JP2003311147A - Reaction tank and manufacturing method for oxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reaction tank and a manufacturing method for oxides which can effectively disperse a product film crystal layer and effectually introduce a dropping oxidizing agent liquid into a liquid inside of the reaction tank when forming an oxide film produced in the liquid surface of a product by oxidation. <P>SOLUTION: The reaction tank 10 having an average diameter of D is provided with agitation blades 11, 12, 13 attached to a rotating shaft 2 for agitating a solution 8. The upper agitation blade 11 and the lower agitation blade 13 located below the upper agitation blade 11 are attached to the rotating shaft 2, and the upper agitation blade 11 is located at the distance of 0.1D to 0.4D from the surface 5 of the solution 8. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a reaction tank for producing an oxide by oxidizing an oxide to be oxidized with an oxidizing agent, and a method for producing the oxide.

[0002]

2. Description of the Related Art Oxides, regardless of whether they are organic or inorganic,
It is used in all fields. Among these, as a method of obtaining an oxide of an organic substance, a method of obtaining an oxide by oxidizing an oxide with an oxidizing agent is known as follows. That is, when the carbon atom of the benzene ring substituted by the hydroxyl group is the 1-position, the i-propyl group or t is attached to the 2-position carbon atom adjacent to the 1-position and / or the 4-position carbon atom facing the 1-position. -Butyl group is substituted. Further, a structure in which two phenolic molecules are coupled to each other at the 6-position by reacting phenols (oxides) in which the carbon atom at the 6-position is bonded to a hydrogen atom with hydrogen peroxide in the presence of a base. Is a method for producing biphenols of
6-135432).

Conventionally, such an oxidative coupling reaction has been carried out using a reaction vessel having anchor blades as shown in FIG. This reaction tank has a cylindrical side wall 103 and contains a solution 108 up to a liquid level 105. Using this reaction tank, the dropping pipe 1 is added to the solution 108 in the reaction tank.
A solution of an oxidizing agent such as hydrogen peroxide is dropped through 04 or the like. The oxidant oxidizes the oxide to be oxidized, and the oxide crystal is precipitated.

[0004]

As shown in FIG. 3, the oxide crystals deposited in the reaction vessel having the anchor blade are:
For unknown reasons, it floats on the surface of the reaction solution. Then, since the crystal layer 109 is formed on the liquid surface 105, the dropped hydrogen peroxide is prevented from entering the solution 108.
Blocked by 09. Therefore, there is a problem that hydrogen peroxide is thermally decomposed and the yield of oxide is reduced.

According to the present invention, when an oxide obtained by dropping an oxidizer into a liquid containing an oxide forms a crystal layer on the liquid surface, a reaction tank and a reaction tank which can prevent the yield of the oxide from decreasing are provided. An object is to provide a method for producing an oxide.

[0006]

That is, the reaction tank of the present invention has the following constitution.

(A) An addition port for adding an oxidant, a charging port for charging at least one of an oxidant and a reaction solvent, and a stirring blade for agitating a liquid containing the oxidant are attached. It is a cylindrical reaction vessel having a rotating shaft and a diameter of D. In this reaction tank, an upper stirring blade and a lower stirring blade located below the upper stirring blade are attached to a rotating shaft, and the upper stirring blade is a liquid surface of a liquid containing an oxide contained in the reaction tank. To a depth range of 0.1D to 0.4D (claim 1).

By arranging the upper stirring blade in the above position range, it is possible to stir the film of the oxidation product floating on the liquid surface and entrain it in the vortex to expose the solution in the reaction tank to the liquid surface. it can. Therefore, the oxidizing agent added from above can be brought into contact with the liquid containing the oxide in the reaction tank,
It is possible to improve the yield of the added oxidizing agent and improve the yield of oxide. When the position of the upper stage stirring blade is deeper than 0.4D, the degree of entrainment of the oxidation product film in the vortex due to stirring is reduced, and the liquid in the reaction tank cannot be sufficiently exposed to the liquid surface. On the other hand, the position of the upper stirring blade is 0.1D
If the depth is shallower, depending on the rotation speed, the stirring blade comes out of the liquid surface into the air during stirring, and the effect is reduced. A more desirable distance from the liquid surface of the upper stirring blade is 0.15D to 0.35D.
And more preferably within the range of 0.2D to 0.3D.

