JPS62240637A - Alkylation of phenolic compound - Google Patents

Abstract

PURPOSE:To obtain a para-alkylated phenol in high efficiency, by alkylating a phenolic compound with an alcohol and/or ether in liquid phase in the presence of a catalyst consisting of a Y-type zeolite containing hydrogenated/ dehydrogenated metal. CONSTITUTION:A phenolic compound (preferably phenol) is alkylated with an alcohol and/or an ether (preferably ethanol and/or diethyl ether) in liquid phase in the presence of a Y-type zeolite catalyst containing a hydrogenated/ dehydrogenated metal (preferably Pd, Pt, Ni, Co, Cu, Zn and/or Ag). A p- alkylated phenol such as p-cresol or p-ethylphenol, etc., useful as an intermediate for antioxidant and synthetic resin, etc., can be produced in high yield, stably keeping the catalytic activity over a long period while suppressing the production of m-alkylated compound which is hardly separable from the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for alkylating phenols. More specifically, 1% for alkylation of phenols with alcohols and/or ethers.
This invention relates to a method for suppressing alkylation at the meta position and efficiently synthesizing alkylated products at the para position by carrying out the reaction in a liquid phase in the presence of a specific catalyst.

Alkylphenols are obtained by selectively alkylating phenols such as phenol or substituted phenols at the ortho and para positions.

It has important industrial uses. Among them, p-alkylphenols such as p-cresol and p-ethylphenol are used as intermediate raw materials for antioxidants, synthetic resins, etc. (occupy an important position).

(Prior Art) The most common method for synthesizing such alkylphenols is to alkylate phenols with olefins using a solid acid catalyst, a Friedel-Krach catalyst, or the like.

- Alkylation with alcohol has long been known as a method for introducing relatively short-chain alkyl groups into phenols. Amorphous - In addition to the usual method using a solid acid catalyst, there is also a gas phase alkylation method using a zeolite catalyst. As a method using a zeolite catalyst, U.S. Pat.
8 and the method described in US Pat. No. 4,532,368 in which a phosphorus-modified ZSM-5 catalyst is used for gas phase alkylation of phenol with ethanol. In addition, a method for producing p-cresol by reacting phenol and methanol in the gas phase using a Y-type zeolite catalyst imparted with solid acidity was published in VF Kosho 52-
No. 12181. Here, as a catalyst,
HY type zeolite and alkali metals, alkaline earth metals, rare earths.

Copper, zinc, cadmium, chromium, mankan, cobalt,
Y-type zeolites ion-exchanged with transition metals such as nickel have been proposed, and among them, HY-type zeolites are p-
It is described that it is suitable for producing cresol, that the selective production of p-cresol decreases as the acidic points of zeolite decrease, and that metal Y-type zeolite is rather suitable for producing anisole.

(Problem to be solved by the invention) Among the above-mentioned known methods, what about phenols? In the method of alkylating with an olefin, when the alkylating agent is a branched olefin, a para-alkylated product can be synthesized with good yield. However, when the alkylating agent is a low molecular weight linear olefin, a mixture of isomers is produced and the yield of useful para-alkylated product is low. For example, alkylation of phenol using ethylene produces a mixture of 0-ethylphenol, m-ethylphenol, and p-ethylphenol. Here, the above 3 of ethylphenol
The boiling points of the isomers are 204° C. for the ortho isomer, 214° C. for the meta isomer, and 218° C. for the para isomer, and since the difference in boiling point between the ortho isomer and the para isomer is relatively large, separation by rectification is possible. However, when the meta-isomer coexists, the boiling point of the para-isomer is close to that of the para-isomer, making it extremely difficult to separate the rt-sequence of the para-isomer. The production of meta-isomers is a serious drawback in that it not only leads to a decrease in the yield of para-isomers, but also makes separation of para-isomers extremely difficult.

On the other hand, amorphous solid acid catalyst in alkylation reaction with alcohol? The conventional methods used produce isomer mixtures dominated by ortho-alkylated products, and the yields of para-alkylated products are generally very low.

Furthermore, as described in U.S. Pat. No. 4,391,998 described in f311, the gas phase alkylation of phenol with isopropanol is carried out using a H-Z SM-5 catalyst. Compared to p-
Although the production selectivity for inpropylphenol is high, a large amount of difficult-to-separate isomers such as m-isopropylphenol and n-propylphenol are produced as by-products.

This was insufficient as an industrial method.

