Method of decomposing cyclohexyl hydroperoxide to produce high yield of cyclohexanol and cyclohexanone

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to technology of air oxidation of cyclohexane followed by treatment of oxidation products to decompose contaminating cyclohexyl hydroperoxide. Decomposition of cyclohexyl hydroperoxide into cyclohexanol and cyclohexanone is accomplished in the following steps: washing cyclohexane oxidation end products with water, separation of phases, and treatment of organic phase with alkali aqueous solution wherein water phase-to-organic phase volume ratio is approximately 0.10:100 to 1.00:100. Thereafter, phases are separated once again and organic phase is brought into contact with catalyst containing cobalt salt in alkali aqueous solution. Resulting two-phase product is stirred, and after next separation of phases, cobalt-containing alkali aqueous phase is removed and organic phases is washed with water. Part of alkali aqueous phase may be optionally reused by recycling it to the first reaction product treatment step. Alkali solution can be prepared from alkali hydroxides or alkali carbonates at concentration of alkali solution 2 to 25%, to which cobalt catalyst is added in amount from 5 to 15 ppm.

EFFECT: achieved essentially full conversion of cyclohexane into cyclohexanol and cyclohexanone.

13 cl, 4 ex

 

The scope of the invention

The present invention relates to a method for producing cyclohexanol and/or cyclohexanone by oxidation of cyclohexane with air, followed by decomposition of cyclohexylpiperazine in aqueous alkaline solution in the presence of cobalt catalyst.

Prior art

Adipic acid is subjected to interaction with hexamethylenediamine were with the formation of nylon salt, which salt is polymerized with the formation of nylon-6,6. One way of producing adipic acid involves the oxidation of cyclohexane with air. The oxidation of cyclohexane is carried out in such a way that results in mixtures containing cyclohexanone (K), cyclohexanol (A) (commonly referred to together as "KA") and cyclohexylpropionic (CGGP). These methods are described in U.S. patent No. 3957876. Cyclohexylpropionic can be subjected to decomposition with mixture of cyclohexanone and cyclohexanol.

In this area describes the different ways of decomposition of cyclohexylpiperazine. Decomposition of cyclohexylpiperazine in the presence of a heterogeneous cobalt catalyst described in patent EP No. 0659726B1 (authors Kragten and Baur).

Decomposition of cyclohexylpiperazine with cobalt catalyst in the presence of derivatives of phosphonic acids described in the patent EP 0230254B1 (author of the Hartig, Herrmann and Lucas).

In the patent EP 0768292B1 (authors Kragten and Housmans) described a method of decomposition of cyclohexylpiperazine in the presence of chromium and/or cobalt at temperatures between 66° 96°C.

The use of heterogeneous cobalt catalyst for the decomposition of CHHP requires special equipment, and the catalyst is exposed to pollution, caused the audience in the way that impurities. The use of special derivatives of phosphonic acids taken in order to facilitate the decomposition CGGP, however, it complicates the process and contributes more to the formation of by-products. Decomposition CGGP in the presence of chromium and cobalt catalysts at temperatures below 96°C leads to high processing time required for completion of the decomposition reaction. High time contributes to the increase in fixed costs of production equipment.

To improve the efficiency of the methods of production of adipic acid required method of decomposition of cyclohexylpiperazine, which leads to increased output KA. The described method is a method of decomposition of cyclohexylpiperazine with high output.

Brief description of the invention

The described method is a method of decomposition of cyclohexylpiperazine to cyclo is hexanol and cyclohexanone, this method includes:

(a) washing with water the final products of the oxidation of cyclohexane with air;

(b) separation of the phases obtained in stage (a);

(c) contacting the washed water of the final products of the oxidation process air with aqueous alkaline solution;

(d) separation of the phases obtained in stage (c);

(e) contacting the organic phase containing the water washed the final products of oxidation by air, with a catalyst containing a salt of cobalt in aqueous alkaline solution;

(f) mixing a two-phase product from step (e);

(g) separation of the phases;

(h) removing the aqueous alkaline phase containing cobalt;

(i) washing the organic phase with water;

(j) the possible reuse of part of the aqueous alkaline phase from step (h) by returning to the step (c).

(k) the possible reuse of water from the previous stage washing (i) by returning to the step (a).

