JP2003112153A - Method for recycling waste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make such waste plastics that are hard to recycle because of inclusion of foreign matters and different types of plastics recyclable as a modifier for asphalt, adhesives, or the like, or additives for heating fuel or, and those such for as cutting oils. SOLUTION: This method comprises of a chemically thermal cracking process 5 wherein insoluble materials such as metals and inorganic materials are separated from thermally cracking/liquidizing synthetic resin portions of waste materials by using a thermal decomposing reaction to convert them into solvents as a high temperature by adding fats and oils to be waste edible heavy oils such as fatty acid glycerides, to the waste of plated synthetic resins, and a distillation/separation process 6 wherein the liquidized portions separated by the chemically thermal cracking process 5 are separated into recyclable light oil portions and heavy oil portions by a reduced pressure (vacuum) distillation. The heavy oil portions generated by the distillation/separation process 6 are utilized as the modifier for asphalt, the adhesives, or the like. The light oil portions generated by the distillation/separation process 6 are utilized as the additives for the heating fuel or the cutting oils.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to a waste recycling method suitable for small-scale dispersion treatment for making waste plastics difficult to recycle materials useful.

[0002]

2. Description of the Related Art In recent years, the tightness of landfills, the increasing national demand for effective use of resources, and the impact of heavy metals on the environment have been regarded as problems. There is an urgent need to reduce and recycle waste. For example, there are many types of plastics used in chemical fibers, office automation equipment, home appliances, and the like, and they are mixed with metals and different types of plastics and discharged as contaminated waste. Therefore, in the past, as a method for separating insoluble parts such as metal and inorganic substances from waste plastic, for example, an automatic part separating device for separating electronic parts mounted on a printed board from the printed board by using heating and external force in combination. Etc. are used. In addition, there are also a light oiling method by only thermal decomposition and a low molecular weight monomer recycling method.

[0003]

However, in the conventional art, fats and oils are consumed as edible oils at 400,000 tons per year, half of which are consumed for business purposes, and the problem of environmental pollution of the waste edible oils has been sought out. The current situation is that there are no effective measures. In addition, the annual production of plastics in Japan is 150
About 10 million tons of waste plastics are discharged, exceeding 100,000 tons, and it has been about 30 years since the environmental pollution was exclaimed, but an effective and appropriate treatment system has not yet been established. This is because there are various types of plastics and their use and discharge forms, and there is no new treatment system to be seen other than the large-scale centralized treatment system used as fuel for the blast furnace, except for incineration. In particular, as for the small-scale distributed processing method, there is almost no commercialization except for the petpet, incineration and landfill processing. For example, a printed circuit board (copper / glass) on which electronic components such as an LSI and a connector (including a large amount of gold) used in OA equipment such as a personal computer for the purpose of shielding electromagnetic waves are mounted by soldering (lead / tin). Fibers / epoxy resin), mainly plated ABS resin / polycarbonate resin, and plated ABS resin used for automobile grills etc. for the purpose of aesthetics and surface protection were discarded. In this case, since it is difficult to remove the plated metal portion, the material cannot be recycled, and it is currently incinerated or landfilled, which causes various problems.

Therefore, the present invention has been made in view of the above existing circumstances. Waste plastic which is difficult to material recycle due to contaminants or mixture of different kinds of plastic is used as an asphalt or adhesive improving agent. Alternatively, it can be made useful by making it recyclable as an additive for heating fuel or cutting oil, etc., and at the same time, waste edible oil and waste plastic, which are the bases of environmental pollution, at the same time can be decomposed by solvation without using incineration or landfill. Providing a waste recycling method suitable for small-scale decentralized processing that can be constructed by a decomposition method, and can construct a new recycling system that is also excellent in novelty and originality that contributes to environmental protection and carbon dioxide reduction The purpose is to do.

