METHOD FOR DECOMPOSING PLASTIC COMPOSITE
20210130569 · 2021-05-06
Assignee
Inventors
Cpc classification
B01J2523/00
PERFORMING OPERATIONS; TRANSPORTING
B01J2523/00
PERFORMING OPERATIONS; TRANSPORTING
Y02W30/62
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
B29B17/04
PERFORMING OPERATIONS; TRANSPORTING
B29K2105/06
PERFORMING OPERATIONS; TRANSPORTING
B01J21/063
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J21/06
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Provided is a method for decomposing a plastic composite with which it is possible to sufficiently decompose the matrix resins of the plastic composite in a short time even when the heating temperature of the plastic composite is low. In this method for decomposing a plastic composite, the plastic composite is brought into contact with an inorganic oxide catalyst having a band gap of 4 eV or less in a reactor, and the atmospheric temperature in the reactor is set at 380 to 530° C. in the presence of oxygen, and the surface temperature of the plastic composite is 480 to 650° C., which is at least 50° C. higher than the atmospheric temperature.
Claims
1. A method for decomposing a plastic composite, the method comprising: bringing the plastic composite into contact with an inorganic oxide catalyst having a band gap of 4 eV or less in a reactor; setting an atmospheric temperature in the reactor to 380 to 530° C. in the presence of oxygen; and setting a surface temperature of the plastic composite to 480 to 650° C., which is at least 50° C. higher than the atmospheric temperature, wherein the catalyst is a granular catalyst and brought into contact with the plastic composite so as to spread the granular catalyst over a front surface and a back surface of the plastic composite and cover all or some surfaces of layered surfaces of the plastic composite.
2. A method for decomposing a plastic composite, the method comprising: bringing the plastic composite into contact with an inorganic oxide catalyst having a band gap of 4 eV or less in a reactor; setting an atmospheric temperature in the reactor to 380 to 530° C. in the presence of oxygen; and setting a surface temperature of the plastic composite to 480 to 650° C., which is at least 50° C. higher than the atmospheric temperature, wherein the catalyst is a honeycomb type catalyst and brought into contact with the plastic composite such that all four surfaces, which are layered surfaces of the plastic composite, are surrounded by the honeycomb type catalyst.
3. The method for decomposing a plastic composite according to claim 1, wherein the atmospheric temperature in the reactor is 380 to 450° C.
4. The method for decomposing a plastic composite according to claim 1, wherein the inorganic oxide having a band gap of 4 eV or less is one kind or a combination of two or more kinds selected from the group consisting of titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, and copper oxide.
5. The method for decomposing a plastic composite according to claim 1, wherein the plastic composite and the catalyst are loaded on a portion of a stainless steel mesh plate in the reactor, and oxygen is supplied from below the mesh plate.
6. The method for decomposing a plastic composite according to claim 2, wherein the atmospheric temperature in the reactor is 380 to 450° C.
7. The method for decomposing a plastic composite according to claim 2, wherein the inorganic oxide having a band gap of 4 eV or less is one kind or a combination of two or more kinds selected from the group consisting of titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, and copper oxide.
8. The method for decomposing a plastic composite according to claim 3, wherein the inorganic oxide having a band gap of 4 eV or less is one kind or a combination of two or more kinds selected from the group consisting of titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, and copper oxide.
9. The method for decomposing a plastic composite according to claim 6, wherein the inorganic oxide having a band gap of 4 eV or less is one kind or a combination of two or more kinds selected from the group consisting of titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, and copper oxide.
10. The method for decomposing a plastic composite according to claim 2, wherein the plastic composite and the catalyst are loaded on a portion of a stainless steel mesh plate in the reactor, and oxygen is supplied from below the mesh plate.
11. The method for decomposing a plastic composite according to claim 3, wherein the plastic composite and the catalyst are loaded on a portion of a stainless steel mesh plate in the reactor, and oxygen is supplied from below the mesh plate.
