WO1998034904A1 - Appareil et procede de decomposition et de recuperation de compose isocyanate - Google Patents
Appareil et procede de decomposition et de recuperation de compose isocyanate Download PDFInfo
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- WO1998034904A1 WO1998034904A1 PCT/JP1998/000450 JP9800450W WO9834904A1 WO 1998034904 A1 WO1998034904 A1 WO 1998034904A1 JP 9800450 W JP9800450 W JP 9800450W WO 9834904 A1 WO9834904 A1 WO 9834904A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to polyurethane resins used in a wide range of fields such as furniture, bedding, vehicles, heat insulating materials for construction materials and home appliances, shoe soles, and, for example, polymers of isocyanate compounds in distillation residues produced as by-products in chemical blunting.
- Decomposition / recovery equipment and method for decomposing and recovering isocyanate-based compounds by contacting them with water that is liquid under high temperature and pressure and hydrolyzing them, and recovering them as raw material compounds or their derivatives for the production of compounds to be decomposed It is.
- isocyanate compound refers to an isocyanate compound having at least one isocyanate group and a group derived from Z or an isocyanate group. Refers to a wide range of compounds. Background art
- Polyurethane resins are manufactured in soft, semi-rigid, and rigid urethane foams, as elastomers, or as RIM (Reaction Injection Molding) products in Japan at a rate of about 400,000 tons per year, and are used in various fields. Recently, environmental protection has gained global importance, and various plastic recycling methods are being considered. Polyurethane resins are no exception.
- the material recycling technology (1) is a technology that recycles the polyurethane resin by performing physical processing such as crushing, while maintaining the characteristics of the resin itself. Studies are being made on the use of such materials as fillers for extruded products, RIM products or concrete.
- the chemical recycling technology (2) recycles polyurethane resin by returning it to raw materials or chemical substances that can be used as raw materials.
- the glycol decomposition method, the amine decomposition method, the hydrolysis method and the like are known.
- the energy recycling technology (3) uses polyurethane resin directly as a fuel or obtains water vapor or fuel gas to use it as an energy resource.
- the present invention is included in the above-mentioned chemical recycling technology (1), but the conventional chemical recycling technology requires the use of other compounds such as glycol, amine, alcohol, etc. Due to the fact that it takes a long time and is not economical, there are few cases where chemical recycling of polyurethane resin is actually in operation.
- Japanese Patent Application Laid-Open No. 54-70377 discloses that polyurethane is prepared at a temperature of up to about 300 in the presence of superheated water vapor and an alkali metal or alkaline earth metal compound. A method of dissolving at a pressure of 0 atm (gauge pressure) is disclosed.
- the inventors of the above-mentioned publications are conducting various studies on a technique for hydrolyzing polyurethane with superheated steam.However, in a low-pressure reaction at a pressure of 10 atm or less, the reaction rate is low, and the reaction may take a long time. Since it cannot be avoided, it also discloses that coexistence of compounds having a catalytic action such as ammonia and aluminum is necessary.
- Japanese Patent Application Laid-Open No. Hei 9-151720 discloses a method of recovering tolylene succinate as trilendiamine, but the optimum decomposition conditions and post-treatment process conditions for recovery are disclosed. Is insufficiently disclosed.
- the waste produced in the production line of polyurethane resin or isocyanate-based low molecular weight compound is produced by using only water substantially without using a special compound as a decomposer.
- the purpose is to provide equipment and methods for efficient decomposition and recovery on a large scale. Disclosure of the invention
- the present invention relates to a decomposition / recovery facility for recovering an isocyanate-based compound having at least one isocyanate group and / or a group derived from an isocyanate group as a compound to be decomposed, and recovering this as a raw material of the compound to be decomposed and decomposed or a derivative thereof.
- a hydrolyzing means for bringing only liquid water at substantially 190 to 370 ° C. into contact with the compound to be decomposed in the reactor under high pressure to hydrolyze the compound;
- Post-treatment means for post-treatment such as dehydration, addition, distillation, separation, and separation of the decomposition reaction product discharged from the reactor are provided.
- FIG. 1 shows a preferred example of the decomposition treatment equipment of the present invention.
- FIG. 2 shows another example of the decomposition treatment equipment of the present invention.
- FIG. 3 shows another example of the decomposition treatment equipment of the present invention.
- FIG. 4 shows another example of the decomposition treatment equipment of the present invention.
- FIG. 5 is a graph showing the effect of the reaction temperature on the decomposition reaction of the polyurethane resin.
