JP2002224652A - Method for recycling waste household electrical appliance and article to be recycled - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for classifying and reusing the shredded dust of waste household electrical appliances while both good classification precision and low cost are realized. SOLUTION: Waste household electrical appliances are crushed, iron and a nonferrous metal are classified and recovered from the crushed appliances and two components of at least olefinic resins and styrenic resins are then classified and recovered from the shredded dust comprising contaminants such as resins and metal. The olefinic resins are formed into a regenerated resin by using a screw type extruder and the styrenic resins are reused as a styrene monomer by thermal decomposition or formed into another regenerated resin by using the screw type extruder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a technology for recycling used home appliances, and more particularly, it has been considered difficult to reuse in addition to iron, non-ferrous metal, glass, etc. which can be reused by existing technologies. The present invention relates to a method of recycling waste home appliances that can achieve a high recycling rate by providing a recycling technology of mixed waste plastic.

[0002]

2. Description of the Related Art The problem of waste disposal in Japan has become increasingly serious in recent years, and the generation of dioxin during incineration, the tightness of landfills, and the like have been greatly highlighted as social problems. The main sources of these wastes include container and packaging materials, building materials, automobiles, home appliances, and the like. Even if it is limited to "four home appliances", it has reached 18 million units and weighed 650,000 tons in 1997 (according to a survey by the Home Appliances Association), and its processing is an urgent issue.

[0003] Against this background, the Law on the Recycling of Specific Home Appliances, the so-called "Household Appliance Recycling Law," was enacted in April 2001 for the above four home appliances. Washing machine 50
%, Television 55%, air conditioner 60%,
In addition, only products sold as valuables can be counted in these recycling rates, and so-called "reverse paid products" that recycling companies pay for processing costs and outsource the processing may be excluded. Stipulated.

Looking at the composition ratio of waste home appliances by material, the average of the four home appliances is 47% iron, 7% non-ferrous metal, 29% plastic, 9% glass, and 8% other (according to the Association of Home Appliances). At present, the recycling rate is 6 even if iron, non-ferrous metals, and glass, which can be economically reused, are combined.
Stays at 3%. Therefore, considering the future increase of the recycling rate target, the improvement of the recycling rate is urgently urgent, and establishing the processing technology for plastics is the biggest issue to achieve this.

[0005] The composition ratio of plastics used in home appliances is 36% polypropylene, 28% polystyrene, AB
S resin 17%, polyurethane 5%, vinyl chloride resin 4
% And other 10% (according to a survey by the Home Appliances Association). After crushing an unspecified large number of waste home appliances and separating and recovering iron and non-ferrous metals, crushed residues composed of contaminants such as resins and metals
Shredder dust), of course,
It contains a mixture of these various resins, which is a major factor preventing effective recycling of plastics.

[0006] For the purpose of solving such a problem of plastic separation, various separation / separation techniques have been proposed. For example, specific gravity separation (Plastic Swage, 1997
Extra edition, p. 67), solvent / dissolution separation, electrostatic separation, selective floating separation, screen changer / melt filter (Plastic Swage, 1998 extra edition, p. 51).

[0007] The specific gravity separation is a technique of separating using a specific gravity difference of a plastic in a medium such as a liquid or a gas, and cannot separate a plastic having a small specific gravity difference.
However, since wet specific gravity separation using a liquid such as water or salt water can also serve as washing of waste plastic, it is widely used, for example, as a system alone or in combination with another method. In particular, it is effective as a method for separating and separating shredder dust in order to regenerate it into a product with higher added value. Solvent and dissolution separation of
The electrostatic separation of the difference in solubility in a specific solvent, the property of plastic particles being positively or negatively charged due to friction, and the selective floating separation, using the difference in the wettability of the plastic surface, This technique is different from that of the first embodiment in that the difference in specific gravity is small. The screen changer is not a technique for separating plastics from each other, but can remove unmelted substances such as metals from plastics melted in an extruder.

[0008] Each of these separation / separation techniques has advantages and disadvantages, and therefore, it is common to construct a system combining a plurality of methods according to the target plastic. For example, in a demonstration plant constructed with the assistance of the Ministry of International Trade and Industry, with the aim of developing a recycling technology that can improve the recycling rate, the Japan Home Appliances Association crushed waste home appliances at once, and first used a wind separator to remove urethane, a refrigerator insulation material. The resin is then recovered by a magnetic separator, and non-ferrous metals such as copper and aluminum are recovered by an eddy current separator. Finally, the remaining shredder dust is separated by gravitational water separation (sink-and-float method) to obtain an olefin-based resin. A system for separating into three components, a resin, a styrene resin, and a vinyl chloride resin, was proposed, and a verification test was conducted until March 1999 (Plastic Swage, 1997, extra edition, p98).

