Method of obtaining phenol and acetone

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining phenol and acetone by acid-catalysable decomposition of hydro-peroxide of cumene in the environment of the reaction products at elevated temperatures in one stage. In this case the process is carried out in the presence of a catalyst, prepared immediately before its introduction into the reactor for the decomposition of hydro-peroxide of cumene by mixing sulfuric acid with phenol at the ratio of from 2:1 till 1:1000 and the waiting time from mixing till putting into the reactor for the decomposition of hydro-peroxide of cumene from 1 to 600 minutes at a temperature from 20 to 80°C. As a rule, sulfuric acid has a concentration of higher than 75% or oleum is used.

EFFECT: it makes it possible to decrease the output of the by-product hydroxyacetone, improves the quality of market-grade phenol and decreases the consumption of sulfuric acid.

2 cl, 4 tbl, 4 ex

 

The present invention relates to the field of industrial organic synthesis, more precisely, to obtain phenol and acetone Kukolnik way.

The known method for production of phenol and acetone by oxidation of cumene with oxygen with subsequent acid-catalyzed decomposition of cumene hydroperoxide allows to obtain both the desired product in high yield (Kruglov D., Golovenko BN. Joint production of phenol and acetone. M: Goskomizdat, 1964). It is widely used to manufacture these products as the major in the world.

Known methods for producing phenol and acetone in which to reduce the output of phenolic resin products of the oxidation of cumene containing cumene hydroperoxide (CHP), cumene, dimethylphenylcarbinol (DMPC), split in two stages in the presence of sulfuric acid. In the first stage at a temperature of 55-80°To carry out the decomposition of the majority (97-99%) of the CCP and synthesis of dicumylperoxide (DCT) of DMPC and the CCP, and the second, at a temperature 80-146°With, in the resulting reaction mixture containing phenol, acetone, dimethylphenylcarbinol (DMPC) and dicumylperoxide (DCT), add acetone in an amount of 1.5-1.8 times its initial concentration, and water. In some cases, acid partially neutralized with ammonia before the second stage of cleavage, to ensure optimal acids is the outer coat of the catalyst. When this occurs, the splitting of the DCT formed in the first stage, decomposition of the remaining CCP and dehydration remaining DMFC (Russian patents№2068404, №2121477, №2142932).

These methods allow to reduce significantly the quantity of generated by-products compared with the decomposition in one stage, at the same time, the resultant byproduct of hydroxyacetone remains at a high level (and sometimes increased).

Hydroxyacetone is a source of formation of 2-methylbenzofuran that it is difficult to separate from phenol and which impairs the color index commodity phenol. Remove hydroxyacetone of phenol with an alkaline processing complicates the process (Vasiliev I.I., Zakashansky VM collection of "Processes of oil refining and petrochemistry", SPb, Giord, 2005, S. 344).

The application of the two-stage method of decomposition of the CCP can improve the performance of the process of synthesis of phenol and acetone, but is associated with greater use of equipment in comparison with the one-stage decomposition process of the CCP and technically more difficult. Therefore, in the ongoing operation of a large number of installations, using the scheme of decomposition of the CCP in one stage. For example, in accordance with U.S. patent No. 4246203 the decomposition process of the CCP carried out in one stage at a temperature of from 120 to 200°and evaporated almost the entire reaction mass, using the heat decomposition reaction. The best catalyst is sulfuric acid, which is fed into the reactor for the decomposition of the CCP in the form of a solution in acetone, acetophenone, cumene or their mixtures with a concentration of from 0.005 to 0.2%. The concentration of acid in the reaction mass is not specified, but it should be higher, because it remains in non-volatile residue after evaporation of the reaction products of decomposition of the CCP.