Description of the invention

Decomposition of cyclohexylpiperazine ("CGGP") according to the present invention is carried out using the alkaline method, catalyzed by cobalt. This method is performed by processing of the final products of the oxidation of cyclohexane with air. Under "final products of the oxidation of cyclohexane with air" refers to all products, arr is generated during the method of oxidation of cyclohexane. These products in General contain cyclohexane, cyclohexanol, cyclohexanone, cyclohexylpropionic, oneonone acid, dienone acid and other by-products.

The method of decomposition CGGP comprises several stages. First, the final products of the oxidation of cyclohexane with air washed with water. The result of two phases: an organic phase and aqueous phase. The two phases are separated by any method known in this field, to effect the separation, you can use this method as decantation. For separation, you can use continuous mode.

Water washed the final products of oxidation by air in contact with the aqueous alkaline solution to reduce impurities acids. These two phases are separated. The phase containing the greatest quantity of water washed the final products of the oxidation process air, is subjected to contact with a catalyst containing a salt of cobalt in aqueous alkaline solution. Two-phase product from the previous stage is stirred, and the resulting phases are separated by removal of the aqueous alkaline phase. The aqueous alkaline phase with the specified stage can be reused for use in re-implementing the method. The organic phase is washed with water. Water can then be reused by repeating the method.

The alkali used p and the implementation of the method, is in the form of a solution of an alkali metal, alkali hydroxide or alkali carbonate. The concentration of the alkaline solution is from about 2 wt.% up to 25 wt.%, preferably from about 7 wt.% up to 20 wt.%. Preferably the alkaline solution contains sodium hydroxide. As mentioned, some of the alkaline solution can be reused during the implementation of the method.

Decomposition CGGP is carried out with the greatest efficiency when the ratio of the aqueous phase to the organic phase is higher than 0,10:100, preferably from 0.15:100 to 1.00:100.

The catalyst according to the present invention is a water-soluble salt of cobalt. Examples of such catalysts are cobalt sulphate and cobalt chloride. The amount of catalyst used in the present method, is approximately from 0.1 to 100 ppm, preferably from 3 to 20 ppm, and most preferably from 5 to 15 h/million it is Important to adjust the optimum concentration of the catalyst depending on the process temperature. In General, higher temperatures require lower concentrations of catalyst.

Other factors affecting the efficiency of the method described here, are the temperature of the method, amount and/or concentration of alkali used and appropriate is its mixing. In General, higher temperatures contribute to high rate of decomposition CGGP. It should be noted that higher temperatures can increase the formation of by-products. Decomposition CGGP according to the present method can be optimized by careful selection of the temperature, concentration of catalyst and length of stay in exposure.

The method can be carried out at temperatures from about 100°C to 150°C, preferably from about 105°C to 145°C. the Method can be carried out in a horizontal reactor with internal compartments or without them, hull reactors, hull reactors with mixing, static mixers, autoclaves with stirring, and similar devices.

Proper mixing will positively influence the effectiveness of the method. It can be done with effective mixing systems or static mixers.

The main reaction during decomposition CGGP can be explained as follows. From 1 mol CGGP after decomposition according to the method receive one (1) mol of a mixture of KA. The mixture contains x mol of compound A, y mol of compound K and z mol of by-products, and x+y+z=1. The output of the method of decomposition CGGP is expressed as:

100[K+A+CGGP]product/[K+A+CGGP]source,

where [K+A+CGG is] productrepresents the concentration of K+A+CGGP in the organic phase at the output of the last of a decanter used in the method; and where [K+A+CGGP]sourcerepresents the concentration of K+A+CGGP in the organic phase supplied to the washing water. All concentrations are expressed in moles.

Typical loss of yield during the decomposition mode CGGP include physical loss (K+A+CGGP) when dissolved in aqueous solution and losses caused by the formation of any side products during the implementation of a method of catalytic and thermal decomposition CGGP. The output of the method of decomposition CGGP may vary depending on the amount of water applied at the stage of removal of impurities, the number of used cobalt catalyst, the relationship of an aqueous solution to the organic phase along with other conditions. The experiments described in the examples was carried out at the change of two parameters: the speed of water flow and the amount of the cobalt catalyst. Excessive water flow can result in the loss of some of the quantities K, A and CGGP in the aqueous phase by dissolving. If water is scarce, some of the impurities will not be deleted.

EXAMPLES

Symbols used in the examples:

"t/h" means tonnes per hour;

"K" means the cyclohexanol;

"A" means cyclohexanone;

"CGGP" means cyclohexyl operated.