In the reaction tank of the present invention, it is preferable that the bottom of the reaction tank is dish-shaped (claim 2).

By making the bottom of the reaction vessel into a dish shape, in cooperation with the rotation of the rotary shaft on which the lower stirring blade is attached, the slurry which easily collects on the bottom of the reaction vessel is deposited on the bottom of the reaction vessel. It can be discharged more efficiently from the discharge port provided.

In the reaction tank of the present invention, the lower stirring blade is a flat paddle blade, and the flat paddle blade is located at a distance of 0.05 D to 0.2 D from the bottom of the reaction tank. Is desirable (claim 3).

With this structure, the stirring effect at the time of discharging the slurry can be obtained, and not only the liquid phase but also the solid phase can be discharged. If the position of the lower stirring blade exceeds 0.2 D from the bottom of the stirring tank, it becomes difficult to obtain the stirring effect at the time of discharging the slurry. On the other hand, if the position of the lower stirring blade is less than 0.05D from the bottom of the reaction tank, the lower stirring blade may come into contact with the slurry accumulated at the bottom of the reaction tank. In order to more reliably obtain the stirring effect at the time of discharging the slurry, there is no risk of contact with the slurry accumulated at the bottom of the reaction tank, and the lower stirring blade is located within the range of 0.1D to 0.15D from the bottom of the reaction tank. It is desirable to do.

In the reaction tank of the present invention, the upper stirring blade is an inclined paddle blade, and the inclined paddle blade has a length from the center of the rotating shaft to the tip thereof in the range of 0.15D to 0.35D. Is preferable (Claim 4).

If the length from the rotary shaft to the tip of the upper inclined paddle blade exceeds 0.35D, the required power becomes large and the energy loss becomes large. On the other hand, if it is less than 0.15D, it becomes difficult to obtain the entrainment effect in the above stirring. A particularly desirable range is 0.2D to 0.3D in order to sufficiently effect stirring and obtain high energy efficiency.

In the reaction tank of the present invention, the length from the center of the rotating shaft to the tip of the flat paddle blade in the lower stage is 0.1D to 0.2D.
It is desirable to set it in the range (Claim 5).

When the length of the lower flat paddle blade exceeds 0.2D, the energy efficiency for the effect is lowered to 0.1D.
If it is less than the above, the stirring effect at the time of discharging the slurry is lost. In order to obtain high energy efficiency and a good stirring effect at the time of discharging the slurry, the range of 0.125D to 0.175D is particularly desirable.

The reaction tank of the present invention may be provided with a position varying mechanism capable of changing the mounting position of the upper inclined paddle blade on the rotary shaft (claim 6).

With this position changing mechanism, the position of the upper inclined paddle blade can be set to the optimum position according to the position of the liquid surface.

The reaction tank of the present invention may further include an intermediate paddle blade located between the upper inclined paddle blade and the lower flat paddle blade (claim 7).

With this intermediate paddle blade, for example, when the depth of the liquid becomes deep, the upper paddle blade or the lower flat paddle blade is not sufficiently agitated as necessary, and supplementary agitation is provided to supplement these. Can be done. Further, it is possible to further promote the homogenization of the concentration of the reaction liquid in the reaction tank.

The oxide production method of the present invention has the following constitution. (B) It has a rotary shaft to which the upper-stage stirring blade and the lower-stage stirring blade located below the upper-stage stirring blade are attached, and the diameter is D
A method of producing an oxide by oxidizing an oxide to be oxidized with an oxidizing agent using a cylinder-shaped reaction tank having a size of
1) introducing the liquid containing the oxide to be introduced into the reaction tank,
The depth position of the upper stirring blade from the liquid surface of the liquid is 0.
A step of setting the range of 1D to 0.4D, and (S
2) A step of rotating the rotating shaft to perform stirring by the upper stirring blade and the lower stirring blade, and (S3) adding the oxidizing agent to the liquid containing the oxide (claim 8). .

