JPH075498B2 - Process for producing alkenyl group-substituted aromatic phenols - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention is a 2-bis (catalyst raw material or 2-bis (catalyst) which has a use as a resin modifier for agrochemical raw materials or polycarbonate, epoxy, polyamide, etc. by catalytic dehydrogenation. The present invention relates to a method for producing alkenyl group-substituted phenols useful as a raw material for producing hydroxyphenyl) propane.

[Prior art]

As a conventional method for obtaining an alkenyl group-substituted phenol, for example, there is a method in which 2-hydroxy-2-propylphenol is dehydrated in the presence of an acid catalyst, but the yield is not so good. As another reaction method, several reactions have been reported so far with respect to the reaction of catalytically dehydrogenating an alkyl group-substituted phenol to obtain an alkenyl group-substituted phenol. For example, Japanese Examined Patent Publication No. 53-43491 discloses a method of using iron oxide as a main active ingredient as a catalyst, alone or in combination with an alkaline earth metal oxide as a carrier. There is a problem that the conversion rate is low and the yield of the target product is low. Further, JP-A-54-55529 and JP-A-55-154930 disclose methods in which a catalyst containing chromium oxide as a main component is used as a catalyst. Is less than 40% and the yield of the desired product is low, which is problematic. When the catalyst composition of these publications is examined in more detail, the catalyst of JP-A-54-55529 is a catalyst containing chromium oxide alone or a combination of chromium oxide and oxides of zinc, manganese, titanium and zirconium. As for its catalytic activity, the yield of the target vinylphenols is
There is a problem as low as 40% or less. Also, as a comparative example, the publication discloses a method for dehydrogenating p-ethylphenol using a commercially available catalyst in which iron oxide-chromium oxide-potassium oxide is combined, but the conversion rate is 11.5%, p-ethanol. The tenylphenol selectivity is even lower at 29.4%. Although the composition ratio of the metal oxide of the commercially available catalyst is not specified in the publication, Fe ₂ O ₃ (73.5%)-C is used as a catalyst corresponding to the three components.
Nissan Gardler G64A with r ₂ O ₃ (1.9%)-K ₂ CO ₃ (21.6%)
Since it is known that there is a commercially available catalyst, the inventors of the present invention also investigated the activity of the catalyst for the dehydrogenation reaction of the present invention, and found that the activity was low and it could not be put to practical use.
The catalyst disclosed in JP-A-55-154930 is a method of using a catalyst in which chromium oxide is a main component and a metal oxide such as tin or iron is combined therewith. Although nothing is mentioned in the above description regarding the ratio of each metal oxide constituting the catalyst, for example, regarding the chromium oxide-iron oxide catalyst shown in Example 2, the composition ratio is 100% chromium oxide. It is a catalyst mainly composed of chromium oxide, which is calculated to be about 50 parts by weight of iron oxide. The activity of the catalyst is low as described above, which is a practical problem.

Further, JP-A-58-49328 discloses a method of obtaining ethenylphenol by reacting ethylphenol in the presence of an oxide containing barium and tin. However, in this method, the conversion rate of the raw material ethylphenol is low, and the yield of the target ethenylphenol is low.

It is well known that, in general, for example, even if the catalyst has the same constituent components, there is a possibility that the catalyst activity can be greatly changed if the content ratio is changed,
Given that it is difficult to predict the relationship between the structure of the catalyst and the activity of the reaction to be used, it is possible to find a new catalyst with higher activity by reviewing the conventional catalyst and making new studies. There seems to be sex.

[Problems to be solved by the invention]

From the viewpoint of the above, the inventors of the present invention, in producing an alkenyl group-substituted phenol by catalytic dehydrogenation of an alkyl group-substituted phenol, yield a higher yield of the alkenyl group-substituted phenol than that in the conventional method. In addition, we studied to develop a catalyst that can be obtained with high selectivity and has a long life.

