JP4536295B2 - Method for producing polyurethane raw material, and method for producing rigid urethane foam and refrigerator using the polyurethane raw material - Google Patents

Description

【Technical field】
[0001]
  The present invention is a compressed urethane powder obtained by compressing and pulverizing a rigid urethane foam separated from a refrigerator.EndIt is related with the manufacturing method of the polyurethane raw material used, and the manufacturing method of the rigid urethane foam and refrigerator using the same.
[Background]
[0002]
  In recent years, recycling of waste home appliances such as refrigerators and televisions has become an extremely important theme from the viewpoint of resource saving, and various efforts have been made. Regarding the recycling of refrigerators, metal materials such as iron plates and copper tubes can be recycled relatively easily. However, plastics, especially hard urethane foam, which is a thermosetting resin, is used in large quantities as a heat insulating material, but it is difficult to melt and regenerate, and it is generally used as landfill, incineration, or a filler. There were many.
[0003]
  Under such circumstances, as a recent technique, a process technique for decomposing a polymer material using supercritical water or subcritical water as a treatment medium has been proposed. For example, in JP-A-10-310663, as a method for decomposing and recovering a polyurethane resin, the polyurethane resin is chemically decomposed using water in a supercritical state or a subcritical state, and a raw material compound of the polyurethane resin or a usable raw material derivative is disclosed. It has been proposed to recover. Japanese Patent No. 2885673 describes a method of decomposing a polymer material using water in a supercritical state or a subcritical state and chemically decomposing it into an oil component.
[Prior art documents]
[Patent Literature]
[0004]
[Patent Document 1]
JP-A-10-310663
[Patent Document 2]
Japanese Patent No. 2885673
SUMMARY OF THE INVENTION
[Problems to be solved by the invention]
[0005]
  However, when processing rigid urethane foam, which is a constituent material of used refrigerators, even if it is treated with supercritical water in the product state, the rigid urethane foam is covered with an iron plate or ABS resin, so it is chemically decomposed. I can't do it. In addition, various polymer materials such as polypropylene resin used for interior parts of refrigerators can be chemically decomposed with supercritical water or subcritical water. Since various low molecular weight materials are dissolved in the raw material mixture as impurities, there is a problem that they cannot be reused as a hard urethane foam raw material.
[0006]
  Therefore, for the purpose of industrial recycling, in order to recover polyol, isocyanate, etc., which are raw materials for rigid polyurethane foam from used refrigerators, take out rigid urethane foam that does not contain foreign materials or impurities, add Therefore, the fundamental challenge is to construct a treatment method that can decompose and recover ferrous and non-ferrous metals and recycle the entire system at a high recycling rate. Moreover, the raw material compound of the rigid urethane foam obtained by chemical decomposition is determined by the chemical structure of the rigid urethane foam that is a substance to be decomposed. Therefore, it is necessary to select a regeneration method according to the raw materials used when manufacturing the original rigid urethane foam, and further, the raw urethane foam raw material compound obtained by chemical decomposition is used as a rigid urethane foam, particularly a refrigerator insulation. Reuse is an important issue in achieving recycling.
[0007]
  In view of the above-mentioned problems, the present invention is a compressed urethane which is light in weight, that is, easy to transport and excellent in reactivity with a urethane decomposing agent, which can improve the material recycling rate of used refrigerators and improve recycling. powderEndProvided are a method for producing a polyurethane raw material used, and a method for producing a rigid urethane foam and a refrigerator using the polyurethane raw material.
[Means for Solving the Problems]
[0008]
  In order to solve the above problems, the present inventionA method for producing a polyurethane raw material includes a rigid urethane foam produced by foaming a diphenylmethane diisocyanate composition as a raw material.Waste refrigeratorIn the crushing step of crushing after extracting the refrigerant in the refrigerator, and the crushing stepIsolatedSaidHard urethane foamWhile heating at 90-130 ° CGrind and compress to a bulk density of 0.1 to 1.2 g / ml and an average particle size of 1 μm to 3 mm., While recovering the blowing agent gas contained in the rigid urethane foam,Compressed urethane powderAnd the compressed urethane powder obtained in the foam heat insulating material treatment step and the glycol or amine having 2 to 4 carbon atoms are mixed and heated at 100 to 250 ° C. to be liquefied, and an impurity solid After removing the particles, the liquefied product and high-temperature high-pressure water are reacted in a supercritical or subcritical state at 190 to 400 ° C. and 10 to 25 MPa, and then dehydrated to obtain a polyurethane raw material. It is characterized by having. This improves the reactivity with the urethane decomposing agent to regenerate the urethane raw material, improves the recycling rate of the hard urethane foam, and transports the hard urethane foam collected from the waste refrigerator to the recycling process. The transportation cost can be reduced.
