WO2011142609A2 - Méthode de récupération de composés d'aluminium et de méthacrylate de méthyle à partir de déchets de marbre artificiel - Google Patents

Méthode de récupération de composés d'aluminium et de méthacrylate de méthyle à partir de déchets de marbre artificiel Download PDF

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WO2011142609A2
WO2011142609A2 PCT/KR2011/003520 KR2011003520W WO2011142609A2 WO 2011142609 A2 WO2011142609 A2 WO 2011142609A2 KR 2011003520 W KR2011003520 W KR 2011003520W WO 2011142609 A2 WO2011142609 A2 WO 2011142609A2
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Prior art keywords
mma
artificial marble
waste artificial
recovering
aluminum compound
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PCT/KR2011/003520
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English (en)
Korean (ko)
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WO2011142609A3 (fr
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김의현
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(주)서정화학
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Priority claimed from KR1020100045472A external-priority patent/KR100982728B1/ko
Priority claimed from KR1020100073424A external-priority patent/KR101145280B1/ko
Priority claimed from KR20110043171A external-priority patent/KR20120125090A/ko
Application filed by (주)서정화학 filed Critical (주)서정화학
Publication of WO2011142609A2 publication Critical patent/WO2011142609A2/fr
Publication of WO2011142609A3 publication Critical patent/WO2011142609A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates

Definitions

  • the present invention relates to a method for recovering MMA from waste artificial marble, and more particularly, to a method for recovering MMA by heating and distilling waste artificial marble.
  • the present invention recovers the liquid aluminum compound produced by acid or alkali treatment of the scrap and dust of artificial marble generated during the production of waste artificial marble or artificial marble, and recovers the remaining PMMA, which is the remaining residue, compared to the conventional method.
  • the present invention relates to a method for recovering an aluminum compound and MMA from waste artificial marble, which is an environmentally friendly method that increases the recovery rate of the liquid aluminum compound and MMA using a small amount of energy.
  • artificial marble In general, artificial marble is described in the prior art as registered in Korean Patent No. 10-0891378, artificial marble has recently been spotlighted building materials, produced about 300,000 tons worldwide, and has a market size of about 600 billion won.
  • the domestic production of artificial marble is more than 100,000 tons, and has a market of about 250 billion won, combined with domestic and export.
  • MMA Metal Methacrylane
  • inorganic substance aluminum hydroxide
  • the artificial marble manufactured at the mixing ratio is processed to the required size after manufacture and used as a top plate of a sink or other article. A large amount of scrap and dust is generated during the processing, and the scrap and dust cannot be used for other products. This is disposed of.
  • the disposal method is a simple landfill or discarded by incineration, causing secondary soil contamination.
  • a method of recovering alumina through a calcination process has been proposed, but MMA corresponding to petroleum has a disadvantage of being lost by combustion.
  • Japanese Laid-Open Patent Publication JP2006-206638 proposes a decomposition method for recovering inorganic filler and thermosetting resin from artificial marble waste.
  • the decomposition method is a method of dissolving thermosetting resin in subcritical state by separating artificial marble waste into water or organic solvent to increase the temperature and pressure of about 180 ⁇ 370 degrees Celsius, and recovering organic matter or recovered MMA and inorganic filler. There is a disadvantage of falling purity.
  • Patent No. 10-0891378 has a process of crushing the scrap of artificial marble made of MMA and aluminum hydroxide through a crusher;
  • the crushed product and the artificial marble dust of the crushing process is supplied to the pyrolysis furnace which is heated by electricity by a screw feeder to thermally decompose, and the pyrolysis furnace is formed by a plurality of horizontal pyrolysis tubes formed with screws inside the screw.
  • a pyrolysis process in which the pyrolysis is carried out while the shredded material is transferred, and the pyrolysis pipe is connected in series so that the internal transport flow paths are continuously connected, and the pyrolysis is repeatedly performed while increasing the internal temperature of the shredded material;
  • An MMA recovery process of receiving a gas component generated in the horizontal transfer pyrolysis process to condense it into a condenser to liquefy, and separate the condensed liquid into a centrifuge and an oil / water separator to receive an MMA component from which water and impurities are removed;
  • a firing step of supplying the residues of the char state left in the horizontal transfer pyrolysis process to a firing furnace, and heating and completely removing the organic substances;
  • a preheating process in which the high temperature exhaust gas generated in the firing process is supplied to a pyrolysis tube into which initial crushed matter is introduced from among a plurality of pyrolysis tubes through a transfer tube to heat the introduced crushed substance to be preheated;
  • artificial marble is rapidly expanding its use in flooring and other applications due to improvements in mechanical properties as well as decorative finishing materials for building walls and furniture. .
