Method for producing BTX composition and BTX composition

Abstract

To provide a method of producing a BTX composition with an enhanced BTX content in the BTX composition.SOLUTION: A method for producing a BTX composition comprises a step A of heating a mixture containing a cured product of a thermosetting resin composition and a zeolite to decompose the cured product of the thermosetting resin composition, wherein the zeolite includes an ion-exchanged zeolite.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a BTX composition and a BTX composition.

Background Art

[0002] Consideration has been made to produce various components by pyrolyzing resins.

[0003] Patent Document 1 discloses a method for producing benzene, which includes a step of obtaining a reaction product containing benzene by contacting a polyphenylene sulfide resin with a zeolite catalyst and subjecting the polyphenylene sulfide resin to pyrolysis and desulfurization reactions, wherein the zeolite catalyst is a proton-exchanged zeolite and the molar ratio of SiO2 to Al2O3 (SiO2 / Al2O3 ratio) is 5 to 100. Further, Patent Document 1 describes that "a method for producing benzene that can obtain benzene, which is a low-molecular hydrocarbon, in a high yield by pyrolysis and desulfurization reactions from PPS (polyphenylene sulfide)" is provided.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Regarding the production of various components by pyrolyzing resins, when producing a BTX composition by pyrolyzing a resin, there is room for improvement in increasing the total content of benzene, toluene, and xylene in the BTX composition. The present invention provides a method for producing a BTX composition with an improved total content of benzene, toluene, and xylene in the BTX composition. The present invention also provides a BTX composition obtained by the method for producing the BTX composition described above.

Means for Solving the Problems

[0006] According to the present invention, there are provided a method for producing a BTX composition and a BTX composition as shown below.

[0007] 1. A method for producing a BTX composition, comprising step A of decomposing a cured product of a thermosetting resin composition by heat-treating a mixture containing the cured product of the thermosetting resin composition and zeolite, wherein the zeolite contains ion-exchanged zeolite. 2. The method for producing a BTX composition according to 1., wherein the ion-exchanged zeolite contains one or more selected from the group consisting of beta-type zeolite, ZSM-5 type zeolite, mordenite type zeolite, and Y type zeolite. 3. The method for producing a BTX composition according to 1. or 2., wherein the cation of the ion-exchanged zeolite contains one or two selected from the group consisting of hydrogen ion and ammonium ion. 4. The specific surface area of the zeolite measured by the BET method is 50 m 2 / g or more and 1000 m 2 / g or less. The method for producing a BTX composition according to any one of 1. to 3. 5. The method for producing a BTX composition according to any one of 1. to 4., wherein the pore diameter of the zeolite is 0.1 Å or more and 40 Å or less. 6. The method for producing a BTX composition according to any one of 1. to 5., wherein the molar number of SiO2 with respect to 1 mol of Al2O3 in the zeolite is 5 mol or more and 200 mol or less. 7. The method for producing a BTX composition according to any one of 1. to 6., wherein the cured product of the thermosetting resin composition contains a cured product of a phenol resin composition. 8. The method for producing a BTX composition according to any one of 1. to 7., wherein the average particle diameter of the cured product of the thermosetting resin composition is 10 μm or more and 10 mm or less. 9. The method for producing a BTX composition according to any one of 1. to 8., wherein the heating temperature in the step A is 300 °C or more and 1200 °C or less. 10. A BTX composition obtained by the method for producing a BTX composition according to any one of 1. to 9. 11. The BTX composition according to 10., wherein the total content of benzene, toluene and xylene in the BTX composition is 3% by mass or more. [Advantages of the Invention]

[0008] According to the present invention, a method for producing a BTX composition with an improved BTX content in the BTX composition can be provided. [Modes for Carrying Out the Invention]

[0009] Hereinafter, the present invention will be described based on embodiments.

[0010] [Method for Producing BTX Composition] Hereinafter, the method for producing the BTX composition of the present embodiment will be described.

[0011] The method for producing a BTX composition of the present embodiment includes a step A of decomposing a cured product of a thermosetting resin composition by heat-treating a mixture containing the cured product of the thermosetting resin composition and zeolite, and the zeolite contains ion-exchanged zeolite.

