WO2004009653A1 - 連続式樹脂回収装置および回収方法 - Google Patents
連続式樹脂回収装置および回収方法 Download PDFInfo
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- WO2004009653A1 WO2004009653A1 PCT/JP2003/009336 JP0309336W WO2004009653A1 WO 2004009653 A1 WO2004009653 A1 WO 2004009653A1 JP 0309336 W JP0309336 W JP 0309336W WO 2004009653 A1 WO2004009653 A1 WO 2004009653A1
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- resin
- drying chamber
- recovery
- solvent
- heating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/10—Removal of volatile materials, e.g. solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/0011—Heating features
- B01D1/0017—Use of electrical or wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/02—Evaporators with heating coils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/16—Evaporating by spraying
- B01D1/18—Evaporating by spraying to obtain dry solids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/005—Removal of residual monomers by physical means from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
- C08F6/28—Purification
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
- F26B5/041—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum for drying flowable materials, e.g. suspensions, bulk goods, in a continuous operation, e.g. with locks or other air tight arrangements for charging/discharging
Definitions
- the present invention relates to a continuous resin recovery apparatus and a recovery method for drying a resin solution to remove volatile components to a high degree. More particularly, the present invention relates to a continuous resin recovery apparatus and a recovery method for recovering a highly purified resin suitable for optical use, in which foreign substances and volatile matter are highly removed.
- resins for semiconductors and optics there is a demand for the purification of resins for semiconductors and optics to remove foreign substances and volatile components as much as possible and to purify the resin to a high degree.
- resins for plastic optical fibers are required to minimize scattering and absorption that prevent light from passing through.
- Filtration is the optimal method for removing foreign matter from the resin.
- a method of producing an optical resin by subjecting a raw material such as a monomer, which is a raw material of the resin, to microfiltration, followed by polymerization.
- a raw material such as a monomer, which is a raw material of the resin
- microfiltration followed by polymerization.
- resins manufactured by various methods for optical applications there is a great demand for using resins manufactured by various methods for optical applications, and it is necessary to remove foreign substances from the manufactured resins.
- in order to directly filter the resin it is necessary to filter the molten resin, and a high temperature and a filter capable of withstanding the high temperature are required. With the current technology, there is no known method of directly filtering the molten resin to obtain an optically satisfactory resin.
- 2000-10210 proposes a method of drying a molten resin using a perforated plate.
- Hosokawa Micron also offers the product name “Clax System”.
- a heating tube is used to heat a resin solution to a temperature equal to or higher than the boiling point of the solvent, and the vaporized solvent vapor is further heated, so that the superheated solvent vapor forms a high-speed jet, and the heating tube is heated.
- This is a method in which the solvent vapor and the resin component are separated without clogging.
- a flow control method in which foreign matter is less mixed into a highly purified molten resin, a method of controlling the flow state of the molten resin by changing the temperature is disclosed in Japanese Patent Application Laid-Open No. 2001-388725. Has been proposed.
- the apparatus has a sliding portion with high-speed rotation. Dust from the part was inevitable. Further, in the method described in Japanese Patent Application Laid-Open No. 2000-210921, it is not possible to directly process a low-concentration solution of a resin because a high-viscosity fluid is premised on drying. That is, it was not possible to treat a low-concentration, low-viscosity resin solution capable of highly removing foreign substances by filtration. Furthermore, in the above-mentioned Clax system, the amount of the residual solvent cannot be reduced to a level required by the optical resin, and the obtained resin is foamed. It was difficult to take pollution control measures such as easy intake.
- the present invention solves the above-mentioned problems, and provides a resin recovery device and a recovery method suitable for an optical resin. Specifically, a specific coarse drying process and a specific precision drying process are combined, and a specific method for controlling the flow of the molten resin is added to this, and the whole is combined into one organic device. The present inventors have found that contamination resistance can be improved by summarizing the results, and have led to the present invention. Disclosure of the invention
- the present invention relates to a continuous resin recovery apparatus for continuously drying a resin solution and recovering the resin from which the solvent has been removed, comprising a liquid sending means for sending the resin solution, and a heating means for heating the resin solution.
- this resin recovery apparatus a resin from which volatile components have been removed to a high degree can be recovered with high productivity.
- a filter between the liquid sending means and the heating pipe it is preferable to have a filter between the liquid sending means and the heating pipe. According to this aspect, it is possible to remove foreign matter to a high degree by using one resin collecting device. Further, it is preferable that a portion other than the liquid sending means has no sliding portion at a portion that comes into contact with the resin solution or the molten resin. Since the recovery device does not have a sliding portion other than the liquid feeding means, dust generated from the sliding portion can be ignored, and foreign matter can be suppressed from being mixed into the purified resin, which is preferable.
- the present invention provides a method for continuously recovering a resin using the above-mentioned continuous resin recovery apparatus, comprising: heating a resin solution in a heating tube to a temperature equal to or higher than the boiling point of the solvent; A step of introducing a resin solution heated to a boiling point or higher into a rough drying chamber kept under reduced pressure, a step of separating resin and solvent vapor in the rough drying chamber, and a step of melting the separated resin.