[Means and Actions for Solving Problems]

As a result, they have found that the above object can be achieved by adopting the following method, and completed the present invention. That is, according to the method of the present invention, in the presence of a catalyst containing iron oxide (a) as a main component and at least one kind (b) of silicon oxide, germanium oxide and zirconium oxide as a subcomponent,
A process for producing an alkenyl group-substituted phenol, which comprises catalytically dehydrogenating an alkyl group-substituted phenol.

〔catalyst〕

The catalyst used in the present invention is mainly composed of iron oxide (a),
It is a catalyst containing at least one kind (b) of silicon oxide, germanium oxide and zirconium oxide as an accessory component.

The catalyst of the present invention may contain at least one of silicon oxide, germanium oxide and zirconium oxide as a subcomponent (b). These oxides can also be used in combination.

In the catalyst of the present invention, the proportion of iron oxide (a) in the catalyst is usually 50 to 99, preferably 60 to 90, based on 100 total metal atoms in the catalyst. Further, the ratio of the oxide (b) in the catalyst as a component constituting the catalyst of the present invention is usually 0, with respect to 100 total metal atoms in the catalyst, the number of germanium and zirconium atoms is 0.
It is 1 to 40, preferably 1 to 30.

In the present invention, as a constituent component of the catalyst, in addition to iron oxide (a) and oxide (b), chromium oxide can be added if necessary, and the content of chromium oxide in the catalyst is the total amount in the catalyst. The number of chromium atoms is usually 100 for 100 metal atoms
0.5 to 10. When chromium oxide is contained as a constituent component of the catalyst, a catalyst having stable catalytic activity over a long period of time without lowering the initial activity of the catalyst, that is, a catalyst having a long life, is preferable.

As a method for preparing the catalyst of the present invention, for example, a mixture of at least one of an iron compound, a silicon compound, a germanium compound and a zirconium compound and, if necessary, a chromium compound is baked at a predetermined temperature described below to obtain a catalyst of the present invention. A method of obtaining the catalyst can be shown. Specific examples of the iron compound, silicon compound, germanium compound, zirconium compound, and chromium compound include oxides, nitrates, hydrochlorides, sulfates, and other inorganic acid salts of these metals, acetates, oxalates, and the like. Examples thereof include compounds known to be capable of being converted into metal oxides by firing such as organic acid salts, organic metal compounds, metal hydroxides and metal alkoxides. In the present invention, more specifically as the compound, iron nitrate, silicon tetrachloride, sodium silicate, germanium nitrate, germanium chloride, zirconium nitrate,
Inorganic acid salts such as zirconium chloride, chromium nitrate, chromium chloride, potassium chromate, organic acid salts such as iron acetate, germanium acetate, magnesium acetate, organometallic compounds such as diethyldichlorosilane, dibenzenechromium, silicon hydroxide, etc. Examples thereof include hydroxides, ethyl orthosilicate, alkoxides such as t-butylalkoxyzirconium. In the present invention, a conventionally known method can be adopted as a method for obtaining a mixture of the above-mentioned compounds. Specific examples of the method include a method of adding an alkali to the mixed salt aqueous solution to obtain a mixed hydroxide, a method of impregnating and supporting another salt aqueous solution in the oxide, or a method of immersing the oxide in the oxide. Examples include a method of kneading and mixing comrades or comrades salt. In the present invention, it is preferable to use the method of adding ammonium water or an aqueous solution containing an alkali metal to the mixed salt aqueous solution.

In the present invention, the catalyst of the present invention can be obtained by calcining a mixture of the various types of metal compounds described above, and the calcining temperature is usually 400 to 100 as the condition in this case.
It is 0 ° C, preferably 500 to 700 ° C. The firing time varies depending on the firing temperature, but is usually 0.5 to 3 hours.
The firing is usually performed in the atmosphere, but it may be performed in an atmosphere of an inert gas such as titanium.

〔reaction〕

In the present invention, an alkenyl group-substituted phenol is produced by reacting an alkyl group-substituted phenol in the presence of the catalyst and catalytically dehydrogenating the same.

