JPS6034528B2 - Process for treating high boiling point byproducts in resorcinol production - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for recovering useful components from high-boiling byproducts produced during the production of resorcinol by an acid decomposition method of m-diisopropylbenzene dihydroberoxide (abbreviated as m-DHP). Regarding how to.

A method for producing phenols by acid decomposition of hydroperoxides of alkyl aromatic hydrocarbons is well known.

m-diisopropylbenzene (abbreviated as m-D flower B)
A method of producing resorcinol by acid decomposition of m-OHP obtained by the oxidation of This is a problem not seen in the production of other ferries. One reason for this is that zorcin is much more reactive than other phenols and condenses with acetone, m-diisoprobenylphenol, etc. during the acid decomposition or distillation separation process. There is. Therefore, it is extremely important to effectively utilize high-boiling byproducts containing these condensates in order to improve the economic efficiency of the process for producing resorcinol from m-DHP. As one of the methods, a method of recovering resorcin by thermally decomposing a high boiling point byproduct is known (for example, Tsubaki Kosho No. 30-688, Samurai Kosho No. 32-4715, U.S. Patent No. 2514, etc.). , has achieved some results.
However, this method usually requires heating to 200°C or higher, and further heating to about 250°C to 300°C for efficient thermal decomposition, and operation at such high temperatures poses few industrial problems. do not have. The present inventors have investigated a method for recovering useful components from high-boiling point products that avoids the high-temperature reactions required in conventional pyrolysis methods and can be processed at lower temperatures. It's arrived. That is, the present invention is a method for treating high-boiling by-products produced during the production of resorcinol by acid decomposition of m-DHP, which is characterized by reacting the high-boiling by-products with hydrogen in the presence of a reduction catalyst. . According to the present invention, by selecting appropriate conditions, it is possible to recover resorcinol and m-diisopropylphenol from high-boiling byproducts.
As is well known, m-DHP is m-DIPB and/or m-DHP.
- Obtained by air oxidation of diisopropylbenzene monohydroperoxide in the liquid phase.

m-DHP to be subjected to acid decomposition may be isolated from the oxidation reaction product of m-DmB and is usually used in a suitable acid decomposition solvent, such as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, It is sent to an acid cracking reactor along with hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. However, m-DHP does not necessarily need to be used after being isolated from the oxidation reaction product, and the oxidation reaction product may be used as it is. Also,
When using the above-mentioned oxidation reaction product, in order to increase the resorcisso yield, in advance or during the acid decomposition reaction,
A method of converting 2-hydroxy-2-propyl-Q,Q-dimethylbenzyl hydroperoxide in the oxidation reaction product into m-DHP by acting with an oxidizing agent such as hydrogen peroxide, ten-butyl hydroperoxide, or peracetic acid. May be adopted.

Acid decomposition reactions are carried out in the presence of acid catalysts such as sulfuric acid, perchloric acid, phosphoric acid, ion exchange resins, clay, and synthetic silica alumina.
It is carried out at a temperature of about 20 to 120q0.

The products of the acid decomposition reaction vary depending on the raw materials used for the acid decomposition reaction, but in addition to acetone and resorcinol, the acid decomposition reaction products include m-isoph.

Mouth pill phenol, m-isoph. Phenols such as lobenylphenol, Kents such as m-isopropyl cumyl alcohol, carbinols such as m-isopropyl cumyl alcohol, and combinations of resorcin and acetone or resorcin and m −
Contains high-boiling byproducts such as condensates with olefins such as isobrobenylphenol and peroxides.
In the present invention, the high boiling point products contained in these acid decomposition reaction products are mainly reacted with hydrogen in the presence of a reduction catalyst, but when the acid decomposition reaction products are distilled as described below, Such high-boiling point products may also be generated during the distillation process, and such high-boiling point products can also be thermally decomposed according to the present invention.

