JPH08119892A - Production of hydroxyaromatic compound - Google Patents

Abstract

PURPOSE: To produce a hydroxyaromatic compound useful as an intermediate for synthetic resins, agrochemicals, dyes, etc., in high yield in a state to enable easy separation and removal of catalyst while suppressing the by-production of hydroxylacetone by decomposing a specific hydroperoxide with an acid in the presence of a specific solid acid catalyst. CONSTITUTION: The objective compound of formula II is produced by the acid decomposition of (A) a compound of formula I [Ar is a (substituted) phenyl; (n) is 1-3] such as cumene hydroperoxide, cymene hydroperoxide, diisopropylbenzene dihydroperoxide or triisopropylbenzene triperoxide in the presence of (B) a solid acid catalyst produced by treating a metal (hydr)oxide such as (hydr)oxide of Ti, Zr, Hf, Ge, Sn, Pb, Fe or Al with sulfuric acid and baking the product. Preferably, the component B has an acid strength of H0 <-12 in terms of Hanamette's acidity function and an S content of 0.5-10wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing a hydroxy aromatic compound which is useful as an intermediate for producing synthetic resins, agricultural chemicals, dyes, pharmaceuticals and the like.

[0002]

2. Description of the Related Art As one of the industrial production methods of hydroxyaromatic compounds, a method of producing hydroperoxides by decomposing them in the presence of an acid catalyst is known. In this method, conventionally, sulfuric acid is generally used as the acid catalyst, but various acid catalysts have already been proposed in addition to sulfuric acid.

For example, Japanese Patent Application Laid-Open No. 50-50311 proposes a method using trifluoromethanesulfonic acid as an acid catalyst. In addition to this, for example, U.S. Pat.No. 4,898,995 proposes an ion exchange resin containing a sulfonic acid group, and European Patent No. 125,065.
In the issue, various zeolites have been proposed. Also, U.S. Pat.No. 4,267,380 proposes Lewis acid catalysts such as tin chloride, antimony chloride, sulfur tetrafluoride, silicon tetrafluoride, and tungsten hexafluoride.
4,267,379 also proposes Lewis acid catalysts such as boron trifluoride and boron trifluoride etherate.

Decomposition of hydroperoxides with acid catalysis produces coketones with hydroxyaromatic compounds. When the hydroperoxides represented by the general formula (1) are acid-decomposed, acetone is also produced as a ketone. At that time, according to the conventional method, hydroxyacetone is easily produced as a by-product due to the reaction between the generated acetone and the raw material hydroperoxides. Therefore, by the conventional decomposition of hydroperoxides using the above-mentioned acid catalyst, In the production method of a hydroxy aromatic compound and acetone, the following problems occur in industrial production.

The first problem is a decrease in the yield of hydroxyaromatic compounds and acetone. The second problem is that the water solubility of hydroxyacetone results in wastewater pollution. The third problem is that, depending on the type of hydroxyaromatic compound, hydroxyacetone is mixed in the product, resulting in a decrease in its purity. Furthermore, the fourth
The problem is that in the case of an acid catalyst that is soluble in the decomposition products of hydroperoxides, it must be neutralized and removed using an alkaline compound, such as sodium hydroxide, for its separation and removal. .

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the conventional method in the production of hydroxyaromatic compounds by the decomposition of hydroperoxides using an acid catalyst. Thus, by-products of hydroxyacetone can be suppressed as much as possible to obtain a hydroxyaromatic compound in a high yield, and it is not necessary to use an alkali compound for separation and removal of the acid catalyst. For example, a fluidized bed reactor was used. In the case of, it is possible to easily separate and remove by filtration or sedimentation separation, and when a fixed bed reactor is used, it is an object of the present invention to propose a method for producing a hydroxyaromatic compound which can directly send the reaction solution to a purification system. And

[0007]

The present invention is the following method for producing a hydroxyaromatic compound. (1) General formula (1)

