2,5-dimethylfuran production method, p-xylene production method, terephthalic acid production method, and polyester production method, and p-xylene, terephthalic acid, polyester composition, fiber material, resin material, film material, fiber product, resin product, and film product

Abstract

A method for producing 2,5-dimethylfuran according to an embodiment of the present application includes a step of reacting a furan compound having a specific structure with hydrogen in a non-aqueous solvent in the presence of a hydrogenation catalyst. In the method for producing 2,5-dimethylfuran, the hydrogenation catalyst includes at least one selected from a first component group and at least one selected from a second component group. The first component group includes chromium, molybdenum, manganese, rhenium, ruthenium, rhodium, iridium, nickel, palladium, platinum, copper, and zinc, etc. The second component group includes alumina, silica, titania, zirconia, and carbon, etc.

Description

Technical Field

[0001] This invention relates to methods for manufacturing 2,5-dimethylfuran, p-xylene, terephthalic acid, and polyester, as well as p-xylene, terephthalic acid, polyester compositions, fiber materials, resin materials, membrane materials, fiber articles, resin articles, and membrane articles. Background Technology

[0002] To address global warming and climate change caused by the increase of greenhouse gases such as carbon dioxide, efforts to achieve carbon neutrality and a decarbonized society are accelerating. Therefore, the sustainable production of petroleum-derived bulk chemicals from biomass is extremely important, and vigorous research and development are underway worldwide.

[0003] Terephthalic acid is a raw material for polyesters, which are used in synthetic fibers, films, plastic bottles, etc. Due to its wide range of uses, there is a very high demand for biomass-derived products.

[0004] In recent years, methods for producing terephthalic acid using biomass-derived p-xylene as a starting material have been studied. A representative method of this process proposes a route to produce p-xylene via a Diels-Alder reaction of 2,5-dimethylfuran with ethylene, followed by an oxidation step to produce terephthalic acid. This 2,5-dimethylfuran can be produced through the chemical conversion of sugars that can be derived from biomass resources. Therefore, both p-xylene and terephthalic acid can be replaced with biomass-derived products.

[0005] A method for hydrogen reduction has been proposed in the process of converting sugars to 2,5-dimethylfuran, where 5-chloromethylfurfural is obtained through a dehydration reaction under acidic hydrochloric acid conditions (see, for example, Patent Document 1). Furthermore, a method for hydrogen reduction after obtaining 5-hydroxymethylfurfural has also been proposed.

[0006] On the other hand, 5-hydroxymethylfurfural is known to be a substance with low thermal stability and poor operability. As a method to improve the thermal stability of 5-hydroxymethylfurfural and suppress side reactions such as polymerization and ring-opening reactions, a method for converting it into an acetal compound was proposed in Non-Patent Literature 1. Furthermore, a method for converting this acetal compound into 2,5-dimethylfuran was proposed in Non-Patent Literature 2 by contacting it with a solid catalyst containing an iron / ruthenium alloy under hydrogen pressure.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2015 / 023918

[0010] Non-patent literature

[0011] Non-patent literature 1: Nakajima, K. et al. Angew. Chem. Int. Ed. 2018, Vol. 57, 8235 pages.

[0012] Non-patent literature 2: Vlachos, D G. et al. Green Chem. 2023, Vol. 25, 9363 pages. Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] The method for manufacturing 2,5-dimethylfuran described in Patent Document 1 requires harsh manufacturing conditions involving the extensive use of hydrochloric acid, and the chlorine atoms contained in 5-chloromethylfurfural are desorbed. Therefore, the manufacturing method described in Patent Document 1 is undesirable from an atom economy point of view.

[0015] Furthermore, the method for producing 2,5-dimethylfuran described in Non-Patent Literature 2 uses a special alloy catalyst containing iron as a metallic component. This catalyst is not only prone to deactivation due to air and moisture, but also suffers from low versatility, making it difficult to achieve industrial-scale production. Therefore, a method for producing 2,5-dimethylfuran in high yield under mild conditions is desired, utilizing a catalyst that is easy to operate, highly versatile, easily separable / recoverable from the post-reaction solution, and reusable.

[0016] The present invention is made in view of the above circumstances, which aims to produce 2,5-dimethylfuran with high efficiency by using an iron-free hydrogenation catalyst, to use the obtained 2,5-dimethylfuran as a raw material to produce p-xylene, to use the obtained p-xylene as a raw material to produce terephthalic acid, and to use the obtained terephthalic acid as a raw material to produce polyester.

[0017] Methods for solving problems

[0018] In order to solve the above-mentioned problems and achieve the objectives, the present invention employs any of the means shown below.

[0019] That is, the method for manufacturing 2,5-dimethylfuran according to the present invention is characterized in that [1] is a method for manufacturing 2,5-dimethylfuran comprising the step of reacting a furan compound of general formula (I) with hydrogen in a non-aqueous solvent in the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst comprises at least one selected from the first group of components below and at least one selected from the second group of components below.

