WO2005087368A1 - Catalyst and method for producing methylnaphthalene - Google Patents

Catalyst and method for producing methylnaphthalene Download PDF

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Publication number
WO2005087368A1
WO2005087368A1 PCT/JP2005/003343 JP2005003343W WO2005087368A1 WO 2005087368 A1 WO2005087368 A1 WO 2005087368A1 JP 2005003343 W JP2005003343 W JP 2005003343W WO 2005087368 A1 WO2005087368 A1 WO 2005087368A1
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Prior art keywords
naphthalene
catalyst
methylnaphthalenes
alumina
methanol
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PCT/JP2005/003343
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French (fr)
Japanese (ja)
Inventor
Guo-Zhu Bian
Ryosuke Yasuda
Masako Inoue
Naonobu Katada
Miki Niwa
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Japan Science And Technology Agency
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding

Definitions

  • Methylnaphthalene production catalyst and production method are Methylnaphthalene production catalyst and production method
  • the present invention relates to a catalyst for producing methylnaphthalenes and a method for producing methylnaphthalenes using the catalyst. More specifically, the present invention relates to a reaction for synthesizing methylnaphthalenes from naphthalene and methanol, which has sufficient activity and high methylnaphthalene.
  • the present invention relates to an alumina-supported tungsten oxide and alumina-supported sulfuric acid catalyst having a low selectivity for the compounds and a low by-product rate of tetrahydronaphthalenes, and a method for producing methylnaphthalenes using these catalysts.
  • the present invention is useful in the field of synthesis of naphthalene derivatives, which is useful as an intermediate material for various industrial products.
  • these problems were certainly solved, given that it was difficult to obtain methylnaphthalenes with high efficiency because the catalyst did not have sufficient activity and there were many by-products.
  • the present invention provides a new catalyst and a method for producing methylnaphthalenes using the catalyst.
  • the methylnaphthalenes produced in the present invention are high-yield, contain little by-products, and do not contain impurities such as sulfuric acid.
  • It is suitable as an intermediate material such as PEN resin and an intermediate material for naphthoic acid, a fluorescent enhancer, a surfactant, a dye, and a pharmaceutical. It is useful as a great driving force for creating new industries.
  • Methylnaphthalenes include methylnaphthalene (1-methylnaphthalene and 2-methylnaphthalene), dimethylnaphthalene (1, 2-, 1, 3-, 1, 4-, 1, 5-, 1, 6-, 1,7-, 1,8-, 2,3-, 2,6-, 2,7-dimethylnaphthalene) and the like.
  • Methyl naphthalenes are useful industrial raw materials.
  • 2-methylnaphthalene is used as a raw material for vitamin K
  • 2,6-dimethylnaphthalene is polyethylene naphthalate (PEN) resin. It is used as a raw material.
  • PEN polyethylene naphthalate
  • methyl naphthalenes are industrial raw materials useful as raw materials for pharmaceuticals, agricultural chemicals, dyes, surfactants, optical brighteners, etc. Charge.
  • 2-methylnaphthalene and 2,6-dimethylnaphthalene are particularly useful compounds, and 2-methylnaphthalene can be produced by isomerization of 1-methylnaphthalene (Patent Document 1), and 2,6-dimethylnaphthalene can be produced by methylidene 2-methylnaphthalene (see Patent Document 2), so that a mixture of methylnaphthalenes is also a useful industrial raw material.
  • Methylnaphthalenes are conventionally produced by purifying components contained in coal tar produced by coking of coal or LCO (light cycle oil) obtained in a petroleum refining process. has been reported (see Patent Documents 3-7). On the other hand, it has been reported to synthesize a fraction rich in methylnaphthalenes ⁇ methylnaphthalenes by a chemical reaction, and the cyclodehydrogenation of noraffin (see Patent Document 8) and the synthesis of tetralins A method for obtaining a mixture of naphthalene and methylnaphthalenes by hydrodehydrogenation (see Patent Document 9) has been reported. The production of methylnaphthalenes by these methods or a combination of these methods has a small power demand! There is a problem that naphthalene remains as a by-product.
  • tetrahydronaphthalenes eg, 1,2,3,4-tetrahydronaphthalene, methyl-1,2,3,4-
  • tetrahydronaphthalenes eg, 1,2,3,4-tetrahydronaphthalene, methyl-1,2,3,4-
  • by-products of tetrahydronaphthalene and dimethyl-1,2,3,4-tetrahydronaphthalene cannot be avoided, and methylnaphthalenes cannot be obtained with high efficiency.
  • Patent Document 1 JP-A-10-167997
  • Patent Document 3 JP-A-07-133239
  • Patent Document 4 JP 08-120281 A
  • Patent Document 5 JP 2001-139503 A
  • Patent Document 7 JP 2003--026614 A
  • Patent Document 8 JP-A-06-305988
  • Patent Document 9 JP 2001-278821 A
  • Patent Document 10 JP-A-2003-104918
  • Patent Document 11 JP-A-2002-128711
  • Patent Document 12 JP-A-2000-344690
  • the present inventors have studied the catalytic action of the various substances to solve the above-mentioned problems on the above reaction, and as a result, have found that With respect to the reaction for obtaining tylnaphthalenes, an alumina-supported tungsten oxide and an alumina-supported sulfuric acid catalyst having sufficient activity and high methyl naphthalene selectivity, low and having a by-product rate of tetrahydronaphthalenes have been found.
  • an object of the present invention is to provide a catalyst for producing naphthalene and methanol naphthalenes and a method for producing methylnaphthalenes.
  • an object of the present invention is to have a sufficient activity for the reaction to obtain methylnaphthalenes from naphthalene and methanol, and to reduce the by-product rate of tetrahydronaphthalenes, which has high selectivity to methylnaphthalenes, It is to provide a catalyst.
  • Another object of the present invention is to provide an alumina-supported tungsten catalyst or an alumina-supported sulfuric acid catalyst which is suitable for producing methylnaphthalenes from naphthalene and methanol.
  • an object of the present invention is to provide a reaction for obtaining methylnaphthalenes from naphthalene and methanol, by using the above-mentioned catalyst, having a sufficient reaction rate and having high selectivity to methylnaphthalenes, which is a by-product of tetrahydronaphthalenes.
  • An object of the present invention is to provide a method for producing methylnaphthalenes having a low rate.
  • the present invention for solving the above-mentioned problems includes the following technical means.
  • a specific surface area of the alumina is 100 m 2 g _1 or more, naphthalene methyl Lee spoon catalyst according to (1), wherein the supported amount of Sani ⁇ tungsten is 5-40 w t%.
  • Methyl naphthalene by reacting naphthalene and methanol in the presence of the alumina-supported oxide catalyst or the alumina-supported sulfuric acid catalyst according to any one of the above 1 to 3.
  • a process for producing methylnaphthalenes characterized by producing the same.
  • naphthalene is methylated with methanol.
  • the catalyst of the present invention and the method for producing the same will be described.
  • tungsten oxide supported on alumina and Z or sulfuric acid supported on alumina are used as catalysts.
  • the alumina preferably is a high purity ⁇ -alumina, for example, Catalysis Society supply reference catalyst set RC- AL04, JRC- AL08, JGC I ⁇ Co. manufactured and sold N611N, etc. are exemplified, 100 m 2 Those having a specific surface area of g- 1 or more are preferably used. If the specific surface area is small, the activity is low, which is not preferable. In the present invention, these are used alone or in combination.
  • tungsten oxide (WO) is determined by the weight of alumina-supported tungsten oxide.
  • Examples of a method for supporting tungsten oxide on alumina include, for example, a method in which alumina is charged into an aqueous solution of salts containing tungsten, the mixture is evaporated to dryness by heating, and calcined.
  • salts containing tungsten for example, ammonium tungstate (5 (NH 2) 0-12WO) and its water
  • Examples include the ammodimium tungstate pentahydrate (5 (NH) 0-12WO-5HO)
  • the firing conditions may be any as long as the solvent evaporates and the salts containing tungsten are converted to tantalum oxide, for example, in oxygen or air at 300-650 ° C., preferably 350-650 ° C. Firing at 500 ° C. is exemplified. If the firing temperature is too high, the specific surface area of the catalyst is lost, and the activity is undesirably reduced.
  • alumina As a method for supporting sulfuric acid, specifically, for example, alumina is put into a solution containing sulfuric acid, organic sulfonic acid, ammonium sulfate, etc., evaporated to dryness by heating, and fired. A method is illustrated.
  • the solution containing an organic sulfonic acid include, for example, an aqueous solution of 2-naphthalenesulfonic acid.
  • the firing conditions are as follows: When the organic sulfonic acid is used as a raw material, the condition is such that the organic sulfonic acid is converted to a sulfate group. — An example is calcination at 650 ° C, preferably 350 to 500 ° C.
  • Examples of the method for supporting tungsten oxide or sulfuric acid include a method in which alumina is charged into the above solution, and the solution is adsorbed in the solution and then filtered.
  • the alumina-supported tungsten oxide and the alumina-supported sulfuric acid of the present invention may be used as a powder or may be used after being molded.
  • an alumina carrier which has been molded may be used as a raw material, or tungsten oxide or sulfuric acid may be molded after supporting it.
  • a pure sample of these substances may be compression molded, or a binder may be used.
  • the present invention relates to the alumina-supported tungsten oxide and / or alumina produced as described above.
  • Methylnaphthalenes are produced from naphthalene and methanol using a supported sulfuric acid catalyst.
  • the naphthalene used as a raw material in the present invention may be a purified naphthalene or a mixture containing naphthalene and methylnaphthalenes.
  • Coal tar manufactured by coaling, LCO (light cycle oil) obtained by a petroleum refining process, or a refined product thereof may be used.