Embedded image (In the formula, Ar represents a phenyl group or a substituted phenyl group, and n represents 1, 2 or 3.) The hydroperoxides are acid-decomposed in the presence of an acid catalyst to give a compound represented by the general formula (2):

[Chemical 4] (In the formula, Ar and n are the same as above.) In the method for producing the hydroxyaromatic compound, as the acid catalyst, a metal hydroxide or a metal oxide is treated with sulfuric acid and then calcined. A method for producing a hydroxyaromatic compound, which comprises using the obtained solid acid catalyst. (2) The method for producing a hydroxyaromatic compound according to (1) above, wherein the hydroperoxides are cumene hydroperoxide, cymene hydroperoxide, diisopropylbenzene dihydroperoxide or triisopropyl trihydroperoxide. (3) The metal hydroxide or metal oxide is a metal hydroxide or oxide selected from the group consisting of titanium, zirconium, hafnium, germanium, tin, lead, iron and aluminum. The method for producing a hydroxyaromatic compound according to 1) or 2). (4) The metal hydroxide or metal oxide is a hydroxide or oxide of a composite compound in which two or more metals selected from the group consisting of titanium, zirconium, hafnium, germanium, tin, lead, iron and aluminum are mixed. The method for producing a hydroxyaromatic compound according to (1) or (2) above, which is characterized by being present. (5) The solid acid catalyst has an acid strength of H _{0 as a} Hammett acidity function.
<-12, sulfur content 0.5 to 10% by weight
The method for producing a hydroxyaromatic compound according to any one of (1) to (4) above, wherein

In the method of the present invention, the above-mentioned general formula (1)
Since n represents 1, 2 or 3, Ar represents an n-valent phenyl group or a substituted phenyl group. When n is 1, specific examples of Ar include, for example, a phenyl group,
Examples thereof include substituted phenyl groups such as tolyl group, isopropylphenyl group, t-butylphenyl group, diisopropylphenyl group, phenylphenyl group, methoxyphenyl group and phenoxyphenyl group. When n is 2, specific examples of Ar include, for example, a phenylene group, and a substituted phenylene group such as a methylphenylene group and an isopropylphenylene group. When n is 3, a specific example of Ar is a benzenetolyl group.

Therefore, the hydroperoxides represented by the above general formula (1) which can be preferably used in the method of the present invention include, for example, cumene hydroperoxide, cymene hydroperoxide, diisopropylbenzene monohydroperoxide and triisopropylbenzene mono. Examples thereof include hydroperoxide, diisopropylbenzene dihydroperoxide, triisopropylbenzene dihydroperoxide, triisopropylbenzene trihydroperoxide and the like. The general formula (1)
These hydroperoxides represented by can be prepared by oxidizing the corresponding isopropyl-substituted aromatic compound with air or molecular oxygen.

The hydroxyaromatic compound represented by the general formula (2) produced by the method of the present invention includes:
Depending on the hydroperoxides used, for example, phenol, cresol, isopropylphenol, diisopropylphenol, resorcin (resorcinol), hydroquinone, isopropylresorcin, phloroglycin (phloroglucinol) and the like can be mentioned.

In the method of the present invention, when acid decomposition of hydroperoxides is carried out in the presence of an acid catalyst, a solid acid catalyst obtained by treating metal hydroxide or metal oxide with sulfuric acid and then calcining it as the acid catalyst. To use. Here, as the metal hydroxide or metal oxide, titanium, zirconium,
Periodic table of hafnium, germanium, tin and lead
Hydroxides or oxides such as Group IV metals and metals selected from the group consisting of iron and aluminum can be used. In addition to these, it is also possible to use a hydroxide or an oxide of a composite compound in which two or more kinds of these metals are mixed.

In the present invention, since the solid acid catalyst has a high hydroperoxide decomposition rate, a purified one is generally used, but an unpurified one may be used depending on the case. Specific examples of unrefined ones include:
For example, the water-containing material can be used. As a method for preparing the above solid acid catalyst, Japanese Patent Publication No. 59-618 can be used.
No. 1 or “Catalyst” Vol.31 No.7 P.512 to 518 (1989) and the like.

