KR101916404B1 - Apparatus for recycling mixture of plastics comprising polyvinyl chloride and method for recycling mixture of plastics comprising polyvinyl chloride using the same - Google Patents

Abstract

In the present specification, disclosed are an apparatus for recycling a recycling mixture of plastics comprising polyvinyl chloride, and to a method for recycling the mixture of plastics comprising the polyvinyl chloride using the same. The apparatus according to one aspect of the present invention primarily pyrolyzes the recycling mixture of plastics through an auger reactor and a fluidized bed reactor, and as a result of filtration using a high-temperature filter machine filled with calcium oxide, it is possible to produce a pyrolysis oil which has a low chlorine content, is wax-free, and has a high content of an aromatic compound.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for recycling a plastic mixture containing polyvinyl chloride and a method for recycling a plastic mixture including the polyvinyl chloride using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recycle- }

Disclosed herein is a device for recycling a plastic mixture comprising polyvinyl chloride and a method for recycling a plastic mixture comprising polyvinyl chloride using the same.

In Korea, about 4 million tons of waste plastics are produced annually, but the recycling rate is as low as 20 ~ 30%, and a large amount is being treated by landfill or incineration. However, landfill of waste plastics can dissolve harmful components, which are bulky compared to the unit weight, which causes storage, transportation and landing problems. In addition, the treatment by incineration can use some of the heat energy generated during incineration, but it causes a lot of economic loss and releases toxic gas, causing problems of environmental destruction. Therefore, the social concern about recycling waste plastic It is getting higher.

Waste plastics are mainly recycled in such a way that they are converted to waste energy (technology to produce fuel and energy from waste). Waste energy includes waste plastic refuel (RPF), waste oil refining oil, plastic pyrolysis fuel oil, .

On the other hand, the success or failure of waste plastic recycling is directly related to the removal of chlorine or chlorine compounds. PVC (polyvinyl chloride) is mixed in the waste plastic generated in the city, because chlorine as a constituent of PVC causes problems in recycling. For example, in the case of pyrolysis oil, the chlorine compound (HCl, etc.) produced during the pyrolysis of PVC causes corrosion of the pyrolysis process, pyrolysis oil containing the pyrolysis oil causes shortening the life of the pyrolysis plant and causes dioxin generation.

However, to date, waste plastic waste energy is known to contain large amounts of chlorine or chlorine compounds. In the case of RPF, the average chlorine content in RPF was found to be 0.87wt.% In Korea from 2008 to 2010 (New & Renewable Energy 2016. 12 Vol 12, No. 4).

In the case of foreign countries, the standard content of chlorine in RPF is strictly defined. In the UK, as shown in the table below, 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 - -

The recycling method of waste plastic is largely divided into a mechanical recycling method in which waste plastic is melted at a low temperature to make recycled particles in the form of pellets or granules and a feedstock that converts waste plastic into a material component necessary for manufacturing other compounds. Recycling method. Among them, the method of mechanical recycling is such that the physical properties of the product manufactured by the process are dropped each time the mechanical recycling is repeated, so that the feedstock recycling method is preferred as the final recycling method.

Feedstock recycling methods are largely divided into pyrolysis, gasification, hydrogenation, and solvolysis, and pyrolysis is the most actively studied. Pyrolysis oil produced from waste plastics through pyrolysis is injected into the petroleum refining process and used as a raw material for new chemicals or fuels. On the other hand, for this reason, it is essential to develop a method that can effectively control the chlorine content of pyrolysis waste plastic containing PVC and ultimately reduce the chlorine content of pyrolysis oil. However, there has not been reported a case in which chlorine is reduced 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 has chlorine content of about 10,000 ppm or more. In order to make practical use of waste plastic pyrolysis oil, the chlorine content in the oil should be 10 ppm or less, but the production of pyrolysis oil having a chlorine content within this value has not been practiced (Energy Conversion and Management 115 (2016) 308-326 ).

KR 10-0748624 B1

In one aspect, an object of the present invention is to prepare pyrolysis oil suitable for recycling waste plastics containing PVC.