[0012] The BTX composition in the present embodiment is a composition containing BTX. The BTX in the present embodiment is one or more selected from the group consisting of benzene, toluene and xylene.

[0013] The zeolite in the present embodiment is a general term for crystalline aluminosilicates. Further, the ion-exchanged zeolite in the present embodiment is one containing a cation capable of ion exchange in the structure of the zeolite.

[0014] Although the mechanism by which the BTX content in the BTX composition is improved by the manufacturing method of the BTX composition of the present embodiment is not clear, it is presumed that the ion-exchanged zeolite functions as a solid acid catalyst, so that the reaction transition state becomes a state suitable for the production of BTX, and thereby the BTX content in the BTX composition is improved.

[0015] From the viewpoint of further improving the BTX content in the BTX composition, the ion-exchanged zeolite of the present embodiment preferably contains one or more selected from the group consisting of beta-type zeolite, ZSM-5 type zeolite, ferrierite type zeolite, mordenite type zeolite, L-type zeolite and Y-type zeolite, more preferably contains one or more selected from the group consisting of beta-type zeolite, ZSM-5 type zeolite, ferrierite type zeolite, mordenite type zeolite and Y-type zeolite, and still more preferably contains one or more selected from the group consisting of beta-type zeolite, ZSM-5 type zeolite, mordenite type zeolite and Y-type zeolite.

[0016] Examples of commercially available products of the ion-exchanged zeolite of the present embodiment include the HSZ (registered trademark) series manufactured by Tosoh Corporation. The HSZ series includes, for example, the HSZ-900 series which is a beta-type zeolite, the HSZ-800 series which is a ZSM-5 type zeolite, the HSZ-700 series which is a ferrierite type zeolite, the HSZ-600 series which is a mordenite type zeolite, the HSZ-500 series which is an L-type zeolite, and the HSZ-300 series which is a Y-type zeolite.

[0017] From the viewpoint of further improving the BTX content in the BTX composition, the cation of the ion-exchanged zeolite of the present embodiment preferably contains one or two selected from the group consisting of hydrogen ions and ammonium ions, and more preferably contains ammonium ions.

[0018] From the perspective of further improving the BTX content in the BTX composition, the specific surface area of the zeolite of the present embodiment measured by the BET method is preferably 50 m 2 / g or more, more preferably 100 m 2 / g or more, still more preferably 150 m 2 / g or more, still more preferably 200 m 2 / g or more, still more preferably 250 m 2 / g or more, and preferably 1000 m 2 / g or less, more preferably 900 m 2 / g or less, still more preferably 800 m 2 / g or less, still more preferably 700 m 2 / g or less, still more preferably 680 m 2 / g or less, and preferably 50 m 2 / g or more and 1000 m 2 / g or less, more preferably 100 m 2 / g or more and 900 m 2 / g or less, still more preferably 150 m 2 / g or more and 800 m 2 / g or less, still more preferably 200 m 2 / g or more and 700 m 2 / g or less, still more preferably 250 m 2 / g or more and 680 m 2 / g or less.

[0019] From the perspective of further improving the BTX content in the BTX composition, the pore diameter of the zeolite of the present embodiment is preferably 0.1 Å or more, more preferably 0.5 Å or more, still more preferably 1 Å or more, still more preferably 2 Å or more, still more preferably 4 Å or more, and preferably 40 Å or less, more preferably 25 Å or less, still more preferably 15 Å or less, still more preferably 12 Å or less, still more preferably 10 Å or less, and preferably 0.1 Å or more and 40 Å or less, more preferably 0.5 Å or more and 25 Å or less, still more preferably 1 Å or more and 15 Å or less, still more preferably 2 Å or more and 12 Å or less, still more preferably 4 Å or more and 10 Å or less.

[0020] In the zeolite of the present embodiment, the molar number of SiO2 with respect to 1 mol of Al2O3 is preferably 5 mol or more, more preferably 6 mol or more, from the viewpoint of further improving the BTX content in the BTX composition, and is preferably 500 mol or less, more preferably 200 mol or less, still more preferably 100 mol or less, still more preferably 70 mol or less, still more preferably 40 mol or less, still more preferably 20 mol or less. The molar number of SiO2 with respect to 1 mol of Al2O3 can be measured by, for example, fluorescent X-ray analysis (XRF).