Specifically, the metal hydroxide or the metal oxide is brought into contact with an aqueous solution of sulfuric acid having a concentration of 0.01 to 5 N, preferably 0.1 to 3 N, and then dried to obtain 350 to 800.
The solid acid catalyst can be produced by calcining at a temperature of C, preferably 400 to 700C. When a metal hydroxide is used, it is dehydrated during firing to obtain a sulfuric acid-treated metal oxide.

The solid acid catalyst thus obtained has an acid strength of Hammett acidity function of usually H ₀ <-12 and a sulfur content of usually 0.5 to 10% by weight. Therefore, the solid acid catalyst used in the present invention has an acid strength of H ₀ <-12 in Hammett acidity function and a sulfur content of 0.5 to 10% by weight, preferably 0.5 to 5%.
Those having physical properties of wt% are preferable.

In the production of hydroxyaromatic compounds from hydroperoxides, sulfuric acid is generally used as an acid catalyst in the conventional method, but sulfuric acid has a Hammett acidity function of H ₀ = -11. Therefore, the solid acid catalyst used in the present invention has a strong acidity. Sulfuric acid has only Brnstedt acid points, whereas the solid acid catalyst used in the present invention has two types of acid, Brenstedt acid point and Lewis acid point, due to the interaction between sulfate ion and metal oxide. Seems to have a point.

In the present invention, as the solid acid catalyst, the powdery one obtained as described above can be used as it is, but it is supported on a carrier having a honeycomb or granular shape, or the catalyst itself is It is preferable to use it as a fluidized bed catalyst by shaping it into a desired shape and use it as a fixed bed catalyst, or to add it to the reaction system as a slurry with a solvent inert to the reaction such as acetone and cumene.

In the method of the present invention, the acid decomposition reaction of hydroperoxides can be carried out batchwise, but industrially it is preferably carried out continuously. As the reactor, either a fluidized bed type flow reactor in which a solid acid catalyst is used in a slurry state and brought into contact with hydroperoxides, or a fixed bed type flow reactor can be adopted. However, since the acid decomposition reaction of hydroperoxides is an exothermic reaction, it is necessary to cool the reaction liquid in the reaction tower.For example, a method in which a cooling pipe is provided inside the reaction tower, a refrigerant flows around the outer circumference of the reaction tower. With a jacket, the reaction heat is removed by using the latent heat of vaporization of acetone co-produced during the reaction, or the raw material hydroperoxides are diluted with the reaction medium, the reaction product solution, or both. Need to be adopted.

The reaction can also be carried out by a reactive distillation system in which the heat of reaction is removed and the generated acetone is separated at the same time. At this time, the acetone produced in the reaction is vaporized by the heat of reaction and withdrawn from the top of the distillation column attached to the upper part of the reaction column. In this case, the reaction temperature is controlled by the overhead pressure and the reflux ratio of acetone. Therefore, it is necessary to select an appropriate reaction pressure from the range of reduced pressure, normal pressure and increased pressure depending on the composition of the reaction solution and the reaction temperature.

When an acid decomposition reaction of hydroperoxides is carried out using a fluidized bed type flow reactor, the amount of the solid acid catalyst used is usually 20 ppm by weight to 10 ppm by weight as a concentration in the reaction mixture.
% By weight, preferably 100 ppm to 2% by weight. The optimum amount used depends on the type of solid acid catalyst, the type of reaction solvent, the reaction temperature, the amount of water in the reaction system, the reaction time, and the like.

