JP4517993B2 - Polymer compound and drug recovery method and apparatus - Google Patents

Description

  The present invention relates to a polymer compound and a drug after reaction treatment when a polymer compound is produced by using a drug such as alcohol to modify the polymer compound, decomposing reaction, or cutting a crosslinking point or molecular chain. The present invention relates to a method for recovering a polymer compound and a drug for separating and recovering each of them and a device therefor.

  In recent years, as environmental issues have become more important, the momentum of recycling has increased. The polymer is no exception, and many polymers have been studied for recycling by various methods such as material recycling and thermal recycling.

  In particular, research on unique reactions to polymers of high-temperature and high-pressure fluids such as supercritical or subcritical fluids has progressed. For example, only cross-linking points by silanol condensation of silane-crosslinked polyethylene are selected in supercritical or subcritical fluids. A method has been developed in which the resin is cut into pieces, restored to a thermoplastic polymer, and recycled (Patent Document 1).

  Unlike the method of thermal recycling by decomposing a crosslinked polymer into an oily material, this technology is characterized by the fact that it can be recycled as a polymer, and it can be used as a raw material for various molded products. Attention has been paid.

  In order to put such technology into practical use, a method of continuously performing a process of mixing a cross-linked polymer with a supercritical or subcritical fluid in an extruder and reacting them to recover a recycled material has been studied.

  In this technology, a supercritical fluid, a subcritical fluid, or a high-temperature and high-pressure gas state drug and a cross-linked polymer are reacted in a reaction vessel or a reaction extruder and then vented to separate the produced regenerated material and the drug. The use of an attached extruder is under consideration.

  As a general method, the chemical discharged from the vent part of the vented extruder is sent to the trapper by the suction force of the vacuum pump (oil pump), and after removing impurities, it is discharged from the vacuum pump to the outside. Can be given.

JP 2002-187976 A

  However, in the above method, it has been difficult to sufficiently recover a supercritical fluid, a subcritical fluid, or a gas-state chemical that has been brought to a high temperature and high pressure only with a vacuum pump.

  Therefore, when the substance used as a medicine is a substance with a high environmental load, it is discharged to the outside as it is, and this is a problem from the viewpoint of environmental considerations.

  Accordingly, an object of the present invention is to react a high-temperature high-pressure fluid such as the supercritical fluid, subcritical fluid, or high-temperature high-pressure gas with a cross-linked polymer, and separate this using a vented extruder. To provide a method and an apparatus for recovering a polymer compound and a drug that can be recovered and recycled without directly discharging the alcohol or a mixture of alcohols or a substance having a high environmental load to the outside as it is. is there.

The invention of claim 1 in order to achieve the above object, a polymer compound and a drug is reacted with the polymer compound is reacted in a reaction vessel, in a method of producing a polymer treated from the reaction vessel The polymer treated product was decompressed and introduced into a vented extruder, and a vent box having a volume more than 1 times the reaction vessel was connected to the vented extruder at the rear of the extrusion side from the introduction position. While extruding the introduced polymer processed product with an attached extruder, the chemical containing impurities as a gas component is separated from the polymer processed product and introduced into the vent box, and the impurities separated by the vent box are included. the gas component of the drug is introduced into the trapper, the inside of the trapper after separation of the impurities contained in by suction by the vacuum pump in the gas fraction, the sucked gas by a vacuum pump through a condenser Retirement to a polymer compound and a method for recovering drug so as to recover the drug.

  As a result, the mixture of the drug and polymer compound is guided to the trapper from the vented extruder by the suction force of the vacuum pump, the polymer compound or other impurities are removed, and only the drug is sucked into the vacuum pump. The polymer compound and the drug to be condensed and stored can be recovered.

  The invention according to claim 2 is the polymer compound and drug recovery method according to claim 1, wherein the gas in the trapper is sucked and exhausted to the vacuum pump using a dry vacuum pump.