- FIG. 6 is a graph showing the effect of the dehydration tower bottom temperature and the dehydration time on the tolylenediamine reduction rate.
- FIG. 7 is a graph showing the effect of distillation column bottom temperature on tolylenediamine reduction rate.
- FIG. 8 is a graph showing the effect of the reactor temperature and the water addition ratio on the recovery of tolylenediamine.
- the decomposition and recovery equipment of the present invention is for hydrolyzing a compound containing a group derived from an isocyanate group, such as a polyurethane resin disocyanate-based low molecular weight compound, and recycling the compound to a usable useful substance.
- a compound containing a group derived from an isocyanate group such as a polyurethane resin disocyanate-based low molecular weight compound
- the compound to be decomposed according to the present invention is an isocyanate-based compound having at least one isocyanate group (—NCO) and / or a group derived from the isocyanate group.
- the compounds to be decomposed include, in addition to the compound having an isocyanate group, a urethane bond, an allohanito bond, and a urea (urea) bond formed by a chemical reaction of an isocyanate compound with another functional group-containing compound.
- compounds having a group (including a bond) derived from an isocyanate group such as a burette bond or an amide bond, and examples thereof include a polyurethane resin.
- a compound formed as a result of a dimerization reaction or a trimerization reaction of a compound having an isocyanate group is also included.
- dimers such as carbodiimide, uretdione, uretonimine, and isocyanurate, and multimers such as trimers and higher. ing.
- polyurethane resin or chemical blunt waste from the viewpoint of resource recycling.
- Polyurethane resins include cut pieces and scraps produced in the molding process of polyurethane resin products, and waste products after being used as products in various fields. It can be an elephant compound.
- Examples of polyurethane resins include foams such as flexible urethane foam, semi-rigid urethane foam, and rigid urethane foam, elastomers (cast, kneaded, thermoplastic elastomer), RIM products, and ISF (integral skin foam). All can be disassembled by the equipment of the present invention.
- Polyurethane resins are mainly made of a compound containing two or more isocyanate groups (polyisocyanate) and, in general, an active hydrogen-containing compound (polyol).
- polyisocyanate a compound containing two or more isocyanate groups
- polyol an active hydrogen-containing compound
- polyurethane resins having various physical properties can be obtained by combining a catalyst, a chain extender, and the like.
- Specific examples of polyurethane resin raw materials include polyisocyanates such as tolylene diisocyanate (TDI), modified TDI, diphenylmethane diisocyanate (MDI), polymeric MDI, hydrogenated MDI, and modified MDI.
- MDI hexamethylene diisocyanate
- HDI hexamethylene diisocyanate
- TOD I tridine diisocyanate
- NDI 1,5-naphthalene diisocyanate
- IPDI isophorone diisocyanate
- p-phene examples include range isocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, and the like.
- polyols examples include 2, 3, 4, 6 or 8 functional polyether polyols derived from an alkylene (ethylene or propylene) oxide and an active hydrogen-containing initiator, polytetramethylene glycol (PTMG), and condensed polyester polyols.
- PTMG polytetramethylene glycol
- polyester polyols such as lactone-based polyester polyols and polycarbonate diols, and acrylacrylol.
- a urethane bond regardless of the molecular structure of the polyurethane resin, and regardless of the type of structural unit for forming the polyurethane resin, a urethane bond, an alohanate bond, a urea (urea) bond, a burette bond,
- a general polyurethane resin such as an amide bond
- a raw material or a derivative usable as a raw material or a raw material of the polyurethane resin as a decomposition target compound that is, polyol and Z or a raw material polyisocyanate
- the corresponding polymer compound can be recovered.
- the decomposition reaction product polyol and polyamide May be difficult to separate.
- ethylene oxide or propylene oxide is subjected to an addition reaction to a mixture of the polyol and the amine to recover the mixture in the form of a polyether polyol.
- the polyether polyol can be directly used as a raw material for the polyurethane without forcibly separating and recovering the polyol and the amine, which leads to a reduction in the number of post-treatment steps and a reduction in cost.
- a compound having a group derived from an isocyanate group or an isocyanate group, which is a relatively low molecular weight compound can be recovered as an amine compound having an amino group (mono-NH 2 ) by hydrolysis.
- TDA Tolylene diisocyanate
- Methylcyclohexanediisocyanate-methylcyclohexanediamine isocyanate formed by the multimerization reaction of the above isocyanate compound.
