KR101424678B1 - Apparatus for recycle processing the cultured marble wastes using a fluidization fast pyrolysis technology and the method thereof - Google Patents

Abstract

The apparatus for recycling waste marble using the fluidized-bed rapid pyrolysis technique according to the present invention comprises a reservoir (10) for storing a crushed product (6a) of a crude marble; A pyrolysis reaction and a calcining apparatus for producing methyl methacrylate and aluminum oxide by pyrolysis reaction at the same time as the pulverized product 6a of the crude marble stored in the storage 10 is heated and heated, 20); A pyrolysis reactor in the pyrolysis reaction and calcining apparatus 20 for pyrolyzing the pulverized product 6a of the crude coal marble with the fluid yarn 240 'to cause pyrolysis into methyl methacrylate and aluminum oxide 21); Solids separation means for separating the solids 251, 252 from the gas discharged from the pyrolysis reaction and calcining apparatus 20; A condensing means for cooling the gas passing through the solids separating means to recover methyl methacrylate in a liquid state; And gas recycling means for supplying at least a part of the gas passing through the condensing means to at least one of the pyrolysis reaction and the calcination apparatus 20 with the storage tank. The present invention has the advantage of facilitating the recovery of aluminum oxide and saving energy by combining a reactor for pyrolysis of waste marble and a firing furnace for firing aluminum oxide together to provide a fluidized bed cracking reactor in the firing furnace.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recycling apparatus for reclaimed marble using fluidized-bed rapid pyrolysis technology,

The present invention relates to an apparatus for recycling waste marble from a fluidized-bed rapid pyrolysis process and a method thereof. More particularly, the present invention relates to a pyrolysis reactor for pyrolysis of crude marble and a calcining furnace for calcining aluminum oxide, And the use of aluminum oxide as the fluidized yarn makes the aluminum oxide itself produced by pyrolysis of the crude marble as a fluidized yarn so that it does not need to replenish the fluidized yarn. Device and method thereof.

Artificial marble has attracted a great deal of attention as a material for construction due to recent trends in the upgrading and comfort of buildings. Artificial marble refers to a synthetic compound that combines natural ores or minerals with resin components or cement, and incorporates various pigments and additives to provide the natural marble texture.

At present, organic artificial marble is mixed with an acrylic resin (organic material) called Methyl methacrylate (MMA) and an inorganic filler. In this artificial marble, composition ratio of each material is methyl methacrylate Is 30 to 45% by weight, the inorganic filler is 45 to 65% by weight, and the remainder is made of an additive. As the inorganic filler, most of the aluminum hydroxide is used, which is good for improving the strength and wear resistance of artificial marble.

Artificial marble is processed to the required size after manufacturing and is widely used as a sink, a counter top, a kitchen top plate, a counter top plate of a public building, a table and other interior materials, and many dusts and scrap are generated in the process of manufacturing these products . In addition to the rapid increase in production volume due to the various advantages of artificial marble, the amount of dust and scrap generated during the processing process is also increasing. Especially, the amount of crude marble discarded in the remodeling or reconstruction process after use is considerable Is coming.

Referring to the production and treatment process of the marble as shown in Fig. 1, the production of methyl methacrylate and the aluminum hydroxide produced in the aluminum hydroxide manufacturer (2) produced in the manufacturer (1) of methyl methacrylate are used as raw materials The artificial marble manufacturer (3) uses artificial marble to produce artificial marble, which is made up of large amounts of fine powder. The artificial marble products produced by the artificial marble manufacturer (3) are supplied to the construction / construction company (4a), the interior company (4b) and the kitchen furniture company (4c) And a crude marble 6, which is a waste made of powder and scrap, is generated. On the other hand, artificial marble products used in the reconstruction work site 5 of a building, an apartment, However, currently marine marble is treated as industrial waste and is simply landfilled and disused. Therefore, it has a disadvantage of causing not only high disposal cost but also environmental problems of soil pollution.

In order to solve the problems of the time, there have been proposed by some companies technologies for recovering methyl methacrylate or aluminum hydroxide, which has been recycled as waste raw marble.

FIG. 2 is a view for explaining an example of a conventional recycling treatment apparatus for marble of a closed garbage, in which a waste marble is heated in a reactor 502 to generate a gas containing methyl methacrylate, and then the gas is cooled to obtain methyl methacrylate FIG. The waste marble is crushed and placed in the storage hopper 501 and then supplied to the reactor 502 and heated while heating the reactor 502 by using the heat of the electric heater 502b while being stirred to thermally decompose pyrolysis, . Polymethyl methacrylate, water, and aluminum oxide (alumina) are formed due to the thermal decomposition of the marble. In this case, the polymethyl methacrylate in the gaseous state, And then decomposed again into acid metal (MMA). 2, the gaseous methyl methacrylate and water are discharged from the reactor 502 and transferred to the condenser 503. After being converted into the liquid state by being condensed by the cooling water supplied from the cooling water supply device 504, 505). In the separator 505, water is located below the methyl methacrylate in the oil component, so that the water is withdrawn from the bottom of the separator 505, and the methyl methacrylate in the upper layer is transferred to the purity adjuster 508. The purity of the methyl methacrylate introduced into the purity adjuster 508 is adjusted by the additives to be added, and then the foreign substances are collected through the filter 509 in a filtered state.

2, reference numeral 506 denotes a vacuum pump for applying a vacuum to absorb moisture remaining in the reactor 12 as much as possible. Reference numeral 507 denotes a moisture pump for removing moisture and odor remaining in the separator 505 It is a bad smell eliminator.

Although the prior art of FIG. 2 only discloses a process for recovering methyl methacrylate after the pyrolysis process of the marine crude, the Korean Patent No. 1022512 discloses a method for recovering methyl methacrylate by condensing the gas after pyrolysis of the crude marble. In addition to the recovery process, the process of recovering aluminum oxide by calcining aluminum oxide is also introduced.

However, both the prior art of FIG. 2 and the prior art of Japanese Patent No. 1022512 are operated in a batch type reactor, and the recovery rate of methyl methacrylate is not so high. In particular, The reactor for pyrolysis and the calcining furnace for calcining aluminum oxide have to be separately operated, resulting in a large energy consumption and a large maintenance cost.

In order to solve the above problems, the present invention provides a fluidized-bed pyrolysis reactor in which a reactor for pyrolysis of marble of a closed vessel and a calcining furnace for calcining aluminum oxide are combined into a fluidized-bed pyrolysis reactor in a calcining furnace, And an object of the present invention is to provide an apparatus for recycling waste marble using a rapid pyrolysis technique and a method therefor.