  • the artificial marble widely used in Korea is manufactured by mixing an aluminum compound having a flame retardant effect with an acrylic resin whose main component is methyl methacrylate (hereinafter, referred to as 'MMA'). It consists of 30 to 45% by weight, about 45 to 65% by weight of inorganic fillers and very small amounts of additives.
  • the aluminum compound which is an inorganic filler
  • the aluminum compound has good properties for enhancing the strength, abrasion resistance, and color development of artificial marble. Therefore, almost all aluminum hydroxide is used as an inorganic filler in artificial marble products produced in Korea.
  • Regeneration (S3) with purified pure resin, and the powdered filler and additive raw materials classified in the pyrolysis treatment step are calcined and heated at high temperature to remove impurities and additives, and to regenerate the calcined filler (S4).
  • a method of treating waste artificial marble is known.
  • the artificial marble scrap and dust are thermally decomposed to separate and purify the volatile MMA, thereby recovering pure MMA, and the pyrolyzed residue is completely burned through a calcination furnace to remove trace impurities.
  • the pure alumina is received.
  • the alumina produced is carbonized by combustion, and the color appears black.
  • This carbonization is carbonized as the organic matter remaining in the first MMA recovery process is fired at a high temperature, which not only causes serious problems in recycling alumina but also thermally decomposes at a high temperature of 200 to 700 ° C. in the process of recovering MMA.
  • MMA which is an organic compound, is partially burned out by high temperature heat, and in addition, a lot of energy is consumed due to high temperature pyrolysis even in a calcination process for recovering alumina.
  • aluminum an inorganic filler
  • alumina aluminum oxide
  • Japanese Patent Laid-Open Publication No. 2006-206638 and Japanese Patent Laid-Open Publication No. 2008-184475 are techniques for separating and recovering organic matters of acrylic resin from waste artificial marble, such as bathroom materials, kitchen counter materials, furniture materials, interior materials, exterior materials, etc. Is an inorganic filler used for building materials of heat-resisting materials, using acrylic artificial marble, a plastic waste containing a thermosetting acrylic resin containing silica, using a subcritical fluid such as water, an alcohol or an ether, or an organic solvent.
  • the present invention has been made to solve the above problems, it is to provide a method for recovering MMA from the waste artificial marble to efficiently recover the MMA from the waste artificial marble by installing a simple yet inexpensive device.
  • the present invention recovers the liquid aluminum compound produced by acid or alkali treatment of scrap and dust of artificial marble generated during the production of waste artificial marble or artificial marble, and recovers the remaining PMMA, which is the remaining residue, from the conventional method.
  • Another object is to provide a method for recovering aluminum compounds and MMA from waste artificial marble, characterized in that the economic method using a small amount of energy due to no pyrolysis when recovering the liquid aluminum compound from the waste artificial marble.
  • the waste artificial marble is thermally decomposed at a high temperature of 200 to 700 ° C., and thus MMA, which is an organic compound, is partially burned and lost by high temperature heat, and thus the recovery of MMA is low.
  • MMA Poly Methyl Methacrylate
  • Another object is to provide a method for recovering aluminum compounds and MMA from waste artificial marble.
  • the present invention is to separate the liquid aluminum compound by the solid-liquid separation after the pretreatment process to the reaction process of the aluminum compound, and to recover the remaining PMMA, so that the content of PMMA components contained in the waste artificial marble scrap and dust 30
  • the content of the PMMA component is relatively increased to 85 to 95% by weight, so that the MMA can be recovered more efficiently, and the MMA recovery rate is higher than the energy input.
  • Another object is to provide a method for recovering aluminum compounds and MMA from waste artificial marble.
  • the present invention relates to a method of recovering MMA from waste artificial marble, the method of recovering MMA from waste artificial marble, the water removal step of removing water from the raw material waste artificial marble in the drying furnace (20); MMA extraction step of extracting MMA in the melting furnace 10 to remove the raw material moisture; Characterized in that it comprises a; purity adjustment step of adjusting the purity using a distillation.