[0020]

[0021] [In general formula (I), R] 1 -CH2OH, alkyl groups with 1 to 5 carbon atoms, -CH2OC(O)R 4 -C(O)OR 5 Any one of the groups shown. R 2 and R 3 Each is an alkyl group with 1 to 5 carbon atoms, which can differ from one another, and can combine with each other to form a ring structure. R 4 It is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. R 5 It is an alkyl group having 1 to 5 hydrogen atoms or carbon atoms.

[0022] (Group 1) Chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, and cadmium

[0023] (Second Component Group) Magnesium aluminate, calcium aluminate, magnesium silicate, calcium silicate, aluminosilicates, boron oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, cerium oxide, yttrium oxide, niobium oxide, zinc oxide, chromium oxide, hydroxyapatite, silicon carbide, magnesium carbonate, calcium carbonate, barium carbonate, carbon, graphite, diamond, silicon nitride, aluminum nitride, boron nitride, aluminosilicate, aluminophosphate, magnesium phosphate, calcium phosphate, strontium phosphate, pyrophosphate, chloroapatite, fluorapatite, calcium sulfate, and barium sulfate.

[0024] Furthermore, the method for manufacturing 2,5-dimethylfuran according to the present invention is characterized in that, [2] in the invention described in [1] above, the non-aqueous solvent is at least one selected from hydrocarbons, alcohols, ethers and esters.

[0025] Furthermore, the method for manufacturing p-xylene according to the present invention is characterized in that [3] it includes the following steps (A) and (B).

[0026] Step (A): A step of manufacturing 2,5-dimethylfuran by the manufacturing method of 2,5-dimethylfuran described in [1] or [2] above.

[0027] Process (B): The process of manufacturing p-xylene using 2,5-dimethylfuran obtained through process (A) as a raw material.

[0028] Furthermore, the method for manufacturing terephthalic acid according to the present invention is characterized in that, [4] it includes a step of manufacturing terephthalic acid using p-xylene obtained by the p-xylene manufacturing method described in [3] above as a raw material.

[0029] Furthermore, the polyester manufacturing method of the present invention is characterized in that, [5] it includes a step of manufacturing polyester using terephthalic acid obtained by the terephthalic acid manufacturing method described in [4] above as a raw material.

[0030] Furthermore, the p-xylene involved in this invention is characterized in that [6] it contains 2,5-dimethylfuran, 2,5-dimethyltetrahydrofuran, toluene, 2-methylfuran and 2-methyltetrahydrofuran as components, and the total content of the above components is 0.001 ppm or more and 500 ppm or less.

[0031] Furthermore, the terephthalic acid involved in this invention is characterized in that [7] it contains 2,5-furandicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, benzoic acid, 2-furancarboxylic acid and tetrahydrofuran-2-carboxylic acid as components, and the total content of the above components is 0.001 ppm or more and 500 ppm or less.

[0032] Furthermore, the polyester composition involved in this invention is characterized in that [8] is obtained by the polyester manufacturing method described in [5] above.

[0033] Furthermore, the polyester composition involved in this invention is characterized in that [9] it is obtained using terephthalic acid as described in [7] above as a raw material.

[0034] Furthermore, the fiber material involved in this invention is characterized in that

[10] uses the polyester composition described in [8] or [9] above.

[0035] Furthermore, the resin material involved in this invention is characterized in that

[11] it uses the polyester composition described in [8] or [9] above.

[0036] Furthermore, the membrane material involved in this invention is characterized in that

[12] uses the polyester composition described in [8] or [9] above.

[0037] Furthermore, the fiber product of the present invention is characterized in that

[13] uses the fiber material described in

[10] above.

[0038] Furthermore, the fiber products involved in this invention are characterized in that,

[14] in the invention described above

[13] , they are clothing, industrial materials, building materials or household materials.

[0039] Furthermore, the resin article of the present invention is characterized in that

[15] uses the resin material described in

[11] above.

[0040] Furthermore, the resin articles involved in this invention are characterized in that,

[16] in the invention described above

[15] , they are electrical / electronic equipment components, automotive components, mechanical components, or residential materials.

[0041] Furthermore, the membrane article of the present invention is characterized in that

[17] uses the membrane material described in

[12] above.

[0042] Furthermore, the film product involved in this invention is characterized in that,

[18] in the invention described above

[17] , it is a release film for manufacturing multilayer ceramic capacitors, a film for dry film resist, a release film for polarizing plates, an optical release film, a process release film, or a film for packaging materials.

[0043] The effects of the invention

[0044] According to the present invention, 2,5-dimethylfuran can be produced with high efficiency, and the resulting 2,5-dimethylfuran can be used to produce p-xylene, terephthalic acid, and polyesters. Detailed Implementation

[0045] The following is a detailed description of suitable embodiments of the present invention. It should be noted that the present invention is not limited to the embodiments described below, but should also be understood to include various modifications implemented without changing the spirit of the present invention.

