JPH0227974B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, R ₁ , R ₂ , R ₃ , R ₄ represent hydrogen or a saturated aliphatic hydrocarbon group such as methyl, ethyl, isopropyl, tertiary butyl, etc.) and methanol in a gas phase. When selectively methylating the ortho position of phenols by contacting them, vanadium oxide, iron oxide and chromium oxide are the main components,
Furthermore, the present invention relates to a method for producing an ortho-methylated phenol compound, which is characterized by using a catalyst to which a small amount of an alkali metal oxide is added, if necessary. The production of ortho-substituted phenols, such as ortho-cresol and 2,6-xylenol, is of great industrial interest because they can be used as raw materials for plastics. Many techniques regarding these synthesis methods have been known for a long time. For example, a method using aluminum oxide as a catalyst (British Patent No. 717588), a method using magnesium oxide as a catalyst (US Patent No. 3446856),
No.) has been proposed. However, when the former catalyst is used, the activity and ortho-position selectivity are low, and methylated phenols at the meta- and para-positions are produced as by-products. Separating 2,6-xylenol from these mixtures requires complicated separation and purification steps, and is not an advantageous method for industrial implementation. Moreover, in the case of the latter catalyst, since the catalytic activity is low, it is necessary to maintain the reaction temperature at an extremely high temperature of 475 to 600° C., and in addition, it has the disadvantage that the activity decreases quickly. On the other hand, in order to solve these drawbacks, a catalyst containing vanadium oxide and iron oxide has been proposed (Japanese Patent Publication No. 47-37943). This catalyst has high activity and 300
It is possible to carry out the reaction at a relatively low temperature of ~400℃, and it also has relatively high ortho-position selectivity, which is sufficient for industrially advantageous implementation. I haven't. Furthermore, since the catalyst activity decreases over time, it is often necessary to stop the reaction and regenerate the catalyst. Japanese Patent Application No. 57-173852 discloses a technique in which the ortho-position selectivity of the catalyst and the deterioration of its activity can be improved by adding an alkali metal to a vanadium-iron catalyst. However, even in this method, the methanol selectivity tends to decrease over time, and it cannot be said that the deterioration of catalyst activity is sufficiently improved in industrial implementation. Japanese Patent Publication No. 51-12610 discloses that the ortho position of phenol or ortho-cresol is removed with methanol at 250 to 550°C in the presence of an oxide of chromium and iron containing iron in an atomic ratio of 9 to 1/9 to chromium. A method for methylation is described. In this method, the activity of the catalyst is low, and the selectivity for methanol alkylation at the ortho position (hereinafter referred to as methanol selectivity) and the ortho position selectivity for phenol (hereinafter referred to as phenol selectivity) are also low. Also, the catalyst life is not sufficient. When ortho-alkylating a phenol compound with methanol, Japanese Patent Publication No. 52-12690 describes a method using iron oxide, chromium oxide, and silica as a catalyst; Japanese Patent Publication No. 52-12692 describes a method using iron oxide, chromium oxide,
Methods using silica and alkali metal oxide catalysts are described. However, all of these methods have the drawbacks of high methanol decomposition rates, generating a large amount of gases such as CO ₂ , CO, and CH ₄ , low methanol selectivity, and furthermore, methanol selectivity decreasing over time. In general, conventional techniques related to this reaction show a tendency for the methanol selectivity to decrease rapidly as the reaction time elapses, which makes it unavoidable to perform regeneration frequently. As a result of studies to overcome these drawbacks, the present inventors found that (V) ₁ (Fe) a (Cr) b (A) c (where A is an element of Li, Na, K, Rb, and Cs) was used as a catalyst. one or more alkali metal elements selected from among; a, b, and c are the atomic ratios to vanadium element 1; a=0.1 to 10; b is a number satisfying 0<b/1+a<0.5; The present inventors have discovered that when an oxide of a metal represented by c=0.2 or less is used, it exhibits excellent properties that could not be predicted from the prior art, and has accomplished the present invention. That is, the present invention provides the general formula (In the formula, R ₁ , R ₂ , R ₃ , R ₄ represent hydrogen or a saturated aliphatic hydrocarbon group such as methyl, ethyl, isopropyl, tertiary butyl, etc.) (V) ₁ (Fe)a(Cr) as a catalyst when selectively methylating the ortho position of phenols by contacting them.