  By adopting a dry pump as a vacuum pump instead of the conventional oil vacuum pump, the drug that has passed through the vacuum pump is condensed and stored in the condenser without being mixed with impurities such as oil and reused. It becomes possible to do.

The invention according to claim 3, said polymeric compound and said drug in a reaction extruder, the recovery method according to claim 1 or 2 polymer compound according the agent is supplied to the reaction vessel in a supercritical or subcritical state It is.

According to a fourth aspect of the present invention, the vented extruder on the discharge side from the introduction position of the polymer processed product from the reaction vessel is provided with a vent for removing a chemical as a gas component from the polymer processed product. The gas discharged from the trapper is sent to the trapper, and with the trapper, the gas in the trapper is sucked with a vacuum pump together with the chemical gas containing impurities supplied from the vent box, and the impurities in the gas are separated. The method of recovering a polymer compound and a drug according to any one of claims 1 to 3, wherein the drug gas from which impurities have been separated is cooled by a condenser.

In this way, by providing a vent on the discharge side in addition to the vent box in the extruder with vent, it is possible to separate the drug gas from the polymer processed product extruded by the vented extruder .

  Invention of Claim 5 is a polymer in which the said high molecular compound is a polymer which has a siloxane bond in a molecule | numerator, and the said chemical | medical agent is a mixture containing alcohols or alcohols. A method for recovering compounds and drugs.

The invention according to claim 6 is an apparatus for producing a polymer processed product by reacting a polymer compound and a chemical to be reacted with the polymer compound in a reaction vessel .
In addition to introducing a polymer processed product that is discharged from the reaction vessel under reduced pressure , a bent box having a volume one or more times that of the reaction vessel is provided behind the introduction position to extrude the introduced polymer processed product. However, an extruder with a vent that introduces and separates a drug containing impurities as a gas component from the polymer processed product into the vent box ;
A trapper that introduces the gas component separated in the vent box of the vented extruder and separates impurities in the gas,
A vacuum pump that sucks and exhausts the trapper;
It is a polymer compound and drug recovery device that is connected to the exhaust side of a vacuum pump and includes a condenser that cools the exhausted gas and recovers the drug.

  A seventh aspect of the present invention is the polymer compound and drug recovery apparatus according to the sixth aspect, wherein the vacuum pump is a dry vacuum pump.

The invention of claim 8 includes a reaction extruder for kneading the polymer compound and the drug and extruding them in a supercritical or subcritical state, and a reaction vessel for reacting the polymer compound and the drug from the reaction extruder. The polymer compound and drug recovery apparatus according to claim 6 or 7, further comprising a decompression means for decompressing and supplying the polymer treated product between the reaction vessel and the vented extruder.

According to a ninth aspect of the present invention, a vent for removing a chemical agent as a gas component from a polymer processed product is provided on the discharge side of the extruder with a vent, and the gas discharged from the vent is provided between the vent and the trapper. A polymer compound and drug recovery device according to any one of claims 6 to 8 , wherein a line for feeding the amount to the trapper is connected , a vacuum pump is connected to the trapper, and a condenser is connected to the exhaust side of the vacuum pump. It is.

  By combining the back vent box with a trapper, a vacuum pump, and a condenser in this order, drug suction, impurity removal, and condensation recovery can be performed continuously and with high accuracy. However, there is a possibility that the order of the combination is changed or a new apparatus is incorporated from the viewpoint of efficiency and cost.

  As described above, the present invention relates to a polymer compound that has been transported to a vented extruder by connecting a device that combines a trapper, a vacuum pump, and a condenser to a back vent box provided in the vented extruder. After the drug is separated, the drug is sent to the trapper by the suction force of the dry vacuum pump to remove impurities, and then sent to the condenser without being mixed with oil. Thereafter, the drug is pseudo-condensed by a condenser and stored.

  Moreover, the chemical | medical agent stored in the capacitor | condenser is what was collect | recovered after removing impurities, such as a high molecular compound and oil, and can be reused after refine | purifying directly or according to a use.

