Method of production of phenol and acetone

FIELD: chemical industry; methods of production of phenol and acetone.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the industrial process of production of phenol and acetone by the cumene method. The method is realized by decomposition of the technological cumene hydroperoxide in the in series connected reactors in two stages with formation on the first stage of the dicumylperoxide at the temperature of 40-65°С at presence as the catalytic agent of 0.003-0.015 mass % of the sulfuric acid with its subsequent decomposition on the second stage in the reaction medium at the temperature of 90-140°С. The process is conducted at the excess of phenol in the reaction mixture at the molar ratio of phenol : acetone exceeding 1, preferentially - from 1.01 up to 5. Excess of phenol is formed either by distillation (blowing) of acetone or addition of phenol in the reaction medium. The technical result of the invention is reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.

EFFECT: the invention ensures reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.

5 cl, 4 ex, 8 tbl

 

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

Widely 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). However, the yield of heavy by-products of this production, the so-called phenolic resin, remains significant.

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 of 80-120°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. When this occurs, the splitting of the DCT formed in the first stage, decomposition of the remaining CCP and the dehydration of the remaining DMFC (Russian patent No. 2068404, No. 2121477).

These methods allow to reduce significantly the quantity of generated by-products in comparison with one-stage decomposition (exit resin 25 kg/t of phenol), 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).

Closest to the proposed method of decomposition of the CCP is a method of decomposition, implemented in two stages (Russian patent No. 2142932 - prototype).

The process is carried out in three series set the reactor mixing in the first stage and in the reactor displacement in the second stage. In the first stage decomposition of the CCP carried out in conditions similar to izotermicheskim at a temperature 47-50°C, concentration of catalyst is sulfuric acid, equal 0,018 of 0.20 wt.% and additional dilution of the reaction mixture with acetone in an amount equal to 5-8 wt.% regarding the amount of the CCP. When this reacts almost all of the CCP, as part of the CCP and DMFC formed DCT.

In the second stage, the process is carried with partial neutralization of sulfuric acid with ammonia with the formation of hydrosulphate of ammonia at a temperature 120-146°and with the addition of a quantity of water. The concentration of sulfuric acid 0,09-0,10 wt.%. The decomposition of the CCP and CSD occurs in a reaction medium containing phenol and acetone formed from HPC and advanced input acetone.

The disadvantage of the prototype method is the existence of hydroxyacetone in the resulting phenol, which significantly reduces its quality.

To reduce output hydroxyacetone decomposition of the CCP proposed decomposition technical CCP to be executed in the environment of the reaction products under the excessive concentration of phenol compared to stoichiometric, that is, when the molar ratio of phenol:acetone is greater than 1 and the concentration of sulfuric acid equal to 0.003 to 0.015 g wt.%.

The process is carried out in two stages in at least two serially connected reactors. At the first stage in the first reactor by circulation of the reaction mass carry out the decomposition of technical CCP at a temperature of 40-65°in the presence of a catalyst is sulfuric acid concentration in the reaction mass of 0.003-of 0.015 wt.% (depending on the reactor temperature and the ratio of phenol:acetone). Amount of input raw materials should not exceed 10% of the volume of circulation of the reaction mass (Lu is higher than 5%), the multiplicity of circulation (the ratio of the flow rate of the circulating mass flow rate of supply of raw materials - technical GPC) is from 8 to 50. In these conditions, the conversion of CCP, equal 95-99,8%, is decomposed with the formation of phenol and acetone, as well as the synthesis of the DCT of the CCP and DMFC.

In the second stage in the last reactor at a temperature of 90-140°To carry out the decomposition of the synthesized DCT and the rest of the CCP. Since the concentration of sulfuric acid at this stage is excessive for optimum operation, it is partially neutralized, for example, ammonia.

In the above process conditions using technical GPK similar composition of output hydroxyacetone decreases from 0.12 to 0.04 wt.%, that 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.

The increase in molar ratio of phenol:acetone greater than 1 can be achieved either by adding to the reaction mass of phenol or phenolic fraction, or the removal from it of the acetone by distillation or Stripping with a gas stream.

To maintain in the reactor is acceptable temperature generated by decomposition of the CCP dissipate heat by means of heat exchangers, preferably embedded in the reactors.

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

Example 1.