b(A)c (Here, A is one or more elements selected from alkali metals, and subscripts a, b, and c are vanadium elements 1
atomic ratio, a=0.1 to 10, b is 0
<b/1+a<0.5, c=0.2 or less) This is a method for producing an ortho-methylated phenol compound using a metal oxide represented by the following formula. The features of the present invention are as follows: 1) There is little decline in catalyst activity over time. 2) Methanol selectivity is high from the beginning and decreases little over time. 3) Phenol selectivity is high from the beginning and does not decrease over time. It has this excellent feature. Adding chromium oxide to vanadium oxide and iron oxide, which are one of the constituent elements of the present invention, has a very large effect in reducing the decline in catalyst activity over time. Normally, in operation to maintain a constant phenol conversion rate, the activity of the catalyst decreases over time, so the reaction temperature must be raised at a rate of about 0.5 to 2°C/day, but when this catalyst is used, this temperature can be increased. The increase range is extremely small, 0.1 to 0.5
It is about ℃/day. This has the advantage that reaction operation management becomes extremely easy in order to obtain products with constant specifications. In this reaction, the methanol selectivity generally decreases over time, making regeneration inevitable from an economical point of view, but surprisingly, this tendency is extremely small for this catalyst, and the initial selectivity is extremely high. methanol selectivity can be maintained for a long period of time. As described above, since the decrease in catalyst activity is small and the tendency for decrease in methanol selectivity is extremely small, the period until regeneration of the catalyst can be extended to an extent unimaginable from the conventional concept. The preferred composition of vanadium, iron, and chromium in the catalyst of the present invention is an atomic ratio of 1 to 1 vanadium element.
This is the case when iron is 0.1 to 10, and chromium is 0.5 or less when the total elements of vanadium and iron are set to 1. More preferably 0.3 to 1 vanadium element
When the total elements of 2 iron, vanadium and iron are set to 1
This is the case when chromium of 0.2 or less and 0.001 or more is used. A small amount of chromium in the catalyst has a great effect on preventing a decrease in catalyst activity, but when the total element of vanadium and iron is 1, if it exceeds 0.5, the activity of the catalyst decreases. The catalyst of the present invention further contains a small amount of one or more alkali metal oxides selected from the elements Li, Na, K, Rb, and Cs in addition to vanadium oxide, iron oxide, and chromium oxide. In the case of the present invention, the addition of an alkali metal oxide is effective in improving the ortho-position selectivity of the catalyst and suppressing carbon deposition on the catalyst. Catalysts containing alkali metal oxides have significantly improved ortho position selectivity;
The production of meta-cresol and para-cresol, which are difficult to separate from 2,6-xylenol, is virtually eliminated, making it possible to obtain an extremely pure 2,6-xylenol product. In addition, when producing 2,6-xylenol using phenol as a raw material,
Even if the conversion rate of phenol is increased to nearly 100%,
The amount of 2,4,6-trimethylphenol produced is small. Furthermore, since the catalyst containing an alkali metal oxide drastically reduces carbon precipitation, the effect of extending the catalyst life by adding chromium oxide is mutually enhanced. The amount of alkali metal oxide added is the atomic ratio of the alkali metal element to 1 vanadium element in the catalyst.
It is 0.2 or less. If the amount of alkali metal oxide is greater than the range of the present invention, the activity of the catalyst will be reduced. The catalyst of the present invention can be carried out without any support, but it can also be used with a suitable support. When used with a support, the type and amount of support must be appropriately selected in order to improve the strength of the catalyst and maintain ortho-position selectivity, and silica is suitable for this purpose. The supported amount of silica is several percent to 95%, particularly preferably 10 to 80%.
is within the range of In particular, when conducting a reaction using a fluidized bed reactor, the wear resistance of the catalyst is required to be significantly higher than that of a fixed bed, but the amount of silica supported is 10%.