[0009]
  in frontThe rigid urethane foam contains, as an essential component, a rigid urethane foam produced by foaming from a diphenylmethane diisocyanate composition. Thereby, the subsequent reaction process is simplified and the hard urethane foam or the refrigerator can be regenerated at a lower cost.
[0010]
  Also,in frontThe rigid urethane foam is produced from a raw material for producing rigid urethane foam using the compressed urethane powder as a raw material.TheAs a result, the rigid urethane foam produced from the recycled raw material can be reused as a resource and recycled for the heat insulating material of the refrigerator.
[0011]
  Next, in the method for producing a polyurethane raw material of the present invention, the compressed urethane powder and a glycol or amine having 2 to 4 carbon atoms are mixed, heated at 100 to 250 ° C. and liquefied, and then the liquefied product and High temperature high pressure water is reacted at 190 to 400 ° C. and 10 to 25 MPa.The
[0012]
  BookInvention methodAccording to the above, the rigid urethane foam lump taken out from the used waste refrigerator is recovered in a form free from impurities such as other resins used in refrigerator parts, and compressed and pulverized into a powder form. Since the compressed urethane powder is used as a raw material, and glycols and amines are added and reacted therewith, part of the urethane bond is selectively chemically decomposed and liquefied. For this reason, it is possible to easily filter and remove impurities such as mixed polypropylene resin with a filter, etc., and by applying supercritical water or subcritical water treatment to the liquefied product after removing impurities, it is easy to obtain high purity liquid. A polyurethane raw material is obtained.
[0013]
  In the method for producing the polyurethane raw material, the mixing amount of the glycols or amines having 2 to 4 carbon atoms is preferably 0.4 to 5.0 times (mass ratio) with respect to the compressed urethane powder. Moreover, it is preferable that the ratio of the said high temperature / high pressure water is 0.4-5.0 times (volume ratio) with respect to the said liquefied material.
[0014]
  The method for producing a polyurethane raw material polyol according to the present invention is characterized in that an alkylene oxide is addition-polymerized to the polyurethane raw material produced by the production method. Thereby, the polyol which can be used for manufacture of a rigid urethane foam is obtained.
[0015]
  In the method for producing the polyurethane raw material polyol, the polyol preferably has a hydroxyl value of 160 to 935 mgKOH / g. Thereby, the characteristic of a rigid urethane foam becomes favorable.
[0016]
  Furthermore, the method for producing a rigid urethane foam according to the present invention comprises mixing and foaming a polyol composition, an isocyanate, a foam stabilizer, a catalyst, and a foaming agent containing the polyurethane raw material polyol produced by the production method as an essential component. Features.
[0017]
  Further, the refrigerator manufacturing method of the present invention comprises mixing a polyol composition containing the polyurethane raw material polyol manufactured by the above manufacturing method as an essential component, an isocyanate, a foam stabilizer, a catalyst and a foaming agent, so that the inner box and the outside of the refrigerator are mixed. It is characterized by being injected between boxes and foam-cured.
[0018]
  BookinventionAccording to the present invention, the polyurethane raw material decomposed and regenerated from the hard urethane foam mainly made of diphenylmethane diisocyanate composition used as the heat insulating material of the refrigerator can be used as the raw material for the hard urethane foam. It is possible to manufacture a refrigerator that is friendly to the global environment. Moreover, when it becomes a used refrigerator in the future, it can be utilized again as a resource.
BEST MODE FOR CARRYING OUT THE INVENTION
[0019]
  In the present invention, the hard urethane foam separated from the refrigerator is ground and compressed to obtain a compressed urethane powder having specific physical properties, and this is mixed with glycols or amines having 2 to 4 carbon atoms in a specific temperature range. After heating to liquefy, the liquefied product and high-temperature high-pressure water are reacted under specific conditions to produce a polyurethane raw material (A). And an alkylene oxide is addition-polymerized to this polyurethane raw material to make a polyurethane raw material polyol, and this polyol is utilized for manufacture of a rigid urethane foam or a refrigerator. Details will be described below.
[0020]
  The compressed urethane powder is obtained by grinding and compressing a rigid urethane foam separated from a waste refrigerator using an appropriate method, such as chlorofluorocarbon contained in the rigid urethane foam. The blowing agent gas is substantially removed.
[0021]
The rigid urethane foam used for the above-mentioned grinding and compression is not particularly limited, but in view of the subsequent reaction process and recycling cost, it is preferably one separated from a refrigerator in which a heat insulating material is foam-produced using a diphenylmethane diisocyanate composition as a raw material. Used. The separation, grinding and compression means of the rigid urethane foam is not particularly limited, and a conventionally known method can be appropriately used.
