Method of producing cyclohexanone

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing cyclohexanone from cyclohexane, involving the following stages: oxidation of cyclohexane to hydroperoxide of cycohexyl with oxygen in the absence of a catalyst, purification of the reaction medium by washing with water, decomposition of hydroperoxide of cycohexyl to cyclohexanol and cyclohexanone in the presence of a catalyst, extraction of the cyclohexanol/cyclohexanone mixture for separating unreacted cyclohexane and separation of products with boiling point higher than that of the cyclohexanol/cyclohexanone mixture, dehydrogenating cyclohexanol contained in the cyclohexanol/cyclohexanone mixture, in the presence of a dehydrogenation catalyst, distillation of the obtained mixture so as to obtain first run (F1) at the first stage, containing compounds with boiling point lower than that of cyclohexanone, and a last run (Q1) and distillation of the last run (Q1) to obtain a first run (F2) at the second stage, formed from cyclohexanone, and a last run (Q2).

EFFECT: obtaining highly pure cyclohexanone, suitable for use as raw material for synthesis of ε-caprolactam.

6 cl, 1 dwg, 3 ex

 

The present invention relates to a method for producing cyclohexanone from cyclohexane.

More specifically, it relates to a method for producing cyclohexanone with such impurities, which allows the use of cyclohexanone as raw material for production of ε-caprolactam.

Indeed, polyamide-6 or polycaprolactam is one of the main thermoplastic materials for the production of filaments, fibers, and various molded products. This polymer is produced by polymerization of ε-caprolactam.

This compound can be obtained in different ways. Among them one of the most frequently used consists in obtaining cyclohexasiloxane of cyclohexanone.

In this way cyclohexanone must have high degree of purity, in order to avoid the introduction of impurities, which could be undesirable, in particular, at the stage of polymerization of caprolactam, and which could also impair the properties of the obtained polyamide, in particular, the coloration of the polyamide and its resistance to aging.

Cyclohexanone are usually obtained by oxidation of cyclohexane in the liquid state gas containing oxygen to obtain a mixture of cyclohexanol/cyclohexanone, and then, after purification and separation of cyclohexanol from cyclohexanone, dehydrogenization of cyclohexanol to cyclohexanone.

This oxidation of cyclohexane is getting a mixture of cyclohexanone/cyclohexanol is carried out or in one stage, in the presence of the oxidation catalyst, or in the first stage by oxidation of cyclohexane hydroperoxide of cyclohexyl, without catalyst, and then the catalytic decomposition of the hydroperoxide to cyclohexanol and cyclohexanone.

During these stages of oxidation formed numerous impurities such as aldehydes, acids, alcohols and ketones. Usually these impurities cannot be converted subsequently into valuable products such as adipic acid or ε-caprolactam. Therefore, these impurities must be removed and separated from cyclohexanone and/or cyclohexanol, especially in case of receipt of cyclohexanone.

Ways oxidation of cyclohexane in the presence of a catalyst include a purification step of a mixture of cyclohexanone/cyclohexanol processing bases or by distillation in a basic environment. Under this treatment grounds impurities are removed.

However, this method requires additional processing using the new reagent, a basic compound such as the hydroxide of the metal. Thus, it is necessary to provide for the separation and extraction of this basic compound in the form of waste, which usually must be processed (burning or otherwise).

In the case of oxidation of cyclohexane hydroperoxide of cyclohexyl, you can also apply the processing of the primary connection, with the same advantage is Tami and disadvantages what is described above.

One of the purposes of the present invention is to eliminate these disadvantages by offering a method of producing cyclohexanone based on the oxidation of cyclohexane, without applying cleaning with the main connection.

For this purpose, the invention proposes a method of producing cyclohexanone, characterized in that it comprises the following stages:

- oxidation of cyclohexane hydroperoxide of cyclohexyl oxygen or gas containing oxygen, in the absence of catalyst,

- purification of the reaction medium by washing with water,

- the decomposition of cumene at cyclohexyl cyclohexanol and cyclohexanone in the presence of a catalyst,

- removing a mixture of cyclohexanol/cyclohexanone to separate unreacted cyclohexane and office products with a higher boiling point than the mixture of cyclohexanol/cyclohexanone,

- dehydrogenase cyclohexanol contained in a mixture of cyclohexanol/cyclohexanone, in the presence of catalyst dehydrogenization,

- distilling the resulting mixture to obtain at the first stage of distillation head wrap (F1), containing compounds with a boiling point below the boiling point of cyclohexanone, and tail wrap (Q1),

- distillation tail of a shoulder strap (Q1to get to the second stage of the distillation head is Oh wrap (F 2)formed cyclohexanone, and tail wrap (Q2).