In one aspect, an object of the present invention is to reduce the content of chlorine in oil obtained by pyrolyzing waste plastics to 10 ppm or less.

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

In one aspect, an object of the present invention is to produce an oil containing no wax from waste plastics.

In one aspect, the present invention provides an auger reactor in series; A fluidized bed reactor; Wherein the product produced from the apparatus comprises one or more of the following characteristics: a) a high-temperature hot-dip filter,

i) the content of aromatics in the oil in the product is at least 90% by weight, based on the total weight of the oil;

ii) the content of wax in the oil in the product is not more than 0.1% by weight; And

iii) The content of chlorine in oil in the product is less than 10 ppm (w / w).

In addition, in one aspect, the present invention provides a method for recycling a plastic mixture comprising PVC, using an apparatus for recycling a plastic mixture comprising the polyvinyl chloride.

An apparatus for recycling a plastic mixture containing polyvinyl chloride, which is one aspect of the present invention, reduces chlorine content of a waste plastic primarily through pyrolysis in an auger reactor, and decomposes a wax component in a fluidized bed reactor, , And finally filtering with a high-temperature filter filled with calcium oxide to produce an oil having a chlorine content of 10 ppm or less.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a block diagram of an apparatus for recycling a plastic mixture comprising polyvinyl chloride according to an aspect of the present invention. Fig.
2 is a schematic diagram of a recycling system for a plastic mixture comprising an apparatus for recycling a plastic mixture comprising 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, which will be readily apparent to those skilled in the art. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

It is to be understood that the terms or words used in the specification and claims are not to be construed in a conventional or dictionary sense and that the inventor may properly define the concept of a term in order to best describe its invention And should be construed in accordance with the principles and meanings and concepts consistent with the technical idea of the present invention.

In the specification of the present invention, when a component is referred to as " comprising ", it means that it can include other components as well as other components, .

Throughout 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 is an apparatus for recycling a plastic mixture comprising polyvinyl chloride (PVC), the apparatus comprising: an auger reactor; A fluidized bed reactor; And a hot filter unit filled with calcium oxide, the product produced from said apparatus comprising one or more of the following characteristics:

i) the content of aromatics in the oil in the product is at least 90% by weight, based on the total weight of the oil;

ii) the content of wax in the oil in the product is not more than 0.1% by weight; And

iii) The content of chlorine in oil in the product is less than 10 ppm (w / w).

Referring to FIG. 1, an apparatus 100 for recycling a polyvinyl chloride-containing plastic mixture according to an embodiment of the present invention includes an auger reactor 200, a fluidized bed reactor 300, Temperature filter (400).

The auger reactor 200 and the fluidized bed reactor 300 are connected in series and the fluidized bed reactor 300 is positioned behind the auger reactor 200 and the high temperature filter 400 filled with calcium oxide behind the fluidized bed reactor is located do. At this time, a gas is introduced into a boundary between the auger reactor 200 and the fluidized bed reactor 300 to form a gas curtain film, for example, a gas curtain film in the hatched region of FIG. 1 Time), although the present invention is not limited thereto.

In one embodiment, the apparatus may further comprise a wax receiver between the auger reactor and the fluidized bed reactor. The wax receiver may be connected to the auger reactor through a pipe pipe extending from the auger reactor, and the pipe pipe may be inclined from top to bottom with respect to a horizontal plane.

When a plastic mixture, a waste plastic, or a powder thereof (hereinafter referred to as a plastic mixture) containing PVC is introduced into the auger reactor 200 of the two-stage pyrolysis apparatus 100 of the present invention, pyrolysis (A first pyrolysis product) such as a plastic mixture in which a chlorine compound (gas or liquid form) is separated and discharged from a plastic mixture or the like and at the same time a chlorine content is reduced. Then, the fraction such as the chlorine-reduced plastic mixture is introduced into the fluidized bed reactor 300 to be connected. At this time, a gas curtain film is formed on the boundary between the auger reactor 200 and the fluidized bed reactor 300 by a gas introduced through a gas inlet (not shown). The fraction of the chlorine- 300, the gas of the chlorine compound separated from the plastic mixture or the like is prevented from being transferred to the fluidized bed reactor 300 by the gas curtain film. The fraction of chlorine - reduced plastics, etc., introduced into the fluidized bed reactor is transformed into liquid / gaseous hydrocarbon compounds by secondary pyrolysis. At this time, gas formed in the fluidized bed reactor 300 is prevented from flowing back to the auger reactor 200 by the gas curtain film.