According to the present invention, there is provided a pyrolysis reaction, which serves as a firing furnace, and a fluidized-bed pyrolysis reactor inside the firing apparatus, wherein aluminum oxide is used as a fluidized silica fills the inside of the pyrolysis reactor, Like the aluminum oxide filled as the first fluidized yarn, it is not necessary to replenish the fluidized yarn during the operation so that the pyrolysis reaction and the continuous operation of the burning device can be performed. And an object thereof is to provide an apparatus and a method thereof.

In addition, the present invention allows continuous operation of a fluidized-bed pyrolysis reactor, which is a core constituent, in a fluidized bed mode rather than a batch mode, thereby allowing the methylated methacrylate to react to an unnecessary additional reaction The present invention aims at providing a recycling treatment apparatus and method of marble, which is capable of significantly improving the recovery rate of methyl methacrylate by allowing the user to proceed to the next step without further experiencing any further problems.

In order to accomplish the above object, there is provided an apparatus for recycling waste marble from a fluidized-bed rapid pyrolysis process, which comprises a crude marble comprising components consisting of Methyl Methacrylate (MMA) and aluminum hydroxide A reservoir 10 for storing the crushed material 6a; A pyrolysis reaction and a calcining apparatus for producing methyl methacrylate and aluminum oxide by pyrolysis reaction at the same time as the pulverized product 6a of the crude marble stored in the storage 10 is heated and heated, 20); A pyrolysis reactor in the pyrolysis reaction and calcining apparatus 20 for pyrolyzing the pulverized product 6a of the crude coal marble with the fluid yarn 240 'to cause pyrolysis into methyl methacrylate and aluminum oxide 21); Solids separation means for separating the solids 251 and 252 from the gas discharged from the pyrolysis reaction and firing apparatus 20; A condensing means for cooling the gas passing through the solids separating means to recover methyl methacrylate in a liquid state; And gas recycling means for supplying at least a part of the gas passing through the condensing means to at least one of the pyrolysis reaction and the calcination apparatus 20 with the storage tank.

In order to achieve the above object, the present invention also provides a method for recycling waste marble from a fluidized bed rapid pyrolysis process, comprising the steps of: (a) disposing of a crude marble comprising components consisting of methyl methacrylate and aluminum hydroxide 6a) into a pyrolysis reaction and firing unit (20); (b) heating the inside of the pyrolysis reaction and firing unit 20 to pyrolyze the crushed material 6a of the waste marble into gaseous materials including methyl methacrylate and steam and aluminum oxide, (C) The pyrolysis reaction and the gas discharged from the burning device 20 are passed through the cyclone 30 and the hot filter 40 so that the solids 251 and 252 in the gas are separated and removed (D) a fourth step of recovering the liquid methyl methacrylate by cooling and condensing the gas passing through the hot filter 40 through a condensing means; And (e) a fifth step of purifying the gas passing through the condensing means and supplying at least a part of the purified gas to the pyrolysis reaction and firing unit (20), wherein the pyrolysis reaction and firing unit A fluidized-bed pyrolysis reactor 21 for pyrolyzing the pulverized product 6a of the waste marble into the fluidized bed 240 'by flowing the pyrolysis product into methyl methacrylate and aluminum oxide is installed inside the fluidized bed pyrolysis reactor 21, Includes a reactor housing (22) having an upper open portion and a vertically extending body portion (22); A lower inclined expanding portion 22d provided at the lower end of the reactor housing 22 and having an inclined shape so as to gradually expand radially outward as it goes down; And a gas injection plate (24) installed near the lower end of the reactor housing (22) and supplying nitrogen containing gas into the inner space of the reactor housing (22), wherein the pyrolysis reaction and burning apparatus The fluidized yarn 240 filled in the fluidized bed cracking reactor 21 and the fluidized yarn 240 'filled in the fluidized bed thermal cracking reactor 21 are both made of aluminum oxide.

The apparatus and method for recycling waste marble using the fluidized-bed rapid pyrolysis technique according to the present invention are characterized in that a reactor for pyrolysis of crude marble is combined with a calcining furnace for calcining aluminum oxide to form a fluidized bed pyrolysis reactor in the calcining furnace Thereby making it possible to drastically reduce the energy consumption by utilizing the electric energy required for the pyrolysis reaction process and the firing process without waste.

In the present invention, aluminum oxide is used as a fluidized bed which is basically filled both inside the pyrolysis reaction and the calcining apparatus and inside the fluidized bed pyrolysis reactor, and then aluminum oxides continuously generated as a result of the pyrolysis of the crude marble are used as fluidized beds It is not necessary to supplement the flow yarn at all during the operation, and as a result, there is an advantage that the pyrolysis reaction and the continuous operation of the firing apparatus are enabled.

Further, according to the present invention, a fluidized bed pyrolysis reactor, which is a core constituent of a waste marble recycling apparatus, is realized by a fluidized bed method rather than a conventional batch method, thereby enabling continuous operation, The methyl methacrylate converted into the gaseous state can be immediately transferred to the next step without any additional reaction that is no longer required, and the recovery of methyl methacrylate can be dramatically enhanced.