[0021] The shape of the zeolite of the present embodiment is not particularly limited, and may be, for example, powder, pellet, or bead.

[0022] When the shape of the zeolite of the present embodiment is powder or bead, the average particle diameter of the zeolite of the present embodiment is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, still more preferably 2 μm or more, from the viewpoint of further improving the BTX content in the BTX composition, and is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, still more preferably 20 μm or less. The average particle diameter of the zeolite of the present embodiment is the value of the cumulative particle diameter 50% (D 50 ) by the laser diffraction / scattering particle size distribution measurement method.

[0023] In the method for producing the BTX composition of the present embodiment, the cured product of the thermosetting resin composition of the present embodiment preferably contains the cured product of the phenol resin composition from the viewpoint of further improving the BTX content in the BTX composition.

[0024] The phenol resin contained in the phenol resin composition of the present embodiment is not particularly limited, and may contain a novolac type phenol resin, a resol type phenol resin, or a mixture of a novolac type phenol resin and a resol type phenol resin. For example, it may contain Sumitomo Bakelite Co., Ltd.'s Sumilite Resin (registered trademark) PR-217, PR-311, PR-50590B, PR-961A, PR-9480, PR-51283.

[0025] The thermosetting resin composition of this embodiment may contain a thermosetting resin other than a phenol resin. For example, it may contain one or two selected from the group consisting of an epoxy resin, a melamine resin, and a urea resin.

[0026] The thermosetting resin composition of this embodiment may contain, for example, an uncured or semi-cured resin.

[0027] The cured product of the thermosetting resin composition of this embodiment is not a concept that only includes the cured product of the thermosetting resin composition alone. For example, a molding material or a molded product containing an inorganic filler such as silica fine particles and glass fibers, or an organic filler such as wood powder; a laminate containing an inorganic substrate such as a glass woven fabric and a glass non-woven fabric, or an organic substrate such as paper and cloth; a metal-clad laminate obtained by laminating a metal foil such as a copper foil on the laminate; and one or two selected from the group consisting of a printed circuit board obtained by processing a metal-clad laminate and the like may be included.

[0028] From the viewpoint of improving the efficiency of the decomposition reaction, the cured product of the thermosetting resin composition of this embodiment is preferably made into particles by a treatment such as pulverization.

[0029] From the viewpoint of reducing the labor required for pulverization, the average particle size of the cured product of the thermosetting resin composition of this embodiment is preferably 10 μm or more, and from the viewpoint of further improving the content of BTX in the BTX composition, it is preferably 10 mm or less. The average particle size of the cured product of the thermosetting resin composition of this embodiment is the value of the cumulative particle size 50% (D 50 ) measured by the laser diffraction / scattering particle size distribution measurement method.

[0030] In step A of the method for producing the BTX composition of the present embodiment, the heating temperature is preferably 300°C or higher, more preferably 400°C or higher, still more preferably 500°C or higher, and still more preferably 550°C or higher, from the viewpoint of further improving the BTX content in the BTX composition. And it is preferably 1200°C or lower, more preferably 1000°C or lower, still more preferably 800°C or lower, and still more preferably 700°C or lower. And it is preferably 300°C or higher and 1200°C or lower, more preferably 400°C or higher and 1000°C or lower, still more preferably 500°C or higher and 800°C or lower, and still more preferably 550°C or higher and 700°C or lower.

[0031] When mixing the zeolite and the cured product of the thermosetting resin composition, the mass of the zeolite of the present embodiment per 1 g of the cured product of the thermosetting resin composition of the present embodiment in the mixture is preferably 1 g or more, more preferably 5 g or more, and still more preferably 8 g or more, from the viewpoint of further improving the BTX content in the BTX composition. And from the viewpoint of the balance between reducing the amount of zeolite used and the amount of BTX generated, it is preferably 50 g or less, more preferably 30 g or less, and still more preferably 20 g or less.

[0032] When mixing the zeolite and the cured product of the thermosetting resin composition, the mixture may contain components other than the cured product of the thermosetting resin composition and the zeolite, for example, it may contain BTX.

