JPH0212936B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to an improved method for selectively converting phenolic compounds into orthoalkylated products using alcohols. Conventionally, among ortho-alkylated phenols, 2,6-dimethylphenol in particular is a raw material for polyphenylene oxide, which is a useful plastic, and many studies have been conducted on methods for producing it. As a method for orthoalkylation of phenols,
One method that has already been industrialized is a method in which phenols and alcohols are reacted in the gas phase using a solid acid such as alumina as a catalyst, but this method does not have selectivity for the position where the phenols are alkylated; Alkylation occurs to a considerable extent not only at the ortho position but also at the meta and para positions, and complex separation and purification steps are required to separate ortho-alkylated products. In addition, as another industrial method, a method using a magnesium oxide catalyst has been implemented, but
Originally, this catalyst system had low reaction activity and the reaction temperature was
If the temperature is not higher than 475℃ (in practice, 500℃ or higher), not only will the reaction not proceed sufficiently, but the life of the catalyst will be short, and unless the catalyst is regenerated after every short use, it will not last for a sufficient amount of time. It has drawbacks such as being unusable. In order to solve these various problems, catalysts in which various second components are added to magnesium oxide,
Catalyst systems containing iron oxide as the main component and various secondary and tertiary components added thereto have been disclosed; Under reaction conditions that sufficiently increase activity, the catalyst has drawbacks such as alkylation reactions at positions other than the ortho position and the formation of polyalkylated products, so it cannot be said to be a catalyst with excellent performance. As a result of various studies aimed at improving these drawbacks, the present inventors have previously developed a catalyst containing chromium oxide and tin oxide (Japanese Patent Application Laid-open No. 1983-66628), a catalyst containing chromium oxide, tin oxide, and iron oxide. Catalyst (JP-A-Sho)
54-79237), chromium oxide, tin oxide,
Catalyst containing iron oxide and sulfate radical
100330). However, as a result of further study, it became clear that these catalysts were still unsatisfactory and that further improvements were desirable. The present invention aims to provide a method for producing an ortho-alkylated phenolic compound which is improved in that it uses a catalyst that has excellent reaction selectivity, particularly selectivity based on alcohol. The present invention further aims to provide a method for producing orthoalkylated phenolic compounds, which is improved in that it uses a catalyst that is excellent in low-temperature activity, stability, and reduction in the rate of attachment of hydrocarbon species to the catalyst surface. be. The method for producing an orthoalkylated phenolic compound of the present invention involves reacting a phenolic compound having a hydrogen atom at the ortho position with an alcohol in the gas phase in the presence of a catalyst to produce an orthoalkylated phenolic compound. In manufacturing, 1. (a) chromium oxide and tin oxide, and (b) at least one oxide selected from the group consisting of germanium oxide, silicon oxide, and lead oxide as a component; The metal atomic ratio of chromium:tin:(b) group metal is 100:0.1~60:0.04~30
2 (a') chromium oxide, tin oxide and iron oxide; and (b) at least one oxide selected from the group consisting of germanium oxide, silicon oxide and lead oxide as a component; Metal atomic ratio of oxide: Chromium: Tin: Iron: Group (b) metals: 100:0.1 to 60:0.01
~20:0.04~30, 3 (a″) chromium oxide, tin oxide and sulfate radical, and (b) at least one oxide selected from the group consisting of germanium oxide, silicon oxide and lead oxide. Contained as a component, the ratio of the metal atom of the component oxide and the sulfur atom of the sulfuric acid group Chromium: Tin: Sulfur: (b)
Catalyst whose group metal is 100:0.1-60:0.25-20:0.04-30 or 4 (a) chromium oxide and tin oxide (b) at least one member selected from the group consisting of germanium oxide, silicon oxide and lead oxide and (c) at least one compound selected from the group consisting of potassium carbonate, potassium silicate, and magnesium oxide as a component, and the metal atomic ratio in the component is chromium:tin:(b) group metal : Potassium and/or magnesium is 100:0.1~60:0.04~30:0.01~
It is characterized by using a catalyst having a molecular weight of 10. Among the catalysts used in the process of the invention (a)
In the case of a catalyst containing chromium oxide, tin oxide, and (b) one or more selected from germanium oxide, silicon oxide, and lead oxide as essential components, the content ratio is chromium: tin: above. (b)