[0005]

In order to achieve the above-mentioned object, in the present invention, a composite material of metal-inorganic fiber or the like and synthetic fiber such as a plated synthetic resin product or a printed wiring board FRP is used. Chemical pyrolysis step 5 in which fats and oils are added to the waste, and the synthetic resin portion of the waste is pyrolyzed and liquefied by utilizing the solvated pyrolysis reaction at high temperature to separate insoluble portions such as metals and inorganic substances. Distillation separation step 6 in which the liquid portion separated in the dynamic thermal decomposition step 5 is separated into reusable light oil portion and heavy oil portion by reduced pressure (vacuum) distillation.
It consists of and. The fat or oil may be a heavy oil for waste food such as fatty acid glyceride. The heavy oil portion produced by the distillation separation step 6 can be made usable as an improving agent such as asphalt or an adhesive, or a resin component such as paint or ink. The light oil portion produced by the distillation separation step 6 can be made usable as an additive for heating fuel or cutting oil. The waste can be a mixed plastic in which metals and contaminants are mixed in polycarbonate resin, ABS resin, polyamide resin, polyurethane resin, unsaturated polyester resin, polyester resin, polyurethane resin and the like. Polyamide-based resin may be added and used as waste that is added together with the addition of oil and fat in the chemical pyrolysis step. Separation of waste Waste of polyamide resin collected or polyamide itself separated as waste products may be added to the oil and fat to be thrown in together with the waste. The polyamide resin added to the fats and oils has a polyamide portion in the range of 10% to 50%, preferably about 20%, relative to 100 of the resin portion, and the temperature condition is 330 ° C to 370.
Within the range of 0 ° C, the high temperature side of 350 ° C to 370 ° C is applied to the waste of olefin resin, while the low temperature side of about 330 ° C is applied to the condensation waste of polyester, polyurethane, polyamide, etc. About 3 hours
It can be within time.

In the waste recycling method according to the present invention configured as described above, the chemical pyrolysis step 5 is carried out by solvent-solvent pyrolysis reaction of fats and oils which are waste edible heavy oils such as fatty acid glyceride at high temperature. The cleavage reaction in the molecule of the product is caused, and the synthetic resin portion of the waste is liquefied (converted into a medium molecule). In the distillation separation step 6, the liquid portion separated in the chemical thermal decomposition step is separated into a reusable light oil portion and heavy oil portion by vacuum (vacuum) distillation. Further, the polyamide-based resin added to fats and oils, in the chemical thermal decomposition step, the amine which is a compound in which the hydrogen atom of ammonia is replaced by a hydrocarbon group is generated by the thermal decomposition of the polyamide-based resin. Increase the decomposition amount and decomposition rate.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described below with reference to the drawings.
Fig. 3 shows a waste recycling process, which is a fat / oil adding step 2 of adding fats and oils to a synthetic resin waste that has been plated, and a synthetic resin portion of the wastes by utilizing a solvated pyrolysis reaction of the fats and oils at a high temperature. By a chemical thermal decomposition step 5 consisting of a heating step 3 for thermally decomposing and liquefying liquefaction and a specific gravity / centrifugal separation step 4 for separating insoluble parts such as metals and inorganic substances, and a chemical thermal decomposition step 5. It comprises a distillation separation step 6 for separating the separated liquid portion into a reusable light oil portion and heavy oil portion by vacuum (vacuum) distillation.

The wastes made of this kind of synthetic resin include polycarbonate resin / ABS resin used in OA equipment such as personal computers, polyamide resin used in nylon fiber, polyurethane resin used in heat insulating material,
The target is mixed plastics in which metals such as unsaturated polyester resin used in FRP and polyester resin used in polyester fiber and impurities are mixed.

The properties of oils and fats are relatively stable up to a high temperature of 300 ° C., and most of the plastics are dissolved from around 250 ° C. to start solvolysis. And 300
The thermal decomposition of fatty acid glyceride begins at around ℃, and free fatty acid and glycerin decomposition products start to be generated. The produced free fatty acid acts as an acid catalyst that cleaves ester bonds, amide bonds, urethane bonds, etc. of waste plastics dissolved in fats and oils. In addition, glycerin degradation products (acrolein and ketones) act as hydrogen donors and react with the terminal groups of the molecules cleaved by the acid catalyst. And 300 ~
At 350 ° C., oils and fats are further thermally decomposed through free fatty acids, acrolein and ketones to be olefins and polymerized to hydrocarbon oils. The solvolysis refers to a decomposition reaction caused by a solvent (waste edible oil) acting on a solute (waste), a metathesis reaction, and an intramolecular cleavage reaction by a solvent.