  Trapper is for trapping all aerosols (liquid, oil and dust diffused in the air) that are evaporated or gasified in the atmosphere or vacuum. After separating from the molecular compound, it captures the impurities diffused in the drug sucked from the vent or back vent box.

  A dry vacuum pump is a vacuum pump that does not use pump oil or water, unlike an oil vacuum pump or a water-sealed vacuum pump, and can produce dry gas because waste oil and wastewater are not generated or mixed. By combining the trapper and the dry vacuum pump, it is possible to perform an exhaust in which oil and water are not mixed and dust accumulation in the pump is prevented.

  A condenser usually refers to a device that cools and liquefies a high-temperature, high-pressure refrigerant gas. Here, it is used for the purpose of liquefying and storing the drug from which impurities exhausted from the dry vacuum pump are removed by connecting downstream of the dry vacuum pump. The drug stored in the condenser can be reused because it contains few impurities.

  The polymer compound referred to in the present invention is a crosslinked polymer, a synthetic polymer of a thermosetting resin such as plastic or rubber, a natural polymer such as lignin, cellulose, or protein, and a synthetic polymer and a natural polymer. Contains a mixture with. Further, a polymer compound such as shredder dust mainly containing other materials may be mixed therewith.

  In particular, when a mixture containing a crosslinked polymer as a polymer compound and an alcohol as a drug is used, such a device configuration functions effectively. In addition, such an apparatus configuration is extremely effective in suppressing pressure fluctuation when a high pressure such as a supercritical state is used in order to facilitate a reaction by a drug.

  According to the present invention, a polymer compound such as a cross-linked polymer is used as a drug when it is recycled as a high-temperature and high-pressure fluid such as a supercritical fluid, a subcritical fluid or a high-temperature and high-pressure gas. It exhibits an excellent effect that it is possible to collect and recycle the alcohols and the mixture of alcohols, or generally substances having a high environmental load without being discharged to the outside.

  A preferred embodiment of the present invention will be described below in detail with reference to the accompanying drawings.

  FIG. 1 is a flow diagram showing an example of a cross-linked polyethylene recycling apparatus according to the present invention.

  In FIG. 1, the cross-linked polyethylene pulverized into pellets or nuggets is fed into the reaction extruder 1 through a hopper 13. On the other hand, ethanol as a drug required for the reaction passes from the drug tank 18 through the drug tank valve 17, is pressurized by the drug injection pump 15, is heated by the drug heater 14, and is injected into the reaction extruder 1. . The injection position is preferably downstream of the position where the cross-linked polyethylene is sufficiently densified in the reaction extruder 1, thereby preventing upstream leakage due to vaporization of the drug.

  As the reaction extruder 1, a twin-screw extruder having two screws 1a was used so that the high-temperature and high-pressure chemical did not flow backward and kneading was sufficiently performed. The chemical injection pump 15 needs to pressurize ethanol to a pressure higher than the internal pressure of the reaction extruder 1, and the chemical heating heater 14 does not lower the temperature of the crosslinked polyethylene heated by the reaction extruder 1. It is desirable to raise the temperature to the extent. In the reaction extruder 1, the charged cross-linked polyethylene and ethanol, which is the injected chemical, are mixed and stirred by the screw 1 a. At this time, if at least a part of the reaction extruder 1 is set to a temperature and pressure conditions in which the ethanol as a medicine is in a supercritical state, the crosslinking and cutting reaction between the crosslinked polyethylene and ethanol proceeds sufficiently, and a good high A molecular processed product is obtained. Here, in order to ensure a sufficient reaction time, a 50 L flow-type reaction vessel 100 was connected to the extruder 1.

  The mixture of the polymerized product of crosslinked polyethylene plasticized with the reaction extruder 1 and the flow-type reaction vessel 100 and ethanol as a medicine is decompressed by a decompression valve 11 (or a discharge valve) as decompression means, and further a step In order to reduce the pressure, the breaker plate 31 is attached as a resistor having a plurality of holes, and the pressure of the resin is reduced stepwise.

