JPS59181232A - Production of o-methylated phenol - Google Patents

Abstract

PURPOSE:Oxides of iron and vanadium and oxides of copper, zinc chromium and phosphorus or sulphates of copper, zinc, chromium, magnesium or manganese are used as a catalyst to effect the ortho-methylation of a phenyl with methanol, thus producing an o-cresol advantageously. CONSTITUTION:In the production of o-methylated phenol by methylation of phenol with methanol in high selectivity of o-substitution, a catalyst composed of oxides of iron and vanadium and at least one selected from the group consisting of oxides of copper, zinc, chromium and phosphorus or at least one selected from the group consisting of sulfates of copper, zinc, chromium, magnesium and manganese is used to effect the gas phase catalytic reactions at 200-450 deg.C, preferably at 250-400 deg.C. USE:A starting material for special phenolic resins.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 0-methylated phenols, and in particular, to a method for producing 0-methylated phenols, which can increase the production rate of 0-cresols when phenols are orthomethylated with methanol. This invention relates to a method for producing methylated phenols.

In recent years, the demand for 0-cresols has increased as they have come to be used as raw materials for special phenolic resins, and it has become necessary to advantageously produce 0-cresols.

Methods for producing such 0-methylated phenols include the use of various catalysts such as alumina-based, magnesium-based, iron oxide-based, and vanadium oxide-based catalysts when phenol is orthomethylated with methanol. This method is known, and is also known as a method of carrying out a gas phase catalytic reaction in the presence of vanadium and iron oxides at a reaction temperature U in the range of 250 to 500°C (@Publication No. 47-379 Hand No. 3, Japanese Patent Publication No. 51-10).
No. 226) has also been proposed. However, the main purpose of all of these conventional orthomethylation methods for phenols is to produce 2,6-xylenol, which is essential as a raw material for producing polyphenylene oxide resins.

The method of using vanadium and iron oxides as reaction catalysts is characterized by excellent activity and selectivity of the orthomethylation reaction, but increasing the conversion rate of phenols leads to a decrease in the conversion of 2,6-xylenol. The production rate becomes high, and if you try to increase the production rate of 0-cresol, you have to lower the conversion rate of phenols. Although it is suitable for producing 2,6-xylenol, There was a problem from the viewpoint of increasing the number as much as possible.

In view of this point of view, the present inventors have conducted intensive research into a method for advantageously producing 0-cresols in the orthomethylation reaction of phenols with methanol. , copper, zinc, chromium, or an oxide selected from the group consisting of copper, zinc, chromium, and phosphorous oxides;
The present invention was achieved by discovering that the object can be achieved by using a catalyst containing a sulfate selected from the group consisting of magnesium and manganese sulfates.

The oxides of iron and vanadium used as catalysts in the present invention include oxides of various valences, but oxides of any valence can be used. For example, iron oxide One of the things is Fe2O3, Fe3O4,
Examples of vanadium oxides include V2O5, V2O11, V2O3, and VO, with Fe2O3 and V205 being preferred.

In addition, oxides of copper, zinc, chromium, or phosphorus can be used as catalyst components together with the iron and vanadium oxides, and these may be oxides of any valence. but preferably CuO+ZnO,
Cr2O3 or P2O5 or their oxyacid salts. At least one of these oxides is contained as a catalyst component.

In another invention of the present application, at least one of the sulfates of copper, zinc, chromium, magnesium or manganese is used as catalyst component, together with oxides of iron and vanadium. These sulfates are sulfates of any valence.
However, preferably CuSO4, ZnSO4,
Cr2(SOa)3 or MnSO4. 'These may be oxidized, reduced, or dehydrated during the production or use of the catalyst, but in the present invention these are also referred to as sulfates. At least one of these sulfates is contained as a catalyst component. Moreover, it is natural that these sulfates and oxides can be used together, and it is also possible to contain small amounts of other components.

Among the catalyst components, the ratio of iron and vanadium oxides is 1 to 50, preferably 9 to 30, in terms of the atomic ratio of iron to vanadium (Fe/V). In addition, regarding the blending ratio of the oxides or sulfates listed in 1-1 to be used together with the oxides of iron and vanadium, the total amount of oxides of iron and vanadium shall be 0.
5 to 20 layers, preferably 1 to 5 layers.

The catalyst used in this invention can be prepared in a variety of ways. For example, the catalyst may be one in which each of the above-mentioned catalyst components, that is, iron and vanadium oxides and the fourth component, is supported on a suitable carrier such as alumina, silica, silica-alumina, 61 algae, etc. These catalyst components may be molded by means such as press molding, or these catalyst components may be mixed with a carrier component and molded.

