100 includes a driving means 181 and a support member 182, and the support member 182 is configured as an arm including a hydraulic cylinder or a pneumatic cylinder. The supporting member 182 is not necessarily configured as an arm including a hydraulic cylinder or a pneumatic cylinder if the elevating means 180 can hold and lift the upper lid member 130. For example, as shown in FIG. The control unit 183, a screw screw 184 connected to the control unit 183, and a set of lifting / lowering unit 180 including a nut 185 embedded in the upper lateral member 111 may be used.

  As shown in FIG. 2, the stirring means 170 of the processing apparatus 100 is provided so as to penetrate the lower horizontal member 112 and the lower lid member 120, but the stirring means 170 is provided in the lower horizontal member 112 and the lower lid member. For example, as illustrated in FIG. 8, the stirring unit 170 may be provided to penetrate the lower lid member 120. In this case, for example, at least one set of mounting tables 115 is formed on the lower horizontal member 112, and the lower lid member 120 is mounted on the mounting table 115.

  Further, as shown in FIGS. 2 to 4, the groove 160 </ b> A formed on the upper surface of the fitting convex portion 120 </ b> B in the lower lid member 120 and the groove 160 </ b> A formed on the lower surface of the fitting convex portion 130 </ b> B in the upper lid member 130 are In any case, the longitudinal section is formed in a substantially hemispherical shape, but the shape of the longitudinal section of the groove 160A may be any shape that can change the direction in which the contents flow, for example, there are many longitudinal sections. It may be square or semi-elliptical.

  Also, as shown by the arrows in FIG. 4, the flow guide means 160 and the stirring means 170 are formed so that the contents rise along the inner wall surface 144 of the reaction vessel main body 140 and circulate up and down. However, it is not always necessary that the flow guide means 160 and the stirring means 170 are formed so that the contents circulate in this way. For example, the contents are lowered along the inner wall surface 144 of the reaction vessel main body 140. Then, it may be formed so as to circulate up and down.

  Further, as shown in FIG. 2, the frame 110 of the processing apparatus 100 is formed to have a square opening 116, but it is not always necessary that the frame 110 has the square opening 116. The opening 116 may have any shape that can receive the pressure applied to the lower lid member 120 and the upper lid member 130 when the internal pressure of the reaction vessel 150 rises. In addition, a U-shaped frame including a lower horizontal member and a vertical member that connects and supports the upper and lower members may be provided, and an opening having one end opened may be provided.

  Further, as shown in FIG. 3, the relief valve 138, the charging means 136 and 137, and the discharging means 135 are provided through the upper lid member 130, respectively, but as long as these functions are provided, positions where these are provided. Is not limited to the upper lid member 130. As shown in FIG. 3, the charging means 136 and 137 are provided separately. For example, a switching valve to which the charging means 137 is coupled is interposed in the middle of the charging means 136. The charging means 136 and 137 may be configured integrally.

  On the other hand, although the raw material collection | recovery apparatus 1 is equipped with the storage tank 4, the predetermined amount alkylene glycol and alkali are directly transferred to the processing apparatus 100 from the storage tank 5 and the storage tank 6, without providing the storage tank 4. FIG. It may be said.

  Moreover, since the raw material collection | recovery apparatus 1 is an apparatus aiming at removing a halogen atom from halogen-containing plastic collection material for a short time, it is equipped with the cutting machine 2, but the raw material collection | recovery apparatus 1 is not necessarily a cutting machine. 2 need not be provided.

  Furthermore, although the raw material collection | recovery apparatus 1 shown by FIG. 1 is a continuous-type raw material collection | recovery apparatus, it can also be used as a batch-type processing apparatus. When used as a batch-type raw material recovery apparatus, the discharge means 135 and the charging means 136 and 137 may not be provided.

  The reaction container 150 described in detail above is basically formed by the reaction container main body 140, the upper lid member 130, and the lower lid member 120. However, the lower lid member and the cylindrical container are integrally formed, that is, The reaction container main body may have a bottomed cylindrical shape with one end opened, and an upper lid member.

  As described above in detail, according to the present invention, it is possible to provide a method for treating a halogen-containing plastic recovered material that can remove halogen atoms from the halogen-containing plastic recovered material in a short time. Therefore, even if the processed product obtained by the method of the present invention is finally incinerated, halogen gas, halogenated hydrogen gas, etc. are not generated by thermal decomposition of the processed product. Hydrogen gas or the like does not damage the incinerator and dioxins are not generated.