[0022]
  The compressed urethane powder has a bulk density in the range of 0.1 to 1.2 g / ml, preferably 0.3 to 1.1 g / ml, particularly preferably 0.5 to 1.0 g / ml. . When the bulk density is less than 0.1 g / ml, the compressed urethane powder becomes bulky, so the transportation cost increases. On the other hand, when it exceeds 1.2 g / ml, the compressed urethane powder aggregates with each other by grinding and compression. This is because the crushability when it becomes a lump is inferior, which is not preferable.
[0023]
  The shape of the compressed urethane powder is not particularly limited, but the average particle diameter is preferably 1 μm to 3 mm, preferably 1 μm to 1 mm, particularly preferably 1 μm to 500 μm. If the average particle size is less than 1 μm, it is difficult to further refine industrially, so that the economy is inferior. If it exceeds 3 mm, the specific surface area is small and the efficiency of the liquefaction treatment decreases. .
[0024]
  In addition, as described above, depending on the type of hard urethane foam separated, grinding, and compression method, the compressed urethane powder after grinding and compression aggregates with each other to form a lump (compression molded body) of compressed urethane powder. In such a case, the lump may be appropriately crushed as necessary, and the crushed one is subjected to the following liquefaction treatment. The crushing means is not particularly limited, and a conventionally known method can be appropriately used.
[0025]
  Next, the compressed urethane powder is mixed with a C2-4 glycol or amine and heated to produce a liquefied substance. The glycols are not particularly limited as long as the urethane bond is chemically decomposed and liquefied, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, and ethylene glycol monoalkyl ether. Of these, ethylene glycol and propylene glycol are preferable in terms of reactivity and cost. The amines are not particularly limited as long as the urethane bond is chemically decomposed and liquefied, and examples thereof include monoethanolamine, diethanolamine, ethylenediamine, propylenediamine, and tolylenediamine. It is done. Of these, monoethanolamine and tolylenediamine are preferable from the viewpoint of reactivity. The glycols or amines can be used alone or in combination, and the mixing ratio is also arbitrary.
[0026]
  Glycols or amines are preferably used in an amount of 40 to 500 parts by mass, more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the compressed urethane powder. If the amount is less than 40 parts by mass, liquefaction will not proceed effectively. On the other hand, if it exceeds 500 parts by mass, the reactor must be enlarged, and the proportion of compressed urethane powder will be low. Energy efficiency for processing the compressed urethane powder per unit volume in the super-subcritical decomposition which is the next step is deteriorated. Further, the reaction is carried out at a temperature of 100 to 250 ° C., preferably 150 to 200 ° C. under normal pressure. The reaction time varies depending on the type of compressed urethane powder and amines or glycols to be used, the reaction temperature, the mixing ratio, etc., but is usually 1 to 12 hours. In order to make the reaction proceed smoothly, a catalyst such as barium acetate, thallium acetate, other metal compounds, or an acid catalyst may be added alone or in combination, and these catalysts are added within the usual range. To do.
[0027]
  Thereafter, the reaction product is subjected to an impurity removal operation such as filter filtration to remove the impurity solid particles present in the reactor. A method for removing impurities such as filter filtration is not particularly limited, and a conventionally known method can be appropriately used.
[0028]
  The liquefied product after impurity removal (filtration) is introduced into the reactor together with high-temperature and high-pressure water, and maintained in a supercritical or subcritical state for about 5 minutes to 1 hour to cause a decomposition reaction. The high-temperature and high-pressure water is introduced at a volume ratio of 0.4 to 5.0 times, preferably 0.5 to 3.0 times the liquefied material. When the ratio of water is less than 0.4 times, the fluidity becomes insufficient and the decomposition does not proceed effectively. On the other hand, when it exceeds 5.0 times, the decomposition efficiency approaches saturation, which is not effective, and the reactor needs to be further enlarged, so that the amount of energy required for the next dehydration step is increased. The reaction pressure is 10 to 25 MPa, preferably 18 to 22 MPa. The reaction temperature is 190 to 400 ° C, preferably 250 to 350 ° C.
[0029]
  After the decomposition reaction, the effluent discharged from the reactor is decompressed, and water, carbon dioxide, and the like are removed (dehydration step) in a dehydration tower to obtain a polyurethane raw material composed of a mixture of polyol and amines. There are many varieties of rigid urethane foams, and they are manufactured from various isocyanates and various polyols. Therefore, the obtained effluent is usually a derivative of isocyanate, which is a raw material for the production of urethane foam that is subject to decomposition. A polyamine and a production raw material polyol are contained. Accordingly, if the polyamine and the polyol are separated by a known separation method before or after the dehydration process or simultaneously with the dehydration process, both can be recovered and the polyurethane raw material of the present invention can be obtained.