12. The method for decomposing a plastic composite according to claim 4, wherein the plastic composite and the catalyst are loaded on a portion of a stainless steel mesh plate in the reactor, and oxygen is supplied from below the mesh plate.
13. The method for decomposing a plastic composite according to claim 6, wherein the plastic composite and the catalyst are loaded on a portion of a stainless steel mesh plate in the reactor, and oxygen is supplied from below the mesh plate.
14. The method for decomposing a plastic composite according to claim 7, wherein the plastic composite and the catalyst are loaded on a portion of a stainless steel mesh plate in the reactor, and oxygen is supplied from below the mesh plate.
15. The method for decomposing a plastic composite according to claim 8, wherein the plastic composite and the catalyst are loaded on a portion of a stainless steel mesh plate in the reactor, and oxygen is supplied from below the mesh plate.
16. The method for decomposing a plastic composite according to claim 9, wherein the plastic composite and the catalyst are loaded on a portion of a stainless steel mesh plate in the reactor, and oxygen is supplied from below the mesh plate.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
[0026] Hereinafter, embodiments of a method for decomposing a plastic composite according to at least one embodiment of the present disclosure will be described with reference to the accompanying drawings.
[0027] In the method for decomposing a plastic composite of the present embodiment, the plastic composite is brought into contact with an inorganic oxide catalyst having a band gap of 4 eV or less in a reactor, and the atmospheric temperature in the reactor is heated to a predetermined setting temperature in the presence of oxygen, so that the surface temperature of the plastic composite is made higher than the atmospheric temperature.
[0028] The plastic composite to be processed is not particularly limited as long as a composite material of a reinforcing fiber and a matrix resin is provided. However, the reinforcing fiber may be carbon fiber or glass fiber, and the matrix resin may be a thermosetting plastic or a thermoplastic. Examples of the thermosetting plastic include phenol resin, urethane foam, polyurethane, urea resin, epoxy resin, unsaturated polyester resin, melamine resin, and alkyd resin. Examples of the thermoplastic resin include polycarbonate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, ABS resin, polyamide, polyimide, methacrylic resin, polyvinyl alcohol, polyacetal, petroleum resin, vinylidene chloride resin, polybutylene terephthalate, polybutene, fluororesin, polyacrylate, and the like.
[0029] Examples of the inorganic oxide having a band gap of eV or less used as the catalyst include respective oxides such as copper (Cu), titanium (Ti), vanadium (V), tungsten (W), molybdenum (Mo), and chromium (Cr). These inorganic oxides may be used alone or in combination of plural of kinds. For example, a catalyst that is currently used as a denitration catalyst, in which a vanadium oxide and a tungsten or molybdenum oxide are added to titanium oxide, can be used. The band gap of the catalyst is preferably 3 eV or less and more preferably 2 eV or less.
[0030] Although the shape of the catalyst may be a honeycomb type, a plate shape, or a granular shape, it is preferable to use a granular catalyst, particularly, in order to make the surface temperature of the plastic composite higher than the atmospheric temperature of the reactor. The lower limit of the diameter of the granular shape is preferably 1 mm or more, more preferably 1.5 mm or more, still more preferably 2 mm or more, in order to facilitate separation from the decomposition product of the plastic composite. The upper limit of the diameter of the granular shape is preferably 10 mm or less, more preferably 5 mm or less, still more preferably 4 mm or less in order to increase the number of contact points between the plastic composite and the granular catalyst and promote the reaction uniformly. Although a granular catalyst having a diameter within such a range is commercially available, the granular catalyst can be obtained, for example, by pressure-forming a commercially available inorganic oxide and then crushing the pressure-formed inorganic oxide to rectify the crushed inorganic oxide with a filter or the like so as to be within a predetermined diameter range.