[0046] (1) Raw material compounds

[0047] In the method for manufacturing 2,5-dimethylfuran according to embodiments of the present invention (hereinafter, sometimes abbreviated as the method for manufacturing 2,5-dimethylfuran of the present invention), a furan compound (hereinafter, sometimes simply referred to as furan compound) represented by the following general formula (I) is used as a raw material compound.

[0048]

[0049] In general formula (I), R 1 -CH2OH, alkyl groups with 1 to 5 carbon atoms, -CH2OC(O)R 4 -C(O)OR 5 Any one of the groups shown. R 2 and R 3 Each is an alkyl group with 1 to 5 carbon atoms, which can differ from one another, and can combine with each other to form a ring structure. R 4 It is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. R 5 It is an alkyl group having 1 to 5 carbon atoms or hydrogen atoms. It should be noted that, in this specification, for example, an alkyl group having 1 to 5 carbon atoms means an alkyl group having 1 to 5 carbon atoms. The same applies to other substituents with specified carbon number.

[0050] R as general formula (I) 1Preferably, it is -CH2OH, methyl, or -CH2OC(O)R 4 or -C(O)OR 5 As R 2 and R 3 Each is preferably methyl, ethyl, ethylene, trimethylene, or dimethyltrimethylene. As R 4 Preferably methyl or phenyl. As R 5 R is preferably a hydrogen atom or a methyl group. R is a component of the furan compound represented by general formula (I). 1 ~R 5 Specific examples of furan compounds having preferred functional groups include, for example, furan compounds shown in any of formulas (I-1) to (I-30) below. From the viewpoint of reducing the number of reaction steps in the synthesis from sugars, as R... 1 More preferably -CH2OH. As R 1 Specific examples of furan compounds with a group represented by -CH2OH include, for example, dimethyl acetal, diethyl acetal, ethylene acetal, trimethylene acetal, and dimethyltrimethyl acetal of 5-hydroxymethylfurfural as shown in formulas (I-1) to (I-5). From the viewpoint of high thermal stability, as R... 2 and R 31 More preferably, it is trimethylene. 1 The group represented by -CH2OH, R 2 and R 3 The furan compound with a trimethylene content is the trimethylene acetal of 5-hydroxymethylfurfural as shown in formula (I-4).

[0051]

[0052] This furan compound can be any of the following: a commercially available product, a synthetic product obtained by known technology, or a synthetic product obtained by a novel method. Specifically, for example, the furan compounds shown in formulas (I-1) to (I-5) above can be synthesized by the method described in Experimental Example 7 of Japanese Patent No. 6900801. Furthermore, petroleum-based feedstocks or biomass-based feedstocks can be used in the same manner with respect to this furan compound.

[0053] In the method for producing 2,5-dimethylfuran of the present invention, the furan compound is preferably derived from biomass. Furthermore, the furan compound is also preferably a substance recovered as unreacted component from the reactants in the method for producing 2,5-dimethylfuran of the present invention, which is then separated / purified and reused as needed.

[0054] (2) Hydrogenation catalyst

[0055] In the method for producing 2,5-dimethylfuran of the present invention, the hydrogenation catalyst comprises at least one selected from the first group of components below and at least one selected from the second group of components below.

[0056] The first component group consists of chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, and cadmium. Among these, the hydrogenation catalyst preferably contains at least one selected from chromium, molybdenum, manganese, rhenium, ruthenium, rhodium, iridium, nickel, palladium, platinum, copper, and zinc, based on the reasons of high hydrogenation catalytic ability and good reaction selectivity.

[0057] The first component can be in either a metallic or cationic state, as long as it exhibits hydrogenation capability. Among these, the metallic state is sometimes preferred because it possesses stronger hydrogenation capability and is more stable under a reducing atmosphere. The first component can be used alone or in combination of two or more, contained within a solid catalyst. Furthermore, when using two or more first components, there are no particular restrictions on their combination, mixing ratio, or form; they can be used as mixtures, alloys, or intermetallic compounds of various metals.

[0058] The second component group comprises magnesium aluminate, calcium aluminate, magnesium silicate, calcium silicate, aluminosilicates, boron oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, cerium oxide, yttrium oxide, niobium oxide, zinc oxide, chromium oxide, hydroxyapatite, silicon carbide, magnesium carbonate, calcium carbonate, barium carbonate, carbon, graphite, diamond, silicon nitride, aluminum nitride, boron nitride, aluminosilicate, aluminophosphate, magnesium phosphate, calcium phosphate, strontium phosphate, pyrophosphate, chloroapatite, fluorapatite, calcium sulfate, and barium sulfate. Among these, the hydrogenation catalyst preferably comprises at least one selected from carbon, aluminum oxide, silicon oxide, titanium oxide, and zirconium oxide, based on the reason for its high hydrogenation catalytic activity.

[0059] The second component can be used alone or in combination of two or more. There are no particular restrictions on the combination, mixing ratio, or form when two or more second components are used together; it can be used as a mixture of individual compounds, a compound compound, or a double salt.

