KR102412546B1 - Waste resin liquefaction apparatus - Google Patents

Abstract

Disclosed is a waste synthetic resin emulsifying device. A waste synthetic resin emulsification apparatus according to an embodiment of the present invention comprises: a decomposition furnace in which the waste synthetic resin is accommodated, and the waste synthetic resin is heated and irradiated with ultraviolet rays to generate oil vapor, which is a heavy oil; a heat exchanger installed in communication with the cracking furnace to cool the oil vapor, which is heavy oil introduced from the cracking furnace, into liquid heavy oil; and a storage tank installed in communication with the heat exchanger to receive and store the heavy oil converted in the heat exchanger.

Description

Waste synthetic resin emulsifier {WASTE RESIN LIQUEFACTION APPARATUS}

The present invention relates to a waste synthetic resin emulsifying device.

In general, waste plastics made from polyethylene, polypropylene, polystyrene, etc. have low recyclability and are mostly disposed of by incineration or landfill.

Incineration or landfilling of waste plastics causes serious environmental pollution and takes a lot of time to decompose into a natural state, so the development of environmentally friendly and economical waste plastic treatment technology has been required.

The raw material of waste synthetic resin such as waste vinyl or waste plastic is crude oil, and gasoline, diesel oil, and liquefied gas are also distilled and extracted from crude oil. The raw material of the waste synthetic resin is a hydrocarbon polymer with a large molecular weight, and gasoline and diesel oil produced by oil refineries are hydrocarbon polymers with a relatively small molecular weight, so it is possible to convert the waste synthetic resin into petroleum by cracking it after liquefying it.

As a cracking method, a pyrolysis emulsification process in which a polymer material is heated under oxygen-free conditions is partly used, but not only pollutants are generated, but also wax, tar, caulking, ash, aluminum foil, and heavy metals are included in the manufactured oil. Its use is currently prohibited due to its low quality.

In the conventional high-temperature pyrolysis emulsification process, the crushed waste synthetic resin is supplied to a high-temperature melting furnace to melt into a gel form, and then the gel-like melt is heated to a high temperature of 450° C. or higher in a pyrolysis reactor to separate it into gas and liquid, and then has an oil component. It is configured to separate heavy oil of a wax component from gaseous gas, and condensate the separated gas again to obtain mixed heavy oil having high viscosity. The mixed heavy oil obtained here is the main product to be produced in the pyrolysis process. It is a dark black brown mixed oil with high viscosity and a lot of various heavy oil components having low to high boiling points are mixed, and contains a large amount of heavy metals and harmful substances.

For example, the following Patent Document 1 discloses 'a direct heating type emulsification apparatus for waste synthetic resin using waste oil'.

A direct heating type waste synthetic resin emulsification apparatus using waste oil according to the following Patent Document 1 is a reactor in which raw materials including waste synthetic resin and waste oil are supplied, and pyrolysis occurs under high temperature and pressure to generate gas; a first heating member including a first heating unit connected to the reactor by a pipe to heat the raw material discharged from the reactor and circulate the heated raw material back to the reactor; and a cooling unit for extracting regenerated oil by cooling and condensing the gas generated in the reactor.

In the reactor, pyrolysis occurs under high temperature and high pressure, and gas is generated while decompressed, and in the first heating member, one end of the pipe passes through the side of the reactor and is connected to the inside of the reactor, and the other end is the first A discharge pipe connected to a heating unit to discharge the raw material inside the reactor to the first heating unit, one end connected to the first heating unit and the other end connected to the inside of the reactor to discharge the first heating unit and a circulation pipe for circulating the raw material heated in the reactor to the reactor.

A first outlet and a second outlet are respectively formed at the other end of the circulation pipe to circulate the raw material to the reactor, and the first outlet is used when thermal decomposition of the raw material is performed in the reactor, and the second The outlet is used in the process of circulating and gasifying the raw material under reduced pressure after the pyrolysis of the raw material in the reactor proceeds, and the first outlet is formed so that the end does not spread outward, and the second outlet has an end Spread outward, the circulated raw material spreads laterally and collides with the inner wall of the reactor.

Patent Document 2 below discloses a 'waste synthetic resin emulsifying device'.

The waste synthetic resin emulsification apparatus according to the following Patent Document 2 may include a heating furnace capable of thermally decomposing the waste synthetic resin while stirring the waste synthetic resin; a heat exchanger connected to the heating furnace and cooling and liquefying the oil gas generated when the waste synthetic resin is thermally decomposed in the heating furnace to generate mixed oil; and a separation unit configured to be connected to the heat exchanger and for separating the mixed oil into light oil and heavy oil by using a boiling point difference.