By this method, in the above manufacturing method, for example, the film of the oxidation product floating on the liquid surface can be scattered by stirring to expose the reaction liquid surface. Therefore, the added oxidizing agent effectively reacts with the oxide before being thermally decomposed, and the oxide can be produced in high yield.

In the method for producing an oxide of the present invention, in particular, when the above-mentioned oxide is a phenol and the carbon atom of the benzene ring substituted by the hydroxyl group in the phenol is the 1st position, it is adjacent to the 1st position. The i-propyl group or t-butyl group is substituted on the carbon atom at the 2-position and / or the carbon atom at the 4-position facing the 1-position, and the carbon atom at the 6-position is bonded to a hydrogen atom. It is preferably used in the case of compounds (Claim 9).

Further, in the method for producing an oxide of the present invention, in particular, the oxide-containing liquid containing the phenols is 2,4
-A liquid containing di-t-butylphenol or an alkali metal salt thereof and water, which is preferably used when the oxidizing agent is hydrogen peroxide (claim 10).

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the embodiments and examples of the present invention will be described in detail, but the present invention is not limited to these embodiments and examples. "Parts" and "%" in the following description are parts by weight and% by weight, respectively.

The reaction tank (a) of the present invention will be described with reference to FIG. 1. An addition port 4 for adding an oxidant,
It has a charging port (not shown) for charging at least one of the oxide and the reaction solvent, and a rotary shaft 2 having stirring blades 11 and 13 for stirring the liquid containing the oxide and having a diameter D. The reaction tank 10 has a cylindrical shape having the dimensions of. In this reaction tank, an upper stage stirring blade 11 and a lower stage stirring blade 13 located below the upper stage stirring blade are attached to a rotating shaft, and the upper stage stirring blade is provided with a liquid containing oxide to be stored in the reaction tank. Liquid level 5
To the depth range of 0.1D to 0.4D.

In the reaction tank of FIG. 1, an intermediate stirring blade 12 is attached to the rotary shaft 2 by a boss 6 between an upper stirring blade 11 and a lower stirring blade 13. Here, the upper stirring blade 1
1 is preferably an inclined paddle blade, and the lower stage stirring blade 13 is preferably a flat paddle blade. Further, the intermediate stirring blade 12 is preferably an inclined paddle blade.
When the upper stirring blade 11 and the intermediate stirring blade 12 are inclined paddle blades, the inclination angle θ is preferably 45 °. When the lower stirring blade 13 is a flat paddle blade, the inclination angle θ is 90 °.

The upper stage stirring blade 11 shown in FIG. 1 has a blade diameter of d.
_1, the lower stirring blade its wings diameter of d _3. The blade diameter of the intermediate stirring blade 12 is preferably substantially the same as the blade diameter d ₁ of the upper stirring blade 11.

The bottom of the reaction vessel shown in FIG. 1 is a dish type, and the gap between the lowermost part of the bottom of the dish type and the lower stirring blade 13 is indicated by C. Further, the distance from the center of the distance in the depth direction of the reaction tank in the upper stirring blade to the liquid surface 5 is indicated as H. Further, the distance from the center of the distance in the depth direction of the reaction tank in the upper stirring blade to the lowermost part of the bottom of the dish is indicated as H '.

Upper stirring blade 11 and intermediate stirring blade 12
Can change the position of the reaction tank in the depth direction freely by changing the mounting position of the boss on the rotary shaft according to the depth (H + H ') of the liquid surface. Also,
When the liquid level is shallow, the stirring blade may be a combination of only the upper stirring blade and the lower stirring blade.

When the lower stage stirring blade is a flat paddle blade, the above-mentioned gap C is preferably located in the range of 0.05D to 0.2D.

When the upper stirring blade is an inclined paddle blade,
The inclined paddle blade preferably has a length from the center of the rotation axis to the tip end in the range of 0.15D to 0.35D,
It is more desirable to set it in the range of 0.2D to 0.3D.

When the lower stage stirring blade is a flat paddle blade, the flat paddle blade has a length from the center of the rotating shaft to the tip of 0.1.
D to 0.2D is desirable, and 0.125
More preferably, it is in the range of D to 0.175D.

