Method of preparing mixture of cyclohexanol and cyclohexanone

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a mixture of cyclohexanol and cyclohexanone which are intermediate products in production of polyamides nylon-6 and nylon-6.6. The method is realised at high temperature and high pressure and involves the following successive cycles: oxidation of cyclohexane - decomposition of cyclohexylhydroperoxide, wherein oxidation of cyclohexane and decomposition of cyclohexylhydroperoxide are carried out in separate series-connected reactors without intermediate separation of the aqueous phase, whereby in each separate cycle, cyclohexane is oxidised with air or an oxygen-containing gas in liquid phase in the absence of a catalyst until conversion of cyclohexane of not more than 1.5 mol %, and the cyclohexylhydroperoxide formed during oxidation of cyclohexane is decomposed on a heterogeneous catalyst in a separate reactor until conversion of not less than 90 mol %.

EFFECT: method increases overall selectivity of converting cyclohexane to cyclohexanone and cyclohexanol and also considerably reduces formation of by-products.

9 cl, 19 ex, 2 tbl, 1 dwg

 

The invention relates to a method of obtaining a mixture of cyclohexanol and cyclohexanone, which are intermediates in the production of polyamides of nylon-6 and nylon-6,6.

The most common way of obtaining them is the oxidation of cyclohexane with oxygen. The oxidation of cyclohexane is carried out in such a way that results in Okidata - mixtures containing ketone - cyclohexanone (K), alcohol, cyclohexanol (a) and cyclohexylpropionic (SNR) in cyclohexane. The end product, the mixture of ketone and alcohol allocated from oxidate, usually called KA-oil.

Describes the different ways of obtaining a mixture of cyclohexanone and cyclohexanol. The most common is the oxidation of cyclohexane with oxygen. Thus get more 60% of the world production of cyclohexanone. The most well-known technology for the oxidation of cyclohexane in the presence of a homogeneous catalyst soluble salts of cobalt (US 3957876, US 4587363, DE 3733782). The disadvantage of this method of producing cyclohexanone and cyclohexanol is the low conversion of cyclohexane (4-6 mol.%) and the relatively low selectivity of the conversion of cyclohexane to KA oil (75-85 mol.%).

Known two-stage method for producing cyclohexanol and cyclohexanone via intermediate formation of cyclohexylpiperazine. For the first hundred and the AI oxidation of cyclohexane is carried out similarly to the above described method, but without adding to the reaction mixture of soluble salts of cobalt. To increase the output SNR in the reaction mixture was added derivatives of phenol (EN 2116290), pyrophosphate Na or K (CA 1262359) or ester of phosphoric acid (US 4675450).

In the second stage SNR turn in KA-oil using heterogeneous catalysts (EP 659726, US 4503257, US 5004837, JP 63277640, US 4499305)and soluble in the reaction mixture of salts of transition metals (US 4257950, US 4508923, US 4704476, US 5206441, US 4482746, US 4918238, CA 1294984, US 4877903, EP 92876, US 4238415). Reduce the formation of by-products of the decomposition process SNR carried out, as a rule, at 20-40°C lower than the oxidation of cyclohexane.

A known method of producing alcohols and ketones (US 5859301, B01J 23/34, C07C 29/132, 12.01.1999), which includes a step of oxidation of the corresponding alkane and/or alkene with formation of a reaction mixture containing alkylhydroperoxide, the stage of processing of the reaction mixture aqueous alkaline solution and the stage of decomposition of alkylhydroperoxide in the presence of a heterogeneous catalyst, the active component which is an oxide of a metal selected from the range of Mn, Fe, Co, Ni and Cu, and the carrier consists of a material resistant to the alkaline aqueous phase. Additional processing stage of the reaction mixture with an alkaline solution complicates instrumentation process. The optimal condition is I oxidation of cyclohexane and decomposition SNR differ. Typically, the decomposition is carried out at a lower temperature, which is accompanied by the need to lower the pressure. According to US 5859301 selectivity of transformation SNR in KA-oil close to 100%, it is obvious that the total selectivity of the process will be determined by the selectivity of the conversion of cyclohexane in SNR. Such organization of the process and conversion of cyclohexane in the range from 3 to 6 mol.% the total selectivity of the process can not be higher than 80-85 mol.%.

As a prototype we have chosen the way of cyclohexanol and cyclohexanone, which is described in patent US 6703529, C07C 35/08, 9.03.04. The method includes: 1) the oxidation of cyclohexane with the formation of steam and gas waste oxidation of cyclohexane and liquid oxidate, including the main oxidation products of cyclohexanone, cyclohexanol and cyclohexylpropionic in cyclohexane; 2) contacting the steam-waste process for the oxidation of cyclohexane with water, 3) mixing the liquid flows generated in stage 1 and 2, and divide the mixture into aqueous and organic phases; 4) decomposition of cyclohexylpiperazine in the organic phase coming from the stage 3 with the formation of cyclohexanone and cyclohexanol; 5) distillation of cyclohexane from its oxidation products and the return of cyclohexane at stage 1; 6) isolation and purification of cyclohexanone and cyclohexanol; 7) non-volatile organic the s residue, formed at stage 6, the amount of which reaches 20% of the amount of the resulting ketone and alcohol, is treated with diluted acid solution for hydrolysis products and the processing of the electrolyte solution for the extraction of Cr in the water layer.