[0031] As the honeycomb type catalyst, the lower limit of one side of each cell is preferably 2.8 mm or more, more preferably 3.5 mm or more, and still more preferably 5.65 mm or more in order to increase the number of contact points between the plastic composite and the honeycomb type catalyst and uniformly promote the reaction. The upper limit of one side of each cell is preferably 9 mm or less, more preferably 6.4 mm or less, and still more preferably 6.25 mm or less in order to increase the number of contact points and uniformly promote the reaction. As the plate-like catalyst, the lower limit of the thickness is preferably 0.3 mm or more, more preferably 0.6 mm or more, and still more preferably 0.7 mm or more in order to sufficiently promote the reaction with the plastic composite. The upper limit of the thickness of the plate-like catalyst is preferably 1 mm or less, more preferably 0.9 mm or less, and still more preferably 0.8 mm or less because if the catalyst is too thick, the catalyst that does not participate in the reaction is generated.
[0032] As the disposition of the catalyst with respect to the plastic composite, first, in order to sufficiently exhibit the effect of the catalyst, it is preferable to dispose the catalyst that the contact percentage of the catalyst with respect to an outer surface area of the plastic composite is 20% or more. Additionally, the plastic composite has a laminated structure manufactured by laminating a plurality of prepregs in which the reinforcing fiber is impregnated with the matrix resin and curing the prepregs under pressure heating conditions. In order to make the surface temperature of the plastic composite higher than the atmospheric temperature of the reactor, it is preferable to dispose the catalyst, particularly, on a surface where the laminated structure of the plastic composite is visible in a cross-section (referred to as “layered surface” in the present specification).
[0033] For example,
[0034] Additionally, for example,
[0035] Moreover, for example, as illustrated in
[0036] Then, as illustrated in
[0037] As illustrated in
[0038] The atmospheric temperature in the reactor 41 is set to 380 to 530° C. By using the inorganic oxide having a band gap of 4 eV or less as the catalyst, even when the inside of the reactor 41 is set to such a low atmospheric temperature, hydrocarbon and carbon monoxide in a gas generated by the decomposition of the matrix resin of the plastic composite can be oxidized by the catalyst of the inorganic oxide, and the surface temperature of the plastic composite can be significantly raised compared with the atmospheric temperature due to the combustion heat generated by the oxidization.
[0039] When the atmospheric temperature is lower than 380° C., the decomposition of the matrix resin does not proceed, and even when the inorganic oxide having a band gap of 4 eV or less is used as the catalyst, the surface temperature of the plastic composite cannot be raised to a sufficient temperature. On the other hand, when the atmospheric temperature exceeds 530° C., and in a case where the inorganic oxide having a band gap of 4 eV or less is used as the catalyst, the surface temperature of the plastic composite rises too much and the reinforcing fiber of the plastic composite is also decomposed or deteriorated, which makes recycling difficult. The atmospheric temperature in the reactor 41 is preferably 380 to 450° C. and more preferably 390 to 420° C.
[0040] The surface temperature of the plastic composite is 480 to 650° C. In order to sufficiently decompose the matrix resin of the plastic composite, 480° C. or higher is required, 490° C. or higher is preferable, and 500° C. or higher is more preferable. The surface temperature of the plastic composite is preferably at least 50° C. or higher, more preferably at least 80° C. or higher, and still more preferably at least 100° C. or higher higher than the atmospheric temperature. In this way, by setting a difference between the atmospheric temperature in the reactor 41 and the surface temperature of the plastic composite to 50° C. or higher, a large amount of energy required to raise the atmospheric temperature by 50° C. or higher can be saved by utilizing the combustion heat generated by the oxidation of hydrocarbon and carbon monoxide by-produced by the decomposition of the plastic composite, and the plastic composite can be efficiently processed. The greater the temperature difference, the higher energy efficiency. In addition, the upper limit of this temperature difference is not particularly limited, but is preferably 270° C. or lower, for example. Such adjustment of the atmospheric temperature and the surface temperature of the plastic composite can be performed by the type and shape of the catalyst and the disposition of bringing the catalyst into contact with the plastic composite. For example, by using the inorganic oxide having a lower band gap value, using the granular shape or in a combination of the granular shape and a honeycomb shape as the shape of the catalyst, or adopting a disposition in which the layered surfaces of the plastic composite are brought into contact with the catalyst, the surface temperature of the plastic composite can be made higher than the atmospheric temperature by 100° C. or higher.
