KR102123842B1 - 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 herein is an apparatus for recycling a polyvinyl chloride-containing plastic mixture including a pyrolysate separator and a method for recycling a polyvinyl chloride-containing plastic mixture using the same. An apparatus for recycling of a plastic mixture containing polyvinyl chloride, which is an aspect of the present invention, is used to remove chlorine from PVC through a pyrolysate separator before the pyrolysate of the PVC-containing plastic mixture generated from the auger reactor is introduced into the fluidized bed reactor. To maximize the recovery of HCl by removing as much as possible, the dechlorinated waste plastic fraction is sent to a fluidized bed reactor for thermal decomposition and finally filtered through a high temperature filter filled with calcium oxide to produce an oil with a significantly reduced chlorine content. Also, during this process, the product (wax) produced in the auger reactor is separated from the auger reactor product flow by using a pyrolysis separator and sent to the fluidized bed reactor, thereby minimizing the amount of auger reactor products that are difficult to process and simultaneously maximizing the product from the fluidized bed reactor. Can induce effects.

Description

Apparatus for recycling of polyvinyl chloride-containing plastic mixtures containing a pyrolysis separator and methods of recycling of polyvinyl chloride-containing plastic mixtures using the same. PLASTICS COMPRISING POLYVINYL CHLORIDE USING THE SAME}

Disclosed herein is an apparatus for recycling a polyvinyl chloride-containing plastic mixture including a pyrolysate separator and a method for recycling a polyvinyl chloride-containing plastic mixture using the same.

In Korea, about 4 million tons of waste plastics are generated annually, but the recycling rate is low at 20 to 30%, and a large amount is processed by landfill or incineration. However, the waste plastics may be filled with hazardous components, and bulky compared to the unit weight causes problems in storage, transportation, and landfill. In addition, the treatment by incineration can use some of the thermal energy generated during incineration, but it causes a lot of economical losses and releases toxic gases, causing environmental damage, so there is social interest in how to recycle waste plastics. It is increasing.

The waste plastic is mainly treated by an energy recovery method for recovering combustion heat, and for this purpose, it is molded and injected into solid fuel, Refuse Plastic Fuel (RPF). Another method of recycling waste plastics is recycling. Mechanical recycling is a method of recycling waste plastics by melting and recycling waste plastics around 300°C to make pellets or granules of recycled particles. It is divided into the method of feedstock recycling, which converts from plastics to the ingredients necessary for the production of other compounds. Among them, the mechanical recycling method, the physical properties of the product produced by the process is dropped whenever the mechanical recycling is repeated, the feedstock recycling method is preferred as the final recycling method. The method of recycling feedstock is largely divided into pyrolysis, gasification, hydrogenation, and sovolysis. Among them, pyrolysis is the most actively studied. Pyrolysis oil manufactured from waste plastics through pyrolysis is put 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 plastics under anaerobic to produce oil, gas, and char, a solid product. The success or failure of pyrolysis of waste plastics is directly related to the removal of chlorine or chlorine compounds. PVC (polyvinyl chloride) is mixed in the waste plastics generated in the city, and chlorine compounds (HCl, etc.) produced during PVC pyrolysis cause corrosion of the process during pyrolysis, and when burning pyrolysis oil containing it, life of the incineration plant It causes shortening and causes dioxins.

It has been found to date that waste plastic solid fuel contains some amount of chlorine or chlorine compounds. In the case of RPF, the average chlorine content in RPF was found to be about 0.87 wt.% in Korea as a result of measurement on samples from Korea Mechanical Research Institute from 2008 to 2010 (New & Renewable Energy 2016. 12 Vol 2016 12, No. 4).

In the case of foreign countries, the standard content of chlorine in the RPF is strictly defined. In particular, in the UK, the solid fuel derived from waste is divided into three classes according to the content of chlorine, 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 to thermally decompose waste plastics by developing a method to control the chlorine compounds produced during thermal decomposition of waste plastics containing PVC and to finally reduce the chlorine content of pyrolysis oil. However, there have been no reports of the results obtained by reducing chlorine to a satisfactory level in pyrolysis oil of waste plastics. It is known that pyrolysis oil produced by pyrolysis of waste plastics containing PVC in Korea contains more than about 10,000 ppm of chlorine. In order to be able to practically use the waste plastic pyrolysis oil, the chlorine content in the oil must be less than 10 ppm, but the production of pyrolysis oil having a chlorine content within this value has not been achieved (Energy Conversion and Management 115 (2016) 308-326 ).