Closest to the proposed method for production of phenol and acetone acid-catalyzed decomposition of cumene hydroperoxide (CHP) is the method described in U.S. patent 3271457. In accordance with the decomposition of the CCP for phenol and acetone occurs in the reactor, which serves the CCP and the catalyst is an acid in such amount that its concentration in the reaction zone is from 0.05 to 10%, preferably from 0.1 to 2%. In the vapor phase above the surface of the reaction mass set mixing and distribution device, in which a raw material containing CPC, mixed with acetone, which evaporates due to heat decomposition reaction of the CCP when injected into the reactor, and then condense in the condenser and re-directed to the dilution of raw materials. Thus is the challenge generated by the reaction heat and dilutes the CCP, which increases the safety of the process. The decomposition process of the CCP carried out in temp is the temperature from 50 to 90° C, preferably from 70 to 85°S. In this arrangement, the process in the zone of expansion of the CCP there is a significant excess of acetone compared with the stoichiometric ratio of phenol/acetone, as well as a very high concentration of acid. The consequence of this approach is the high output hydroxyacetone, which degrades the quality of commercial phenol.

To reduce output hydroxyacetone decomposition of the CCP proposed decomposition technical CCP to be executed in the environment of the reaction products in the presence of a catalyst which is prepared by mixing phenol with sulfuric acid immediately prior to its entry into the reactor for the decomposition of the CCP. To do this, molten phenol is mixed with sulfuric acid in a concentration above 75% or oleum in the ratio from 1:2 to 1000:1, respectively, and maintain the mixture in a separate reactor at a temperature of from 20 to 80°for 1-600 minutes, after which the catalyst enters the reactor for the decomposition of the CCP. Thus obtained catalyst has higher activity compared to the amount of sulfuric acid, from which it was cooked.

The decomposition process of the CCP carried out in one stage. Generated by decomposition of the CCP heat away using either a heat exchanger or by evaporation is added to the reaction mass of acetone, which is the outdoor the comfort and return to the reactor for the decomposition of the CCP. The process is carried out at a temperature of 60-80°C.

In the above process conditions using technical GPK similar composition concentration hydroxyacetone decreases from 0.12 to 0.2 to 0.07 and 0.12 wt.% in reaction mass leaving the reactor for the decomposition of the CCP, which has a significant impact on the quality of commercial phenol. In addition, the reduction of use of sulfuric acid leads to the reduction of consumption of alkali used to neutralize the acid, which ultimately reduces the amount of mineral waste products, in particular sodium sulfate.

Industrial applicability the present invention is illustrated by the following examples.

Example 1.

The decomposition of cumene hydroperoxide is performed on the pilot plant, which is a reactor with a volume of 12 ml, equipped with a circulating loop for mixing the reaction mass and the water jacket to maintain the set temperature. For the preparation of the catalyst using a reactor with a volume of 10 μl, which serves sulfuric acid and phenol in two pumps. In the flow of the reaction mixture at the inlet of the reactor serves as a catalyst and raw materials, the composition of which is summarized in table 1. When carrying out reactions involving raw material of another composition results will differ from those shown in the examples of this invention, however, the positive effect is t from the application of this invention will remain.

Table 1
Raw materials used for the decomposition of CPC
Component aContent, wt.%
1Cumene hydroperoxide (CHP)81,48
2The cumene10,9
3Dimethylphenylcarbinol (DMPC)5,48
4The acetophenone1,0
5Water0,3
6Dicumylperoxide (DCT)0,35
7Unidentified0,49

In the synthesis reactor, the catalyst also serves sulfuric acid with a speed of 3 ál/h and phenol with a speed of 6 µl/h, which corresponds to its concentration in the reaction medium of 0.02 wt.%, and the dwell time in the reactor at a temperature of 45°With approximately 70 minutes. The feed rate into the reactor for the decomposition of the CCP is 27 ml/h of the Speed of circulation of the reaction mass is 500 ml/hour, the Temperature in the reactor is maintained at 75°With through coolant supply proper temperature in the jacket of the reactor.

Coming out of the reactor for the decomposition of CPC stream is cooled to room temperature and analysed the comfort by GLC. The composition of the reaction mixture decomposition of the CCP are given in table 2.

