The method of producing cyclohexanone

 

(57) Abstract:

Cyclohexanone is obtained from the bottoms of the process of obtaining cyclohexanone. Are hydrolytic decomposition of cyclohexanone dimer in the vapor phase at a temperature of 360 - 460oWith a heterogeneous catalyst: 1 - 10% NaOH based on the weight of the porous media. The process is preferably carried out in the presence of 1 to 3% aqueous NaOH solution in the stoichiometric ratio of NaOH to the dimers of cyclohexanone. 1 C.p. f-crystals, 7 PL.

The invention relates to an improved process for the preparation of cyclohexanone (Chona), which is an intermediate for the synthesis of caprolactam.

A known method of producing cyclohexanone hydrolytic decomposition products seal Chona, in particular of cyclohexylcyclohexanes (cyclohexanone dimer - DCG) at 105 - 130oC and atmospheric pressure in the presence of two mass excess catalyst cation exchanger in relation to DCG. Output Chona is 70-72 mol. % reacted DCG.

the disadvantages of this method is the high consumption of catalyst, the complexity of its regeneration and low yield of the target product [1].

A method of obtaining Chona hydrolytic razrisovanny DCG [2].

The disadvantages of this method is the complexity of the design process and the presence of high pressure.

The closest in technical essence is a way of decomposition DCG in the presence of solid potassium hydroxide (KOH) with the simultaneous processing of the product superheated steam in the liquid phase at a temperature of 180oC [3].

Disadvantages of the method are: the use of large amounts of superheated steam at a temperature of 400oC (consumption of the process), low output Chona (78% of theory) due to prolonged contact of the reaction products with solid alkali and deficit KOH.

Technical solution to the problem is to obtain the target products Chona and cyclohexanol (Chola) hydrolytic decomposition in the gas phase products of the condensation of cyclohexanone contained in the VAT balance of caprolactam production. Currently, the VAT residue to be burning.

This task is solved by the method of hydrolytic decomposition products seal DCG, wherein the process is conducted in the vapor phase in the presence of a heterogeneous catalyst NaOH on a porous carrier with a NaOH content of 1-10 wt.% when 360-460oC and the contact time between 2-10 C. To maintain actively processing in this way is used CBM product of the column selection cyclohexanol (Chola) caprolactam production by oxidation of cyclohexane following composition, wt.%: DCG 64,9; the amount of impurities 28,2; Chona 1,1; Zgola 5,8.

Processing of the cubic product is carried out according to the following scheme: CBM product of the column selection Chola from the intermediate tank is mixed in the stoichiometric ratio (in terms of DCG) with 3% aqueous NaOH solution and then flows through the heater in an isothermal tubular reactor. The temperature in the reactor 360-460oC supported flue gases. After the reactor can produce arrives on cooling, and then into the production scheme Chona and Chola. The following examples illustrate the method of hydrolytic decomposition DCG.

Example 1. Fraction DCG without additional purification composition, wt.%: DCG 64,9; Zgola 5,8; Chona 1,1); the amount of unidentified impurities 28,2 in the amount of 49.5 ml/h in 3% aqueous NaOH solution and through the heater comes with 400oC in an isothermal tubular reactor. The reactor is made of stainless steel AISI IXI8H9T (inner diameter 22 mm, length 400 mm). In the Central part of the reactor were placed ball catalyst with a diameter of 4 mm Al2O3with 5% NaOH in 20 %. The upper and lower part of the reaction tube was filled with an inert nozzle - rings process.

The reactor was placed in thermosta vapors in the reaction zone is 2-3 temperatures 400oC.

After the reactor was obtained organic layer in amounts to 48.6 ml/h composition, wt. %: DCG 40,0; Zgola 5,9; Chona 29,3; impurities 24,8. Conversion DCG 39,5; output Chona on decomposed DCG to 98.4% (see tab. 1).

Example 2. The process is carried out analogously to example 1, using as catalyst in 20 ml of 1 wt.% NaOH/Al2O3. Decomposition temperature DCG 400oC, the contact time of the vapors in the reaction zone 2 C.

After the reactor was received for 48.7 ml/h organic layer composition, wt.%: DCG 44,7; Zgola 5,9; Chona 21,2; impurities 28,2. Conversion DCG 32,2%, output Chona 86.2 per cent (see table. 2).

Example 3. The process is carried out analogously to example 1, using as catalyst 20 ml of 10 wt.% NaOH/Al2O3. This limits the amount of NaOH, because further increase leads to fusion of the catalyst. After the reactor was received for 48.7 ml/h organic layer composition, wt.%: DCG 40,1; Zgola 6,1; Chona 28,6; impurities 25,2. Conversion DCG 39,1%, output Chona to 96.9% (see tab. 3).

Example 4. The process is carried out analogously to example 1, using as catalyst 5 wt.% NaOH/Al2O3. The decomposition process DCG led with 360oC, contact time of the vapors in the reaction zone 2 C. After the reactor had been the heat (selectivity) to 98.1% (see table. 4).

Example 5. The process is carried out analogously to example 1, using as catalyst 5 wt.% NaOH/Al2O3. The decomposition process was conducted at 460oC, contact time 2 C. After the reactor has been 48,7 ml/h organic layer composition, wt.%: DCG 35,8; Zgola 5,0; Chona 29,7); the amount of impurities to 29.5. Conversion DCG of 45.7%, output Chona on decomposed DCG 86,3% (table. 5).

Example 6. The process is carried out analogously to example 1, using as catalyst a 5 wt. % NaOH on hard-shelled media (refractory brick, the fraction with a diameter of 5 mm). After the reactor received 48.6 ml/h of the organic layer, wt.%: DCG 39,1; Zgola 5,7; Chona 29,8); the amount of impurities 25,4. Conversion DCG 40,8, output Chona on decomposed DCG to 96.9% (see tab. 6).

The obtained data are given in the summary table 7.

1. The method of producing cyclohexanone hydrolytic decomposition products of the condensation of cyclohexanone in the presence of a catalyst at atmospheric pressure, wherein the process is conducted in the vapor phase at 360 - 460oIn the presence of a heterogeneous catalyst, which is used as NaOH on a porous carrier in a quantity of 1 to 10% by weight of the carrier.

2. The method according to p. 1, characterized in that the decomposition of waikaremoana in the original seal products.

 

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