(B) of the present invention has a cylindrical reaction vessel having a rotating shaft to which an upper stirring blade and a lower stirring blade located below the upper stirring blade are attached, and having a diameter of D. Is a method for producing an oxide by oxidizing an oxide with an oxidizing agent, and is a production method comprising the following three steps. (S1) A liquid containing an oxide is introduced into the reaction tank, and the depth position from the liquid surface of the upper stirring blade is 0.1D to 0.4.
A step of keeping the range of D, (S2) a step of rotating the rotary shaft to perform stirring by the upper stirring blade and the lower stirring blade, (S3) a step of adding an oxidant to the liquid containing the oxide.

In the step (b) of the present invention, it is desirable to carry out the steps (S2) and (S3) simultaneously in parallel. By performing the steps (S2) and (S3) in parallel at the same time, thermal decomposition of the added oxidizing agent is further suppressed, and the yield of oxide can be increased.

In (b) of the present invention, various oxides are used. For example, when the carbon atom of the benzene ring substituted by phenols, specifically, a hydroxyl group, is the 1st position as the oxide, the 2nd position carbon atom adjacent to the 1st position and / or the 4th position opposite to the 1st position. To the carbon atom of
Phenols in which a propyl group or a t-butyl group is substituted and the 6-position carbon atom is bonded to a hydrogen atom are used.

In particular, when the above-mentioned oxide is a phenol and the carbon atom of the benzene ring substituted by the hydroxyl group in the phenol is the 1-position,
The 2-position carbon atom adjacent to the 2-position and / or the 4-position carbon atom facing the 1-position is substituted with an i-propyl group or a t-butyl group, and the 6-position carbon atom is bonded to a hydrogen atom. It is preferably used in the case of the compound. Further, in (b) of the present invention, the liquid containing the oxide is 2,4-di-
A liquid containing t-butylphenol or an alkali metal salt thereof and water, which is particularly preferably used when the oxidizing agent is hydrogen peroxide.

For example, the phenols are 2,4-
When di-t-butylphenol is used, the oxide-containing liquid is a liquid containing 2,4-di-t-butylphenol or its alkali metal salt and water. This liquid may optionally contain a small amount of aliphatic lower alcohol. Further, this oxidation reaction is preferably carried out in the presence of an alkali metal salt or an alkaline earth metal salt of a higher aliphatic carboxylic acid. The amount of the alkali metal salt or alkaline earth metal salt of the above higher aliphatic carboxylic acid,
Preferably, 0.001 to 0. 0 per 1 mol of 2,4-di-t-butylphenol or its alkali metal salt.
It is in the range of 1 mol.

In the above reaction, the amount of water used is preferably in the range of 0.5 to 10 parts by weight with respect to 1 part by weight of 2,4-di-t-butylphenol or alkali metal salt.

Hydrogen peroxide is preferably used as the oxidizing agent for oxidizing 2,4-di-t-butylphenol. Hydrogen peroxide having a concentration of 35% by weight is preferably used, and the amount thereof is preferably 25 to 35 per 100 parts by weight of 2,4-di-t-butylphenol.
The range is parts by weight. The preferred reaction temperature is 80 to 90.
It is in the range of ° C. After completion of the reaction, if necessary, an inorganic acid is added for neutralization, and then with an organic solvent such as aromatic hydrocarbons, aliphatic hydrocarbons, ethers, esters, ketones and halogenated hydrocarbons. If the oxidation product is extracted and the above organic solvent is removed from the organic solvent layer by distillation,
2'-dihydroxy-3,3 ', 5,5'-tetra-t
-Butyl biphenyl can be obtained.