[0030]
  However, when diphenylmethane diisocyanate (MDI) is used as the isocyanate of the rigid urethane foam, it is difficult to separate the polyamine and the polyol obtained after the decomposition, and the cost increases when trying to separate them. Therefore, the effluent is used as it is as a starting material for the polyurethane raw material polyol without being separated into amines and polyols. In this case, it is much more economical than the case where polyamines and polyols which are difficult to separate are forcibly separated, and this is a preferred embodiment from the viewpoint of recycling. In addition, if the rigid urethane foam contains the rigid urethane foam foamed and produced from the diphenylmethane diisocyanate composition as an essential component, the above-described method for regenerating diphenylmethane diisocyanate can be used, and the tolylene diisocyanate composition can be used. A rigid urethane foam produced by foaming may be included as a raw material.
[0031]
  A polyurethane raw material polyol is produced by adding alkylene oxide to the above polyurethane raw material by a conventionally known method. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide, and these can be used alone or in an arbitrary mixing ratio. From the viewpoints of economy and the like, ethylene oxide and propylene oxide are preferably used. The number of added moles of alkylene oxide is not particularly limited, and is appropriately determined so as to have a hydroxyl value suitable for the production of rigid urethane foam. In particular, when using rigid urethane foam as a heat insulating material for a refrigerator, the polyol has a hydroxyl value of preferably 160 to 935 mgKOH / g, more preferably 200 to 600 mgKOH / g, and particularly preferably 350 to 500 mgKOH / g. is there. Generally, an alkylene oxide is added in a range of 1 to 100 moles with respect to 1 mole of a polyurethane raw material to produce a polyurethane raw material polyol.
[0032]
  In the production of the rigid urethane foam, a polyol composition containing the polyurethane raw material polyol as an essential component, an isocyanate, a foam stabilizer, a catalyst and a foaming agent are mixed and foamed by a conventionally known method. In addition, when the substance which can act as a foam stabilizer, a catalyst, or a foaming agent is contained in a polyol composition, these addition can also be abbreviate | omitted. Moreover, a conventionally well-known thing can be used for the said foam stabilizer, a catalyst, and a foaming agent, A reaction preparation agent etc. can also be added as needed.
[0033]
  Further, conventionally known isocyanates are used alone or in any combination. Examples of the isocyanate include tolylene diisocyanate (TDI), modified TDI, diphenylmethane diisocyanate (MDI), polymeric MDI, hydrogenated MDI, modified MDI, hexamethylene diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, p. -Phenylene diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI and the like. From the viewpoint of recycling cost and the like, MDI isocyanate is preferable.
[0034]
  In the polyol composition, the polyurethane raw material polyol of the present invention can be used alone, but other polyols can also be used in combination for facilitating the handling during the reaction and allowing the reaction to proceed smoothly. The combination ratio is arbitrary, but from the viewpoint of resource saving, the polyurethane raw material polyol should be used in an amount of 30% by mass or more, preferably 50% by mass or more of the entire polyol composition. A polyurethane raw material polyol and other polypolyols mixed in a range of 30/70 to 100/0 (mass ratio), preferably 50/50 to 98/2 (mass ratio) may be used.
[0035]
  Here, there is no limitation in particular as a polyol which can be used together, A conventionally well-known thing can be used in the range which does not inhibit the objective of this invention. For example, polyfunctional alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, glycerin, sorbitol, sucrose, bisphenol A, ethylenediamine, diethylenetriamine, piperazine, ethanolamine, Examples include compounds obtained by adding a predetermined amount of ethylene oxide, propylene oxide or styrene oxide to one or two or more compounds selected from polyfunctional amines such as propanolamine, and compounds in which the ends of these compounds are blocked. It is done. Moreover, said polyfunctional alcohol, polyfunctional amine, etc. can also be mixed at the time of rigid urethane foam manufacture.
[0036]
  The rigid urethane foam obtained by the production method of the present invention can be used for a wide range of uses such as refrigerators, various uses in which the rigid urethane foam is used, for example, furniture, cars, building materials, and shoe soles.
[0037]
  Next, an example of an embodiment of the present invention will be described in detail with reference to FIGS.
[0038]
  (Embodiment 1)
  FIG. 1 is a process diagram showing a method for producing a urethane production raw material in the first embodiment.
[0039]
  First, an outline of the waste processing procedure will be described. The transported refrigerator first passes through the crushing process 1 and proceeds to the sorting process 2. In the sorting process step 2, the waste crushed in the crushing step 1 is divided into a waste having a large specific gravity and a waste having a small specific gravity, and separated and recovered for each predetermined material. Here, the hard urethane foam and the foam gas contained in the refrigerator are recovered in the foam heat insulating material treatment step 3 in the sorting process of the waste having a small specific gravity. Next, the discharged rigid urethane foam proceeds to the re-raw material production process 4, where it is decomposed into polyols and amines.