[0009] However, in the above system, the separation accuracy of the shredder dust is not sufficient, for example, a large amount of styrene resin is mixed in the olefin resin and the styrene resin is mixed in a large amount. Urethane resin, olefin resin,
No effective recycling method has been found for any of the styrene resins and the vinyl chloride resins. In fact, even in the above demonstration plant, part of the separated resin was pyrolyzed to oil,
At present, it has only been reused as fuel for boilers in factories.

On the other hand, as a method for efficiently recycling shredder dust, a method for reusing the same as a reducing agent for a blast furnace in the steelmaking industry, a method for reusing it as a raw material for a coke oven in the steelmaking industry, and a method for recycling shredder dust. A method has been proposed in which carbon monoxide and hydrogen are generated by pyrolysis gasification and reused as a synthesis raw material such as methanol, acetic acid, and ammonia (JCII NEW).
S, No. 49, VOL13 No. 3, 1999 10
Mon), these chemical recycling methods are attracting attention as material recycling technology in a broad sense.

[0011] As described above, the biggest problem in the recycling of waste home electric appliances is that a recycling method of shredder dust cannot be found at present. There is a chemical recycling method without separating shredder dust,
Since the added value as a recycled product is low, it is inevitably a reverse paid process. In addition, if the material is separated to a state where it can be recycled, the added value as a recycled product increases, so it may be possible to treat it as a valuable resource.However, it is an issue whether a process that can balance separation accuracy and cost can be found. ing.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for separating shredder dust, which achieves both separation accuracy and cost. To provide.

[0013]

Means for Solving the Problems Accordingly, the present inventors have:
In order to solve the issues in the recycling technology of waste home appliances, we conducted intensive studies on how to separate and separate the various resin components that constitute shredder dust in a reusable state. Sorting,
By skillfully combining sorting means such as eddy current sorting and specific gravity sorting, plastics are separated into multiple components, and by developing and applying the optimal regeneration technology for each component,
The present invention has been achieved by achieving a recycling rate that cannot be achieved by the conventional technology.

[0014] That is, the invention according to claim 1 provides at least an olefin-based shredder dust composed of contaminants such as resin and metal after crushing an unspecified large number of waste home appliances and separating and recovering iron and non-ferrous metals. The resin and the styrene resin are separated and recovered, and the olefin resin is converted into a regenerated resin by kneading and granulating using a screw-type extruder, and the styrene resin is thermally decomposed to generate oil. This is a method for recycling waste home appliances, wherein a styrene monomer obtained by distilling a produced oil is reused as a chemical raw material.

[0015] The invention according to claim 2 is to provide an at least olefin-based resin from shredder dust composed of contaminants such as resin and metal after crushing an unspecified large number of waste home appliances and separating and recovering iron and non-ferrous metals. Styrene resin 2
A recycling method for waste home appliances, wherein components are separated and collected, and an olefin-based resin and a styrene-based resin are kneaded and granulated by using a screw-type extruder to form a regenerated resin.

According to a third aspect of the present invention, at least a part of a waste household electric appliance is a refrigerator, and at least a urethane-based resin and an olefin-based resin are obtained from shredder dust after separating and recovering iron and non-ferrous metals from those products. 3. The method according to claim 1 or 2, wherein the three components of styrene-based resin and styrene-based resin are separated and recovered, and the urethane-based resin is thermally decomposed to generate carbides, various distillate oils and gases, and these are reused as fuels or chemical raw materials. It is a method of recycling waste home appliances.

According to a fourth aspect of the present invention, a part of a resin component is separated and recovered in advance before crushing a waste home appliance, and is kneaded and granulated by using a screw type extruder to be converted into a regenerated resin. It is a recycling method of the waste electric home appliances described in any one of 1 to 3. The separated and recovered resin part may be converted into a recycled resin for each resin type, or may be mixed with the resin separated and recovered from the shredder dust for each resin type and then converted to a recycled resin.

According to a fifth aspect of the present invention, at least a part of the waste home appliances is a product using a flame-retardant resin part such as a television, a personal computer, a copying machine, etc. The method according to claim 4, wherein at least a part of the resin parts separated and recovered is the flame-retardant resin parts.

[0019] The invention according to claim 6 is the method according to any one of claims 1 to 5, wherein after the waste home appliances are crushed, iron is separated using a magnetic separator and non-ferrous metal is separated using an eddy current separator. The recycling method of waste home electric appliances described in (1).

[0020] The invention according to claim 7 is the method for recycling waste household electrical appliances according to any one of claims 3 to 6, wherein when separating and recovering the urethane foam resin from the shredder dust, a wind separator is used.

[0021] The invention according to claim 8 is the method for recycling waste electrical home appliances according to claim 7, wherein fluorocarbon used in producing the resin is removed from the separated and recovered urethane foam resin.

According to a ninth aspect of the present invention, when the olefin-based resin and the styrene-based resin are separated and recovered from the shredder dust, the shredder dust is pulverized to an average particle diameter of 20 mmφ or less, and then the olefin-based resin and The resin and the styrene resin are levitated, separated from other resins such as vinyl chloride resin that do not float, and contaminants such as metals, and the levitated resin mixture is mainly separated from the olefin resin by using a liquid 2 having a specific gravity different from the above. Surfaced,
The recycling method of waste home electric appliances according to any one of claims 1 to 8, wherein the method is separated into non-floating styrene resins.