(Example) A reaction vessel 10 equipped with a three-stage stirring blade shown in FIG. 1 was used. An upper stirring blade 11, an intermediate stirring blade 12, and a lower stirring blade 13 are attached to a rotary shaft 2 arranged along the vertical direction so as to extend in the horizontal direction. The rotating shaft is provided with a boss 6 for mounting these stirring blades. The stirring blade may have two blades, three blades, or four blades or more. The angles of these stirring blades are variable. Normally, the upper stirring blade has an angle in the direction of pressing the solution downward, for example, 45 °, and the lower stirring blade has a right angle.
That is, an angle is set so that the rotation direction intersects the wing surface perpendicularly. The side wall 3 of the reaction vessel is cylindrical and the diameter D can be easily defined. The side wall of the reaction tank does not have to be cylindrical, and in that case, the diameter takes an average value in the height direction. The solution is usually introduced into the reaction tank 10 so that the liquid level 5 is located above the upper stirring blade 11. When referring to the liquid level 5 such as the distance from the bottom of the reaction tank, it refers to the liquid level at rest before the start of stirring. When proceeding with the chemical reaction, a heating medium such as steam is passed through a jacket provided on the side wall of the reaction tank (not shown in FIG. 1) to heat the liquid to a predetermined temperature, and then the drip pipe 4 is fed from outside the reaction tank. Hydrogen peroxide solution is dripped through.

The dimensions of the above reaction tank are as follows. Diameter D: 2000 mm Height (depth) from the bottom of the reaction tank to the liquid surface H + H ': 19
00 mm Distance from bottom of reaction tank of upper stirring blade H ': 1800 mm Distance from bottom of reaction tank of lower stirring blade c: 100 mm Distance from bottom of reaction tank of intermediate stirring blade: 670 mm Center of rotation axis of upper stirring blade To the tip (d ₁ /
2): 500 mm Blade width of upper stirring blade: 200 mm Inclination angle of upper stirring blade θ: 45 ° Length from center of rotation axis of lower stirring blade to tip (d ₃ /
2): 250 mm Lower stirring blade width: 100 mm Lower stirring blade inclination angle θ: 90 ° Intermediate stirring blade inclination angle θ: 45 ° The liquid level of the solution in the reaction tank is 2 stages of upper blade and lower blade. In the case of a reaction tank having only a stirring blade, the position is 0.9D to 1.1D from the bottom of the reaction tank. In the present invention, the position of the upper stirring blade is in the range of 0.1D to 0.4D from the liquid surface, and therefore is most widely estimated to be 0.5D to 1.D from the bottom of the reaction tank.
It is located within the range of 0D. The lower stirring blade is located in the range of 0.05D to 0.2D from the bottom of the reaction tank.

322 parts of water was charged into the reaction vessel, 3 parts of lauric acid was added at an internal temperature of 85 ° C. with stirring, and then 28 parts of
209 parts of% caustic soda were added. At the same temperature, 299 parts of 2,4-di-t-butylphenol was added, and after stirring for a while, 70 parts of 35% hydrogen peroxide was slowly added so as to keep the internal temperature at 80 to 90 ° C, and at the same temperature, 30%. Stir for minutes. Then add another 9 parts of 35% hydrogen peroxide,
After the addition was completed, the mixture was stirred at the same temperature for a while. Then, the internal temperature was cooled to 65 ° C., and 37 parts of 10% sodium sulfite was added to decompose excess hydrogen peroxide. After decomposition, 71 parts of 98% sulfuric acid was added, and then 725 parts of xylene was added to dissolve the reaction product. After dissolution, stirring was stopped and the aqueous layer was separated. After washing the xylene tank left in the reaction tank with water, the aqueous layer was separated. The obtained xylene solution was concentrated under reduced pressure at an internal temperature of 120 ° C. After the concentration was completed, a residue containing 3,3 ′, 5,5′-tetra-t-butylbiphenyl 2,2 ′ diol was obtained. The yield at this time was 96% (versus 2,4-di-t).
-Butylphenol).

(Comparative Example) As shown in FIG.
The procedure of Example was repeated, except that a reaction vessel equipped with an anchor stirring blade 101 attached to No. 2 was used. After concentrating the xylene solution, the yield of the residual liquid containing 3,3 ′, 5,5′-tetra-t-butylphenyl-2,2′-diol was 70%.
(Vs. 2,4-di-t-butylphenol) was obtained.

By comparing the above-mentioned examples with the comparative examples, in the present invention example, the oxidizing agent dropped from above such as hydrogen peroxide was not wastefully consumed, and the yield was excellent. The resulting reaction product (oxide) can be obtained in high yield.

The embodiments disclosed this time are to be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope.