On the other hand, the fluidized bed reactor 300 requires a fluidizing gas, which may be an inert gas, a gas produced and discharged in the apparatus, in particular a non-condensing gas discharged from a fluidized bed reactor, or a mixture thereof .

The gas forming the gas curtain film is preferably heated after being heated to a temperature inside the auger reactor 200 before being introduced into the auger reactor 200, but may not be limited thereto.

The gas curtain film is heated at an angle of about 0 degree to about 30 degrees with respect to the cross section perpendicular to the traveling direction of the auger reactor, that is, the flow direction of the fraction such as the plastic mixture in which the chlorine content in the auger reactor 200 is reduced But the present invention is not limited thereto. As a non-limiting example, it is preferable that the gas inlet (not shown) is located at the upper part of the boundary between the auger reactor 200 and the fluidized bed reactor 300, and the gas curtain film is formed such that the introduced gas falls downward by gravity. But is not limited thereto.

The gas inlet (not shown) may be a gas selected from the group consisting of an inert gas, a gas generated and discharged from the apparatus (pyrolysis gas), and a mixed gas thereof. The gas injected through the gas inlet (not shown) is preferably an inert gas, and the inert gas may be nitrogen gas, helium gas, or argon gas.

The auger reactor 200 may include a discharge unit (not shown) through which the generated product is discharged. The outlet of the auger reactor (200) is not directly connected to the fluidized bed reactor (300).

The fluidized bed reactor 300 may include a discharge unit (not shown) through which the generated product is discharged. The outlet of the fluidized bed reactor (300) is not directly connected to the auger reactor (200).

In the pyrolysis product discharged through the second pyrolysis in the fluidized bed reactor 300, the solid pyrolysis char is collected by the cyclone and then passed through the high temperature filter 400 filled with CaO. At this time, the HCl in the pyrolysis gas reacts with CaO to convert to CaCl ₂ and water, and the pyrolysis gas is cooled and condensed with the Cl reduced, and is collected into the oil. The non-condensed gas can be used as a fluid medium.

The apparatus 100 for recycling a plastic mixture comprising polyvinyl chloride may further include a temperature controller (not shown), which is connected to the auger reactor 200, the fluidized bed reactor 300, It is preferable that the temperature of each of the high-temperature filters 400 filled with the calcium oxide can be independently changed. The temperature controller may include a temperature detector, a temperature controller, and a heater.

2 is a configuration diagram of a system for recycling a PVC-containing plastic mixture according to an embodiment of the present invention.

Referring to FIG. 2, a plastic recycling system according to an embodiment of the present invention includes an apparatus 100 for recycling a PVC-containing plastic mixture, a plastic mixture supply system 500, a pyrolysis char separation system 600, A high-temperature filter 400 filled with calcium oxide, chrominance systems 700 and 700 ', impact separators 800 and 800', electrostatic precipitators 900 and 900 'and a gas circulation system (not shown) .

On the other hand, 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 PVC is from 1 to 10% by weight, more specifically from 2 to 8% by weight, more specifically from 2 to 6% by weight, more specifically from 2 to 5% by weight, based on the total weight of the plastic mixture %. ≪ / RTI >

In relation to this, the content of PVC in the plastic mixture is based on the PVC content present in domestic waste plastics, and in Korea it is known that 2.4-4.0 wt% of PVC is present in mixed waste plastics in 2010 A study on the development of a specific gravity screening system, Ryu Jae-myung, 2010.) As the plastic classification technology progresses, the PVC content is gradually decreasing, and many recent studies have set the PVC content target at 0.35 wt%.