According to a tenth aspect of the present invention, the liquid 1 is an aqueous solution of an inorganic salt adjusted to have a specific gravity of more than 1.0 and less than 1.3, and the liquid 2 is water having a specific gravity of 1.0. 9
It is a recycling method of the waste home appliances described in the description.

According to the eleventh aspect of the present invention, when recycling an unspecified large number of waste home appliances, first, a CRT glass such as a television and a personal computer monitor is separated from a refrigerant Freon and a part of resin parts such as a refrigerator and an air conditioner. After collecting and then crushing the remaining product, urethane foam resin is separated using a wind separator, iron is separated using a magnetic separator, and non-ferrous metal is separated and collected using an eddy current separator. After shredding the shredder dust to an average particle diameter of 20 mmφ or less, first use the liquid 1 to float mainly the olefin resin and the styrene resin, and remove the non-floating vinyl chloride resin and other contaminants such as resin and metal. The resin mixture thus floated is further separated into two components, an olefin resin that floats and a styrene resin that does not float, using a liquid 2 having a specific gravity different from that described above. A method for recycling waste household electrical appliances, characterized in that the separated resin or resin parts are converted into recycled resin by the method according to claims 1 to 4.

The twelfth aspect of the present invention relates to the first to first aspects.
The olefin-based resin separated and recovered in any one of 1) is supplied to a screw-type extruder, and solids such as metal foreign matter are passed through a screen mesh filter of No. 20 or more (with a sieve opening of 0.84 mm or less) with an ASTM standard sieve. A recycled product comprising an olefin-based resin composition characterized by kneading and granulating while removing foreign matter.

The invention according to claim 13 is the invention according to claims 2-1.
The styrene-based resin separated and recovered in any one of 1) is supplied to a screw-type extruder, and passed through an ASTM standard sieve.
A recycled product comprising a styrene-based resin composition characterized by kneading and granulating while removing solid foreign substances such as metal foreign substances using a screen mesh filter of No. 20 or more (a sieve opening of 0.84 mm or less).

According to a fourteenth aspect of the present invention, there is provided a process for thermally decomposing the styrene-based resin separated and recovered in any one of the first to third aspects and distilling the resulting oil to obtain a styrene monomer. Purity 99% or more as a recycled product, wherein a pyrolysis oil having a yield of 80% or more and a styrene monomer concentration of 50% or more is distilled to give a styrene monomer having a purity of 99% or more. Is a styrene monomer.

The invention according to claim 15 is the invention according to claims 3-1.
A recycled product comprising a carbide, various distillate oils or gases obtained by pyrolyzing a urethane resin separated and recovered by any one of the methods described in 1.

The invention according to claim 16 is the invention according to claims 9-1.
After separating and recovering the olefin-based resin and the styrene-based resin from the shredder dust by any of the methods described in 1, the remaining contaminants such as other resins such as vinyl chloride-based resins and metals are supplied to a screw type extruder. Resin usable as solid plastic fuel characterized by recovering chlorine contained in vinyl chloride resin as hydrogen chloride by thermal decomposition and kneading and granulating the residue with other non-chlorine resin added as necessary It is a recycled product comprising the composition.

Hereinafter, the present invention will be described specifically. The unspecified large number of waste home appliances referred to in the present invention are not limited to four types of refrigerators, washing machines, televisions, and air conditioners that are subject to the so-called "Home Appliance Recycling Law", and include personal computers, printers, and copiers. Includes all kinds of home appliances such as telephones, fax machines, video tape recorders, audio equipment, clothes dryers, vacuum cleaners, electric fans, microwave ovens, electric rice cookers, electric carpets, hair dryers, etc.

In the present invention, before crushing these unspecified and large number of waste home appliances at once, it is possible to manually separate and collect specific parts and substances as necessary in consideration of the effect on the environment. it can. Examples of such parts and substances include cathode ray tubes such as televisions and personal computer monitors for collecting lead-containing glass, televisions, personal computers, copiers and the like for collecting flame-retardant resins, and refrigerants for refrigerators and air conditioners. Can be exemplified.

For the purpose of obtaining a higher-purity recycled plastic, parts that can be easily decomposed are collected manually, pulverized, and then kneaded and granulated using a screw-type extruder to form a recycled resin. It is also possible and belongs to the invention.

After the specific parts are separated and collected, the remaining waste home appliances are crushed at once. The crushing method is not particularly limited, for example, may be crushed by means such as room temperature cutting and crushing, frozen cutting and crushing, shear crushing and the like, and its shape is also irregular, cullet-shaped, and elongated. Any shape such as shape and particle shape may be used.