[0060] To improve the catalytic activity and selectivity of hydrogenation, the hydrogenation catalyst may contain additives in addition to the first and second components mentioned above. Examples of such additives include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, gallium, silicon, germanium, tin, lead, antimony, bismuth, tellurium, fluorine, chlorine, bromine, and iodine. One additive may be used alone, or two or more may be used in combination.

[0061] (3) Non-aqueous solvents

[0062] In the method for producing 2,5-dimethylfuran of the present invention, a non-aqueous solvent is used in the solvent for the hydrogenation deoxygenation reaction. By using a non-aqueous solvent, side reactions can be suppressed, and the target substance can be obtained efficiently. Specifically, the non-aqueous solvent is preferably selected from at least one of hydrocarbons, alcohols, ethers, and esters. Examples of hydrocarbons include saturated aliphatic hydrocarbons such as pentane, neopentane, hexane, cyclohexane, heptane, methylcyclohexane, octane, isooctane, nonane, decane, decahydronaphthalene, dodecane, and isododecane, as well as aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, tetrahydronaphthalene, and methylnaphthalene. Examples of alcohols include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol, and diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and neopentanediol. Examples of ethers include diethyl ether, tetrahydrofuran, dimethoxyethane, methyl-tert-butyl ether, tetrahydropyran, dipropyl ether, diisopropyl ether, methyltetrahydropyran, and cyclopentylmethyl ether. Examples of esters include methyl acetate, ethyl acetate, methyl propionate, propyl acetate, ethyl propionate, methyl butyrate, and butyl acetate.

[0063] (4) Reaction conditions

[0064] The method for producing 2,5-dimethylfuran of the present invention includes a step of reacting the furan compound represented by the above general formula (I) with hydrogen in a non-aqueous solvent in the presence of a hydrogenation catalyst. Preferably, the reaction is carried out as shown in formula (1), obtaining the target compound 2,5-dimethylfuran through a hydrogenation deoxygenation reaction, with water, alcohol, and / or diol as byproducts. The reaction conditions, such as the feed rate to the reactor and the reaction temperature, are appropriately adjusted according to the type and amount of the hydrogenation catalyst.

[0065]

[0066] In the method for producing 2,5-dimethylfuran of the present invention, the reaction temperature is not particularly limited, but is preferably 20°C or higher, more preferably 50°C or higher, and even more preferably 90°C or higher. Furthermore, the upper limit of this reaction temperature is preferably 500°C or lower, more preferably 400°C or lower, and even more preferably 300°C or lower. There is a tendency that the higher the reaction temperature, the more the consumption of raw materials is promoted with the same amount of catalyst. On the other hand, if the reaction temperature is too high, there is a tendency that the selectivity of the product decreases.

[0067] In the method for producing 2,5-dimethylfuran of the present invention, there is no limitation on the hydrogen pressure inside the reactor. The hydrogen pressure inside the reactor, measured by a gauge pressure, is preferably 0.1 MPa or more, more preferably 0.3 MPa or more, and even more preferably 0.4 MPa or more. Furthermore, the upper limit of the aforementioned hydrogen pressure inside the reactor is preferably 20 MPa or less, more preferably 10 MPa or less, and even more preferably 5 MPa or less. The higher the hydrogen pressure inside the reactor, the more promoted the hydrogen supply to the hydrogenation catalyst, and the higher the reaction rate. On the other hand, in order to carry out the reaction at high hydrogen pressure, a reaction apparatus with high pressure resistance is required, and there is a tendency for a decrease in the selectivity of the products.

[0068] In the method for producing 2,5-dimethylfuran of the present invention, there is no limitation on the amount of furan compound used relative to the non-aqueous solvent. The concentration of the furan compound (raw material compound) relative to the non-aqueous solvent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. If the concentration of the raw material compound is too low, a large amount of non-aqueous solvent is used, thus the reaction vessel becomes too large, resulting in a tendency for reduced production efficiency.

[0069] (5) Separation / Purification

[0070] The 2,5-dimethylfuran obtained by the method of manufacturing 2,5-dimethylfuran of the present invention can be separated / purified by known methods according to the content of 2,5-dimethylfuran and the types of impurities.

[0071] In the method for producing 2,5-dimethylfuran of the present invention, when the reactants contain a furan compound as an unreacted starting material, as described above, the 2,5-dimethylfuran and its starting material compound are separated / recovered, and further purified as needed. This yields 2,5-dimethylfuran as the target compound and an unreacted furan compound, and preferably, the unreacted furan compound is reused as a starting material compound for 2,5-dimethylfuran. Furthermore, if alcohols or diols are present in the reactants as byproducts of a hydrogenation-deoxygenation reaction or through hydrolysis of the starting material compound, they are separated / recovered, and further purified as needed. This yields 2,5-dimethylfuran as the target compound and an alcohol or diol, and preferably, the alcohol or diol is reused in the synthesis of the furan compound as a starting material compound.

[0072] (6) Transformation of 2,5-dimethylfuran

[0073] The method for manufacturing p-xylene according to embodiments of the present invention (hereinafter, sometimes abbreviated as the method for manufacturing p-xylene of the present invention) includes the following steps (A) and (B).

