KR20190131208A - Apparatus comprising pyrolysis-products seperator for recycling mixture of plastics comprising polyvinyl chloride and method for recycling mixture of plastics comprising polyvinyl chloride using the same - Google Patents

Abstract

Disclosed by an embodiment of the present invention are: equipment for recycling a polyvinyl chloride (PVC)-containing plastic mixture including a pyrolytic separator; and a method for recycling a PVC-containing plastic mixture using the same. According to an embodiment of the present invention, the equipment for recycling a plastic mixture including polyvinyl chloride: maximizes HCI recovery by removing chlorine from PVC as much as possible through a pyrolytic separator before pyrolyzed products of a PVC-containing plastic mixture generated from an auger reactor enters a fluidized bed reactor; and is able to produce oil with a greatly reduced chlorine content by sending dechlorinated waste plastic fractions to the fluidized bed reactor, performing pyrolysis, and finally filtering through a high temperature filter filled with calcium oxide. The present invention can minimize the amount of auger reactor products which are difficult to process and at the same time, induce an effect of maximizing products from the fluidized bed reactor by separating products (wax) generated in the auger reactor from the flow of products of the auger reactor by using the pyrolytic separator during the above process, and sending the products to the fluidized bed reactor.

Description

APPARATUS COMPRISING PYROLYSIS-PRODUCTS SEPERATOR FOR RECYCLING MIXTURE OF PLASTICS COMPRISING POLYVINYL CHLORIDE AND METHOD FOR RECYCLING MIXTURE OF PLASTICS COMPRISING POLYVINYL CHLORIDE USING THE SAME}

Disclosed herein is an apparatus for recycling a polyvinyl chloride containing plastic mixture comprising a pyrolyte separator and a method of recycling a polyvinyl chloride containing plastic mixture using the same.

In Korea, about 4 million tons of waste plastics are generated every year, but the recycling rate is low at 20-30%, and a large amount is disposed of by landfill or incineration. However, the landfill of waste plastics may be eluted with harmful components, and the problems of storage, transportation, and landfilling arise due to their large volume compared to the unit weight. In addition, the treatment by incineration can utilize some of the thermal energy generated by incineration, but it causes a lot of economic losses and releases toxic gases, which causes environmental problems, so there is a social interest in recycling waste plastics. It is rising.

Waste plastic is mainly processed by energy recovery (Energy Recovery) to recover the heat of combustion, for this purpose is molded into a plastic fuel (RPF, Refuse Plastic Fuel) is injected into. Another waste plastic treatment method is recycling. The recycling method of waste plastics is mainly performed by mechanical recycling method in which waste plastic is melted at about 300 ° C. to make pellets or granules of regenerated particles. It is divided into Feedstock Recycling, which converts plastics into the ingredients required to make other compounds. Among them, the mechanical recycling method, the physical properties of the product produced by the process is dropped every time the mechanical recycling is repeated, the feedstock recycling method is preferred as the final recycling method. Feedstock recycling methods are divided into pyrolysis, gasification, hydrogenation, and solvation, and pyrolysis is the most actively studied. Pyrolysis oil produced from waste plastic through pyrolysis is introduced into a petroleum refining process and used as a raw material for new chemicals or fuels.

Pyrolysis is one of the feedstock recycling methods. It is an environmentally friendly waste plastic recycling method that thermally decomposes waste plastic under anoxic to produce oil, gas, and solid product, char. The success of pyrolysis of waste plastics is directly related to the removal of chlorine or chlorine compounds. Waste plastics generated in the city are mixed with polyvinyl chloride (PVC), and chlorine compounds (HCl, etc.) generated during the pyrolysis of PVC cause corrosion of the process during pyrolysis, and the lifetime of the incineration plant when the pyrolysis oil containing them is burned. It causes shortening and causes dioxins.

It has been found to date that waste plastic solid fuels are known to contain some chlorine or chlorine compounds. In the case of RPF, the average chlorine content in RPF was about 0.87 wt.% Based on the samples from the Korea Mechanical Research Institute from 2008 to 2010 (New & Renewable Energy 2016. 12 Vol 12, No. 4).