  • the reaction when producing methylnaphthalenes from naphthalene and methanol using tungsten oxide supported on alumina and sulfuric acid supported on alumina, the reaction can be carried out in a gas phase or a liquid phase.
  • the reaction temperature is set at 300-500 ° C, preferably 350-450 ° C. At a reaction temperature of 300 ° C or lower, not only a sufficient reaction rate cannot be obtained, but also the product does not detach from the catalyst surface, which may cause deactivation.
  • reaction temperature 500 ° C or higher
  • a large amount of carbonaceous material is generated by polymerization of the reactants and products, which may poison the catalyst surface, deactivate the catalyst, and lower the selectivity of methylnaphthalenes.
  • the reaction can be performed in a liquid phase or a gas phase.
  • the gas phase is preferable.
  • the reaction pressure may be any of normal pressure, pressurization and depressurization. For depressurization or large pressurization, there is no advantage in power if a device for changing the pressure or energy cost is required, so 115 atm is preferable. Better ,.
  • the molar ratio of naphthalene Z methanol is less than 0.005
  • a large amount of methanol must be recovered from the product after the reaction and reused. Energy costs increase.
  • the molar ratio of naphthalene Z methanol is larger than 0.1, a large amount of carbonaceous material is generated by the polymerization of naphthalene, which may poison the catalyst surface and deactivate it.
  • the molar ratio of naphthalene to methanol is preferably 0.005 to 0.1, more preferably 0.01 to 0.05.
  • the supply amount of the naphthalene 'methanol mixture, production efficiency is in contrast catalyst lg 0. Olgh- 1 or less is not sufficient conversion is obtained with Teigu 5GH _1 more. Accordingly, the supply amount of the naphthalene 'methanol mixture, 0. 01 is preferably a 5 g h _1 tool and more preferably from 0. 05- 2gh- 1 the catalyst lg.
  • the reaction may be of a continuous type or a batch type, but is preferably performed by a continuous method from an industrial viewpoint.
  • a continuous method for example, a method in which a catalyst is packed in a packed column and a mixture of naphthalene and methanol is supplied thereto, or a method in which naphthalene and methanol are separately supplied, or a method in which these are added to an inert solvent, is used.
  • a method of supplying by melting In addition, these raw materials are mixed with an inert diluent gas (eg, nitrogen).
  • an inert diluent gas eg, nitrogen
  • a method of supplying a mixture of naphthalene and methanol for example, a method of dissolving naphthalene in methanol and supplying this liquid to an evaporator and supplying it as a gaseous mixture, or a method of dissolving naphthalene in liquid naphthalene
  • the method include a method in which methanol vapor is passed through to obtain and supply a gas mixture, and a method in which liquid naphthalene and methanol are separately supplied to an evaporator and supplied as a gas mixture.
  • the removed gaseous product usually contains an excess amount of methanol and unreacted naphthalenes.
  • a method of cooling the gaseous product recovering naphthalene and methylnaphthalenes which are firstly precipitated, and separating and purifying the methylnaphthalenes by recovery and distillation. .
  • the present invention provides a novel catalyst for producing methyl naphthalenes from naphthalene and methanol, which produces a small amount of by-products, and a methyl naphthalene using the catalyst.
  • the basic mechanism by which the present invention achieves superior effects as compared with the related art can be described as follows.
  • Conventionally known zeolite catalysts have high activity but produce by-produced tetrahydronaphthalenes.
  • a monolayer of tungsten oxide or sulfuric acid covers the surface and exhibits the acid properties peculiar to the monolayer.
  • 10 to 30 wt% of silicon nitride is used, or It has been found that, when 5 to 30% by weight of sulfuric acid is supported and calcined at 300 to 650 ° C., the acid properties peculiar to the monolayer are exhibited, and the above preferable properties are exhibited.
  • a catalyst for producing methylnaphthalenes and a method for producing the same can be provided.
  • Methyl naphthalene has sufficient activity for the reaction to obtain methylnaphthalenes from naphthalene and methanol,
  • a catalyst having a high selectivity to naphthalenes and a low by-product rate of tetrahydronaphthalenes can be provided.
  • the following will specifically describe the catalyst of the present invention, a method for preparing the same, and a reaction example using the catalyst, based on examples.
  • the present invention is not limited to these examples. is not.
  • ammonium tungstate - ⁇ arm pentahydrate (Wako Pure Chemical manufactured and sold) in a beaker of 100 cm 3, was dissolved in water 50 cm 3, having a specific surface area 151m 2 g- 1 1g of RC-AL04, a reference material of alumina distributed by the Catalysis Society of Japan, was charged, and heated on a hot plate at 160 ° C to evaporate water. The obtained solid was calcined in air at 400 ° C. for 4 hours to produce a catalyst of the present invention.
  • naphthalene (Wako pure Chemical manufacturing sales) and methanol mixed solution of (Wako pure Chemical manufactured and sold) (naphthalene Z methanol molar ratio 0 01) is supplied at a speed of 1.06 gh- 1 and the product that appears at the outlet of the reaction tube is cooled to 0 ° C to collect liquids and solids.
  • the analysis was performed using a gas chromatograph equipped with DMN-267) (GC-2010, manufactured by Shimadzu Corporation). Table 1 shows the obtained meth The yield of lunaphthalenes and the by-product rate of tetrahydronaphthalenes were shown.
  • the yields of methylnaphthalenes are as follows: 1-methylnaphthalene, 2-methylnaphthalene, 1,2 dimethylnaphthalene, 1,3 dimethylnaphthalene, 1,4 dimethylnaphthalene, 1,6 dimethylnaphthalene, 1
  • the total yield of 2,7-dimethylnaphthalene, 1,8-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, and 2,7-dimethylnaphthalene was calculated by dividing the total yield by the amount of naphthalene supplied. However, the yields of other methylnaphthalenes were ignored because they were extremely low.
  • the by-product rates of tetrahydronaphthalenes are as follows: 1,2,3,4-tetrahydronaphthalene, 5-methinoley 1,2,3,4-tetrahydronaphthalene, 6-methynolae 1,2,3,4 -Tetrahydronaphthalene, 5,6-dimethyl-1,2,3,4-tetrahydronaphthalene, 5,7-dimethyl-1,2,3,4-tetrahydronaphthalene, 5,8 dimethyl-1,2,3
  • the sum of the yields of 4-tetrahydronaphthalene and 6,7-dimethyl-1,2,3,4-tetrahydronaphthalene was shown by a value obtained by dividing the total yield of naphthalene. However, the yields of other tetrahydronaphthalenes were ignored because they were extremely low.
  • the yield of methylnaphthalenes was sufficiently high at 5% or more, and the by-product rate of tetrahydronaphthalenes was as low as 1% or less.
  • the yield of methylnaphthalenes was as high as 10% or more.
  • Example 16 Using the above catalyst, the same operation as in Example 16 was performed to produce methylnaphthalenes. As shown in Table 1, in Comparative Example 1 in which the supported amount of sulfuric acid was 2.9 wt%, the yield of methylnaphthalene was as low as 2.8%, but in Example 7 where the supported amount of sulfuric acid was 5 to 20 wt%. In Example 10, the tetrahydronaphthalene by-product rate was as high as not less than the yield power of methylnaphthalene and was a low value of not more than 0.6%. [0034] Comparative Example 2
  • Example 16 Using zeolite beta (VALFOR CP 811BL-25, manufactured and sold by PQ Corp.), the same operation as in Example 16 was performed. As a result, the yield of methylnaphthalene was 12.9%, which was almost the same as that of Example 3 and the like, whereas the by-product rate of tetrahydronaphthalenes was an extremely high value of 77.1%.
  • 2-naphthalenesulfonic acid 0. 132g was dissolved in water 50 cm 3 in a beaker of 100 cm 3, an alumina reference catalyst set RC- AL04 of Catalysis Society supplied lg turned heated on a hot plate at 180 ° C, water was evaporated. Pure oxygen (Iwatani gas Manufacturing sold) in a stream of the resulting solid ⁇ 1, and calcined for 24 hours at 400 ° C, to prepare a catalyst of the present invention.
  • the calculated amount of sulfuric acid in the obtained alumina-supported sulfuric acid catalyst is 5.8 wt%, which is the same as in Example 7.
  • the yield of methylnaphthalenes was as high as 4.9%, and the by-product rate of tetrahydronaphthalenes was as low as 1.34%. .
  • Example 1 Alumina ⁇ Oxidative oxidation 0.077 7.0 6.5 0.53 Tungsten
  • Example 2 Alumina w Oxidation 0.122 1 1.0 1 1.7 0.66 Tungsten
  • Example 3 Alumina ⁇ Oxidation 0.160 14.5 12.9 0.73
  • Example 5 Alumina persistent oxidation 0.237 21.5 15.1 0.91 Tungsten
  • Example 6 Alumina.Oxidative oxidation 0.321 29.1 M .9 0.42
  • Example 2 Sulfuric acid on alumina 0.030 2.9 2.8 0.16
  • Example 7 Sulfuric acid on alumina 0.062 5.8 5.1 0.25
  • Example 8 Sulfuric acid on alumina 0.076 7.1 5.7 0.42
  • the present invention relates to a catalyst for producing methylnaphthalenes and a method for producing the same.
  • the catalyst has a sufficient activity and high methyl activity for the reaction of obtaining methylnaphthalenes from naphthalene and methanol. It is possible to provide an alumina-supported tungsten oxide and alumina-supported sulfuric acid catalyst having naphthalene selectivity and a low by-product rate of tetrahydronaphthalenes, and a method for producing methylnaphthalenes using these catalysts.
  • the present invention is a naphthalene derivative useful as an intermediate material for various industrial products.
  • the industrial production technology for methyl naphthalenes does not provide sufficient activity of the catalyst and has many by-products.