- a compound having a group or a bond derived from a protein can also be recovered as a corresponding amine compound.
- a hydrolyzing means for bringing only liquid water at substantially 190 to 370 ° C. into contact with the compound to be decomposed in the reactor under high pressure to hydrolyze the compound;
- Post-treatment means for post-treatment such as dehydration, addition, distillation, separation, and separation of the decomposition reaction product discharged from the reactor are provided.
- the target compound By bringing liquid (not steam) into contact with the target compound at 190-370 ° C, the target compound can be rapidly hydrolyzed without using other compounds that promote hydrolysis. Can be disassembled.
- the hydrolysis means essentially includes a reactor capable of high-pressure reaction.
- a reactor capable of high-pressure reaction.
- the hydrolysis means of (1) is not particularly limited as long as it can introduce water heated and pressurized in advance into the reactor.
- a heating device and a pump installed at any position of a water supply line between a water supply source and a reactor may be mentioned. Either the heating device or the pump may be installed on the reactor side (downstream).
- the hydrolysis means of (2) is not particularly limited as long as it can heat and pressurize after introducing water into the reactor.
- (1) and (2) can be used in combination as a hydrolytic means.
- a batch type or a continuous supply can be adopted.
- decomposing and recovering polyurethane resin put After adding a certain amount of polyurethane resin, it may be hydrolyzed by a hydrolysis means.
- the decomposition and recovery equipment further includes a supply means for continuously supplying the compound to be decomposed to the reactor. Since waste is continuously discharged, it is wasteful to carry out the hydrolysis reaction in a batch manner. For example, the energy loss when cooling and raising the temperature of the reactor or when reducing and raising the pressure during batch change is large. In addition, a waste storage tank is required, and the degradation of the decomposition target compound during storage in the storage tank is unavoidable. As will be described later, when a volume reducing means for reducing the volume of the polyurethane foam is also provided, it is preferable to employ a supplying means for continuously supplying the reduced foam to the reactor.
- the supply means is, for example, a pump, an extruder, or a pressure accumulator.
- the compound to be decomposed may be introduced into the reactor in a heated state using an extruder provided with a heating unit.
- the post-treatment means is a means for performing post-treatments such as dehydration, addition, distillation, separation, and liquid separation on the decomposition reaction product discharged from the reactor, and includes dehydration, addition, distillation, separation, It is not limited to liquid separation but includes various treatment means performed on the product obtained after hydrolysis.
- post-treatments such as dehydration, addition, distillation, separation, and liquid separation on the decomposition reaction product discharged from the reactor, and includes dehydration, addition, distillation, separation, It is not limited to liquid separation but includes various treatment means performed on the product obtained after hydrolysis.
- Dehydration treatment means Additional treatment means such as distillation, contact with a dehydrating agent (which adsorbs water), drying, filtration, etc. Reactors capable of chemical reaction
- Distillation Distillation equipment that can perform distillation, extractive distillation, molecular distillation, etc.
- Separation Devices that can perform degassing, extraction, centrifugation, filtration, squeezing, separation, etc. Separation: Separation device
- Each treatment may be performed under reduced pressure or increased pressure.
- the post-processing means may be a single one or a combination of a plurality.
- the separation and recovery equipment of the present invention may include a volume reducing means.
- the volume reducing means is useful, for example, when a polyurethane foam is used as a compound to be decomposed. Volume reduction measures can reduce the volume of the foam and reduce the size of the reactor Because it can be.
- a means for reducing the volume it is preferable to employ a device capable of compressing the polyurethane foam while heating it at 100 to 250 ° C.
- rigid foams can be reduced in volume (increased density) by heating them to an appropriate temperature and compressing them to achieve volume reduction.
- Examples of the means for reducing the volume include a pressurizer equipped with a heating unit and an extruder equipped with a heating unit (single screw, twin screw, etc.).
- volume reducing means also has a function as a supply means.
- a pressurizing machine equipped with a heating unit it is advisable to use another supply means or to introduce the volume-reduced product into the reactor in a batch system.
- Fig. 1 shows an example of a decomposition and recovery facility for continuous decomposition. This equipment is particularly useful for the decomposition and recovery of polyurethane foam.
- the hydrolysis means 1 comprises a reactor 2, a supply pump 3 provided between the water supply source and the reactor 2, and a heater 4. Liquid water pressurized and heated by the pump 3 and the heater 4 is continuously sent to the reactor 2.