[0047]

INDUSTRIAL APPLICABILITY By using the reaction tank and the method for producing an oxide of the present invention, when the product of the oxidation reaction forms a product film on the liquid surface, the product layer is dispersed and the oxidizing agent is added. Can be effectively introduced into the liquid to be oxidized in the reaction tank, and the reaction can proceed at a high yield.

[Brief description of drawings]

FIG. 1 is a diagram showing a reaction tank according to a first embodiment of the present invention.

FIG. 2 is a view showing a conventional reaction tank.

FIG. 3 is an enlarged view of a liquid level in a conventional reaction tank.

[Explanation of symbols]

2 rotation axis, 3 reaction vessel side wall, 4 dropping pipe, 5 liquid level,
6 Boss, 8 Oxide-containing liquid, 10 Reaction tank, 11
Upper stirring blade, 12 Intermediate stirring blade, 13 Lower stirring blade,
Distance from H 'reaction tank bottom to the upper stirring blade, the distance from H liquid surface to the upper stirring blade, the distance from the rotation axis center of d _1/2 upper stirring blade to the tip, the rotation of d _3/2 lower stirring blade Distance from the axis center to the tip.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kunihito Miyake             3-1,98-1 Kasugade, Konohana-ku, Osaka             Tomo Chemical Co., Ltd. F-term (reference) 4G075 AA13 BA06 BB05 BD15 EA01                       EB01 ED02 ED08                 4H006 AA02 AA04 AC23 BB31 BB45                       BD84 BE10 BE32 FC52 FE13

Claims (10)

[Claims] 1. An addition port for adding an oxidant, a charging port for charging at least one of an oxidant and a reaction solvent, and a stirring blade for agitating a liquid containing the oxidant. A cylindrical reaction vessel having a rotating shaft and having a diameter of D, wherein an upper stirring blade and a lower stirring blade located below the upper stirring blade are attached to the rotating shaft, The stirring blade
A reaction tank, which is located within a depth range of 0.1D to 0.4D from the liquid surface of the liquid containing the oxide to be stored in the reaction tank. 2. The bottom of the reaction vessel is dish-shaped.
The reaction tank according to 1. 3. The lower stirring blade is a flat paddle blade,
And the distance from the bottom of the reaction tank is 0.05D-0.2D
The reaction tank according to claim 1 or 2, which is located in the range. 4. The upper stirring blade is an inclined paddle blade, and the length from the center of the rotating shaft to the tip of the inclined paddle blade is in the range of 0.15D to 0.35D. The reaction tank according to any one of 1 to 3. 5. The reaction tank according to claim 3, wherein the length from the center of the rotation axis of the flat paddle blade to its tip is in the range of 0.1D to 0.2D. 6. A position changing mechanism capable of changing a mounting position of the inclined paddle blade on the rotating shaft,
The reaction tank according to claim 4 or 5. 7. The intermediate paddle vane located between the upper stage inclined paddle vane and the lower stage flat paddle vane is further attached to the rotary shaft, according to any one of claims 4 to 6. Reaction tank. 8. A tubular reaction vessel having a rotating shaft to which an upper stirring blade and a lower stirring blade located below the upper stirring blade are mounted, and a reaction chamber having a cylindrical shape with a diameter of D is used, and an oxidizing agent is used. A method for producing an oxide by oxidizing an oxide to be oxidized, wherein a liquid containing the oxide to be introduced is introduced into the reaction tank, and a depth position from the liquid surface of the upper stirring blade is 0. 1D
To 0.4 D, a step of rotating the rotary shaft and stirring with the upper stirring blade and the lower stirring blade, and adding the oxidant to the liquid containing the oxidant. The manufacturing method of an oxide provided with the process. 9. The oxidizable substance has a carbon atom of a benzene ring substituted by a hydroxyl group at the 1-position, a carbon atom at the 2-position adjacent to the 1-position and / or at a 4-position opposite to the 1-position. The method for producing an oxide according to claim 8, which is a phenol in which a carbon atom is substituted with an i-propyl group or a t-butyl group, and the 6-position carbon atom is bonded to a hydrogen atom. 10. The liquid containing the oxide is 2,4-
A liquid containing di-t-butylphenol or an alkali metal salt thereof and water, wherein the oxidizing agent is hydrogen peroxide,
The method for producing an oxide according to claim 8.