The decomposition of cumene hydroperoxide is conducted on a pilot plant consisting of two reactors: the first stage reactor with a volume of 12 ml and reactor displacement of the second stage with a volume of 7 ml of the Reaction mass from the first stage reactor partially served on the second reactor, and partially returned to the inlet of the first reactor, carrying out, so its circulation. In the flow of the reaction mass at the entrance to the first stage reactor serves the catalyst and the raw material, the composition of which is summarized in table 1. Specified raw material was prepared by adding pure phenol to technical cumene hydroperoxide. 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 of this invention will remain.

Dimethylphenylcarbinol (DMPC)
Table 1.

Raw materials used for the decomposition of CPC
ComponentSoderzhanie, wt.%
1Cumene hydroperoxide (CHP)79,91
2The cumene12,13
33,29
4The acetophenone0,23
5Water0,1
6Dicumylperoxide (DCT)0,25
7Phenol3,96
8Unidentified0,13

The feed rate is 26 ml/h Into the reactor also serves sulfuric acid as the catalyst at a rate of 1 μl/h, which corresponds to its concentration in the reaction medium 0.007 wt.%. The speed of circulation of the reaction mass is 500 ml/hour, the Temperature in the reactor is maintained at level 48-50°With through coolant supply proper temperature in the jacket of the reactor.

Emerging from the first stage reactor stream is fed into the second stage reactor, heated to a temperature of 140°C. effluent from the second stage reactor stream is cooled to room temperature, neutralized with sodium bicarbonate and analyzed by GLC. The composition of the reaction mixture decomposition of the CCP are given in table 2.

Table 2.

The composition of the reaction mixture decomposition of the CCP.
ComponentConcentration, wt.%
Phenol52,97
Acetone30,29
Dicumylperoxide (DCT)0,01
Dimethylphenylcarbinol (DMPC)0,03
Cumylphenol0,43
The amount of dimers α-methylstyrene0,19
The acetophenone0,37
α-Methylsterol (AMC)2,18
The cumene12,69
Hydroxyacetone0,04
The oxide mesityl0,01
Unidentified0,34
Water0,45

The molar ratio of phenol:acetone is 1.08.

For analysis of the output of heavy components, which are not analyzed by GLC, the portion of the reaction mixture was distilled in vacuum at a residual pressure of 15 kPa and a temperature in the cube up to 215°C. the Residue from the distillation weighed. The total number of by-products formed in this case is 48 kg per 1000 kg of the obtained phenol, including these heavy components.

Example 2.

The decomposition of the CCP produced on the same equipment as in example 1, but used as raw material mixture composition is shown in table 3.

The raw material is fed into the reactor at a rate of 25 ml/h, sulfuric acid serves at the rate of 2 ál/h, which is relevant to the duty to regulate its concentration of 0.015 wt.%. The circulation rate of the reaction mixture to 500 ml/hour, the Temperature in the first stage reactor 40°in the second stage reactor 90°C.

Table 3.

Raw materials used for the decomposition of CPC
ComponentSoderzhanie, wt.%
1Cumene hydroperoxide (CHP)80,46
2The cumene12,31
3Dimethylphenylcarbinol (DMPC)5,31
4The acetophenone0,54
5Water0,1
6Dicumylperoxide (DCT)0,61
7Phenol0,46
8Unidentified0,21

The composition of the obtained reaction mass is presented in table 4.

Table 4.

The composition of the reaction mixture decomposition of the CCP.
ComponentConcentration, wt.%
Phenol51,62
Acetone31,48
Dicumylperoxide (DCT)0,17
Dimethylphenylcarbinol the ol (DMFC) 0,26
Cumylphenol0,38
The amount of dimers α-methylstyrene0,19
The acetophenone0,57
α-Methylsterol (AMC)1,84
The cumene12,48
Hydroxyacetone0,09
The oxide mesityl0,01
Unidentified0,32
Water0,59

The molar ratio of phenol:acetone is 1.01.

Analysis of the yield of heavy products of decomposition of the CCP produced analogously to example 1. The total number of by-products formed at the same time, is 75 kg per 1000 kg of the obtained phenol.

Example 3.

The decomposition of the CCP produced on the same equipment as in example 1, but used as raw material mixture composition is shown in table 5.