- a heater may not be required, but the structure of the reactor becomes complicated. Either the pump 3 or the heater 4 may be on the reactor side.
- the polyurethane is sent from the storage tank 5 to the reactor 2 through the volume reducing means including the extruder 6. Therefore, in this example, the extruder is provided with six power supply means and volume reduction means. Note that a supply means such as a gear pump may be further provided between the extruder 6 and the reactor 2.
- the polyurethane is usually compressed while being heated to 100 to 250 ° C. More preferably, the lower limit of the heating temperature is 120 ° C., and the upper limit is 180 ° C.
- the compression conditions are preferably adjusted according to the performance of the extruder so that the time required for the heat compression treatment is about 5 to 60 minutes.
- Estimated heat compression state of polyurethane is The density after heating and compression is 300 kg / m 3 or more for general flexible foam, and 500 kg / m 3 or more for rigid foam.
- a polyurethane resin product other than the foam it can be heated by the extruder 6 and then supplied to the reactor 2 as in the case of the foam. This is because, even if the polyurethane resin is not heated in the reactor, the hydrolysis reaction is rapidly performed by the contact between the heated polyurethane resin and the heated and pressurized water in the reactor.
- a polyurethane resin with high rigidity that does not provide fluidity even when heated must be hydrolyzed after finely pulverized polyurethane resin is placed in a reactor having a heating section.
- the internal pressure of the reactor 2 is preferably 3 to 30 MPa. If the pressure is low, the reaction takes too long. A more preferable lower limit of the pressure is 6 MPa. In addition, within the above pressure range, the decomposition rate of polyurethane becomes 100% in a short time, so that it is not necessary to increase the pressure to 30 MPa or more.
- the upper limit of the pressure is more preferably 25 MPa or less, and further preferably 2 OMPa or less.
- the weight (water ratio) of water to be brought into contact with the polyurethane in the reactor 2 is preferably at least 1.0 times. If the ratio exceeds 10.0 times, it is necessary to increase the size of the reactor, or the time and energy required for separating (dehydrating) the decomposition reaction product and water in the post-treatment process increase. It is recommended that it be 0.0 or less. The more preferable upper limit of the water addition ratio is 4.0 times.
- the water temperature (reaction temperature) in the reactor 2 is preferably 200 to 370 ° C. 370. If it exceeds C, the polyurethane decomposition rate approaches 100%. Polyamine condensation and polyol decomposition proceed, and the recovery rate of polyamine / polyol, which is the target of recovery, decreases. A more preferred upper limit of the water temperature is 340 ° C. If the water temperature is lower than 200 ° C, the polyurethane will take a long time to decompose, making it inefficient. A more preferred lower limit of the water temperature is 250 ° C.
- the decomposition reaction product discharged from the reactor 2 is sent to the aftertreatment means 7. If poly urethane foam is decomposed products, decomposition reaction products, polyamine, polyol - Le, water, C0 2, is undegraded and the like. Polyurethane foams are available in a wide variety and are produced from various polyisocyanates and various polyols.
- the decomposition reaction product contains polyamine, which is a derivative of polyisocyanate, which is a raw material for producing a polyurethane foam to be decomposed, and polyol, which is also a raw material for production.
- the post-processing means 7 includes a degassing device 8, a dehydration tower 9, and a separator 10.
- degasser 8 various bonds derived from Isoshianeto groups in the polyurethane is hydrolyzed to an amino group - C 0 2 to generate when changed to (NH 2) is removed from the decomposition reaction product. Some of the water vapor is also removed.
- the dehydration column 9 to remove the C 0 2 and water.
- the effluent after dehydration is sent to a separator 10 for separating polyol and polyamine, and is separated into decomposed and recovered light substances mainly composed of polyamine and heavy substances mainly composed of polyol.
- a plurality of degassing devices 8, dehydration towers 9, and separators 10 may be provided respectively, and the order of installation is not limited to the example shown in the drawings. Further, a purification device may be further provided downstream of the separator 10 as the post-treatment means 7.
- Polyamine in the effluent acts as an initiator for the addition reaction, and the reaction of adding an alkylene oxide such as ethylene oxide to propylene oxide to the polyol proceeds.
- polyether polyol can be used as a raw material in the production of polyurethane, this method can also decompose the polyurethane resin to recover the raw material for polyurethane production, and forcibly separate polyamine and polyol, which are difficult to separate. It is much more economical than it is. Therefore, it is recommended that equipment for decomposing and recovering polyurethane resin made from polymeric MDI II prepolymer type polyisocyanate, etc. be equipped with a post-treatment means equipped with a reactor capable of performing an addition reaction.