  • the present invention relates to, for example, PEN (polyethylene naphthalate) resin which is excellent as a starting material for vitamin K, excellent in heat resistance and gas-reactivity and is expected to be a substitute for PET resin, naphthoic acid, a fluorescent enhancer, It is useful as providing a technique for producing methylnaphthalenes suitable as an intermediate material such as a surfactant.
  • PEN polyethylene naphthalate

Abstract

A catalyst used for producing methylnaphthalenes by reacting naphthalene and methanol is disclosed which produces less by-products. Specifically disclosed is a catalyst for methylation of naphthalene used for reaction between naphthalene and methanol which is composed of an alumina-supported tungsten oxide or an alumina-supported sulfuric acid. Also disclosed is a method for producing methylnaphthalenes wherein such a catalyst is used. By using this catalyst, methylnaphthalenes can be produced at a sufficient reaction rate with high selectivity of naphthalenes while suppressing the by-product production rate of tetrahydronaphthalenes low.

Description

メチルナフタレン製造触媒及び製造法  Methylnaphthalene production catalyst and production method
技術分野  Technical field
[0001] 本発明は、メチルナフタレン類の製造触媒及び当該触媒を使用したメチルナフタレ ン類の製造法に関し、更に詳しくは、ナフタレンとメタノールからメチルナフタレン類の 合成反応において、充分な活性と高いメチルナフタレン類の選択性、低いテトラヒドロ ナフタレン類の副生率を有するアルミナ担持酸化タングステン及びアルミナ担持硫酸 触媒及びこれらの触媒を使用したメチルナフタレン類の製造法に関するものである。 本発明は、様々な工業製品の中間原料として有用である、ナフタレン誘導体の合成 技術の分野において、従来、メチルナフタレン類は、石油精製プロセスで得られる成 分からの回収、ナフタレンのメチルイ匕等により製造されていたが、触媒の十分な活性 が得られず、副生成物が多いため、高い効率で、メチルナフタレン類を得ることは困 難であったことを踏まえ、これらの問題点を確実に解決することが可能な、新しい触 媒及び当該触媒を使用したメチルナフタレン類の製造方法を提供するものである。 本発明で製造されるメチルナフタレン類は、高収率で、副生成物が少なぐし力も、硫 黄等の不純物を含まないため、例えば、ビタミン Kの出発原料、 PET榭脂の代替物と して期待されている、 PEN榭脂等の中間原料、また、ナフトェ酸、蛍光増伯剤、界面 活性剤、染料、医薬品等の中間原料として好適であり、これからの分野における、新 技術の開発、新産業の創出に大きな推進力となるものとして有用である。  The present invention relates to a catalyst for producing methylnaphthalenes and a method for producing methylnaphthalenes using the catalyst. More specifically, the present invention relates to a reaction for synthesizing methylnaphthalenes from naphthalene and methanol, which has sufficient activity and high methylnaphthalene. The present invention relates to an alumina-supported tungsten oxide and alumina-supported sulfuric acid catalyst having a low selectivity for the compounds and a low by-product rate of tetrahydronaphthalenes, and a method for producing methylnaphthalenes using these catalysts. INDUSTRIAL APPLICABILITY The present invention is useful in the field of synthesis of naphthalene derivatives, which is useful as an intermediate material for various industrial products. However, these problems were certainly solved, given that it was difficult to obtain methylnaphthalenes with high efficiency because the catalyst did not have sufficient activity and there were many by-products. The present invention provides a new catalyst and a method for producing methylnaphthalenes using the catalyst. The methylnaphthalenes produced in the present invention are high-yield, contain little by-products, and do not contain impurities such as sulfuric acid. It is suitable as an intermediate material such as PEN resin and an intermediate material for naphthoic acid, a fluorescent enhancer, a surfactant, a dye, and a pharmaceutical. It is useful as a great driving force for creating new industries.
背景技術  Background art
[0002] メチルナフタレン類は、メチルナフタレン（1ーメチルナフタレンと 2—メチルナフタレン )、ジメチルナフタレン（1, 2—、 1, 3—、 1, 4—、 1, 5—、 1, 6—、 1, 7—、 1, 8—、 2, 3— 、 2, 6—、 2, 7-ジメチルナフタレン)等の、（式 1)で表される化合物の総称である。メ チルナフタレン類は、有用な工業原料であり、例えば、 2—メチルナフタレンは、ビタミ ン Kの原料として用いられており、また、 2, 6—ジメチルナフタレンは、ポリエチレンナ フタレート（PEN)榭脂の原料として用いられている。その他にも、このメチルナフタレ ン類は、医薬、農薬、染料、界面活性剤、蛍光増白剤等の原料として有用な工業原 料である。 [0002] Methylnaphthalenes include methylnaphthalene (1-methylnaphthalene and 2-methylnaphthalene), dimethylnaphthalene (1, 2-, 1, 3-, 1, 4-, 1, 5-, 1, 6-, 1,7-, 1,8-, 2,3-, 2,6-, 2,7-dimethylnaphthalene) and the like. Methyl naphthalenes are useful industrial raw materials. For example, 2-methylnaphthalene is used as a raw material for vitamin K, and 2,6-dimethylnaphthalene is polyethylene naphthalate (PEN) resin. It is used as a raw material. In addition, methyl naphthalenes are industrial raw materials useful as raw materials for pharmaceuticals, agricultural chemicals, dyes, surfactants, optical brighteners, etc. Charge.
[0003] [化 1]  [0003] [Formula 1]
(R = CH3または H， CH3の数は 1以上)
Figure imgf000003_0001
(R = CH 3 or H, number of CH 3 is 1 or more)
Figure imgf000003_0001
[0004] これらの化合物の中で、特に有用な化合物は、 2—メチルナフタレン、 2, 6—ジメチ ルナフタレンであるが、 2—メチルナフタレンは 1ーメチルナフタレンの異性化によって 製造でき (特許文献 1参照）、 2, 6—ジメチルナフタレンは 2—メチルナフタレンのメチ ルイ匕によって製造できるので (特許文献 2参照）、メチルナフタレン類の混合物もまた 有用な工業原料である。  [0004] Among these compounds, particularly useful compounds are 2-methylnaphthalene and 2,6-dimethylnaphthalene, and 2-methylnaphthalene can be produced by isomerization of 1-methylnaphthalene (Patent Document 1), and 2,6-dimethylnaphthalene can be produced by methylidene 2-methylnaphthalene (see Patent Document 2), so that a mixture of methylnaphthalenes is also a useful industrial raw material.
[0005] メチルナフタレン類は、従来、石炭のコーキングにより製造されるコールタールや、 石油精製プロセスで得られる LCO (light cycle oil)に含まれる成分を精製して製 造されており、その精製方法に関する報告がなされている (特許文献 3— 7参照)。一 方、化学反応によってメチルナフタレン類ゃメチルナフタレン類に富む留分を合成す る報告もなされており、ノ ラフィンの環化脱水素反応 (特許文献 8参照）によって、ま た、テトラリン類の環化脱水素（特許文献 9参照）によって、ナフタレンとメチルナフタ レン類の混合物を得る方法が報告されている。これらの方法、あるいはこれらの組み 合わせによってメチルナフタレン類を製造することはできる力 需要の小さ!/、ナフタレ ンが副生 '残余するという問題点がある。  [0005] Methylnaphthalenes are conventionally produced by purifying components contained in coal tar produced by coking of coal or LCO (light cycle oil) obtained in a petroleum refining process. Has been reported (see Patent Documents 3-7). On the other hand, it has been reported to synthesize a fraction rich in methylnaphthalenes ゃ methylnaphthalenes by a chemical reaction, and the cyclodehydrogenation of noraffin (see Patent Document 8) and the synthesis of tetralins A method for obtaining a mixture of naphthalene and methylnaphthalenes by hydrodehydrogenation (see Patent Document 9) has been reported. The production of methylnaphthalenes by these methods or a combination of these methods has a small power demand! There is a problem that naphthalene remains as a by-product.
[0006] そこで、固体酸触媒の存在下で、ナフタレンをメタノールによってメチルイ匕する反応 が有用と考えられ、既に報告がなされている。例えば、ナフタレン、メチルナフタレン 類の混合物とメタノールから、 2, 6—ジメチルナフタレンを選択的に製造する方法が 報告されている（特許文献 10— 12参照）力 この反応ではナフタレンとメタノールから メチルナフタレン類を得る反応がその一部をなしている。これらの報告では、ナフタレ ンとメタノールからメチルナフタレン類を得る反応に対する触媒として、ゼォライト類が 用いられている。しかし、ゼォライト類を触媒として用いると、（式 2)で表される、テトラ ヒドロナフタレン類（例えば、 1, 2, 3, 4ーテトラヒドロナフタレン、メチルー 1, 2, 3, 4— テトラヒドロナフタレン、ジメチルー 1, 2, 3, 4ーテトラヒドロナフタレン等）の副生が避け られず、高 、効率でメチルナフタレン類を得ることができな ヽと 、う問題点がある。 [0006] Therefore, a reaction of methyl naphthalene with methanol in the presence of a solid acid catalyst is considered to be useful, and has already been reported. For example, a method for selectively producing 2,6-dimethylnaphthalene from a mixture of naphthalene and methylnaphthalenes and methanol has been reported (see Patent Documents 10 to 12). In this reaction, methylnaphthalenes are converted from naphthalene and methanol. Is part of that reaction. In these reports, zeolites are used as catalysts for the reaction to obtain methylnaphthalenes from naphthalene and methanol. However, when zeolites are used as a catalyst, tetrahydronaphthalenes (eg, 1,2,3,4-tetrahydronaphthalene, methyl-1,2,3,4- However, there is a problem that by-products of tetrahydronaphthalene and dimethyl-1,2,3,4-tetrahydronaphthalene cannot be avoided, and methylnaphthalenes cannot be obtained with high efficiency.