In foreign countries, the standard content of chlorine in RPF is strictly determined. Especially in the UK, waste-derived solid fuel is divided into three grades according to the chlorine content and the maximum allowable value is 0.8 wt% (Standard BS EN 15359). .

Classification property Unit Class 1 Class 2 Class 3 Class 4 Class 5 Chlorine content (dry) % (wt / wt) (mean) ≤0.2 ≤0.6 ≤0.8 - -

For this reason, it is essential for the pyrolysis of waste plastics to develop a method for controlling chlorine compounds generated during the pyrolysis of waste plastics containing PVC and finally reducing the chlorine content of pyrolysis oil. However, there have been no reported cases of reducing chlorine to a satisfactory level in pyrolysis oil of waste plastic. It is known that pyrolysis oil prepared by pyrolyzing waste plastic containing PVC in Korea contains about 10,000 ppm or more of chlorine. In order to make practical use of waste plastic pyrolysis oil, chlorine content in oil should be less than 10 ppm, and no pyrolysis oil with chlorine content within this value has been produced (Energy Conversion and Management 115 (2016) 308-326). ).

Thus, the present inventors have introduced a technique for reducing the chlorine content from pyrolysis oil through Patent Application No. 10-2018-0016972, but the pyrolysis of PVC-containing plastic in the auger reactor is not sufficiently achieved, the chlorine reduction effect is The limitation was found to be not large and the present invention was completed.

KR 10-0748624 B1

In one aspect, an object of the present invention is to maximize the recovery of HCl by maximizing the generation of chlorine-containing material in the auger reactor and then sending the generated chlorine-containing material to the auger reactor outlet.

In one aspect, an object of the present invention is to minimize the content of the auger reactor product except HCl by injecting the wax generated in the auger reactor to the fluidized bed as possible.

In one aspect, an object of the present invention is to significantly reduce the content of chlorine in oil obtained by pyrolyzing waste plastic in a fluidized bed reactor to 10 ppm or less.

In one aspect, an object of the present invention is to prepare an oil containing a high content of aromatic compounds from waste plastics.

In one aspect, an object of the present invention is to prepare an oil free of wax from waste plastics.

In one aspect, the present invention, the pyrolysis reactor; And a pyrolyse separator, wherein the pyrolyse separator comprises: a separator in which pyrolysates introduced from the pyrolysis reactor collide; And a baffle that collides with the separator and induces a downward flow of the separated pyrolysis product. Provided is an apparatus for recycling a plastic mixture comprising polyvinyl chloride, comprising a baffle for separating wax present in an upward flow in a pyrolyte separator.

In the aspect as described above, the present invention, the thermal decomposition product that collides with the separator is seated on one end of the baffle located at the bottom of the separator flows to the other end, the baffle is inclined downward from the one end to the other end And so that the wax remaining in the upstream once passed through the baffle may again collide, such that the wax collides downwardly by a group of baffles attached to the separator, which impedes upflow in the pyrolyte separator. Provided is an apparatus for recycling a plastic mixture comprising polyvinyl chloride, comprising another baffle attached on top of the baffle.

In the above aspect, the present invention, the baffle includes a plurality of baffles spaced apart from each other and disposed up and down, the baffle located at the bottom of the separator is a first baffle; And a second baffle positioned below the first baffle, wherein the pyrolysate is seated at one end of the first baffle and flows to the other end of the first baffle, and the pyrolysate introduced from the other end of the first baffle is It is seated on one end of the second baffle, flows to the other end of the second baffle, and the wax present in the upstream in the pyrolyte separator collides and flows downward by one end of the baffle attached to the separator. Provided is an apparatus for recycling a plastic mixture comprising polyvinyl chloride flowing downwards when the wax remaining in one upstream impinges another baffle on the one baffle.