The upper limit of the average particle size of the crushed particles is 50 mm or less, preferably 40 mm or less, from the viewpoint of removing metallic foreign matter. If the average particle diameter exceeds 50 mm, separation of metal parts and plastic parts becomes insufficient, and the separation accuracy is undesirably reduced. The lower limit is at least 20 mm, preferably at least 30 mm, from the viewpoint of the crushing speed. Attempting to crush to an average particle size of less than 20 mm requires equipment with an unnecessarily large capacity as a crushing device, increasing equipment costs, and increasing the running cost due to the long time required for crushing work. It is not preferable from the point of view.

Next, from the above-mentioned crushed particles, a low specific gravity material, mainly a urethane foam resin mainly made of a heat insulating material of a refrigerator, is separated using a wind separator. The model, structure, etc. of the wind separator used for this purpose are not particularly limited, and a general-purpose device can be used as it is.

Since metals such as iron, copper, and aluminum are mixed in the crushed mixture after the urethane resin is separated, iron is separated by a magnetic separator, and copper and eddy current is separated by an eddy current separator.
It is preferable to remove non-ferrous metals such as aluminum,
The type and structure of the magnetic separator and eddy current separator used for this purpose are not particularly limited, and general-purpose devices can be used as they are.

The shredder dust thus obtained is
It is a resin containing a small amount of urethane resin, a mixture of metals and other various materials that could not be removed by a magnetic separator or an eddy current separator, and it was difficult to recycle all of them. In the present invention, this shredder dust is separated by a specific gravity sorter, thereby finding a new use for recycling and realizing an improvement in the recycling rate.

First, the above shredder dust is secondarily pulverized for the purpose of increasing the accuracy of specific gravity selection. This pulverization method is not particularly limited, for example, room temperature cutting and crushing, frozen cutting and crushing, may be crushed by means such as shearing crushing, the shape may be an irregular shape,
Any shape such as a cullet shape, an elongated shape, and a particle shape may be used, but from the viewpoint of kneading workability in a single screw extruder or a twin screw extruder thereafter, a cullet shape or a particle shape is preferable.

The upper limit of the average particle size of the pulverized particles is 20 mm or less, preferably 10 mm or less from the viewpoint of the separation accuracy in specific gravity separation. If the average particle diameter exceeds 20 mm, in the case of plastic parts composed of different materials, the separation of the materials becomes insufficient, and the separation accuracy of the specific gravity separation is undesirably reduced. Although the lower limit is not particularly limited, it is 1 mm or more, preferably 5 mm or more, from the viewpoint of cost reduction relating to the pulverization treatment. If the average particle diameter is to be crushed to a size of less than 1 mm, crushing equipment requires equipment with a larger capacity than necessary and equipment costs will increase, and running costs will increase due to the long time required for crushing work. It is not preferable from the point of view.

The secondary pulverized shredder dust is separated in two stages using two kinds of liquids having different specific gravities.
First, the liquid 1 whose specific gravity is adjusted to be more than about 1.0 and less than 1.3 is mainly composed of a vinyl chloride resin and a metal that cannot be completely removed by a magnetic force sorter or an eddy current sorter. The specific gravity is separated into a weight component and other components mainly composed of an olefin resin and a styrene resin. Next, using the liquid 2 whose specific gravity is adjusted to about 1.0, the other components are used to separate the specific gravity of the light component mainly composed of the olefin resin and the medium component mainly composed of the styrene resin. Separate. Here, as long as the liquids 1 and 2 have a specific gravity capable of separating the above specific gravity, and do not have a property of chemically changing the plastics to be separated, any liquid can be used. Although liquid 1 may be used, from the viewpoint of economy, liquid 1 is prepared by dissolving inorganic salts such as soda ash (sodium carbonate) in water and adjusted to the above specific gravity range, but water is preferably used as liquid 2.

The separation accuracy of the secondary pulverized shredder dust is preferably as high as possible from the viewpoint of maintaining the physical properties of the recycled plastic.
0% or less, preferably 5% or less, more preferably 1% or less.

The model, structure, and the like of the specific gravity separator used for this purpose are not particularly limited as long as the above-described separation accuracy can be realized, and a general-purpose device can be used as it is. However, a wet specific gravity sorter using water or an aqueous solution is preferably used in terms of being capable of high-precision separation and of being able to wash highly dirty materials.

According to the separation method described above, the plastics constituting the waste electric home appliances should be separated into five components, that is, a recovered resin before crushing, a urethane resin, a vinyl chloride resin, a styrene resin, and an olefin resin. Is possible. Hereinafter, regeneration of each component,
The re-commercialization method will be described in detail.

The resin parts separated and recovered by manual work or the like before the crushing at a time are separated for each type of resin, and after each pulverization, if necessary, dirt is removed by washing with water or the like. And kneaded and granulated for reuse as recycled resin. The type and structure of the screw type extruder used for this purpose are not particularly limited, and a general-purpose single-screw or twin-screw extruder is preferably used. When the resin component is made of a plurality of resins or when the type of the resin is unknown, it can be subjected to secondary pulverization to perform specific gravity separation and the like.

