JPS59155331A - Production of p-ethylphenol - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing tuunol and ethanol or rapafetylphenol (hereinafter abbreviated as PEP) with high selectivity and high yield. More specifically, phenol and ethanol are combined in the presence or absence of a reaction medium.
Heteroho! J This invention relates to a method for producing PEP with high selectivity and high yield by reacting in the presence of an acid catalyst.

Currently, known industrial methods for producing PEP include sulfonating ethylbenzene, melting it with an alkali to synthesize a mixture of ethyltunol isomers, and further distilling and crystallizing this mixture. However, this method often generates meta-isomers for ethyltunols.
There are numerous problems such as the process is complicated, large amounts of sulfuric acid and alkali are used, workability is poor, wastewater pollution occurs, sodium sulfite is produced as a by-product, and equipment corrosion is a concern.

In addition, regarding the manufacturing method of PEP using thunol and ethanol as raw materials, which is the subject of the present invention, AJ22 (P
O4)-3/AJh Method using O3 as a catalyst (Industrial and Engineering Chemistry:
Product Research and Development/+ 71-
(Industrial and Engineer
ingChemistry: Product Re
5earch and develop-1o1)ment
') Vol, 10, No. 4.362 (1971))
, method using γ-AI1203 as a catalyst (Hokkaido University Faculty of Engineering Research Report 76 147 (1975)), ZnO/F
A method using e2es as a catalyst (Japanese Patent Publication No. 49-82640) is known. However, in the methods using these catalysts, the main components of the product are orthoethyl phenol (hereinafter abbreviated as OEP) and metaethyltunol (hereinafter abbreviated as MEP), and the target PEP is the ethyltunol produced. The highest selectivity to PEP is 7 mol %, and it may be necessary to lower the reaction temperature to 25 mol%.
These methods have disadvantages such as the need to raise the temperature to a relatively high temperature of 0 to 420° C., and thus these methods have not yet been adopted as industrial manufacturing methods.

Therefore, the present inventors have developed a method for easily industrially producing PE'P with high selectivity and high yield through an economical and simple operation through an alkylation reaction using thunol and ethanol as raw materials. As a result of various investigations to develop the above-mentioned catalyst, we found that if a catalyst prepared by supporting a heteropolyacid or its salt on silisobar alumina or activated carbon is used as a catalyst in the alkylation reaction, the above-mentioned known catalyst can be used. .

The selectivity to PEP and its yield have improved significantly, and the reaction temperature can be lowered to 150 to 300°C, making it possible to produce PEP with an economical and simple operation.
The present invention was completed by discovering that EP can be produced with high selectivity and high yield.

That is, the gist of the present invention is that when producing ethylfunol by reacting funol and ethanol in the presence of an acid catalyst, a heteropolyacid or its salt is used as an acid catalyst, silica, alumina and Paraethylfuric acid or its salt, which is characterized by using a catalyst prepared by supporting it on a carrier selected from activated carbon, is not particularly limited and various types can be used. Representative examples that can be suitably used include 12-tungstosilicic acid, 12-tungstophosphoric acid, 12-molybdophosphoric acid, and salts thereof, such as Group I, Group II, Group II, Group II of the Periodic Table, etc. metal salts, etc. These may be used in -product or multiple types.

In carrying out the present invention, it is important that the heteropolyacid or its salt be supported on a carrier selected from silica, alumina or activated carbon and used as a catalyst.

If the heteropolyacid or its salt is used as it is without being supported on a carrier, the selectivity to PEP will decrease,
The amount of by-products such as MEP and 2,4-shetylfunol is increased, and the conversion rate of funol is also relatively low, so that favorable results are not obtained. In addition, if a heteropolyacid or its salt is used as it is, it has the disadvantage that it is extremely difficult to separate and recover the heteropolyacid from the homogeneous liquid phase reaction system without altering its properties. be. Even if this heteropolyacid or its salt is supported on a carrier and used as a catalyst, if a carrier other than the above-mentioned silica alumina or activated carbon is used, the conversion rate of -nol will be extremely low. However, the object of the present invention cannot be achieved because of the increased production of by-products such as MEP and founetol.

The silica, alumina, or activated carbon used as a carrier in the present invention is not particularly limited, and known or commercially available ones may be used as they are, or they may be treated with acid or other treatments as necessary.

The method for supporting the heteropolyacid or its salt on the carrier of silisoba alumina or activated carbon may be any method and is not particularly limited.