[0040]
  Next, the processing procedure will be described in detail with reference to FIG. In FIG. 1, the refrigerator that has been transported to the waste disposal facility is put into the crushing process 1 at step 21. The refrigerator draws out the refrigerant in the refrigerator before charging the material. And after removing a refrigerator, the refrigerator with which material was thrown in is transferred to a pre-shredder with a conveyor (step 22).
[0041]
  The refrigerator crushed by the pre-shredder in the rough crushing in step 23 is put into a crusher. In step 24, the waste roughly crushed in the previous process is further finely crushed by a single-shaft car shredder having an output of about 1000 horsepower.
[0042]
  In the sorting process 2, in step 25, waste having a small specific gravity excluding heavy iron, non-ferrous metals and rubbers is separated by a vibrating conveyor disposed below the take-out portion of the car shredder. It is transferred by the conveyor.
[0043]
  The waste is separated into those containing ferrous metal and those not containing by the magnetic separator of step 27, the vibrating conveyor of step 28, and the magnetic separation drum of step 29.
[0044]
  In step 27A, the light dust that soars in steps 26 and 27 is collected and transferred to a dust collection process via a duct.
[0045]
  The waste separated in step 29 is transferred by a conveyor (step 30), and is sorted into iron and other motor scraps, cables, etc. by manual sorting on this conveyor (step 31). The iron selected by the manual selection in step 31 is transferred to a cart for accumulation and transportation by a conveyor (step 32), and wastes other than iron such as motor waste and cables are separated by manual selection.
[0046]
  The waste containing no ferrous metal separated in step 29 is sorted by non-ferrous metal (step 53) by hand sorting while being transported by a conveyor (step 52, step 54), and the remaining dust such as rubber. The waste containing is separated and accumulated.
[0047]
  As described above, the crushing process 1 is performed by each means and process from step 21 to step 24, and the sorting process 2 is performed by each means and process from step 25 to step 32, and from step 52 to step 54. It corresponds to each process.
[0048]
  Next, the rigid urethane foam separated in the crushing step is sucked into the cyclone in the foam heat insulating material processing step 3 through the duct (step 33). In this cyclone, a relatively large lump of rigid urethane foam is separated and collected (step 35). The foaming agent gas in the rigid urethane foam collides with the cyclone bag filter together with a small piece of the rigid urethane foam (step 36), and the blowing agent gas passes through to the recovery device and is recovered (step 37).
[0049]
  The rigid urethane foam blocks and small pieces separated by the cyclone (step 35) and the bag filter (step 36) are sent to the foam volume reducer (step 41). The foam volume reduction machine (Step 41) is composed of a press or screw type compressor, and hard urethane foam lumps and small pieces are ground and pulverized by the shearing force during compression to reduce the volume. The contained foaming agent gas (for example, chlorofluorocarbon) is removed and recovered. At the time of compression milling, the foaming agent gas (for example, Freon gas) dissolved in the rigid urethane foam can be vaporized and efficiently recovered by heating at 20 to 150 ° C., preferably 90 to 130 ° C. under normal pressure. it can.
[0050]
  As described above, the foam heat insulating material treatment process 3 corresponds to each means and process from Step 33 to Step 41, respectively.
[0051]
  Next, the lump of the hard urethane foam powder reduced in volume in the foam heat insulating material treatment step 3 is crushed into powder, and the crushed compressed urethane powder is sent to the reaction vessel. In the re-raw material process 4, the liquefied material is generated by mixing and heating with the compressed urethane powder and ethylene glycol (step 42, first reaction process in FIG. 4).
[0052]
  Thereafter, the impurity solid particles are removed by filter filtration (step 43, separation process of FIG. 4), introduced into the reactor together with high-temperature and high-pressure water, and kept in a supercritical or subcritical state for a predetermined time to cause a decomposition reaction. (Step 44, 2nd reaction process of FIG. 4). After the decomposition reaction, water, carbon dioxide and the like are removed from the effluent by a dehydration tower (step 45, dehydration step in FIG. 4), and then a polyurethane raw material (A) composed of a mixture of polyols and amines is obtained.
[0053]
  As above, the bookinventionThe polyurethane raw material (A) production method corresponds to each means and process from step 42 to step 45, respectively.
[0054]
  (Embodiment 2)
  The manufacturing method of the polyurethane raw material (A) and polyurethane raw material polyol (B) in Embodiment 2 is demonstrated using FIG. Note that a description of the same processing procedure as in the first embodiment will be omitted.