Next, a concrete waste recycling method of the present invention will be described. First, for example, 20 to 40% of oil or fat, which is a heavy edible oil for waste food such as fatty acid glyceride, is added to waste such as waste plastic in which foreign substances and foreign substances that are difficult to recycle are mixed, and the temperature is 300 to 350 ° C. The waste plastic is heated to 50 ° C. and solvated by thermal decomposition of the oil and fat at a high temperature, and the molecular weight of the waste plastic is reduced to 5000 in 0.5 to 1 hour.
It is made into middle molecules before and after, and the metal and insoluble parts are separated by specific gravity difference or centrifugal separation at a liquid temperature of 150 to 200 ° C, and the separated liquid part is at a liquid temperature of 250 to 300 ° C and a vacuum degree of 10 to 20 Torr.
It is distilled under reduced pressure to distill the light oil portion and separate it from the remaining heavy oil portion. For example, as a test example, 80% of waste ABS resin and 20% of waste edible oil in the production process are used at a temperature of 350 ° C.
When pyrolyzed for about 1 hour, the product yield is 60% heavy oil.
(Liquid temperature 250 ° C, 20 Torr vacuum distillation), light oil 30
%, Moisture and gas content became 10%. Thus, as a result of the experiment, by adding the waste edible oil, it was possible to reduce the volume of the resin component to a heavy oil by converting the resin component into a medium molecule at normal pressure and low temperature and in a short time, as compared with the conventional thermal decomposition method.

Next, a specific method of reusing the heavy oil portion and the light oil portion produced in the distillation separation step 6 will be described. The heavy oil portion produced by the distillation separation step 6 can be used as a modifying / improving agent such as asphalt or adhesive for paving and waterproofing. on the other hand,
The light oil portion produced by the distillation separation step 6 can be used as an additive for heating fuel or cutting oil. For example, metal and insoluble parts are separated from heavy oil by specific gravity difference.
The heavy oil portion obtained by centrifuging and removing the light oil portion from the separated liquid portion by distillation under reduced pressure has good compatibility with asphalt, and 10% or more can be added.
In addition, it improves the adhesion of asphalt to metals and inorganic aggregates, and can be effectively used as a modifier and improver for asphalt. At this time, in the production of the asphalt modifier, it is necessary to add a vacuum distillation apparatus, but no further refining step is required. On the other hand, the distilled light oil portion can be used as a cutting oil additive or a heating fuel.

The waste recycling method according to the present invention is applicable to the recycling of asphalt waterproofing materials for construction waste materials and industrial wastes in the factory for manufacturing the same as asphalt, or the waste carpet tiles are crushed into a PVC compound for backing. Is applied to reduce the volume of bulky waste, mainly nylon fiber, and to treat industrial waste clothing and FRP abandoned vessels that have been incinerated, and to reduce industrial waste at urethane insulation material manufacturing plants. It can be applied to capacity treatment and curable resin waste treatment.

Next, another embodiment of the waste recycling method according to the present invention will be described. That is, in the present embodiment, as the waste plastic to be added in the fat and oil adding step 2 in the chemical thermal decomposition step 5, a polyamide resin that is a polymer having an amide bond (commonly called nylon resin: nylon 6, nylon 66, etc.) Is used. Alternatively, waste of polyamide resin collected separately from waste,
Alternatively, the polyamide itself, which has been separated and treated as a waste product, is added to the fats and oils introduced together with the waste.

In particular, polyamide resins include those synthesized by polycondensation of diamine and dicarboxylic acid and those synthesized by polycondensation of ω-aminocarboxylic acid or ring-opening polymerization of lactam. Polyamide-based resins are mainly used as engineering plastics, and the scraps separately collected from the plastics or the polyamide itself separated and treated as a waste product are added to the oil and fat such as the fatty acid glyceride from the beginning. By doing so, in the chemical pyrolysis process, the amine, which is a compound in which the hydrogen atom of ammonia is replaced by a hydrocarbon group, is generated by the pyrolysis of the polyamide resin, and this amine decomposes the amount and decomposition of the waste in the heating process. It will increase the speed.