[化 2] CH3または H)
Figure imgf000004_0001
[Formula 2] CH 3 or H)
Figure imgf000004_0001
[0008] 特許文献 1 特開平 10- -167997号公報 [0008] Patent Document 1 JP-A-10-167997
特許文献 2 特開 2002- -128711号公報  Patent Document 2 JP 2002-128711 A
特許文献 3 特開平 07- -133239号公報  Patent Document 3 JP-A-07-133239
特許文献 4特開平 08- -120281号公報  Patent Document 4 JP 08-120281 A
特許文献 5 特開 2001- -139503号公報  Patent Document 5 JP 2001-139503 A
特許文献 6 特開 2002- -114718号公報  Patent Document 6 JP 2002-114718 A
特許文献 7 特開 2003- -026614号公報  Patent Document 7 JP 2003--026614 A
特許文献 8 特開平 06- -305988号公報  Patent Document 8 JP-A-06-305988
特許文献 9 特開平 2001— 278821号公報  Patent Document 9 JP 2001-278821 A
特許文献 10：特開 2003— 104918号公報  Patent Document 10: JP-A-2003-104918
特許文献 11 :特開 2002— 128711号公報  Patent Document 11: JP-A-2002-128711
特許文献 12：特開 2000— 344690号公報  Patent Document 12: JP-A-2000-344690
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0009] このような状況の中で、本発明者らは、上記従来技術に鑑みて、工業的に有用な 原料である、メチルナフタレン類の製造において、副生成物が少なぐ高い効率で、 メチルナフタレン類を得ることができる新し 、合成システムを開発することを目標にし て、鋭意研究を積み重ねた結果、アルミナ担持タングステン、又はアルミナ担持硫酸 触媒を用いることにより、これらの問題点を確実に解決することが可能なことを見出し 、本発明を完成させるに至った。即ち、本発明者らは、上記の課題を解決すベぐ各 種物質の上記反応に対する触媒作用を検討した結果、ナフタレンとメタノールからメ チルナフタレン類を得る反応に対して、充分な活性と高 ヽメチルナフタレン類選択性 、低 、テトラヒドロナフタレン類の副生率を有するアルミナ担持酸ィ匕タングステン及び アルミナ担持硫酸触媒を見出し、また、これらの触媒を使用して上記反応を行った結 果、充分な反応速度と高いメチルナフタレン類選択性、低いテトラヒドロナフタレン類 選択性を有するメチルナフタレン類の製造法を見出し、本発明を完成した。 [0009] Under such circumstances, the present inventors have considered, in view of the above-mentioned conventional technology, the production of methylnaphthalenes, which are industrially useful raw materials, has a high efficiency with few by-products. As a result of intensive studies with the aim of developing a new synthesis system capable of obtaining methylnaphthalenes, these problems have been reliably solved by using tungsten-on-alumina or sulfuric acid-on-alumina catalysts. They have found that it can be solved, and have completed the present invention. In other words, the present inventors have studied the catalytic action of the various substances to solve the above-mentioned problems on the above reaction, and as a result, have found that With respect to the reaction for obtaining tylnaphthalenes, an alumina-supported tungsten oxide and an alumina-supported sulfuric acid catalyst having sufficient activity and high methyl naphthalene selectivity, low and having a by-product rate of tetrahydronaphthalenes have been found. As a result of carrying out the above reaction using the above catalyst, a process for producing methylnaphthalenes having a sufficient reaction rate, high selectivity for methylnaphthalenes, and low selectivity for tetrahydronaphthalenes was found, and the present invention was completed.
[0010] 即ち、本発明の目的は、ナフタレンとメタノール力 メチルナフタレン類を製造する 触媒及びメチルナフタレン類の製造方法を提供することである。  [0010] That is, an object of the present invention is to provide a catalyst for producing naphthalene and methanol naphthalenes and a method for producing methylnaphthalenes.
また、本発明の目的は、ナフタレンとメタノールからメチルナフタレン類を得る反応 に対して、充分な活性を有し、メチルナフタレン類への選択性が高ぐテトラヒドロナフ タレン類の副生率が低 、触媒を提供することである。  Further, an object of the present invention is to have a sufficient activity for the reaction to obtain methylnaphthalenes from naphthalene and methanol, and to reduce the by-product rate of tetrahydronaphthalenes, which has high selectivity to methylnaphthalenes, It is to provide a catalyst.
また、本発明の目的は、ナフタレンとメタノールからメチルナフタレン類の製造に好 適な、アルミナ担持タングステン触媒、又はアルミナ担持硫酸触媒を提供することで ある。  Another object of the present invention is to provide an alumina-supported tungsten catalyst or an alumina-supported sulfuric acid catalyst which is suitable for producing methylnaphthalenes from naphthalene and methanol.
更に、本発明の目的は、ナフタレンとメタノールからメチルナフタレン類を得る反応 に関して、上記触媒を用いて、充分な反応速度を有し、メチルナフタレン類への選択 性が高ぐテトラヒドロナフタレン類の副生率が低いメチルナフタレン類の製造方法を 提供することである。  Furthermore, an object of the present invention is to provide a reaction for obtaining methylnaphthalenes from naphthalene and methanol, by using the above-mentioned catalyst, having a sufficient reaction rate and having high selectivity to methylnaphthalenes, which is a by-product of tetrahydronaphthalenes. An object of the present invention is to provide a method for producing methylnaphthalenes having a low rate.
課題を解決するための手段  Means for solving the problem
[0011] 上記課題を解決するための、本発明は、以下の技術的手段から構成される。  [0011] The present invention for solving the above-mentioned problems includes the following technical means.
(1)ナフタレンをメタノールによってメチルイ匕してメチルナフタレン類を製造する反応 に用いるナフタレンメチルイ匕触媒であって、アルミナに、酸ィ匕タングステン又は硫酸を 担持したことを特徴とするナフタレンメチルイ匕触媒。  (1) A naphthalene methyl iodide catalyst used in a reaction for producing methyl naphthalenes by converting naphthalene with methanol to produce methyl naphthalenes, wherein alumina is supported with tungsten iodide or sulfuric acid. catalyst.
(2)アルミナの比表面積が 100m2g_1以上で、酸ィ匕タングステンの担持量が 5— 40w t%であることを特徴とする前記（1)に記載のナフタレンメチルイ匕触媒。 (2) a specific surface area of the alumina is 100 m 2 g _1 or more, naphthalene methyl Lee spoon catalyst according to (1), wherein the supported amount of Sani匕tungsten is 5-40 w t%.
(3)アルミナの比表面積が 100m2g_1以上で、硫酸の担持量が 5— 20wt%であるこ とを特徴とする前記（1)に記載のナフタレンメチン化触媒。 (3) The naphthalene methination catalyst according to the above (1), wherein the specific surface area of alumina is 100 m 2 g_1 or more, and the supported amount of sulfuric acid is 5 to 20 wt%.
(4)前記 1から 3のいずれか〖こ記載のアルミナ担持酸ィ匕タングステン触媒又はアルミ ナ担持硫酸触媒の存在下に、ナフタレンとメタノールを反応させてメチルナフタレン 類を製造すること特徴とするメチルナフタレン類の製造方法。 (4) Methyl naphthalene by reacting naphthalene and methanol in the presence of the alumina-supported oxide catalyst or the alumina-supported sulfuric acid catalyst according to any one of the above 1 to 3. A process for producing methylnaphthalenes, characterized by producing the same.
(5)ナフタレンとメタノールの反応を、反応温度 300— 500°Cで行うことを特徴とする 前記 (4)に記載のメチルナフタレン類の製造方法。  (5) The method for producing methylnaphthalenes according to (4), wherein the reaction between naphthalene and methanol is performed at a reaction temperature of 300 to 500 ° C.
(6)原料の、ナフタレン Zメタノールのモル比を、 0. 005—0. 1とし、触媒 lgに対し て、 0. 01— 5gh_1の供給量で反応を行うことを特徴とする前記 (4)に記載のメチルナ フタレン類の製造方法。 (6) of the raw material, the molar ratio of naphthalene Z methanol, and 0.1 005-0. 1, with respect to the catalyst lg, above, wherein the reaction is carried out in the supply amount of 0. 01- 5GH _1 (4 The method for producing methylnaphthalenes according to the above.
(7)ナフタレンとメタノールの反応を、気相で行うことを特徴とする前記 (4)に記載のメ チルナフタレン類の製造法。  (7) The method for producing methyl naphthalenes according to (4), wherein the reaction between naphthalene and methanol is performed in a gas phase.
(8)アルミナに、タングステン塩類、硫酸、スルホン酸類又は硫酸アンモ-ゥムを担持 させた後、 300— 650°Cで焼成することを特徴とする、ナフタレンをメタノールによつ てメチルイ匕してメチルナフタレン類を製造する反応に用いるナフタレンメチルイ匕触媒 の製造方法。  (8) After supporting tungsten salts, sulfuric acid, sulfonic acids or ammonium sulfate on alumina, baking at 300 to 650 ° C. is performed, and naphthalene is methylated with methanol. A method for producing a naphthalene methyl iodide catalyst used in a reaction for producing methyl naphthalenes.
[0012] 次に、本発明を、更に詳細に説明する。  Next, the present invention will be described in more detail.