The appropriate atomic ratio of the components is 100:0.1 to 60:0.04 to 30, preferably 100:1 to 30:0.04 to 15. In the case of a catalyst containing iron oxide in addition to component (a) above, the content ratio is chromium:iron atomic ratio of 100:
0.01 to 20 is suitable, particularly preferably 100:0.1
-11, and particularly when silicon is contained in the catalyst, the iron:silicon atomic ratio is preferably 100:20 or more. In the case of a catalyst containing a sulfuric acid group in addition to component (a) above, the content ratio is chromium:sulfur atomic ratio of 100:
0.25 to 20 is suitable, particularly preferably 100:0.5
~10 range. In the case of a catalyst containing potassium carbonate, potassium silicate and/or magnesium oxide as component (c) in addition to components (a) and (b) above, the content ratio is the chromium:potassium and/or magnesium atomic ratio. The ratio of 100:0.01 to 10 is suitable, and the range of 100:0.05 to 5 is particularly preferred. Although it is not possible to completely separate and understand the effects of each added component in the catalyst used in the method of the present invention, (b)
The components germanium oxide, silicon oxide, and lead oxide mainly improve the selectivity based on alcohols, and the iron oxide or sulfate radical added to component (a) improves the reaction activity at low temperatures. Furthermore, (c)
The components potassium carbonate, potassium silicate, and magnesium oxide reduce the rate of deposition of hydrocarbon species on the catalyst surface, which is the main cause of reduced catalyst activity. The phenolic compound used in the method of the present invention is a phenolic compound having at least one hydrogen atom in the ortho position, and has the general formula (1). (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms,
Or it represents an aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl. ). For example, phenols, ortho-, meta- or para-cresols, 2,3
-, 2,4-, 2,5-, 3,4- or 3,5
- xylenol, trimethylphenol,
Tetramethylphenols, n- or iso-propylphenols, n-/iso- or tert
The present invention is also applicable to phenol compounds in which two or more different alkyl groups are added to the benzene nucleus. The alcohols used in the present invention are lower saturated aliphatic alcohols having 1 to 4 carbon atoms,
For example, methyl alcohol, ethyl alcohol, iso-propyl alcohol, n-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol. As raw materials for various metal oxides used in the method of the present invention, commercially available metal oxides can be used, but metal hydroxides, halides, carbonates, various mineral acid salts, organic acid salts, etc. Depending on the situation, sulfides, hydrides, etc. can be used. Various known methods can be used to produce the catalyst, such as mixing the various raw materials mentioned above, adding a small amount of water, and thoroughly kneading with a kneader, mixer, etc.
There are methods such as drying, making an aqueous solution of various raw materials and adding basic ingredients to it to co-precipitate as an insoluble precipitate, or adding some ingredients separately by dipping, kneading, etc. It is possible. The resulting catalyst composition is usually
Dry at a temperature of 200℃ or less, if necessary,
Known additives such as PVA, crystalline cellulose,
Molding aids and the like are added, and the mixture is molded and fired by methods such as extrusion molding, compression molding, and rolling molding, and is used for reaction after treatment such as activation if necessary. When carrying out the method of the present invention, the molar ratio of the phenolic compound and alcohol to be supplied is 1:1 to 1:1.
A ratio of 1:10 is suitable, and a ratio of 1:1 to 1:8 is more preferred. Further, it is preferable to use nitrogen, carbon dioxide, hydrogen, steam, or gas components generated when carrying out the present invention to supply raw materials to the reaction system. In the method of the present invention, the reaction temperature is in the range of 270 to 450°C, preferably 290 to 430°C, and the raw material supply to the reaction system preferably has a liquid hourly hourly velocity (LHSV) of 0.1 to 10. The reaction can be carried out under normal pressure, reduced pressure, or increased pressure, and the reaction mode can be fixed bed, fluidized bed, or moving bed, although the fixed bed method is common. According to the method of the present invention, ortho-alkylated products of phenolic compounds can be produced from phenolic compounds and alcohols with good selectivity, particularly good selectivity based on alcohol. Furthermore, it increases the reaction activity of the catalyst at low temperatures and the stability of the catalyst, and also reduces the rate of deposition of hydrocarbon species on the catalyst surface, which is the main cause of the decrease in catalyst activity, and reduces the ortho-alkylation of phenolic compounds. can be manufactured. The present invention will be explained below with reference to Examples. Example 1 100g of chromium nitrate ()9 hydrate, tin chloride ()