- Continuous resin recovery characterized by comprising a step of introducing the molten resin into a precision drying chamber maintained at a reduced pressure, and a step of passing the molten resin in the precision drying chamber through a perforated plate. Provide a way.
- a resin from which volatile components have been removed to a high degree can be recovered with high productivity.
- a resin from which foreign matter has been removed at the same time as volatile matter can be recovered with high productivity.
- the process of heating the resin to make it in a molten state and allowing it to flow, and the process of cooling the resin to a solid state and stopping the flow are alternately performed. Is preferred.
- the foreign matter in the step of taking out the resin from which volatile matter and foreign matter have been removed to a high degree outside the apparatus, the foreign matter can be prevented from being mixed without touching the sliding portion such as the extraction valve.
- the resin is preferably an optical resin, and particularly preferably the resin is a fluorinated transparent resin.
- the resin recovery method of the present invention is a method suitable for recovering an optical resin that needs to highly remove foreign substances and volatiles and to highly purify the resin.
- FIG. 1 is a schematic diagram showing an example of a continuous resin recovery apparatus according to the present invention.
- FIG. 1 is a schematic diagram showing an example of a continuous resin recovery apparatus according to the present invention.
- the resin collecting apparatus 1 has a liquid sending pump 10 as a liquid sending means, a heating pipe 20, a rough drying chamber 30, and a precision drying chamber 40.
- a first vacuum pump 51 as a pressure reducing means is connected to the rough drying chamber 30, and a second vacuum pump 52 as a pressure reducing means is connected to the precision drying chamber 40.
- two perforated plates 41 are provided horizontally.
- a stock solution storage tank 11 is provided on the opposite side of the heating pipe 20 of the liquid sending pump 10, that is, on the upstream side of the liquid sending pump 10, and between the liquid sending pump 10 and the heating pipe 20, that is, A filter 12 is provided downstream of the liquid sending pump 10.
- the heating tube 20 is provided inside the heating tank 21.
- a heat exchanger 53 is provided between the rough drying chamber 30 and the first vacuum pump 51, and a solvent storage tank 54 is provided below the heat exchanger 53.
- a resin recovery section 60 is provided below the precision drying chamber 40.
- the precision drying chamber 40 and the resin recovery section 60 are connected by a resin recovery channel 63.
- a resin recovery container 61 is attached to the resin recovery section 60, and a purified resin 62 is recovered.
- there is no sliding part such as a valve at a portion that comes into contact with the resin solution or the molten resin.
- a fixed-rate liquid sending pump such as a plunger pump or a diaphragm pump is preferable, and a diaphragm pump is particularly preferable because there are few sliding parts.
- the solution can be sent by pressurizing the undiluted solution storage tank 11 with an inert gas. Control tends to be unstable, which is not preferable.
- the material of the diaphragm in the diaphragm pump is not particularly limited as long as the material has corrosion resistance to the resin solution. Examples of the material include a resin such as polytetrafluoroethylene resin and a corrosion-resistant steel such as stainless steel. Also, the capacity of the pump is appropriately selected according to the resin solution sending speed.
- the stock solution storage tank 11 stores a resin solution as a raw material. It is preferable that the stock solution storage tank 11 has an airtight structure that can be replaced with an inert gas. In addition, it is preferable that the stock solution storage tank 11 be installed on a load cell and measure the weight of the contents. It is preferable that the stock solution storage tank 11 is provided with a heating means such as an electric heater. However, the heating of the resin solution is preferably lower than the boiling point of the solvent. It is preferable that the resin solution is heated because the viscosity of the resin solution decreases to facilitate filtration, the viscosity of the resin solution is kept constant, and the heating in the heating tube is easily controlled later.
- the resin solution is filtered. Since the filter 12 is provided on the downstream side of the liquid feed pump 10, foreign substances generated by the liquid feed pump 10 can also be removed.
- the size of the foreign matter removed by the filter is determined by the aperture of the filter. The smaller the opening, the smaller the foreign matter can be removed, but this will cause a pressure loss in feeding.
- the problem of increased pressure loss can be solved by using a filter with a large filtration area.
- the opening is a measurement method based on the Sematec standard (SEMA SPEC 9209409B), and 99% of particles having a particle diameter equal to or larger than the numerical value of the opening. It refers to the numerical value of the aperture when collecting the above.
- the opening is preferably 0.5 x m or less, more preferably 0.2 m or less, and particularly preferably 0.1 to 0.1 m.
- the material of the filtration surface (filtration media) include polytetrafluoroethylene resin, polyethylene resin, polypropylene resin, nylon resin, polyethersulfone resin, etc. Among them, polytetrafluoroethylene resin, polyethylene resin Polypropylene resins are preferred.
- the heating pipe 20 is provided downstream of the liquid sending pump 10 and the filter 12.
- the end opening of the heating tube 20 is provided inside the rough drying chamber 30.
- the length and inner diameter of the heating tube 20 are determined mainly by the properties of the solvent in the resin solution. Further, it is preferable that the heating tube 20 can be heated by a heat medium.
- the structure for heating the heating tube 20 is as follows.
- the heating tube may be housed inside a heating tank 21 filled with a heating medium, as shown in FIG.
- a structure in which a heating tube 20 is housed inside a heating tank 21 filled with a heating medium is preferable because the structure is simple and the thermal efficiency is high and easy to take.