- FIG. 2 shows another example of a polyurethane resin decomposition and recovery facility.
- Hydrolysis means 1 comprises three reactors 21, 22, 23, a feed pump 3 and a heater 4.
- the configuration of the storage tank 5 and the extruder 6 and the configuration of the post-processing means 7 are the same as those in FIG.
- a certain amount of the polyurethane was introduced into the reactor 21 at the same time as the heated and pressurized water, or first, and then the valves 21 a and 2 Close 1 b.
- the valve 21 c is opened and the decomposition reaction product is sent to the post-treatment means 7.
- valves 21a and 21b When the valves 21a and 21b are closed, i.e., when the introduction of water and polyurethane into the reactor 21 is completed, the valves 22a and 22b are then opened and the reactor 22 is opened. Water and polyurethane are introduced, a hydrolysis reaction is performed, and the decomposition reaction product of the reactor 21 is sent to the post-processing means 7, and then the decomposition reaction product of the reactor 22 is sent to the post-processing means 7. send. Similarly, a hydrolysis reaction was carried out using the reactor 23, and water and polyurethane were introduced into the reactor 21 or 22 while the decomposition reaction product was sent to post-treatment means.
- batch or semi-continuous decomposition and recovery can be performed simultaneously on multiple lines.
- FIG. 3 shows a configuration in which the post-processing means 7 includes a degassing device 8, a liquid separator 11, and a dehydration column 9. After separating into a water-soluble decomposition recovery product and a water-insoluble decomposition recovery product by a liquid separator 11, the water-soluble decomposition recovery product is dehydrated in a dehydration tower 9 to obtain a dehydrated decomposition recovery product. is there.
- a decanter or the like may be used as the liquid separator 11, a decanter or the like may be used.
- Fig. 4 shows an example of a decomposition and recovery facility that continuously decomposes distillation residues containing isocyanate-based low molecular weight compounds.
- the hydrolysis means 1 has the same configuration as in FIG. In consideration of the continuous discharge of the distillation residue from the chemical plant, no storage tank is provided, and the compound to be decomposed is continuously supplied. There is no need for volume reduction measures.
- a supply means a supply pump 12 is provided, and a heater 13 is added.
- an isocyanate-based decomposition target compound such as a distillation residue is introduced into the reactor 2 without being converted into a low-viscosity liquid with a solvent or the like, the decomposition target compound is in a fluid state.
- the heater 13 be in a molten state at 120 ° C. or higher.
- heating above 180 ° C may accelerate the polymerization reaction of the isocyanate-based decomposition target compound in the distillation residue.
- the temperature of the melt when introduced into the reactor 2 is 1
- the temperature is preferably set to 80 ° C. or lower.
- a more preferred introduction temperature is 130 to 170 ° C.
- a vessel equipped with a stirrer may be provided upstream of the reactor 2, and a solvent may be added to the isocyanate-based compound to be decomposed, such as distillation residue, and stirred, and then introduced into the reactor 2 in a solution state.
- a solvent such as distillation residue, and stirred, and then introduced into the reactor 2 in a solution state.
- a solvent in this case, a halogenated hydrocarbon such as dichlorobenzene, an ether-based solvent such as diethylene glycol getyl ether, or the like can be used alone or as a mixture.
- These solvents are used in an appropriate amount to ensure the fluid state of the isocyanate-based compound to be decomposed.
- a heating unit in the container with a stirrer and stir while heating. The heating temperature at this time is also set to 18 CTC or lower, preferably 130 to 170 ° C.
- the water temperature (reaction temperature) in the reactor 2 is set to 190 to 300 ° C.
- a more preferred water temperature range is from 200 to 290 ° C.
- the water temperature is preferably set lower than in the case of polyurethane in order to avoid heat polymerization before the isocyanate compound is hydrolyzed.
- the reaction pressure may be appropriately adjusted so that the hydrolysis reaction is performed in the above temperature range. Preferably, it is 9.8 to 14.7 MPa (100 to 150 kg / cm 2 ).
- the water addition ratio in the reactor 2 is preferably 0.5 times or more. If it is less than 0.5 times, sufficient fluidity may not be secured.
- the water addition ratio be 1.0 times or more.
- the upper limit of the hydrolysis ratio is 5.0 times the decomposition target compound in the reactor 2, and it is not necessary to supply more.