Figure 1 illustrates the generation and treatment process of the present marine marble.
FIG. 2 is a view for explaining a conventional recycled marble processing apparatus. Referring to FIG. 2, a waste marble is heated in a reactor 502 to generate a gas containing methyl methacrylate, and the gas is cooled to recover methyl methacrylate Lt; / RTI >
FIG. 3 is a block diagram of a recycling apparatus for waste marble using the fluidized-bed rapid pyrolysis technique according to the present invention.
FIG. 4 shows the internal construction of the pyrolysis reaction and firing apparatus 20 in the apparatus for recycling waste marble using the fluidized-bed rapid pyrolysis technique shown in FIG. 3, The fluidized yarn 240 'filled in the outer portion and the fluidized yarn 240 filled in the outer portion are all the same material as aluminum oxide.
FIG. 5 is a graph showing the degree of fluidization of the medium as the pressure or flow rate of gas applied to the medium filled in the reactor 21 'is increased. FIG. 5 (a) (C) shows a state in which bubbles 29a are generated in the medium, and FIG. 4 (d) shows a state in which small bubbles 29 are generated, Shows a case where a turbulent flow occurs due to a gas pressure increasing to its maximum state.
6 and 7 illustrate the case where pyrolysis and bubbling flow of the crude marble crushed material 6a, which is a waste in the fluidized bed pyrolysis reactor 21, have elapsed from the state of FIG. 4, The remaining aluminum oxide particles 240a are spilled through the upper end of the fluidized bed cracking reactor 21 and discharged to the outside (that is, the inside of the calcining furnace 200) ). ≪ / RTI >
8 is a plan view of the gas injection plate 24 shown in Figs. 4, 6 and 7, in which the nozzles 25 are inserted into a plurality of gas injection holes 24a formed on the upper surface of the gas injection plate 24 Respectively.
FIG. 9 is an enlarged view of the lower part of the fluidized-bed pyrolysis reactor 21 shown in FIGS. 4, 6 and 7, in which a gas injection plate 24 is installed at the lower end of the fluidized bed pyrolysis reactor 21, The gas injected from the nozzles 25 of the plate 24 collides with the upper surface of the gas injection plate 24 and is reflected and supplied into the fluidized bed 23.
Fig. 10 is an enlarged view of the cyclone 30 and the hot filter 40 shown in Fig.
FIG. 11 shows the whole process of recovering the methyl methacrylate 250a and the aluminum oxide 240b by recycling the disintegrated marble 6a according to the present invention.
FIG. 12 is a conceptual diagram of an economical utilization plan of methyl methacrylate (250a) and aluminum oxide (240b) recovered by a recycling apparatus for waste marble by using the fluidized bed rapid thermal decomposition technique of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout.

FIG. 3 is a block diagram of a recycling apparatus for waste marble using the fluidized-bed rapid pyrolysis technique according to the present invention. 3, the closed marble recycling apparatus of the present invention comprises a storage 10 for storing a crushed marble 6a of a closed marble, and a crushed material 6a of a closed marble for storage stored in the storage 10, A pyrolysis reaction and firing apparatus 20 for producing methyl methacrylate and aluminum oxide by a pyrolysis reaction while simultaneously heating the aluminum oxide, and a pyrolysis reaction and firing apparatus 20 for pyrolyzing the pyrolysis reaction from the gas discharged from the pyrolysis reaction and firing apparatus 20 A cyclone 30 and a hot filter 40 as solids separating means for separating the solids 251 and 252 and cooling the gas passing through the cyclone 30 and the hot filter 40, A first condenser 51 and a second condenser 52a for collecting methyl methacrylate and a second condenser 52b for collecting the methyl methacrylate and a second condenser 52b for collecting the methyl methacrylate, Before removing substances A dust collector 60, and is configured to recycle the gas after a purification treatment in the electric dust collector 60 in the gas recycling means for re-supply to the reservoir 10 and the pyrolysis reaction and the firing device (20).

First, the crude marbles collected from the artificial marble manufacturing and processing companies and various reconstruction sites are crushed to a predetermined particle size or less and put into the silo 10. It is preferable that the particle size of the crushed materials is maintained at a size of about 3 mm or smaller so that the crushed materials of the crushed marble are smoothly fluidized in the fluidized-bed pyrolysis reactor 21 and pyrolysis is performed.

The storage tank 10 is formed in the form of a tank and an agitator 10b capable of mixing and mixing pulverized marbles of the waste granules is installed therein and a first driving motor 10b capable of rotating the agitator 10b 10a.

The crushed product 6b of the crude marble contained in the storage 10 is introduced into the pyrolysis reaction and firing device 20 by the first screw feeder 12 and the second screw feeder 13 connected to the lower part of the storage tank 10, It is injected into. The first screw feeder 12 and the second screw feeder 13 are respectively provided with screw conveyors 12b and 13b rotatably installed in a tubular passage and first and second screw feeders 12b and 13b rotatingly driving the screw conveyors 12b and 13b. And includes a screw driving motor 12a and a second screw driving motor 13a.

The pyrolysis reaction and firing apparatus 20 can function as a firing furnace itself as a whole, and a fluidized bed cracking reactor 21 is installed therein. In the pyrolysis reaction and calcination apparatus 20 and the fluidized bed cracking reactor 21 therein, fluidized beds are filled at a constant height, and when the gas is injected from the lower portion thereof, the fluidized beds as solid particles are fluidized A state in which a solid (fluid yarn) and a gas (injection gas) are mixed is obtained. Particularly, if the velocity of the gas injected into the fluidized bed thermal cracking reactor 21 is increased to a predetermined speed or higher, gas bubbles are formed between the fluidized yarns to actively mix the solid particles (fluidized yarn) with the gas The solid particles are in a liquid-like state, which is called "bubbling fluidization". That is, in the present invention, the pyrolysis reaction and the fluidized-bed pyrolysis reactor 21 installed inside the firing unit 20 are operated by the gas injected from the gas injection plate 24 (see FIG. 4) And as a result, the waste crude marble crushed materials 6a injected by the screw feeders 12, 13 can be easily mixed in between the floating yarns and mixed well.

Meanwhile, the remaining space in the inner space of the pyrolysis reaction and firing unit 20, except where the fluidized bed cracking reactor 21 is installed, functions as a 'firing furnace' 200. Although the pyrolysis reaction and calcination apparatus 20 of the present invention includes a fluidized bed pyrolysis reactor 21 of another nature in the present invention, the pyrolysis reaction and calcination apparatus 20 itself is the calcination furnace 200 and the fluidized bed pyrolysis reactor 21 The upper and lower ends of the pyrolysis reaction and calcining apparatus 200 are all opened so that they may be substantially a part of the calcining furnace 200. In this specification, For the sake of convenience, the names of both components should be used in combination.

Methyl methacrylate and water vapor generated after pyrolysis of the crude marble escape to the cyclone 30 through the first gas transfer line 131, so that only the aluminum oxide remains in the pyrolysis reaction and firing unit 20 , The particles of aluminum oxide are coated with carbon atoms, which makes industrial use less efficient. Therefore, it is necessary to burn and remove the carbon components coated on the surfaces of the aluminum oxide particles, and this firing operation can be carried out directly in the firing furnace 200. The firing furnace 200 is a kind of electric furnace in which electric heaters 201 are provided on the outside of the firing furnace 200 and is heated to a high temperature of about 750 to 900 ° C. by using the electricity provided by the high- When nitrogen (N ₂ ) and a little amount of oxygen (O ₂ ) are supplied in the state of being heated at such a high temperature, the calcining action naturally proceeds and the carbon components coated on the surface of the aluminum oxide are removed. At this time, the carbon components on the surface of the aluminum oxide are combined with oxygen to become carbon dioxide or carbon monoxide, and are discharged to the outside of the pyrolysis reaction and burning apparatus 20 through the first gas transfer line 131.

