The process of co-production of phenol, acetone and alpha - methylstyrene

 

(57) Abstract:

Use: technology joint production of phenol and acetone by decomposition of gidroperekisi cumene. The inventive obtaining phenol, acetone and a-methylstyrene lead acid decomposition gidroperekisi of cumene in two stages at a temperature of 60 - 70oWith the first stage and 80 - 100oWith the second environment of the reaction mass, which impose additional isopropylbenzene in the number of 18 - to 25 wt.%. Spread out the reaction mass is subjected to the washing of the catalyst with water in the amount of 15 - 20 vol.%. 5 table.

The invention relates to the technology of basic organic synthesis, specifically to obtain phenol and acetone via cumene.

Phenol is used in the manufacture of caprolactam, diphenylolpropane phenol-formaldehyde resins, in medicine.

Acetone is widely used as a solvent in the production of diphenylolpropane, as well as for the synthesis of many organic substances.

-methylsterol is a monomer in the manufacture of synthetic rubbers, plastics.

Industrial process of co-production of phenol and acetone is getting cumene hydroxide (GPIB) after the product adverse reactions, its clean and allocate commodity GOST-19916-74.

Known methods of decomposition GPIB

in the presence of sulfuric acid and water in an amount of 0.4 to 4.5% at a temperature of 50 120oC (1);

decomposition in the presence of sulfuric acid and additives water at a mass ratio Gidropress of cumene and water 1 (0,008 0,023) (2);

a known method for simultaneous production of phenol, acetone and alpha-methylstyrene by acid decomposition of cumene hydroperoxide in two stages, the 1st stage at a temperature of 40 70oIn the presence of additives ammonia or water at a ratio of acid ammonia (7,6 - 11,5) 1 or water acid (16,7 50) 1, followed by exposure of the reaction mass in the second stage reactor displacement at a temperature of 80 - 100oC and a pressure of 0.3 to 0.5 MPa.

In the reactor displacement impose additional acetone in an amount of 10 to 40 wt. to the reaction mass decomposition. The shutter speed of the reaction mass in the reactor displacement is usually carried out for 5 to 25 minutes

The shortcomings of the existing known methods of decomposition GPIB is the relatively low yield of the target products of phenol and a-methylstyrene from theoretically possible that the high content of salts, sulfates, phenolic resin because nizkoenergeticheskikh threads in the phenol resin causes clogging of equipment, interferes with use of the resin as a boiler fuel, complicates the process of destructive processing.

The catalyst, sulfuric acid in the reaction mass in existing processes is neutralized with alkali. Because of the formation of stable emulsions during this sucks reaction mass from sodium sulphate ineffective. For this reason, frequent driving boilers rectification columns remaining in the reaction mass salts are concentrated in the phenolic resin.

The aim of the invention is to increase the yield of phenol and a-methylstyrene, full extraction from the reaction mass of the catalyst, salts with obtaining desalinated phenolic resin.

The objective is achieved by the acid decomposition of cumene hydroperoxide in two stages at a temperature of 60 70oC on the 1st level and 80 - 100oC on the second.

The decomposition of lead in the environment of the reaction mass, which impose additional isopropylbenzene in the number of 18 to 25 wt. Spread out the reaction mass is subjected to the washing of the catalyst with water, the amount of water for washing take 15 to 20 about.

Dilution GPIB the cumene allows you to increase the selectivity of the output of the phenol.

The presence of a diluent, entered cumene, the reaction mass within the specified limits contributes to the full recovered catalyst, sulfuric acid, water, and so full desalination phenolic resin.

Distinctive features of the method are:

the decomposition of cumene hydroperoxide are in the environment of the reaction mass, which impose additional isopropylbenzene in the number of 18 to 25 wt. spread out the reaction mass is subjected to the washing water from the catalyst, the amount of water for washing take 15 to 20 about.

Example 1. In technical of cumene hydroperoxide containing 1.8% of cumene, 6.5% of dimethylphenylcarbinol (DMPC), 1% of acetophenone, 90.7 percent cumene cumene, add 20 wt. of cumene.

In a reactor with a stirrer and a jacket for coolant continuously serves a cooked mixture and an aqueous solution of sulfuric acid in the amount of 0.5% Decomposition GPIB carried out at a temperature of 65oC. the resulting reaction mass was incubated for 6 min in a boiling water bath. Then the mixture was added water in the amount of about 15. and washed by shaking from sulfuric acid. After stratification for 4 h sulfuric acid in reactioni 99.7% of the Output of a-methylstyrene 75,9% of the sulfate Content of the resin no.

Example 2 (comparison). In a reactor with a stirrer and a jacket for coolant continuously served the technical of cumene hydroperoxide containing 1.9% of IPA, 1% of acetophenone, 6.2% of DMPC, 90,9% GPIB. In the hydroperoxide put the acetone in the amount of 17.9 wt. the weight of the CCP, the water in the ratio of water to acid 20 1 and an aqueous solution of sulfuric acid in the amount of 0.5%

The decomposition is carried out at a temperature of 65oC on the 1st stage and in a boiling water bath (100oC) on the 2nd stage. The shutter speed on the 2nd level are within 7 minutes Then the reaction mass is neutralized with an aqueous solution of alkali and leave for delamination within 4 hours

The composition of the obtained reaction mass shown in the table. 2.