In the auger reactor, the primary pyrolysis of the PVC-containing plastics mixture is carried out. The internal temperature of the auger reactor may be about 280-400 ° C.

In one aspect, in the fluidized bed reactor, the PVC-containing plastic mixture that has been heat treated in the auger reactor may be heat-treated (secondary thermal decomposition) again. In the above aspect, the internal temperature of the fluidized bed reactor may be 680 to 750 ° C, preferably 700 to 750 ° C, and more preferably 700 to 720 ° C.

The operation temperature of the high-temperature filter packed with calcium oxide may be 400 to 700 ° C, preferably 600 to 700 ° C.

The high-temperature filter unit filled with the calcium oxide may include a granulate calcium oxide (burnt lime) heat-treated at 850 to 1000 ° C.

In one embodiment, when calcium oxide other than calcium oxide is used at the above-mentioned temperature, differential pressure in the reactor may be generated and the process operation efficiency may be lowered.

In addition, in one aspect, when the calcium oxide is charged into the reactor without using a high-temperature filter, slagging phenomenon occurs in which CaCl ₂ produced by the reaction of calcium oxide with hydrogen chloride in the reactor melts, De-fluidization may be induced and the process efficiency may be greatly reduced, such as stopping the process operation.

In one aspect, the plastic mixture may comprise waste plastics containing PVC. In addition, the plastic mixture containing PVC may be made of plastics other than PVC, further comprising at least one of polyethylene terephthalate (PET), high density polyethylene (HDPE), low density polyethylene (LDPE), polystyrene (PS), and polypropylene ≪ / RTI >

In one aspect, the pyrolysis oil of the product produced by the apparatus may be wax-free.

In this specification, 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 apparatus may be less than 50 ppm (w / w).

The chlorine content in the oil of the product produced by the apparatus is significantly lower than the known amount of chlorine charge of 10,000 ppm, which has been known so far.

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

In one aspect, the present invention is a method of 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 comprises: a first pyrolysis step of pyrolyzing a plastic mixture comprising PVC in an auger reactor; A second pyrolysis step of pyrolyzing a plastic mixture containing pyrolyzed PVC in the auger reactor 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 packed with calcium oxide.

In one embodiment, the first pyrolysis step may be performed at 280-400 < 0 > C. The second pyrolysis step may be performed at a temperature of 680 to 750 ° C, preferably 700 to 750 ° C, and more preferably 700 to 720 ° C.

The filtering step may be performed at 400 to 700 ° C, preferably at 600 to 650 ° C.

Hereinafter, the constitution 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 illustrative purposes only in order to facilitate understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples.

[Example]

1. Preparation of sample

The samples used are waste PE / virgin PVC mixtures (96: 4). The properties of the feed materials are shown in Table 1. The proximate analysis was conducted according to ASTM D3172. In each experiment, waste plastics showed high volatile matter. As a result of elemental analysis, the content of PE and PVC chlorine was 0.2 and 21.4 wt%, respectively. The total input Cl content was about 1 wt%.

Proximate analysis
(wt.%) PE PVC Ultimate analysis
(wt.%) PE PVC Moisture 0.1 0.1 C 92.3 50.1 Volatile matter 99.9 66.6 H 7.4 6.2 Fixed carbon N.D. 29.0 O N.D. 22.3 Ash N.D. 4.3 Cl 0.2 21.4

* N.D .: not detected

2. Experimental conditions

In the present experiment, a two-stage pyrolysis apparatus and a CaO-filled high temperature filter unit were used in the experiment (Examples). The two-stage pyrolysis apparatus includes an auger reactor and a fluidized bed reactor. The auger reactor is connected directly to the fluidized bed reactor. Experiments using a two - stage pyrolysis unit were considered for chlorine removal in the auger reactor. The reaction temperature of the auger reactor was 300 ° C in the examples and the fluidized bed reactor temperature was 700 ° C. The operation temperature of a hot filter (hereinafter referred to as a high temperature filter) filled with CaO, which was connected in series to an auger reactor, was 400 ° C.