[0074] Step (A): The step of manufacturing 2,5-dimethylfuran by the method of the present invention.

[0075] Process (B): The process of manufacturing p-xylene using 2,5-dimethylfuran obtained through process (A) as a raw material.

[0076] Regarding step (A), as described in relation to the above-described method for manufacturing 2,5-dimethylfuran of the present invention.

[0077] Regarding step (B), a known method can be used as a method for manufacturing p-xylene using 2,5-dimethylfuran as a raw material. Specifically, the method described in Example 2 of Japanese Patent No. 6047162 can be cited as an example. Thus, p-xylene can be manufactured using 2,5-dimethylfuran obtained by the method for manufacturing 2,5-dimethylfuran of the present invention.

[0078] The method for manufacturing p-xylene of the present invention may further include a step of separating / purifying the p-xylene after step (B). The method for separating / purifying the p-xylene is not particularly limited, and methods known in the art related to the separation / purification of the p-xylene may be directly applied as the method for separating / purifying the p-xylene.

[0079] The p-xylene (hereinafter, sometimes abbreviated as p-xylene of the present invention) according to embodiments of the present invention contains 2,5-dimethylfuran, 2,5-dimethyltetrahydrofuran, toluene, 2-methylfuran, and 2-methyltetrahydrofuran as components. For example, 2,5-dimethylfuran is a compound represented by formula (II-1) below. 2,5-dimethyltetrahydrofuran is a compound represented by formula (II-2) below. Toluene is a compound represented by formula (II-3) below. 2-methylfuran is a compound represented by formula (II-4) below. 2-methyltetrahydrofuran is a compound represented by formula (II-5) below. In the p-xylene of the present invention, the total content of these components is preferably 0.001 ppm or more and 500 ppm or less, more preferably 0.001 ppm or more and 400 ppm or less, and even more preferably 0.001 ppm or more and 300 ppm or less. The lower the total content of these components (the aforementioned compounds) in the p-xylene of the present invention, the more effectively impurities can be prevented from contaminating the terephthalic acid produced by oxidizing the p-xylene, thereby improving the purity of the terephthalic acid. On the other hand, in order to achieve a low total content of the aforementioned components, there is a tendency to increase the size of the refining equipment used.

[0080]

[0081] The method for manufacturing terephthalic acid according to embodiments of the present invention (hereinafter, sometimes abbreviated as the method for manufacturing terephthalic acid of the present invention) includes a step of manufacturing terephthalic acid using p-xylene obtained by the p-xylene manufacturing method of the present invention as a raw material. Regarding the method for manufacturing terephthalic acid using p-xylene as a raw material, known methods can be used. Specifically, examples include the method described in the embodiments of Japanese Patent Application Publication No. 2017-095391. Therefore, terephthalic acid described later can be manufactured using p-xylene obtained by the p-xylene manufacturing method of the present invention as a raw material.

[0082] The method for manufacturing terephthalic acid of the present invention may further include a step of separating / purifying terephthalic acid. The method for separating / purifying terephthalic acid is not particularly limited; for example, the method described in the embodiments of Japanese Patent Application Publication No. 2017-095391 can be cited as an example.

[0083] The terephthalic acid (hereinafter, sometimes abbreviated as the terephthalic acid of the present invention) according to embodiments of the present invention contains 2,5-furandicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, benzoic acid, 2-furancarboxylic acid, and tetrahydrofuran-2-carboxylic acid as components. For example, 2,5-furandicarboxylic acid is the compound shown in formula (III-1) below. Tetrahydrofuran-2,5-dicarboxylic acid is the compound shown in formula (III-2) below. Benzoic acid is the compound shown in formula (III-3) below. 2-Furancarboxylic acid is the compound shown in formula (III-4) below. Tetrahydrofuran-2-carboxylic acid is the compound shown in formula (III-5) below. In the terephthalic acid of the present invention, the total content of these components is preferably 0.001 ppm or more and 500 ppm or less, more preferably 0.001 ppm or more and 400 ppm or less, and even more preferably 0.001 ppm or more and 300 ppm or less. The lower the total content of these components (the aforementioned compounds) in the terephthalic acid of the present invention, the less coloring the polymer produced by polycondensation of the terephthalic acid and glycol can be, and the hue can be controlled. On the other hand, in order to reduce the total content of the aforementioned components, there is a tendency to increase the size of the refining equipment used.

[0084]

[0085] The polyester manufacturing method according to embodiments of the present invention (hereinafter, sometimes abbreviated as the polyester manufacturing method of the present invention) includes a step of manufacturing polyester using terephthalic acid obtained by the terephthalic acid manufacturing method of the present invention described above as a raw material. Regarding the method of manufacturing polyester using terephthalic acid as a raw material, known methods can be used. Specifically, examples of such methods include, for instance, Example 1 of Japanese Patent Application Publication No. 2004-231831, Example 1 of Japanese Patent Application Publication No. 2016-60759, or the manufacturing example described in International Publication No. 2023 / 146235. Therefore, the polyester composition described later can be manufactured using terephthalic acid obtained by the terephthalic acid manufacturing method of the present invention as a raw material.