- the rough drying chamber 30 has an opening at the end of the heating pipe 20 therein, and a pipe connected to the first vacuum pump 51 via the heat exchanger 53 is connected thereto.
- a precision drying chamber 40 is provided below the coarse drying chamber 30, and a lower opening of the coarse drying chamber 30 is provided inside the precision drying chamber 40.
- the coarse drying chamber 30 is provided with a heating means (not shown in FIG. 1) such as an electric heater for melting the resin.
- the volume of the rough drying chamber 30 is appropriately determined by referring to the processing speed of the resin solution and the like.
- the lower part of the rough drying chamber 30 is preferably conical so that the molten resin can flow down.
- the first vacuum pump 51 is preferably a vacuum pump such as an oil rotary vacuum pump or a dry vacuum pump.
- the exhaust capacity is appropriately determined from the processing speed of the resin solution.
- a heat exchanger 53 is provided between the first vacuum pump 51 and the rough drying chamber 30.
- the heat exchanger 53 may be of any type, but a structure that does not easily cause exhaust resistance is preferred.
- the heat exchange capacity of the heat exchanger 53 is appropriately determined based on the processing speed of the resin solution, it is necessary to have a capability of sufficiently condensing the solvent vapor evaporated from the resin solution.
- a refrigerant is used to cool the heat exchanger 53, and the refrigerant is appropriately determined from the throughput of the solvent vapor and the like.
- the control temperature of the refrigerant is preferably lower by 50 or more, more preferably 70 or lower, and more preferably 90 or lower with respect to the boiling point of the solvent. Particularly preferred.
- a plurality of heat exchangers 53 may be arranged in series. Below the heat exchanger 53, a solvent storage tank 54 is provided. The capacity of the solvent storage tank 54 is appropriately determined from the processing speed of the resin solution.
- a valve is preferably provided between the solvent storage tank 54 and the heat exchanger 53 for the convenience of discharging the recovered solvent out of the apparatus. Further, it is preferable that the solvent storage tank 54 is cooled and kept at a temperature equal to or lower than that of the heat exchanger 53.
- the precision drying chamber 40 is roughly dried so that the roughly dried molten resin flows down and is introduced. It is provided below the chamber 30. Inside the precision drying chamber 40, a lower opening of the coarse drying chamber 30 is provided. Further, a pipe connected to the second vacuum pump 52 is connected to the precision drying chamber 40.
- the second vacuum pump 52 is preferably a vacuum pump such as an oil rotary vacuum pump or a dry vacuum pump.
- the pumping capacity is appropriately determined from the processing speed of the resin solution, but may be smaller than that of the first vacuum pump 51.
- the degree of vacuum (ultimate vacuum pressure) is preferably higher than that of the first vacuum pump 51. That is, a vacuum pump capable of achieving a higher vacuum is preferable.
- the ultimate vacuum degree is preferably 0.1 lkPa or less.
- the second vacuum pump 52 is preferably provided with a cooling trap for protecting the vacuum pump and for preventing dust from the vacuum pump from flowing back to the apparatus.
- a perforated plate 41 is provided horizontally. Although the number of perforated plates 41 is not limited, it is preferable to provide 2 to 6 perforated plates.
- the perforated plate 41 is provided so that the molten resin passes therethrough. That is, it is preferable that the resin is provided over the entire area through which the molten resin can pass.
- a disperser 42 for dispersing the molten resin flowing down from the lower opening of the coarse drying chamber 30 through the porous plate 41 is provided inside the precision drying chamber 40.
- the disperser 42 does not need a special structure, and may be a slightly deeper dish-shaped container.
- the disperser 42 is supported by a support or the like inside the precision drying chamber 40.
- the precision drying chamber 40 is provided with a heating means such as an electric heater (not shown in FIG. 1) for keeping the molten resin warm. It is preferable that the disperser 42 is also provided with a similar heating means.
- the volume of the precision drying chamber 40 is determined as appropriate with reference to the processing speed of the resin solution.
- the lower part of the precision drying chamber 40 is preferably conical so that the molten resin can flow down.
- the resin recovery section 60 is provided below the precision drying chamber 40.
- the lower part of the precision drying chamber 40 is connected to a resin recovery channel 63 and further connected to a resin recovery section 60.
- a resin recovery container 61 is attached to the resin recovery section 60, and the purified resin 62 is recovered.
- the resin recovery flow path 63 is preferably a single pipe, and a temperature control means capable of heating and cooling is provided outside thereof.
- a temperature control means a detachable electric heater or the like is preferable. Cooling can be performed by blowing and air cooling without the electric heater.
- the resin collecting section 60 has a heat retaining means. The resin melted by this heat retention makes the resin recovery container 6 1 It is cooled during filling to prevent insufficient filling. It is preferable that a load cell be provided at the bottom of the resin recovery unit with a reflection plate therebetween. The reflector is provided to protect the load cell from normal operation in a high temperature environment from heat.
- Part of the resin recovery section 60 can be opened and closed, and the recovered resin 62 can be taken out of the apparatus.
- Only one resin recovery unit 60 may be provided below the precision drying chamber 40, or two or more resin recovery units may be provided.