[0055]
  Waste such as a waste refrigerator containing rigid urethane foam produced by foaming a diphenylmethane diisocyanate composition as a raw material is first treated in the crushing step 1 and proceeds to the sorting step 2. In the sorting process step 2, the waste crushed in the crushing step 1 is divided into a waste having a large specific gravity and a waste having a small specific gravity, and separated and recovered for each predetermined material. Here, the hard urethane foam and the foamed gas (for example, chlorofluorocarbon) contained in the refrigerator are recovered in the foam insulation process step 3 in the sorting process of the waste having a small specific gravity.
[0056]
  Next, the discharged compressed urethane powder is mixed and heated with ethylene glycol to be liquefied in the re-raw material process 4, and then the impurity solid particles are removed by filter filtration and decomposed. Thereafter, water is removed by evaporation to decompose and produce polyols and amines (p-methylenedianiline and the like) as raw materials for the rigid urethane foam. After this, addition polymerization of ethylene oxide or propylene oxide to the decomposition product (Step 5)ShiA polyurethane raw material polyol (B) having a hydroxyl value of 450 mgKOH / g is produced.
[0057]
  (Embodiment 3)
  FIG. 2 is a diagram showing a manufacturing method of the refrigerator in Embodiment 3, and FIG. 3 is a diagram showing the refrigerator.
[0058]
  In FIG. 2, 7 is a heat insulation box, which is composed of an inner box 8 and an outer box 9, and injects a rigid urethane foam raw material into the space 10 to be formed and accommodates it in a jig to perform integral foaming. The jig temperature is set to 30 to 60 ° C. and the reaction is cured for 6 minutes.
[0059]
  As a polyurethane raw material, a premix prepared by mixing a polyol having a hydroxyl value of 450 mgKOH / g obtained in Embodiment 2 with a catalyst, a foam stabilizer, a foaming agent, and a reaction modifier is prepared in advance, and then c-diphenylmethane diisocyanate. Alternatively, mechanically mixed with p-diphenylmethane diisocyanate to produce rigid urethane foam 12 (step 6). Thereafter, it is released from the jig 11 and sent to the next assembly process, and a refrigerator 13 is obtained by incorporating refrigeration system parts (not shown) such as a compressor and a condenser, and plastic interior parts (not shown). .
[0060]
  In addition, FIG. 2 shows the state at the time of injecting rigid urethane foam into the box of the refrigerator, and in the refrigerator usage state, the right side of the drawing is the bottom surface of the refrigerator and the left side of the drawing is the top surface.
[0061]
  (Embodiment 4)
  The manufacturing method of the polyurethane raw material (A) and polyurethane raw material polyol (B) in Embodiment 4 is demonstrated using FIG. Note that description of the same processing procedure as in the first and second embodiments is omitted.
[0062]
  Waste such as a waste refrigerator including a hard urethane foam produced by foaming using a tolylene diisocyanate composition as a raw material is treated in the same steps as in the first embodiment to become a compressed urethane powder. This compressed urethane powder is mixed and heated with ethylene glycol to be liquefied in the re-raw material production process 4, and then the impurity solid particles are removed by filter filtration, and decomposed at a temperature of 260 ° C. and a pressure of 20 MPa to produce a polyol. And amines (p-tolylenediamine). Thereafter, the water is removed by evaporation.
[0063]
  Thereafter, the decomposition product, which is the residue after water removal, is fractionated (not shown), and tolylene diisocyanate is obtained from tolylenediamine, one of the components obtained by fractional distillation, using a conventionally known method. Is synthesized. Moreover, the polyol (hydroxyl value 450 mgKOH / g) which is the residue of a fractionation component is used as a manufacturing raw material of a polyurethane raw material polyol (B).
[0064]
  (Embodiment 5)
  The manufacturing method and refrigerator of the refrigerator in Embodiment 5 are demonstrated using FIG.2 and FIG.3. Note that a description of the same processing procedure as in the third embodiment will be omitted.
[0065]
  A rigid urethane foam raw material is injected into a space 10 formed from the inner box 8 and the outer box 9 to perform integral foaming. The reaction curing conditions at this time are 8 minutes at a jig temperature of 35 to 60 ° C., and then released from the jig 11 and sent to the next assembly step.
[0066]
  The polyurethane raw material is mechanically mixed with a premix in which the tolylene diisocyanate obtained in Embodiment 4 and the polyol, catalyst, foam stabilizer, foaming agent, and reaction modifier obtained as a fractional distillation residue are mixed to form a rigid urethane foam 12. Generate. After integral foaming, a refrigerator 13 is obtained by incorporating refrigeration system components (not shown) such as a compressor and a condenser, and plastic interior components (not shown).