本発明の触媒及びその製造方法について説明すると、本発明においては、アルミ ナ担持酸化タングステン及び Z又はアルミナ担持硫酸を触媒として使用する。アルミ ナとしては、好適には，純度の高い αアルミナ、例えば、触媒学会供給の参照触組 RC— AL04、 JRC— AL08、 日揮ィ匕学株式会社製造販売の N611N、等が例示され 、 100m2g— 1以上の比表面積を有するものが好適に使用される。比表面積が小さいと 活性が低ぐ好ましくない。本発明では、これらは単独で、又は両方を併用して使用さ れる。 The catalyst of the present invention and the method for producing the same will be described. In the present invention, tungsten oxide supported on alumina and Z or sulfuric acid supported on alumina are used as catalysts. The alumina preferably is a high purity α-alumina, for example, Catalysis Society supply reference catalyst set RC- AL04, JRC- AL08, JGC I匕学Co. manufactured and sold N611N, etc. are exemplified, 100 m 2 Those having a specific surface area of g- 1 or more are preferably used. If the specific surface area is small, the activity is low, which is not preferable. In the present invention, these are used alone or in combination.
[0013] 酸化タングステン (WO )の含有量としては、アルミナ担持酸化タングステンの重量  [0013] The content of tungsten oxide (WO) is determined by the weight of alumina-supported tungsten oxide.
3  Three
に対して、 5— 40%の範囲であることが好ましぐ更に好ましくは、 10— 30%の範囲 である。硫酸 (H SO )の含有量としては、アルミナ担持硫酸の重量に対して、 5— 20  Is preferably in the range of 5-40%, and more preferably in the range of 10-30%. The content of sulfuric acid (H 2 SO 4) is 5-20
2 4  twenty four
%の範囲であることが好ましい。この範囲にあれば、ナフタレンとメタノール力 メチル ナフタレン類を得る反応に対して、充分な活性と、高いメチルナフタレン類の選択性 、低 、テトラヒドロナフタレン類の副生率を有する触媒を得ることができる。  % Is preferable. Within this range, it is possible to obtain a catalyst having sufficient activity, high selectivity for methylnaphthalenes, a low ratio of by-products of tetrahydronaphthalenes, and a sufficient activity for the reaction for obtaining naphthalene and methanolic methylnaphthalenes. .
[0014] 酸ィ匕タングステンをアルミナに担持する方法としては、例えば、タングステンを含む 塩類の水溶液にアルミナを投入し、加熱によって蒸発乾固し、焼成する方法、タンダ ステンを含む塩類の水溶液にアルミナを投入し、前駆体を吸着させた後に濾過や遠 心分離によって水を除去し、焼成する方法等が例示される。タングステンを含む塩類 としては、例えば、タングステン酸アンモニゥム（5 (NH ) 0 - 12WO )、及びその水 [0014] Examples of a method for supporting tungsten oxide on alumina include, for example, a method in which alumina is charged into an aqueous solution of salts containing tungsten, the mixture is evaporated to dryness by heating, and calcined. A method in which alumina is added to an aqueous solution of a salt containing stainless steel, the precursor is adsorbed, water is removed by filtration or centrifugal separation, and calcination is used. As salts containing tungsten, for example, ammonium tungstate (5 (NH 2) 0-12WO) and its water
4 2 3  4 2 3
和物のタングステン酸アンモ -ゥム 5水和物（5 (NH ) 0 - 12WO - 5H O)等が例示  Examples include the ammodimium tungstate pentahydrate (5 (NH) 0-12WO-5HO)
4 2 3 2  4 2 3 2
される。焼成条件としては、溶媒が蒸発し、タングステンを含む塩類が酸化タンダステ ンに転ィ匕する条件であれば良ぐ例えば、酸素あるいは空気中で、 300— 650°C、好 ましくは、 350— 500°C、での焼成が例示される。焼成温度が高すぎると、触媒の比 表面積が失われ、活性が低下するので好ましくない。  Is done. The firing conditions may be any as long as the solvent evaporates and the salts containing tungsten are converted to tantalum oxide, for example, in oxygen or air at 300-650 ° C., preferably 350-650 ° C. Firing at 500 ° C. is exemplified. If the firing temperature is too high, the specific surface area of the catalyst is lost, and the activity is undesirably reduced.
[0015] 硫酸を担持する方法としては、具体的には、例えば、硫酸、有機スルホン酸、硫酸 アンモ-ゥム等を含む溶液中にアルミナを投入し、加熱によって蒸発乾固し、焼成す る方法が例示される。有機スルホン酸を含む溶液としては、例えば、 2—ナフタレンス ルホン酸水溶液が例示される。焼成条件としては、溶媒が蒸発する温度に加熱する 力 有機スルホン酸を原料とする場合には、有機スルホン酸が硫酸根に転化する条 件であれば良ぐ例えば、酸素あるいは空気中で、 300— 650°C、好ましくは、 350 一 500°Cの焼成が例示される。焼成温度が高すぎると、触媒の比表面積が失われ、 活性が低下するので好ましくな、。酸ィ匕タングステンあるいは硫酸を担持する方法と しては、上記溶液中にアルミナを投入し、溶液中で吸着させたのちに濾過する方法も 例示される。 [0015] As a method for supporting sulfuric acid, specifically, for example, alumina is put into a solution containing sulfuric acid, organic sulfonic acid, ammonium sulfate, etc., evaporated to dryness by heating, and fired. A method is illustrated. Examples of the solution containing an organic sulfonic acid include, for example, an aqueous solution of 2-naphthalenesulfonic acid. The firing conditions are as follows: When the organic sulfonic acid is used as a raw material, the condition is such that the organic sulfonic acid is converted to a sulfate group. — An example is calcination at 650 ° C, preferably 350 to 500 ° C. If the calcination temperature is too high, the specific surface area of the catalyst is lost, and the activity is undesirably reduced. Examples of the method for supporting tungsten oxide or sulfuric acid include a method in which alumina is charged into the above solution, and the solution is adsorbed in the solution and then filtered.
[0016] 本発明のアルミナ担持酸ィ匕タングステン及びアルミナ担持硫酸は、粉末で用いても 、また、成型して用いても良い。成型体とするには、既に成型されたアルミナ担体を原 料として用いても良 ヽし、酸化タングステンある 、は硫酸を担持した後に成型しても 良い。成型方法としてはこれらの物質の純粋な試料を圧縮成型しても良いし、バイン ダーを用いても良い。  [0016] The alumina-supported tungsten oxide and the alumina-supported sulfuric acid of the present invention may be used as a powder or may be used after being molded. In order to form a molded body, an alumina carrier which has been molded may be used as a raw material, or tungsten oxide or sulfuric acid may be molded after supporting it. As a molding method, a pure sample of these substances may be compression molded, or a binder may be used.
[0017] 次に、本発明の触媒を使用して、メチルナフタレン類を製造する方法につい説明す ると、本発明は、上記のようにして製造したアルミナ担持酸ィ匕タングステン及び/又 はアルミナ担持硫酸触媒を用いて、ナフタレンとメタノールからメチルナフタレン類を 製造する。本発明で原料として使用するナフタレンとしては、精製されたナフタレンで も、ナフタレン及びメチルナフタレン類を含む混合物でも良ぐ例えば、石炭のコーキ ングにより製造されるコールタールや、石油精製プロセスで得られる LCO (light cy cle oil)、あるいはこれらを精製したものでも良い。 Next, the method for producing methylnaphthalenes using the catalyst of the present invention will be described. The present invention relates to the alumina-supported tungsten oxide and / or alumina produced as described above. Methylnaphthalenes are produced from naphthalene and methanol using a supported sulfuric acid catalyst. The naphthalene used as a raw material in the present invention may be a purified naphthalene or a mixture containing naphthalene and methylnaphthalenes. Coal tar manufactured by coaling, LCO (light cycle oil) obtained by a petroleum refining process, or a refined product thereof may be used.
[0018] 本発明の方法により、アルミナ担持酸ィ匕タングステン及びアルミナ担持硫酸を用い てナフタレンとメタノールからメチルナフタレン類を製造するに際し、その反応は気相 でも液相でも行うことができる。メチルナフタレン類を高収率で得るには、反応温度を 300— 500°C、好ましくは 350— 450°Cとする。反応温度が 300°C以下では、充分な 反応速度が得られないばかりか、生成物が触媒表面から脱離せず、失活の原因とな るおそれがある。反応温度が 500°C以上では、反応物や生成物の重合によって炭素 質が多く生成して触媒表面を被毒し、失活のおそれがあり、また、メチルナフタレン類 の選択性を下げる。反応は液相でも気相でも行える力 前記のような反応温度で実 施するためには、気相が好ましい。反応圧力は、常圧、加圧、減圧のいずれでも良い 力 減圧や大きな加圧では圧力を変えるための装置やエネルギーコストがかかるば 力りで何ら利点はな 、ので、 1一 5気圧が好まし 、。  According to the method of the present invention, when producing methylnaphthalenes from naphthalene and methanol using tungsten oxide supported on alumina and sulfuric acid supported on alumina, the reaction can be carried out in a gas phase or a liquid phase. To obtain methylnaphthalenes in high yield, the reaction temperature is set at 300-500 ° C, preferably 350-450 ° C. At a reaction temperature of 300 ° C or lower, not only a sufficient reaction rate cannot be obtained, but also the product does not detach from the catalyst surface, which may cause deactivation. At a reaction temperature of 500 ° C or higher, a large amount of carbonaceous material is generated by polymerization of the reactants and products, which may poison the catalyst surface, deactivate the catalyst, and lower the selectivity of methylnaphthalenes. The reaction can be performed in a liquid phase or a gas phase. In order to carry out the reaction at the reaction temperature as described above, the gas phase is preferable. The reaction pressure may be any of normal pressure, pressurization and depressurization. For depressurization or large pressurization, there is no advantage in power if a device for changing the pressure or energy cost is required, so 115 atm is preferable. Better ,.