Aluminum oxide which has undergone the calcination process in the pyrolysis reaction and calcination apparatus 20 or the calcination furnace 200 is discharged to the outside by the screw conveyor 203 installed at the lower part of the calcination furnace 200 and is stored in the hopper 204. In FIG. 3, reference numeral 203a denotes a second drive motor 203a for rotating the screw conveyor 203. As shown in FIG.

The gases generated from the pyrolysis reaction and the gases discharged from the burning unit 20, that is, the gases due to the methyl methacrylate, steam, and other additive substances generated by thermal decomposition of the crude marble, and the carbon dioxide And carbon monoxide are introduced into the cyclone 30 through the first gas transfer line 131, the gases introduced into the cyclone 30 are rotated therein, and the solid particulates fall down to be stored in the first solids reservoir 31, Only the gas component passes through the second gas transfer line 132 to the next hot filter 40. The hot filter 40 also serves to separate the solid particulates from the gas using a filter element, wherein the separated solid particulates are stored in the second solid reservoir 41.

The gas passing through the hot filter 40 enters the first condenser 51 through the third gas transfer line 133 and the first condenser 51 has a water jacket 51a filled with water 51b at room temperature So that condensation takes place as the gas passes through the pipeline in contact with the water jacket 51a so that the liquid component is separated down and separated and only the gas components are passed through the fourth gas transfer line 134 to the next second condensers 52a, 52b. Since the liquid separated from the first condenser 51 is composed of methyl methacrylate and water, methyl methacrylate can be recovered by removing water located below the separated liquid.

The second condensers 52a and 52b are preferably installed in a structure in which two condensers are connected to each other and the cooling water supply device 53 supplies cold water of about 0 to 5 ° C to the condensers 52a and 52b do. As the gas passes through the second condensers 52a and 52b, condensation occurs again to separate methyl methacrylate and water, and the gas is passed through the sixth gas transfer line 136 to the next electrostatic precipitator (60). Since the liquid separated from the second condensers 52a and 52b is also composed of methyl methacrylate and water, methyl methacrylate can be easily recovered by removing the water located below the separated liquid.

The electrostatic precipitator 60 has a structure having a plurality of dust collecting plates and discharge electrodes therein, and a high voltage is applied between the discharge electrode and the dust collecting plates to generate a corona discharge, whereby dusts contained in the gas and mist So that fine particles are attached to the dust collecting plate to purify the air.

3, reference numeral 135 denotes a fifth gas transfer line for transferring the gas from the second-1 condenser 52a to the second-2 condenser 52b.

The gas discharged through the electrostatic precipitator 60 is adjusted to a proper pressure through the gas return line 137 and is then discharged to the reservoir 10, the screw feeders 12 and 13, and the pyrolysis reaction and calcination apparatus 20 All or part of it. Such a gas is called a product gas when the gas used once in the recycling apparatus or the gas generated is recycled and put into the line.

The closed marble recycling apparatus of the present invention supplies gas to the storage tank 10, the screw feeders 12 and 13, and the pyrolysis reaction and firing apparatus 20, wherein most of the gases used are nitrogen gas. The nitrogen gas initially introduced into the apparatus of the present invention can be purchased and supplied with gaseous nitrogen gas or liquefied nitrogen. However, after the recycling apparatus of the present invention is operated once, the pyrolysis reaction and the calcining apparatus 20 proceed It is not necessary to additionally supply nitrogen gas because the gas is continuously generated by the pyrolysis and firing process of the crude marble. Rather, the gas pressure in the entire line continuously increases due to the pyrolysis reaction and the gas continuously generated in the firing unit 20, so it is necessary to adjust the gas pressure so that the gas pressure is not excessively increased by appropriately discharging the gas. A burner 72 is installed in the gas return line 137 so that the gas can be drawn and burned. The gas meter 70 measures the flow rate of the gas burned by the burner 70. 3, reference numeral 111 denotes an eleventh valve provided in front of the gas meter 70, 112 denotes a twelfth valve that allows sampling of a gas sample, and numeral 113 denotes a valve disposed at the front of the burner 72 Thirteenth valve.

The gas recovered by the gas return line 137 is delivered to the gas pressure regulators 91, 92, 93 and 94 through the seventh valve 107 or the eighth valve 108, If pressure is insufficient, it acts to pressurize. The sixth valve 106 may be connected to the nitrogen tank 11 as a valve for introducing nitrogen.

A fifth-valve 105a, a fifth-valve 105b, a fifth-third valve 105b, and a third valve 105b are disposed between the first through fourth gas pressure regulators 91, 92, 93, 94 and the compressor 80, The gas after passing through the first gas pressure regulator 91 is transferred to the reservoir 10 through the second gas supply line 122 and the second gas supply line 122 The gas after passing through the gas pressure regulator 92 is supplied to the screw feeders 12 and 13 through the third gas supply line 123. The gas after passing through the third gas pressure regulator 93 is transferred to the lower portion of the firing furnace 200 through the fourth gas supply line 124 to supply gas for fluidization of the firing furnace 200. Since it is necessary to mix an appropriate amount of oxygen (O ₂ ) into the gas introduced into the firing furnace in order to smoothly perform the firing work of the aluminum oxide in the firing furnace 200, It is preferable to connect it with the gas supply line 124.

The gas after passing through the fourth gas pressure regulator 94 is heated to a predetermined temperature by a preheater 206 and then introduced into the fluidized bed cracking reactor 21 through a gas injecting gas for bubbling fluidization And is provided as a jet plate 24 (see Fig. 4). It is preferable that the temperature of the fluidized bed cracking reactor 21 is maintained at 450 to 550 ° C. The temperature of the fluidized bed reactor is lowered by passing through the first condenser 51, the second condenser 52a, and the gas return line 137, If the gas is directly injected into the gas injection plate 24 under the fluidized bed thermal cracking reactor 21, the temperature of the fluidized bed thermal cracking reactor 21 is abruptly lowered and the pyrolysis reaction can be inhibited. Therefore, it is preferable that the gas to be introduced for the 'bubbling fluidization' of the fluidized bed cracking reactor 21 is raised to a temperature of at least about 300 to 400 ° C. by passing through the preheater 206, and then introduced.