- the resin recovery flow paths 63 are branched so as to correspond to each other.
- only one resin recovery container 61 may be mounted inside the resin recovery unit 60, or two or more resin recovery containers may be mounted side by side.
- the end opening of the resin collection flow path 63 (this opening is inside the resin collection part 60). ) Is preferably branched so as to correspond.
- the resin collecting section 60 is connected to a vacuum pump. This vacuum pump may be shared with the second vacuum pump 52 that maintains the precision drying chamber 40 at reduced pressure.
- a portion other than the liquid feed pump has no sliding portion at a portion that comes into contact with the resin solution or the molten resin.
- a sliding portion is not provided at a position downstream of the above-mentioned filter in contact with the resin solution or the molten resin.
- the chambers are sealed with the resin itself. More specifically, a portion between the rough drying chamber 30 and the precision drying chamber 40 and a portion between the precision drying chamber 40 and the resin recovery section 60 are sealed by being separated by molten resin. In particular, the space between the coarse drying chamber 30 and the precision drying chamber 40 is sealed by the molten resin in the disperser 42.
- the material of the portion where the resin solution or the molten resin can come into contact in the device is a corrosion-resistant steel such as stainless steel, a corrosion-resistant metal such as nickel, or a Hastelloy alloy.
- Corrosion-resistant alloys such as Inconel alloy and trade name: Monel alloy are preferred.
- a corrosion-resistant metal such as nickel or a corrosion-resistant alloy such as a Hastelloy alloy, an Inconel alloy, or a Monel alloy is particularly preferable from the viewpoint of corrosion resistance at a high temperature.
- the roughness of the inner surface is preferably 0.3 m or less. It is preferable that the roughness of the inner surface is small because dust generation due to corrosion or the like can be suppressed.
- the resin recovery method of the present invention comprises the steps of: heating a resin solution in a heating tube 20 at a temperature higher than the boiling point of the solvent; A step of introducing the resin into the chamber 30, a step of separating the resin and the solvent vapor in the coarse drying chamber 30, a step of melting the separated resin, and a precision drying chamber 40 in which the molten resin is kept under reduced pressure. And a step of allowing the resin melted in the precision drying chamber 40 to pass through the perforated plate 41. Further, in FIG. 1, the resin solution is introduced into the heating tube 20 after being filtered by the filter 12.
- the resin recovery method of the present invention when recovering the molten resin from the lower part of the precision drying chamber 40 to the resin recovery section 60, a step of heating the resin to make it in a molten state so that the resin can be distributed, The step of cooling the fat to a solid state and stopping the flow is alternately performed.
- the resin is preferably an optical resin.
- the resin recovery method of the present invention is suitable for recovering an optical resin. That is, highly purified resin can be recovered.
- applications of the optical resin include plastic optical fibers and optical waveguides.
- the resin include a hydrocarbon-based transparent resin and a fluorine-containing transparent resin.
- the hydrocarbon-based transparent resin include polymethyl methacrylate, polystyrene, and polycarbonate.
- Specific examples of the fluorinated transparent resin include poly (perfluoro (3-oxa-1,6-butadiene)), fluoro (2,2-dimethyl-1,3, -dioxole), and tetrafluoroethylene. And the like.
- fluorinated transparent resins have low C-H bonds or do not have C-H bonds, so they transmit light in a wide range from the visible region to the near-infrared region with extremely low loss. can do. That is, the above-mentioned fluorinated transparent resin is suitable as a material for plastic optical fibers, and is also suitable as a target to be purified by the resin recovery method of the present invention.
- the solvent for dissolving the above resin is appropriately selected from known ones. Examples of the solvent for dissolving the hydrocarbon-based transparent resin include acetone and dichloromethane.
- Solvents for dissolving the fluorinated transparent resin include perfluoro (butylethyltetrahydrofuran) (boiling point: 97 ° C), perfluoro-n-octane (boiling point: 102), perfluoro-n-hexane (boiling point: 56 ) And the like. These solvents are appropriately selected depending on the solubility of the resin and the like, and two or more kinds thereof may be used as a mixture. As the solvent, it is preferable to select a solvent having a high resin solubility and a low foreign matter solubility.
- the concentration of the resin in the resin solution is preferably from 0.01 to 25% by mass, more preferably from 1 to 15% by mass. This concentration is determined with reference to the viscosity of the resin solution. That is, the viscosity of the resin solution at 20 is preferably from 1 to: L0OmPas, and more preferably from 1 to 200 mPas. If the concentration of the above resin is higher than the above range, it becomes unfavorably easy to handle due to high viscosity and also difficult to filter. If the above concentration is lower than the above range, it is uneconomical and not preferable.
- the resin solution is subjected to adsorption purification in advance. Since solid foreign matter can be removed by filtration and volatile foreign matter can be removed at the same time in the process of evaporating and separating the solvent, an adsorption treatment is preferable for removing non-volatile unnecessary components dissolved in the resin solution.
- the non-volatile unnecessary components dissolved in the resin solution include a coloring component obtained by oxidatively modifying the resin, and a component mixed in the resin production process. All of these are often trace components, and existing analytical methods often cannot identify specific compounds. It is also preferable to remove the acid which causes corrosion of the apparatus by adsorption purification.