In the present invention, resin components in an unspecified number of waste home appliances are separated and recovered as described above. Resin to be separated and recovered is roughly classified into urethane resin, vinyl chloride resin, styrene resin and olefin resin. It is advantageous to separate the resin contained in a small amount separately when it is collected.However, if the amount is small, it is often mixed with the above resin within the allowable limit, or mixed into the final waste to become fuel or incinerated. And so on.

Among the separated and recovered resins, thermoplastic resins such as vinyl chloride resin, styrene resin and olefin resin can be granulated and used as a regenerated resin. In addition to a regenerated resin, it can be thermally decomposed into a styrene monomer-containing oil and purified by distillation to regenerate polystyrene production grade styrene monomer.

The vinyl chloride resin is thermally decomposed into a gas containing chlorine or hydrogen chloride, an oil, and a solid, and the dechlorinated or dehydrochlorinated gas and the oil are converted into a fuel or a chemical raw material. It is advantageous to knead and granulate by adding other resins as necessary to obtain a regenerated resin.

It is advantageous that the urethane resin is thermally decomposed to generate gas, oil, and carbide, which are used as a fuel or a chemical raw material.

On the other hand, the olefin resin is kneaded and granulated by using a screw type extruder to obtain a regenerated resin. Hereinafter, a method of kneading and granulating a recycled resin will be described.

[0050] The crushed particles having a specific gravity of 1 or less, which are collected through the respective steps of magnetic force sorting, eddy current sorting and specific gravity sorting after crushing the waste home appliances, are referred to as "used polyolefin resin crushed products". In the used polyolefin resin pulverized product, it is preferable that the mixing ratio of metal foreign substances is reduced to less than 2% in the sorting step. If the mixing ratio of the metallic foreign matter is 2% or more, clogging due to the metallic foreign matter frequently occurs in the kneading and granulating step using an extruder, and efficient operation becomes impossible.

The screw extruder used for the purpose of kneading and granulating the used polyolefin resin pulverized product of the present invention has a model, a structure, etc., of a screen mesh filter for filtering unmelted matter including metal foreign matter. Hereinafter, SMF
Is not particularly limited as long as it can be installed, and a general-purpose single-screw or twin-screw extruder is suitably used. In the present invention, the SMF filters a large amount of unmelted matter including metal foreign matter, and the unmelted matter accumulates on the upstream side (with respect to the resin flow) of the filter, and eventually blocks the filter. Become. Therefore, SMF
The part is preferably of a so-called "auto screen changer type" in which a plurality of filter surfaces can be switched and filtered so that the filter can be replaced without interrupting the kneading and granulating operation. Further, it is more preferable that the filter is an auto screen changer having a so-called “backwashing mechanism” in which the unmelted material deposited by applying pressure from the downstream to the upstream of the closed filter is washed and discharged outside the extruder.

The SMF used in the present invention is manufactured using an ASTM standard sieve from the viewpoint of the appearance and mechanical properties of the recycled product.
It is preferable that it is o.20 or more (a sieve opening of 0.84 mm or less), and more preferably No. 100 or more (a sieve opening of 0.149 mm or less). SM of number less than No.20
When F is used, foreign substances having a large particle size pass through, which impairs the appearance of the recycled product, and significantly degrades mechanical properties, particularly physical properties relating to toughness such as impact resistance and tensile elongation at break. Although the upper limit of the SMF count is not particularly limited, it is No. 250 or less (a sieve opening of 0.062 mm
Or more). If the SMF has a count higher than No. 250, the frequency of clogging of the filter increases, and the production efficiency is remarkably reduced.

In the present invention, a used polyolefin resin pulverized product is supplied to a screw type extruder and subjected to ASTM.
A product manufactured by kneading and granulating while using a screen mesh filter of No. 20 or more (with a sieve opening of 0.84 mm or less) with a formula standard sieve while removing metal foreign substances is referred to as "recycled polyolefin resin".

The recycled polyolefin resin of the present invention has a physical property level that can be used as it is as long as it is a general-purpose product that does not have high requirements for physical properties.
Impact resistance is considerably reduced as compared with virgin resin. The main cause is the low compatibility between polyethylene and polypropylene as described above.

The present inventors have solved this problem by adding a small amount of a thermoplastic elastomer (hereinafter referred to as TPE) as an auxiliary material when kneading and granulating a used polyolefin resin pulverized product. TPE itself has high impact resistance, and is known as an "impact modifier" which improves impact resistance by adding a large amount of 20 to 30% to a brittle resin. However, in the present invention, since TPE functions as a compatibilizer for polyethylene and polypropylene, the amount of TPE added is one.
A small amount of 10% to 10% is sufficient. If the addition amount is less than 1%, the effect as a compatibilizer is small and sufficient physical properties cannot be improved, which is not preferable. On the other hand, if the addition amount exceeds 10%, the impact resistance gradually increases, but the elastic modulus drops sharply, and the addition of a large amount of an expensive thermoplastic elastomer leads to an increase in the regeneration cost. After all it is not desirable.