Obtaining a mixture of cyclohexanol/cyclohexanone as described in the first stages, it is not possible to eliminate all impurities and, in particular, α,β-cyclopenten-1-carboxaldehyde (cyclopentenyl), which is also found in a mixture of cyclohexanol/cyclohexanone.

This compound, having a boiling point close to the boiling temperature of cyclohexanone, it is very difficult to separate from it by distillation. However, this compound reacts to certain tests for compliance with applicable currently to assess cyclohexanone, in particular, the suitability for the synthesis of caprolactam as a test using UV conducted with the light rays of a certain wavelength, or a test for oxidation.

In the method according to the invention this connection, i.e. cyclopentenyl, chemically convert at the stage of dehydrogenization in products that can be separated from cyclohexanone, for example, by the classical operation of the distillation of what is provided for in the scheme of the sequence of processes described above.

Stage dehydrogenization cyclohexanol contained in a mixture of cyclohexanol/cyclohexanone, carried out in the presence of a catalyst of dehydrogenization and under normal conditions of temperature and pressure, the description is the R in the literature, as, for example, at temperature of from 200°C to 450°C and absolute pressure of from 1 to 3 bar. As an example of the description of this stage of dehydrogenization you can refer to patent US 4918239.

In one embodiment of the invention this stage of dehydrogenization carried out in the presence of a catalyst based on oxides of copper, magnesium, zinc and/or mixtures thereof.

Thus, the method according to the invention allows to obtain cyclohexanone, meet the criteria of purity required, in particular, to obtain ε-caprolactam, in particular, UV-test, consisting in determining the transmittance of light rays with a wavelength of 230 nm through a volume of cyclohexanone. This transmission should be higher than 86%.

According to another distinctive feature of the invention the tail wrap Q2distilled at the third stage of distillation, to obtain a head wrap (F3), consisting of a mixture of cyclohexanol/cyclohexanone, and tail wrap (Q3)formed by compounds with high boiling point.

Head wrap (F3) it is advantageous to return to the stream of the mixture of cyclohexanol/cyclohexanone entered on the stage of dehydrogenization of cyclohexanol.

According to another distinctive feature of the invention the head wrap (F1) is distilled to obtain a new head wrap (F4)formed by compounds with a time less high boiling point, and a new tail wrap (Q4), consisting mainly of cyclohexanone. This tail wrap (Q4) profitable return in a mixture of cyclohexanol/cyclohexanone entered on the stage of dehydrogenization.

The method according to the invention allows to remove the cyclohexanone in the head rush (F2)that meets the high criteria of purity and, in particular, UV-test (% transmittance at λ = 230 nm above the required specifications). Thus, cyclohexanone obtained by the method according to the invention, advantageously be used to obtain ε-caprolactam by oxymorphine.

Other advantages and details of the invention will appear more clearly when considering the examples given below solely for the information, and from the description of embodiments of the method according to the invention, made with reference to the single attached drawing, which shows a block diagram of the implementation of this option.

Example 1

A mixture of cyclohexanol containing 600 ppm of cyclopentenes, served by line 1 in the reactor column 2.

In column 2 is the catalyst in the form of a fixed layer. This catalyst based on copper oxide. The temperature in the column 2 is 230°C. the Degree of conversion of cyclohexanol to cyclohexanone 30%. The concentration of cyclopentenes in the reaction medium at the outlet of the reactor 2 is below the limit found is ugenia known measuring methods, that is, below 30 h/million

Example 2

In the reactor 2 serves mixture containing 59% by weight cyclohexanone, 39 wt.% cyclohexanol, 0.5 wt.% water and 1.5 wt.% light or heavy products, regarded as impurities that need to be addressed. As a concrete admixtures can be called cyclopentenyl, which is present in a concentration of 2950 h/million

The flow rate of the mixture in the reactor 2 is equal to 215 g/h

The temperature of the reactor is equal to 310°C.

The reaction medium at the outlet from the reactor contains of 80.6 wt.% cyclohexanone, 16.5 wt.% cyclohexanol and heavy or light particles. The concentration of cyclopentenes in the environment below the detection limit, i.e. below 30 h/million

The degree of conversion of cyclohexanol to cyclohexanone equal to 55%.