[0033] The method for producing the BTX composition of the present embodiment may include steps other than step A, for example, it may include a step of purifying the BTX composition.

[0034] [BTX composition] Hereinafter, the BTX composition of the present embodiment will be described.

[0035] The BTX composition of the present embodiment is obtained by the method for producing the BTX composition of the present embodiment.

[0036] The total content of benzene, toluene, and xylene in the BTX composition of this embodiment is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, and, for example, 99% by mass or less.

[0037] As described above, embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the range that can achieve the object of the present invention are included in the present invention.

Examples

[0038] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the examples.

[0039] (Examples 1 to 9, Comparative Example 2) A pyrolysis test was conducted using an apparatus in which a gas chromatography-mass spectrometer (manufactured by Agilent Technologies, gas chromatography model name: 7890B, mass spectrometer model name: 5977B) was connected to a pyrolysis apparatus (manufactured by FRONTIER LAB, model name: EGA / PY-3030D). The samples for the pyrolysis test were prepared by the following procedure. PR-217 manufactured by Sumitomo Bakelite Co., Ltd. was cured under the conditions of 200°C for 1 hour to obtain a cured product. The obtained cured product was pulverized and used as a sample. A mixture of 0.2 mg of the obtained sample and 2.0 mg of the zeolite described in Table 1 was set in the above pyrolysis apparatus, heated from 80°C to 600°C at a heating rate of 50°C / min, maintained at 600°C for 2 minutes, and the identification and quantification of BTX contained in the pyrolysis products generated by pyrolysis were performed using the above gas chromatography-mass spectrometer. In this example, the total amount of the contents of benzene, toluene, and xylene was taken as the content of BTX. All the zeolites described in Table 1 are of the HSZ (registered trademark) series manufactured by Tosoh Corporation.

[0040] (Comparative Example 1) A thermal decomposition test was conducted in the same manner as in Examples 1 to 9 and Comparative Example 2, except that no zeolite was used. The results are shown in Table 1.

[0041] [Table 1]

[0042] According to the production method of the examples, a BTX composition (a composition containing BTX) could be produced. Also, according to the production method of the examples, the content of BTX in the BTX composition was improved compared to the comparative examples. From this, it can be seen that according to the production method of this embodiment, the content of BTX in the BTX composition can be improved.

Claims

1. A method for producing a BTX composition, comprising a step A of decomposing a cured product of the thermosetting resin composition by heat-treating a mixture containing the cured product of the thermosetting resin composition and zeolite, wherein the zeolite contains ion-exchanged zeolite.

2. The method for producing a BTX composition according to claim 1, wherein the ion-exchanged zeolite contains one or more selected from the group consisting of beta-type zeolite, ZSM-5 type zeolite, mordenite type zeolite, and Y-type zeolite.

3. The method for producing a BTX composition according to claim 1 or 2, wherein the cation of the ion-exchanged zeolite contains one or two selected from the group consisting of hydrogen ion and ammonium ion.

4. The specific surface area of the zeolite measured by the BET method is 50 m ２ / g or more and 1000 m ２ / g or less, and the method for producing a BTX composition according to claim 1 or 2.

5. The method for producing a BTX composition according to claim 1 or 2, wherein the pore diameter of the zeolite is 0.1 Å or more and 40 Å or less.

6. In the zeolite, the number of moles of SiO₂ per mole of Al ２ O ３ is 5 moles or more and 200 moles or less, and the method for producing a BTX composition according to claim 1 or 2. ２ ​

7. The method for producing a BTX composition according to claim 1 or 2, wherein the cured product of the thermosetting resin composition contains a cured product of a phenol resin composition.

8. The method for producing a BTX composition according to claim 1 or 2, wherein the average particle diameter of the cured product of the thermosetting resin composition is 10 μm or more and 10 mm or less.

9. The method for producing a BTX composition according to claim 1 or 2, wherein the heating temperature in the step A is 300 °C or more and 1200 °C or less.

10. A BTX composition obtained by the method for producing a BTX composition according to claim 1 or 2.

11. The BTX composition according to claim 10, wherein the total content of benzene, toluene, and xylene in the BTX composition is 3% by mass or more.

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