In the above aspect, the present invention, the reactor, auger reactor; And a fluidized bed reactor, the apparatus for recycling a plastic mixture comprising polyvinyl chloride.

In this aspect, the invention comprises a polyvinyl chloride, the apparatus comprising an auger reactor, a pyrolyte separator and a fluidized bed reactor, comprising an auger reactor, a pyrolyte separator and a fluidized bed reactor in series. It provides a device for recycling the plastic mixture.

In the above aspect, the present invention, the temperature of the auger reactor is 280 ~ 400 ℃, the temperature of the pyrolyte separator is 300-500 ℃, the temperature of the fluidized bed reactor is 680 ~ 750 ℃, polyvinyl chloride Provided is an apparatus for recycling a containing plastic mixture.

In this aspect, the invention further comprises a hot filter group filled with calcium oxide or calcium hydroxide, the apparatus being connected in series with an auger reactor, a pyrolyte separator, a fluidized bed reactor and The high temperature filter comprising one provides an apparatus for recycling of a plastic mixture comprising polyvinyl chloride, which is located behind a fluidized bed reactor.

In this aspect, the present invention provides an apparatus for recycling a plastic mixture comprising polyvinyl chloride, wherein the content of PVC in the plastic mixture is 4% by weight or less, based on the total weight of the plastic mixture.

In the above aspect, the present invention provides a device for recycling the plastic mixture comprising polyvinyl chloride, the temperature of the high temperature filter is 400 ~ 700 ℃.

In the above aspect, the present invention, the high temperature filter provides a device for recycling the plastic mixture comprising polyvinyl chloride, comprising at least one of calcium oxide and calcium hydroxide heat-treated at 850 ~ 1000 ℃.

In this aspect, the present invention provides an apparatus for recycling a plastic mixture comprising polyvinyl chloride, wherein the plastic mixture comprises waste plastic.

In another aspect, the present invention provides a method for recycling a plastic mixture comprising polyvinyl chloride using the apparatus.

An apparatus for recycling a plastic mixture comprising polyvinyl chloride, which is an aspect of the present invention, includes chlorine from PVC through a pyrolyte separator before the pyrolysate of the PVC-containing plastic mixture from the auger reactor is introduced into the fluidized bed reactor. HCl recovery is maximized by maximal removal, the dechlorinated waste plastic fractions are sent to a fluidized bed reactor and pyrolyzed and finally filtered through a high temperature filter filled with calcium oxide to produce an oil having a significantly reduced chlorine content. In addition, the product (wax) produced in the auger reactor during this process is separated from the auger reactor product stream using a pyrolysis separator and sent to the fluidized bed reactor, minimizing the amount of auger reactor product that is difficult to process due to impurities, and at the same time from the fluidized bed reactor. It can induce the effect of maximizing the product.

1 is a schematic diagram of a system for recycling a plastic mixture comprising polyvinyl chloride according to one aspect of the present invention.
2 is a schematic diagram of a reactor and pyrolyte separator included in the apparatus of the present invention.
3 is a block diagram of a recycling system of a plastic mixture including an apparatus for recycling a plastic mixture including polyvinyl chloride according to an aspect of the present invention.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

The terms or words used in the specification and claims of the present invention are not to be construed in a conventional or dictionary sense, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way. Based on the principle, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.

Throughout the specification of the present invention, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated. .

In the specification of the present invention, "A and / or B" means A or B, or A and B.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited thereto.

In one aspect, the present invention provides an apparatus for recycling a plastic mixture comprising polyvinyl chloride (PVC), the apparatus comprising: a pyrolysis reactor; And a pyrolyte separator,

The pyrolyte separator may include a separator in which pyrolysates introduced from the pyrolysis reactor collide with each other; And a baffle that collides with the separator and induces a downward flow of the separated pyrolysis product.

The pyrolyte separator may be for effectively reducing chlorine from the pyrolysate of the PVC-containing plastic mixture introduced from the pyrolysis reactor, preferably the auger reactor, and effectively transferring the wax to a subsequent pyrolysis step, such as a fluidized bed reactor.