- Examples of the method for adsorption purification include a method in which the adsorbent is sufficiently dispersed in the resin solution and then the adsorbent is removed by filtration, a method in which the adsorbent is purified through a packed column filled with the adsorbent, and the like.
- the adsorbent an inorganic adsorbent that does not dissolve in a solvent is preferable.
- Specific examples of the adsorbent include activated carbon, activated alumina, silica gel, acid clay, and synthetic adsorbent.
- Examples of the synthetic adsorbent include synthetic alumina, synthetic silica alumina, and synthetic alumina magnesia.
- the conditions for adsorption purification are determined appropriately according to the characteristics of the adsorbent. 1
- the resin solution be filtered and deoxygenated in advance (before putting it into the raw material storage tank 11 in FIG. 1). Filtration is preferable because the life of the filter provided immediately before the heating tube is extended.
- coloring of the resin due to oxidation of the resin or the solvent when heated can be prevented.
- the resin solution is first stored in the raw material storage tank 11. It is preferable that the resin solution has been subjected to the aforementioned preliminary purification.
- the resin solution is kept at a predetermined temperature in the raw material storage tank 11. This resin solution is fed by a feed pump 10.
- a filter 12 is provided downstream of the liquid sending pump 10, and the resin solution is filtered by the filter 12. On the downstream side of the filter 12, it is preferable that a sliding portion is not provided at a portion where the resin solution or the molten resin comes into contact. It is also preferable not to provide a stagnation portion such as a branch pipe at the same time. Further, the filter 12 is preferably provided as close as possible to the heating pipe 20.
- the resin solution is introduced into the heating tube 20 via the filter 12.
- the heating temperature in the heating tube 20 is preferably higher than the boiling point of the solvent of the resin solution by 10 or more, and particularly preferably higher by 20 or more than the boiling point of the solvent.
- the heating temperature is preferably lower than the lower one of the decomposition temperatures of the resin or the solvent so that the resin or the solvent is not thermally decomposed.
- the heating temperature is preferably lower than the phase separation temperature. This is to prevent the heating tube 20 from being blocked due to phase separation.
- the heating temperature is preferably 20 to 50 higher than the boiling point of the solvent.
- the resin solution is heated, the solvent evaporates, and further heated at a temperature equal to or higher than the boiling point of the solvent, so that the superheated solvent vapor separates from the resin component while being jetted inside the heating tube 20. proceed.
- the resin component is conveyed without adhering into the heating tube 20 by the solvent vapor in the jet state, and is jetted from the terminal opening.
- the feeding speed of the resin solution is determined with reference to the following conditions.
- the linear velocity of the superheated solvent vapor at the end opening of the heating pipe 20 is preferably 250 to 600 mZs, and is 300 to 40 Om / s. Is more preferable. Line above 2 If the speed is lower than 25 O m / s, the heating tube is easily clogged, which is not preferable. On the other hand, if the speed is higher than 600 mZs, the solvent vapor is considerably heated, which is uneconomical and not preferable. That is, the feeding speed of the resin solution is determined such that the evaporated solvent vapor has the above-mentioned speed at the terminal opening of the heating tube 20.
- the heating tube 20 preferably has a final linear portion.
- the final linear portion means a portion where the evaporated solvent vapor is superheated and the resin component separated from the solvent vapor is conveyed by the high-speed solvent vapor. If this portion is a straight line, a high-speed jet of solvent vapor is stably formed, and it is possible to prevent the resin component from blocking the heating tube, which is preferable.
- the length of the heating tube 20 (however, the length of the portion to be heated) and the inner diameter are based on the specific heat of the solution and the heat transfer coefficient of the heating tube 20 while referring to the above conditions. It is decided.
- the ratio between the length and the inner diameter of the heating tube is preferably 500 or more when expressed by (length) / (inner diameter).
- these numerical values are preferably determined by the following procedure. First, the heating temperature is temporarily determined based on information such as the boiling point and specific heat of the resin solution and the solvent. Next, the processing speed of the temporary resin solution is determined. Based on this assumption, the length and inner diameter of the heating tube are determined. The length of the final linear portion is determined from these values.
- the solvent vapor and the resin component ejected from the heating tube 20 are introduced into the rough drying chamber 30.
- the pressure in the coarse drying chamber 30 pressure when the solvent vapor is supplied
- the pressure in the coarse drying chamber 30 is preferably 5 kPa or less, more preferably 1 kPa or less, and 0.5 kPa or less. Particularly preferred. If the pressure is higher than 5 kPa, the separation and recovery of the solvent vapor will not proceed, and the crude drying of the resin will be insufficient, which is not preferable.
- the temperature of the rough drying chamber 30 is preferably maintained at a temperature higher by at least 40 than the glass transition point of the resin, or at a temperature higher than the higher of the heating temperatures of the heating tubes 20.
- the upper limit of the temperature of the rough drying chamber 30 is the lower one of the decomposition temperature of the resin and the solvent.
- the solvent vapor is discharged from the rough drying chamber by the first vacuum pump 51, cooled by the heat exchanger 53, condensed, and collected in the solvent storage tank 54.
- One resin component is heated and melted in the rough drying chamber 30.