The experiment was started by injecting the sample at a rate of about 2 g / min. The total sample weight was 200 g and the run time of the experiment was about 100 minutes. Before operation, the pyrolysis unit was purged with nitrogen gas for 1 hour. The reactor was purged and heated to the reaction temperature determined by an electric furnace. 1.2 Kg of silica was used as the fluid phase material. As the velocity of the fluidized bed reactor, three times the minimum fluidization velocity was the flow rate of each experiment. In the auger reactor, the residence time of the feed material was about 10 minutes. The amount of CaO used was about 0.4 kg.

3. Pyrolysis Plant

A waste plastics processing system (plant) including a two-stage pyrolysis apparatus and a high-temperature filter for the embodiment was as shown in Fig.

As shown in FIG. 2, the two-stage pyrolyzer is connected to the auger reactor before the fluidized bed reactor. The examples were carried out in a two-stage pyrolysis apparatus. The two-stage pyrolysis unit consists of auger reactor and fluidized bed reactor By boundary Nitrogen (N ₂ ) gas was introduced and the nitrogen gas stream was passed from the silo 410 through an auger reactor to a liquid product collector (not shown).

The auger reactor is an acid-treated 310S tube material. The auger reactor had an inner diameter of 23 mm and a length of 650 mm. The quenching system located in the auger reactor included a condenser, which was cooled in water to 20 < 0 > C. Impact separators and battery dust collectors were used to capture large molecular weight compounds and aerosols, and noncondensing gases were released into the flare stack without circulation.

The fluidized bed reactor was made of a 310S tube with a height of 550 mm and an inner diameter of 70 mm. The reactor had three thermocouples and the reaction temperature was defined as an average value calculated from the values measured by the thermocouple. After the fluidized bed reactor, a pyrolytic cyclone, a high temperature filter filled with calcium oxide, a shaking system, an impact separator, an electrostatic precipitator, and a gas circulation system were provided. The cyclone was installed to capture pyrolytic char particles larger than 10 μm. The high-temperature filter filled with calcium oxide was a 310S tube on the outside, and the inside was a ceramic filter, and the inside thereof was filled with calcium oxide. This ceramic filter was installed to capture pyrolytic char particles larger than 2 ㎛. The quenching system used two steel capacitors, one of which was subjected to continuous cooling in water at 20 ° C and the other was continuously cooled in ethanol at -20 ° C. The impact separator disposed after the condenser captures a large amount of molecules and the electrostatic precipitator is installed after the impact separator to remove aerosols in the gas. In the gas circulation system, the noncondensable gas was circulated to the fluidized bed reactor by a compressor (N0150ATE, KNF). The produced gas product was collected using a Teflon gas bag for analysis and the remaining gas was taken from the flare stack. To monitor the temperature of the entire plant, two additional thermocouples were installed in the pipeline and the gas vent line. A heating band and a glass wool were used to prevent vapor condensation. A schematic view of the waste plastics pyrolysis system (plant) is shown in Fig.

4. Analysis of pyrolysis products

The liquid product obtained from the auger reactor contained wax and high molecular weight compounds and no qualitative, quantitative analysis was performed. For quantitative and qualitative analysis of fluid bed liquid products, gas chromatography-flame ion detector (GC-FID) and gas chromatography-mass spectrometer (GC-MS) were used. GC-FID (7890A, Agilent Instruments) and GC-MS (5975C, Agilent Instruments) had HP-5MS (30 m X 250 mm i.d., 0.25 m film thickness) and helium was used as the carrier gas. Qualitative analysis of the oil was carried out using a commonly used library (NIST, Wiley). The compounds finally selected in the qualitative analysis were compounds with a probability of over 80%. Next, quantitative analysis of the oil was performed using the relative value of the relative response factor (RRF). The relative response factor was used by multiplying the peak area of each compound detected by CG-FID.