All of the following examples was carried out using a cobalt catalyst. During all experiments the method was carried out at steady state. Data analyses cyclohexanone ("K"), cyclohexanol (A) and cyclohexylpiperazine (CGGP) represent the average result of three different samples. During the experiments, all the process parameters, except the parameters selected for optimization, remained constant. After you change the settings to achieve steady-state experiments were performed within 12 hours.

EXAMPLE 1

In the example 1360 t/h final products of the oxidation process air containing 0,71% of cyclohexanol, 1,12% cyclohexanone or 3.24% of cyclohexylpiperazine, mixed in a static mixer with 1.0 t/h of water reused in the method, at a temperature of 120°C. the Ratio of aqueous and organic phases was estimated at 0.28:100. The separated water decantation using decantation. The organic phase at 118°C was subjected to alkaline treatment with a cobalt solution containing 5 ppm Co, and CHHP was subjected to decomposition in the reactor for the decomposition CGGP.

The alkaline solution was separated with the help of decantation and the organic phase is washed with water. The concentration of cyclohexanol in the organic phase after washing was 1.71 wt.% and cyclohexanone 2,47 wt.%, th is corresponds 91,30%final output of the method of decomposition CGGP.

EXAMPLE 2

In this experiment, the amount of recycled water increased up to 1.5 t/h, the ratio of aqueous and organic phases were 0,43:100, while other parameters remained the same as in example 1. The output of the method of decomposition CGGP in this case was 90,56 (%).

EXAMPLE 3

Example 3 was carried out analogously to example 1, except that the concentration of the cobalt catalyst was increased to 10 h/million Out of the way of decomposition CGGP was about to 96.9%. Example 3 shows that increasing the concentration of the catalyst at a lower flow rate of recycled water (1.0 t/h) increases the output.

EXAMPLE 4

Stage was carried out analogously to example 3, except that the flow rate of recycled water increased up to 1,5 t/h Output method decomposition CGGP was 95,75%. Example 4 shows that increasing the flow rate of recycled water to 1.5 t/h at high cobalt concentration (10 ppm) has a small negative influence on the yield of the method of decomposition CGGP. Higher outputs method of decomposition CGGP were obtained with 10 ppm Co-catalyst and 1.0 t/h of recycled water (example 3).

1. The method of decomposition of cyclohexylpiperazine to cyclohexanol and cyclohexanone, including

(a) washing with water the final product is economical process for the oxidation of cyclohexane with air;

(b) separation of the phases obtained in stage (a);

(c) contacting the washed water of the final products of the oxidation process air with aqueous alkaline solution;

(d) separation of the phases obtained in stage (C);

(e) contacting the organic phase containing the water washed the final products of oxidation by air, with a catalyst containing a salt of cobalt in aqueous alkaline solution;

(f) mixing a two-phase product from step (e);

(g) separation of the phases;

(h) removing the aqueous alkaline phase containing cobalt;

(i) washing the organic phase with water;

(j) the possible reuse of part of the aqueous alkaline phase from step (h) by returning to the step (C);

(k) the possible reuse of water from the previous stage washing (i) by returning to the step (a).

2. The method according to claim 1 where the alkaline solution is selected from the group consisting of alkali metal, alkali hydroxides, alkali carbonates.

3. The method according to claim 2, where the alkaline solution contains sodium hydroxide.

4. The method according to claim 1 where the concentration of the alkaline solution is in the range from 2 to 25 wt.%.

5. The method according to claim 5, where the concentration of the alkaline solution is in the range from 7 to approximately 20%.

6. The method according to claim 1, where the stage (C) is carried out at temperatures in d is apatone from 105 to 145° C.

7. The method according to claim 1, where the number of used cobalt catalyst is between 3 and 20 hours/million

8. The method according to claim 7, where the number of used cobalt catalyst is between 5 and 15 hours/million

9. The method according to claim 1, where the water from the stage of removal of alkali reused for irrigation of the end products of oxidation by air at stage (a).

10. The method according to claim 1, where the separation of the aqueous phase from the organic phase carried out by decantation.

11. The method according to claim 10, where the decantation is carried out in a continuous mode.

12. The method according to claim 1, where the ratio of aqueous phase:organic phase to phase (a) is from about 0.10 to:100 to 1.00:100.

13. The method according to item 12, where the volume ratio of aqueous phase to organic phase is between 0.10:100 and 0.80:100.



 

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