  • Solid-liquid separation process for separating the aluminum compound and the PMMA in a solid state using a solid-liquid separation device (P400);
  • a method for recovering an aluminum compound and MMA from the waste artificial marble comprising a
  • An aluminum compound reaction step (P300) in which water is mixed with the slurry formed in the step and then heated to react the aluminum component with the alkali compound;
  • Solid-liquid separation process for separating the aluminum compound and the PMMA in a solid state using a solid-liquid separation device (P400);
  • Another method for solving the problem is a method of recovering an aluminum compound and MMA from the waste artificial marble comprising a.
  • the aluminum compound produced in the first aspect of the invention is an aluminum acid compound
  • the aluminum compound produced in the second aspect of the invention is an aluminum base compound
  • the present invention is the aluminum compound reaction step (P300) is heated for 1 to 3 hours at a temperature of 60 ⁇ 200 °C,
  • PMMA in the solid state separated in the MMA separation process (P400) is subjected to a PMMA powdering process (P500), which is dehydrated and dried and powdered after washing 3 to 5 times,
  • the PMMA powdered in the powdering process (P500) is characterized in that it comprises a MMA recovery process (P600) for recovering the condensed MMA liquid pyrolyzed to a temperature of 150 ⁇ 350 °C.
  • the present invention has the significant effect of efficiently recovering MMA from waste artificial marble using a simple but inexpensive method.
  • the present invention is an economic method for recovering a liquid aluminum compound using a small amount of energy as it does not pyrolyze at a high temperature when recovering the liquid aluminum compound from waste artificial marble or artificial marble scrap or powder.
  • the conventional method pyrolyzes waste artificial marble at a high temperature of 200 to 700 ° C, the organic compound PMMA is partially burned and lost by high temperature heat, and thus the recovery rate of MMA is low. It is an advantage that the recovery rate of MMA is high because there is no loss of PMMA, and first, the liquid aluminum compound is separated from the waste artificial marble and then the PMMA is recovered.
  • FIG. 1 is a schematic diagram of the present invention.
  • Figure 2 is a front view of the melting furnace of the present invention
  • Figure 3 is a side view of the melting furnace of the present invention
  • FIG. 6 is a block diagram showing a process for recovering MMA and alumina from waste artificial marble according to a conventional method
  • FIG. 7 is a block diagram showing a process for recovering MMA and alumina from waste artificial marble in accordance with another conventional method
  • FIG. 8 is a block diagram showing a process for recovering the aluminum compound and MMA from the waste artificial marble in accordance with the present invention.
  • filter 110 secondary capacitor
  • vent 10a raw material input pipe
  • the present invention relates to a method of recovering MMA from waste artificial marble, the method of recovering MMA from waste artificial marble, the water removal step of removing water from the raw material waste artificial marble in the drying furnace (20); MMA extraction step of extracting MMA in the melting furnace 10 to remove the raw material moisture; Characterized in that it comprises a; purity adjustment step of adjusting the purity using a distillation.
  • the MMA extracted in the MMA extraction step is characterized in that the impurities are removed by filtering in the filter 90 before being introduced into the distillation (60).
  • FIG. 1 is a system diagram of the present invention
  • Figure 2 is a front view of the melting furnace of the present invention
  • Figure 3 is a side view of the melting furnace of the present invention
  • Figure 4 is a front view of the still distiller of the present invention
  • Figure 5 is a plan view of the distiller of the present invention.
  • the present invention is a device used in the method for recovering MMA from the waste artificial marble, waste artificial marble which is a raw material is introduced into the raw material input pipe formed in the drying furnace 20, the raw material dried in the drying furnace 20 is a raw material The discharged raw material is discharged through the discharge pipe, and the discharged raw material is introduced into the input pipe of the melting furnace 10, and the raw material which is pyrolyzed and vaporized in the melting furnace 10 is discharged through the gas discharge pipe of the melting furnace 10, and the primary capacitor 30 After passing through the primary condenser 30, the liquefied MMA passes through the filter 90, through the distillation apparatus 60, and again through the secondary capacitor 110 to the storage tank 70 Stored.
