JP2012250956A - Method for producing phenol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a phenol compound having a simple process route, and not depending on a method related to aromatic compounds, such as a cumene method, a toluene raw material oxidative decarboxylation reaction method, a benzene chlorination hydrolysis method, a benzenesulfonic acid alkali fusion method, concerning phenol and alkylphenol compounds which are very important compounds as various synthetic resins, pharmaceuticals or chemical products.SOLUTION: In this method for producing a phenol compound, ethanol, preferably methanol and ethanol are reacted in the presence of a solid catalyst containing iron.

Description

The present invention relates to a method for producing a phenol compound.

Phenol and alkylphenol compounds are very important compounds as raw materials for various synthetic resins, pharmaceuticals and chemical products. The main methods for producing phenol are as follows: 1) Method of producing cumene hydroperoxide obtained by oxygen oxidation of cumene simultaneously with acetone (Patent Document 1) 2) Oxidation of benzoic acid obtained by oxidation of toluene A method for producing by decarboxylation (Patent Document 2), 3) a method for hydrolyzing monochlorobenzene obtained by chlorinating benzene, 4) a method for alkali-melting benzenesulfonic acid obtained by sulfonating benzene, etc. It is. (Non-patent Document 1) As a method for producing an alkylphenol compound, a method for producing phenol by alkylating phenol with alcohol, halogenated alkyl, olefin or the like is known. (Non-Patent Document 2)

  In these methods, in most cases, aromatic compounds contained in crude oil and coal, or obtained by decomposition, are used as starting materials, so the process route to the final product phenol or alkylphenol compound is long and intermediate. This is a manufacturing method with a large environmental impact, such as a large amount of energy consumed due to decomposition and refining operations in the process and a large amount of by-product waste.

  On the other hand, ethanol is produced in large quantities by fermenting plant-derived biomass raw materials, and has recently attracted attention as a compound with little environmental impact. Methanol is a compound with little by-product waste that can be directly produced from synthesis gas obtained by steam reforming or partial oxidation of petroleum gas such as methane. If phenol can be directly synthesized from these, a process with a very low environmental load can be constructed, but there has been no disclosure regarding such a method.

Japanese Examined Patent Publication No. 62-047855 Japanese Patent Application Laid-Open No. 07-017866

Industrial Organic Chemistry 4th Edition, Klaus Weissermel, Hans-Jurgen Arpe, Translated by Takashi Deguchi, Tokyo Chemical Doujin, p.389-399, 1996 Industrial Organic Chemistry 4th Edition, Klaus Weissermel, Hans-Jurgen Arpe, translated by Takashi Deguchi, Tokyo Chemical Doujin, p403-405, 1996

  An object of the present invention is to solve the above-described problems in the prior art, and to provide a method for producing a phenol compound that has a simple process route and does not depend on an aromatic compound.

As a result of intensive studies to solve the above problems, the present inventors have found that the following items can be solved.

[1] A method for producing a phenol compound, comprising reacting ethanol or methanol and ethanol in the presence of a solid catalyst containing iron.
[2] The production method according to [1], wherein the solid catalyst includes at least one selected from metallic iron, iron oxide, iron hydroxide, and iron oxyhydroxide.
[3] The method according to [1] or [2], wherein the reaction is carried out in a flow system under gas phase conditions.
[4] The method according to any one of [1] to [3], wherein the phenol compound is a compound in which at least one hydrogen on an aromatic ring of phenol or phenol is substituted with a methyl group or an ethyl group.

  According to the present invention, a phenol compound can be produced by a very simple process of reacting ethanol or methanol and ethanol in the presence of a solid catalyst containing iron.

The present invention is a method for producing a phenol compound by a very simple process of reacting ethanol or ethanol and methanol in the presence of a solid catalyst containing iron. Although ethanol can be used alone, it is preferable to use both ethanol and methanol because the yield of the phenol compound increases when mixed with methanol. When both alcohols are used, they need only exist on the catalyst in a mixed state, and there are no particular restrictions on the mixing method, supply method, and the like. The supply ratio onto the catalyst is 25 or less in terms of methanol / ethanol molar ratio, but is preferably in the range of 0.1 to 20, particularly preferably 0.5 to 10.

There is no restriction | limiting in particular in the methanol used for this reaction. Methanol produced by any method can be used. For example, a synthesis gas (containing carbon monoxide and hydrogen) obtained by steam reforming or partial oxidation of a substance mainly composed of carbon and hydrogen such as methane, butane and coal. Produced by high-pressure catalytic reaction using a copper-based catalyst, etc., or produced by direct or indirect partial oxidation of methane, obtained from dry distillation of wood, carboxylic acid What was collect | recovered from the methyl ester manufacturing process, the methylation reaction process, etc. can be used. Although there is no restriction | limiting in particular in the purity and moisture content, It is preferable to use a thing with the highest purity as possible.