The separation unit is connected to the heat exchanger and includes an inclined flow path part inclined upward at a set angle, an auxiliary heating part installed at a front start end of the inclined flow path part, and heating the mixed oil, and the auxiliary in the inclined flow path part. An auxiliary cooling unit installed at the rear of the heating unit for cooling the mixed oil gas vaporized by the auxiliary heating unit, and connected to the inclined flow path at the rear of the auxiliary cooling unit, the heavy oil liquefied by the auxiliary cooling unit It includes a first branch flow path to separate, and a second branch flow path connected to an end of the inclined flow path part and separating light oil liquefied by the auxiliary cooling part.

However, in the conventional pyrolysis emulsification process described above, since the waste synthetic resin supplied to the reactor must be heated to 450° C. or higher using indirect heating for each process, the heating time is relatively long, so a large amount of waste synthetic resin cannot be treated quickly. There is this.

Republic of Korea Patent Publication No. 10-2012-0019346 Republic of Korea Public Utility Model No. 20-2012-0007128

Therefore, the technical problem to be solved by the present invention is to provide a waste synthetic resin emulsifier that rapidly produces mixed heavy oil (C ₂₄ ~ C ₆₀ ) in a way that cracks and decomposes waste synthetic resin at a relatively low temperature.

One aspect of the present invention is a decomposition furnace in which the waste synthetic resin is accommodated and the waste synthetic resin is heated and at the same time irradiated with ultraviolet rays to generate oil vapor, which is a heavy oil; a heat exchanger installed in communication with the cracking furnace to cool the oil vapor, which is heavy oil introduced from the cracking furnace, into liquid heavy oil; and a storage tank installed in communication with the heat exchanger to receive and store the heavy oil converted in the heat exchanger.

The decomposition furnace, the body in which the waste synthetic resin is accommodated; a heating unit provided inside the body to heat the waste synthetic resin; an ultraviolet generating unit provided inside the body and heated by the heating unit to emit ultraviolet rays irradiated to the waste synthetic resin; and an oil vapor outlet provided on the upper part of the body to discharge the generated oil vapor, which is the heavy oil, to the heat exchanger.

The heating unit is heated so that the temperature inside the body is 180 to 270 ℃, and the ultraviolet generating unit is heated by the heating unit, and emits ultraviolet rays with a wavelength of 120 to 250 nm to decompose the hydrocarbon chains contained in the waste synthetic resin. it could be

The UV generating unit includes at least one ceramic composite receiving unit in which a plurality of ceramic composites are accommodated, and the ceramic composite includes any one or two or more ceramic powders selected from Al ₂ O ₃ , ZrO ₂ and MgO and LiF, MgF ₂ and CaF Any one or two selected from fluoride powder selected from ₂ or a mixture of two or more, and any one or two selected from terbium (Tb), cerium (cerium, Ce), europium (Europium, Eu), and dysprosium (Dy) The above mixture, which is a thermofluorescent rare-earth phosphor material, is mixed, molded, and sintered, and the ceramic composite may emit ultraviolet rays having a wavelength of 120 to 250 nm at a temperature of 180 to 270°C.

The waste synthetic resin emulsification device, a temperature sensor connected to the decomposition furnace to measure the temperature inside the decomposition furnace; a pressure sensor connected to the decomposition furnace to measure the atmospheric pressure inside the decomposition furnace; and a control unit configured to receive a temperature value and an atmospheric pressure value measured by the temperature sensor and the pressure sensor to adjust the temperature of the heating unit.

The waste synthetic resin emulsification apparatus further comprises a flow meter connected to the heat exchanger to measure the flow rate of heavy oil supplied from the heat exchanger to the storage tank and supply the measured flow rate value to the control unit, wherein the control unit is the flow rate value If it is less than this set value, the operation of the heating part may be stopped.