- the molten resin is roughly dried in the rough drying chamber 30 and is introduced into the precision drying chamber 40 through the lower part of the rough drying chamber 30. Here, the resin flows down by gravity.
- the resin melted in the coarse drying chamber 30 flows down into the precision drying chamber 40 and is introduced.
- the molten resin introduced into the precision drying chamber 40 is dispersed by the disperser 42 and passes through the perforated plate 41.
- the pressure in the precision drying chamber 40 is preferably maintained at about 0.1 to 5 kPa lower than the pressure in the coarse drying chamber 30, and specifically, 0.5 kPa or less is preferable. It is more preferably 0.1 kPa or less. If the pressure in the precision drying chamber 40 is higher than the pressure in the coarse drying chamber 30, the molten resin will not easily flow down from the coarse drying chamber 30 to the precision drying chamber 40, which is not preferable.
- the temperature of the precision drying chamber 40 is preferably 0.1 to 20 more preferably than the temperature of the coarse drying chamber 30 and is preferably maintained at a high temperature.
- the upper limit of the temperature of the precision drying chamber 40 is equal to or lower than the decomposition temperature of the resin.
- the resin that has flowed into the precision drying chamber 40 is dispersed by the disperser 42, and the disperser 42 also serves as a seal. That is, by filling the inside of the diffuser 42 with the molten resin, a material seal is formed, and the environment of the coarse drying chamber 30 and the precision drying chamber 40 is separated.
- the molten resin dispersed by the disperser 42 passes through the perforated plate 41.
- the molten resin that has passed through the perforated plate 41 flows down in the form of a number of threads, and drying proceeds during the flow.
- the molten resin is precisely dried by passing through the perforated plate 41, and the residual solvent is removed to a trace amount.
- the solvent remaining amount of the resin after precision drying is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, based on the resin.
- the precisely dried molten resin is stored in a molten state in the lower part of the precision drying chamber 40.
- the molten resin stored in the lower part of the precision drying chamber 40 flows down to the resin recovery section 60 through the resin recovery channel 63.
- the resin that has flowed down is filled in a resin recovery container 61 mounted inside the resin recovery section 60.
- the amount of the resin 62 filled in the resin recovery container 61 may be controlled by the falling time, but is preferably controlled by a load cell provided at the bottom of the resin recovery unit 60.
- a valve is not provided in the resin recovery channel 63. This is because the valve has a sliding part and is likely to generate dust.
- the following method is employed.
- the resin 4 is heated to a molten state to enable distribution. Specifically, by heating the resin recovery channel 63 all night long, the resin inside the resin recovery channel 63 melts and can be distributed.
- the recovery of the molten resin into the resin recovery section 60 is stopped, the resin is cooled to a solid state and the flow is stopped.
- the electric heater that heated the resin recovery flow path 63 was removed, and the air was blown by a blower, thereby cooling the resin recovery flow path 63 and cooling the resin inside the resin recovery flow path 63.
- the resin is degraded and the distribution of the resin is stopped.
- the resin recovery container 61 filled with the appropriately purified resin 62 is taken out of the apparatus while continuously purifying the resin in the precision drying chamber.
- the shape and material of the collection container 61 are appropriately selected depending on the subsequent resin processing method. Examples of the material include ceramics, glass, metal, fluororesin, and the like. Metal is preferable in consideration of heat resistance and corrosion resistance. As the specific metal, the same metal as that used for the device body can be used.
- the evaluation of the purification is appropriately performed according to the purpose. Specifically, it can be evaluated by the following methods.
- the remaining volatile components were evaluated by a gas chromatography analysis method using a sample heating vaporizer (head space).
- An analysis method such as a thermal desorption method for analyzing volatile components can be employed.
- a method for evaluating the contamination a method of visually observing using a high-intensity light source, a scattered light analysis method of transmitting a laser beam and measuring side scattering by the foreign material can be adopted.
- the residual volatile matter is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, of the recovered resin.
- the stock solution storage tank 11 is a container made of stainless steel and has an inner volume of about 70 L.
- Pump 10 is a diaphragm made by Nikkiso Eiko It is a 5 ram pump and has a maximum liquid supply capacity of 14 L / min.
- the material of the diaphragm is polytetrafluoroethylene resin.
- the filter 12 is a cartridge type filter having an opening of 0.07 xm, a length of a cylindrical portion of about 26 cm, and a filtration surface made of polyethylene resin.
- the heating tube 20 is a stainless steel tube having an inner diameter of 4.86 mm, a length of 23.8 m, and a length of the final straight section of 80 cm.
- the rough drying chamber 30 is a cylindrical tank having an inner diameter of about 40 cm and an inner volume of about 55 L made of nickel and having a conical portion at a lower portion.
- the lower part of the rough drying chamber 30 is a tube with an inner diameter of 2.8 cm, and is inserted into the precision drying chamber.
- the precision drying chamber 40 is a cylindrical vessel having an inner diameter of about 21 cm and an inner volume of about 15 L and made of nickel and having a conical portion at a lower portion.
- the disperser 42 is a nickel dish having an inner diameter of 6.5 cm and a liquid contact part height of 18 cm.
- the tube extending from the lower part of the rough drying chamber 30 is arranged to open inside the disperser 42.