The alkyl group-substituted phenols as the raw material of the present invention are monovalent or polyvalent phenols having one or more alkyl groups, one of the alkyl groups having 2 or more carbon atoms, preferably Has 2 to 5 carbon atoms, and more specifically, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, n-pentylphenol, methyl (ethylphenol), methyl -N-propylphenol, methylisopropylphenol, diethylphenol, dimethylisopropylphenol, ethylnaphthol, isopropylnaphthol and the like can be exemplified. Among them, o-ethylphenol, m-ethylphenol, p-ethylphenol, m-isopropylphenol. , P-isopropylphenol, mn-propyi Alkyl-substituted phenols having an alkyl group having 2 to 4 carbon atoms such as ruphenol, pn-propylphenol, and pn-butylphenol are preferable.

In the present invention, as the reaction conditions for carrying out the catalytic dehydrogenation reaction, the reaction temperature is usually 400 to 700 ° C, preferably 500 to 600 ° C.
And the feed rate of the raw material to the catalyst layer is usually 0.1 to 10 hr ^-1 , expressed as liquid hourly space velocity (LHSV), preferably
It is in the range of 0.1 to 3 hr ^-1 . Further, in the present invention, an inert gas such as titanium and / or a diluent such as steam can be used as necessary. When adding steam,
The steam is usually used in an amount of 3 to 30 times, preferably 7 to 20 times the mol of the reaction raw material. The addition of steam is preferable because it improves the selectivity of the desired alkenyl group-substituted phenols and prolongs the life of the catalyst.

In the present invention, the reaction is usually carried out by a contact flow system, and the catalyst bed used may be a fixed bed, a moving bed, a fluidized bed, or the like.

The alkenyl group-substituted phenols obtained by the method of the present invention correspond to the starting alkyl group-substituted phenols, and specifically, ethenylphenol, isopropenylphenol, 1-propenylphenol, 2-propenylphenol, Examples thereof include ethenylnaphthol and isopropenylnaphthol.

〔The invention's effect〕

According to the method of the present invention, alkenyl group-substituted phenols can be obtained in high yield and high selectivity. Also, the life of the catalyst is longer than that of the conventional one.

〔Example〕

Hereinafter, the method of the present invention will be specifically described with reference to Examples.

Was dissolved Example 1 ferric nitrate _{[Fe (NO 3) 3 · 9H} 2 O ] 303g and chromium nitrate _{[Cr (NO 3) 3 · 9H} 2 O ] 12.8g of about 3l of distilled water, further Nissan Chemical 20.6 g of 20 wt% silica sol manufactured by Co., Ltd. was added and mixed thoroughly. To this solution, 250 ml of about 25% by weight of commercially available aqueous ammonia was added at room temperature with vigorous stirring during a few minutes. The pH of the solution was 10.5. After continuing stirring for about 5 minutes, the resulting brownish brown slurry was washed by repeating decantation and filtration, and the cake obtained was dried in a dryer at about 90 ° C. for 20 hours. Furthermore, this cake was baked in the air at 650 ° C. for 3 hours.

When the composition of the composite oxide thus obtained was measured by atomic absorption spectrometry, it was found that the atomic ratio was Fe: Si: Cr = 87: 9: 4.
Agglomerate catalyst is crushed into 20 to 32 mesh, sieved to 20 ml
Was charged into a normal quartz reaction tube having an inner diameter of 30 mmΦ. The temperature of the catalyst bed was set to 560 ° C., and m-isopropylphenol and water were quantitatively supplied to the catalyst bed through a preheating vaporization mixer kept at about 330 ° C., and passed through the catalyst layer. In this case, the liquid hourly space velocity (LHSV) was 0.3 hr ⁻¹ with respect to m-isopropylphenol, while the water LHSV was 0.4 hr ⁻¹ . The reaction product is analyzed by gas chromatography,
The conversion rate of the raw material m-isopropylphenol and the selectivity of the product were determined. Table 1 shows the results when a steady reaction result was obtained by continuing the reaction for about 5 hours.