Table 2

The composition of the reaction mass decomposition of CPC
ComponentConcentration, wt.%
Phenol48,82
Acetone30,42
Dicumylperoxide (DCT)0,63
Dimethylphenylcarbinol (DMPC)0,46
Cumylphenol1,06
The amount of dimers α-methylstyrene0,74
The acetophenone1,16
α-methylsterol (AMC)2,00
The cumenethere is a 10.03
Hydroxyacetone0,07
The oxide mesityl0,01
Unidentified0,68
Heavy components phenolic resin3,02
Water0,9

Example 2.

The decomposition of the CCP produced on the same equipment as in example 1, but the reactor for the synthesis of the catalytic system has a volume of 20 μl and used as raw material mixture composition is shown in table 3.

The raw material is fed into the reactor at a rate of 10 ml/h, concentrated (96%) sulfuric acid is served with a speed of 1.1 µl/h, which then corresponds to a concentration of 0.02 wt.%, the phenol to the mixture with sulfuric acid is served with rate of 0.9 ál/h, which corresponds to the ratio of sulfuric acid/phenol of 2:1. A mixture of phenol and sulfuric acid was incubated for 600 minutes at a temperature of 20°C. the Speed of circulation of the reaction mixture of 200 ml/h, the temperature in the reactor 70°C.

Example 3.

The decomposition of the CCP produced on the same equipment and under the same conditions as in example 2, but for the preparation of the catalyst in the reactor serves 30% oleum with a speed of 0.7 µl/h, and the phenol at a speed of 1200 ál/h (corresponds to the ratio of phenol : sulfuric acid 1000:1 and the concentration of sulfuric acid 0,018 wt.%). The residence time of the mixture in the reactor at a temperature of 80°C is 1 minute.

Example 4.

The decomposition of the CCP produced on the same equipment as in example 1, but for the preparation of the catalyst in the reactor serves 75%sulfuric acid with a speed of 3 ál/h, and phenol at 7 μl/h, the residence Time of the mixture in the reactor at a temperature of 60°approximately 60 minutes. The temperature in the reactor for the decomposition of CPC support 85°C.

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Table 3

Raw materials used for the decomposition of CPC
ComponentSoderzhanie, wt.%
1Gasoperated cumene (CCP)81,02
2The cumene10,79
3Dimethylphenylcarbinol (DMPC)6,1
4The acetophenone1,06
5Water0,3
6Dicumylperoxide (DCT)0,35
7Phenol0,01
8Unidentified0,37

The compositions obtained in examples 2-4, the reaction mass is presented in table 4.

Table 4

The composition of the reaction mass decomposition of CPC
ComponentConcentration, wt.%
Example 2Example 3Example 4
Phenol48,1653,6248,68
Acetone29,9726,8329,77
Dicumylperoxide (DCT)0,330,250,59
Dimethylphenylcarbinol (DMPC)0,370,310,51
Cumylphenol1,671,591,19
The amount of dimers α-methylstyrene1,09 0,940,99
The acetophenone1,10,901,04
α-methylsterol (AMC)2,331,982,75
The cumene10,619,7910,84
Hydroxyacetone0,090,090,08
The oxide mesityl0,010,010,01
Unidentified0,630,670,49
Heavy components phenolic resin2,962,452,43
Water0,680,570,63

1. Method for production of phenol and acetone by acid-catalyzed decomposition of cumene hydroperoxide in the environment of the reaction products at elevated temperature in one stage, wherein the process is carried out in the presence of a catalyst prepared immediately before introduction into the reactor for the decomposition of cumene hydroperoxide by mixing sulfuric acid with phenol in a ratio of from 2:1 to 1:1000 and the exposure time from mixing prior to submission to the reactor for the decomposition of cumene hydroperoxide from 1 to 600 minutes at a temperature of from 20 to 80°C.

2. The method according to claim 1, wherein the sulfuric acid has to the ncentratio above 75% or use oleum.



 

Same patents:

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5 cl, 4 ex, 8 tbl

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,

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17 cl, 2 dwg, 13 ex

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