- the water ratio exceeds 3.0 times, the decomposition efficiency is almost saturated. Therefore, considering the energy load in the dehydration step of the post-treatment means, the water ratio is preferably 3.0 times or less.
- the post-treatment means 7 includes a degassing device 8, a dehydration column 9, and a vacuum distillation column 14. Have been. Decomposition reaction products, Amin compound, C 0 2, water, in addition to such heavy components, are included, such as by-products having a HC 1 or chloro group by cases (chlorine ions state is also included) . In degasser to remove C 0 2, followed by dehydration column 9, water and C 0 2 is separated and removed. At this time, the effluent from the degassing device 8 is introduced into the dehydration column 9 at a temperature of 60 ° C. or higher, more preferably 8 (TC or higher. If the temperature is too low, solids may precipitate.
- TC preferably 8
- the dehydration temperature in the dehydration tower 9 be 240 ° C. or less. It is preferably at most 220 ° C, more preferably at most 200 ° C, even more preferably at most 180 ° C.
- the upper limit of the dehydration treatment temperature is used when using a decomposition target compound containing almost no HC1 or chlorine groups or when the recovery target is a compound that does not decompose by reacting with HC1 or chlorine groups. It is not necessary to control.
- the effluent after the dehydration is used to purify the phantom compound in a vacuum distillation column 14.
- a compound containing almost no HC1 or chlorine groups is used as a decomposition target compound, or when the target product to be recovered is a compound that does not react with HC1 or chlorine groups to cause decomposition, There is no need to set an upper limit for the distillation temperature.
- the decompression condition can be appropriately selected according to the temperature condition.
- the post-treatment means 7 may be configured so as not to include the vacuum distillation column 13. In this case, collect the crude waste discharged from the dehydration tower 9 and transfer it to another location, for example. Then, a purified amine compound can be obtained using an existing distillation column or other purification equipment.
- a flexible urethane foam (apparent density before compression of 19.5 kg / m 3 ) produced from tolylene diisocyanate (TD I) and polyether polyol (trifunctional; molecular weight 3000) was subjected to a decomposition treatment.
- TD I tolylene diisocyanate
- polyether polyol trifunctional; molecular weight 3000
- the decomposition rate of the polyurethane resin in Table 2 was determined by the following equation.
- the recovery rate (% by weight) of TDA is the amount of TDA actually recovered compared to the theoretical recovery amount when all TDI in the polyurethane foam charged into the reactor is recovered as TDA. The same applies to the recovered amount of the polyol.
- a rigid urethane foam (density before compression: 36 kg / m 3 ) manufactured from polymeric MDI and polyester polyol (sorbitol type; hydroxyl value: 42 OmgKOH / g) was subjected to a decomposition treatment. As in Example 1, the conditions for reducing the volume were examined. Table 3 shows the temperature and time during heat compression and the density of the obtained compact. Table 3
- the heated and compressed polyurethane resin was introduced into a reactor, and hydrolyzed at a reaction temperature of 240 to 255 ° C and a pressure of 1 OMPa.
- the decomposition reaction product was introduced into a separator and dehydrated.
- the effluent after dehydration was charged into a autoclave, and propylene oxide was sequentially added thereto at 110 ° C. and 2.5 kg / cm 2 (0.245 MPa).
- a polyol with a hydroxyl value of 450 mg KOHZg and a viscosity of 20,000 OmPa ⁇ s (25 ° C) was obtained.
- the residence time in the dehydration tower and the bottom temperature are determined by TDA (TDI).
- TDA TDI
- the effect on the rate of reduction of the decomposition products of The results are shown in FIG.
- the higher the temperature during dehydration the faster the decomposition of TDA by HC1 and chlorine groups.
- the decrease rate of TDA sharply increased as the residence time in the tower increased.
- T The purification (distillation) process for decomposing and recovering DA is 250 considering the yield of TDA. It is preferable to carry out at a temperature not exceeding C. It is more preferable to carry out the reaction at 240 ° C or lower, further preferably at 230 ° C or lower.
- TDA recovery rate (% by weight) is calculated based on the theoretical recovery amount of TDA (TDI), assuming that all of the distillation residue introduced into the reactor is TDI and that all of them are recovered as TDA. It is the ratio of TDA (weight) actually obtained to (weight).
- “Hydration ratio” is the weight of high-pressure high-temperature water in the reactor z The weight of the compound to be decomposed.