According to the present invention, the waste synthetic resin is vaporized into oil mist, which is heavy oil, through a direct cracking decomposition reaction using both optical wave energy and thermal energy emitted by heating a ceramic composite having thermofluorescence properties and then condensed to mix heavy oil (C ₂₄ ~ C ₆₀ ) can be obtained. Because thermal energy and light wave energy are used at the same time, high-quality heavy oil can be obtained quickly under relatively low temperature conditions. It has the effect of being able to manufacture heavy oil of

1 is a view schematically showing a waste synthetic resin emulsification apparatus according to an embodiment of the present invention.
2 is a view showing a decomposition furnace according to an embodiment of the present invention.
3 is a graph showing the results of measuring the wavelength and intensity of light emitted from the ceramic composite according to an embodiment of the present invention.
4 is a graph showing the results of thermogravimetric analysis for confirming the performance of decomposing the waste synthetic resin of the ceramic composite according to an embodiment of the present invention.
5 is a graph showing a thermogravimetric analysis result for confirming the degradation performance of a waste synthetic resin of a ceramic composite according to an embodiment of the present invention.
6 is a graph showing a gas chromatograph-mass spectrometer (GC-MS) analysis spectrum of the heavy oil produced according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the drawings and examples. The terms and descriptions described below are merely exemplified in order to clearly explain the present invention, and the scope of the present invention should not be construed as being limited thereto.

The terms first, second, etc. used in the description of the present invention are used only for the purpose of distinguishing one element from another element. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. and/or includes a combination of a plurality of related listed items or any of a plurality of related listed items.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

1 is a view schematically showing a waste synthetic resin emulsification apparatus according to an embodiment of the present invention.

1, the waste synthetic resin emulsification apparatus according to an embodiment of the present invention is a decomposition furnace 10 for receiving the waste synthetic resin and heating the waste synthetic resin and irradiating ultraviolet rays to generate oil vapor, which is a heavy oil; a heat exchanger 20 installed in communication with the cracking furnace 10 and cooling oil vapor, which is heavy oil introduced from the cracking furnace 10, into liquid heavy oil; and a storage tank 40 installed in communication with the heat exchanger 20 to receive and store the heavy oil converted in the heat exchanger 20 .

The waste synthetic resin emulsifier according to an embodiment of the present invention decomposes the waste synthetic resin to generate heavy oil vapor, and then liquefies the produced heavy oil oil vapor to obtain heavy oil, thereby extracting heavy oil from the waste synthetic resin.

Unlike the conventional thermal decomposition emulsification process, which required a high temperature process of 450 ° C. or higher, the waste synthetic resin emulsification device of the present invention uses thermal energy and at the same time, through the wave energy of irradiated ultraviolet rays, it is possible to quickly decompose the waste synthetic resin at a relatively low temperature. of heavy oil can be produced in a short time.

Here, the waste synthetic resin may include waste plastic, waste vinyl, etc., and means a thermoplastic resin that can be cracked into a low molecular weight material by heat.

Thermoplastic resins are polyethylene, polypropylene, polystyrene, ABS resin, acrylonitrile styrene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfite, polyphenylene oxide, polyacetal, polycarbonate, acrylic resin, nylon, poly amide, Teflon, synthetic rubber, polyvinyl chloride, and the like.

Here, heavy oil may be defined as oil containing wax components, and bunker seed oil may be exemplified.

The waste synthetic resin emulsification apparatus according to an embodiment of the present invention is configured to include a decomposition furnace 10 and a heat exchanger 20, which will be described for each configuration as follows.

The decomposition furnace 10 according to an embodiment of the present invention is to generate oil vapor, which is heavy oil, by receiving the waste synthetic resin and heating it.

The decomposition furnace 10, the body 11 in which the waste synthetic resin is accommodated; a heating unit 13 provided inside the body 11 to heat the waste synthetic resin; an ultraviolet generating unit 14 provided inside the body 11 and heated by the heating unit 13 to emit ultraviolet rays irradiated to the waste synthetic resin; and an oil vapor outlet 16 provided at the upper portion of the body 11 to discharge the generated oil vapor, which is the heavy oil, to the heat exchanger 20 .

The main body 11 may be configured in a cylindrical shape or a rectangular parallelepiped shape with a structure in which a waste synthetic resin can be put therein.

The waste synthetic resin is loaded on the bogie 17 and can be moved to the main body 11 through the inlet 12 installed on one surface of the decomposition furnace 10, and the waste synthetic resin is loaded on the inner bottom surface of the main body 11 A rail 18 for moving one bogie 17 may be installed.

The heating unit 13 heats the inside of the body 11 to a temperature of 180 to 270° C., and the ultraviolet generating unit 14 is heated by the heating unit 13, and hydrocarbons contained in the waste synthetic resin. It may be one that emits ultraviolet light with a wavelength of 120 to 250 nm that decomposes the chain.

A heating unit 13 capable of increasing the internal temperature of the body 11 to 180 to 270° C. is installed inside the body 11, and the heating unit 13 may have a plate shape or a cylinder shape.