  Further, according to the method of the present invention, by using alkylene glycol, particularly ethylene glycol, as a solvent, halogen atoms can be removed in a very short time regardless of the relatively low processing temperature.

  Furthermore, according to the present invention, it is possible to provide a processing apparatus 100 for a halogen-containing plastic recovered material that can remove halogen atoms from the halogen-containing plastic recovered material in a short time. Since the method of the present invention heats the halogen-containing plastic recovered material under normal pressure, the processing apparatus 100 of the present invention does not need to consider the fatigue life due to high pressure processing.

  In addition, the halogen-containing plastic recovered material processing apparatus 100 according to the present invention can attach and detach the opening portions 141 and 142 and the lower lid member 120 and the upper lid member 130 in the reaction vessel main body 140 in a short time. Since the frame 110 receives the pressure applied to the lower lid member 120 and the upper lid member 130 when the internal pressure of 150 increases, the bending moment due to the internal pressure does not occur, and the life of the processing apparatus 1 based on this bending moment is shortened. Is prevented.

  Furthermore, since the processing apparatus 100 of the present invention includes the flow guiding means 160 and the stirring means 170 through which the contents are circulated up and down, the contents in the reaction vessel 150 can be efficiently stirred. . Therefore, when the processing apparatus 100 of the present invention is used in the method of the present invention, the reaction time of the method of the present invention can be further shortened.

  The following examples are experimental examples of the present invention.

(Experimental example 1)
The raw material collection | recovery apparatus 1 shown by FIG. 1 and the processing apparatus 100 shown by FIGS. 2-4 were used. The soft polyvinyl chloride film was washed with water, and then cut into a size of about 200 μm square by a cutting machine 2 to obtain a 0.5 g sample.

  In addition, according to the information from the sample supplier, the sample had a chlorine atom content of 35.70% and a DOP content of 29.70% in terms of phthalic acid.

  This 0.5 g sample was put into a reaction vessel 150 having an internal volume of 100 mL equipped with a microwave heating device 145 (trade name “Microsys” manufactured by Milestone General Co., Ltd.) and a stirring means 170, and then water 50 mL of ethylene glycol and sodium hydroxide were added so that an ethylene glycol solution having a sodium oxide concentration of 0.5 mol / L was obtained.

  Next, the heating device 145 and the stirring means 170 were started, and the ethylene glycol dispersion containing this sample and alkali was heated to 130 ° C. for 10 minutes under normal pressure while circulating through the through-hole 151 of the reaction vessel 150 up and down. . A mixture of liquid and solid content was obtained after heating. The mixture was filtered to recover a liquid component. This liquid component is diluted 1000 times with pure water, and the resulting diluted solution is analyzed by an ion chromatograph (7310-20 model, Nikkiso Co., Ltd.), and the amount of chloride ions and DOP contained in this liquid component are analyzed. The amount of phthalate ion, which is a hydrolyzate, was measured. The measured amount of chlorine atoms and the amount of DOP were converted to a ratio when the above-mentioned sample 0.5 g was 100, and the converted values were extracted chlorine concentration (%) and extracted phthalic acid concentration (%), respectively. . These extracted chlorine concentration and extracted phthalic acid concentration indicate that the larger the value, the higher the removal rate, and the smaller the value, the smaller the removal rate. For example, if the calculated extracted chlorine concentration is 35.70%, it indicates that 100% of chlorine atoms contained in the 0.5 g sample have been removed.

(Experimental Examples 2 to 14)
Subsequently, the ethylene glycol dispersion containing the sample and the alkali was heat-treated in the same manner as in Experimental Example 1 except that the heating temperature, the heating time, and the alkali concentration were changed to the conditions shown in Table 1, respectively.

  In the same manner as in Experimental Example 1, the liquid content was recovered, and the amount of chlorine ions contained in the liquid content and the amount of phthalate ions that were hydrolyzed DOP were measured. The measured amount of chlorine atoms and the amount of DOP were converted to a ratio when the above-mentioned sample 0.5 g was 100, and the converted values were extracted chlorine concentration (%) and extracted phthalic acid concentration (%), respectively. .

  Among the experimental examples, the experimental examples 1 to 8 correspond to examples, and the experimental examples 9 to 14 correspond to comparative examples.

(Experimental example 15)
In the same manner as in Experimental Example 1, a 0.5 g sample was collected.