- Theoretical recovery when all TD I residues are TD I Amount of TD A (g) From Table 5 and FIG. 8, it was confirmed that TDA was recovered at each temperature when the water addition ratio was 0.5 or more. In addition, if the water addition ratio is 1.0 times or more and the reaction temperature is 190 to 300 ° C, 20% by weight or more of TDA can be recovered, and especially at 200 to 290 ° C, 70% by weight or more and 250 ° C. It was found that the recovery rate was around 100% by weight around C. It was also clarified that the decomposition reaction was greatly affected by the temperature, and that the increase in recovery was saturated when the water addition ratio exceeded 3.0 times at the same temperature.
- the experiment was conducted at 180 ° C and 9.8 MPa at a water ratio of 0.5 to 5.0 times, and at 310 ° C at 14.7 MPa at a water ratio of 0.5 to 5.0 times. Experiments were performed with a 5.0-fold change, but the recovery of TDA was less than 5% by weight in each case.
- TDI TDI or a multimer of TDI can be recovered in high yield as TDA, and this superior advantage is apparent because TDA can be used as an intermediate material in the TDI synthesis process. It is.
- Example 3 The same distillation residue as used in Example 3 and diclo-mouth benzene were mixed at a weight ratio of 1: 1 to form a solution, and then 25 CTC, water at a pressure of 150 kg / cm 2 (14.7 MPa) was used. Was contacted at a water ratio of 1.8 to effect hydrolysis, and the TDA recovery was 90% by weight.
- a compound to be decomposed such as a polyurethane resin or an isocyanate-based low-molecular compound can be recovered as a raw material or an intermediate raw material (derivative) for producing the compound.
- the decomposition target compound can be continuously decomposed, so that, for example, the decomposition target compound discharged as waste in a chemical plant in a molten state or in a solution state can be continuously fixed. Can be processed under conditions.
- polymers such as polyurethane resins can also be recovered as polyols / polyamines with the equipment of the present invention, which greatly contributes to the promotion of recycling. Furthermore, the optimal dehydration and purification conditions for the recovery of amine compounds, especially from low-molecular-weight isocyanate compounds, could be found, so that the amine compounds could be recovered with high efficiency and the production of isocyanate-based compounds It has become possible to effectively reuse it as a raw material for the process.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1998628498 DE69828498T2 (de) | 1997-02-05 | 1998-02-04 | Apparat und verfahren zum hydrolysieren und zum recycling von isocyanatverbindungen |
BR9807306A BR9807306A (pt) | 1997-02-05 | 1998-02-04 | Aparelho e processo para hidrolisar e reciclar derivados de poliisocianato |
US09/355,338 US6630517B2 (en) | 1997-02-05 | 1998-02-04 | Process for hydrolyzing and recycling a polyurethane |
EP19980901495 EP0976719B1 (en) | 1997-02-05 | 1998-02-04 | Apparatus and method for decomposing and recovering isocyanate compound |
KR10-1999-7006987A KR100536858B1 (ko) | 1997-02-05 | 1998-02-04 | 이소시아네이트 화합물의 분해회수 방법 |
CA 2279541 CA2279541A1 (en) | 1997-02-05 | 1998-02-04 | Apparatus for and process of hydrolyzing and recycling polyisocyanate derivatives |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2299897 | 1997-02-05 | ||
JP9/22998 | 1997-02-05 | ||
JP9119798A JPH10310663A (ja) | 1997-05-09 | 1997-05-09 | ポリウレタン樹脂の分解回収方法 |
JP9/119798 | 1997-05-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998034904A1 true WO1998034904A1 (fr) | 1998-08-13 |
Family
ID=26360295
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/000450 WO1998034904A1 (fr) | 1997-02-05 | 1998-02-04 | Appareil et procede de decomposition et de recuperation de compose isocyanate |