EXAMPLES
Example 1: Effect of Catalyst
[0041] Tests were performed to decompose the plastic composite using various catalysts. As the plastic composite, a carbon fiber reinforced resin having a size of width 30 mm×length 200 mm×height 12 mm and epoxy resin as the matrix resin was used. As the catalyst, no catalyst used in Test Example 1, and a honeycomb type denitration catalyst (a ternary catalyst of TiO.sub.2/V.sub.2O.sub.5/WO.sub.3 or MoO.sub.3) with a cell size of 6.4 mm×6.4 mm×10 mm) was used in Test Example 2. In Test Example 3, a TiO.sub.2 granular catalyst (CS-200S-24 manufactured by SAKAI CHEMICAL CO., LTD., diameter: 2 to 4 mm) was used as it was. In Test Example 4, CuO (special grade reagent manufactured by KANTO CHEMICAL CO., INC.) was pressure-formed, crushed, rectified into granular shapes having a diameter of 2 to 4 mm, and then used.
[0042] In a case where the honeycomb type denitration catalyst was used, as illustrated in
[0043] The test conditions were as follows: dry air (moisture: 1.38 vol %) was heated such that the atmospheric temperature in the reactor was 400° C. or 500° C. while the dry air flows in an upward direction from below the mesh plate at a gas flow rate of 6.7 NL/min and a gas flow velocity of 0.76 Nm/s and was maintained for 2.5 hours after reaching the setting temperature. Then, in addition to the atmospheric temperature (reactor temperature) in the reactor during the test, the temperature of the front surface of the plastic composite (sample surface temperature), the temperature of the catalyst 10 mm below the back surface of the plastic composite (the temperature 10 mm below the sample) was measured, and the respective concentrations of CO, CO.sub.2, and THC contained in the gas in the reactor were measured. Additionally, the weight of the plastic composite after the test was measured, the weight decrease rate of the plastic composite before and after the test was calculated, and whether or not the matrix resin remained in the residual after the test was visually confirmed. The results are shown in Table 1 and
TABLE-US-00001 TABLE 1 Weight Residual Decrease Presence/Absence Catalyst Rate (%) of Matrix Resin Test Example 1 None 35.2 Yes Test Example 2 Honeycomb type 36.1 None denitration catalyst Test Example 3 TiO.sub.2 granular 37.6 None catalyst Test Example 4 CuO granular 38.6 None catalyst
[0044] In Test Example 1 in which the setting temperature was 500° C. without a catalyst, as illustrated in
[0045] In Test Example 2 in which the setting temperature was 500° C. using the honeycomb type denitration catalyst, from when the temperature 10 mm below the sample reached 400° C. after the start of the heating, the respective concentrations of THC, CO, and CO.sub.2 increased sharply. At the same time, the sample surface temperature also rose sharply. Although this is a conjecture, it is considered that the temperature of the plastic composite rose above the setting temperature and the decomposition of the plastic composite proceeded due to the heat storage effect of a catalyst molded body. No matrix resin remained in the residual, and the weight decrease rate of the plastic composite was as excellent as 36.1%.
[0046] In Test Example 3 in which the setting temperature was 500° C. using the TiO.sub.2 granular catalyst, from when the temperature 10 mm below the sample reached 400° C. after the start of the heating, the respective concentrations of THC, CO, and CO.sub.2 increased and simultaneously the sample surface temperature also rose largely. Similarly to Test Example 2, it is considered that the decomposition of the plastic composite proceeded due to the heat storage effect of the catalyst. No matrix resin remained in the residual, and the weight decrease rate of the plastic composite was 37.6%, which was excellent.