If it is above, preferably 20% or more, it can sufficiently withstand even a fluidized bed. Raw materials for iron oxide, vanadium oxide, chromium oxide, and alkali metal oxides used in preparing catalysts include hydroxides of the respective metals, halides such as chlorides, nitrates, sulfates, organic acid salts, etc. be. Various known methods can be used to prepare the catalyst. (Example of unsupported catalyst preparation) (1) A coprecipitate obtained by neutralizing a mixed aqueous solution of salts of vanadium, iron, and chromium with an alkali such as ammonia is washed with water, filtered, and dried at 100 to 200°C to obtain an alkali metal salt. A method of preparing a catalyst by immersing it in an aqueous solution, evaporating it to dryness, and then calcining it. (2) A method in which a mixed aqueous solution of vanadium, iron, chromium, and alkali metal salts is dried and then fired. (3) A method can be used in which a hydroxide precipitate cake is prepared by a precipitation method from an aqueous solution of iron and chromium salts, and this is immersed in an aqueous solution of ammonium metavanadate and an alkali metal salt, and then calcined to dryness while kneading. (Example of catalyst preparation using silica as a carrier) (1) Preparation of fixed bed catalyst Ferric nitrate and chromium nitrate are added to a solution in which ammonium metavanadate is dissolved in hot water, dissolved, and then treated with an alkali such as ammonia. Neutralize. The formed precipitate is washed with water, filtered, dried and ground. After adding an aqueous solution of alkali metal salt and silica sol to this material and adjusting the moisture content to an appropriate amount for easy molding,
Mold. Alternatively, an aqueous solution containing ammonium metavanadate, ferric nitrate, chromium nitrate, and alkali metal salts is dried in a known spray dryer, and the dried particles are kneaded with denitrifying silica sol at a low temperature, then molded into an appropriate shape, and fired. and used as a catalyst. (2) Preparation of catalyst for fluidized bed First, a raw material slurry is prepared by adding ferric nitrate, chromium nitrate, nitrate of component A, and silica sol to a solution of ammonium metavanadate in hot water while stirring. It can be carried out suitably. Here, a slurry of fine suspended solids uniformly dispersed in a silica colloid sol is obtained. The slurry is then dried using a known spray dryer to obtain spherical dry fine particles. Atomization of the raw material slurry can be carried out by any of the centrifugal, two-fluid nozzle, or high-pressure nozzle methods commonly used in industrial practice, but the centrifugal method is particularly preferred. In the centrifugal system, the particle size can be distributed between 10 and 150 microns, which is suitable for use in a fluidized bed reactor, by adjusting the rotation speed of the disk and the feed rate of the slurry. The dried fine particles thus obtained are denitrified and calcined at a low temperature and used as a catalyst for a fluidized bed. For the present invention, the ratio of methanol to phenols in the feed is from 1:1 to 20, preferably from 1:2 to 8. Moreover, water vapor or inert gas can also be introduced as necessary. The reaction temperature is suitably in the range of 250 to 500°C, preferably 280 to 400°C. The reaction pressure may be normal pressure, but it can also be carried out under reduced pressure or increased pressure, if necessary. The contact time between the gas and the catalyst is 0.5 to 50 seconds, preferably 1 to 50 seconds.
20 seconds is suitable. The present invention will be explained in more detail with reference to Examples below, but it goes without saying that the scope of the present invention is not limited to these. In addition, the reaction results in the Examples were defined by the following formula. All are on a molar basis. Phenol compound conversion rate (%) = (1-reacted phenol compound/supplied phenol compound) x 10
0 Phenol compound selectivity (%) = Total of compounds methylated only at ortho position / Reacted phenolic compound x 100 Methanol selectivity (%) = Methanol reacted with ortho position of phenolic compound / Reacted methanol x 100 Reference example 1 Ammonium metavanadate 0.044 mol, oxalic acid
Dissolve 0.088 mol in 100 ml of water. Ferric nitrate nonahydrate 0.044 mol, chromium nitrate 9
A solution of 8.8 x 10 ^-4 moles of hydrate dissolved in 300 ml of water was added to the above solution, and then 25% ammonia water was added dropwise from a biuret while vigorously stirring with a stirrer, and the dropping was stopped at pH 8.0. Thereafter, stirring was continued for 1 hour, and the resulting precipitate was filtered and dried at 150°C for 5 hours. After pre-calcining this material at 450℃ for 3 hours, it was heated to 600℃ for 4 hours.