  Further, a subsequent discharge line 23 is connected to the vented extruder 2, and the viscous liquid polymer treated product introduced into the vented extruder 2 is extruded in the discharge direction of the vented extruder 2 by the screw 2 a. At the same time, the gas flows into the vent box 8 of the back vent having a low pressure, so that the polymer processed material and ethanol are separated.

  The vent box 8 is heated by a vent box heater 10 which is an electric heater, and the polymer processed product is maintained at a temperature at which the polymer processed product exhibits fluidity.

  Further, in place of the vent box heater 10, although not shown in the figure, a jacket provided with an outer peripheral portion of the polymer processed material storage section of the vent box 8 in which the heat medium circulates and a heat medium for supplying the heat medium to the jacket The vent box 8 may be heated by a circulation device.

  The vent box 8 was 100 L, twice the volume of the reaction vessel 100. Thus, by making the vent box 8 larger than the volume of the flow-type reaction vessel 100, the pressure inside the vent box 8 is made equal to the pressure of the flow-type reaction vessel 100 even when resin and ethanol gas are discharged intermittently. It can be reduced to 1/2 or less. A safety valve 21 is connected to the vent box 8 to release the pressure when the pressure in the vent box 8 rises abnormally.

  The inside of the vent box 8 is maintained at a pressure slightly higher than the normal pressure and lower than that of the reaction vessel 100, whereby the polymer processed material is easily discharged out of the vent box 8 through the line 24. In the vent box 8, light ethanol gas is separated from the upper part of the tank, and a polymer processed product in a molten state is accumulated under the tank, and is sent to the vented extruder 2 by its own weight from a hole provided in the lower part of the tank. And pushed out by the screw 2a to the die 3 side of the tip.

  The vented extruder 2 can be a single-screw or twin-screw extruder. Here, it is formed as a thread-like strand 5 by the die 3 and is cooled and solidified to substantially normal temperature by the cooler 4. The strand 5 becomes a pellet 7 by the strand cutter 6.

  On the discharge side of the extruder 2 with a vent, a vent 9 is provided in order to completely remove ethanol from the resin, and a gas such as ethanol discharged from the vent 9 is connected to the line 25 and the line 25. The gas is sent to a trapper 16 to be described later via 91, and discharged from the safety valve 22 when the gas pressure from the vent 9 is abnormally high.

  On the other hand, ethanol, which is a chemical separated from the polymer-treated product in the vent box 8, becomes a normal pressure through a tank pressure adjusting valve 12 as a tank pressure adjusting means, and is sent to the trapper 16 by the suction force of the dry vacuum pump 19. It is done. At the same time, a gas such as ethanol appropriately discharged from the vent 9 is sent to the trapper 16 at normal pressure by the adjusting valve 91.

  The trapper 16 collects impurities having a high boiling point, resin powder, and the like that are produced during the reaction and mixed in ethanol as a drug. Ethanol from which impurities have been removed by the trapper 16 is sucked into the dry vacuum pump 19 and sent to the condenser 20.

  In the condenser 20, the gasified ethanol is stored by being cooled and liquefied. The stored ethanol is recovered from a drain valve (not shown) and then reused. At this time, since the ethanol in the trapper 16 is sucked and exhausted by the dry vacuum pump 19, no oil is mixed in the ethanol, and the medicine recovered by the condenser 20 can be put into the medicine tank 18 and repeatedly used. it can.

  Using such an apparatus, as a result of processing by continuous stable operation within the range of 2 to 500 kg per unit time that the discharge capacity of the extruder allows the throughput of the crosslinked polyethylene, ethanol as a drug is transferred to the reaction extruder 1. 95.05% of the injected amount was stored in the condenser 20.

  As a result, ethanol could be reused.

  Next, another embodiment of the present invention will be described.

  In the recycling process of the cross-linked polyethylene of the above-described embodiment, ethanol was used as a chemical, but in this embodiment, methanol was used instead of ethanol.