At the time of addition at this time, the ratio of the polyamide resin is preferably in the range of 10% to 50% of the polyamide portion with respect to 100 of the resin portion, preferably about 20%. Moreover, the temperature condition is 330 ° C. to 3
The temperature is in the range of 70 ° C., and particularly, the high temperature side of 350 ° C. to 370 ° C. is preferable for the waste of olefin resin, and the low temperature side of about 330 ° C. is preferable for the condensation type waste of polyester, polyurethane, polyamide, etc. It is preferably within about 3 hours. For example, polycarbonate resin and AB
For wastes made from S resin, both the amount and rate of decomposition are 5 to 8
It will be about twice as big. At this time, a bipolar distribution with a low molecular weight and a medium molecular weight occurs along with the decomposition. In addition, in the case of waste made of polyethylene-based resin or polypropylene-based resin, both the amount of decomposition and the decomposition rate become about 2 to 5 times larger. Moreover, conventionally, for example, hard deposits such as polycarbonate are generated on the reactor wall at 330 ° C. to 350 ° C., but according to the method of the present embodiment, such coking, that is, deposition of coke substances is eliminated.

[0016]

EFFECTS OF THE INVENTION Since the present invention is constructed as described above, waste plastics that are difficult to recycle materials due to the inclusion of contaminants and different kinds of plastics can be used as an improving agent such as asphalt or an adhesive, or a fuel for heating or cutting. It is possible to provide a waste recycling method suitable for small-scale dispersion treatment for making it useful as an additive such as oil or the like and making it useful. Moreover, waste cooking oil and waste plastic, which are the sources of environmental pollution, can be treated at the same time by a new thermal decomposition method called solvolysis that does not rely on incineration or landfill, which helps to conserve the environment, reduce carbon dioxide gas, and effectively use resources. It is possible to build a new recycling system that is also excellent in novelty and originality that can make a great contribution to In addition, compared with the conventional simple thermal decomposition method, 3
The decomposition temperature is as low as 00 to 350 ° C., the decomposition time can be shortened, and the energy can be saved. In addition, the existing thermal decomposition oiling device can be used as it is.
Since the waste plastic melts at 0 to 250 ° C, local overheating can be reduced as compared with the conventional oil system.

That is, according to the present invention, fats and oils are added to a synthetic resin waste that has been plated, and the synthetic resin portion of the waste is pyrolyzed and liquefied by utilizing a solvated thermal decomposition reaction at high temperature. A chemical thermal decomposition step 5 for separating insoluble parts such as metals and inorganic substances, and a liquid portion separated by the chemical thermal decomposition step 5 is subjected to reduced pressure (vacuum) distillation to produce a reusable light oil portion and heavy oil portion. Distillation separation process 6
This makes it possible to provide an energy-saving method as compared with the conventional light oil conversion method by only simple thermal decomposition. In addition, it is safer than the conventional low molecular weight monomer recycling system that uses a dangerous organic solvent such as methanol or toluene, or requires a highly accurate distillation process or a complicated manufacturing process. Furthermore, it is possible to make waste into medium molecule, heavy oil, volume reduction, and usefulness at low temperature in a short time by chemical pyrolysis called solvolysis under normal pressure with safe fats and oils, that is, waste edible oil, Moreover, a safe and simple recycling system that does not require any purification step other than vacuum distillation can be realized. Also,
Since the product is heavy oil, the regulations of the Fire Service Law are lenient, and the product itself is not subject to tax regulation.

Since the fats and oils are heavy oils for waste food such as fatty acid glycerides, the decomposition temperature can be lowered, the reaction time can be shortened, energy can be saved, and coke is not generated, and discharge is easy. In addition, even with waste plastics, which have a low yield of light oil and are easy to be coked by the conventional oiling method, heavy oil and volume reduction can be easily performed.

Waste is polycarbonate resin / ABS
Resin, polyamide resin, polyurethane resin, unsaturated polyester resin, polyester resin, polyurethane resin, etc. are mixed plastics in which metals and contaminants are mixed, and the heavy oil portion produced by the distillation separation step 6 is asphalt. Alternatively, it can be used as an improving agent for adhesives and the like, while the light oil portion produced by the distillation separation step 6 can be used as an additive for heating fuel or cutting oil. Waste that is difficult to recycle due to mixed materials, such as waste plastic, can be easily recycled and made useful, and can contribute greatly to environmental protection, carbon dioxide reduction, and effective use of resources. A thing recycling method can be provided.