Oxides of iron and vanadium can be produced by any method, but for example, an acid, alkali, or reducing agent is added to a solution of water-soluble compounds of iron and vanadium to cause coprecipitation, and then this is mixed with oxygen. Calcining in a gas stream makes it possible to obtain an oxide with a uniform composition. In addition, this aqueous solution contains copper,
By dissolving water-soluble compounds of zinc, chromium, or phosphorus, a homogeneous composition containing iron, vanadium, and oxides of lead, chromium, or phosphorus can be obtained. Further, when using a sulfate, it is possible to obtain a uniform composition after firing by adding an aqueous solution of the sulfate to the iron and vanadium oxides obtained as described above. In some cases, for example, when a carrier is used, the carrier is impregnated with or coated with an aqueous solution of water-soluble compounds of iron and vanadium, and this is fired as it is or after hydrolysis to form an oxide. It is also possible to

In the present invention, the molar ratio of phenols to methanol (Pb/Me) in the feedstock is usually in the range of 0.05 to 0.05 l, but is preferably 0.1 to 0.05 in order to increase the production rate of 0-cresols. is within the range of

In addition, in the present invention, other components such as nitrogen, hydrogen, carbon oxide, carbon dioxide, methane, etc. may coexist in the feedstock, and in particular, the coexistence of water vapor is preferable to the catalyst layer of the reactor. This is advantageous in preventing an increase in flow resistance and achieving smooth continuous operation for a long period of time. The amount of water vapor added for this purpose is usually 0 per mole of phenol.
It is 5 to 10 moles.

The reactor used in carrying out the method of the present invention includes:
It may be of any type, such as a fixed bed, moving bed, or fluidized bed, as long as it allows good solid-liquid contact.

Regarding the reaction temperature, the lower the reaction temperature, the milder the reaction and the higher the production rate of O-cresols, but the lower the conversion rate of phenols, and the higher the temperature, the more intense the reaction is. While this improves the conversion rate of phenols,
The production rate of 0-cresols tends to decrease, and the temperature is usually 20°C to 450°C, preferably 250 to 400°C. Regarding space velocity (SV), although it varies depending on other reaction conditions such as reaction temperature, there is a tendency that the faster the conversion rate of phenols, the lower the conversion rate of phenols. From the relationship with the generation rate of
Usually 001-05 phenols (g)/catalyst (CC)・
time (Ph-g/Cat-cc-hr), preferably 0
．． 03 to 0.20 ph-g, /Cat-cc·hr.

According to the method of the present invention, the selectivity of 0-cresols can be improved, and in particular, the conversion rate of raw material phenols can be improved without reducing the production rate of 0-cresols. As a result, 0-methylated phenols, particularly 0-cresols, can be advantageously produced.

The method of the present invention will be specifically explained below based on Examples and Comparative Examples.

Examples 1-6 and Comparative Example 1 Ferric nitrate, ferric sulfate and/or 7-11 as iron source
Then, the catalyst of Comparative Example 2 was prepared, and the same reaction as in Examples 1 to 6 was carried out by applying the reaction d1.3 to this catalyst, changing the molar ratio of the starting material 1, and changing the molar ratio of the raw material 1. The reaction was carried out, and the production ratio of 0-cresol and 2.6-xylenol (Q
C/26XY)! 'i(11511 and 65/''A5
The phenol conversion rate at the time of was determined. The results are shown in Table 2.

Example 12 The atomic ratio of iron to vanadium (
Fezα-V20 with different Fe/V)! , powder was prepared in the same manner as in Example 6, and C1・”C20,■2o4.-p
The molar ratio of phenol to orthoalkyl water by methanol is 1:3, and the SV is fl. lOPh-g
/Cat-cchr. The results are shown in Table 3.

Procedural amendment dated July 2nd, 1981 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case Patent Application No. 513852 of 1982, Title of the invention 0 - Process for producing methylated phenols 8, Amendment Relationship with the case of the person who filed the patent application Address of the patent applicant: 6-17-2 Ginza, Chuo-ku, Tokyo Name (6(
14) Nippon Steel Chemical Industry Co., Ltd. Representative Yasu
Kazutomi Ei 4 Agent 104 Phone OR (548) 1675 Address 8th floor, Ebara Building, 7-14-2 Ginza, Chuo-ku, Tokyo Name
(8273) Patent Attorney Katsuo Naruse (1 other person) 7 "Detailed Description of the Invention" column 8 of the specification to be amended Contents of the amendment Contents of the amendment 1 As shown in the attached sheet, the statement on the last line of page 6 of the specification Correct r(Pb/Me)J to 1(ph/Me)U.

2. IU03 described in Example 5 of Table 1 on page 10 of the specification
V2O5 MuSO4J wor Fe203 V
Correct as tOs-MnSO<j.

8 [Fe2 described in Comparative Example 1 in Table 1 on page 10 of the specification]
03 N206 J is corrected as r Fe2Q2-v2o5J.

Claims (1)

[Scope of Claims] ■ Phenols and methanol are combined with at least one oxide selected from the group consisting of oxides of iron and nazicum and oxides of copper, zinc, chromium and iron. A method for producing O-methylated phenols, characterized by carrying out a gas phase contact reaction at a reaction humidity of 200 to 4.50°C in the presence of a catalyst containing O-methylated phenols.2. and at least one sulfate selected from the group consisting of sulfates of copper, zinc, chromium, red sium, and manganese, F, reaction temperature 20
0 characterized by carrying out a gas phase catalytic reaction at 0 to 450°C
- A method for producing methylated phenols.