[0086] The polyester composition according to embodiments of the present invention (hereinafter, sometimes abbreviated as the polyester composition of the present invention) is obtained by the manufacturing method of the polyester of the present invention described above. That is, the polyester composition of the present invention can be manufactured using the terephthalic acid of the present invention as a raw material. Examples of polyesters included in the polyester composition of the present invention include polyethylene terephthalate, polybutylene terephthalate, and polybutylene terephthalate-adipate.

[0087] The fiber material (hereinafter, sometimes abbreviated as the fiber material of the present invention) according to embodiments of the present invention uses the polyester composition of the present invention described above. For example, the fiber material of the present invention can be obtained by spinning using the polyester composition of the present invention described above. Regarding the method of spinning using the polyester composition, known methods can be used. Specifically, examples of such methods include, for instance, the method described in Example 1 of Japanese Patent Application Publication No. 2023-170756. Thus, the fiber material can be obtained using the polyester composition of the present invention.

[0088] The fiber material of the present invention can be used as a raw material for various fiber products. That is, the fiber products according to the embodiments of the present invention (hereinafter, sometimes abbreviated as fiber products of the present invention) use the fiber material of the present invention described above. There are no particular limitations on the fiber products of the present invention; for example, clothing, industrial materials, building materials, or household goods can be cited as examples. Examples of clothing include, for example, shirts, trousers, women's shirts, skirts, short jackets, hoodies, coats, jackets, fleece sweaters, sweaters, cardigans, sportswear, outdoor clothing, underwear, formal wear, accessories, and workwear. Examples of industrial materials include, for example, belts, ropes, filters, nonwoven fabrics, tire cords, rubber hoses / belt reinforcements, and nets. Examples of building materials include, for example, wallpaper, breathable and waterproof sheets, sound insulation materials, heat insulation materials, sound-absorbing materials, and roofing materials. Examples of household goods include, for example, packaging materials, bag materials, labeling materials, and printing substrates. The fiber products of the present invention can be selected from any of these garments, industrial materials, building materials and household goods.

[0089] The resin material according to embodiments of the present invention (hereinafter, sometimes abbreviated as the resin material of the present invention) uses the polyester composition of the present invention described above. For example, the resin material of the present invention can be obtained by melt-blending the polyester composition of the present invention with other components according to the intended purpose. As a method for melt-blending the polyester composition, known methods can be used. Specifically, as a method, examples include the method described in Example 1 of Japanese Patent Application Publication No. 2024-3891. Thus, the resin material can be obtained using the polyester composition of the present invention.

[0090] The resin material of the present invention, through molding processing, can be used as a raw material for various resin products. That is, the resin products according to the embodiments of the present invention (hereinafter, sometimes abbreviated as the resin products of the present invention) use the resin material of the present invention described above.

[0091] The resin products of this invention are not particularly limited. Examples of resin products include electrical / electronic equipment components, automotive parts, mechanical parts, and residential materials. Examples of electrical / electronic equipment components include, for example, circuit breakers, electromagnetic switches, focusing boxes, flyback transformers, copier and printer mounting units, general household appliances, OA equipment housings, variable capacitor housings, terminal blocks, current transformers, printed wiring boards, wiring boards, conduits, connectors, relays, disk drive chassis, transformers, switch components, socket components, motor components, sockets, plugs, capacitors, various housing types, and resistors. Examples of automotive parts include, for example, automotive ignition device components, automotive connectors, and various automotive electrical components. Examples of mechanical parts include, for example, computer-related components, audio components, lighting components, telecommunications equipment-related components, telephone equipment-related components, air conditioner components, household appliance components, copier components, fax machine components, and optical equipment components. Examples of residential materials include, for example, roofing materials, exterior wall materials, and flooring materials.

[0092] The membrane material according to embodiments of the present invention (hereinafter, sometimes abbreviated as the membrane material of the present invention) uses the polyester composition of the present invention described above. For example, the membrane material of the present invention can be obtained by forming a membrane using the polyester composition of the present invention described above. Regarding the method of forming a membrane using the polyester composition, known methods can be used. Specifically, examples of such methods include, for instance, the method described in Example 1 of Japanese Patent Application Publication No. 2024-123912. Thus, the membrane material can be obtained using the polyester composition of the present invention.

[0093] The membrane material of the present invention can be used as a raw material for various membrane products. That is, the membrane products according to the embodiments of the present invention (hereinafter, sometimes abbreviated as the membrane products of the present invention) use the membrane material of the present invention described above.

[0094] The film products of the present invention are not particularly limited, and examples can be made from substances selected from the following: release film for manufacturing multilayer ceramic capacitors, film for dry film resist, release film for polarizing plates, optical release film, process release film, and film for packaging materials.

[0095] Example

[0096] The present invention will now be described in detail through examples, but the present invention is not limited to the following examples.