Furthermore, as described in US Pat. No. 4,532,368 marked with #, the method of gas-phase alkylation of phenol with ethanol using a ZSM-5 catalyst modified with phosphorus produces a mixture of isomers centered on m-ethylphenol. Therefore, it could not be said to be a one-selective alkylation method.

As described in the above-mentioned Japanese Patent Publication No. 52-12181, HYY
The method of gas-phase alkylation of phenol with methanol using a type of zeolite catalyst has a high yield of p-cresol.
It also has the excellent feature of producing very little m-cresol. However, reports on this reaction (
Catalysis by zeolites
, Elsevier Scientific Publi
Shining Company.

Amsterdam, 1980, pp. 105-111)
According to the authors, this method was still unsatisfactory as an industrial method because the catalyst performance changed significantly over time, such as the phenol conversion rate decreasing by about 20% per hour.

The object of the present invention is to solve the problems of the above-mentioned known techniques. That is, the present invention aims to provide a method for alkylating phenols that can produce a para-alkylated product in good yield without producing a meta-alkylated product that is difficult to separate, and that can maintain stable catalyst performance for a long time. purpose.

(Means for Solving Problems) As a result of unique research aimed at achieving the above object, the present inventors found that hydrogenation/dehydrogenation in alkylation with phenolic alcohols or (and) ethers It was discovered that the problem could be solved by using YW zeolite containing metal as a catalyst and carrying out the reaction in the liquid phase.

The raw material phenols used in the alkylation method of the present invention are those that can be alkylated at least at the ortho ortho position of the hydroxyl group, and therefore at the para or ortho position, or at the ortho and ortho positions. It has a hydrogen atom.

Such phenols may have various nuclear substituents. Specific examples include phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, octylphenol, and nonylphenol.

These include hydrocarbon substituted products such as dibutylphenol, cyclohexylphenol, phenylphenol, and cumylphenol, and halogenated phenols such as chlorophenol, bromophenol, and dichlorophenol sodium.

In the process of the invention, alcohols or/and ethers may be used as alkylating agents.

The alcohols used in the invention include primary or secondary alcohols having 1 to 12 carbons. Specific examples include methanol, ethanol, 1-glopanol, 2-propanol.

Examples include 1-butanol, 2-butanol, octatool, decanol, dodecanol, cyclohexanol, and benzyl alcohol. Also.

The ethers used in the present invention are those obtained by intermolecular dehydration of the alcohols described above, and specific examples include dimethyl ether, diethyl ether, di-n-propyl ether, diimpropyl ether, and diimbutyl ether.

Examples include diimbutyl ether.

The alkylating agent in the process of the invention may be either an alcohol or an ether, or any mixture of both. When carrying out the process of the present invention using alcohol as the alkylating agent, some of the alcohol may be converted to ether during the ashing process. In such cases, the alcohol and ether mixture can be recovered and reused as a dual alkylating agent.

Hydrogenation/dehydrogenation metals in the method of the present invention include:
Palladium, platinum, rhodium, ruthenium, iridium, osmium, nickel.

Cobalt, iron, copper, silver, gold, zinc, cadmium.

Examples include vanadium, chromium, manganese, molybdenum, and tungsten, with palladium, platinum, nickel, cobalt, copper, zinc, and silver being particularly preferred.

The catalyst used in the method of the present invention is a Y-type zeolite containing one or more of these hydrogenation/dehydrogenation metals. Preferably, it is deposited in YW zeolite by an ion exchange operation or an impregnation operation, or by mixing it into a zeolite platform. After the metal is deposited, it can be fixed in place by reduction to a metallic elemental metal form or by oxidation by firing. The preferable range of the content of the above metals in Y-type zeolite varies depending on the type of metal, but the amount of metal in elemental state is about 0.0
Examples include a range of 5 to about 15% by weight, more preferably about 0.1 to about 10% by weight.

In the present invention, the Y-type zeolite may contain a hydrogenation/dehydrogenation metal and at the same time may contain other metals. As other metals, alkali metals and alkaline earth metals are preferred, and lithium, which belongs to the alkali metals, is particularly preferred.

Sodium and potassium are preferred. However, substitution with hydrogen at the ion exchange point of Y-type zeolite, that is, H
Forming the structure of Y-type zeolite and adding acidic points increases the amount of etherified phenols by-products,
Moreover, it is not a good idea because it lowers the yield of the para-alkylated product.

In the method of the present invention, it is preferable to carry out the reaction by adjusting the charging ratio at of the raw material phenols and the alkylating agent in advance. What is the preparation ratio?