  • the filter (90) Before the liquefied MMA is passed through the primary capacitor 30 is introduced into the filter (90), first through the oil and water separator (41) to remove the water not yet dried in the drying furnace, the intermediate storage tank (80) After passing through), the water is introduced into the filter 90, and the water is removed through the oil / water separator 42 before being stored in the storage tank 70 through the MMA through the secondary capacitor 110.
  • the melting furnace 10 has a cell 17 concentrically installed in the cylindrical case 16, the heater 11 and the scraper 12 is installed in the cell 17, the scraper ( 12 is located in the center of the case 16 and a plurality of rotary blades are radially installed on the rotary shaft 13 which is rotated by the motor 12, the rotary blades and the arm 14 is fixed to the rotary shaft 13 and It consists of two members of the wear piece 15 rotatably coupled to the arm 14, the wear piece 15 is installed in contact with the inner wall of the heating furnace, it is possible to replace after wear.
  • the wear piece 15 is to adjust the length of the arm 14 is coupled, so that some parts are in direct contact with the inner wall of the cell 17, the rest is to be spaced apart from the inner wall of the cell 17 .
  • the inner cylinder 18 is provided concentrically on the rotary shaft 13, a plurality of rotary blades are radially installed on the inner cylinder 18.
  • drying furnace 20 is the same structure as the melting furnace 10, only the heating heat source is to heat the outside of the case with light oil or gas instead of the heater.
  • the still cell 60 is provided with a cell 62 inside the cylindrical case 61, a rotation shaft 63 is installed at the center of the cell 62, and a plurality of impellers 64 are installed at the rotation shaft 63.
  • the inlet tube 65 and the outlet tube 66 are formed in the case 61 and the cell 62, the distillation motor 67 is installed on the side of the case 61, the diesel oil or gas Distillation by heating outside the case.
  • the present invention relates to a method for recovering MMA from waste artificial marble by heating and distillation.
  • waste artificial marble which is a raw material
  • waste artificial marble which is a raw material
  • the raw material dried in the drying furnace 20 is discharged through the raw material discharge pipe is introduced into the input pipe of the melting furnace (10).
  • the raw material which is pyrolyzed and vaporized in the melting furnace 10 is discharged through the gas discharge pipe of the melting furnace 10 and passes through the primary capacitor 30 which is a cooler.
  • the MMA liquefied through the primary capacitor 30 passes through the oil and water separator 41 and then removes moisture that has not been dried in the drying furnace, then passes through the intermediate storage tank 80 and then passes through the filter 90. After the impurities are removed, the purity is adjusted via the distillation apparatus 60, and then stored in the storage tank 70 via the secondary capacitor 110 again.
  • the melting furnace 10 is installed in the cylindrical case 16, the inner cylinder of the cell 17 is concentrically installed. And the heater 11 and the scraper 12 is installed in the cell 17, the scraper 12 is located in the center of the case 16 and a plurality of rotary shafts 13 that are rotated by the motor 12 A rotary blade is radially installed, and the rotary blade is composed of two members: an arm 14 fixed to the rotary shaft 13 and a wear piece 15 rotatably coupled to the arm 14.
  • the wear piece 15 is installed in contact with the inner wall of the melting furnace, and can be replaced after wear.
  • the wear piece is coupled to the arm with a pin. When the arm rotates about the rotation axis, the end of the wear piece is attached to the inner wall of the melting furnace. The raw material adhering to the cell is scraped out by contacting the installed cell.
  • the wear piece 15 is adjusted by the length of the arm 14 is coupled, so that a part is in direct contact with the inner wall of the cell 17, the rest is installed spaced apart from the inner wall of the cell 17.
  • the case and cell are made of stainless steel and the arm and wear pieces are made of 45C heat treated steel.
  • the inner cylinder 18 is installed concentrically on the rotary shaft 13, a plurality of rotary blades may be radially installed on the inner cylinder 18.
  • the heater may be installed outside the case.
  • drying furnace 20 is the same structure as the melting furnace 10, only the heating heat source is to heat outside the case with light oil or gas instead of the heater.
  • the drying furnace is made of 45C heat-treated steel.
  • the distillation apparatus 60 of the present invention the cell 62 is installed in the cylindrical case 61, the rotating shaft 63 is installed in the center of the cell 62, the plurality of impellers (rotating shaft 63) ( 64 is installed, the inlet tube 65 and the outlet tube 66 are formed in the case 61 and the cell 62, the still motor 67 is installed on the side of the case 61.