As the TPE used in the present invention, specifically, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-propylene-
Rubber (EPR), ethylene-propylene-diene monomer copolymer (EPDM), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylenebutylene-styrene copolymer Coalesced (SEBS), PVC-based TPE, urethane-based TPE, polyester-based TPE, polyamide-based TPE, fluororesin-based TPE, and the like. These may be used alone or as a mixture of two or more. It can be used, but is not limited to this. However, from the viewpoint of the balance between the effect as a compatibilizer and the price, ethylene-propylene-rubber (EPR) and its analogs are preferably used.

The reclaimed polyolefin resin composition of the present invention is a reclaimed resin kneaded and granulated by the method for producing a reclaimed polyolefin resin described above, and has a flexural modulus (according to ASTM D790) of 1000 MPa or more; In addition, the Izod impact strength (according to ASTM D256) is 3 kg / m ² or more. As described above, since it has a good balance of rigidity and good physical properties comparable to virgin resin, it can be used for products for various uses. Packaging materials from which the recycled polyolefin resin composition of the present invention is discharged, automobiles, home appliances and OA equipment, can be reused as plastic parts such as buildings, but as a so-called cascade recycling, park bench,
It can also be used for artificial wood, sleepers, resin pallets, containers, concrete forms, etc.

The reclaimed polyolefin resin composition produced according to the present invention can be used for various applications as it is, but virgin resin is used for products requiring more beautiful appearance and high mechanical properties. It is also possible to mix and use the resin in an arbitrary ratio, and it is included in the present invention. In the recycled polyolefin resin composition used for this purpose, the mixing ratio of the virgin resin is 10 to 90.
% By weight, preferably 20 to 60% by weight. If the content of the recycled resin is less than 10% by weight, the significance of the present invention of promoting plastic recycling is lost, which is not preferable.

To the reclaimed polyolefin resin composition of the present invention, resin components other than thermoplastics, pigments, organic / inorganic fillers, various additives, etc. may be added as required, without departing from the object of the present invention. be able to. Among these, as the organic / inorganic filler used for the purpose of imparting rigidity to the molded product, any of plate-like, granular, and fibrous shapes may be used. Specifically, examples of the plate-like or granular filler include metal powders such as aluminum powder, metal oxides such as magnesium oxide, titanium oxide, and alumina; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; calcium,
Carbonates and sulfates such as magnesium carbonate and barium sulfate; synthetic silicates such as magnesium silicate and aluminum silicate; natural silicates such as talc, mica and kaolin; silicon carbide powder; synthetic and natural silica; carbon black; Wood flour, cotton flour and the like can be mentioned. Examples of the fibrous filler include synthetic polymer fibers such as nylon, PET fibers, aramid fibers, and Teflon (registered trademark) fibers, natural polymer fibers such as wool, cotton, and pulp, glass fibers, carbon whiskers, and graphite fibers. And carbon fibers such as silica / alumina fibers and potassium titanate fibers, and metal fibers such as silicon carbide fibers / whiskers, boron fibers, steel fibers, and aluminum fibers. In addition, various additives include a plasticizer, a flame retardant, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a release agent, a foaming agent, a nucleating agent, a colorant, and a crosslinking agent. Agents, dispersing aids and the like.

The styrenic resin can be kneaded and granulated by using a screw type extruder in the same manner as the above-mentioned olefin resin to obtain a regenerated resin.

[0061]

EXAMPLES Example 1 Resin product parts were removed before shredding several kinds of waste home appliances by a shredder, and the used resin type, polystyrene GP, polystyrene HI, polypropylene (PP)
Separated every time. Each resin was crushed by a shredder, washed with water, and further polished with an ASTM type standard sieve. The metal screen was further removed by an auto screen changer equipped with an SMF of No. 20 or more (with a sieve opening of 0.84 mm or less). Knead and granulated to a particle size of about 5 mm, regenerated GP,
Three types of regenerated pellets composed of regenerated HI and regenerated PP were obtained. For test specimens obtained by injection molding each regenerated pellet,
Tensile test (according to ASTM D638), bending test (according to ASTM D790), IZ impact strength test (AS
TM D256) and MFR measurement (ASTM D1)
238) is shown in Table 1.

The waste home appliances from which the resin product parts have been removed as described above are crushed by a shredder, and the crushed particles are used to remove iron by a magnetic separator and non-ferrous metals such as copper and aluminum by an eddy current separator to remove average particles. Shredder dust having a diameter of 40 mm was used. Next, the shredder dust was secondarily crushed by a commercially available shear crusher, and the average particle size was 10
mm. The urethane foam was separated by airflow separation, and then separated by two-stage specific gravity selection. Liquid 1
After removing metallic foreign matter and vinyl chloride resin using an aqueous solution of sodium carbonate having a specific gravity of 1.1, the liquid 2 was separated into a styrene resin and an olefin resin using tap water.