3, reference numeral 121 denotes a first gas supply line for supplying nitrogen in the nitrogen tank 11 to the reservoir 10; 101, a first valve installed in the first gas supply line 121; Reference numeral 102 denotes a second valve provided in the second gas supply line 122. Reference numeral 10c denotes a gas discharge valve for discharging gas from the storage tank 10, and reference numeral 10d denotes a charging pipe for charging a waste of the crude marble into the storage tank 10. Reference numeral 123a denotes a third valve connected to the third gas supply line 123 to supply gas to the first screw feeder 12 and 104 denotes a fourth valve connected to the second screw feeder 13. [

Reference numeral 109 denotes a ninth valve installed in the first gas transfer line 131 for discharging the gas from the pyrolysis reaction and firing unit 20. Reference numeral 110 denotes a tenth valve for discharging the solid matter separated from the cyclone 30. [ to be.

FIG. 4 shows the internal construction of the pyrolysis reaction and firing apparatus 20 in the apparatus for recycling waste marble using the fluidized-bed rapid pyrolysis technique shown in FIG. 3, The fluidized yarn 240 'filled in the outer portion and the fluidized yarn 240 filled in the outer portion are all the same material as aluminum oxide. It is preferable that the particle size of the aluminum oxide used as the flow yarn is maintained at about 3 mm or smaller.

4, the fluidized bed cracking reactor 21 is installed inside the pyrolysis reaction and firing unit 20 in a floating state, and the fluidized bed cracking reactor 21 has an upper support 22a and a lower support 22b, Is fixed to the inside of the pyrolysis reaction and firing apparatus 20, that is, the firing furnace 200, by the firing furnace 22b. Since the second screw feeder 13 penetrates the firing furnace 200 and extends to the inside of the fluidized bed cracking reactor 21 installed inside the firing furnace 200, Can be directly introduced into the inside of the fluidized bed cracking reactor (21).

The fluidized bed cracking reactor 21 mixes and fluidizes the pulverized product 6a of the waste marble with the fluid yarn 240 'by using the gas injected by the gas injection plate 24, (6a) of pyroclastic marble by pyrolysis of methyl methacrylate and aluminum oxide.

The pyrolysis reaction and firing apparatus 20 (firing furnace 200) is maintained at a temperature of 750 to 900 ° C by an electric heater 201. The firing furnace 200 is provided with an electric heater 201 surrounding the outside of the firing furnace 200 The temperature is relatively lower in the central portion than in the outer edge region of the firing furnace. In addition, since the pulverized materials 6a of the crude marble, which is the waste kept at the normal ambient temperature, are introduced into the fluidized bed cracking reactor 21 at the central portion of the calcining furnace 200, The internal temperature is formed to be much lower than the temperature of the firing furnace 200.

On the other hand, the fluidized bed cracking reactor (21) is open at the upper part and the lower part is open when there is no gas injection plate (24). The fluidized-bed pyrolysis reactor 21 has a reactor housing 22 having an open upper part and a vertically extending shaped body, and a lower inclined expansion part 22d at the lower end of the reactor housing. The lower inclined expansion part 22d is inclined so as to gradually expand toward the outside in the radial direction as it goes downward. As a result, the fluidized bed thermal decomposition reactor 21 has a structure in which the diameter of the lower end part is larger than the diameter of the upper end part.

At the lower end of the fluidized bed cracking reactor (21), a gas injection plate (24) is provided in a state of being slightly spaced apart. The gas injection plate 24 serves to supply a gas containing nitrogen to the inner space of the reactor housing 22. A plurality of gas injection holes 24a (FIG. 8) are formed on the upper surface of the gas injection plate 24 Shaped nozzles 25 are coupled to the gas injection holes 24a so that the gas injected from the nozzle 25 collides with the upper surface of the gas injection plate 24 and is reflected by the diffusion And then proceeds to the upper part of the fluidized bed cracking reactor 21.

The gas injection plate 24 is connected to the gas supply pipe 27 for the inner fluidized bed and the gas supply pipe 27 for the inner fluidized bed refers to the rear end of the fifth gas supply line 125 shown in FIG. A gas supply pipe 207 for an external fluidized bed having a plurality of gas injection holes for injecting gas is provided in the lower portion of the firing furnace 200. The gas supply pipe 207 for the external fluidized bed is connected to the fourth gas And the rear end of the supply line 124.

The pressure of the gas injected into the fluidized bed cracking reactor 21 through the gas injection plate 24 should be such that the fluidized bed 23 therein will cause bubbling fluidization. Suggesting that injection of gas at a pressure of at least 0.5 bar results in sufficient 'bubbling fluidization' in the fluidized bed cracking reactor 21.

In the initial state of the pyrolysis reaction and firing apparatus 20, the fluidized yarns 240 and 240 'made of the same material are filled in the firing furnace 200 and the fluidized bed cracking reactor 21 have. However, in the apparatus for recycling crude marble in accordance with the present invention, it is preferable that the fluidized bed of the calcining furnace 200 and the fluidized bed pyrolysis reactor 21 is made of aluminum oxide Al ₂ O ₃ ) is used. Aluminum oxide, also called alumina, is an important material for fine ceramics with a melting point of 2,050 ° C and a high hardness next to diamonds.

In view of the fact that aluminum oxide is generated in the course of performing thermal decomposition of crude marble composed of methyl methacrylate and aluminum hydroxide, aluminum oxide itself continuously produced by pyrolysis can be used as a fluidized yarn , It is not necessary to add a separate fluidizing yarn and it is possible to evenly mix the crushed materials of the crude marble and accelerate the heat transfer and decomposition reaction. In addition, the aluminum oxide itself is refined after finishing from the calcining furnace 200 to the calcining The present invention has the most important feature that it can be easily recovered at a time and thus it is the most important feature that it is realized as an invention. As a result, the present invention greatly simplifies the process facility of the recycling treatment apparatus of the marble, It is possible to achieve an effect of drastically reducing the cost.

An alumina discharging device 203b for discharging aluminum oxide subjected to the baking treatment in the baking furnace 200 is provided in the lower portion of the baking furnace 200. The alumina discharge device 203b is constituted by a screw conveyor 203 rotated by a second drive motor 203a and the discharged aluminum oxide is stored in the hopper 204. [

4, reference numeral 208 denotes a gas discharge port for discharging the gas of the firing furnace 200.