For example, the heating unit 13 may be installed at regular intervals on both inner walls and bottom surfaces of the main body 11 in a plate shape, and the heating unit 13 is cylindrical in the inner wall of the main body 11 . Adjacent to the lower surface may be provided with one or a plurality of vertically or horizontally spaced apart. The shape of the heating unit 13 is not limited thereto, and may be appropriately designed and changed in consideration of the shape, capacity, target temperature, and the like of the decomposition furnace 10 .

The ultraviolet generating unit 14 includes at least one ceramic composite receiving unit 15a in which a plurality of ceramic composites 15b are accommodated,

The ceramic composite 15b may include any one or two or more ceramic powders selected from Al ₂ O ₃ , ZrO ₂ and MgO, and any one or two or more ceramic powders selected from LiF, MgF ₂ and CaF ₂ , a mixture of fluoride powder and terbium (Terbium). , Tb), cerium (cerium, Ce), europium (Europium, Eu), and dysprosium (dysprosium, Dy) are mixed, molded and then sintered manufactured, and the ceramic composite 15b may emit ultraviolet rays having a wavelength of 120 to 250 nm at a temperature of 180 to 270 °C.

In more detail, an ultraviolet generating unit 14 for decomposing hydrocarbon chains contained in the waste synthetic resin by emitting ultraviolet rays is installed inside the decomposition furnace 10 . The ultraviolet generating unit 14 may be installed on the inner wall surface of the main body 11 in the shape of the tile or block.

The ultraviolet generating unit 14 includes at least one ceramic composite accommodating part 15a in which the plurality of ceramic composites 15b are accommodated. The ceramic composite accommodating part 15a is made of a material that can withstand the heat applied by the heating part 13 without blocking the ultraviolet rays emitted from the accommodated ceramic composite 15b, for example, using a metal mesh. can

The ceramic composite 15b emits ultraviolet light having a wavelength of 120 to 250 nm corresponding to UV-C at a temperature of 180 to 270° C. due to its thermo-fluorescence characteristics. The wavelength of the emitted UV-C is discontinuous in the range of 120 to 250 nm, and corresponds to a pulse wave having strong wave energy. When the wave energy of the emitted ultraviolet (pulse wave) is converted according to the wavelength, it corresponds to 989 to 480 kJ/mol.

Since the carbon-to-carbon single bond (C-C) energy contained in polymers such as polyethylene, polypropylene, and polystyrene generally included in the waste synthetic resin is 347 kJ/mol, the ultraviolet light emitted from the ceramic composite 15b is a single bond between carbons. It has sufficient energy to cause direct cracking of

Therefore, unlike the conventional pyrolysis emulsification process in which a high temperature process of 450 ° C. or higher is essential, the waste synthetic resin emulsification apparatus of the present invention adds thermal energy to the wave energy emitted from the ceramic composite 15b, so that even at a relatively low temperature of 180 to 270 ° C. It is possible to decompose the synthetic resin so that the heating time can be shortened, and the effect of reducing the energy required to maintain a high temperature of 450 ℃ or higher can be obtained. In addition, unlike the case of decomposing the waste synthetic resin using only thermal energy, since the wave energy by UV irradiation is used at the same time, the decomposition of the waste synthetic resin occurs more rapidly, and thus a large amount of heavy oil can be produced quickly.

In addition, in the existing high-temperature pyrolysis process, coke, tar, and ash are generated and deposited on the inner wall of the pyrolysis reactor. In order to perform the next operation, the residues on the inner wall of the reactor must be removed every time, so there is a problem that the reactor cannot be operated continuously. . However, since the waste synthetic resin emulsification apparatus of the present invention is processed at a relatively low temperature, coke, tar, ash, etc. are not generated, so this problem can be solved.

In addition, although the high-temperature pyrolysis process inevitably involves the emission of harmful substances such as dioxins and dust, in the present invention, harmful substances are not released by the low-temperature process, so it is environmentally friendly, and costs for preventing and recovering harmful substances are saved. It is economical to do

Hydrocarbon chains contained in the waste synthetic resin are decomposed by the thermal energy supplied from the heating unit 13 and the wave energy of ultraviolet rays emitted by the ceramic composite 15b, and the hydrocarbon chains with reduced molecular weight are mostly heavy oil having 24 to 60 carbon atoms. It is vaporized with phosphorus oil vapor.