The operating principle of the pyrolyte separator is as follows. The pyrolysate introduced from the pyrolysis reactor primarily collides with the separator of the pyrolyte reactor by the flow pressure. After the collision, the chlorine-containing gas, such as hydrogen chloride, present in the pyrolysate moves to the upper layer of the pyrolyte separator, is discharged from the pyrolyte reactor through a separate gas outlet, and has a liquid phase of pyrolysate ( The melt flows downward through a baffle arranged so that the melt flows downward.

In one embodiment, the pyrolyte separator has a temperature condition that allows the melt flowing in the separator to pyrolyze so that it can again pyrolyze the pyrolyte (melt) once again while flowing through the baffle. Therefore, chlorine-containing gas such as hydrogen chloride generated from the melt flowing through the baffle may be separated and lifted from the melt and discharged through a separate gas outlet. At this time, the ascending fluid such as gas is disturbed by the collision with the baffle located relatively above, and the wax or the like contained in the ascending fluid is a melt flow formed in the baffle. It can be incorporated into.

Based on the operation principle as described above, the baffle may include a slope inclined downward from the one end to the other end so that the thermal decomposition product separated by collision with the separator flows to the other end by seating on one end of the baffle.

In addition, the baffle may include a plurality of baffles spaced apart from each other and arranged up and down, specifically, the baffle may include a first baffle; And a second baffle positioned below the first baffle, wherein the pyrolysate is seated on one end of the first baffle and flows to the other end of the first baffle, and pyrolysis introduced from the other end of the first baffle. Water may be seated on one end of the second baffle and flow to the other end of the second baffle.

The first baffle and the second baffle may be preferably arranged such that the pyrolysate flowing from the first baffle may be transferred to the second baffle in total, and specifically, one end of the first baffle and the second baffle may be It may be in close contact with the wall of the pyrolyte separator, and the other end of the first baffle opposite to the one in close contact with the pyrolyte separator may be one inclined downward to induce a downward flow of the pyrolyte, and the first baffle Pyrolysate introduced from the other end of the may be disposed to be seated on one end of the second baffle located relatively lower than the first baffle.

The first baffle or the second baffle may also be located on one side of the separator, preferably on the side opposite to the side on which the fluid flows from the pyrolysis reactor (see FIG. 1).

In addition, in one aspect, the pyrolysis reactor may comprise one or more of an auger reactor and a fluidized bed reactor, preferably may comprise both an auger reactor and a fluidized bed reactor.

In one embodiment, the apparatus may comprise an auger reactor, a pyrolyte separator and a fluidized bed reactor, and may comprise an auger reactor, a pyrolyte separator and a fluidized bed reactor in series.

In the above embodiment, the pyrolysate (primary pyrolysis product) of the PVC-containing plastic mixture, which is primarily pyrolyzed from the auger reactor, is introduced into the pyrolyte separator to remove the chlorine component remaining in the pyrolysate, and then the fluidized bed May be introduced into the reactor.

Fractions (such as pyrolysis products via pyrolyte separators), such as plastic mixtures with reduced chlorine content, are fed directly into the fluidized bed reactor by a screw feeder at the bottom of the pyrolyte separator.

Fluidized bed reactors require fluidized gases, which may be inert gases, gases produced and discharged in the apparatus, in particular non-condensed gases discharged from fluidized bed reactors, or mixtures thereof.

The fluidized bed reactor may include an outlet (not shown) through which the generated product is discharged.

In the fluidized bed reactor, pyrolysis 인, which is a solid in the pyrolysis product discharged, is collected by a cyclone and then passed through a CaO-filled high temperature filter. At this time, HCl in the pyrolysis gas reacts with CaO to convert into CaCl ₂ and water, and the pyrolysis gas is collected into oil through cooling and condensation with Cl reduced. Uncondensed gas can be used as a fluidized medium.