  • the purity of the MMA is adjusted using a distillation machine, and the distillation temperature is 55-180 ° C.
  • the raw material storage step stores the received raw materials in an underground storage tank.
  • the raw material transfer step transfers the raw materials from the storage tank to the drying furnace using a conveyor.
  • the water removal step is to remove the moisture of the raw material transferred to the drying furnace, the heating temperature is 100 ⁇ 250 °C.
  • Water evaporation temperature is 100 °C, if it is higher than 250 °C MMA is easy to thermal decomposition, it is determined as 100 ⁇ 250 °C.
  • the dehydrated raw materials are transferred to the melting furnace and MMA is extracted.
  • Heating temperature is 300-450 degreeC. Pyrolysis is good from 300 °C, and MMA is easily burned out above 450 °C, so set the heating temperature to 300 ⁇ 450 °C.
  • the extracted MMA is then stored in the primary storage tank. On the other hand, raw material sludge from which water and MMA are removed from the furnace is discharged.
  • the impurity removal step removes impurities by filtering the MMA stored in the primary storage tank.
  • Purity adjustment step is to adjust the purity of the MMA using a still. Distillation temperature is 55 ⁇ 180 °C.
  • the secondary storage step stores the purified MMA in a storage tank. In the shipping stage, the MMA is shipped using tank lorry.
  • the present invention can efficiently recover MMA from waste artificial marble using a simple and inexpensive method.
  • the technology for recovering alumina and MMA from waste artificial marble is mainly derived from alumina from waste artificial marble by high temperature pyrolysis It is an invention that improves the problem of the large amount of energy required to recover MMA and the problem that MMA, which is an organic compound contained in the waste artificial marble, is burned and lost in the process, from waste artificial marble or artificial marble scrap or powder.
  • the recovery of the liquid aluminum compound does not thermally decompose at high temperature, so that the MMA is not lost and the recovery rate of the aluminum compound and the MMA is increased by using a small amount of energy.
  • the invention basket case crude marble powder slurry sulfuric acid, hydrochloric acid, by adding an acid compound such as nitric acid reacts with the aluminum contained in the basket case crude marble powder component of the liquid aluminum sulfate [Al 2 (SO 4 ) 3 ], the first aspect of the invention (hereinafter referred to as "first aspect of the invention") for producing and recovering aluminum compounds such as aluminum chloride (AlCl 3 ), aluminum nitride [Al (NO 3 ) 3 ], and
  • the present invention relates to a second embodiment of the present invention in which a slurry is added by adding water to a waste artificial marble powder, followed by the addition of an alkali compound such as sodium hydroxide and potassium hydroxide to form and recover liquid aluminum hydroxide (hereinafter referred to as 'second embodiment invention'). It is divided into
  • the invention of the two embodiments according to the present invention differs only in the kind of the solvent for dissolving the aluminum component contained in the waste artificial marble powder selected in the slurry (Plu) and aluminum compound reaction step (P300) Only the pretreatment step P100 and the solid-liquid separation step P400 are performed by the same method.
  • Solid-liquid separation process for separating the aluminum compound and the PMMA in a solid state using a solid-liquid separation device (P400);
  • the second aspect of the invention according to another embodiment of the present invention is a method for recovering the aluminum compound and MMA from waste artificial marble
  • An aluminum compound reaction step (P300) in which water is mixed with the slurry formed in the step and then heated to react the aluminum component with the alkali compound;
  • Solid-liquid separation process for separating the aluminum compound and the PMMA in a solid state using a solid-liquid separation device (P400);
  • the pretreatment process (P100) is a process for sorting the scrap and dust of the artificial marble generated during the production of waste artificial marble or artificial marble, when using the waste artificial marble as raw materials using a waste artificial marble using a grinder Use powder powdered and then sieved.
  • the grinding process is omitted or the grinding process is omitted, and the powder filtered through the mesh is used.
  • a standard mesh having a size of 50 to 200 Mesh so that the selected waste artificial marble powder is uniformly mixed with the fluid to be suitable for the size of powder particles that are easily slurryed.
  • the slurry (slurry) process (P200) is slurryed by adding water to the waste artificial marble powder.