  As a result, when the apparatus of FIG. 1 is used, the processing amount of the cross-linked polyethylene can be processed by continuous stable operation within a range of 2 to 500 kg per unit time allowed by the discharge capacity of the extruder, and methanol as a chemical is reacted. 90.09% of the amount injected into the extruder 1 was stored in the condenser 20. As a result, the recovered methanol could be reused.

  As still another embodiment, in the recycling treatment of the crosslinked polyethylene, the same treatment was performed using n-propanol instead of ethanol as a drug.

  As a result, when the apparatus of FIG. 1 is used, the processing amount of the cross-linked polyethylene can be processed by continuous stable operation within a range of 2 to 500 kg per unit time allowed by the discharge capacity of the extruder, and n-propanol which is a medicine. 99.89% of the amount injected into the reaction extruder 1 was stored in the condenser 20. As a result, the recovered n-propanol could be reused.

  Next, a comparative example using the drug recovery apparatus shown in FIGS. 2 to 4 will be described in comparison with the above-described embodiment.

Comparative Example 1
FIG. 2 shows a drug recovery apparatus in which a trapper 16 and a dry vacuum pump 19 are connected in combination to a vent box 8 of a back vent provided in the extruder 2 with a vent, and the other configuration is the same as that of the embodiment of FIG. The same.

  When this method is used, the polymer compound and the drug conveyed to the vented extruder 2 are stably separated, and the drug is sent to the trapper 16 by the suction force of the dry vacuum pump 19. In the trapper 16, impurities having a high boiling point among impurities generated in the reaction and mixed in alcohol as a drug are collected, and the drug is sent to the dry vacuum pump 19. Drugs that are free of oil and water are directly discharged to the outside.

  In the case of such an apparatus, when alcohols such as methanol, ethanol, n-propanol, etc. are used as the drug, the discharge of the drug to the outside is a problem in terms of the environment.

Comparative Example 2
FIG. 3 shows a drug recovery apparatus in which a dry vacuum pump 19 and a condenser 20 are combined and connected to a vent box 8 of a back vent provided in the extruder 2 with a vent.

  When this method is used, the polymer compound and the drug conveyed to the vented extruder 2 are stably separated, and the drug is sucked and sent to the dry vacuum pump 19. Here, since the impurities generated during the reaction and mixed in the alcohol which is a drug are sent to the dry vacuum pump 19 as they are, the resin powder and oil components which are impurities stay in the dry vacuum pump 19. Then, it is sent to the condenser 20 together with alcohol. For this reason, the problem that the dry vacuum pump 19 is likely to break down and the alcohols containing impurities are stored in the condenser 20, and therefore it is difficult to reuse them as they are.

Comparative Example 3
FIG. 4 shows a drug recovery apparatus in which a dry vacuum pump 19 is connected to a vent box 8 of a back vent provided in the extruder 2 with a vent.

  When this method is used, the polymer compound and the drug conveyed to the vented extruder 2 are stably separated, and the drug is sucked and sent to the dry vacuum pump 19. Here, since the impurities generated during the reaction and mixed in the alcohol as the drug are sent to the dry vacuum pump 19 as they are, the resin powder and oil components as impurities stay inside the dry vacuum pump 19, It is discharged to the outside together with alcohol.

  As in Comparative Example 1 having the drug recovery device as shown in FIG. 2, the discharge of the drug to the outside is a problem in terms of the environment.

  As shown in these Comparative Examples 1 to 3, the present invention in which the trapper 16, the dry vacuum pump 19, and the condenser 20 are connected in combination to the back vent vent box 8 provided in the vented extruder 2 is optimal. I understand that there is.

  As described above, the present invention stably separates only the drug from the vented extruder mixed with the polymer processed product and the drug, and enables the recovery of the drug not mixed with the resin powder or oil component as impurities. It is. As a result, it is possible to expect an environmentally valuable effect that prevents harmful drugs from being discharged to the outside and enables recycling of the drugs.