Although it is possible to react the acid decomposition reaction product as it is with hydrogen by the method of the present invention, it is preferable to remove the acid catalyst in advance by neutralization, filtration, etc. before the reaction with hydrogen. Furthermore, the method of the present invention may be carried out in the coexistence of acetone and the solvent used in the acid decomposition reaction. Only the high-boiling point product obtained by removing it in advance by means such as distillation or extraction may be used in the reaction. In the present invention, the reduction catalyst used for the reaction with hydrogen is a reduction catalyst that is effective in ordinary hydrogenation reactions.

More specifically, examples include palladium such as palladium black and palladium sol; platinum such as platinum black and platinum sol; rhodium, ruthenium, nickel, cobalt, copper, and copper-chromium catalysts. Additionally, catalysts in which these metals are supported on carriers such as activated carbon, silica, silica alumina, alumina, titania, silica, talc, activated white oxide, calcium carbonate, barium sulfate, fibers, etc. can also be used. . Among these reduction catalysts, it is particularly preferable to use palladium catalysts. In the reaction with hydrogen, suitable solvents such as ketones, ethers, esters, alcohols, aromatic hydrocarbons, water, etc. can be used. When reacting hydrogen, the reaction temperature varies depending on the type of catalyst used or the type of useful component to be recovered, but is usually about 30 to 200 degrees Celsius.

In particular, when the purpose is to recover resorcin, in order to suppress the condensation reaction and nuclear hydrogenation reaction of resorcin once produced, the concentration is generally 150 oo or less, particularly 75 to 100 oo.
Preferably, the reaction is carried out in a temperature range of Under such conditions, even if Kent is used as a solvent, there is no risk of hydrogenation of the ketone. The hydrogen pressure also varies depending on the type of catalyst, etc., but it is usually 1 or 100 kg.
/, preferably without 15 and 25k9/. In the present invention, useful components such as resorcinol and inpropylphenol can be recovered by the operations described above.

In order to separate and recover these useful components from the hydrogenation reaction mixture, common separation operations such as extraction and distillation can be used. Next, an example will be explained.

Examples 1 to 7 The oxidation reaction products of m-DIPB were subjected to acid decomposition in an acetone-toluene mixed solvent to obtain acid decomposition products having the compositions shown in Table 1.

Table 1 Into a stainless steel autoclave with an internal volume of 50', put 10 liters of raw materials (acid decomposition products in Table 1), 0.10 liters of 5% Pd-carbon (powdered), and 20 k9 of hydrogen. / Filled with enemies.

The autoclave was soaked in oil and rubbed at a specified temperature.
After cooling, the concentrations of resorcinol and m-isopropylphenol in the reaction solution were analyzed by gas chromatography, and the rate of increase was determined from the amount of change before and after the reaction. The results are shown in Table 2.
Table 2 *Increase rate = Concentration in reaction solution - Concentration in raw material X.

〇Concentration in raw materials Example 8 100 g of the acid decomposition products in Table 1 were distilled to remove acetone, and 20.0 g of water was added to the resulting concentrate for water extraction to obtain the composition shown in Table 3. An aqueous phase of 36.1 hours was obtained.

When a reaction was carried out under the conditions of Example 2 using 10.0 parts of this aqueous phase (containing 2.27 parts of resorcin and 0.17 parts of m-isopropylphenol) as raw materials, 2.0 parts of resorcin.
After 50 minutes, a reaction solution containing 0.30 hours of m-isobutylphenol was obtained.・Table 3 Example 9 The reaction was carried out in the same manner as in Example 2 except that 0.05% Raney nickel was used instead of 5% Pb-carbon as a catalyst. After the reaction, resorcinol, m-in The concentrations of propylphenol are 9.20 and 4.15, respectively.
The weight percent and increase rate were 6.4% and 9.2%, respectively.

Claims (1)

[Scope of Claims] 1. A high-boiling by-product produced during the production of resorcinol by an acid decomposition method of m-diisopropylbenzene dihydroperoxide, which is characterized in that the high-boiling by-product is reacted with hydrogen in the presence of a reduction catalyst. processing method. 2. The method according to claim 1, wherein the reaction temperature is 30 to 150°C. 3. The method according to claim 1 or 2, using a palladium catalyst as the reduction catalyst.