[0047] In Test Example 4 in which the setting temperature was 400° C. using a CuO granular catalyst, when the temperature 10 mm below the sample reached 400° C. after the start of heating, the increase in the THC and CO concentrations was extremely small, while the CO.sub.2 concentration increased sharply. It is considered that this is because the CuO granular catalyst oxidized the generated THC and CO. Also, it is considered that, since the combustion heat of THC and CO was generated in a large amount, the setting temperature was 400° C., but the sample surface temperature rose to a maximum of 550° C., and the sample surface temperature was maintained at 500° C. or higher for more than 2 hours. In Test Example 4, the setting temperature was the lowest at 400° C., but no matrix resin remained in the residual, and the weight decrease rate of the plastic composite was the best at 38.6%.
[0048] Additionally, it is considered from the results of Test Examples 1 to 4 that the catalysts such as CuO and TiO.sub.2 have the ability to decompose carbon monoxide and hydrocarbon and has a role of preventing the heat generated by the decomposition of the plastic composite from being deprived of by the atmospheric gas.
Example 2: Relationship Between Band Gap and Performance of Catalyst at Setting Temperature of 400° C.
[0049] 5 g of respective granular catalysts (diameter of 2 to 4 mm) having Cr.sub.2O.sub.3, CuO, amorphous α-Al.sub.2O.sub.3 (alpha type alumina), V.sub.2O.sub.5, and TiO.sub.2 (anatase type) having different band gaps were placed on the front surface of 2 g of the plastic composite that is the same material as in Example 1, and tests were performed in the atmosphere with the setting temperatures of 400° C. and the holding time of 1.5 hours. Additionally, as a comparative example, a test was performed under the same conditions even in a case where the catalyst was not placed. The results are shown in
[0050] As illustrated in
Example 3: Performance of Denitration Catalyst at Setting Temperature of 400° C.
[0051] Regarding the honeycomb type denitration catalyst of Test Example 2 of Example 1 that is a TiO.sub.2-based catalyst, a test was performed under the same conditions as in Example 1 except that the setting temperature of the reactor was set to 400° C., gas (O.sub.2: 21 vol %, H.sub.2O: 1.38 vol %, N.sub.2: the balance) was caused to flow at a flow rate of 1 NL/min, the holding time was set to 4.5 hours, and the weight of the plastic composite during the test was continuously measured. In addition, as a comparative example, a test was performed under the same conditions even in a case where no catalyst was placed. The results are shown in
[0052] As illustrated in
Example 4: Disposition of Catalyst
[0053] In a case where the plastic composite of the same material as in Example 1 was sized to have a width of 30 mm, a length of 30 mm, and a height of 12 mm, and the honeycomb type denitration catalyst of Test Example 2 of Example 1 was disposed only on the front surface, in a case where the plastic composites were disposed on both the front surface and the back surface, and in a case where the plastic composites were disposed on the four side surfaces that are the layered surfaces, a test was performed with the setting temperature as 500° C. under the same conditions as in Example 1 except that a gas (O.sub.2: 21 vol %, H.sub.2O: 1.38 vol %, and N.sub.2: balance) was caused to flow at a flow rate of 1 NL/min. Additionally, as a comparative example, a test was performed under the same conditions even in a case where no catalyst was used. The results are shown in
[0054] As illustrated in
REFERENCE SIGNS LIST
[0055] 10: plastic composite [0056] 11: front surface [0057] 12: layered surface [0058] 13: back surface [0059] 20: catalyst [0060] 21: cell of honeycomb type catalyst [0061] 22: granular catalyst [0062] 23: overhanging portion [0063] 30: object to be processed in which catalyst is brought into contact with plastic composite [0064] 41: reactor [0065] 42: transportation means [0066] 43: mesh plate [0067] 44: recovery means