The apparatus for recycling the plastic mixture including PVC may further include a temperature control device (not shown), wherein the temperature control device is filled with the auger reactor, the pyrolyte separator, the fluidized bed reactor and the calcium oxide. It is desirable to be able to change the temperature of each of the high temperature filters independently. The temperature control device may include a temperature detector, a temperature controller, and a heater.

3, the plastic recycling system according to an embodiment of the present invention is a device for recycling PVC-containing plastic mixture 100, plastic mixture supply system 600, pyrolysis and separation system 700, quenching system 800, 800 ′, impact separators 900, 900 ′, electrostatic precipitators 1000, 1000 ′, and gas circulation systems (not shown).

Meanwhile, the content of PVC in the plastic mixture may be 1% by weight or more based on the total weight of the plastic mixture. Specifically, the content of the PVC, based on the total weight of the plastic mixture, may be 1 to 4% by weight, more specifically, 1 to 2% by weight.

In this regard, the content of PVC in the plastic mixture is based on the amount of PVC present in the municipal waste plastics, and in 2010, 2.4-4.0 wt% of PVC is known to be present in mixed waste plastics (mixed waste plastic resources). A Study on the Development of Specific Gravity Separation System, Jae-myung Ryu, 2010.) With the development of plastic sorting technology, the PVC content is decreasing and many recent studies have set the PVC content target of 0.35 wt%.

In the auger reactor, the first pyrolysis of the PVC containing plastic mixture is carried out. The internal temperature of the auger reactor may be about 280 ~ 400 ℃.

In one aspect, in the pyrolyte separator, the PVC-containing pyrolysate pyrolyzed first in the auger reactor may be pyrolyzed again. The temperature of the pyrolyte separator is 300-500 ° C.

In the fluidized bed reactor, the PVC containing plastic mixture pyrolyzed in the auger reactor and pyrolyte separator can be pyrolyzed again. In the above aspect, the internal temperature of the fluidized bed reactor may be 680 ~ 750 ℃, preferably, 700 ~ 750 ℃, more preferably, may be 700 ~ 720 ℃.

In addition, the operating temperature of the high temperature filter may be 400 ~ 700 ℃, preferably 600 ~ 700 ℃.

The high temperature filter may include at least one of granule-type calcium oxide (burnt lime) and calcium hydroxide heat-treated at 850 ~ 1000 ℃.

In one embodiment, when the finely divided calcium oxide or calcium hydroxide other than the heat-treated calcium oxide or calcium hydroxide at the temperature is used, the differential pressure in the reactor occurs, the process operation efficiency may be reduced.

In one aspect, the plastic mixture may comprise waste plastic containing PVC. In addition, the plastic mixture including the PVC further includes at least one of polyethylene terephthalate (PET), high density polyethylene (HDPE), low density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) in addition to PVC. It can mean a mixture of.

In one aspect, the pyrolysis oil in the product produced by the device may be wax free.

In the present specification, the term wax refers to hydrocarbons having 19 or more carbon atoms (Predel et al., Polymer Degradation and Stability 70 (3), p 373-385, 2000).

In addition, in one aspect, the content of chlorine in the oil of the product produced by the device may be less than 50ppm (w / w).

The chlorine content in the oil in the product produced by the device is significantly less than 10,000 ppm, the pyrolysis oil chlorine content known to date.

In one embodiment, the auger reactor and the fluidized bed reactor may be connected in series.

In one aspect, the invention is a method for recycling a plastic mixture comprising polyvinyl chloride (PVC) using the apparatus.

The method may be for reducing the content of chlorine in pyrolysis oil produced from a plastic mixture comprising polyvinyl chloride (PVC).

In one aspect, the method includes a first pyrolysis step of pyrolysing a plastic mixture comprising PVC in an auger reactor; A pyrolyte separation step of removing chlorine from the pyrolysate pyrolyzed in the auger reactor; A second pyrolysis step of pyrolyzing in a fluidized bed reactor; And filtering the pyrolysis vapor of the PVC plastic mixture pyrolyzed in the fluidized bed reactor in a high temperature filter filled with calcium oxide or calcium hydroxide.