There is no restriction | limiting in particular in ethanol used for this reaction. Ethanol produced by any method can be used, for example, one produced by hydration reaction of ethylene, or a rhodium-based heterogeneous catalyst (solid catalyst), cobalt and / or ruthenium-based homogeneous catalyst (from a synthesis gas) And those produced by hydrogenation reaction of acetic acid or acetate ester, those produced by hydrolysis reaction of carboxylic acid ethyl ester, and the like. Since ancient times, ethanol production by fermentation of plant raw materials containing carbohydrates and starches has been widely performed around the world, but in recent years, it has attracted attention as a chemical raw material and fuel that does not depend on fossil fuels, and is edible. The production amount of “biomass ethanol” produced from biomass including other raw materials is rapidly increasing and can be used.
There is no particular limitation on its purity and moisture content. An azeotropic composition of water and ethanol (about 96% by weight), a product further reduced in water content by adding another azeotropic agent and distillation, or one arbitrarily selected from anhydrous ethanol can be used. However, it is preferable to use one having as high purity as possible.

The solid catalyst containing iron used in the present invention is not limited as long as metallic iron or an iron compound is present on the catalyst surface and acts with an alcohol compound.
There are no particular restrictions on the starting material of the iron component contained in this catalyst, and iron oxide, iron hydroxide, iron oxyhydroxide, iron chloride, iron bromide, iron nitrate of the valence that metal iron and iron atoms can take, Compounds such as iron sulfate, iron acetate, iron formate, and iron oxalate can be used. In particular, an iron compound capable of deriving iron hydroxide is particularly suitable because the formation of a phenol compound is well observed in a catalyst using trivalent iron hydroxide as a starting material.
Furthermore, at least a portion of the iron hydroxide on the catalyst during the reaction was dehydrated by heating and reduced by the raw alcohol compound, so it was generated not only from iron hydroxide but also dehydrated and / or reduced. An iron compound is also effective. Specifically, metallic iron or iron oxides such as FeO, α-Fe ₂ O ₃ , γ-Fe ₂ O ₃ and Fe ₃ O ₄ , and iron hydroxide such as Fe (OH) ₂ and Fe (OH) ₃ In particular, iron oxyhydroxides such as FeO (OH), and mixtures or mixed crystal compositions thereof are particularly preferably used as catalysts.
There is no particular limitation on the iron content in the catalyst of the present invention. Moreover, there is no special restriction | limiting also about the shape and particle size of a catalyst, The optimal thing can be used according to the reaction system, the utilization method of a catalyst, etc.

The catalyst of the present invention may contain additives in addition to the active component mainly composed of iron. The additive includes a co-catalyst for increasing the catalytic action, a molding aid added for forming the catalyst, and a catalyst carrier used for supporting the catalyst component. Examples of the promoter component include compounds of one or more elements selected from Groups 2 to 17 of the periodic table. When potassium or the like is added as an alkali metal element of Group 1 of the periodic table, side reactions accompanied by decomposition of methanol remarkably proceed, which is not preferable. Examples of molding aids include graphite, smectite, talc, and alumina gel. Examples of the catalyst carrier include silica, alumina, silica-alumina, magnesia, zirconia, titania, activated carbon, silicon carbide and the like.

There is no restriction | limiting in particular in the manufacturing method of the solid catalyst containing the iron of this invention, A conventionally well-known manufacturing method of a catalyst can be used. For example, a) a method of precipitating from an iron compound solution using an appropriate precipitant, b) a method of mixing and kneading the iron compound with the catalyst carrier, c) a method of impregnating the catalyst carrier with the iron compound solution, etc. These methods or a combination of these methods can be used. Moreover, when adding catalyst addition components other than iron, there is no restriction | limiting in particular in the addition method, A conventionally well-known method can be used. For example, a) a method of dissolving the compound of the additive component in the iron compound solution and precipitating with an appropriate precipitant, b) a method of mixing and kneading the iron compound and the compound of the additive component, c) a solution of the iron compound For example, a compound of an additive component is dissolved and impregnated and supported on a catalyst carrier. These methods or a combination of these methods can be used as appropriate. Furthermore, the catalyst can be subjected to pretreatment such as drying, calcination, and reduction in the reaction, and the pretreatment conditions are not limited.

The reaction of the present invention can be carried out in either a gas phase or a gas-liquid mixed phase (including a trickle phase). For this purpose, a method of supplying a raw alcohol and bringing it into contact with a gas or liquid alcohol and a catalyst, or a method of supplying an alcohol together with a solvent having a boiling point higher than that of the raw alcohol and bringing it into contact with the catalyst can be used. A gas phase reaction that can be easily carried out at a low reaction pressure is more preferred. The method of using the catalyst in the reaction of the present invention is not particularly limited as long as it is a reaction method using a solid catalyst, and conventionally known methods such as a fixed bed, a fluidized bed, and a suspension bed can be employed. The reaction method of the present invention may be either a distribution method or a batch method. Since the contact time between the catalyst and the raw material alcohol can be easily controlled, a reaction method of the flow method is more preferable. As reaction conditions, the reaction temperature is usually 200 to 600 ° C., preferably 250 to 450 ° C., and the reaction pressure is usually gauge pressure and normal pressure to 15 MPa. , Preferably normal pressure to 5 MPa. , Particularly preferably normal pressure to 0.5 MPa. It is.