The separated olefin-based resin was further removed by an automatic screen changer equipped with an SMF of No. 20 or more (with a sieve opening of 0.84 mm or less) using an ASTM standard sieve. The mixture was kneaded and granulated to a degree to obtain a recycled PP pellet mainly composed of polypropylene. Also, the separated styrene resin is kneaded and granulated by the same method as the olefin resin to obtain
S pellets were obtained. Table 2 shows the results of the tensile test, the bending test, the IZ impact strength test, and the MFR measurement performed on the recycled PP pellet and the recycled PS pellet in the same manner as in Example 1.

The separated styrene resin was subjected to a thermal decomposition treatment by a flask test, separately from the formation of a regenerated PS pellet by kneading and granulation. The flask test is a batch type with an input amount of 300 g, a thermal decomposition temperature of 300 to 400 ° C., and a pressure of 50 Toor. By the thermal decomposition treatment, 87% by weight of a dark black liquid product, 5% by weight of a residue, and 1% by weight of a substance attached to a cooling pipe were obtained, and the remainder was a decomposition gas. When this liquid product was analyzed by gas chromatography, 55% by weight of styrene, 0.7% by weight of acrylonitrile, 2.6% by weight of toluene, 2.6% by weight of ethylbenzene, 4.9% by weight of α-methylstyrene, and the balance Was a high boiling oil. The chlorine content of the liquid product is 200pp
m. From the analysis results, it was confirmed that the styrene monomer with a reusable purity can be recovered by distilling the liquid product, if necessary, by removing chlorine compounds by washing with water, etc., and then distilling it with a precision distillation device of a styrene monomer production facility. Was done.

Further, a thermal decomposition test was performed on a large amount of urethane foam contained in the waste refrigerator separated from the airflow by using a tubing cylinder for evaluating a coke raw material. The tubing cylinder filled with the sample is immersed in a fluidized bath at 480 ° C., maintained at a pressure of 2 kg / cm ² for 16 hours, and the generated high-temperature gas is guided from the top of the cylinder into a receiver immersed in ice water to condense the liquid material and be retained. Oil was obtained and uncondensed gas was led to a gas collector and collected. The yields of char, distillate and gas produced were 36.1%, 43.1% and 23.3% by weight. Distillate oil and gas were analyzed by gas chromatography. Table 3 shows the composition (% by volume) of the distillate oil, and Table 4 shows the composition (% by volume) of the recovered gas. The composition of the recovered gas is shown by the composition after removing oxygen and nitrogen, which are considered to be due to air mixed in during the thermal decomposition test.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

According to the present invention, shredder dust derived from waste home appliances can be separated at a higher separation accuracy and at a lower cost, and the separated products can be reused according to the composition and properties. Efficient recycling could be achieved by applying. As a result, in addition to iron, non-ferrous metals, glass, and the like that can be reused with existing technology, mixed waste plastic that has been difficult to reuse has been realized from waste home appliances.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) B03C 1/00 B29B 17/00 1/23 17/02 B09B 3/00 C07C 4/22 B29B 17/00 15/06 17 / 02 C08J 11/12 C07C 4/22 C10G 1/10 15/06 B29K 23:00 C08J 11/12 25:00 C10G 1/10 75:00 // B29K 23:00 C08L 25:04 25:00 75: 04 75:00 B09B 5/00 ZABC C08L 25:04 B03C 1/24 A 75:04 B09B 3/00 Z F term (reference) 4D004 AA22 AA28 AC05 BA02 BA03 BA06 BA10 CA04 CA08 CA09 CA10 CA12 CA14 CA25 CA26 CA27 DA03 DA20 4D071 AA43 AA46 AB14 CA03 DA15 4F301 AA12 AA15 AA17 AA29 AB03 BC13 BC25 BC26 BC40 BD06 BD31 BF08 BF09 BF12 BF26 BF27 BF32 BG53 CA09 CA25 CA26 CA33 CA68 4H006 AA02 AC91 4H029 CA01 CA14 CA16

Claims (16)