In one embodiment, the first pyrolysis step may be performed at 280 ~ 400 ℃. In addition, the temperature of the pyrolyte separator is 300 ~ 500 ℃, the second pyrolysis step, may be carried out at 680 ~ 750 ℃, preferably, 700 ~ 750 ℃, more preferably, 700 ~ 720 ℃ It can be performed in.

The high temperature filter filled with calcium oxide may be operated at 400 ° C to 700 ° C, and preferably at 600 ° C to 650 ° C.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Test Examples. However, these examples and test examples are provided only for the purpose of illustration in order to help the understanding of the present invention is not limited to the scope and scope of the present invention by the following examples.

100: apparatus for recycling of plastic mixtures comprising polyvinyl chloride (PVC)
200: auger reactor
300: pyrolyte separator
400: fluidized bed reactor
500: CaO filled high temperature filter
600: plastic mixture supply system
610, 620: screw feeder
700: pyrolysis and separation system
710: silo, 720: CaO filled high temperature filter
800, 800 ': quenching system
900, 900 ': Impact separator
1000, 1000 ': electrostatic precipitator

Claims (12)

An apparatus for recycling a plastic mixture comprising polyvinyl chloride (PVC),
The device,
Pyrolysis reactor; And a pyrolyte separator,
The thermal decomposition product separator,
A separator in which pyrolysis products introduced from the pyrolysis reactor collide; And
And a baffle that collides with the separator to induce a downward flow of the separated pyrolyte. The method of claim 1,
Pyrolysates separated by collision with the separator are seated on one end of the baffle and flow to the other end,
And the baffle comprises one inclined downward from one end to the other end. The method of claim 1,
The baffle includes a plurality of baffles spaced apart from each other and arranged up and down,
The baffle comprises a first baffle; And a second baffle positioned below the first baffle,
The pyrolysate is seated on one end of the first baffle and flows to the other end of the first baffle,
The pyrolysate introduced from the other end of the first baffle is seated at one end of the second baffle, and flows to the other end of the second baffle, the apparatus for recycling the plastic mixture comprising polyvinyl chloride. The method of claim 1,
The reactor, auger reactor; And at least one of a fluidized bed reactor. The method of claim 4, wherein
The apparatus comprises an auger reactor, a pyrolyte separator and a fluid bed reactor,
Apparatus for recycling a plastic mixture comprising polyvinyl chloride, comprising serially connected auger reactor, pyrolyte separator and fluidized bed reactor. The method of claim 1,
The temperature of the auger reactor is 280 ~ 400 ℃, the temperature of the pyrolyte separator is 300-500 ℃,
Apparatus for recycling the plastic mixture comprising polyvinyl chloride, the temperature of the fluidized bed reactor is 680 ~ 750 ℃. The method of claim 1,
The apparatus further comprises a hot filter group filled with at least one of calcium oxide and calcium hydroxide,
The apparatus is a device for recycling of a plastic mixture comprising polyvinyl chloride, wherein the high temperature filter comprising an auger reactor, a pyrolyte separator, a fluid bed reactor and serially connected in sequence is located behind the fluid bed reactor. The method of claim 1,
The content of PVC in the plastic mixture,
An apparatus for recycling a plastic mixture comprising polyvinyl chloride, wherein the plastic mixture is at most 4% by weight, based on the total weight of the plastic mixture. The method of claim 7, wherein
Apparatus for recycling the plastic mixture containing polyvinyl chloride, the temperature of the high temperature filter filled with calcium oxide is 400 ~ 700 ℃. The method of claim 7, wherein
The high temperature filter filled with the calcium oxide,
An apparatus for recycling a plastic mixture comprising polyvinyl chloride, comprising at least one of calcium oxide and calcium hydroxide heat treated at 850-1000 ° C. The method of claim 1,
And said plastic mixture comprises waste plastic. A process for recycling a plastic mixture comprising polyvinyl chloride (PVC) using the apparatus of claim 1.

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