4, the diameter of the fluidized-bed pyrolysis reactor 21 is preferably about 1/2 of the diameter of the firing furnace 200, and the total height of the fluidized bed cracking reactor 21 is preferably set to a height of the firing furnace 200 Is about 1/3 of that of the first embodiment. For example, according to the design of the present inventor, the inner diameter of the fluidized bed cracking reactor 21 is 300 mm, the height thereof is 1200 mm, the inner diameter of the firing furnace 200 is 600 mm, and the height is preferably 3600 mm .

FIG. 5 is a graph showing the degree of fluidization of the medium as the pressure or flow rate of gas applied to the medium filled in the reactor 21 'is increased. FIG. 5 (a) (C) shows a state in which bubbles 29a are generated in the medium, and FIG. 4 (d) shows a state in which small bubbles 29 are generated, Shows a case where a turbulent flow occurs due to a gas pressure increasing to its maximum state.

The initial or minimum flow state to the extent shown in FIG. 5 (b) is a state in which the solid particles in the reactor 21 'are slightly swirling, which may be referred to as a' general type of fluidization '. The fluidized state of the aluminum oxide fluidized yarn 240 (see FIG. 4) occurring in the calcining furnace 200 of the present invention is the 'general type of fluidizing' shown in FIG. 5 (b), whereas the fluidized bed pyrolysis reactor The fluidized state of the aluminum oxide fluid yarns 240 'occurring in the fluidized bed 21 is the' bubbling fluidization 'shown in FIG. 5 (c). As shown in FIG. 5 (c), when the flow rate and the flow rate of the gas become large enough to cause 'bubbling fluidization', a large number of large and small bubbles 29a are generated in the fluidized bed, and the space of the bubbles 29a is utilized So that the crushed material 6a of the crude marble which is the waste of the screw feeder 13 can be easily pushed into the fluidized bed cracking reactor 21.

The pressure drop? P of the gas causing the fluidization in the reactor 21 'is proportional to the flow rate of the gas and has an inverse relationship with the diameter D of the reactor vessel and the density? _C of the fluidized yarn.

6 and 7 illustrate the case where pyrolysis and bubbling flow of the crude marble crushed material 6a, which is a waste in the fluidized bed pyrolysis reactor 21, have elapsed from the state of FIG. 4, The remaining aluminum oxide particles 240a are spilled through the upper end of the fluidized bed cracking reactor 21 and discharged to the outside (that is, the inside of the calcining furnace 200) ). ≪ / RTI >

Referring to FIG. 6, as compared with FIG. 4, the pulverized product 6a of crude marble is continuously introduced into the fluidized-bed pyrolysis reactor 21 as a result of which the height of the fluidized bed in the fluidized bed pyrolysis reactor 21 significantly increases have. The temperature of the calcining furnace 200 as a whole is raised to a temperature of 750 to 900 ° C (preferably maintained at a temperature of 800 to 850 ° C), and the temperature of the fluidized bed cracking reactor 21 therein also increases to 450 to 550 ° C Therefore, when the waste marble crushed material 6a enters the fluidized-bed pyrolysis reactor 21, it does not take long to pyrolyze. As a result, the organic material, that is, polymethyl methacrylate (PMMA), which is present in the waste marble, is decomposed into methyl methacrylate (MMA), is gasified and exits through the gas outlet port 208, And only aluminum oxide as an inorganic substance is present inside the fluidized-bed pyrolysis reactor (21).

When the crushed material 6a of the crude marble is further introduced as shown in FIG. 7 and the height of the fluidized bed 23 in the fluidized bed cracking reactor 21 becomes higher than the height of the housing 22 itself, The aluminum oxide 240a in the furnace 200 is combined with the outer fluidized bed 230 in the firing furnace 200 outside the wall of the housing 22. When the aluminum oxide 240a generated due to the pyrolysis of the crude marble has fallen into the outer fluidized bed 230 beyond the fluidized-bed pyrolysis reactor 21, the aluminum oxide 240a is coated with a carbon component on its surface, But there was no difference from the aluminum oxide existing as the external fluidized bed 230 from the beginning.

Aluminum oxide 240a is fired at a high temperature of 800 to 900 ° C in the firing furnace 200 to remove the carbon component coated on the surface of the fired furnace 200. Thereafter, the aluminum oxide 240b is refined, Is discharged to the outside of the firing furnace 200 by the alumina discharge device 203b.

8 is a plan view of the gas injection plate 24 shown in Figs. 4, 6 and 7, in which the nozzles 25 are inserted into a plurality of gas injection holes 24a formed on the upper surface of the gas injection plate 24 Respectively. FIG. 9 is an enlarged view of the lower part of the fluidized bed cracking reactor 21 shown in FIGS. 4, 6 and 7. The gas injection plate 24 is installed at the lower end of the fluidized bed cracking reactor 21, The gas injected from the nozzles 25 of the injection plate 24 collides with the upper surface of the gas injection plate 24 and is reflected and supplied into the fluidized bed 23.

The gas injection plate 24 used in the present invention has the gas injection holes 24a of 3 to 5 mm and the height of the nozzle 25 protruding from the upper surface of the gas injection plate 24 is 12 to 20 Mm. According to the design of the present inventor, it is most preferable that the protruded height of the nozzle 25 is 15 mm.

Fig. 10 is an enlarged view of the cyclone 30 and the hot filter 40 shown in Fig. 10, the gas 250 discharged from the firing furnace 200 includes solid matter such as fine dust, in addition to the gaseous methyl methacrylate, water vapor, and nitrogen, carbon dioxide, carbon monoxide, etc., (30) and the hot filter (40) to separate the solid particulates contained in the gas (250).

The fine dust particles and the solid particles 251 'contained in the gas 250 drop downward to be discharged to the solids discharge pipe 33. In this case, when the gas 250 flows through the upper side surface of the cyclone 30, Into the first solids storage (31). The gas 250 exhausted from the cyclone 30 rides on the second gas transfer line 132 to the subsequent hot filter 40 and the gas 250 is removed by the filter element 42 installed in the hot filter 40. [ The particles of the dust are again filtered. That is, the gas 250 passes through the filter element 42 and then to the first condenser 51 (see FIG. 3) through the gas discharge line 44 and the third gas transfer line 133, The trapped solids particles 252 'enter the second solids reservoir 41 through the solids discharge pipe 43. In FIG. 10, reference numerals 251 and 252 refer to solids contained in the gas 250, respectively, and filtered.