  0.5 g of this sample was put into an electric heater heating type reactor (autoclave: trade name “batch type plastic reactor”: manufactured by Nitto High Pressure Co., Ltd.) equipped with a pressure-tight airtight container having a stirring means and an electric heater. Subsequently, 50 mL of a 16 mol / L aqueous sodium hydroxide solution was added.

  Subsequently, the electric heater and the stirring means were started, and this sample and the sodium hydroxide aqueous solution were heated to 350 ° C. for 60 minutes. A mixture of liquid and solid content was obtained after heating. The mixture was filtered to recover a liquid component. This liquid component is diluted 1000 times with pure water, and the resulting diluted solution is analyzed by an ion chromatograph (7310-20 model, Nikkiso Co., Ltd.), and the amount of chloride ions and DOP contained in this liquid component are analyzed. The amount of phthalate ion, which is a hydrolyzate, was measured. As a result, it was confirmed that the chlorine atoms and DOP in the sample were almost 100% removed.

  Moreover, the solid content collected by filtering the mixture was subjected to elemental analysis using an elemental analyzer (trade name “2400II manufactured by Perkin Elmer). As a result, chlorine atoms were not detected, and even in elemental analysis, It was confirmed that almost 100% of the chlorine atoms were removed, while the molar ratio of hydrogen atoms to carbon atoms calculated by elemental analysis was 1.07. Since the molar ratio was about 1, it was confirmed in the elemental analysis that chlorine atoms, additives and the like in the sample were almost removed.

(Experimental example 16)
In the same manner as in Experimental Example 1, a 0.5 g sample was collected.

  This 0.5 g sample was put into a reaction vessel 150 having an internal volume of 100 mL equipped with a microwave heating device 145 (trade name “Microsys”: manufactured by Milestone General Co., Ltd.) and stirring means 170, and then 16 mol. 50 mL of / L sodium hydroxide aqueous solution was added.

  Next, the heating device 145 and the stirring means 170 were started, and the sample and the sodium hydroxide aqueous solution were heated to 235 ° C. for 30 minutes. A mixture of liquid and solid content was obtained after heating. The mixture was filtered to recover a liquid component. This liquid component is diluted 1000 times with pure water, and the resulting diluted solution is analyzed by an ion chromatograph (7310-20 model, Nikkiso Co., Ltd.), and the amount of chloride ions and DOP contained in this liquid component are analyzed. The amount of phthalate ion, which is a hydrolyzate, was measured. As a result, it was confirmed that the chlorine atoms and DOP in the sample were almost 100% removed.

  Further, the solid content collected by filtering the mixture was subjected to elemental analysis using the elemental analyzer. As a result, no chlorine atom was detected, and it was confirmed by elemental analysis that almost 100% of the chlorine atom in the sample was removed. On the other hand, the molar ratio of hydrogen atoms to carbon atoms calculated by elemental analysis is 1.05, and the molar ratio of hydrogen atoms to carbon atoms of polyene, which is a solid content, is about 1. It was confirmed that chlorine atoms and additives in the sample were almost removed.

  As is clear from Table 1, in Experimental Examples 1 to 8 in which an alkylene glycol dispersion containing a sample of a soft polyvinyl chloride film and an alkali was heated to 130 to 150 ° C., the heat treatment time was short for 10 to 30 minutes. In time, chlorine atoms could be removed at a high extraction chlorine concentration of 27.7 to 35.3%, whereas an alkylene glycol dispersion containing a sample of a soft polyvinyl chloride film and an alkali was treated at 120 ° C. and 100 ° C. In Experimental Examples 9 to 14 heated at ° C., chlorine atoms could be removed only at an extracted chlorine concentration of 3.1% at the highest.

  Therefore, it has been found that chlorine atoms can be sufficiently removed in a short time by heating an alkylene glycol dispersion containing a sample of a soft polyvinyl chloride film and an alkali to 125 to 196 ° C. In particular, when the alkali concentration is 0.5 mol / L, it has been found that chlorine atoms can be sufficiently removed even in an extremely short heating time of 10 minutes.

  Moreover, in the said Experimental Examples 1-8, DOP was able to be removed with the extraction phthalic acid density | concentration of 15.8-29.1% in the heat processing time for 10 to 30 minutes for a short time. Accordingly, it was found that not only chlorine atoms but also DOP can be sufficiently removed in a short time by heating an alkylene glycol dispersion containing a sample of a soft polyvinyl chloride film and an alkali to 125 to 196 ° C. .