Country Status (9)
Country | Link |
---|---|
US (1) | US6630517B2 (ja) |
EP (1) | EP0976719B1 (ja) |
KR (1) | KR100536858B1 (ja) |
CN (1) | CN1272309C (ja) |
BR (1) | BR9807306A (ja) |
CA (1) | CA2279541A1 (ja) |
DE (1) | DE69828498T2 (ja) |
TW (1) | TW358106B (ja) |
WO (1) | WO1998034904A1 (ja) |
Cited By (2)
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EP1006143A1 (en) * | 1998-11-30 | 2000-06-07 | TAKEDA CHEMICAL INDUSTRIES, Ltd. | Apparatus for decomposition and recovery of polyurethane resin |
US6489373B2 (en) | 1998-10-02 | 2002-12-03 | Mitsui Takeda Chemicals Inc. | Method for decomposition and recovery of polyurethane resin |
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CA2342464A1 (en) * | 2000-04-04 | 2001-10-04 | Takashi Kumaki | Method of decomposing a polyurethane |
US6660779B2 (en) | 2000-04-28 | 2003-12-09 | Matsushita Refrigeration Company | Method of manufacturing rigid polyurethane foam material, method of manufacturing refrigerator, and refrigerator |
JP4705425B2 (ja) | 2005-07-12 | 2011-06-22 | 三井化学株式会社 | ポリイソシアネート残渣の分解装置およびそのスタートアップ方法 |
EP1903026B1 (en) | 2005-07-12 | 2012-12-26 | Kabushiki Kaisha Kobe Seiko Sho | Method for decomposing and recovering an isocyanate compound and apparatus for decomposing and recovering the same |
JP5116954B2 (ja) | 2005-07-12 | 2013-01-09 | 三井化学株式会社 | ポリイソシアネート残渣の濃縮方法、処理方法、濃縮装置および処理装置 |
DE102006060181A1 (de) * | 2006-12-18 | 2008-06-19 | Bayer Materialscience Ag | Verfahren zur Herstellung von Toluylendiisocyanat |
US9000219B2 (en) | 2009-12-24 | 2015-04-07 | Mitsui Chemicals, Inc. | Method for treatment of isocyanate residue, and method for treatment of carbonate |
US20120289746A1 (en) * | 2011-05-09 | 2012-11-15 | Basf Se | Process for working up an isocyanate-comprising stream |
JP5744619B2 (ja) | 2011-05-18 | 2015-07-08 | 三井化学株式会社 | トリレンジイソシアネートの製造方法 |
US8329455B2 (en) | 2011-07-08 | 2012-12-11 | Aikan North America, Inc. | Systems and methods for digestion of solid waste |
TW201930259A (zh) * | 2017-12-27 | 2019-08-01 | 日商旭化成股份有限公司 | 有機胺之回收方法 |
WO2023208946A1 (de) | 2022-04-27 | 2023-11-02 | Covestro Deutschland Ag | Verfahren zur wiedergewinnung von rohstoffen aus isocyanurat-haltigen polyurethanprodukten |
DE102022113374A1 (de) | 2022-05-26 | 2023-11-30 | Neveon Germany Gmbh | Umsetzung von Polyurethan in einem sich verjüngenden Reaktor |
CN115925580B (zh) * | 2022-11-22 | 2024-06-07 | 宁夏瑞泰科技股份有限公司 | 资源化利用hdi精馏残渣的方法及缩二脲多异氰酸酯 |
EP4403589A1 (en) | 2023-01-19 | 2024-07-24 | Basf Se | A process for preparing at least one polyisocyanate from solid material w |
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- 1998-02-04 US US09/355,338 patent/US6630517B2/en not_active Expired - Lifetime
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6489373B2 (en) | 1998-10-02 | 2002-12-03 | Mitsui Takeda Chemicals Inc. | Method for decomposition and recovery of polyurethane resin |
EP1006143A1 (en) * | 1998-11-30 | 2000-06-07 | TAKEDA CHEMICAL INDUSTRIES, Ltd. | Apparatus for decomposition and recovery of polyurethane resin |
US6660236B1 (en) | 1998-11-30 | 2003-12-09 | Takeda Chemical Industries, Ltd. | Apparatus for decomposition and recovery of polyurethane resin |
Also Published As
Publication number | Publication date |
---|---|
BR9807306A (pt) | 2000-03-21 |
EP0976719A4 (en) | 2001-04-18 |
EP0976719A1 (en) | 2000-02-02 |
EP0976719B1 (en) | 2005-01-05 |
CN1251570A (zh) | 2000-04-26 |
KR100536858B1 (ko) | 2005-12-14 |
TW358106B (en) | 1999-05-11 |
DE69828498T2 (de) | 2006-01-19 |
CN1272309C (zh) | 2006-08-30 |
CA2279541A1 (en) | 1998-08-13 |
US20030012710A1 (en) | 2003-01-16 |
KR20000070737A (ko) | 2000-11-25 |
US6630517B2 (en) | 2003-10-07 |
DE69828498D1 (de) | 2005-02-10 |
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