[0019] 原料として用いるナフタレンとメタノールの混合比率については、ナフタレン Zメタノ ールモル比が 0. 005より小さいと、大量のメタノールを反応後に生成物から回収して 再利用しなければならず、装置とエネルギーコストが高くなる。一方、ナフタレン Zメタ ノールモル比が、 0. 1より大きいと、ナフタレンの重合により炭素質が多く生成し、触 媒表面を被毒し、失活のおそれがあり、また、メチルナフタレン類の選択性を下げる。 したがって、ナフタレン Zメタノールモル比は、 0. 005—0. 1力 子ましく、更に好まし くは 0. 01-0. 05である。ナフタレン'メタノール混合物の供給量は、触媒 lgに対し て 0. Olgh— 1以下では生産効率が低ぐ 5gh_1以上では充分な転化率が得られない 。したがって、ナフタレン'メタノール混合物の供給量は、触媒 lgに対して 0. 01— 5g h_1であることが好ましぐ更に好ましくは 0. 05— 2gh— 1である。 [0019] Regarding the mixing ratio of naphthalene and methanol used as raw materials, if the molar ratio of naphthalene Z methanol is less than 0.005, a large amount of methanol must be recovered from the product after the reaction and reused. Energy costs increase. On the other hand, if the molar ratio of naphthalene Z methanol is larger than 0.1, a large amount of carbonaceous material is generated by the polymerization of naphthalene, which may poison the catalyst surface and deactivate it. Lower. Therefore, the molar ratio of naphthalene to methanol is preferably 0.005 to 0.1, more preferably 0.01 to 0.05. The supply amount of the naphthalene 'methanol mixture, production efficiency is in contrast catalyst lg 0. Olgh- 1 or less is not sufficient conversion is obtained with Teigu 5GH _1 more. Accordingly, the supply amount of the naphthalene 'methanol mixture, 0. 01 is preferably a 5 g h _1 tool and more preferably from 0. 05- 2gh- 1 the catalyst lg.
[0020] 本発明では反応は、連続式、回分式のいずれであっても良いが、工業的見地から 連続法で行うことが望ましい。連続法で行う場合には、例えば、触媒を充填塔に詰め 、これにナフタレンとメタノールの混合物を供給する方法、あるいはナフタレンとメタノ ールを別個に供給する方法、あるいはこれらを不活性な溶媒に溶力して供給する方 法等が挙げられる。また、これらの原料を不活性な希釈ガス (例えば、窒素）とともに 供給する方法も挙げられる。 [0020] In the present invention, the reaction may be of a continuous type or a batch type, but is preferably performed by a continuous method from an industrial viewpoint. In the case of the continuous method, for example, a method in which a catalyst is packed in a packed column and a mixture of naphthalene and methanol is supplied thereto, or a method in which naphthalene and methanol are separately supplied, or a method in which these are added to an inert solvent, is used. There is a method of supplying by melting. In addition, these raw materials are mixed with an inert diluent gas (eg, nitrogen). There is also a method of supplying.
[0021] ナフタレンとメタノールの混合物を供給する方法としては、例えば、ナフタレンをメタ ノールに溶解し、この液体を蒸発器に供給し、気体混合物として供給する方法、ある いは液ィ匕したナフタレン中にメタノール蒸気を流通させ、気体混合物を得て供給する 方法、液ィ匕したナフタレンとメタノールを別々に蒸発器に供給し、気体混合物として 供給する方法等が例示される。  As a method of supplying a mixture of naphthalene and methanol, for example, a method of dissolving naphthalene in methanol and supplying this liquid to an evaporator and supplying it as a gaseous mixture, or a method of dissolving naphthalene in liquid naphthalene Examples of the method include a method in which methanol vapor is passed through to obtain and supply a gas mixture, and a method in which liquid naphthalene and methanol are separately supplied to an evaporator and supplied as a gas mixture.
[0022] 反応器力 取り出した気体生成物には、通常、過剰量のメタノールと未反応のナフ タレン類が含まれる。この気体生成物からメチルナフタレン類を取り出すには、気体 生成物を冷却し、最初に析出するナフタレンとメチルナフタレン類を回収し、回収物 力 蒸留によってメチルナフタレン類を分離精製する方法が例示される。  Reactor Power The removed gaseous product usually contains an excess amount of methanol and unreacted naphthalenes. In order to extract methylnaphthalenes from this gaseous product, there is exemplified a method of cooling the gaseous product, recovering naphthalene and methylnaphthalenes which are firstly precipitated, and separating and purifying the methylnaphthalenes by recovery and distillation. .
[0023] 以上説明したように、本発明は、ナフタレンとメタノールからメチルナフタレン類を製 造する反応に使用するための、副生物の生成が少ない新規な触媒、及び当該触媒 を用いたメチルナフタレン類の製造方法を提供するものである。本発明が、従来技術 と比較して、優れた効果を奏するための基本的な機構については、次のように説明 することができる。従来知られていたゼォライト触媒類は、高活性ではあるが、テトラヒ ドロナフタレン類を副生する。これは、ゼォライトが有する強酸点によって、メタノール 力も一酸ィ匕炭素と水素が発生し、この水素がナフタレンを水素化するため、あるいは メタノール力 ナフタレンへの水素の移行が気相水素を経な 、で直接起きるためと考 えられる。一方、ナフタレンのメチルイ匕に対しては、本発明のアルミナ担持酸化タンダ ステン及びアルミナ担持硫酸は、不要な強い酸点を持たず、弱い酸点のみを有する [0023] As described above, the present invention provides a novel catalyst for producing methyl naphthalenes from naphthalene and methanol, which produces a small amount of by-products, and a methyl naphthalene using the catalyst. Is provided. The basic mechanism by which the present invention achieves superior effects as compared with the related art can be described as follows. Conventionally known zeolite catalysts have high activity but produce by-produced tetrahydronaphthalenes. This is because, due to the strong acid point of zeolite, methanol power also generates carbon and hydrogen, and this hydrogen hydrogenates naphthalene, or the transfer of hydrogen to methanol power naphthalene does not pass through gas-phase hydrogen, It is thought that this happens directly at the site. On the other hand, with respect to methylphthalide of naphthalene, the alumina-supported tantalum oxide and alumina-supported sulfuric acid of the present invention do not have unnecessary strong acid sites but have only weak acid sites.
1S 弱い酸点でも充分な活性を持っために、メチルナフタレン類を製造するには、充 分な活性と、高い選択性を持つものと推測される。 1S Since it has sufficient activity even at weak acid sites, it is assumed that it has sufficient activity and high selectivity to produce methylnaphthalenes.
[0024] 一方、本発明者らは、以前の論文 (J. p ys. Chem. , B, Vol. 103, p. 7206— 7 213 (1999)及び J. Phys. Chem. , B, Vol. 104, p. 5511— 5518 (2000) )にお いて、 100m2g— 1程度の比表面積を有するジルコユア（ZrO )に、酸化タングステンを [0024] On the other hand, the present inventors have reported in a previous paper (J. pys. Chem., B, Vol. 103, p. 7206-7213 (1999) and J. Phys. Chem., B, Vol. 104, p. 5511-5518 (2000)), tungsten oxide was added to zirconia (ZrO) having a specific surface area of about 100m 2 g- 1.
2  2
10— 30wt%、もしくは硫酸を 5— 20wt%担持して 300— 650°Cで焼成すると、酸化 タングステンもしくは硫酸の単分子層が表面を覆い、単分子層特有の酸性質を発現 することを報告している力 本発明では、酸ィ匕タングステンを 10— 30wt%、もしくは 硫酸を 5— 30wt%担持して 300— 650°Cで焼成した際に、単分子層特有の酸性質 を発現し、上記のような好適な性質を示すことを見出したものである。 When baked at 300-650 ° C with 10-30wt% or 5-20wt% sulfuric acid supported, a monolayer of tungsten oxide or sulfuric acid covers the surface and exhibits the acid properties peculiar to the monolayer. In the present invention, 10 to 30 wt% of silicon nitride is used, or It has been found that, when 5 to 30% by weight of sulfuric acid is supported and calcined at 300 to 650 ° C., the acid properties peculiar to the monolayer are exhibited, and the above preferable properties are exhibited.
発明の効果  The invention's effect
[0025] 本発明により、 1)メチルナフタレン類の製造触媒及びその製造方法を提供すること ができる、 2)ナフタレンとメタノールからメチルナフタレン類を得る反応に対して、充分 な活性を有し、メチルナフタレン類への選択性が高ぐテトラヒドロナフタレン類の副 生率が低い触媒を提供できる、 3)当該触媒を用い、充分な反応速度を有し、メチル ナフタレン類への選択性が高ぐテトラヒドロナフタレン類の副生率が低い、ナフタレ ンとメタノールからメチルナフタレン類を製造方法を提供できる、 t ヽぅ格別の効果が 奏される。  [0025] According to the present invention, 1) a catalyst for producing methylnaphthalenes and a method for producing the same can be provided. 2) Methyl naphthalene has sufficient activity for the reaction to obtain methylnaphthalenes from naphthalene and methanol, A catalyst having a high selectivity to naphthalenes and a low by-product rate of tetrahydronaphthalenes can be provided.3) A tetrahydronaphthalene having a sufficient reaction rate and a high selectivity to methyl naphthalenes using the catalyst. It can provide a method for producing methyl naphthalenes from naphthalene and methanol, which has a low by-product rate, and has an extraordinary effect.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0026] 以下に、本発明の触媒、その調製法、及びその触媒を用いた反応例を実施例に基 づいて具体的に説明する力 本発明は、これらの実施例によって何ら限定されるもの ではない。 The following will specifically describe the catalyst of the present invention, a method for preparing the same, and a reaction example using the catalyst, based on examples. The present invention is not limited to these examples. is not.