[0097] [Analysis of reactants]

[0098] The conversion rate of furan compound raw materials before and after the reaction was determined by gas chromatography (GC-2010 manufactured by Shimadzu Corporation, column: Agilent). The following calculations were performed using DB-5 manufactured by Technologie Co., Ltd.

[0099] Conversion rate of furan compound feedstock = {1 - [amount of furan compound in solution after reaction (moles)] / [amount of furan compound in feedstock (moles)]} × 100 (%)

[0100] The yield of 2,5-dimethylfuran was determined by gas chromatography (GC-2030, manufactured by Shimadzu Corporation, column: Agilent). The following calculations were performed using DB-WAX (manufactured by Technologie Co., Ltd.).

[0101] Yield of 2,5-dimethylfuran = [Amount of 2,5-dimethylfuran in the solution after reaction (moles)] / [Amount of furan compound in the starting material (moles)] × 100%

[0102] [Example 1]

[0103] In Example 1, 0.1 g of a furan compound (the furan compound shown in formula (I-4) above) prepared by the method described in the prior art (ChemCatChem.2022, 14, e202200191.) was dissolved in 10 g of tetrahydrofuran (manufactured by Fuji Film & Wako Pharmaceutical Co., Ltd.), and hydrogen gas was injected at 0.9 MPa (gauge pressure) in the presence of 0.2 g of Ru / C (Ru5%) (manufactured by NECHEMCAT Co., Ltd.) in an autoclave. The reaction was carried out at 200°C for 3 hours. The reaction solution obtained by this hydrogenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. As a result, 2,5-dimethylfuran was obtained in a yield of 27%. In addition, 2,5-hexanedione was obtained in a yield of 4%, and 1,3-propanediol was obtained in a yield of 65%.

[0104] [Comparative Example 1]

[0105] [Effects of non-aqueous solvents]

[0106] In Comparative Example 1, the solvent was changed from tetrahydrofuran to water, and the hydrogenation deoxygenation reaction was carried out using the same method as in Example 1. As a result, 2,5-dimethylfuran was obtained in a yield of 2%. Furthermore, 2,5-hexanedione was obtained in a yield of 8%, and 1,3-propanediol was obtained in a yield of 61%.

[0107] In Comparative Example 1, which used an aqueous solvent, the yield of 2,5-dimethylfuran was significantly lower than that of Example 1, which used tetrahydrofuran as a non-aqueous solvent, while the yield of 2,5-hexanedione, formed by the hydrolysis of 2,5-dimethylfuran, was increased. Thus, the advantage of using a non-aqueous solvent for the starting compound is demonstrated in the production of 2,5-dimethylfuran.

[0108] [Example 2]

[0109] In Example 2, 0.1 g of a furan compound (the furan compound shown in formula (I-4) above) prepared by the method described in the prior art (ChemCatChem.2022, 14, e202200191.) was dissolved in 10 g of tetrahydrofuran (manufactured by Fuji Film and Wahko Pharmaceutical Co., Ltd.), and hydrogen gas was injected at 2 MPa (gauge pressure) in an autoclave in the presence of 16 mg of Pd / C (Pd5%) (manufactured by Fuji Film and Wahko Pharmaceutical Co., Ltd.), and a hydrogenation-deoxygenation reaction was carried out at 200°C for 2 hours. The reaction solution obtained by this hydrogenation-deoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. As a result, 2,5-dimethylfuran was obtained in a yield of 9%. In addition, 2,5-hexanedione was not formed, and 1,3-propanediol was obtained in 72% yield.

[0110] [Example 3]

[0111] In Example 3, the catalyst was changed to Pt / C (Pt5%) (manufactured by Fuji Film & Koko Pharmaceutical Co., Ltd.), and the hydrogenation deoxygenation reaction was carried out in the same manner as in Example 2. The reaction solution obtained by this hydrogenation deoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. As a result, 2,5-dimethylfuran was obtained in a yield of 21%. In addition, 2,5-hexanedione was not formed, and 1,3-propanediol was obtained in a yield of 73%.

[0112] [Example 4]

[0113] In Example 4, the catalyst was changed to Rh / C (Pt5%) (manufactured by Fuji Film & Koko Pharmaceutical Co., Ltd.), and the hydrogenation deoxygenation reaction was carried out in the same manner as in Example 2. The reaction solution obtained by this hydrogenation deoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. As a result, 2,5-dimethylfuran was obtained in 60% yield. In addition, 2,5-hexanedione was not formed, and 1,3-propanediol was obtained in 92% yield.

[0114] [Example 5]

[0115] In Example 5, the reaction temperature was set to the temperatures shown in Table 1 below, and the hydrogenation deoxygenation reaction was performed in the same manner as in Example 4. The reaction solution obtained by this hydrogenation deoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. The results are shown in Table 1.

[0116] [Table 1]

[0117] [Example 6]

[0118] In Example 6, the hydrogen pressure was as shown in Table 2 below, and the hydrogenation deoxygenation reaction was performed in the same manner as in Example 4. The reaction solution obtained by this hydrogenation deoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. The results are shown in Table 2.