In more detail with respect to the manufacturing method of the ceramic composite 15b, the ceramic composite 15b may be prepared by mixing and molding the ceramic powder, the fluoride powder, and a thermofluorescent rare-earth phosphor material to prepare a molded body; and sintering the molded body at a temperature of 1300 to 1450 °C.

The ceramic composite 15b may have a plate shape or a spherical shape with a diameter of 8 to 15 mm, but is not limited thereto, and the shape of the ceramic composite 15b may be appropriately selected for convenience of installation.

The oil vapor outlet 16 discharges oil vapor, which is a heavy oil vaporized by thermal energy and wave energy. The oil vapor outlet 16 may be preferably installed in the upper portion of the main body 11 in consideration of the rise of vaporized oil vapor, but is not limited thereto.

The decomposition furnace 10 may include a hydraulic cylinder for sealing the inside. Since the decomposition furnace 10 sealed by the hydraulic cylinder does not introduce external air to form an anaerobic atmosphere, any additional reaction other than the cracking reaction of the carbon-to-carbon bond of the waste synthetic resin by the ultraviolet rays emitted from the ceramic composite 15b this doesn't happen Therefore, there is no need for a pretreatment process for the waste synthetic resin, no pollutants are generated, and the decomposition residue is converted into a charcoal-like carbon mass. Impurities such as inorganic substances or metals that are not decomposed by the ceramic composite 15b may be separately collected from the decomposition residues, and the decomposition residues may also be reused as high-calorie solid fuel having a high carbon content.

A foreign material outlet for discharging foreign substances or moisture contained in the waste synthetic resin may be formed in the lower portion of the main body 11 .

In addition, the waste synthetic resin emulsification apparatus, the temperature sensor 51 connected to the decomposition furnace 10 to measure the temperature inside the decomposition furnace 10; a pressure sensor 52 connected to the decomposition furnace 10 to measure the atmospheric pressure inside the decomposition furnace 10; and a control unit 50 configured to receive a temperature value and an atmospheric pressure value measured by the temperature sensor 51 and the pressure sensor 52 and adjust the temperature of the heating unit 13 .

The temperature sensor 51 and the pressure sensor 52 are installed to be connected to the inside of the decomposition furnace 10 so as to easily measure the temperature and pressure inside the decomposition furnace 10 .

The control unit 50 recognizes the temperature and pressure values measured from the temperature sensor 51 and the pressure sensor 52, and when the temperature and pressure are excessively high, increases the temperature of the heating unit 13, and the measured temperature And when the pressure is excessively low, it is possible to control to lower the temperature of the heating unit (13).

The heat exchanger 20 according to an embodiment of the present invention communicates with the cracking furnace 10 and is for cooling and liquefying the heavy oil vapor introduced from the cracking furnace 10 to produce heavy oil.

The heat exchanger 20 may be connected to the oil vapor outlet 16 of the cracking furnace 10 . The heat exchanger 20 may include a cooling water tank in which cooling water is stored, and the oil vapor, which is heavy oil introduced into the heat exchanger 20, loses heat by the cooling water tank and is cooled and liquefied to be converted into heavy oil.

Since the heat exchanger 20 is made of a heat exchanger 20 of a well-known technique in the art, a more detailed description of the configuration of the heat exchanger 20 itself will be omitted.

The waste synthetic resin emulsifier is connected to the heat exchanger 20 to measure the flow rate of heavy oil supplied from the heat exchanger 20 to the storage tank 40 and supply the measured flow rate value to the control unit 50 It further includes a flow meter 53, the control unit 50 may stop the operation of the heating unit 13 when the flow rate value is less than a set value.

When the flow rate of the heavy oil measured by the flow meter 53 is less than a certain value, it means that oil vapor, which is a heavy oil that can be extracted from the waste synthetic resin, is exhausted, and at this time, the control unit 50 controls the operation of the heating unit 13 It can be stopped to end the waste synthetic resin emulsification process. The set value may be set differently depending on the amount of waste synthetic resin put into the decomposition furnace 10, for example, when 6000 kg of waste synthetic resin is input, the set value may be set to 100 l/hr.

The control unit 50 is preferably the same as the control unit 50 receiving temperature and pressure values from the temperature sensor 51 and the pressure sensor 52 described above, and may be operated automatically or manually.

The waste synthetic resin emulsifier is installed in communication with the heat exchanger 20, removes moisture contained in the heavy oil supplied from the heat exchanger 20, and transfers the heavy oil from which moisture has been removed to the storage tank 40. It may further include an oil-water separator 30 to supply.