[0067]
  (Embodiment 6)
  The manufacturing method of the polyurethane raw material (A) and polyurethane raw material polyol (B) in Embodiment 6 is demonstrated using FIG. Note that a description of the same processing procedure as in the first to third embodiments is omitted.
[0068]
  Waste such as a waste refrigerator including hard urethane foam produced by foaming from a diphenylmethane diisocyanate composition as a raw material is collected at a recovery site 14 and separated and recovered for each predetermined material to obtain compressed urethane powders 141 to 145. This compressed urethane powder is transported to the re-raw material factory and is supplied to the re-raw material process 4.
[0069]
  The compressed urethane powder is decomposed and produced into polyols and amines (p-methylenedianiline, etc.), which are raw materials of rigid urethane foam, in the re-raw material production process 4, and addition polymerization of ethylene oxide and propylene oxide into the decomposition products (Step 5). To produce a polyurethane raw material polyol (B) having a hydroxyl value of 450 mgKOH / g.
[0070]
  The polyurethane raw material polyol (B) is carried to the refrigerator manufacturer and foamed in the refrigerator manufacturers 61 to 64 (foaming step 6) to obtain the refrigerator.
【Example】
[0071]
  Next, the present invention will be specifically described with reference to examples. In the following examples and the like, “parts by mass” is abbreviated as “parts” unless otherwise specified.
[0072]
  Example 1
  Hard urethane foam produced by foaming using diphenylmethane diisocyanate composition as a raw material is crushed and pulverized to obtain a lump of rigid urethane foam from which foaming gas has been removed, and this is crushed to obtain a bulk density of 0.5 g / ml, average particle A compressed urethane powder having a diameter of 200 μm was obtained. To 100 parts of this powder, 200 parts of ethylene glycol was placed in a reactor and reacted at 160 ° C. under normal pressure. The produced liquefied product was filtered and then doubled (volume ratio) of high-temperature and high-pressure water was added to the liquefied product and decomposed at a temperature of 260 ° C. and a pressure of 20 MPa. Thereafter, water was removed by evaporation to obtain a polyurethane raw material comprising a mixture of a polyol and an amine (p-methylenedianiline or the like).
[0073]
  Thereafter, propylene oxide was addition-polymerized to the polyurethane raw material to produce a polyurethane raw material polyol having a hydroxyl value of 450 mgKOH / g.
[0074]
  30 parts of a polyurethane raw material polyol having a hydroxyl value of 450 mgKOH / g and 70 parts of a commercially available polyol for refrigerator are mixed, and 3 parts by mass of a catalyst (“Kaolyzer No. 1” manufactured by Kao Corporation) and a foam stabilizer ( A premix prepared by mixing 3 parts by mass of a silicone surfactant “F-317”, 20 parts by mass of a foaming agent (cyclopentane), and 0.5 parts by mass of formic acid as a reaction modifier in advance is manufactured by Shin-Etsu Chemical Co., Ltd. Prepared, and then mechanically mixed with crude diphenylmethane diisocyanate to produce rigid urethane foam, and after integrated foaming, refrigerators such as compressors and condensers and plastic interior parts were incorporated to produce a refrigerator.
[0075]
  (Example 2)
  Grinding and pulverizing a rigid urethane foam produced using the tolylene diisocyanate composition as a raw material to obtain a lump of rigid urethane foam from which the foaming gas has been removed, and crushing it to obtain a bulk density of 1.0 g / ml, average A rigid urethane foam powder having a particle size of 150 μm was obtained. To 100 parts of this powder, 200 parts of propylene glycol was placed in a reactor and reacted at 160 ° C. under normal pressure. The produced liquefied product was filtered and then doubled (volume ratio) of high-temperature and high-pressure water was added to the liquefied product and decomposed at a temperature of 260 ° C. and a pressure of 20 MPa. Thereafter, water was removed by evaporation to obtain a decomposition product composed of a mixture of a polyol and an amine (p-tolylenediamine). Thereafter, water was removed from the decomposition product. Thereafter, the decomposition product which is the residue after water removal was fractionated to obtain a polyurethane raw material mainly composed of polyol as the residue of the fractionation component.
[0076]
  Thereafter, propylene oxide was addition-polymerized to the polyurethane raw material to produce a polyurethane raw material polyol having a hydroxyl value of 450 mgKOH / g.
[0077]
  30 parts of a polyurethane raw material polyol having a hydroxyl value of 450 mgKOH / g and 70 parts of a commercially available polyol for refrigerator are mixed, and 3 parts by mass of a catalyst (“Kaolyzer No. 1” manufactured by Kao Corporation) and a foam stabilizer ( A premix prepared by mixing 3 parts by mass of a silicone surfactant “F-317”, 20 parts by mass of a foaming agent (cyclopentane), and 0.5 parts by mass of formic acid as a reaction modifier in advance is manufactured by Shin-Etsu Chemical Co., Ltd. Prepared, and then mechanically mixed with tolylene diisocyanate to produce a rigid urethane foam, and after integrated foaming, refrigeration system parts such as compressors and condensers, and plastic interior parts were incorporated to produce a refrigerator.