5 g of dihydrate and 65 g of urea were dissolved in 1 part of water and heated on a heater to form a precipitate. After thoroughly washing the generated precipitate, 0.3 g of water glass No. 3 (JIS Sodium Silicate No. 3) was added, mixed with limescale, and dried at 140°C. The obtained catalyst composition
The particles were calcined at 600° C. in air for 10 hours, and then the particle size was adjusted to 20 to 32 meshes, and 10 c.c. thereof was filled into a glass reaction tube. A mixture of phenol and methanol with a molar ratio of 1:6 was vaporized by heating at 250°C, and then introduced into a reaction tube whose external temperature was adjusted to 425°C at a rate of 3.5 g per hour to carry out the reaction. Ta. The reaction product was condensed through a cooling water condenser and subjected to gas chromatography analysis. The results are shown in Table 1. Comparative Example 1 In the same manner as in Example 1, a catalyst was prepared without adding Water Glass No. 3, and the reaction was carried out under the same conditions. The results are shown in Table 1. Example 2 Chromium nitrate () 9-hydrate salt 100g, tin chloride ()
10g dihydrate, 5g iron nitrate nonahydrate, and urea
65g was dissolved in 1 water and heated on a heater to form a precipitate. After thoroughly washing the formed precipitate, 0.6 g of Mizugarasu No. 3 was added, mixed with a sieve, and dried at 140°C. The obtained catalyst composition
The particles were calcined at 600° C. in air for 15 hours, and then the particle size was adjusted to 20 to 32 meshes, and 10 c.c. of the particles were filled into a glass reaction tube. A mixture of phenol and methanol at a molar ratio of 1:6 was vaporized by heating at 250°C, and then introduced into a reaction tube whose external temperature was adjusted to 395°C at a rate of 3.5 g per hour to carry out the reaction. Ta. The reaction products were analyzed in a similar manner to Example 1. The results are shown in Table 1. Comparative Example 2 In the same manner as in Example 2, a catalyst was prepared without adding Water Glass No. 3, and the reaction was carried out under the same conditions. The results are shown in Table 1. Example 3 In the same manner as in Example 2, a catalyst was prepared by adding 0.2 g of germanium oxide instead of water glass No. 3, and the reaction was carried out under the same conditions. The results are shown in Table 1. Example 4 100g of chromium nitrate ()9 hydrate, tin chloride ()
10 g of dihydrate and 65 g of urea were dissolved in 1 part of water and heated on a heater to form a precipitate. After thoroughly washing the formed precipitate, 2 c.c. of a 1N sulfuric acid aqueous solution and 0.1 g of germanium oxide were added, thoroughly mixed, and dried at 140°C. The obtained catalyst composition was calcined at 600°C in air for 15 hours, and then the particle size was adjusted to 20 to 32 mesh.
10 c.c. of the solution was filled into a glass reaction tube. Mixing molar ratio of o-cresol and methanol: 1:
After heating and vaporizing the mixture of step 4 at 250℃, 370℃
The reaction was carried out by introducing the solution into a reaction tube whose external temperature was adjusted at a rate of 3 g per hour. The reaction product was analyzed in the same manner as in Example 1. The results are shown in Table 2. Example 5 A catalyst composition before calcination obtained in the same manner as in Example 4 was mixed with an aqueous potassium carbonate solution (potassium carbonate 20
mg dissolved in 200 c.c. of water) and approx.
The same procedure as in Example 4 was carried out except that the immersion treatment was carried out for 20 hours. The results are shown in Table 2.

【table】

[Table] Example 6 Chromium nitrate ()9 hydrate 100g, tin sulfate 7.5g
and 100 g of urea were dissolved in 1 water and heated on a heater to form a precipitate. After thoroughly washing the formed precipitate, 0.01 g of germanium oxide was added, thoroughly mixed, and dried at 140°C. The obtained catalyst composition was calcined at 550° C. in air for 15 hours, then compressed into tablets, and 10 c.c. thereof was filled into a glass reaction tube. A mixture of phenol and ethanol with a molar ratio of 1:3 was vaporized by heating at 250°C, and then introduced into a reaction tube whose external temperature was adjusted to 400°C at a rate of 3.5 g per hour to carry out the reaction. Ta. The reaction product was analyzed in the same manner as in Example 1. The results are shown in Table 3. Example 7 Chromium nitrate ()9 hydrate 100g, tin sulfate 7.5g
1 g, 7.5 g of iron nitrate nonahydrate, and 100 g of urea were dissolved in 1 part of water and heated on a heater to form a precipitate. After thoroughly washing the generated precipitate, add 5 c.c. of 1N sulfuric acid aqueous solution and germanium oxide.
0.01 g was added, thoroughly mixed, and dried at 140°C. The obtained catalyst composition was calcined at 550°C in air for 15 hours, and then the particle size was adjusted to 20 to 32 mesh.