The oil-water separator 30 separates the moisture contained in the heavy oil liquefied by the heat exchanger 20 using a gravity method or centrifugal separation using a density difference.

Since this oil-water separator 30 is made of an oil-water separator 30 of a well-known technique in the art, a more detailed description of the heat exchanger 20 itself will be omitted.

The generated heavy oil may be transferred to and stored in a storage tank 40 connected to the heat exchanger or the oil-water separator 30 .

Due to the above configuration, the waste synthetic resin emulsifier of the present invention can decompose the carbon-carbon bond contained in the waste plastic by utilizing the wave energy of the ultraviolet light emitted from the ceramic composite 15b even at a low temperature of 180 to 270 ° C. Hydrocarbons with reduced carbon number can be smoothly vaporized. The generated oil vapor can be cooled and liquefied to obtain high-quality heavy oil having a carbon number of C ₂₄ to C ₆₀ .

Hereinafter, the operation and preferred embodiments of the waste synthetic resin emulsification apparatus of the present invention configured as described above will be described in detail.

The waste synthetic resin is loaded into the automatically transferred bogie 17 and put into the decomposition furnace 10 . The waste synthetic resin is put into a total of 6 plastic packs, 3 each on the 2 bogies 17, and is put into the decomposition furnace 10. After charging, the inlet 12 is sealed using a hydraulic cylinder, and the cooling water of the heat exchanger 20 is When the flow rate of the reaches a constant state, the operation of the heating unit 13 is started.

The heating unit 13 has a cylindrical shape, and 12 pieces are installed on both sides of the main body 11 in the vertical direction with the lower surface, and 24 pieces are installed on the inner surface of the main body 11 in the horizontal direction with the lower surface. do.

The internal temperature of the body 11 is initially set at 60° C., and after the waste synthetic resin is injected, the heating unit 13 operates to increase the temperature inside the body 11 to 270° C.

The ultraviolet generating unit 14 disposed adjacent to the heating unit 13 installed on the upper surface and both sides of the body 11 absorbs thermal energy and the ceramic composite receiving unit included in the ultraviolet generating unit 14 ( The ceramic composite 15b accommodated in 15a) emits ultraviolet rays having a wavelength of 120 to 250 nm. Due to the wave energy of the emitted ultraviolet rays, the bond between carbons contained in the waste synthetic resin is decomposed, and it evaporates into oil vapor, which is a heavy oil having 24 to 60 carbon atoms, and is discharged to the oil vapor outlet 16 installed at the upper side of the decomposition furnace 10. .

The discharged oil vapor, which is the heavy oil, passes through the heat exchanger 20, is cooled and condensed, and is converted into liquid heavy oil. The heavy oil is then supplied to the oil-water separator 30 , and a small amount of moisture contained in the heavy oil is separated and removed in the oil-water separator 30 . The heavy oil that has passed through the oil-water separator 30 is supplied to and stored in a storage tank.

The flow meter 53 connected to the heat exchanger 20 measures the flow rate of the generated heavy oil and supplies it to the control unit 50 . When the flow rate decreases below a predetermined value, the control unit 50 stops the operation of the heating unit 13 to end the process.

Experimental Example 1. Ceramic Composite UV Emission Measurement Experiment

In order to analyze the ultraviolet emission characteristics of the ceramic composite, the wavelength and intensity of light emitted at a temperature of 180 to 270° C. of the ceramic composite were measured.

The ceramic composite was prepared by the following method. Based on 100 parts by weight of a ceramic powder pulverized by alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ) and magnesia (MgO) with a purity of 99.99% or more to a mesh #2400 or higher, LiF, MgF ₂ and CaF ₂ are mixed fluoride powder 7 3 parts by weight of a thermofluorescent rare earth material obtained by mixing terbium oxide (Tb ₃ O) powder, dysporosium oxide (Dy ₂ O ₃ ) powder, and cerium oxide (CeO ₂ ) powder was mixed. The mixture was molded into a spherical shape with a diameter of 10 mm, and then sintered at 1400° C. to prepare a ceramic composite.

3 is a graph showing the results of measuring the wavelength and intensity of light emitted when the ceramic composite is heated to a temperature of 180 to 270 °C. As shown in FIG. 3 , it was confirmed that ultraviolet rays having a wavelength in the range of 120 to 250 nm were emitted, and discontinuous wavelength distributions (121, 124, 130, 220, 225, 249 nm) were observed in the wavelength range. .