It is a figure which shows one embodiment of this invention. It is a figure which shows the comparative example as a chemical | medical agent collection | recovery apparatus. It is a figure which similarly shows the comparative example as a chemical | medical agent collection | recovery apparatus. It is a figure which similarly shows the comparative example as a chemical | medical agent collection | recovery apparatus.

Explanation of symbols

1 Extruder for Reaction 2 Extruder with Vent 8 Vent Box 16 Trapper 18 Chemical Tank 19 Vacuum Pump 20 Condenser

Claims (9)

A polymer compound and a drug is reacted with the polymer compound is reacted in a reaction vessel, in a method of producing a polymer treated, the vented extruder under vacuum the polymer treated from the reaction vessel Then , a vent box having a volume one or more times that of the reaction vessel is connected to the vented extruder at the rear side of the extrusion side from the introduction position , and the introduced polymer processed product is extruded by the vented extruder. However, the agent containing impurities as a gas component is separated from the polymer-treated product and introduced into the vent box, and the agent gas component containing impurities separated by the vent box is introduced into the trapper. After separating the impurities contained in the gas by suction with a vacuum pump, the gas sucked with the vacuum pump is cooled through a condenser to recover the drug. Compound recovery method of drug.   The method for recovering a polymer compound and a drug according to claim 1, wherein the gas in the trapper is sucked and exhausted to the vacuum pump using a dry vacuum pump. Wherein said agent and polymer compounds, a reaction extruder, according to claim 1 or 2 polymer compound according the recovery method of drug supplied to the reaction vessel in a supercritical or subcritical state. The vented extruder on the discharge side from the introduction position of the polymer processed product from the reaction vessel is provided with a vent for removing the chemical agent as a gas component from the polymer processed product, and the gas discharged from the vent is removed. sent to the trapper, at its trapper, with an agent of a gas containing impurities is supplied from the vent box, the gas in the trapper by sucking with a vacuum pump, the impurities in the gas are separated, impurities are separated The method for recovering a polymer compound and a drug according to any one of claims 1 to 3, wherein the drug gas is cooled by a condenser.   The method for recovering a polymer compound and a drug according to any one of claims 1 to 3, wherein the polymer compound is a polymer having a siloxane bond in the molecule, and the drug is an alcohol or a mixture containing alcohols. In an apparatus for producing a polymer processed product by reacting a polymer compound and an agent to be reacted with the polymer compound in a reaction vessel ,
While introducing said discharged is depressurized from the reaction vessel a polymer treated has a vent box having 1 or more times the volume of the reaction vessel to the rear than its introduction position, extruding the introduced polymer treated However, an extruder with a vent that introduces and separates a drug containing impurities as a gas component from the polymer processed product into the vent box ;
A trapper that introduces the gas component separated in the vent box of the vented extruder and separates impurities in the gas,
A vacuum pump that sucks and exhausts the trapper;
A polymer compound and drug recovery apparatus comprising a condenser connected to an exhaust side of a vacuum pump and recovering a drug by cooling the exhausted gas.   The polymer compound and drug recovery apparatus according to claim 6, wherein the vacuum pump is a dry vacuum pump. A reaction extruder for kneading the polymer compound and the drug and extruding the polymer compound in a supercritical or subcritical state; and a reaction vessel for reacting the polymer compound and the drug from the reaction extruder. The polymer compound and drug recovery apparatus according to claim 6 or 7, further comprising a decompression means for decompressing and supplying the polymer processed product between the extruders. The vented extruder on the discharge side from the introduction position of the polymer processed product from the reaction vessel is provided with a vent for removing a chemical as a gas component from the polymer processed product, and between the vent and the trapper, from the vent The polymer compound according to any one of claims 6 to 8, wherein a line for sending discharged gas to the trapper is connected , a vacuum pump is connected to the trapper, and a condenser is connected to an exhaust side of the vacuum pump. Drug recovery device.

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