The raw material is fed into the reactor at a rate of 25 ml/h, sulfuric acid is served with rate of 3 ál/h, which corresponds to its concentration of 0.003 wt.%. The circulation rate of the reaction mixture to 500 ml/hour, the Temperature in the reactor of the first stage 65°in the second stage reactor 135°C. circulating Through the loop of the first stage reactor miss nitrogen with a rate of 4.5 l/h, which allows the output from the reactor portion of the acetone.

Table 5.

Raw materials used for the decomposition of CPC
ComponentSoderzhanie, wt.%
1Cumene hydroperoxide (CHP)81,38
2The cumene12,90
3Dimethylphenylcarbinol (DMPC)4,36
4The acetophenone0,49
5Water0,1
6Dicumylperoxide (DCT)0,45
7Phenol0,11
8Unidentified0,21

The composition of the obtained reaction mass is presented in table 6.

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Table 6.

The composition of the reaction mixture decomposition of the CCP.
ComponentConcentration, wt.%
Phenol68,41
Acetone8,39
Dicumylperoxide (DCT)0,94
Dimethylphenylcarbinol (DMPC)0,04
Cumylphenol0,46
The amount of dimers α-methylstyrene0,10
The acetophenone
α-Methylsterol (AMC)3,23
The cumene16,43
Hydroxyacetone0,05
The oxide mesityl0,01
Unidentified0,61
Water0,58

The molar ratio of phenol:acetone is 5.0.

Analysis of the yield of heavy products of decomposition of the CCP produced analogously to example 1. The total number of by-products formed when it is 65 kg per 1000 kg of the obtained phenol.

Example 4 (for comparison).

The decomposition of the CCP produced on the same equipment as in example 1, but used as raw material mixture composition is shown in table 7.

The raw material is fed into the reactor with a rate of 26 ml/h, sulfuric acid is served with a rate of 4 μl/h of the Speed of circulation of the reaction mixture and the temperature setting mode are the same as in example 1.

Table 7.

Raw materials used for the decomposition of CPC
ComponentSoderzhanie, wt.%
1Cumene hydroperoxide (CHP)77,81
2The cumeneup 11,86
3Dimethylphenyl rbinom (DMFC) 4,16
4The acetophenone0,51
5Water0,1
6Dicumylperoxide (DCT)0,43
7Acetoneequal to 4.97
8Unidentified0,16

Simultaneously with the reaction products emerging from the first stage reactor, the reactor of the second stage serves a 5% aqueous solution of ammonia at a rate of 8 μl/h

The composition of the obtained reaction mass is presented in table 8.

0,01
Table 8.

The composition of the reaction mixture decomposition of the CCP.
ComponentConcentration, wt.%
Phenol45,92
Acetone36,99
Dicumylperoxide (DCT)0,01
Dimethylphenylcarbinol (DMPC)0,06
Cumylphenol0,58
The amount of dimers α-methylstyrene0,29
The acetophenone0,70
α-Methylsterol (AMC)2,85
The cumene11,48
Hydroxyacetone0,12
The oxide mesityl
Unidentified0,33
Water0,66

The molar ratio of phenol:acetone is 0.77.

Analysis of the yield of heavy products of decomposition of the CCP produced analogously to example 1. The total number of by-products formed during this amounts to 57 kg per 1000 kg of the obtained phenol, including these heavy components.

1. Method for production of phenol and acetone by acid-catalyzed decomposition of cumene hydroperoxide in the series connected reactors in two stages at an elevated temperature in the presence of a catalyst is sulfuric acid with the simultaneous formation of the first stage of dicumylperoxide and its subsequent decomposition in the reaction medium in the second stage, wherein the process is conducted at a molar ratio of phenol: acetone is greater than 1 and the concentration of sulfuric acid at both stages equal to 0.003 to 0.015 g wt.%.

2. The method according to claim 1, wherein the process is conducted at a temperature of 40-65°in the first reactor and 90-140°in the last reactor.

3. The method according to claim 1, characterized in that the molar ratio of phenol: acetone in the reaction mass decomposition of cumene hydroperoxide support in the range of from 1.01 to 5.

4. The method according to claim 1, characterized in that the desired ratio of phenol: acetone support relax the tion in the reaction mass of phenol.

5. The method according to claim 1, characterized in that the desired ratio of phenol: acetone supported by distillation or Stripping of the reaction mixture of acetone.



 

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