[0119] [Table 2]

[0120] [Example 7]

[0121] In Example 7, the non-aqueous solvent was one of the solvents shown in Table 3 below, and the hydrogenation deoxygenation reaction was performed in the same manner as in Example 4. The reaction solution obtained by this hydrogenation deoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. The results are shown in Table 3.

[0122] [Table 3]

[0123] Industry availability

[0124] This invention provides a highly efficient way to obtain 2,5-dimethylfuran, which is useful as a polymer raw material. In particular, when using a furan compound derived from biomass, 100% biomass-derived 2,5-dimethylfuran is obtained. By combining the obtained 100% biomass-derived 2,5-dimethylfuran with biomass-derived ethylene, 100% biomass-derived p-xylene is obtained. By combining such 100% biomass-derived p-xylene with biomass-derived diol, 100% biomass-derived polyester can be obtained. Furthermore, terephthalic acid can be obtained using the aforementioned p-xylene as a raw material, and a polyester composition can be obtained using this terephthalic acid as a raw material. By using this polyester composition, fiber materials, resin materials, and membrane materials can be obtained. Furthermore, fiber products, resin products, and membrane products can be obtained.

Claims

1. A method for producing 2,5-dimethylfuran, comprising the step of reacting a furan compound of general formula (I) with hydrogen in a non-aqueous solvent in the presence of a hydrogenation catalyst. The hydrogenation catalyst comprises at least one selected from the first component group below and at least one selected from the second component group below. In general formula (I), R 1 -CH2OH, alkyl groups with 1 to 5 carbon atoms, -CH2OC(O)R 4 -C(O)OR 5 Any one of the groups shown; R 2 and R 3 Each is an alkyl group with 1 to 5 carbon atoms, which can differ from one another, and can combine with each other to form a ring structure; R 4 It is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms; R 5 It is an alkyl group having 1 to 5 hydrogen atoms or carbon atoms; The first component group consists of chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, and cadmium. The second component group consists of magnesium aluminate, calcium aluminate, magnesium silicate, calcium silicate, aluminosilicates, boron oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, cerium oxide, yttrium oxide, niobium oxide, zinc oxide, chromium oxide, hydroxyapatite, silicon carbide, magnesium carbonate, calcium carbonate, barium carbonate, carbon, graphite, diamond, silicon nitride, aluminum nitride, boron nitride, aluminosilicate phosphate, aluminum phosphate, magnesium phosphate, calcium phosphate, strontium phosphate, pyrophosphate, chloroapatite, fluorapatite, calcium sulfate, and barium sulfate.

2. The method for manufacturing 2,5-dimethylfuran according to claim 1, wherein the non-aqueous solvent is selected from at least one of hydrocarbons, alcohols, ethers and esters.

3. A method for manufacturing p-xylene, comprising the following steps (A) and (B), Step (A): A step of manufacturing 2,5-dimethylfuran by the method for manufacturing 2,5-dimethylfuran according to claim 1. Step (B): A step of manufacturing p-xylene using 2,5-dimethylfuran obtained by step (A) as a raw material.

4. A method for manufacturing terephthalic acid, comprising the step of using p-xylene obtained by the method for manufacturing p-xylene according to claim 3 as a raw material to manufacture terephthalic acid.

5. A method for manufacturing polyester, comprising a step of manufacturing polyester using terephthalic acid obtained by the method for manufacturing terephthalic acid according to claim 4 as a raw material.

6. A type of p-xylene comprising 2,5-dimethylfuran, 2,5-dimethyltetrahydrofuran, toluene, 2-methylfuran, and 2-methyltetrahydrofuran as components. The total content of the components is above 0.001 ppm and below 500 ppm.

7. A terephthalic acid comprising 2,5-furandicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, benzoic acid, 2-furancarboxylic acid and tetrahydrofuran-2-carboxylic acid as components. The total content of the components is above 0.001 ppm and below 500 ppm.

8. A polyester composition obtained by the method of manufacturing the polyester according to claim 5.

9. A polyester composition obtained using terephthalic acid as described in claim 7 as a raw material.

10. A fibrous material that uses the polyester composition of claim 8 or 9.

11. A resin material that uses the polyester composition of claim 8 or 9.

12. A membrane material that uses the polyester composition of claim 8 or 9.

13. A fiber article that uses the fiber material of claim 10.

14. The fiber product according to claim 13, wherein the fiber product is clothing, industrial material, building material or household material.

15. A resin article that uses the resin material of claim 11.

16. The resin article according to claim 15, wherein the resin article is an electrical / electronic equipment component, an automotive component, a mechanical component, or a residential material.

17. A membrane article that uses the membrane material of claim 12.

18. The membrane product according to claim 17, wherein the membrane product is a release film for manufacturing multilayer ceramic capacitors, a film for dry film resist, a release film for polarizing plates, an optical release film, a process release film, or a film for packaging materials.

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