FIG. 11 shows the whole process of recovering the methyl methacrylate 250a and the aluminum oxide 240b by recycling the disintegrated marble 6a according to the present invention. 11, the polymethyl methacrylate (PMMA) 6b, the aluminum oxide 240a and the water 260 (a) are decomposed by thermal decomposition of the crushed product 6a of the crude marble 6 constituted of methyl methacrylate and aluminum hydroxide, And the additive / curing agent 270 are decomposed. At this time, the methyl polymethacrylate is immediately cut off from the polymerization linkages and decomposed again into methyl methacrylate (MMA, 250), and the methyl methacrylate discharged in the pyrolysis reaction and the gaseous state in the firing unit 20 is then condensed And is recovered as methyl methacrylate oil 250a. Meanwhile, the aluminum oxide 240a is fired at a high temperature in the firing furnace 200 (FIGS. 4, 6, and 7) to be refined 240b. In FIG. 11, the dotted line 21 represents the reaction occurring in the fluidized bed cracking reactor, and the dotted line 200 represents the calcination process occurring in the calcination furnace.

FIG. 12 is a conceptual diagram of an economical utilization plan of methyl methacrylate (250a) and aluminum oxide (240b) recovered by a recycling apparatus for waste marble by using the fluidized bed rapid thermal decomposition technique of the present invention.

In the past, it has been inevitable to reclaim waste marbles generated in various industries and sites. However, the present invention is not limited to the recycling process of waste marbles composed of crushing 601, pyrolysis 602, refining 603 and calcining 604 By implementing the process 600 as a plant facility, the methyl methacrylate 250a and alumina 240b can be successfully recovered from the waste marble. The recovered methyl methacrylate (MMA) may again be supplied to the artificial marble manufacturer 3 as an adhesive, or recycled as a raw material for acrylic or as a raw material for an LCD light guide plate. The aluminum oxide 240b recovered by the present invention is very high in purity and can be used as a valuable raw material because it can ensure good quality. That is, the aluminum oxide 240b can be supplied as a raw material for ceramics and cement to a ceramic / cement manufacturer or can be used as a raw material for manufacturing LCD and semiconductor substrates.

As described above, the apparatus for recycling waste marble using the fluidized-bed rapid pyrolysis technique according to the present invention and method thereof are characterized in that a reactor for pyrolysis of crude marble and a calcining furnace for calcining aluminum oxide are combined into a single furnace By installing a fluidized bed pyrolysis reactor, it is possible to drastically reduce the energy consumption by maximizing utilization of electric energy required in the pyrolysis reaction process and the firing process without waste.

The present invention can realize continuous operation without interruption by implementing a fluidized bed pyrolysis reactor, which is a core component of a waste marble recycling apparatus, in a fluidized bed mode rather than a conventional batch system, Methyl methacrylate converted into gaseous state by pyrolysis of marble can be passed to the next recovery process without any additional reaction that no longer needs, and thus the purity and recovery rate of methyl methacrylate can be dramatically increased have.

In addition, the present invention uses aluminum oxide as a fluidized bed which is basically filled both inside the pyrolysis reaction and calcination apparatus and inside the fluidized bed cracking reactor, and the aluminum oxide decomposed in the crude granite is transferred to the calcination furnace, The recovery of aluminum can be easily achieved and there is no need to replenish the flow yarn at all during the operation, which makes it possible to simplify the operation and maintenance of the recycling processing apparatus.

1: MMA processing company 2: aluminum hydroxide manufacturer
3: artificial marble manufacturer 3a, 6:
6a: broken marble crushed material 6b: PMMA
4a: Construction / Contractor 4b: Interior Builder
4c: Kitchen furniture manufacturer 5: reconstruction construction site
7: Transport vehicle 8: Landfill
8a: Landfill 10: Closet Marble Storage
10a: first driving motor 10b:
10c: gas discharge valve 10d: input pipe
11: Nitrogen tank 12: First screw feeder
12a: First screw drive motor 12b, 13b: Screw conveyor
13: second screw feeder 13a: second screw driving motor
20: Pyrolysis reaction and calcination apparatus 21: Fluidized bed pyrolysis reactor
21 ': Reactor 22: Cylindrical housing
22a: upper support 22b: lower support
22d: lower inclined extension portion 23: inner fluidized bed
24: gas injection plate 24a: gas injection hole
24b: internal space 25: nozzle
27: gas supply pipe for internal fluidized bed 29:
29a: bubble 29b: large gap
30: Cyclone 31: First solids storage
32: gas discharge pipe 33: solid discharge pipe
40: hot filter 41: second solids storage
42: filter element 43: solids discharge pipe
44: gas discharge pipe 45: electric power supply device
46: electric heater 51: first condenser
51a: water jacket 51b: water
52a: second-1 condenser 52b: second-2 condenser
53: Cooling water supply device 60: Electrostatic precipitator
70: gas meter 72: burner
80: compressor 91, 92, 93, 94: gas pressure regulator
101, 102, 103, 104: valves 105a, 105b: valves
106, 107, 108, 109, 110, 111, 112, 113: valve
121, 122, 123, 123a, 124, 125: gas supply line
131, 132, 133, 134, 135, 136: gas transfer line
137: gas return line 200: calcination furnace
201: electric heater 201a: electric wire
202: High power generating device 203: Screw conveyor
203a: second drive motor 203b: alumina discharge device
204: hopper 205: oxygen supplier
206: preheater 207: gas supply pipe for external fluidized bed
208: gas outlet 230: external fluidized bed
240, 204 ': fluidized bed (fluidized bed) 240a, 240b: alumina
250: MMA 251, 252: solids
251 ', 252': Solid particles 260: Water
270: additive / curing agent 501: storage hopper
502: Reactor 502a:
502b: heater 503: condenser
504: Cooling water supply device 505: Separator
506: Vacuum pump 507: Water smell odor remover
508: Purity adjuster 509: Filter
600: recycled processing step 601: crushing step
602: Pyrolysis process 603: Refining process
604: Firing process

Claims (10)