Polyamide-based resin is added and used as waste to be added together with addition of fats and oils in the chemical pyrolysis step, or as waste of polyamide-based resin separately collected as waste, or waste product. Since the separated polyamide itself is added to the fat and oil added together with the waste, amine is generated by the thermal decomposition of the polyamide resin in the chemical thermal decomposition step,
This amine can increase the decomposition amount and decomposition rate of waste in the heating step.

The polyamide resin added to the fats and oils has a resin portion of 100% and a polyamide portion of 10% to 50%.
%, Preferably about 20%, and the temperature condition is in the range of 330 ° C. to 370 ° C., in which the waste of olefinic resin is on the high temperature side of 350 ° C. to 370 ° C., while polyester, For condensation waste such as polyurethane and polyamide, the low temperature side of about 330 ° C is applied and the reaction time is assumed to be within about 3 hours.
For example, in the case of waste products made of polycarbonate resin or ABS resin, both the amount of decomposition and the decomposition rate can be increased by about 5 to 8 times. Further, in the case of waste made of polyethylene-based resin or polypropylene-based resin, both the amount of decomposition and the decomposition rate can be increased by 2 to 5 times. In addition, conventionally, for example, hard polycarbonate deposits are generated on the reactor wall at 330 ° C. to 350 ° C., but according to the present invention, such coking, that is, deposition of coke substances is completely eliminated.

[Brief description of drawings]

FIG. 1 is a flowchart showing a waste recycling process according to an embodiment of the present invention.

[Explanation of symbols]

1 waste recycling process 2 Addition process of fats and oils to waste 3 heating process 4 Specific gravity / centrifugation process 5 Chemical pyrolysis process 5 6 Distillation separation process

Claims (8)

[Claims] 1. Addition of fats and oils to a waste of a composite material of a synthetic resin product and a synthetic fiber, such as a synthetic resin product or a printed wiring board FRP, which has been subjected to plating treatment, and a solvated thermal decomposition reaction at high temperature is utilized. Can be reused by chemical pyrolysis process in which synthetic resin part of waste is pyrolyzed and liquefied to separate insoluble parts such as metals and inorganic substances, and liquid part separated by chemical pyrolysis process is decompressed (vacuum) distillation A method for recycling waste, comprising a distillation separation step of separating a light oil portion and a heavy oil portion. 2. The waste recycling method according to claim 1, wherein the fat or oil is a heavy oil for waste food such as fatty acid glyceride. 3. The heavy oil portion produced by the distillation separation step can be used as an improving agent such as asphalt or an adhesive, or a resin component such as a paint or an ink.
Or the waste recycling method described in 2. 4. The method of recycling waste according to claim 1, wherein the light oil portion produced by the distillation separation step can be used as an additive for heating fuel or cutting oil. 5. Waste is polycarbonate resin / AB
The waste according to any one of claims 1 to 4, which is a mixed plastic in which impurities such as metals and inorganic fibers are mixed in S resin, polyamide resin, polyurethane resin, unsaturated polyester resin, polyester resin, polyurethane resin and the like. Recycling method. 6. The waste recycling method according to any one of claims 1 to 5, wherein a polyamide resin is added and used as the waste that is added together with the addition of the oil and fat in the chemical pyrolysis step. 7. The method according to claim 1, wherein the waste of the polyamide-based resin collected separately from the waste or the polyamide itself separated as a waste product is added to the oil and fat to be added together with the waste. How to recycle waste. 8. The polyamide-based resin added to fats and oils is
Resin portion is 100% and polyamide portion is 10% to 5
In the range of 0%, preferably about 20%, and the temperature condition is in the range of 330 ° C to 370 ° C, of which the waste of olefinic resin is on the high temperature side of 350 ° C to 370 ° C while the polyester is The waste recycling method according to claim 6 or 7, wherein a low temperature side of about 330 ° C is applied to condensation waste such as polyurethane and polyamide, and a reaction time is within about 3 hours.