The phenol compound obtained by the present invention is a compound in which at least one hydrogen on the aromatic ring of phenol or phenol is substituted with a methyl group and / or an ethyl group. Examples include phenol, o-cresol, p-cresol, m-cresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2,3- Examples thereof include dimethylphenol, 2,3,6-trimethylphenol, 2,4,6-trimethylphenol, and 2-ethyl-5-methylphenol.

Phenol and alkylated phenolic compounds are almost always obtained as a mixture, the ratio of which depends largely on the reaction conditions and the nature of the catalyst. Phenol formation can be favored when the reaction temperature is lower or the contact time between the catalyst and the raw material is short, and the aromatic ring is alkylated when the reaction temperature is higher or the contact time is long It is possible to make the production of phenolic compounds superior. Although the production mechanism of the phenol compound according to the present invention is not clear, it is presumed that phenol is first produced and then converted into a phenol compound that is sequentially alkylated with raw material alcohol or the like.

Hereinafter, the method of the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist.

  The space-time yields of alkylphenol compounds are simultaneously generated o-cresol (2-methylphenol), m-cresol (3-methylphenol), 2,6-dimethylphenol, 2-ethylphenol, 2,4-dimethylphenol, 2 , 3-dimethylphenol.

Example 1
A water-containing cake of iron hydroxide (reagent manufactured by Soekawa RIKEN) was spread on a magnetic dish and dried at 100 ° C. for 6 hours. The obtained lump was crushed and sized to obtain a catalyst having a particle size of 0.5 to 1.4 mm. 1.58 g of this catalyst was filled in a glass reaction tube (inner diameter: 12 mm), heated to 380 ° C. while flowing nitrogen gas at 30 ml / min, and held for 3 hours. Thereafter, the reaction was carried out by supplying 83.9 wt% methanol-16.1 wt% ethanol mixed solution (both mixed with Wako Reagent) at 2.7 g / h with nitrogen gas flowing. The product was collected at the outlet of the reaction tube using a dry ice-methanol trap and analyzed by gas chromatography. The results are shown in Table 1.

Example 2
An aqueous copper acetate solution was added to and kneaded with iron hydroxide (reagent manufactured by Soekawa Richemical Co., Ltd.) so that the supported amount was 4.0 wt% as copper acetate. Thereafter, a catalyst was prepared by the same treatment as in Example 1, and a reaction was carried out in the same manner as in Example 1 using 1.58 g of this catalyst. The results are shown in Table 1.

Example 3
Example 1 except that 1.61 g of the catalyst of Example 1 was used, and 58.2 wt% methanol-41.8 wt% ethanol mixed solution (both Wako Reagent) was supplied at 2.7 g per hour, and the reaction temperature was 400 ° C. The reaction was carried out in the same manner as above. The results are shown in Table 1.

Example 4
Example 1 except that 1.71 g of the catalyst of Example 1 was used, and 41.0 wt% methanol-59.0 wt% ethanol mixed solution (both Wako Reagent) was supplied at 2.7 g per hour, and the reaction temperature was 400 ° C. The reaction was carried out in the same manner as above. The results are shown in Table 1.

Example 5
The reaction was carried out in the same manner as in Example 1 except that 1.64 g of the catalyst of Example 1 was used, only Wako Pure Chemical reagent ethanol was supplied at 2.7 g per hour, and the reaction temperature was 400 ° C. The results are shown in Table 1.

Comparative Example 1
The reaction was carried out in the same manner as in Example 1 except that 1.56 g of the catalyst of Example 1 was used and only reagent methanol manufactured by Wako Pure Chemical Industries was supplied at 2.7 g per hour. The results are shown in Table 1.

The present invention is effective in the field of manufacturing chemical products such as synthetic resins, pharmaceuticals, and agricultural chemicals.

Claims (4)

A method for producing a phenol compound, comprising reacting ethanol or methanol and ethanol in the presence of a solid catalyst containing iron. The production method according to claim 1, wherein the solid catalyst contains at least one selected from metallic iron, iron oxide, iron hydroxide, and iron oxyhydroxide. The method according to claim 1 or 2, wherein the reaction is carried out in a flow mode under gas phase conditions. The production method according to any one of claims 1 to 3, wherein the phenol compound is a compound in which at least one hydrogen on an aromatic ring of phenol or phenol is substituted with a methyl group or an ethyl group.