実施例  Example
[0027] 実施例 1一 6 Example 11
表 1に記載した量の、タングステン酸アンモ-ゥム 5水和物（和光純薬製造販売）を 、 100cm3のビーカー中で、水 50cm3に溶解し、比表面積 151m2g— 1を有する触媒 学会配付のアルミナ参照触組 RC— AL04を lg投入し、 160°Cのホットプレート上で 加熱、水を蒸発させた。得られた固体を、空気中、 400°Cで 4時間焼成して、本発明 の触媒を作製した。 The amounts listed in Table 1, ammonium tungstate - © arm pentahydrate (Wako Pure Chemical manufactured and sold) in a beaker of 100 cm 3, was dissolved in water 50 cm 3, having a specific surface area 151m 2 g- 1 1g of RC-AL04, a reference material of alumina distributed by the Catalysis Society of Japan, was charged, and heated on a hot plate at 160 ° C to evaporate water. The obtained solid was calcined in air at 400 ° C. for 4 hours to produce a catalyst of the present invention.
[0028] 次に、上記触媒 0. 2gを内径 8mmのパイレックス (登録商標)ガラス製反応管に詰 め、 410°Cで 50cm3min— 1のヘリウム (イワタ-ガス製造販売）気流中で 1時間前処理 した後、 410°Cで 50cm3min— 1のヘリウムを流通させつつ、ナフタレン（和光純薬製 造販売）とメタノール (和光純薬製造販売）の混合溶液 (ナフタレン Zメタノールモル 比 0. 01)を、 1. 06gh— 1の速度で供給し、反応管出口に現れた生成物を、 0°Cに冷 やして液体'固体を捕集し、キヤビラリ一力ラム (信和化工製 DMN— 267)を備えたガ スクロマトグラフ（島津製作所製 GC— 2010)を用いて分析した。表 1に、得られたメチ ルナフタレン類の収率及びテトラヒドロナフタレン類の副生率を示した。 Next, 0.2 g of the above catalyst was packed in a Pyrex (registered trademark) glass reaction tube having an inner diameter of 8 mm, and placed in a stream of helium (manufactured and sold by Iwata-Gas) of 50 cm 3 min- 1 at 410 ° C. after time preprocessing, while flowing 50 cm 3 min- 1 in helium at 410 ° C, naphthalene (Wako pure Chemical manufacturing sales) and methanol mixed solution of (Wako pure Chemical manufactured and sold) (naphthalene Z methanol molar ratio 0 01) is supplied at a speed of 1.06 gh- 1 and the product that appears at the outlet of the reaction tube is cooled to 0 ° C to collect liquids and solids. The analysis was performed using a gas chromatograph equipped with DMN-267) (GC-2010, manufactured by Shimadzu Corporation). Table 1 shows the obtained meth The yield of lunaphthalenes and the by-product rate of tetrahydronaphthalenes were shown.
[0029] 表 1中、メチルナフタレン類の収率は、 1ーメチルナフタレン、 2—メチルナフタレン、 1 , 2 ジメチルナフタレン、 1, 3 ジメチルナフタレン、 1, 4 ジメチルナフタレン、 1, 6 ジメチルナフタレン、 1, 7 ジメチルナフタレン、 1, 8 ジメチルナフタレン、 2, 3—ジ メチルナフタレン、 2, 6 ジメチルナフタレン、 2, 7 ジメチルナフタレンの収量の合計 をナフタレンの供給量で除した数値で示した。但し、他のメチルナフタレン類の収量 は、極めて低い値であったので無視した。  In Table 1, the yields of methylnaphthalenes are as follows: 1-methylnaphthalene, 2-methylnaphthalene, 1,2 dimethylnaphthalene, 1,3 dimethylnaphthalene, 1,4 dimethylnaphthalene, 1,6 dimethylnaphthalene, 1 The total yield of 2,7-dimethylnaphthalene, 1,8-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, and 2,7-dimethylnaphthalene was calculated by dividing the total yield by the amount of naphthalene supplied. However, the yields of other methylnaphthalenes were ignored because they were extremely low.
[0030] また、テトラヒドロナフタリン類の副生率は、 1, 2, 3, 4—テトラヒドロナフタレン、 5—メ チノレー 1, 2, 3, 4ーテトラヒドロナフタレン、 6—メチノレー 1, 2, 3, 4ーテトラヒドロナフタレ ン、 5, 6—ジメチル— 1, 2, 3, 4—テトラヒドロナフタレン、 5, 7—ジメチル— 1, 2, 3, 4— テトラヒドロナフタレン、 5, 8 ジメチルー 1, 2, 3, 4ーテトラヒドロナフタレン、 6, 7—ジメ チルー 1, 2, 3, 4ーテトラヒドロナフタレン収量の合計を、ナフタレンの供給量で除した 数値で示した。但し、他のテトラヒドロナフタレン類の収量は、極めて低い値であった ので無視した。  [0030] The by-product rates of tetrahydronaphthalenes are as follows: 1,2,3,4-tetrahydronaphthalene, 5-methinoley 1,2,3,4-tetrahydronaphthalene, 6-methynolae 1,2,3,4 -Tetrahydronaphthalene, 5,6-dimethyl-1,2,3,4-tetrahydronaphthalene, 5,7-dimethyl-1,2,3,4-tetrahydronaphthalene, 5,8 dimethyl-1,2,3 The sum of the yields of 4-tetrahydronaphthalene and 6,7-dimethyl-1,2,3,4-tetrahydronaphthalene was shown by a value obtained by dividing the total yield of naphthalene. However, the yields of other tetrahydronaphthalenes were ignored because they were extremely low.
[0031] 表 1に示したように、メチルナフタレン類の収率は 5%以上と充分高ぐテトラヒドロナ フタレン類副生率は 1%以下と低い値であった。中でも、酸ィ匕タングステン含有量が 1 0— 30%の範囲にある実施例 2— 6では、メチルナフタレン類収率が 10%以上と高 い値であった。  [0031] As shown in Table 1, the yield of methylnaphthalenes was sufficiently high at 5% or more, and the by-product rate of tetrahydronaphthalenes was as low as 1% or less. Among them, in Examples 2-6 in which the content of tungsten oxide was in the range of 10-30%, the yield of methylnaphthalenes was as high as 10% or more.
[0032] 実施例 7— 10及び比較例 1  Examples 7-10 and Comparative Example 1
表 1に記載の量の、硫酸を含む 0. 5moldm— 3の硫酸 (和光純薬製造販売）を、 100 cm3のビーカー中で、水 20cm3に希釈し、触媒学会配付のアルミナ参照触組 RC— AL04を lg投入し、 160°Cのホットプレート上で加熱、水を蒸発させた。得られた固 体を空気中、 400°Cで 4時間焼成して、本発明の触媒を作製した。 The amount shown in Table 1, the sulfuric acid 0. 5moldm- 3 containing sulfuric acid (Wako Pure Chemical manufactured and sold), in 100 cm 3 beaker, diluted with water 20 cm 3, alumina reference catalyst of sets of Catalysis Society distribution 1 g of RC-AL04 was charged, and heated on a hot plate at 160 ° C. to evaporate water. The obtained solid was calcined in air at 400 ° C. for 4 hours to produce a catalyst of the present invention.
[0033] 上記触媒を用いて実施例 1一 6と同様の操作を行ない、メチルナフタレン類を製造 した。 表 1に示したとおり、硫酸の担持量が 2. 9wt%である比較例 1では、メチルナ フタレン収率が 2. 8%と低いが、硫酸担持量が 5— 20wt%である実施例 7— 10では 、メチルナフタレン収率力 以上と高ぐテトラヒドロナフタレン類副生率は 0. 6%以 下で低い値であった。 [0034] 比較例 2 Using the above catalyst, the same operation as in Example 16 was performed to produce methylnaphthalenes. As shown in Table 1, in Comparative Example 1 in which the supported amount of sulfuric acid was 2.9 wt%, the yield of methylnaphthalene was as low as 2.8%, but in Example 7 where the supported amount of sulfuric acid was 5 to 20 wt%. In Example 10, the tetrahydronaphthalene by-product rate was as high as not less than the yield power of methylnaphthalene and was a low value of not more than 0.6%. [0034] Comparative Example 2
ゼォライトベータ (VALFOR CP 811BL— 25、PQ Corp.製造販売）を用いて 、実施例 1一 6と同様の操作を行った。その結果、メチルナフタレン収率が 12. 9%で 、実施例 3等と同程度であるのに対し、テトラヒドロナフタレン類の副生率が 77. 1%と 極めて高い値であった。  Using zeolite beta (VALFOR CP 811BL-25, manufactured and sold by PQ Corp.), the same operation as in Example 16 was performed. As a result, the yield of methylnaphthalene was 12.9%, which was almost the same as that of Example 3 and the like, whereas the by-product rate of tetrahydronaphthalenes was an extremely high value of 77.1%.
[0035] 実施例 11 Example 11
2-ナフタレンスルホン酸 0. 132gを、 100cm3のビーカー中で水 50cm3に溶解し、 触媒学会供給のアルミナ参照触組 RC— AL04を lg投入し、 180°Cのホットプレート 上で加熱、水を蒸発させた。得られた固体を δΟοπΛιώΤ1の純酸素 (イワタニガス製 造販売)気流中、 400°Cで 24時間焼成して、本発明の触媒を作製した。得られたァ ルミナ担持硫酸触媒中の、硫酸の計算量は、実施例 7と同じぐ 5. 8wt%である。こ の触媒を用いて実施例 1一 6と同様の操作を行ったところ、メチルナフタレン類収率 は 4. 9%と高ぐテトラヒドロナフタレン類副生率は 1. 34%と低い値であった。 2-naphthalenesulfonic acid 0. 132g, was dissolved in water 50 cm 3 in a beaker of 100 cm 3, an alumina reference catalyst set RC- AL04 of Catalysis Society supplied lg turned heated on a hot plate at 180 ° C, water Was evaporated. Pure oxygen (Iwatani gas Manufacturing sold) in a stream of the resulting solid δΟοπΛιώΤ 1, and calcined for 24 hours at 400 ° C, to prepare a catalyst of the present invention. The calculated amount of sulfuric acid in the obtained alumina-supported sulfuric acid catalyst is 5.8 wt%, which is the same as in Example 7. When the same operation as in Example 16 was performed using this catalyst, the yield of methylnaphthalenes was as high as 4.9%, and the by-product rate of tetrahydronaphthalenes was as low as 1.34%. .