  • the amount of water to be mixed is preferably mixed 100 to 120 parts by weight with respect to 100 parts by weight of waste artificial marble powder. If the mixing amount of water is less than 100 parts by weight, the slurry may not form properly due to the lack of water contained in the waste artificial marble powder. If the mixing amount of water exceeds 120 parts by weight, the slurry may be formed.
  • the waste artificial marble powder contained in the waste water may contain an excessive amount of water, thereby reducing the efficiency of workability in a later step.
  • the slurry (slurry) step (P200) is slurryed by adding an alkali compound to the waste artificial marble powder.
  • the added alkali compound functions to react with the aluminum contained in the waste artificial marble powder while slurrying the waste artificial marble powder.
  • the mixed amount of the alkali compound added to the waste artificial marble powder is preferably mixed with 115 to 150 parts by weight based on 100 parts by weight of the waste artificial marble powder. If the mixing amount of the alkali compound is less than 115 parts by weight, the waste artificial marble powder may not be slurried properly, or the lack of the alkali compound contained in the waste artificial marble may not sufficiently react with aluminum in the next step.
  • the mixing amount of the alkali compound exceeds 150 parts by weight, the excess alkali compound is added compared to the aluminum content contained in the waste artificial marble powder, so that excess water must be mixed in the subsequent process, so there is a concern that the efficiency of workability may decrease. have.
  • the mixing amount of the alkali compound is an amount calculated based on the alkali compound having an alkali purity of 45 to 50%.
  • the alkali compound usable in the present invention is preferably recovered from the liquid sodium aluminate by adding an alkali compound such as sodium hydroxide and potassium hydroxide, and in the case of a hydroxide compound exhibiting equivalent or more performance in addition to the alkali compound defined above. It can be used regardless.
  • the aluminum compound reaction step (P300) is performed by mixing an acid compound in a waste artificial marble powder slurry and then reacting the aluminum compound with the acid contained in the waste artificial marble powder to generate a liquid aluminum compound. It is a process to dilute and produce a liquid aluminum compound by adding water.
  • the amount of the acid compound added to the waste artificial marble powder is preferably mixed with 115 to 150 parts by weight based on 100 parts by weight of the waste artificial marble powder.
  • the mixed amount of the acid compound is less than 115 parts by weight, aluminum may not be sufficiently dissolved due to the lack of the acid compound contained in the waste artificial marble powder, and when the mixed amount of the acid compound exceeds 150 parts by weight, the waste artificial Since an excess amount of an acid compound is contained in marble powder, there exists a possibility that workability efficiency may fall in a post process.
  • the mixed amount of the acid compound is an amount calculated based on the agricultural compound having an acid purity of 90% or more.
  • the amount of water added to the waste artificial marble powder slurry is preferably added to 100 to 500 parts by weight based on 100 parts by weight of the waste artificial marble powder, the amount of water is not necessarily limited to the above limited range, the liquid aluminum compound produced The purity can be adjusted accordingly.
  • an acid compound usable in the present invention sulfuric acid, hydrochloric acid, nitric acid, acetic acid, or the like is preferably used.
  • an acid compound may be used regardless of the type.
  • the aluminum compound reaction process (P300) is to produce aluminum hydroxide by the reaction of aluminum and an alkali compound dissolved by heating and dissolving the waste artificial marble powder slurry, followed by adding water to the liquid sodium aluminate It is a process of diluting.
  • the amount of water added to the waste artificial marble powder slurry is preferably added to 100 to 120 parts by weight based on 100 parts by weight of the waste artificial marble powder, and the mixing amount of water is not necessarily limited to the range defined above, and the resulting liquid aluminum sulfate The purity can be adjusted accordingly.
  • the reaction conditions of the first aspect and the second aspect of the present invention are preferably heated at a temperature of 60 to 200 ° C. for 1 to 3 hours for reaction. If the reaction conditions are less than the above-mentioned reaction conditions, the aluminum compound may not be sufficiently produced. If the reaction conditions exceed the above-mentioned reaction conditions, the aluminum content contained in the waste artificial marble may be reduced. Since at least a corresponding amount of aluminum compound is not produced, there is a fear that it becomes an uneconomical manufacturing method.
  • both the first aspect invention and the second aspect invention according to the present invention are carried out through the same process.
  • Solid-liquid separation process is a process of separating a liquid aluminum compound, such as aluminum sulfate or aluminum hydroxide, and MMA in a solid state using a filter press or the like by a conventional method.