The product was calcined for an hour, and the product was crushed to use particles of 15 to 35 mesh as a catalyst. The composition of this catalyst is V ₁ Fe ₁ Cr _0.02
It was hot. 2.5 g of the catalyst prepared in this way was 18 mm in inner diameter.
into a Pyrex reactor, and the temperature of the catalyst layer was
The temperature was set at 330°C, and a reaction solution containing phenol, methanol, and water in a molar ratio of 1:5:3 was supplied and reacted for a contact time of 3.0 seconds. The reaction products were collected in an air-cooled trap and the reaction results were analyzed using gas chromatography. This reaction was carried out continuously for 240 hours. The results are shown in Table 1. Comparative Example 1 In the same manner as in Example 4 of Japanese Patent Publication No. 47-37943, an aqueous solution in which ferric nitrate nonahydrate was dissolved in advance was neutralized with aqueous ammonia, and the resulting precipitate was treated with ammonium metavanadate. After adding an aqueous acid solution and concentrating to dryness on a hot water bath, the mixture was calcined at 450°C for 3 hours, and further calcined at 600°C for 4 hours to prepare a catalyst. The composition of this catalyst was V ₁ Fe ₁ . The same reaction as in Reference Example 1 was carried out using this product as an iron-vanadium binary oxide catalyst. The results are shown in Table 1. Comparative Example 2 0.05 mol of ferric nitrate (Fe(NO ₃ ) ₃ 9H ₂ O) and chromium nitrate (Cr
(NO ₃ ) ₃ 9H ₂ O) 25% solution of 0.001 mol
The precipitate generated by neutralization with aqueous ammonia was washed with water, dried at 110°C for a day and night, calcined at 450°C for 3 hours, and further calcined at 600°C for 4 hours to prepare a catalyst. The composition of this catalyst was Fe ₁ Cr _0.02 . The same reaction as in Reference Example 1 was carried out using this product as an iron-chromium binary oxide catalyst. The results are shown in Table 1.

[Table] In Reference Example 1, no decrease in catalyst activity was observed even after 240 hours, and the methanol selectivity remained at the initial high selectivity. On the other hand, in Comparative Examples 1 and 2, the reaction activity and methanol selectivity decreased significantly as the reaction progressed. Example 1 Ammonium metavanadate 0.044 mol% 90
Dissolve ferric nitrate (Fe(NO ₃ ) ₃・9H ₂ O) in 110 g of pure water heated to ℃ and add it to the solution while stirring vigorously.
0.044 mol, chromium nitrate (Cr(NO ₃ ) ₃ 9H ₂ O) 8.8×
After adding 5.07 g of silica sol (manufactured by Nissan Chemical, trade name Snotex N) containing 10 ^-4 mol of potassium nitrate, 8.8 x 10 ^-4 mol of potassium nitrate, and 30% by weight of SiO ₂ , it was evaporated to dryness and further heated at 350°C for 2 hours. 3 at 700℃ after pre-drying
Baked for an hour. This material was crushed and 15 to 35 mesh was used as a catalyst. The composition of this catalyst was V ₁ Fe ₁ Cr _0.02 K _0.02 /20% SiO ₂ . The same procedure as in Reference Example 1 was carried out except that 2.5 g of this catalyst was used. As a result, the phenol conversion rate after 24 hours, 120 hours, and 240 hours was 97%, 96%, 96%, the phenol selectivity was 98.2%, 98.7%, 98.8%, and the methanol selectivity was 76.0, 77.2, 76.0. It was %. It can be seen that the phenol selectivity is improved by adding the alkali metal oxide. Reference Examples 2 to 6 Catalysts having the compositions shown in Table 2 were prepared in the same manner as in Example 1. Using these catalysts and using the same reaction tube as in Reference Example 1, the reaction temperature was set so that the phenol conversion rate was approximately 90%, and the reaction was carried out for 48 hours. The reaction solution used had a composition of phenol, methanol, and water in a ratio of 1:7:3. The results are shown in Table 2. Comparative Examples 3 to 5 Catalysts whose compositions of vanadium, iron, and chromium in the catalyst were outside the scope of the present invention were prepared in the same manner as in Example 1, and used as catalysts for Comparative Examples 3 to 5 in Reference Examples 2 to 5.
The reaction was carried out in the same manner as in 6. The results are shown in the second
Shown in the table.

[Table] Catalysts with compositions outside the scope of the present invention (Comparative Examples 3 to 3)
All of 5) have slightly low reaction activity and high reaction temperature. It can also be seen that the phenol conversion rate and methanol selectivity change significantly over time. Example 2 Ammonium metavanadate 0.0549 mol, oxalic acid
Dissolve 0.11 mol in 100 ml of water. Ferric nitrate nonahydrate 0.044 mol, chromium nitrate 9
A solution of 1.1 x 10 ^-3 moles of hydrate dissolved in 300 ml of water was added to the above solution, and then 25% ammonia water was added dropwise from a biuret while stirring vigorously with a stirrer, and the dropping was stopped at pH 8.0. . then 1
After stirring for an hour, the precipitate formed was filtered and heated to 150°C.