[0036] [表 1] mm タングステン 酸化タンダス メチルナ テ ト ラ ヒ ド 酸アンモニゥ テンあるいは フタレン 口ナフタ レ ム 5水和物あ 硫酸把持 Μ 類 収 率 ン類 Θ!|生 るいは硫酸添 (wt %) (%) (%) [Table 1] mm tungsten tungsten oxide methyl tantalate ammonium nitrate ammonium nitrate or phthalene-opened naphthalene pentahydrate sulfuric acid gripping 類 Class yield Θ! | Raw or sulfated (wt% ) (%) (%)
加虽 (g)  Heating (g)
施例 1 アルミナ ^持酸化 0.077 7.0 6.5 0.53 タングステン  Example 1 Alumina ^ Oxidative oxidation 0.077 7.0 6.5 0.53 Tungsten
施例 2 アルミナ w持酸化 0.122 1 1.0 1 1.7 0.66 タングステン  Example 2 Alumina w Oxidation 0.122 1 1.0 1 1.7 0.66 Tungsten
実施例 3 アルミナ^持酸化 0.160 14.5 12.9 0.73  Example 3 Alumina ^ Oxidation 0.160 14.5 12.9 0.73
タングステン  Tungsten
'太施例 4 アルミナ w持酸化 0.199 18.0 16.9 0.74  '' Taita Example 4 Alumina w Oxidation 0.199 18.0 16.9 0.74
タングステン  Tungsten
施例 5 アルミナ抝持酸化 0.237 21.5 15.1 0.91 タングステン  Example 5 Alumina persistent oxidation 0.237 21.5 15.1 0.91 Tungsten
¾施例 6 アルミナ .持酸化 0.321 29.1 M .9 0.42  Example 6 Alumina.Oxidative oxidation 0.321 29.1 M .9 0.42
タングステン  Tungsten
比較例 2 アルミナ担持硫酸 0.030 2.9 2.8 0.16 施例 7 アルミナ担持硫酸 0.062 5.8 5.1 0.25 実施例 8 アルミナ 持硫酸 0.076 7.1 5.7 0.42  Comparative Example 2 Sulfuric acid on alumina 0.030 2.9 2.8 0.16 Example 7 Sulfuric acid on alumina 0.062 5.8 5.1 0.25 Example 8 Sulfuric acid on alumina 0.076 7.1 5.7 0.42
アルミナ担持硫酸 ϋ.11 1 10.0 5.5 0.47 灾施例 10 アルミナ担持硫酸 0.185 15.6 4.9 0.57 比較例 3 ベー夕ゼォライト - - 12.9 77.1 産業上の利用可能性 Sulfuric acid on alumina ϋ.11 1 10.0 5.5 0.47 灾 Example 10 Sulfuric acid on alumina 0.185 15.6 4.9 0.57 Comparative example 3 Beyonce zeolite--12.9 77.1 Industrial applicability
以上詳述したように、本発明は、メチルナフタレン類製造触媒及びその製造方法に 係るものであり、本発明により、ナフタレンとメタノールからメチルナフタレン類を得る 反応に対して、充分な活性と高いメチルナフタレン類選択性、低いテトラヒドロナフタ レン類の副生率を有するアルミナ担持酸化タングステン及びアルミナ担持硫酸触媒 、及びこれらの触媒を使用したメチルナフタレン類の製造方法を提供することができ る。本発明は、様々な工業製品の中間原料として有用であるナフタレン誘導体のな かで、従来、メチルナフタレン類の工業的製造技術では、触媒の十分な活性が得ら れず、副生成物が多いため、高い効率でメチルナフタレン類を得ることが困難である 等の従来技術の問題点を確実に解決することが可能な、新規な触媒、及び当該触 媒を用いたメチルナフタレン類の製造技術を提供することを可能とするものである。 本発明は、例えば、ビタミン Kの出発原料、耐熱性、ガスノ リア一性に優れ PET樹脂 の代替物として期待されている PEN (ポリエチレンナフタレート)榭脂、また、ナフトェ 酸、蛍光増伯剤、界面活性剤等の中間原料として好適なメチルナフタレン類の製造 技術を提供するものとして有用である。  As described in detail above, the present invention relates to a catalyst for producing methylnaphthalenes and a method for producing the same. According to the present invention, the catalyst has a sufficient activity and high methyl activity for the reaction of obtaining methylnaphthalenes from naphthalene and methanol. It is possible to provide an alumina-supported tungsten oxide and alumina-supported sulfuric acid catalyst having naphthalene selectivity and a low by-product rate of tetrahydronaphthalenes, and a method for producing methylnaphthalenes using these catalysts. The present invention is a naphthalene derivative useful as an intermediate material for various industrial products.Conventionally, the industrial production technology for methyl naphthalenes does not provide sufficient activity of the catalyst and has many by-products. To provide new catalysts that can surely solve the problems of the prior art, such as difficulty in obtaining methylnaphthalenes with high efficiency, and a technology for producing methylnaphthalenes using the catalyst. It is possible to do. The present invention relates to, for example, PEN (polyethylene naphthalate) resin which is excellent as a starting material for vitamin K, excellent in heat resistance and gas-reactivity and is expected to be a substitute for PET resin, naphthoic acid, a fluorescent enhancer, It is useful as providing a technique for producing methylnaphthalenes suitable as an intermediate material such as a surfactant.

Claims

請求の範囲 The scope of the claims
[1] ナフタレンをメタノールによってメチルイ匕してメチルナフタレン類を製造する反応に 用いるナフタレンメチルイ匕触媒であって、アルミナに、酸ィ匕タングステン又は硫酸を担 持したことを特徴とするナフタレンメチルイ匕触媒。  [1] A naphthalene methyl iodide catalyst for use in a reaction for producing methyl naphthalenes by converting naphthalene with methanol to produce methyl naphthalenes, characterized in that naphthalene methyl iodide is characterized in that alumina is supported with tungsten oxide or sulfuric acid. Dani catalyst.
[2] アルミナの比表面積が 100m2g_1以上で、酸ィ匕タングステンの担持量が 5— 40wt[2] The specific surface area of alumina is 100 m 2 g _1 or more, and the loading amount of tungsten oxide is 5-40 wt.
%であることを特徴とする請求項 1に記載のナフタレンメチルイ匕触媒。 2. The naphthalene methyl iodide catalyst according to claim 1, wherein
[3] アルミナの比表面積が 100m2g_1以上で、硫酸の担持量が 5— 20wt%であることを 特徴とする請求項 1に記載のナフタレンメチン化触媒。 [3] The naphthalene methination catalyst according to claim 1, wherein the specific surface area of alumina is 100 m 2 g_1 or more, and the supported amount of sulfuric acid is 5 to 20 wt%.
[4] 請求項 1から 3の 、ずれかに記載のアルミナ担持酸ィ匕タングステン触媒又はアルミ ナ担持硫酸触媒の存在下に、ナフタレンとメタノールを反応させてメチルナフタレン 類を製造すること特徴とするメチルナフタレン類の製造方法。 [4] A method for producing methylnaphthalenes by reacting naphthalene and methanol in the presence of the alumina-supported tungsten oxide catalyst or the alumina-supported sulfuric acid catalyst according to any one of claims 1 to 3. A method for producing methylnaphthalenes.
[5] ナフタレンとメタノールの反応を、反応温度 300— 500°Cで行うことを特徴とする請 求項 4に記載のメチルナフタレン類の製造方法。 [5] The method for producing methylnaphthalenes according to claim 4, wherein the reaction between naphthalene and methanol is performed at a reaction temperature of 300 to 500 ° C.
[6] 原料の、ナフタレン/メタノールのモル比を、 0. 005—0. 1とし、触媒 lgに対して、[6] The molar ratio of naphthalene / methanol of the raw material is set to 0.005-0.1,
0. 01- 5gh_1の供給量で反応を行うことを特徴とする請求項 4に記載のメチルナフ タレン類の製造方法。 Mechirunafu array type such method according to claim 4, wherein the reaction is performed at a feed rate of 0. 01- 5gh _1.
[7] ナフタレンとメタノールの反応を、気相で行うことを特徴とする請求項 4に記載のメチ ルナフタレン類の製造法。  [7] The method for producing methylnaphthalenes according to claim 4, wherein the reaction between naphthalene and methanol is performed in a gas phase.
[8] アルミナに、タングステン塩類、硫酸、スルホン酸類又は硫酸アンモ-ゥムを担持さ せた後、 300— 650°Cで焼成することを特徴とする、ナフタレンをメタノールによってメ チルイ匕してメチルナフタレン類を製造する反応に用いるナフタレンメチルイ匕触媒の製 造方法。 [8] Alumina is loaded with tungsten salts, sulfuric acid, sulfonic acids or ammonium sulfate, and then calcined at 300 to 650 ° C. Naphthalene is methylated by methanol with methanol. A method for producing a naphthalenemethylidani catalyst used in a reaction for producing naphthalenes.
PCT/JP2005/003343 2004-03-10 2005-02-28 Catalyst and method for producing methylnaphthalene WO2005087368A1 (en)

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