  • the separately separated solid state PMMA was washed three to five times with water using a powdering process (P500), followed by dehydration of moisture contained in the PMMA. Dry to powder PMMA.
  • the powdered PMMA is recovered through the MMA recovery step (P600) of recovering the condensed MMA liquid pyrolyzed to dryness at a temperature of 150 ⁇ 350 °C. If the pyrolysis temperature is lower than 150 °C, MMA may not be sufficiently dried from the powdered PMMA, and if the pyrolysis temperature exceeds 350 °C, MMA is no longer significantly dried from the powdered PMMA. Therefore, there is a risk of uneconomical manufacturing method.
  • the first aspect and the second aspect of the invention according to the present invention after the pretreatment step (P100) to the aluminum compound reaction step (P300) after the first liquid-liquid separation of the liquid aluminum compound to separate the remaining solid state
  • the content of PMMA component mixed with waste artificial marble scrap and dust is 30-45% by weight
  • the content of PMMA component is 85-95% by weight by separation of liquid aluminum compound.
  • MMA can be recovered more efficiently, and MMA recovery rate is higher than energy input.
  • Synthetic marble was prepared by using 40 wt% MMA, 57 wt% aluminum hydroxide as an inorganic filler, and 3 wt% of a small amount of additives. Then, a slurry was prepared by mixing 100 parts by weight of water with 100 parts by weight of the artificial marble and then slurry 115 parts by weight of concentrated sulfuric acid is added to the solution for reaction. At this time, the reaction temperature is maintained at 60 °C 1 hour. Thereafter, 254 parts by weight of water is added to produce a liquid aluminum sulfate. Solid aluminum sulfate containing liquid aluminum sulfate and the remaining residual PMMA were separated by a liquid press to separate liquid aluminum sulfate and solid PMMA, and only liquid aluminum sulfate was recovered separately.
  • the solid PMMA separated by solid-liquid separation is washed 3 ⁇ 5 times using purified water using ion exchange resin, etc., and then powder is prepared by dehydration and drying.
  • MMA dried using heat is introduced into a pyrolysis process at 280 ° C to collect the gas generated by pyrolysis of PMMA, and condensed using a condenser to prepare an MMA liquid.
  • the MMA solution and water were separated and stored first by using an oil / water separator, and the first stored MMA solution was distilled at 100 ° C. or lower for secondary purification, and the purified MMA solution was condensed to recover MMA.
  • Example 1 Using the artificial marble having the same components as in Example 1, by mixing 150 parts by weight of 50% caustic soda to 100 parts by weight of artificial marble dust and then maintained the slurry solution at 120 °C for 3 hours or more water 110 parts by weight was added to produce sodium aluminate, an alkaline liquid, and then the solids containing PMMA were separated using a filter press to separate the liquid sodium aluminate and the solid PMMA, and the liquid sodium aluminate was recovered separately.
  • the solid MMA 40 kg separated through solid-liquid separation was washed 3 to 5 times using purified water using an ion exchange resin, and then dehydrated and dried to prepare a powder.
  • MMA dried using heat was introduced into a pyrolysis process at around 350 ° C. to decompose MMA, and the gas generated was collected and condensed using a condenser to prepare an MMA solution, followed by purification in the same manner as in Example 1.
  • the MMA solution was condensed to recover MMA.
  • Example 1 460 parts by weight of liquid aluminum sulfate (based on 8% aluminum oxide) and 39.9 parts by weight of MMA, was recovered, In the case of Example 2, the recovered sodium aluminate (based on 10% aluminum oxide) recovered 365 parts by weight and MMA 39.9.
  • Example 1 is 56.3 parts by weight when converted to the amount of aluminum hydroxide
  • Example 2 the liquid sodium aluminate (based on 10% aluminum oxide) is 365 parts by weight, so when it is converted into the amount of aluminum hydroxide, it corresponds to 55.8 parts by weight, and the components of the artificial marble used in this embodiment Considering that the weight of the aluminum oxide is 57% by weight, it was confirmed that the recovery of aluminum showed a high recovery of 97.9 to 98.7%.
  • the recovery rate of the MMA of Examples 1 and 2 are all higher than 99.7% It can be seen that it represents.
  • the present invention is characterized by being able to increase the recovery of MMA and aluminum, as confirmed in Examples 1 and 2, even with a small amount of energy.