It was dried for 5 hours. After crushing this material, add 0.82 mmol of potassium nitrate.
After immersing it in a solution dissolved in 100 ml of water, it was evaporated to dryness while stirring on a water bath. This material was calcined at 450°C for 3 hours and then fired at 600°C for 4 hours. 15-35 meshes were used as catalysts. The composition of this catalyst was V ₁ Fe _0.8 Cr _0.02 K _0.015 .
The catalyst thus prepared was packed in the same reaction tube as in Reference Example 1, and the molar ratio of phenol, methanol,
Contact time of 6.0 seconds for reaction solution with water composition of 1:7:3
Operation was carried out for 240 hours to maintain the phenol conversion rate close to 90% by adjusting the supply and reaction temperature. The results are shown in Table 3. Comparative Example 6 Ferric nitrate nonahydrate (Fe(NO ₃ ) _{3.9H 2} O) was prepared in the same manner as in Example 1 of Japanese Patent Publication No. 52-12692.
0.74 mol, chromium nitrate nonahydrate (Cr(NO ₃ ) ₃ .
0.0074 mol of 9H ₂ O) was dissolved in 3 water, and 1.65 g of water glass (SiO ₂ min 30%) was diluted in water and added while stirring at room temperature. The mixture was then neutralized with 10% aqueous ammonia and stirred for 1 hour to age the hydrogel.
The hydrogel precipitate was filtered, washed with water, and pre-dried at 180°C for 10 hours. Next, the dried gel was ground into 15 to 35 meshes and immersed in 75 ml of an aqueous solution containing 0.127 mmol of potassium carbonate for 16 hours.
After that, pass through the immersion gel and dry at 180℃ for 4 hours.
A catalyst was obtained by calcining at 470°C for 7 hours. The catalyst composition is Fe ₂ O ₃ : SiO ₂ : Cr ₂ O ₃ : K ₂ CO ₃ =
The molar ratio was 100:2:1:0.018. Using this product as a catalyst in Comparative Example 6, the same reaction as in Example 2 was carried out. The results are shown in Table 3.

[Table] In this way, the reaction temperature and phenol conversion rate of the catalyst of Example 2 hardly changed after 240 hours of reaction, and the methanol selectivity remained almost constant, whereas the catalyst of Comparative Example 6 The increase in reaction temperature and decrease in methanol selectivity are noticeable. Example 3 Ammonium metavanadate (NH ₄ VO ₃ ) 0.2
Dissolve the mole in 500 g of pure water heated to 90°C, add ferric nitrate (Fe
(NO ₃ ) ₃・9H ₂ O) 0.2 mol, chromium nitrate (Cr
(NO ₃ )・9H ₂ O) 0.012 mol, sodium nitrate
The raw material slurry obtained by adding 0.005 mol was evaporated to dryness on a hot water bath, and then preliminarily calcined at 350°C for 2 hours. Take 20g of this and grind it to 30% by weight.
Add 28.6 g of silica sol (Snowtex N manufactured by Nissan Chemical Co., Ltd.) containing SiO ₂ and knead thoroughly while heating on a hot water bath. After adjusting the moisture concentration to an appropriate level that allows molding, the mixture is 5 mm in diameter and 5 mm in length. It was molded into a cylindrical shape. This was dried at 100°C for 12 hours and then fired at 700°C for 3 hours. The catalyst composition was 20% by weight of V ₁ Fe ₁ Cr _0.06 Na _0.025 /SiO ₂ . 6 g of this catalyst was packed in a glass reaction tube with an inner diameter of 2 cm, and the molar ratio of phenol, methanol, and water was 1:1.
A 5:3 reaction solution was supplied with a contact time of 6.5 seconds, and 312
The reaction was carried out at ℃ for 48 hours. The reaction result after 48 hours was a phenol conversion rate of 95.2.
%, phenol selectivity 98.9%, methanol selectivity
It was 79.2%. After the reaction, the catalyst is taken out and sieved through a 16-mesh sieve, and the powdering rate is defined as the ratio of the catalyst that passed through the mesh to the total weight.The powdering rate is 0.1.