Thus, the present inventor has introduced a technique for reducing chlorine content from pyrolysis oil through patent application No. 10-2018-0016972, but does not sufficiently decompose PVC-containing plastics in the auger reactor, thereby reducing chlorine. The limitation of not being large was discovered, and the present invention was completed.

KR 10-0748624 B1

In one aspect, the object of the present invention is to generate the maximum amount of chlorine-containing material in the auger reactor, and then send the generated chlorine-containing material to the auger reactor outlet to recover HCl to the maximum.

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

In one aspect, the object of the present invention is to significantly reduce the content of chlorine in oil obtained by thermal decomposition of waste plastics 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, the object of the present invention is to prepare an oil free of wax from waste plastics.

In one aspect, the present invention, a pyrolysis reactor; And a pyrolysate separator, wherein the pyrolysate separator comprises: a separator in which pyrolysate introduced from the pyrolysis reactor collides; And a baffle colliding with the separator to induce downward flow of the separated pyrolysis products. An apparatus for recycling a plastic mixture comprising polyvinyl chloride, comprising a baffle separating wax present in an upward stream in a pyrolysate separator.

In the above aspect, the present invention, the thermal decomposition product separated by collision with the separator is seated at one end of the baffle located at the bottom of the separator and flows to the other end, so that the baffle is inclined downward from the one end to the other end Containing, to prevent the upward flow in the pyrolysate separator, the wax collides with the baffle attached to the separator and flows downward, so that the remaining wax in the upward flow through the baffle can collide once again. An apparatus for recycling of 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 vertically, and the baffles located at the bottom of the separator are first baffles; And a second baffle located under the first baffle, wherein the thermal decomposition product is seated at one end of the first baffle and flows to the other end of the first baffle, and the thermal decomposition product introduced from the other end of the first baffle is Seated at one end of the second baffle, flows to the other end of the second baffle, and the wax present in the upward flow in the pyrolysate separator collides and flows downward, and passes through the one end of the baffle by one end of the baffle attached to the separator. Provided is an apparatus for recycling a plastic mixture comprising polyvinyl chloride, which flows downward by impacting the wax remaining in one upward stream onto another baffle on the 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 the above aspect, the present invention, the apparatus comprises a polyvinyl chloride, comprising an auger reactor, a pyrolysate separator and a fluidized bed reactor, and in series connection of the auger reactor, the pyrolysate separator and the fluidized bed reactor It provides a device for recycling the plastic mixture.

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

In the above aspect, the present invention, the apparatus further comprises a hot filter (hot filter) filled with calcium oxide or calcium hydroxide, the high temperature filter, the plastic mixture containing polyvinyl chloride, located behind the fluidized bed reactor It provides a device for recycling.

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

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

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

In the aspect as described above, the present invention, the plastic mixture, the waste plastic, comprising a polyvinyl chloride containing a plastic mixture for recycling apparatus.

In addition, in one aspect, the present invention provides a method of recycling a plastic mixture containing polyvinyl chloride using the device.

An apparatus for recycling of a plastic mixture containing polyvinyl chloride, which is an aspect of the present invention, is used to remove chlorine from PVC through a pyrolysate separator before the pyrolysate of the PVC-containing plastic mixture generated from the auger reactor is introduced into the fluidized bed reactor. To maximize the recovery of HCl by removing as much as possible, the dechlorinated waste plastic fraction is sent to a fluidized bed reactor for thermal decomposition and finally filtered through a high temperature filter filled with calcium oxide to produce an oil with a significantly reduced chlorine content. Also, during this process, the product (wax) produced in the auger reactor is separated from the product flow of the auger reactor using a pyrolysis separator and sent to the fluidized bed reactor to minimize the amount of auger reactor products that are difficult to process due to impurities and the like. It can induce the effect of maximizing the product.

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

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

The terms or words used in the specification and claims of the present invention are not to be construed as being limited in a conventional or lexical sense, and the inventor can appropriately define the concept of terms to describe his or her invention in the best way. Based on the principles, it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

Throughout the specification of the present invention, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless specifically stated otherwise. .

In the entire 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 is an apparatus for recycling of a plastic mixture containing polyvinyl chloride (PVC), the apparatus comprising: a pyrolysis reactor; And a pyrolysate separator,

The pyrolysate separator includes a separator in which pyrolysate introduced from the pyrolysis reactor collides; And a baffle colliding with the separator to induce a downward flow of the separated pyrolysate, and recycling of the plastic mixture containing polyvinyl chloride.