A suitable range of 0.1 to 10 moles of alcohol or (and) ether per mole of phenol, and preferably a range of 0.5 to 5 moles per 1%.

The method of the invention carries out the alkylation reaction in the liquid phase. Therefore, it is necessary to carry out the reaction under pressure at which the raw material phenols and the alkylating agent do not substantially vaporize and escape. The reaction pressure is generally suitably from a naturally occurring pressure to about 150 atm, and preferably from a naturally occurring pressure to about 120 atm.

When the reaction is carried out under a pressure higher than the naturally occurring pressure, it is possible to pressurize with an inert gas such as nitrogen, or with hydrogen gas.

The reaction temperature can usually be selected within the range of 100 to 400°C, but
The temperature is preferably 200 to 320°C in terms of scheelite rate and selectivity.

In the present invention, the alkylation reaction can be carried out either patchwise or continuously. As continuous methods, fixed bed, suspended bed or fluidized bed methods are possible. For example, when performing a patch reaction using a powdered catalyst, the amount of catalyst used is about 2 to about 40% by weight of the raw material phenol.
A range of 0.2 to 5 hours is appropriate, and one reaction is usually completed in 0.2 to 5 hours. In addition, in a fixed bed reaction using a seijin rope, the weight hourly space velocity (WH8V) is 0.2 to 15% based on the catalyst.
．． It can be brought into contact with the charging feed stream.

(Operation) When an alkylation reaction is carried out in the gas phase using the liquid phase alkylation catalyst of the present invention, there is almost no catalytic activity, or the catalytic activity disappears after the reaction is continued for several hours. objective cannot be achieved.

On the other hand, according to the above-mentioned Japanese Patent Publication No. 52-12181, in the gas phase alkylation method of phenol with methanol, a zeolite catalyst for HY is optimal for producing p-cresol, and a metal Y-type zeolite catalyst is more suitable for producing anisole. However, the liquid phase alkylation reaction of the present invention exhibits a completely opposite tendency. i.e. 1
According to the liquid phase alkylation method of the present invention.

HYFJl theolite catalyst produces a large amount of etherified products of phenols such as anisole, but the yield of alkylated products is low, and conversely, Y containing hydrogenated/dehydrogenated metals
type zeolite shows good catalytic performance.

(Effects of the Invention) According to the method of the present invention, no or almost no meta-alkylated product, which is difficult to separate, is produced as a by-product, and a para-alkylated product can be obtained in good yield. In addition, when alkylated by the method of the present invention, stable catalyst performance can be maintained for a long time, so for example, in a patch reaction, it can be used repeatedly, and in a continuous Nitani stone, it can be used continuously for a long time. .

(Examples and Reference Examples) The present invention will be explained in more detail using Examples and Reference Examples below, but the present invention is not limited to the Examples.

(11 catalyst commercially available powdered NaY type zeolite) (LindeMSK
-40: Composition (wt%) Si 02 = 64°A/2
03=23, Na20-13: (mole ratio) Si
O2/At203= 4.7, Na2O/A1203=
0.93] 1001I 1N sodium nitrate aqueous solution
i1.5! and heated in a constant temperature bath at 80° C. for 8 hours. Then, it was dispersed in a 1N aqueous nickel acetate solution III and heated in a constant temperature bath at 80° C. for 2 hours. Nickel acetate aqueous solution [-Renew and perform the same ion exchange operation three times in total, wash thoroughly with water, dry at 120°C,
It was further calcined at 430°C for 3 hours to produce a NiY type zeolite catalyst. Analysis by atomic absorption spectrometry □ value (weight %) is Ni = 9.0. Na=2.4.

A Y-type zeolite catalyst containing palladium was produced in the same manner as above, using tetraminedichloropalladium instead of nickel acetate. Y-type zeolite catalysts containing other hydrogenation/dehydrogenation metals were prepared in the same manner using water-soluble metals in place of nickel acetate.

(2) 5U with capacity 100ml equipped with alkylation reaction heating and stirring device
Touch an-5, which was prepared by the above method in a S316 autoclave! i', 20.31 liters of phenol and 19.711 liters of ethanol were added, and after replacing the inside of the system with nitrogen gas, the temperature was raised to 250° C. while stirring.

(3) Results The reaction was carried out at 250° C. for 2 hours to obtain a reaction solution having the composition shown in Table 1 (excluding the alkylating agent).