10 c.c. of the solution was filled into a glass reaction tube. A mixture of phenol and ethanol with a molar ratio of 1:3 was heated and vaporized at 250°C, and then introduced into a reaction tube whose external temperature was adjusted to 375°C at a rate of 3.3 g per hour to carry out the reaction. Ta. The results are shown in Table 3. Example 8 A precipitate was produced in a manner similar to Example 7. After thoroughly washing the generated precipitate, add 0.1 g of germanium oxide and 0.5 g of magnesium hydroxide.
was added, mixed thoroughly, and dried at 140°C. The resulting composition was fired at 600°C in nitrogen for 15 hours, and then the particle size was adjusted to 20 to 32 meshes.
10 c.c. was filled into a glass reaction tube. A mixture of phenol and ethanol with a molar ratio of 1:3 was heated and vaporized at 250°C, and then introduced into a reaction tube whose external temperature was adjusted to 385°C at a rate of 3.4 g per hour to carry out the reaction. Ta. The results are shown in Table 3. Example 9 A precipitate was generated in the same manner as in Example 7, and after washing the generated precipitate, 50% potassium carbonate was added.
mg and 50 mg of potassium silicate were added, and heating was continued for an additional hour. 5 c.c. of a 1N sulfuric acid aqueous solution and 0.01 g of germanium oxide were added, mixed with limescale, and dried at 140°C. The resulting catalyst composition was heated to 550
C. in air for 15 hours, and then the particle size was adjusted to 20 to 32 meshes, and 10 c.c. thereof was filled into a glass reaction tube. A mixture of phenol and ethanol with a molar ratio of 1:3 was heated and vaporized at 250°C, and then introduced into a reaction tube whose external temperature was adjusted to 375°C at a rate of 3.4 g per hour to carry out the reaction. Ta. The results are shown in Table 3.

[Table] Example 10 In the same manner as in Example 1, 0.15 g of lead oxide was added instead of water glass No. 3 to prepare a catalyst, and the reaction was carried out under the same conditions. The results are shown in Table 4. Example 11 In the same method as in Example 2, 0.1 g of lead oxide and 0.05 g of germanium oxide were used instead of water glass No. 3.
A catalyst was prepared by adding g, and the reaction was carried out under the same conditions. The results are shown in Table 4. Example 12 In the same manner as in Example 2, water glass No. 3 was reduced to 0.1 g, and 0.08 g of germanium oxide was added and mixed with a sieve to prepare a catalyst, and the reaction was carried out under the same conditions. . The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1. In producing an ortho-alkylated product of a phenolic compound by reacting a phenolic compound having a hydrogen atom at the ortho position with an alcohol in the presence of a catalyst in the gas phase, (a ) chromium oxide and tin oxide, and (b) at least one oxide selected from the group consisting of germanium oxide, silicon oxide, and lead oxide as a component, and the metal atomic ratio of the component oxides is chromium:tin:( b) Group metal is 100: 0.1~60: 0.04~30
1. A method for producing an orthoalkylated phenolic compound, the method comprising using a catalyst. 2. When reacting a phenolic compound having a hydrogen atom at the ortho position with an alcohol in the gas phase in the presence of a catalyst to produce an orthoalkylated product of the phenolic compound, (a') chromium oxide, oxidized Contains tin and iron oxide, and (b) at least one oxide selected from the group consisting of germanium oxide, silicon oxide, and lead oxide as components, and the metal atomic ratio of the component oxides is chromium:tin:iron:( b) Group metal is 100:0.1~60:0.01
~20: A method for producing an orthoalkylated phenolic compound, characterized by using a catalyst having a ratio of 0.04 to 30. 3. In producing an ortho-alkylated product of a phenolic compound by reacting a phenolic compound having a hydrogen atom at the ortho position with an alcohol in the presence of a catalyst in the gas phase, (a″) chromium oxide, oxidized Contains as a component tin and a sulfate radical, and (b) at least one oxide selected from the group consisting of germanium oxide, silicon oxide, and lead oxide, and the ratio of the metal atom of the component oxide to the sulfur atom of the sulfate radical. Chromium: Tin: Sulfur: (b)
1. A method for producing an orthoalkylated phenolic compound, characterized in that a catalyst having a group metal ratio of 100:0.1 to 60:0.25 to 20:0.04 to 30 is used. 4. When reacting a phenolic compound having a hydrogen atom at the ortho position with an alcohol in the gas phase in the presence of a catalyst to produce an ortho-alkylated product of the phenolic compound, (a) chromium oxide and tin oxide (b) at least one oxide selected from the group consisting of germanium oxide, silicon oxide, and lead oxide; and (c) at least one compound selected from the group consisting of potassium carbonate, potassium silicate, and magnesium oxide. as a component, and the metal atomic ratio of chromium:tin:(b) group metal:potassium and/or magnesium is 100:0.1~60:0.04~30:0.01~
1. A method for producing an orthoalkylated phenolic compound, the method comprising using a catalyst according to No. 10.