- each perforated plate 41 is a nickel mesh having a wire diameter of 0.8 mm and 8 mesh.
- the lower part of the precision drying chamber 40 is connected to a resin recovery channel 63.
- the resin recovery channel 63 is a nickel tube having an inner diameter of the narrowest portion of 1.5 cm.
- the resin recovery flow channel 63 is open inside the resin recovery section 60.
- the resin collecting section 60 is a stainless steel container having an inner diameter of 13.3 cm and a length of about lm.
- a load cell is provided at the bottom inside the resin collecting section 60 with four stainless steel reflectors interposed therebetween.
- the resin recovery container 61 is a nickel cylindrical container having an inner diameter of 33 mm and a length of 47 cm and a lid at the bottom.
- the first vacuum pump 51 is an oil rotary vacuum pump manufactured by Sato Vacuum Co., Ltd., with a pumping speed of 600 L / min and an ultimate pressure of 0.1 Pa.
- the second vacuum pump 52 is an oil rotary vacuum pump manufactured by Vacuum Machine Co., and has a pumping speed of 135 L / min and an ultimate pressure of 0.07 Pa.
- the heat exchanger 53 is a stainless steel heat exchanger having a transfer surface of about 0.76 m 2 .
- the solvent storage tank 54 is a container made of stainless steel and has an internal volume of about 66 liters.
- the heat retention of the stock solution storage tank 11, the coarse drying chamber 30, the precision drying chamber 40, the disperser 42, the resin recovery flow channel 63, and the resin recovery unit 60 was performed all over the electric power station. Heating of heating tube 20 was carried out by introducing steam into the heating tank 21.
- the heat exchanger 53 was cooled using the refrigerant cooled in step 7, and the solvent storage tank 54 was cooled using the refrigerant cooled in step 20.
- the following were used as the resin solution.
- the intrinsic viscosity (measured in perfluoro (butyltetrahydrofuran) at 30) of this resin was 0.24.
- This resin was dissolved in perfluoro (butyltetrahydrofuran) to obtain a resin solution having a resin concentration of 10% by mass.
- the molecular end of the resin was subjected to a stabilization treatment using fluorine gas.
- This resin solution was subjected to adsorption and purification treatment using synthetic alumina magnetera (Kyowa Chemical Industry Co., Ltd., trade name: Kyoichi Word 2000). After the adsorption treatment, the solution was filtered through a filter having an opening of 1, and then charged into the stock solution storage tank 11 under a nitrogen atmosphere.
- the above resin solution was fed at 10 kg / Hr using a feed pump 10.
- the temperature of the heating tube 20 was 140.
- the set temperature of the wall of the rough drying chamber 30 was 250, and the pressure was 5 kPa.
- the solvent vapor was separated in the rough drying chamber 30, and the roughly dried resin was melted and flowed down to the precision drying chamber 40.
- the temperature of the disperser 42 and the precision drying chamber 40 was 250.
- the pressure in the precision drying chamber 40 was 1 kPa.
- the molten resin flowing down from the lower part of the precision drying chamber 40 passed through the heated resin recovery channel 63 in a molten state, and was recovered in a resin recovery container 61 installed inside the resin recovery unit 60. When a predetermined amount was recovered, the resin recovery flow channel 63 was air-cooled to stop the flow of the resin. As a result, 550 g of the resin was recovered.
- the total amount of the residual volatile content was 0.008% by mass.
- the amount of foreign substances was evaluated by measuring the scattered light using a single 650 nm laser beam. It was measured using a static light scattering photometer (product name: SLS-6000) manufactured by Otsuka Electronics Co., Ltd.
- SLS-6000 static light scattering photometer
- the angle is measured scattering 20 to 120 °, and analyzed their strength, the average value of the isotropic scattering intensity 2.
- 5 X 10 - 6 cm_ 1 the average value of the anisotropic scattering intensity 4.2 It was 7 cm- 1 - X 10.
- a graded-index optical fiber was fabricated using this resin, and its transmission loss was measured. As a result, it showed 22 dBZkm for 1300 nm light. 7 Industrial applicability
- the resin from which the remaining volatile components and foreign substances have been highly removed can be continuously recovered.
- it is suitable for purifying resins that are easily charged and easily contaminated, such as fluorine resins.