  • the present invention is a high-industrial invention as a new method for recycling industrial wastes by using an environmentally friendly method that increases the recovery rate of aluminum compounds and MMA from waste artificial marble or artificial marble scrap or powder using a small amount of energy.

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  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne une méthode de récupération de composés d'aluminium et de méthacrylate de méthyle à partir de déchets de marbre artificiel, les composés d'aluminium étant récupérés en réalisant un traitement à l'acide et aux alcalis des déchets de marbre artificiel ou des morceaux et de la poudre de marbre artificiel produits lors du processus de transformation du marbre artificiel en produit, et le polyméthacrylate de méthyle est isolé et récupéré en réalisant la distillation à sec de la fraction restante. Cette méthode industrielle est rentable, puisque les composés d'aluminium sont récupérés en utilisant une petite quantité d'énergie, car on ne réalise pas de décomposition thermique lors de la récupération de composés d'aluminium dans les déchets de marbre artificiel. La présente invention a aussi l'avantage d'un rendement élevé de récupération de méthacrylate de méthyle puisque les composés d'aluminium sont récupérés sans perte de méthacrylate de méthyle, car les déchets de marbre artificiel sont soumis à un traitement à l'acide et aux alcalis.
PCT/KR2011/003520 2010-05-14 2011-05-12 Méthode de récupération de composés d'aluminium et de méthacrylate de méthyle à partir de déchets de marbre artificiel WO2011142609A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2010-0045472 2010-05-14
KR1020100045472A KR100982728B1 (ko) 2010-05-14 2010-05-14 폐인조대리석으로부터 산처리에 의해 알루미늄 화합물과 ｍｍａ를 회수하는 방법
KR1020100073424A KR101145280B1 (ko) 2010-05-14 2010-07-29 폐인조대리석으로부터 알칼리 처리에 의해 알루미늄 화합물과 ｍｍａ를 회수하는 방법
KR10-2010-0073424 2010-07-29
KR10-2011-0043171 2011-05-06
KR20110043171A KR20120125090A (ko) 2011-05-06 2011-05-06 폐인조대리석으로부터 ｍｍａ를 회수하는 방법

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WO2011142609A2 true WO2011142609A2 (fr) 2011-11-17
WO2011142609A3 WO2011142609A3 (fr) 2012-03-01

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CN109232973A (zh) * 2018-09-10 2019-01-18 夏美佳 一种废旧有机玻璃塑料连续裂解装置

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JP2006206638A (ja) * 2005-01-25 2006-08-10 Matsushita Electric Works Ltd 人造大理石の分解方法
KR100883365B1 (ko) * 2007-10-12 2009-02-11 제일모직주식회사 폐아크릴계 수지의 재활용 방법 및 이를 이용한 아크릴계인조대리석용 조성물
KR100891378B1 (ko) * 2008-08-27 2009-04-02 (주)알앤이 폐인조대리석으로부터 ｍｍａ와 알루미나의 회수방법
KR20090083042A (ko) * 2008-01-29 2009-08-03 이선근 폐인조 대리석 열분해 처리 장치 및 이를 이용한 폐인조 대리석 처리 방법
JP2009227980A (ja) * 2008-02-26 2009-10-08 Panasonic Electric Works Co Ltd プラスチックの分解・回収方法

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Publication number Priority date Publication date Assignee Title
JP2006206638A (ja) * 2005-01-25 2006-08-10 Matsushita Electric Works Ltd 人造大理石の分解方法
KR100883365B1 (ko) * 2007-10-12 2009-02-11 제일모직주식회사 폐아크릴계 수지의 재활용 방법 및 이를 이용한 아크릴계인조대리석용 조성물
KR20090083042A (ko) * 2008-01-29 2009-08-03 이선근 폐인조 대리석 열분해 처리 장치 및 이를 이용한 폐인조 대리석 처리 방법
JP2009227980A (ja) * 2008-02-26 2009-10-08 Panasonic Electric Works Co Ltd プラスチックの分解・回収方法
KR100891378B1 (ko) * 2008-08-27 2009-04-02 (주)알앤이 폐인조대리석으로부터 ｍｍａ와 알루미나의 회수방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109232973A (zh) * 2018-09-10 2019-01-18 夏美佳 一种废旧有机玻璃塑料连续裂解装置

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