[Claims] At least two components of olefin-based resin and styrene-based resin from shredder dust composed of contaminants such as resin and metal after crushing an unspecified large number of waste home appliances and separating and recovering iron and non-ferrous metals. Are separated and recovered, and the olefin resin is converted into a regenerated resin by kneading and granulating using a screw extruder, and the styrene resin is thermally decomposed to produce oil, and the resulting oil is obtained by distillation. A method for recycling waste home appliances, characterized by reusing styrene monomer as a chemical raw material. 2. A shredder dust consisting of a mixture of resins and metals after crushing an unspecified large number of waste home appliances and separating and recovering iron and non-ferrous metals, at least two components of an olefin resin and a styrene resin. Characterized by separating and recovering olefin-based resin and styrene-based resin into a regenerated resin by kneading and granulating the olefin-based resin and the styrene-based resin, respectively, using a screw-type extruder. At least a part of the waste home appliances is a refrigerator, and at least three urethane-based resins, olefin-based resins and styrene-based resins are obtained from shredder dust after separating and recovering iron and non-ferrous metals from those products. 3. The method of claim 1 or 2, wherein the components are separated and recovered, and the urethane-based resin is thermally decomposed to generate carbides, various distillate oils and gases, and these are reused as fuels or chemical raw materials. . 4. The method according to claim 1, wherein a part of the resin component is separated and recovered in advance before the waste home appliances are crushed, and kneaded and granulated by using a screw type extruder to be converted into a regenerated resin. How to recycle waste home appliances described in 4. 5. At least a part of a waste home appliance is a product using a flame-retardant resin component such as a television, a personal computer, a copying machine, etc., and is made of a resin separated and recovered in advance before crushing the waste home appliance. The method according to claim 4, wherein at least a part of the component is the flame-retardant resin component. 6. The waste home appliance according to claim 1, wherein after the waste home appliance is crushed, iron is separated and a non-ferrous metal is separated and recovered using a magnetic separator and an eddy current separator, respectively. Recycling method. 7. A method for separating and recovering urethane foam resin from shredder dust using a wind separator.
A method for recycling waste home appliances according to any of the above. 8. From the urethane foam resin separated and recovered,
The recycling method for waste home appliances according to claim 7, wherein the fluorocarbon used in producing the resin is removed. 9. When the olefin resin and the styrene resin are separated and recovered from the shredder dust, the shredder dust is pulverized to an average particle diameter of 20 mmφ or less. Floating, separating from non-floating non-floating resin and other contaminants such as metals, and further floating the resin mixture using the liquid 2 having a specific gravity different from the above, mainly floating the olefin-based resin and not floating The method for recycling waste home appliances according to any one of claims 1 to 8, wherein the method is separated into styrene-based resins. 10. The waste electrical home appliance according to claim 9, wherein the liquid 1 is an aqueous solution of an inorganic salt adjusted to have a specific gravity of more than 1.0 and less than 1.3, and the liquid 2 is water having a specific gravity of 1.0. Recycling method. 11. When recycling an unspecified large number of waste home appliances, first, a CRT glass such as a television and a personal computer monitor and a part of a refrigerant Freon and a resin component such as a refrigerator and an air conditioner are separated and collected, and then the remaining part is recovered. After crushing the product, the urethane foam resin is separated using a wind separator, iron is separated using a magnetic separator, and non-ferrous metal is separated and collected using an eddy current separator.The remaining shredder dust is averaged. After crushing to a particle diameter of 20 mmφ or less, first, the olefin-based resin and the styrene-based resin are first floated using the liquid 1, separated from non-floating vinyl chloride-based resin and other contaminants such as metals and metals, and further lifted. The separated resin mixture is separated into an olefin resin that floats and a styrene resin that does not float using the liquid 2 having a specific gravity different from the above, and the separated resin or resin Recycling method of waste household appliances, characterized in that the recycled resin of the claims 1-4, wherein the method is for goods. 12. The olefin resin fractionated and recovered in any one of claims 1 to 11 is supplied to a screw type extruder, and is passed through an ASTM type standard sieve with a size of No. 20 or more (mesh size of 0.84 mm or less). A recycled product comprising an olefin-based resin composition, which is kneaded and granulated while removing solid foreign matter such as metal foreign matter by a screen mesh filter. 13. The styrenic resin separated and recovered in any one of claims 2 to 11 is supplied to a screw type extruder, and the styrenic resin having a size of No. 20 or more (a sieve opening of 0.84 mm or less) is passed through an ASTM standard sieve. A recycled product comprising a styrene-based resin composition, which is kneaded and granulated while removing a solid foreign substance such as a metallic foreign substance using a screen mesh filter. 14. A process for thermally decomposing the styrene resin fractionated and recovered in any one of claims 1 or 3 to 11 and distilling the obtained oil to obtain a styrene monomer, wherein the yield is 80% or more. A styrene monomer having a purity of 99% or more as a recycled product, wherein a pyrolysis oil having a styrene monomer concentration of 50% or more is distilled into a styrene monomer having a purity of 99% or more. 15. A recycled product comprising a carbide, various distillate oils or gases obtained by pyrolyzing a urethane resin fractionated and recovered by the method according to any one of claims 3 to 11. 16. The method according to claim 9, wherein after separating and recovering the olefin resin and the styrene resin from the shredder dust, the remaining resin such as a vinyl chloride resin or a metal is mixed. The product is supplied to a screw type extruder, chlorine contained in the vinyl chloride resin is recovered as hydrogen chloride by thermal decomposition, and the residue is kneaded and granulated with other non-chlorine resin added as necessary. A recycled product comprising a resin composition that can be used as a solid plastic fuel.