Example 2 To 2 l of an aqueous solution in which 202 g of ferric nitrate nonahydrate and 4.28 g of chromium nitrate nonahydrate were dissolved, 0.5 l of an aqueous solution in which 5.03 g of germanium oxide was dissolved was added, and then 25% aqueous ammonia was added. The pH of the solution was adjusted to 7 by adding gradually. The precipitate formed was washed with water, filtered, dried at 90 ° C. for one day and then calcined at 700 ° C. for 3 hours to prepare a Fe ₂ O ₃ .GeO ₂ .Cr ₂ O ₃ catalyst. The composition of this composite oxide was Fe: Ge: Cr = 88.8: 9.1: 2.1 in atomic ratio. The agglomerated catalyst was crushed to 20 to 32 mesh and 20 ml was filled in a usual quartz reaction tube. The temperature is 560 ℃ and m
-Ethylphenol and water were reacted. The results are shown in Table 2.
Shown in.

Example 3 In the catalyst preparation of Example 1, after adding silica sol,
Further, a composite metal oxide of Fe ₂ O ₃ .SiO ₂ .CaO.Cr ₂ O ₃ was prepared in the same manner as in Example 1 except that the calcium hydroxide powder was mixed. Its composition is atomic ratio% Fe: Si: C
It was a: Cr = 86: 8: 2: 4.

Dehydrogenation of 6-methyl-3-isopropylphenol was carried out using this catalyst. The results are shown in Table 3.

Example 4 In the same manner as in Example 1, except that 49.1 g of zirconyl nitrate [ZrO (NO ₃ ) ₂ .2H ₂ O] was added instead of adding silica sol, Fe ₂ O ₃ —ZrO ₂ — The composite oxide of Cr ₂ O ₃ was prepared and its composition was 78: 18: 4 in atomic ratio. Table 4 shows the results of carrying out a dehydrogenation reaction of p-isopropylphenol using this as a catalyst.

COMPARATIVE EXAMPLE 1 20 catalysts G64A manufactured by Nissan Gardler Co., which contains iron oxide as a main component, are used.
Approximately 32 mesh was used after crushing and sieving. The catalyst composition was roughly as follows. Fe ₂ O ₃ is 73.5 wt%, Cr ₂ O ₃ is 1.9 w
t%, K ₂ CO ₃ is 21.6 wt%.

The dehydrogenation reaction of m-isopropylphenol was carried out in the same manner as in the example. The results are shown in Table 5.

Comparative Example 2 A catalyst composed of iron oxide and chromium oxide was prepared in the same manner as in Example 1 except that silica sol was not added. The composition was atomic ratio of Fe: Cr = 94: 6. Using this catalyst, the dehydrogenation reaction of m-isopropylphenol was carried out in the same manner as in Example 1. As a result m-
The conversion rate of isopropylphenol was 13%, and the selectivity of m-isopropenylphenol was 67%, showing low catalytic performance.

Comparative Example 3 Iron oxide-strontium oxide obtained by using ferric nitrate and strontium nitrate as raw materials (composition: atomic ratio: Fe: S
Using r = 92: 8, the miscellaneous hydrogen reaction of m-isopropylphenol was carried out in the same manner as in Example 1. Single yield is 17.5%,
The selectivity of m-isopropenylphenol was 65%.

Comparative Example 4 Table 6 shows the results of carrying out a dehydrogenation reaction of m-isopropylphenol using silicon oxide alone prepared from the silica sol manufactured by Nissan Chemical Industries, Ltd. used in Example 1 as a catalyst.

Comparative Example 5 Using zirconium oxide prepared from zirconyl nitrate
The dehydrogenation reaction of m-ethylphenol was performed. The results are shown in Table 7.
Shown in.

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Claims (2)

[Claims] 1. An alkyl group-substituted phenol is contacted in the presence of a catalyst containing (a) iron oxide as a main component and (b) at least one of silicon oxide, germanium oxide and zirconium oxide as an auxiliary component. A method for producing an alkenyl group-substituted phenol, which is characterized by dehydrogenation. 2. A catalyst containing chromium oxide in addition to iron oxide (a) and at least one of silicon oxide, germanium oxide and zirconium oxide (b).
The method described in the section.