  On the other hand, in Experimental Example 15 in which a sample of a soft polyvinyl chloride film was heat-treated with an electric heater in an aqueous sodium hydroxide solution, in order to sufficiently remove chlorine atoms from the sample of the soft polyvinyl chloride film, an extremely high temperature of 350 ° C. or higher was used. In Experimental Example 16, which required a high temperature and a long processing time of 60 minutes, and a sample of a soft polyvinyl chloride film was heat-treated in a sodium hydroxide aqueous solution by a microwave heating apparatus, the sample of the soft polyvinyl chloride film was taken from To sufficiently remove chlorine atoms, a high temperature of 235 ° C. was required.

  Therefore, as shown in Experimental Examples 1 to 8, the processing temperature is a relatively low temperature of 130 to 150 ° C. by heating the sample of the flexible polyvinyl chloride film in the alkylene glycol dispersion containing alkali. Nevertheless, it has been found that the dehalogenation reaction is significantly accelerated and that halogen atoms can be removed from the halogen-containing plastic recovery in a very short time.

FIG. 1 is a schematic explanatory view showing an apparatus for recovering a halogen-containing plastic recovered material as an example capable of carrying out the method of the present invention. FIG. 2 is a schematic cross-sectional view showing a cross section of a halogen-containing plastic recovered material processing apparatus as an example capable of carrying out the method of the present invention. FIG. 3 is a schematic cross-sectional view of the upper lid member. FIG. 4 is a schematic cross-sectional view of the heat treatment container illustrating how the contents filled in the heat treatment container are circulated up and down. FIG. 5 is a schematic cross-sectional view of the reaction vessel main body showing a modification of the attachment state of the heating means. FIG. 6 is a cross-sectional view showing a modification of the upper lid member and the heat treatment tank main body. FIG. 7 is a cross-sectional view showing a modified example of the lifting means. FIG. 8 is a cross-sectional view showing a modification of the method for attaching the stirring device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Raw material collection | recovery apparatus of halogen-containing plastic collection material 2 Cutting machine 3, 6 Storage tank 3B, 5B, 6B, 7C, 8C Manual valve 4, 5, 7B Storage tank 5A, 6A, 8 Fluid transfer means 7 Filtration apparatus 7A Filter 8A Pump 100 Halogen-containing plastic recovered material processing apparatus 110 Frame 111 Upper horizontal member 112 Lower horizontal member 113, 114 Vertical member 115 Mounting table 116 Opening portion 120 Lower lid member 120A Lower lid body portion 120B Fitting protrusion 121, 131 Flange Portions 130, 139 Upper lid member 130A Upper lid body portion 130B Fitting protrusion 135 Discharge means 136, 137 Insertion means 138 Relief valve 140 Reaction vessel body 141, 142 Opening 142A Bottom face portion 143 Annular end 144 Inner wall surface 145 Heating means 150 Reaction vessel 151 Inside 160 Distribution Inner means 160A groove 170 stirrer 171 stirbar 172 canned motor 180 elevating means 181, 183 control means 182 support member 184 screw 185 nut

Claims (6)

  A method for treating a halogen-containing plastic recovered material, comprising heating the halogen-containing plastic recovered material, an alkylene glycol dispersion containing an alkali and an alkylene glycol to 125 to 196 ° C.   2. The method for treating a halogen-containing plastic recovered product according to claim 1, wherein the alkylene glycol dispersion has an alkali concentration of 0.25 to 1.5 mol / L.   The method for treating a halogen-containing plastic recovered product according to claim 1 or 2, wherein the alkylene glycol dispersion is heated for 5 to 35 minutes.   A frame formed in a frame shape, a closing member provided in the frame, a reaction vessel main body having an opening that can be transferred into the frame and is closed by the closing member in the frame, and A flow guide means for circulating the contents up and down formed inside the reaction vessel formed by the closing member for closing the opening of the reaction vessel body and the reaction vessel body; and the reaction vessel An apparatus for treating a halogen-containing plastic recovered product, comprising: stirring means for stirring the contents in the container; and heating means for heating the contents in the reaction vessel.   The closing member is a lower lid member and an upper lid member provided on the frame, and the reaction vessel main body is provided with both-end openings that are closed by the lower lid member and the upper lid member in the frame. The apparatus for treating a halogen-containing plastic recovered product according to claim 4, characterized in that it is characterized in that: 6. The apparatus for treating a halogen-containing plastic recovered product according to claim 4, wherein the reaction container includes a halogen-containing plastic recovered material insertion means and a discharge means for discharging the contents in the reaction container.

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