% or less, and no powdering of the catalyst occurred. Example 4 Ammonium metavanadate (NH ₄ VO ₃ ) 0.20
Dissolve the mole in 500g of pure water heated to 90℃, and add ferric nitrate (Fe
(NO ₃ ) ₃ 9H ₂ O) 0.20 mol, chromium nitrate (Cr
(NO ₃ ) ₃・9H ₂ O) 0.01 mol, potassium nitrate (KNO ₃ ) 0.005 mol and 30% by weight of SiO ₂ silica sol (Snowtex N manufactured by Nissan Chemical) 118 g
was added and evaporated to dryness, further pre-dried at 350°C for 2 hours, and calcined at 700°C for 3 hours. This material was crushed and 15 to 35 mesh was used as a catalyst. The composition of this catalyst was V ₁ Fe ₁ Cr _0.05 K _0.025 /SiO ₂ 50% by weight. 2.5 g of the catalyst thus prepared was packed into the same reaction tube as in Reference Example 1. Molar ratio of phenol, methanol, and water is 1:
A reaction solution having a composition of 7:3 was supplied for a contact time of 6.0 seconds, and the reaction was carried out at a reaction temperature of 315° C. for 48 hours. The reaction result after 48 hours was a phenol conversion rate of 91.0.
%, phenol selectivity 98.2%, methanol selectivity
It was 78.0%. Example 5 Ammonium metavanadate (NH ₄ VO ₃ ) 585
Dissolve g in 12,400 g of pure water heated to 90°C, add ferric nitrate [Fe
(NO ₃ ) ₃・9H ₂ O〕2020g, Chromium nitrate (Cr
(NO ₃ ) ₃ 9H ₂ O) 120g, potassium nitrate (KNO ₃ )
12.8g, 3.5g lithium nitrate ( _LiNO3 ) and 30
A raw material slurry obtained by adding 2950 g of silica sol (Snowtex N, manufactured by Nissan Chemical Industries, Ltd.) containing % by weight of SiO ₂ was sent to a co-current spray dryer and dried. The obtained dry powder was pre-calcined at 350°C for 2 hours using a tunnel kiln, and then
Firing was performed at 700°C for 3 hours. The composition of this catalyst is
It is expressed as V ₁ Fe ₁ Cr _0.06 Li _0.01 K _0.025 /50% by weight SiO ₂ . The surface area of this catalyst was measured by the BET method and was 4.0 m ² /g, and electron microscopic examination showed that it had a spherical shape that was consistent with the fluidized bed method. 300g of this catalyst was put into a fluidized bed reactor with a diameter of 1.5 inches, the reaction temperature was maintained at 325℃, the pressure was maintained at atmospheric pressure, and the ratio of phenol, methanol, and water was 1:5:
The raw material solution No. 3 was introduced into the reactor through the evaporator.
At this time, the flow rate was adjusted so that the contact time between the raw material gas and the catalyst was 8.0 seconds. All of the gas flowing out from the reactor was passed through a condenser, and the condensed liquid was analyzed by gas chromatography. This reaction was carried out continuously for 600 hours. The reaction results are summarized in Table 4. In addition, an abrasion resistance test was conducted on the catalyst before and after the reaction. The abrasion resistance test is carried out as a normal test method for FCC catalysts.
The catalyst was placed in a 1.5 inch inner diameter vertical tube with a perforated disc with three 64 inch orifices.
50 g was accurately weighed and air was forced through the perforated disk at a rate of 15 cubic feet per hour to create a vigorous flow. The degree of catalyst abrasion was determined as the ratio of the weight of the catalyst that atomized and escaped from the top of the vertical tube over a period of 5 to 20 hours to the initial input amount.

[Table] 〓
Results 〓 Post-reaction catalyst 1.1
Examples 6-7 Catalysts having the compositions shown in Table 5 were prepared in the same manner as in Example 11. Example 5 was repeated using this catalyst. The results are shown in Table 5.

【table】

Claims (1)

[Claims] 1 General formula () (In the formula, R ₁ , R ₂ , R ₃ , R ₄ represent hydrogen or a saturated aliphatic hydrocarbon group such as methyl, ethyl, isopropyl, tertiary butyl, etc.) (V) ₁ (Fe) a (Cr) b (A) c (where A is one or more elements selected from alkali metals) as a catalyst when selectively methylating the ortho position of phenols by contacting them. The subscripts a, b, and c are the atomic ratios to vanadium element 1, and the metal oxides shown are A method for producing an ortho-methylated phenol compound.