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

The principle of operation of the pyrolysate separator is as follows. The pyrolysis product introduced from the pyrolysis reactor collides primarily with the separator of the pyrolysis reactor by the flow pressure. After the collision, the chlorine-containing gas present in the thermal decomposition product, such as hydrogen chloride, moves to the upper portion of the thermal decomposition separator, and is discharged from the thermal decomposition reactor through a separately provided gas outlet, and a liquid material having liquid properties in the thermal decomposition product ( The melt) flows downward through a baffle arranged so that the melt can flow downward.

In one embodiment, the pyrolysate separator may be thermally decomposed of the pyrolysate (melt) once again while having a temperature condition in which the melt flowing in the separator can be pyrolysed. Accordingly, chlorine-containing gas such as hydrogen chloride generated from the melt flowing through the baffle can be separated and raised from the melt, and discharged through a separate gas outlet. At this time, the rising fluid, such as gas, is impeded by the collision with the baffle located at the upper part, and the wax or the like contained in the rising fluid flows in the form of a melt formed in the baffle. Can be incorporated in.

On the basis of the above operating principle, the thermal decomposition product separated by collision with the separator may be seated at one end of the baffle and flow to the other end, so that the baffle may include an inclined downward direction from the one end to the other end.

In addition, the baffles may include a plurality of baffles spaced apart from each other and disposed vertically, and specifically, the baffles may include a first baffle; And a second baffle located under the first baffle, wherein the thermal decomposition product is seated at one end of the first baffle and flows to the other end of the first baffle, and the thermal decomposition introduced from the other end of the first baffle. Water may be settled at one end of the second baffle and flow to the other end of the second baffle.

The first baffle and the second baffle, preferably, may be disposed so that the total amount of thermal decomposition products flowing from the first baffle can be transferred to the second baffle, specifically, one end of the first baffle and the second baffle, respectively The thermal decomposition separator may be in close contact with the wall surface, and one end of the first baffle that is in close contact with the thermal decomposition separator may be inclined downward to induce a downward flow of the thermal decomposition product, and the first baffle The thermal decomposition product flowing from the other end of the may be disposed to be seated at one end of the second baffle positioned relatively lower than the first baffle.

In addition, the first baffle or the second baffle may be located on one side of the separator, preferably, on the opposite side of the side where the fluid flows from the pyrolysis reactor (see FIG. 1 ).

Further, in one aspect, the pyrolysis reactor may include at least one of an auger reactor and a fluidized bed reactor, and preferably may include both an auger reactor and a fluidized bed reactor.

In one embodiment, the apparatus may include an auger reactor, a pyrolysate separator and a fluidized bed reactor, and may include those connected in series in the order of the auger reactor, the pyrolysate separator and the fluidized bed reactor.

In the above embodiment, a pyrolysate (primary pyrolysis product) of the PVC-containing plastic mixture primarily pyrolized from the auger reactor is introduced into the pyrolysate separator, and after removing the chlorine component remaining in the pyrolysis product, the fluidized bed It can be introduced into the reactor.

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

The fluidized bed reactor requires a fluidized gas, and the fluidized gas may be an inert gas, gas generated and discharged from the apparatus, in particular, non-condensed gas discharged from the fluidized bed reactor, or a mixed gas thereof.

The fluidized bed reactor may be to include a discharge portion (not shown) through which the produced product is discharged.

In the fluidized bed reactor, pyrolysis 촤, which is a solid in the pyrolysis product discharged through pyrolysis, is collected by a cyclone, and then passed through a high temperature filter filled with CaO. At this time, HCl in the pyrolysis gas reacts with CaO to convert to CaCl ₂ and water, and the pyrolysis gas is collected as an oil through a cooling and condensation process while reducing Cl. Gas that is not condensed can be used as a fluid medium.

The apparatus for recycling the plastic mixture containing PVC may further include a temperature control device (not shown), wherein the temperature control device is filled with the auger reactor, the pyrolysate separator, the fluidized bed reactor, and the calcium oxide. It is preferable that the temperature of each of the high temperature filters can be changed independently. The temperature control device may include a temperature detection unit, a temperature control unit, and a heating unit.

Referring to Figure 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 분해 separation system (700), ?? Systems (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 relation to this, the content of PVC in the plastic mixture is based on the PVC content present in the living waste plastics, and it is known in Korea that 2.4-4.0 wt% of PVC is present in the mixed waste plastics in 2010 (mixed waste plastics resource A Study on the Development of Specific Gravity Selection System, Jae-Ryu Ryu, 2010.). With the development of plastic classification technology, the PVC content is gradually decreasing, and many recent studies have set the PVC content target to 0.35 wt%.