For example, when carrying out the reaction continuously in a fixed bed,
There is a method of using a reactor having a circulation loop as shown in FIG. In FIG. 1, a reactor 1 has a catalyst bed 3 formed of a fixed bed in a reaction tower 2, a top end and a bottom end of the reaction tower 2 are connected by a circulation loop 4, and the outer circumference of the reaction tower 2 is cooled. The jacket 5 with the function is formed. FIG.
In order to carry out the reaction using the reactor 1 of No. 2, the hydroperoxides are introduced into the reaction tower 2 through the raw material supply passage 6, and the catalyst bed 3
The solution is passed upward through the interior to carry out an acid decomposition reaction. At this time, the reaction temperature is kept constant by passing the cooling liquid 7 through the jacket 5 and by diluting a part of the reaction liquid taken out from the upper part of the reaction tower 2 through the circulation loop 4 into the raw material. On the other hand, the reaction product is taken out of the system through the product take-out path 8.

In the present invention, the reaction can be carried out without using a reaction solvent, but it is preferably carried out using a reaction solvent. As the reaction solvent, compounds that are stable under the reaction conditions of the method according to the present invention can be used. For example, ketones such as acetone; aromatic hydrocarbons such as benzene, toluene, cumene; fats such as hexane, heptane, octane, etc. Group hydrocarbons; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and cyclooctane; halogenated hydrocarbons such as dichloroethane and chlorobenzene; phenols such as phenol and cresol. These reaction solvents may be used alone or in combination of two or more. When a reaction solvent is used in the present invention, the amount used is based on the hydroperoxides.
Usually, 0.1 to 5 times by weight is suitable.

Whether the reaction is carried out in a fluidized bed system or a fixed bed system, the reaction temperature is usually from 20 ° C to 150 ° C.
C., preferably 40.degree. C. to 140.degree. C., reaction time is usually 0.1 minutes to 1.5 hours, preferably 0.5 minutes to 30.
The reaction pressure may be any of reduced pressure, normal pressure and increased pressure.

After completion of the reaction, when the reaction is carried out in a fluidized bed system, the solid acid catalyst can be easily removed from the reaction mixture by filtration, sedimentation separation or the like. The hydroxyaromatic compound can be isolated by further purification by distillation, crystallization or the like. When the reaction is carried out in a fixed bed system, the reaction product solution can be immediately sent to the purification system,
The hydroxy aromatic compound can be isolated by purification by distillation, crystallization, or the like.

[0024]

The present invention will be described below with reference to examples.
The invention is not limited by these examples. In each example, ppm is based on weight. Reference Example 1 Cumene was added to 70-115 in the presence of an aqueous sodium carbonate solution.
Air-oxidation was carried out at 0 ° C., then oil-water separation and concentration were carried out to prepare a cumene hydroperoxide solution having the composition shown in Table 1.

[0025]

[Table 1]

Reference Example 2 Zirconium hydroxide was soaked in a 1N aqueous sulfuric acid solution for one day, dried, and calcined at 650 ° C. to prepare a solid acid catalyst (sulfuric acid-treated zirconium oxide catalyst). The acid strength of the obtained solid acid catalyst is a Hammett acidity function of H ₀ <-14.
5. The sulfur content was 2.0% by weight.

Reference Example 3 Titanium hydroxide was immersed in a 1N aqueous solution of sulfuric acid for one day, dried, and calcined at 550 ° C. to prepare a solid acid catalyst (sulfuric acid-treated titanium oxide catalyst). The acid strength of the obtained solid acid catalyst was H ₀ <−13.8 as a function of Hammett's acidity, and the sulfur content was 1.9 wt%.

Reference Example 4 Iron hydroxide was immersed in a 0.5N sulfuric acid aqueous solution for one day, dried, and calcined at 500 ° C. to prepare a solid acid catalyst (sulfuric acid-treated iron oxide catalyst). The acid strength of the obtained solid acid catalyst was H ₀ <-13.4 as a function of Hammett's acidity, and the sulfur content was 1.2% by weight.

Example 1 A stainless steel one-tank continuous reactor having a hold-up capacity of 60 ml equipped with a stirrer, a water condenser, a hot water jacket, a temperature detector, a raw material introduction pipe, a catalyst introduction pipe and a reaction mixture withdrawal pipe. The solution of cumene hydroperoxide prepared in Reference Example 1 was added to acetone at a rate of 120 g / hour.
An acetone solution containing 1.0% by weight of the obtained solid acid catalyst obtained in Reference Example 2 as a slurry was added at a rate of 0 g / hour and at a rate of 12 g / hour, respectively.
In this method, the concentration of zirconium metal in the reaction mixture was 270 ppm. In this way, while maintaining the temperature of the reaction solution at 75 ° C., the reaction was carried out in a continuous mode with a residence time of 20 minutes.