The reaction medium leaving the reactor 2, is fed into the heat exchanger 3, then line 4 in the first distillation column 5.

This column contains 22 theoretical stages and operates at normal temperature and pressure conditions known to the expert in the field of distillation cyclohexanone.

Tail wrap Q1is introduced into the second distillation column 6, containing 22 theoretical plates.

Fraction F2retrieved from above, is cyclohexanone with a degree of purity higher than 99.8 per cent and in the UV-test at a wavelength of 230 nm detects the degree of transmission at 88.5%.

In the illustrated what the manual implementation of tail wrap Q 2can be fed to the third distillation column 7 that allows you to separate the heavy products (products with a higher boiling point than cyclohexanone) in the form of fractions Q3. Head wrap F3containing cyclohexanone and cyclohexanol can be returned to the reactor 2 dehydrogenization.

According to the method of implementation, shown in the attached drawing, head wrap F1taken from distillation column 5 may be fed to the decanter 8 to be separated then the aqueous phase, and then to distillation column 9. Assembled tail wrap Q4containing cyclohexanone, may be returned to the reactor 2.

Head wrap F4containing light products, i.e. with a low boiling point, is treated as waste.

Example 3

Repeat example 2, but feeding into the reactor a mixture containing 59% by weight cyclohexanone, 39 wt.% cyclohexanol, 0,5% water and 1.5% heavy or light impurities, of which 360 ppm is cyclopentenyl.

The flow rate of the mixture in the reactor 2 is equal to 135 g/H.

The temperature of the reactor is equal to 270°C.

The composition of the reaction mixture at the outlet of the reactor 2 is as follows:

to 75.2 wt.% cyclohexanone, 22.3 wt.% cyclohexanol and heavy or light particles. The concentration of cyclopentenes in the environment below the detection limit, i.e. below 30 h/million

Degree pravr the assumptions of cyclohexanol to cyclohexanone is equal to 44%.

Cyclohexanone extract as a fraction F2with the content of cyclopentenes below 30 mg/kg and the degree of transmittance in the UV-test at 230 nm, equal to 89.5%.

1. The method of producing cyclohexanone, characterized in that it comprises the following stages:
the oxidation of cyclohexane hydroperoxide of cyclohexyl oxygen in the absence of catalyst,
purification of the reaction medium by washing with water,
decomposition of cumene at cyclohexyl cyclohexanol and cyclohexanone in the presence of a catalyst,
removing a mixture of cyclohexanol/cyclohexanone to separate unreacted cyclohexane and office products with a higher boiling point than the mixture of cyclohexanol/cyclohexanone,
dehydrogenase cyclohexanol contained in a mixture of cyclohexanol/cyclohexanone, in the presence of catalyst dehydrogenization,
distillation of the resulting mixture to obtain at the first stage of distillation head wrap (F1), containing compounds with a boiling point below the boiling point of cyclohexanone, and tail wrap (Q1),
distillation of the tail of a shoulder strap (Q1to get to the second stage of distillation head wrap (F2)formed cyclohexanone, and tail wrap (Q2).

2. The method according to claim 1, characterized in that tail wrap (Q2) is distilled in the third hundred of the AI distillation, to get a head wrap (F3), consisting of a mixture of cyclohexanol/cyclohexanone, and tail wrap (Q3)formed by compounds with high boiling point.

3. The method according to claim 2, characterized in that the head wrap (F3) is mixed with a mixture of cyclohexanol/cyclohexanone entered on the stage of dehydrogenization.

4. The method according to one of the preceding paragraphs, characterized in that the head wrap (F1) is distilled in the fourth stage distillation to obtain a head wrap (F4), formed with a low-boiling compounds, and tail wrap (Q4consisting of cyclohexanone.

5. The method according to claim 4, characterized in that tail wrap (Q4) are added to a mixture of cyclohexanol/cyclohexanone entered on the stage of dehydrogenization.

6. The method according to claim 1, characterized in that the stage of dehydrogenization carried out in the presence of a catalyst selected from the group consisting of oxides of copper, magnesium, zinc and mixtures thereof.



 

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

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5 cl, 4 ex, 8 tbl

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EFFECT: improved method for decomposition.

8 cl, 24 ex

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EFFECT: increased selectivity of decomposition at lesser recycle apparatus volume and reduced investment expenses.

11 cl, 1 dwg, 9 ex

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