Gas products were analyzed by gas chromatography-thermal conductivity detector (GC-TCD) and GC-FID. The GC-TCD had a Carboxen 1000 column and the GC-FID was installed with an HP-plot Al ₂ O ₃ / KCl column. The carrier gas of GC-TCD and GC-FID was argon gas.

The chlorine content in the liquid product was measured by Combustion Ion Chromatograph (IC). This process was carried out according to the EPA5050 and EPA9056a methods. When a certain amount of the absorption liquid is filled in the oxygen bomb and the pyrolysis oil is burned in a sealed state, the chlorine in the oil is absorbed into the absorption liquid in the form of hydrogen chloride. When the liquid sample (absorption liquid) is injected into the IC, the separation is caused by the difference in ionic bonding force between the liquid phase and the fixed phase chromatography column together with the eluent as the mobile phase, and the anion (chlorine ion) is analyzed through the conductivity detector.

5. Results Analysis

5.1. Mass balance

The results shown in Table 3 below are the products and their content (mass balance) in each reactor.

Reactor type Products Wt.% Auger reactor
: ~ 300 ° C Gases 16.40 Oil + wax 12.87 Residues 3.75 Fluidized bed reactor
: ~ 700 ° C Gases (sum) 45.14 Hydrogen 0.17   Methane 10.92   Ethane 2.89   Ethene 19.98   Propene 7.14   Butenes 1.08   1,3-butadiene 2.29   Other gases 0.68 Oils (sum) 21.60 Aliphatics (sum) 0.03   Cyclooctatetraene 0.01 Other aliphatics 0.02 Aromatics (sum) 19.86  Mono aromatics (sum) 13.15   Benzene 10.07   Toluene 0.93   Ethylbenzene 0.05 Xylene 0.05   Styrene 0.11   Allylbenzene 0.08   Isopropenylbenzene 0.01   Methylphenylacetylene 0.05   Dialin 0.96   Methylindene 0.73   Other mono aromatics 0.09 Poly aromatics (sum) 8.45   Naphthalene 3.83   메틸 나aphthalene 1.32   Ethenylnaphthalene 0.27   Anthracene 0.26   Fluorene 0.67   Other polyaromatic compounds 2.10 Unknowns 1.81 Char 0.25 Total 100.00

5.2. Analysis of aromatics in pyrolysis oil

The following Table 4 relates to the kind and content of the aromatic compounds contained in the pyrolysis oil recovered under the pyrolysis conditions. From Table 4 below, it can be confirmed that no compound having a carbon number of 19 or more is present, and thus it was confirmed that oil without wax was produced.

Compound Content (wt%) Aliphatics 0.36 1,3,5-heptatriene 0.06 1-octene 0.02 Cyclooctatetraene 0.18 Nonane 0.13 Aromatics 99.64 Benzene 36.91 Toluene 6.84 Ethylbenzene 0.86 o-Xylene 0.98 Styrene 5.75 Cumene 0.23 Allylbenzene 4.30 1-methyl-4-ethylbenzene 0.29 Isopropenylbenzene 0.29 3-Methylphenylacetylene 5.34 Indene 0.57 1,3-divinylbenzene 0.22 Dialin 4.55 1-methylindene 2.35 Naphthalene 12.32 2-methylnaphthalene 4.25 Biphenyl 0.88 1,8-dimethylnaphthalene 0.24 1-ethylnaphthalene 0.23 2-ethenylnaphthalene 0.87 Acenaphthene 0.84 Biphenylene 0.95 Fluorene 2.17 2-methylbiphenyl 0.40 Phenanthrene 1.09 2-methylanthracene 0.17 1-phenylnaphthalene 0.08 Pyrene 0.32 Unknown 5.68 Total 100.00

The aromatics in the oil were 99.64 wt%, and no wax-free oil was produced because there were no compounds having 19 or more carbon atoms.

5.3. Content of chlorine in pyrolysis oil

Chlorine content in pyrolysis oil recovered from this experiment was found to be about 9.25 ppm (average value of filter oil 1 (yield: 14.12 wt%) and 2 (yield: 7.49 wt%) in pyrolysis oil) (Table 5).