In the auger reactor, primary pyrolysis of the PVC-containing plastic mixture is performed. The internal temperature of the auger reactor may be about 280 ~ 400 ℃.

In one aspect, in the pyrolysate separator, the pyrolysis product containing PVC that is primarily pyrolized in the auger reactor may be pyrolysed again. The temperature of the pyrolysate separator is 300-500°C.

In the fluidized bed reactor, the PVC-containing plastic mixture thermally decomposed in the auger reactor and the pyrolysate separator may 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 one or more of granulated calcium oxide (burnt lime) and calcium hydroxide heat-treated at 850 to 1000°C.

In one embodiment, in the case of using the finely divided calcium oxide or calcium hydroxide other than the heat-treated calcium oxide or calcium hydroxide at the temperature, a differential pressure in the reactor occurs, so that the process operation efficiency may decrease.

In one aspect, the plastic mixture may include waste plastic containing PVC. In addition, the plastic mixture containing the PVC may further include one or more 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 means 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 in the product produced by the device may be 50ppm (w / w) or less.

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

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

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

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

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

In one embodiment, the first thermal decomposition step, may be performed at 280 ~ 400 ℃. In addition, the temperature of the thermal decomposition separator is 300 to 500° C., and the second thermal decomposition step may be performed at 680 to 750° C., preferably, 700 to 750° C., more preferably 700 to 720° C. Can be performed at

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

Hereinafter, the structures 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 for purposes of illustration only to aid understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples.

100: apparatus for recycling of a plastic mixture containing polyvinyl chloride (PVC)
200: Auger reactor
300: pyrolysis separator
400: fluidized bed reactor
500: CaO filled high temperature filter
600: plastic mixture supply system
610, 620: screw feeder
700: pyrolysis 촤 separation system
710: silo, 720: CaO filled high temperature filter
800, 800': ??ching system
900, 900': impact separator
1000, 1000': Electrostatic precipitator

Claims (12)

Apparatus for recycling of plastic mixtures comprising polyvinyl chloride (PVC),
The device,
Pyrolysis reactor; And a pyrolysate separator,
The pyrolysis reactor includes an auger reactor and a fluidized bed reactor,
The pyrolysate separator,
A separator in which pyrolysis products introduced from the pyrolysis reactor collide; And
And a baffle that collides with the separator and induces a downward flow of separated pyrolysis products,
The auger reactor, the pyrolysis separator and the fluidized bed reactor,
Apparatus for recycling of plastic mixtures comprising polyvinyl chloride, including those connected in series in order of auger reactors, pyrolysate separators and fluidized bed reactors. According to claim 1,
The thermally decomposed product colliding with the separator is settled at one end of the baffle and flows to the other end.
The baffle is a device for recycling of a plastic mixture containing polyvinyl chloride, comprising a downward slope from one end to the other. According to claim 1,
The baffles include a plurality of baffles spaced apart from each other and arranged vertically,
The baffle includes a first baffle; And a second baffle located under the first baffle,
The thermal decomposition product is seated at one end of the first baffle and flows to the other end of the first baffle,
A device for recycling a plastic mixture containing polyvinyl chloride, wherein the thermal decomposition product 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. delete delete According to claim 1,
The temperature of the auger reactor is 280 ~ 400 ℃, the temperature of the pyrolysis separator is 300-500 ℃,
The temperature of the fluidized bed reactor is 680 ~ 750 ℃, a device for recycling of a plastic mixture containing polyvinyl chloride. According to claim 1,
The apparatus further includes a hot filter unit filled with at least one of calcium oxide and calcium hydroxide,
The high temperature filter is located behind the fluidized bed reactor, an apparatus for recycling of a plastic mixture containing polyvinyl chloride. According to claim 1,
The content of PVC in the plastic mixture,
Apparatus for recycling of plastic mixtures comprising polyvinyl chloride, which is 4% by weight or less, based on the total weight of the plastic mixture. The method of claim 7,
The temperature of the high temperature filter is 400 ~ 700 ℃, a device for recycling of a plastic mixture containing polyvinyl chloride. The method of claim 7,
The high temperature filter,
Apparatus for recycling of plastic mixtures containing polyvinyl chloride, comprising at least one of calcium oxide and calcium hydroxide heat-treated at 850 to 1000°C. According to claim 1,
The plastic mixture is an apparatus for recycling of a plastic mixture containing polyvinyl chloride, including waste plastic. A method for recycling a plastic mixture comprising polyvinyl chloride (PVC), using the apparatus of any one of claims 1 to 3 and 6 to 11.

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