A reservoir 10 for storing a crushed product 6a of a crude marble made up of components including Methyl Methacrylate (MMA) and aluminum hydroxide;
A pyrolysis reaction and a calcining apparatus for producing methyl methacrylate and aluminum oxide by pyrolysis reaction at the same time as the pulverized product 6a of the crude marble stored in the storage 10 is heated and heated, 20);
A pyrolysis reactor in the pyrolysis reaction and calcining apparatus 20 for pyrolyzing the pulverized product 6a of the crude coal marble with the fluid yarn 240 'to cause pyrolysis into methyl methacrylate and aluminum oxide 21);
Solids separation means for separating the solids 251 and 252 from the gas discharged from the pyrolysis reaction and firing apparatus 20;
A condensing means for cooling the gas passing through the solids separating means to recover methyl methacrylate in a liquid state; And
And gas recycling means for supplying at least a part of the gas passing through the condensing means to at least one of the pyrolysis reaction and the calcination apparatus 20 with the storage tank 10,
The fluidized bed cracking reactor (21)
A reactor housing (22) having a top open and a vertically extending shape;
A lower inclined extension portion 22d provided at a lower end of the reactor housing and having an inclined shape so as to gradually expand radially outward as it goes down; And
And a gas injection plate (24) installed near the lower end of the reactor housing (22) and supplying nitrogen containing gas into the inner space of the reactor housing (22)
The fluidized yarn 240 filled in the fluidized bed cracking reactor 21 and the fluidized yarn 240 'filled in the fluidized bed cracking reactor 21 in the pyrolysis reaction and firing unit 20 are all oxidized Aluminum,
A fluidized bed 23 including a plurality of bubbles 29a is formed in the fluidized bed cracking reactor 21 by the gas supplied into the fluidized bed cracking reactor 21 through the gas injection plate 24,
The pulverized material 6a of the crude marble put into the fluidized bed 23 is pyrolyzed to produce gaseous materials including methyl methacrylate and water vapor and aluminum oxide,
Wherein the aluminum oxide is moved beyond the upper end of the fluidized-bed pyrolysis reactor (21) to the outside of the pyrolysis reactor (21). The pyrolysis apparatus according to claim 1, further comprising: a pyrolysis reaction and calcination apparatus (10) installed between the storage tank (10) and the pyrolysis reaction and firing apparatus (20) Further comprising a screw feeder (12, 13) for forcibly charging the internal space of the fluidized bed cracking reactor (21)
The screw feeders 12 and 13 include screw conveyors 12b and 13b for rotating the crushed material 6a of the waste marble while rotating in the pipe body and rotating the screw conveyors 12b and 13b And a drive motor (12a, 13a) for driving the pulverized marble. delete The gas injection device according to claim 1, wherein the gas injection plate has an area corresponding to a plane area of a lower end of the reactor housing, the gas injection plate has an empty space in the interior thereof, A plurality of gas injection holes 24a are formed in the upper surface of the gas injection plate 24 so that the nozzles 25 are coupled to each other so that the nozzles 25 are bent Characterized in that it is a recycling treatment device for waste marble using fluidized bed rapid pyrolysis technology. The pyrolysis and firing apparatus (20) according to claim 1, wherein the pyrolysis reaction and firing apparatus (20) is equipped with an electric heater and is heated to a temperature of 750 to 850 ° C, wherein the pyrolysis reaction and the temperature gradient in the firing apparatus Wherein the internal temperature of the reactor (21) is maintained at a temperature of 450 to 550 ° C. delete The apparatus according to claim 1, wherein the solid-
A cyclone 30 for taking in the gas from the pyrolysis reaction and firing unit 20 and rotating it in the inner space so that the solid material falls downward to be separated from the gas and to discharge only gas to the outside; And
And a hot filter (40) for receiving the gas discharged from the cyclone (30) and passing the filter element (42) to separate solids and discharge only gas to the outside, A recycling treatment system for marble waste. The apparatus according to claim 1,
A first condenser (51) for separating methyl methacrylate by passing a gas from the solids separating means through a conduit in contact with a water jacket (51a) containing water at room temperature; And
A second condenser 52a for separating methyl methacrylate by passing a gas from the first condenser 51 through a conduit in contact with the cooling water at a temperature lower than room temperature and provided at the rear end of the first condenser 51, , 52b). ≪ / RTI > An apparatus for recycling waste marble as claimed in claim 1, [2] The apparatus of claim 1, further comprising an electrostatic precipitator connected to a rear end of the condensing unit, the electrostatic precipitator including dust collecting plates and discharge electrodes therein,
The electrostatic precipitator causes a corona discharge to occur between the dust collecting plate and the discharge electrode while passing the discharged gas through the condensing means to clean the gas by causing fine particulate matter in the gas to adhere to the dust collecting plate Characterized in that it is a recycling treatment device for waste marble using fluidized bed rapid pyrolysis technology. (a) a first step of introducing a pulverized product (6a) of crude marble, which is composed of components including methyl methacrylate and aluminum hydroxide, into a pyrolysis reaction and calcining apparatus (20);
(b) heating the inside of the pyrolysis reaction and firing unit 20 to pyrolyze the crushed material 6a of the waste marble into gaseous materials including methyl methacrylate and steam and aluminum oxide, Second step of firing treatment:
(c) a third step in which the gas discharged from the pyrolysis reaction and burning apparatus 20 passes through the cyclone 30 and the hot filter 40 so that the solids 251 and 252 in the gas are separated and removed;
(d) a fourth step of recovering methyl methacrylate in a liquid state by cooling and condensing the gas passing through the hot filter 40 through a condensing means; And
(e) a fifth step of purifying the gas passing through the condensing means and supplying at least a part of the gas to the pyrolysis reaction and firing unit 20,
The pyrolysis reaction and pyrolysis reactor 21 for pyrolyzing the pulverized product 6a of the marble with the fluidized yarn 240 'to flow into the pyrolysis reaction and firing unit 20 to pyrolyze them into methyl methacrylate and aluminum oxide Installed,
The fluidized bed cracking reactor (21) comprises a reactor housing (22) having an open top and a shape extending vertically; A lower inclined expanding portion 22d provided at the lower end of the reactor housing 22 and having an inclined shape so as to gradually expand radially outward as it goes down; And a gas injection plate (24) installed near the lower end of the reactor housing (22) and supplying nitrogen containing gas into the inner space of the reactor housing (22)
The fluidized yarn 240 filled in the fluidized bed cracking reactor 21 and the fluidized yarn 240 'filled in the fluidized bed thermal cracking reactor 21 in the pyrolysis reaction and firing apparatus 20 are all mixed with aluminum oxide Lt;
A fluidized bed 23 including a plurality of bubbles 29a is formed in the fluidized bed cracking reactor 21 by the gas supplied into the fluidized bed cracking reactor 21 through the gas injection plate 24,
The pulverized material 6a of the crude marble put into the fluidized bed 23 is pyrolyzed to produce gaseous materials including methyl methacrylate and water vapor and aluminum oxide,
Wherein the aluminum oxide is transferred to the outside of the upper part of the fluidized bed cracking reactor (21).

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