- the resin obtained by this resin recovery method is highly purified, so it can be used not only as an optical material but also as an electronic material that requires a high degree of purification.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003252247A AU2003252247A1 (en) | 2002-07-24 | 2003-07-23 | Continuous resin recovery apparatus and method of recovery |
EP03765366A EP1535933A4 (en) | 2002-07-24 | 2003-07-23 | DEVICE FOR THE CONTINUOUS RECOVERY OF RESIN AND CONTINUOUS RESIN RECOVERY PROCESS |
JP2004522784A JP4506464B2 (ja) | 2002-07-24 | 2003-07-23 | 連続式樹脂回収装置および回収方法 |
US11/039,919 US7057011B2 (en) | 2002-07-24 | 2005-01-24 | Continuous resin recovery apparatus and recovery method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2002215340 | 2002-07-24 | ||
JP2002-215340 | 2002-07-24 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/039,919 Continuation US7057011B2 (en) | 2002-07-24 | 2005-01-24 | Continuous resin recovery apparatus and recovery method |
Publications (1)
Publication Number | Publication Date |
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WO2004009653A1 true WO2004009653A1 (ja) | 2004-01-29 |
Family
ID=30767921
Family Applications (1)
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PCT/JP2003/009336 WO2004009653A1 (ja) | 2002-07-24 | 2003-07-23 | 連続式樹脂回収装置および回収方法 |
Country Status (7)
Country | Link |
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US (1) | US7057011B2 (ja) |
EP (1) | EP1535933A4 (ja) |
JP (1) | JP4506464B2 (ja) |
KR (1) | KR20050030203A (ja) |
CN (1) | CN1671751A (ja) |
AU (1) | AU2003252247A1 (ja) |
WO (1) | WO2004009653A1 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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ITTV20090051A1 (it) * | 2009-03-20 | 2010-09-21 | M S M Snc Di Masiero G Semenzat O L E Masiero | Apparecchiatura e procedimento per la cristallizzazione e deumidificazione di materie plastiche poliesteri. |
WO2012173153A1 (ja) * | 2011-06-15 | 2012-12-20 | 旭硝子株式会社 | 含フッ素共重合体の製造方法 |
JP6175460B2 (ja) * | 2014-03-31 | 2017-08-02 | 富士フイルム株式会社 | 溶剤回収調製方法、及び溶液製膜方法 |
AR106558A1 (es) * | 2015-11-03 | 2018-01-24 | Spraying Systems Co | Aparato y método de secado por pulverización |
CN108619775A (zh) * | 2018-06-30 | 2018-10-09 | 贵州中伟资源循环产业发展有限公司 | 废旧锂电池中锂金属提取用锂盐反萃液过滤烘干设备 |
CN118139899A (zh) * | 2021-10-26 | 2024-06-04 | 中国石油化工股份有限公司 | 促进聚合物溶液相分离的方法和制备烯烃聚合物的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5515645A (en) * | 1978-07-21 | 1980-02-02 | Hitachi Ltd | Volatile remover for high-viscosity material |
JPH0632821A (ja) * | 1992-07-16 | 1994-02-08 | Tokuyama Sekisui Ind Corp | 塩素化塩化ビニル系樹脂の後処理方法 |
JP2002119811A (ja) * | 2000-10-17 | 2002-04-23 | Teijin Ltd | 金属繊維焼結フィルター |
WO2003004550A1 (fr) * | 2001-07-06 | 2003-01-16 | Nippon Shokubai Co., Ltd. | Poudre de resine hydro-absorbante ; procede de fabrication et utilisation de cette poudre de resine |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6150498A (en) * | 1996-07-12 | 2000-11-21 | The Dow Chemical Company | Polymer recovery |
DE19835744A1 (de) * | 1998-08-07 | 2000-02-17 | Bayer Ag | Verfahren zum Eindampfen von Polymerlösungen thermoplastischer Polymere |
JP3834807B2 (ja) * | 1998-09-29 | 2006-10-18 | 旭硝子株式会社 | 乾燥方法 |
JP3993797B2 (ja) | 2001-07-06 | 2007-10-17 | 株式会社日本触媒 | 吸水性樹脂粉末、その製造方法およびその用途 |
-
2003
- 2003-07-23 CN CNA038175282A patent/CN1671751A/zh active Pending
- 2003-07-23 WO PCT/JP2003/009336 patent/WO2004009653A1/ja not_active Application Discontinuation
- 2003-07-23 AU AU2003252247A patent/AU2003252247A1/en not_active Abandoned
- 2003-07-23 EP EP03765366A patent/EP1535933A4/en not_active Withdrawn
- 2003-07-23 JP JP2004522784A patent/JP4506464B2/ja not_active Expired - Lifetime
- 2003-07-23 KR KR1020057001054A patent/KR20050030203A/ko not_active Application Discontinuation
-
2005
- 2005-01-24 US US11/039,919 patent/US7057011B2/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5515645A (en) * | 1978-07-21 | 1980-02-02 | Hitachi Ltd | Volatile remover for high-viscosity material |
JPH0632821A (ja) * | 1992-07-16 | 1994-02-08 | Tokuyama Sekisui Ind Corp | 塩素化塩化ビニル系樹脂の後処理方法 |
JP2002119811A (ja) * | 2000-10-17 | 2002-04-23 | Teijin Ltd | 金属繊維焼結フィルター |
WO2003004550A1 (fr) * | 2001-07-06 | 2003-01-16 | Nippon Shokubai Co., Ltd. | Poudre de resine hydro-absorbante ; procede de fabrication et utilisation de cette poudre de resine |
Also Published As
Publication number | Publication date |
---|---|
US7057011B2 (en) | 2006-06-06 |
JP4506464B2 (ja) | 2010-07-21 |
KR20050030203A (ko) | 2005-03-29 |
EP1535933A1 (en) | 2005-06-01 |
AU2003252247A1 (en) | 2004-02-09 |
CN1671751A (zh) | 2005-09-21 |
US20050197487A1 (en) | 2005-09-08 |
JPWO2004009653A1 (ja) | 2005-11-17 |
EP1535933A4 (en) | 2007-04-11 |
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