[0078]
【The invention's effect】
  As described above, the present invention uses hard urethane foam separated from the refrigerator, and uses compressed urethane powder that has been compressed as a reaction raw material to decompose urethane under specific conditions. That is, the polyurethane raw material can be produced industrially at low cost. In particular, by using compressed urethane powder, the urethane powder easily liquefies, so that impurities such as other polypropylene resins can be filtered with a filter, and a polyurethane raw material consisting of high-purity decomposition products can be obtained. It is done.
[0079]
  Moreover, according to the method of the present invention, it is possible to separate and collect iron plates and non-ferrous metals at the same time, which can contribute to the establishment of an overall system for recycling.
[0080]
  In addition, according to the present invention, a polyurethane raw material polyol which is a raw material for rigid urethane foam can be produced by addition polymerization of ethylene oxide or propylene oxide to the obtained polyurethane raw material, which is used as a heat insulating material for a refrigerator. The hard urethane foam can be used again as a heat insulating material. Furthermore, a compressed urethane powder is obtained again from a refrigerator manufactured using recycled raw materials, and a rigid urethane foam can be manufactured by the same manufacturing method.
[0081]
  Therefore, according to the present invention, it is possible to provide a global environment-friendly refrigerator that improves the material recycling rate of the used refrigerator and enables resource saving, and resources obtained from the refrigerator can be used for other purposes. It can be used. Therefore, its industrial value is great.
[Brief description of the drawings]
[0082]
FIG. 1 is a process diagram according to a first embodiment of the present invention.
FIG. 2 is a schematic view of a heat insulating box in a refrigerator manufacturing process according to Embodiment 3 of the present invention.
FIG. 3 is a schematic view of a refrigerator according to Embodiment 3 of the present invention.
FIG. 4 is a process diagram according to Embodiment 6 of the present invention.
[Explanation of symbols]
[0083]
1 Crushing process
2 sorting process
3 Foam insulation process
4 Re-raw material production process
5 Addition polymerization process
6 Foaming process
7 Insulated box
8 Inner box
9 Outer box
11 Jig
12 Hard urethane foam
13 Refrigerator
14 collection bases

Claims (7)

Waste refrigerator comprising rigid polyurethane foam obtained by foaming produce a diphenylmethane diisocyanate composition as a starting material, the crushing step for crushing after withdrawn freezer refrigerant, the rigid polyurethane foam separated by the crushing process at 90 to 130 ° C. While heating, it is ground and compressed to a bulk density of 0.1 to 1.2 g / ml and an average particle size of 1 μm to 3 mm to recover the blowing agent gas contained in the rigid urethane foam and compress it. Foam heat insulating material treatment step for obtaining urethane powder, and the compressed urethane powder obtained in the foam heat insulating material treatment step and glycols or amines having 2 to 4 carbon atoms are mixed and heated at 100 to 250 ° C. to be liquefied, After removing the impurity solid particles, the liquefied product and the high-temperature high-pressure water are supercritical or subcritical at 190 to 400 ° C. and 10 to 25 MPa. In After reacting, the production method of the polyurethane raw material; and a re-material reduction process dehydrated to obtain a polyurethane material. The mixing amount of glycols or amines having 2 to 4 carbon atoms, the production method of the polyurethane material according to the compressed urethane 0.4 to 5.0 times the powder according to claim 1 which is (weight ratio). The method for producing a polyurethane raw material according to claim 1 or 2 , wherein a ratio of the high-temperature high-pressure water is 0.4 to 5.0 times (volume ratio) with respect to the liquefied material. Polyurethane raw material manufactured by the manufacturing method according to any one of claims 1 to 3, the manufacturing method of the polyurethane raw polyol, wherein the addition polymerization of alkylene oxide. The method for producing a polyurethane raw material polyol according to claim 4 , wherein the polyol has a hydroxyl value of 160 to 935 mgKOH / g. A rigid urethane foam characterized by mixing and foaming a polyol composition comprising a polyurethane raw material polyol produced by the production method according to claim 4 or 5 as an essential component, an isocyanate, a foam stabilizer, a catalyst and a foaming agent. Manufacturing method. A polyol composition containing the polyurethane raw material polyol produced by the production method according to claim 4 or 5 as essential components, an isocyanate, a foam stabilizer, a catalyst and a foaming agent are mixed and injected between the inner box and the outer box of the refrigerator. And a method for producing a refrigerator, which is foam-cured.

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