The reaction mixture continuously extracted was filtered through a sintered metal filter having a diameter of 5 μm to remove the solid acid catalyst, and phenol and hydroxyacetone were quantitatively analyzed by gas chromatography. The yield with respect to the total number of moles of cumene hydroperoxide and dicumyl peroxide (hereinafter the same) was 97 mol%, and the amount of hydroxyacetone by-product (weight ratio to phenol, the same below) was 320 ppm.

Examples 2 and 3 and Comparative Examples 1 to 5 In Example 1, instead of the solid acid catalyst of Reference Example 2, the solid acid catalyst obtained in Reference Example 3 or Reference Example 4, or Table 2
Reaction and analysis were conducted in the same manner as in Example 1 except that the catalyst shown in 1 was used. Table 2 shows the results.

[0032]

[Table 2] * 1 Weight ratio to phenol

Example 4 and Comparative Examples 6 to 7 Same as Example 1 except that a cymene solution of cymene hydroperoxide was used as the raw hydroperoxide, and the catalyst shown in Table 3 was used in the comparative example. The reaction and analysis were carried out. The results are shown in Table 3.

[0034]

[Table 3] * 1 Weight ratio to cresol

Example 5, Comparative Example 8 and Comparative Example 9 In Example 1, m was used as the starting hydroperoxide.
-M- of diisopropylbenzene dihydroperoxide
A diisopropylbenzene solution was used, and Table 4 is used in Comparative Example.
Reaction and analysis were conducted in the same manner as in Example 1 except that the catalyst shown in 1 was used. The results are shown in Table 4.

[0036]

[Table 4] * 1 Weight ratio to resorcin

Example 6, Comparative Example 9 and Comparative Example 10 In Example 1, a 1,3,5-triisopropylbenzene solution of 1,3,5-triisopropylbenzene trihydroperoxide was used as the raw hydroperoxide. In Comparative Example, except that the catalyst shown in Table 5 was used,
Reaction and analysis were carried out in the same manner as in Example 1. The results are shown in Table 5.

[0038]

[Table 5] * 1 Weight ratio to phloroglysin

Example 7 A stainless steel fluidized bed tank reactor with a hold-up capacity of 100 ml equipped with a stirrer, a water condenser, a hot water jacket, a temperature detector, a raw material introduction pipe, a catalyst introduction pipe and a reaction mixture withdrawal pipe. In addition, the cumene hydroperoxide solution prepared in Reference Example 1 was continuously supplied, and acetone was continuously supplied so that the concentration of acetone in the reaction solution was 40% by weight. The solid acid catalyst prepared in Reference Example 2 was used, and the concentration of the solid acid catalyst in the reaction mixture was 5% by weight. While maintaining the temperature of the reaction solution at 80 ° C, the residence time is 2
The reaction was carried out continuously in 7 minutes. Only the reaction solution was continuously withdrawn from the reactor through a sintered metal filter having a diameter of 5 μm. The reaction solution composition was quantitatively analyzed by gas chromatography. The results are shown in Table 6.

[0040]

[Table 6] The phenol yield was 98 mol%, and from the analysis results of the other components in Table 6, the amount of hydroxyacetone by-product was 200 ppm per phenol.

Comparative Example 12 In Example 7, sulfuric acid was used instead of the solid acid catalyst,
Reaction and analysis were conducted in the same manner as in Example 7 except that the concentration was 0.5% by weight. As a result, the yield of phenol was 97 mol%, and the amount of by-product of hydroxyacetone was 9000 ppm per phenol.