A generally preferred method is to dissolve a predetermined amount of a heteropolyacid or its salt in a solvent that dissolves the heteropolyacid or its salt to form a solution, and add a predetermined amount of carrier to the solution.
This is a method in which the solvent is evaporated to dryness with sufficient stirring at room temperature or below the boiling point of the solvent. The supported catalyst thus obtained may be calcined at 100 to 400° C. in air or other atmosphere, if necessary. The carrier layer of heteropolyacid or its salt is generally suitable in a range of 5 to 20% by weight, preferably in a range of 10 to 15% by weight.

In carrying out the present invention, the reaction temperature is 150 to 300°C.
A range of is appropriate. If the temperature is below 150°C, the conversion rate will be low, and if it exceeds 300°C, the MEP, 2.4
- This is not preferable because by-products such as diethyltunol increase, and in either case, the yield of PEP decreases. The reaction pressure is suitably in the range of 1 to 30 atm. There is no need to particularly limit the charging ratio of tunaol and tanol, and it is preferably 1 to 2.5 moles of phenol to 1 mole of ethanol. Further, a reaction medium may be used as necessary. Examples of the reaction medium include nitrogen, carbon dioxide, water, and ethylene.

The reaction type may be a liquid phase reaction or a gas phase reaction, and the reaction type is not particularly limited, but a fixed bed flow type is preferable. Raw material supply amount () = total of nol and ethanol)
If expressed in liquid hourly space velocity (LH5V), it is 0.0.
A suitable range is 5 to 30 hr-1, preferably 0.1 to 1 Qhr-1.

The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1] 12-tungstosilicic acid 8.8! ethanol 250
Dissolved in rnl and added silica gel (Davison Silica Gel 923) 50. r was added, and the mixture was evaporated to dryness while heating and stirring on a hot water bath. Next, dry at 110°C for 3 hours,
It was baked at 0° C. in air for 3 hours.

Silica gel carrying 15% by weight of 12-tungstosilicic acid thus obtained 3. Q me inside diameter 1.2c
A mixture of ethanol and thunol (ethanol/phenol molar ratio 1:1.2) was filled in the center of a flow-through quartz glass reaction tube with a length of 25 C, and heated at 220°C.
, LH3V2hr' was passed. As a result, the conversion rate of phenol was 46 mol% in one pass, and the composition of the reaction product obtained by removing unreacted thoonol and ethanol from the reaction mixture was as shown in Table 1. . From the composition of the reaction product in Table 1, it will be easily understood that according to the present invention, the selectivity to PEP is high and the conversion rate of thunol is also high.

Table 1 Reaction product composition x 2.4-diethylphenol [Example 2] Except for using γ-Ap, 203 as a carrier and using 12-tungstophosphoric acid instead of 12-tax 1-silicic acid. It was carried out in the same manner as in Example 1.

As a result, the composition of the reaction product obtained is shown in Table 2, and the conversion rate of thunol was 4 J mol %.

Table 2 Composition of reaction product [Example 3] The same procedure as in Example 1 was carried out except that activated carbon (Macropore Bonn ■ manufactured by Dia Catalyst) was used as the carrier.

As a result, the composition of the reaction product obtained was as shown in Table 3, and the conversion rate of thunol was 55 mol%.

Table 3 Composition of reaction product [Comparative Example 1] The same procedure as in Example 1 was carried out except that diatom was used as the carrier.

As a result, the composition of the reaction product obtained was as shown in Table 4, and the conversion rate of thunol was only 6 mol %.

Table 4 Composition of Reaction Product [Comparative Example 2] The same procedure as in Example 1 was carried out except that pumice was used as the carrier.

As a result, the conversion rate of thunol was only 5 mol%.

[Comparative Example 3] Two-nor 112.8/and ethanol 46! and 12-tungstosilicic acid 4 as a catalyst! was placed in a 300 m1 stainless steel autoclave and heated to 20 kl/a with nitrogen.
The reaction mixture was stirred at 200° C. for 2 hours under pressure of 150° C. to react in a homogeneous liquid phase system.

As a result, the conversion rate of thunol was 30 mol %, and the composition of the reaction product excluding unreacted thunol and ethanol was as shown in Table 5.

Claims (1)

[Claims] A method for producing paraethyltunol, which comprises -\telopolyacid or the like as an acid catalyst in producing paraethyltunol by reacting funol and ethanol in the presence of an acid catalyst.