Meanwhile, in Table 1 below, the binding energy according to the type of chemical bond present in mixed plastics such as polyethylene, polypropylene, and polystyrene included in general waste synthetic resins is shown, and Table 2 below shows the wavelength of light emitted from the ceramic composite. Wave energy conversion values are shown. Conversion was done through Equation 1 below.

[Equation 1]

where E is the energy, h is the Planck's constant (6.626×10 ^-34 J/s), c is the speed of light (3×10 ⁸ m/s), and λ is the wavelength.

type of bonding Binding energy (kJ/mol) C=C (double bond between carbons) 607 C-H (carbon-hydrogen bond) 431 C-Cl (carbon-chlorine bond) 397 C-C (single bond between carbons) 347 C-S (carbon-sulfur bond) 259

Light wavelength (nm) Wave energy conversion value (kJ/mol) 121 ~989 124 ~965 130 ~920 220 ~704 225 ~532 249 ~480

As can be seen in Tables 1 and 2, the wave energy of light having a wavelength of 120 to 250 nm is greater than the binding energy (347 kJ/mol) of single bonds between carbons that exist most in waste synthetic resins.

Therefore, it was confirmed that the light emitted from the ceramic composite had sufficient energy to break the single bond between carbons in the waste synthetic resin.

Experimental Example 2. Thermogravimetric analysis

Thermogravimetric analysis (TGA) was performed to confirm the degradation performance of the waste synthetic resin of the ceramic composite.

After the high-density polyethylene (HDPE) sample alone was put into a thermogravimetric analyzer, the temperature was increased at a temperature increase rate of 2° C./min to measure the weight. In addition, the weight was measured under the same conditions except that the high-density polyethylene sample was put into the thermogravimetric analyzer together with the ceramic composite. The analysis results are shown in FIG. 4 . 4A is a thermogravimetric analysis result of a high-density polyethylene sample alone, and FIG. 4B is a thermogravimetric analysis result of a high-density polyethylene sample and a ceramic composite.

As shown in FIGS. 4a and 4b, when the high-density polyethylene sample was added alone, a decrease in mass was observed from a temperature of 220 °C, whereas when the ceramic composite was added together, the mass decrease started from a temperature of 110 °C was able to confirm

In addition, thermogravimetric analysis was performed on the high-density polyethylene sample alone for 300 minutes at a constant temperature of 250° C., and the same analysis was performed with the high-density polyethylene sample and the ceramic composite for comparison. The analysis results are shown in FIG. 5 .

As shown in FIG. 5 , in the case of single input of the high-density polyethylene sample, the mass reduction started after 85 minutes, and it was confirmed that after the analysis was completed, a weight reduction of 12% compared to the initial sample input weight occurred.

On the other hand, when the ceramic composite was added together, decomposition started in 7 minutes, and after the analysis was completed, it was confirmed that the weight decreased by 68% compared to the weight of the initial input sample.

Therefore, from the result of the thermogravimetric analysis, it was confirmed that the ceramic composite can decompose a large amount of synthetic resin at a lower temperature and at a high speed.

Experimental Example 3. Results physical properties and component analysis

Heavy oil was produced from the waste synthetic resin according to a preferred embodiment of the waste synthetic resin emulsification apparatus described above, and the physical properties and components of the produced heavy oil and residues were analyzed. The results of analyzing the physical properties of the produced heavy oil are shown in Table 3 below, and GC-MS (gas chromatograph-mass spectrometer) analysis spectrum of the produced heavy oil is shown in FIG. 6 . In addition, the results of analyzing the physical properties and components of the residue are shown in Table 4 below.

Test Items Test result state of matter liquid at 20 ℃ Softening point (closed type) 50 ℃ flash point Does not spontaneously ignite below 200 ℃ pH 4.8 to 5.8 importance 0.9 at 20 ℃ water solubility Insoluble in water at 20 ℃ spontaneous ignition test Does not spontaneously ignite at 20 ℃ water reactivity test No risk of reaction with water at 20 ℃
- Combustible gas generation rate: < 0.1 ℓ/kgh oxidation test Burning time: > 300 s at 20 °C
* Hazard criteria: ≤ 135 s

division unit Measures moisture wt.% 5 or less low calorific value ㎉/kg over 5,000 ash wt.% 15.0 or less Goat wt.% 1.5 or less sulfur wt.% 0.5 or less Mercury (Hg) mg/kg 1.0 or less Cadmium (Cd) mg/kg 3.0 or less Lead (Pb) mg/kg 100.0 or less Arsenic (As) mg/kg 10.0 or less

As shown in Table 3, high-viscosity liquid heavy oil was produced at room temperature, and no problems were found in the spontaneous ignition test, water reactivity test, and oxidation test in the produced heavy oil, confirming that safe production was possible.