Example 8 A hydroxyaromatic compound was produced using the reactor shown in FIG. That is, the heating / cooling capacity is 200 ml
50 g of the cumene hydroperoxide solution prepared in Reference Example 1 was placed in a fixed catalyst bed 3 formed by filling 80 ml of a solid acid catalyst in pellet form (sulfuric acid-treated zirconium oxide catalyst) into a reaction tower 2 having a circulation loop of The liquid was passed in an upward flow at a flow rate of / hour. The catalyst bed 3 was maintained at the set temperature by the liquid circulating in the jacket. The pressure of the reaction tower is 10 kg / nitrogen
The flow rate of the circulation loop was set to 450 g / hr, keeping it at cm ² G.

The liquid product effluent was collected and quantitatively analyzed by gas chromatography. The results are shown in Table 7.

[Table 7] The phenol yield was 97 mol%, and from the analysis results of the other components in Table 7, the amount of hydroxyacetone by-product was 210 ppm per phenol.

Comparative Examples 13 and 14 Reactions and analyzes were carried out in the same manner as in Example 8 except that the solid acid catalyst was replaced by the catalyst shown in Table 8 in the amounts shown in Table 8. Table 8 shows the results.

[Table 8] * 1 Weight ratio to phenol * 2 Made by Rohm and Haas * 3 Made by Tosoh

[0045]

As described above, according to the production method of the present invention, in the production of a hydroxy aromatic compound by acid decomposition of hydroperoxides using an acid catalyst, a metal hydroxide or a metal oxide is used as an acid catalyst. By using a solid acid catalyst obtained by subjecting the above to a sulfuric acid treatment and then calcining, by-products of hydroxyacetone can be suppressed as much as possible, and a hydroxy aromatic compound can be obtained in a high yield. Moreover, it is not necessary to use an alkaline compound in the separation and removal of the acid catalyst. For example, when a fluidized bed reactor is used, it can be easily separated and removed by filtration or sedimentation separation, and when a fixed bed reactor is used, the reaction Liquid can be sent to purification system immediately

[Brief description of drawings]

FIG. 1 is a system diagram showing a reactor having a circulation loop which can be preferably used when the production method of the present invention is carried out in a continuous system with a fixed bed.

[Explanation of symbols]

 1 Reactor 2 Reaction Tower 3 Catalyst Bed 4 Circulation Loop 5 Jacket 6 Raw Material Supply Channel 7 Coolant 8 Product Extraction Channel

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (5)

[Claims] 1. A compound represented by the general formula (1): (Wherein Ar represents a phenyl group or a substituted phenyl group, and n represents 1, 2 or 3), the hydroperoxides are acid-decomposed in the presence of an acid catalyst to give a compound represented by the general formula (2) 2] (In the formula, Ar and n are the same as above.) In the method for producing a hydroxyaromatic compound, a metal hydroxide or a metal oxide is treated with sulfuric acid and then calcined as the acid catalyst. A method for producing a hydroxyaromatic compound, which comprises using the obtained solid acid catalyst. 2. The method for producing a hydroxyaromatic compound according to claim 1, wherein the hydroperoxides are cumene hydroperoxide, cymene hydroperoxide, diisopropylbenzene dihydroperoxide or triisopropyl trihydroperoxide. 3. The metal hydroxide or metal oxide is titanium, zirconium, hafnium, germanium, tin,
The method for producing a hydroxyaromatic compound according to claim 1 or 2, which is a hydroxide or oxide of a metal selected from the group consisting of lead, iron and aluminum. 4. The metal hydroxide or metal oxide is titanium, zirconium, hafnium, germanium, tin,
3. The method for producing a hydroxyaromatic compound according to claim 1, which is a hydroxide or oxide of a composite compound in which two or more metals selected from the group consisting of lead, iron and aluminum are mixed. 5. The solid acid catalyst has an acid strength of H ₀ <-12 in a Hammett acidity function and a sulfur content of 0.5 to 1.
It is 0 weight%, The manufacturing method of the hydroxy aromatic compound in any one of Claim 1 thru | or 4 characterized by the above-mentioned.