Example 10 The same NaY used as the raw material for catalyst preparation in Examples 1 to 9
Type zeolite 100F was dispersed in 1N sodium nitrate aqueous solution 1651 and heated in a constant temperature bath at 80°C for 8 hours. After washing with water, palladium sodium chloride (Pdct2
-2 Na(J-3H20)1,649 was impregnated with dissolved water, dried at 120°C, and further calcined at 430°C for 3 hours to produce a Na Y 111 zeolite catalyst containing 0.5% Pd.

In the same autoclave used in Examples 1-9, 5I of the above catalyst and 20.3. of phenol were added. 1 L ethanol
9.7.9, and after purging the system with nitrogen gas, the temperature was raised to 300°C while stirring. Table 2 shows the composition of the reaction solution obtained by stirring at 300° C. for 4 hours (excluding the alkylating agent).

Example 11 Commercially available 0.5% Pt-CaY'll zeolite catalyst [L
5K-200 made by inde; Composition (weight%) Pt=0.5
%, Ca=10.3%] Practical example 10
The reaction was carried out in the same manner as above to obtain a reaction solution having the composition shown in Table 1-2 (excluding the alkylating agent).

Reference example 1 The same NaY used as the raw material for catalyst preparation in fire examples 1 to 9
type zeolite) 100. ! i+ was dispersed in 1.5j of 1N ammonium nitrate aqueous solution, and 2
heated for an hour. After renewing the ammonium nitrate aqueous solution and repeating the same ion exchange operation a total of 4 times, washing with water,
Except for using the above HY type zeolite catalyst, which was dried at 20°C and further calcined at 550°C for 3 hours to produce a HY type zeolite catalyst.

The reaction was carried out in the same manner as in Example 10. As shown in Table 2, the HY type zeolite catalyst.

Many etherified products of phenol (phenethole) are produced as by-products, and the yield of p-ethylphenol is low at t-1. 51° Phenol 20
．． 3,9. Add 19.71 liters of ethanol and heat at 250℃ for 2 hours.
Allowed time to react. After the reaction was completed, the catalyst was collected in a glass filter, washed with ethanol, and then reused.

When the same catalyst was collected and reused 16 times in this manner, almost no change in catalyst performance was observed.

Example 13 In the same autoclave as used in Examples 1 to 9, the NiY type zeolite catalyst of Example 1 was mixed with 59° phenol at 20°C.
．． 3.9. Add 321 1-butanol and heat at 250℃ for 2
Allowed time to react. Composition of reaction amount (excluding alkylating agent)
was as follows.

Unreacted phenol 57.3 (lockstitch %) n
-Butoxybenzene 2.7iso-butoxybenzene 0.7on-butylphenol 9.8 (wt%)o-iso-butylphenol 4.4p-n-butylphenol
20.5 p-iso-butylphenol 3.2 Others 1.4 Example 14 Into the same autoclave as used in Examples 1 to 9, a real rj
N1YW zeolite catalyst J15Ji' of Example 1 and phenol were added at 20.3. Add L methanol tt20F, 300℃
The mixture was allowed to react for 2 hours. The composition of the reaction solution (excluding the alkylating agent) was as shown in Table 3.

Reference Example 2 The same reaction as in Example 14 was carried out except that the same HY type zeolite catalyst used in Reference Example 1 was used, and the results shown in Table 1-3 were obtained. The HY type zeolite catalyst can produce anisole, but the yield of cresol is low.

Table 3 Example 15 In the same autoclave as used in Examples 1 to 9, the NjY type zeolite catalyst of Example 1 was heated to 51°phenol'2.
0.3,9. Add 18g of diethyl ether and heat to 250°C.
The mixture was allowed to react for 2 hours. The composition of the reaction solution (excluding the alkylating agent) was as follows.

Unashite phenol 21.0 (wt%)
. -Ethylphenol 12.Om-Ethylphenol 0.1p-Ethylphenol
23,5 diethylphenols 7
．． 4 Phenetol 17.4 Ethyl phenetol 6.5 Heavy substances
12.1

Claims (1)

[Claims] 1. In alkylating phenols with alcohol or (and) ether, the reaction is carried out in a liquid phase using Y-type zeolite containing a hydrogenation/dehydrogenation metal as a catalyst. A method for alkylating phenols. 2. The method of claim 1, wherein the hydrogenation/dehydrogenation metal is selected from the group consisting of palladium, platinum, nickel, cobalt, copper, zinc, silver and mixtures of two or more thereof. 3. The method according to claim 1 or 2, wherein the phenol is phenol. 4. The method according to any one of claims 1 to 3, wherein the alcohol or (and) ether is ethanol or (and) diethyl ether.