Test Items Measurement result Cl (mg / kg) CaO filter Oil 1 CaO filter Oil 2 CaO filter Oil 3 CaO filter auger 10.3 7.27 115 897 Yield: 14.12 wt% Yield: 7.49 wt% Yield: 9.99 wt% -

In Table 5, the pyrolysis fluid derived from the fluidized bed is CaO filter oil 1 and 2. CaO filter oil 1 refers to the oil condensed in a water condenser, while CaO filter oil 2 refers to the oil that is broken in the ethanol quencher. The oil in the ethanol quencher was phase separated with the water phase, while the CaO filter oil 3 was the Cl content in the water phase. This water phase is easily separated from pyrolysis oil by separating funnel method. The CaO filter auger refers to the oil produced from the auger reactor.

100: Apparatus for recycling a plastic mixture comprising polyvinyl chloride (PVC)
200: auger reactor
300: fluidized bed reactor
400: CaO filled high temperature filter unit
500: Plastics mixture supply system
510: Silos 520, 530: Screw feeder
600: pyrolysis char separation system
610: silo, 620: CaO high-temperature filter unit
700, 700 ':? System 710, 720: condenser
800, 800 ': Impact separator
900, 900 ': Electrostatic precipitator

Claims (15)

An apparatus for recycling a plastic mixture comprising polyvinyl chloride (PVC)
The apparatus comprises:
Auger reactor; A fluidized bed reactor; And a hot filter unit filled with calcium oxide,
The temperature of the auger reactor is 280 to 400 ° C,
The temperature of the fluidized bed reactor is 680 to 750 ° C,
The temperature of the high-temperature filter is 400 to 700 占 폚,
Wherein the auger reactor and the fluidized bed reactor comprise pyrolyzing a plastic mixture comprising polyvinyl chloride,
Wherein the auger reactor and the fluidized bed reactor comprise a series connection,
An apparatus for recycling a plastic mixture comprising polyvinyl chloride, wherein the product produced from the apparatus comprises one or more of the following characteristics:
i) the content of aromatics in the oil in the product is at least 90% by weight, based on the total weight of the oil;
ii) the content of wax in the oil in the product is not more than 0.1% by weight; And
iii) The content of chlorine in oil in the product is less than 10 ppm (w / w). The method according to claim 1,
The content of PVC in the plastic mixture is,
An apparatus for recycling a plastic blend comprising polyvinyl chloride, the blend being at least 2% by weight based on the total weight of the plastic blend. delete delete delete delete The method according to claim 1,
Wherein the plastic mixture comprises waste plastic. ≪ RTI ID = 0.0 > 8. < / RTI > The method according to claim 1,
An apparatus for recycling a plastic mixture comprising polyvinyl chloride, wherein the product produced from the apparatus is wax-free. delete The method according to claim 1,
The high-temperature filter unit filled with the calcium oxide,
An apparatus for recycling a plastic mixture comprising polyvinyl chloride, comprising calcium oxide heat-treated at 850 to 1000 占 폚. A method of recycling a plastic mixture comprising polyvinyl chloride (PVC) using the apparatus of any one of claims 1, 2, 7, 8 and 10. 12. The method of claim 11,
The method comprises:
A first pyrolysis step of pyrolyzing the plastic mixture containing PVC in an auger reactor;
A second pyrolysis step of pyrolyzing a plastic mixture containing pyrolyzed PVC in the auger reactor in a fluidized bed reactor; And filtering the pyrolysis vapor of a plastic mixture comprising pyrolyzed PVC in the auger reactor. ≪ Desc / Clms Page number 19 > 13. The method of claim 12,
Wherein the first pyrolysis step is carried out at a temperature of 280 to 400 占 폚. 13. The method of claim 12,
Wherein the second pyrolysis step is carried out at a temperature of 680 to 750 占 폚. 13. The method of claim 12,
Wherein the filtering step is performed at 400 to 700 占 폚.

Images