In addition, as shown in the GC-MS measurement result of FIG. 6 , it was confirmed that the produced heavy oil showed a C ₂₃ ~ C ₅₄ carbon number distribution, and contained the most C ₃₄ ~ C ₄₄ paraffinic wax component. .

On the other hand, as shown in Table 4, the residue remaining after the production of heavy oil was a black solid similar to charcoal, and it was confirmed that it contained a small amount of metal components such as moisture, ash, chlorine, sulfur and mercury, cadmium, lead, and arsenic. there was. In particular, it was confirmed that the residue itself can be used as a solid fuel because it has a lower calorific value of 5000 kcal/kg or more.

Therefore, from the above results, it was confirmed that high-quality heavy oil can be produced from the waste synthetic resin emulsification apparatus according to the preferred embodiment of the present invention, and the residue can be used as a solid fuel.

The above-described embodiment is an example for explaining the present invention, but the present invention is not limited thereto. Those of ordinary skill in the art to which the present invention pertains will be able to practice the present invention with various modifications therefrom, so the technical protection scope of the present invention should be defined by the appended claims.

10: decomposition furnace 11: main body
12: inlet 13: heating part
14: UV generating unit 15a: ceramic composite receiving unit
15b: ceramic composite
16: oil vapor outlet 17: bogie
18: rail 20: heat exchanger
30: oil-water separator 40: storage tank
50: control unit 51: temperature sensor
52: pressure sensor 53: flow meter

Claims (6)

a decomposition furnace in which the waste synthetic resin is accommodated and the waste synthetic resin is heated and at the same time irradiated with ultraviolet rays to generate oil vapor, which is a heavy oil;
a heat exchanger installed in communication with the cracking furnace to cool the oil vapor, which is heavy oil introduced from the cracking furnace, into liquid heavy oil; and
and a storage tank installed in communication with the heat exchanger to receive and store the heavy oil converted in the heat exchanger,
In the decomposition,
The body in which the waste synthetic resin is accommodated;
a heating unit provided inside the body to heat the waste synthetic resin;
an ultraviolet generating unit provided inside the body and heated by the heating unit to emit ultraviolet rays for decomposing hydrocarbon chains contained in the waste synthetic resin; and
and an oil vapor outlet provided on the upper part of the body to discharge the generated oil vapor, which is the heavy oil, to the heat exchanger,
The ultraviolet generating unit includes at least one ceramic composite receiving unit in which a plurality of ceramic composites that are heated by the heating unit and emit ultraviolet rays to decompose hydrocarbon chains contained in the waste synthetic resin are accommodated,
The ceramic composite is Al ₂ O ₃ , ZrO ₂ Any one or two or more ceramic powders selected from MgO, LiF, MgF ₂ and CaF ₂ Any one or a mixture of two or more selected from fluoride powder and terbium (Terbium, Tb) , cerium (Ce), europium (europium, Eu), and dyspropium (dysprosium, Dy) any one or a mixture of two or more thermofluorescent rare earth-based phosphor materials are mixed, molded, and then sintered,
The ceramic composite is a waste synthetic resin emulsifier that emits ultraviolet rays of a wavelength of 120 to 250 nm at a temperature of 180 to 270 °C.
According to claim 1,
The heating unit is heated so that the temperature inside the body is 180 to 270 ℃,
The ultraviolet generating unit is heated by the heating unit, waste synthetic resin emulsifying device for emitting ultraviolet rays with a wavelength of 120 to 250 nm to decompose hydrocarbon chains contained in the waste synthetic resin.
According to claim 1,
The waste synthetic resin emulsifying device,
a temperature sensor connected to the decomposition furnace to measure a temperature inside the decomposition furnace;
a pressure sensor connected to the decomposition furnace to measure the atmospheric pressure inside the decomposition furnace; and
Waste synthetic resin emulsification apparatus further comprising; a control unit for receiving the temperature value and the atmospheric pressure value measured by the temperature sensor and the pressure sensor to adjust the temperature of the heating unit.
4. The method of claim 3,
The waste synthetic resin emulsifying device,
Further comprising a flow meter connected to the heat exchanger to measure the flow rate of heavy oil supplied from the heat exchanger to the storage tank and supply the measured flow rate value to the control unit,
The control unit is a waste synthetic resin emulsification device to stop the operation of the heating unit when the flow rate value is less than a set value.

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