The yield of phenol from theory 99,01% Yield of a-methylstyrene 76% of the Content of sodium sulfate in the reaction mass of 0.04 wt. in the phenol resin 0.5

Example 3. In technical of cumene hydroperoxide, containing 1.2% of cumene, 6.9% of dimethylphenylcarbinol, 1% of acetophenone, 90,9% GPIB enter 25 wt. of cumene.

In a reactor with a stirrer continuously served the resulting mixture and a solution of sulfuric acid in the amount of 0.5% Decomposition is carried out at a temperature of 60oC. the resulting reaction mass is kept on boiling videoke 4 h of settling sulfuric acid in the reaction mass is missing.

The composition of the reaction mixture decomposition shown in the table. 3.

The yield of phenol from theory 99,62% Yield of a-methylstyrene 72.2% of the Washing of the reaction mixture from the catalyst full, new BaCl2ions SO-4-after 4 h of sludge are missing.

Example 4. Into the reactor continuously served the technical hydroperoxide composition: cumene 20 wt. acetophenone 1% dimethylphenylcarbinol 5.2% cumene hydroperoxide 73,8% solution of sulfuric acid in the amount of 0.5 rpm. The decomposition is carried out at a temperature of 65oC.

The resulting reaction mass was incubated for 10 min in a boiling water bath. Then the mixture was added water in the amount of about 18. and washed by shaking from sulphuric acid.

After 4 h of separation sulfuric acid in the reaction mass is missing. Sulphates of sodium in the phenol resin is 0.005%

The composition of the reaction mixture decomposition shown in the table. 4.

The yield of phenol from theory 99,56% Output-methylstyrene 90,8%

The results of the experiments decomposition GPIB in comparison with the prototype shown in the table. 5.

Application of the method of decomposition of cumene hydroperoxide in the environment of the reaction mass, which impose additional isopropylbenzene in number 18

25 masulipatam, that will greatly simplify its applicability as a boiler fuel and in the process of destructive processing.

The economic effect from the implementation of the method for production of phenol, acetone and alpha-methylstyrene consists of additional production of phenol and a-methylstyrene by increasing their output, simplifying the technology of processing of phenolic resins, simplify the scheme of allocation of cumene hydroperoxide.

Sources of information

1. U.S. patent N 4358618, 1982.

2. A. S. USSR N 1208757, 1985.

The process of co-production of phenol, acetone and alpha-methylstyrene by the decomposition of cumene hydroperoxide in two stages at 60 70oWith the first stage 100 and 60oC at the second stage in the presence of an acid catalyst with subsequent removal and distillation of the reaction mixture, characterized in that technical hydroperoxide add isopropylbenzene in the number of 18 to 25% by weight of the total reaction mixture and the products of decomposition washed with water, taken in an amount of 15 to 25% of the volume of the reaction mixture.

 

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2 cl, 3 tbl, 6 ex

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SUBSTANCE: invention relates to production of phenol via acid catalytic decomposition of cumene hydroperoxide followed by isolation of phenol from decomposition products and purification of phenol to remove trace impurities including acetol. Purification of phenol is accomplished through hetero-azeotropic rectification with water. Acetol is isolated as a part of liquid-phase side stream from semiblind plate located within exhausting section of hetero-azeotropic rectification column. Side stream is supplemented by cumene and used to supply stripping column, from which fraction of acetol/cumene azeotropic mixture is taken as distillate and residue is returned under semiblind plate of hetero-azeotropic rectification column to be further exhausted. From the bottom of the latter, crude phenol is withdrawn and passed to final purification from the rest of reactive trace impurities. Acetol/cumene azeotropic mixture is subjected to heat treatment at 310-350°C, which may be performed in mixtures with high-boiling production waste or in mixtures with bottom product of rectification column for thermal degradation of high-boiling synthesis by-products, which bottom product is recycled via tubular furnace. Above-mentioned semiblind plate, from which side stream is tapped, is disposed in column zone, wherein content of water is minimal and below which contact devices are positioned with efficiency at least 7.5 theoretical plates. Side stream with cumene added to it is passed to the vat of stripping column with efficiency at least 15 theoretical plates.

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11 cl, 1 dwg, 9 ex

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5 cl, 3 dwg, 6 tbl, 4 ex

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SUBSTANCE: invention relates to joint phenol-acetone production via selective decomposition of cumene hydroperoxide. Process is conducted in several in series connected reactors constructed in the form of shell-and-tube heat-exchangers, wherein part of decomposition product is recycled into reaction zone and mixed with feed stream to be decomposed, weight ratio of recycled stream to feed stream being less than 10. Reactors with tubular hydrodynamic characteristic have volumetric heat-exchange surface equal to or larger than 500 m2/m3. Preferably, residual concentration of cumene hydroperoxide is 0.1-0.3 wt % and its residence time in decomposition zone ranges from 0.5 to 10 min.

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