The main disadvantage of the prototype (US 6703529) is the formation during the oxidation of cyclohexane large number of products, including organic acids that interact with the walls of the equipment lead to the extraction of chromium from high-alloy steels. Accumulation of chromium in non-volatile organic residue leads to the extraction of chromium before using this non-volatile residue and consequently to a significant complication of technology for cyclohexanone and cyclohexanol.

The invention solves the problem of increasing the efficiency of the oxidation of cyclohexane.

Method for obtaining a mixture of cyclohexanol and cyclohexanone at elevated temperature and elevated pressure, characterized in that the process includes a number of consecutive cycles: the oxidation of cyclohexane decomposition of cyclohexylpiperazine SNR, in which the oxidation of cyclohexane and decomposition of cyclohexylpiperazine SNR carried out in a separate series-connected with each other reactors without Prohm is filling the separation of the aqueous phase, moreover, in each cycle, the oxidation of cyclohexane is carried out with air or oxygen-containing gas in the liquid phase in the absence of catalyst to the conversion of cyclohexane, not more than 1.5 mol.%, and decomposition formed during oxidation of cyclohexane cyclohexylpiperazine carried out on a heterogeneous catalyst in a separate reactor to a conversion of at least 90 mol.%.

The temperature and pressure of the oxidation of cyclohexane and decomposition of cyclohexylpiperazine SNR close and are, respectively, 160-180°C and 7-9 ATM.

The number of consecutive cycles: the oxidation of cyclohexane decomposition of cyclohexylpiperazine SNR must be at least 2-X.

The conversion of cyclohexane in each cycle at the stage of oxidation should be no more than 0.5 mol.%.

Conversion cyclohexylpiperazine SNR in each cycle at the stage of decomposition must be at least 99 mol.%.

As catalyst for the decomposition of cyclohexylpiperazine use a catalyst containing as an active ingredient one of the elements, or any combination of elements selected from the group of Co, Fe, Cu, Ni, Mn, Cr, Re, Os, Ru, Au, Pt, Pd supported on a carrier, preferably a catalyst containing as the active component of gold Au supported on a carrier.. as a carrier heterogen the first catalyst decomposition using SiO 2, Al2O3, TiO2, MgO, carbon, or any combination thereof. The catalyst for the decomposition used in the form of granules and/or in the form of mono-and/or textile materials.

In order to increase the efficiency of conversion of cyclohexane to KA oil and thus reduce the formation of non-volatile residue, we offer the process of obtaining oxidate (a mixture of cyclohexanone and cyclohexanol in cyclohexane) to split into several consecutive cycles: "the oxidation of cyclohexane decomposition SNR" - "oxidation of cyclohexane decomposition SNR" - "oxidation of cyclohexane decomposition SNR" etc. without intermediate removal of the aqueous phase.

The drawing shows a diagram of the receiving oxidate: 1 - reactor oxidation of cyclohexane, 2 - reactor decomposition SNR. Here each individual cycle is a sequence of stages of the oxidation-decomposition", which are repeated several times. The more cycles, the higher the efficiency of the process, the less is formed of non-volatile by-products.

The oxidation of cyclohexane on the first and subsequent stages carried out without the introduction into the reaction mixture of any additives and catalyst, and the conversion of cyclohexane into separate oxidation steps should not exceed 0.5 mol.%. The reaction mixture from stage oxidation without pre-cooling the post who becomes cyclohexylpropionic SNR. The catalyst decomposition should provide more complete transformation SNR when the selectivity of not less than 98 mol.%. Conversion SNR to cyclohexanol and cyclohexanone with a heterogeneous catalyst should be at least 90 mol.%, preferably above 99 mol.%. Next, the reaction mixture is fed to the next reactor in the oxidation of cyclohexane, where additional conversion of cyclohexane in SNR. Then the reaction mixture containing SNR and KA-oil in cyclohexane, is sent to another reactor for the decomposition SNR in which there is a transformation SNR in the ketone and alcohol.

The combination of three consecutive cycles of the oxidation-decomposition enables the total selectivity of transformation SNR in KA-oil 92-94% conversion of cyclohexane of at least 3 mol.%. The increase in the number of consecutive cycles of the oxidation of cyclohexane decomposition SNR allows to increase the selectivity of the conversion of cyclohexane in the ketone and the alcohol of up to about 97 mol.% when the conversion of cyclohexane is not less than 3 mol.%, either by increasing the conversion of cyclohexane to 5 mol.% save selectivity at 91-93 mol.%.

The method of producing cyclohexanone and cyclohexanol according to the present invention consists of a number of consecutive cycles of the oxidation of cyclohexane decomposition SNR" without intermediate separation of the reaction mixture at the same and the organic phase and removal of the aqueous phase.

The process is non-catalytic liquid-phase oxidation of cyclohexane is carried out in any of the known reactors (column, vessel, horizontal) at a temperature of 130-200°C and a pressure of 4 to 15 ATM air or any oxygen-containing gas. Preferably the oxidation is carried out at a temperature of 160-180°C and a pressure of 7-10 ATM air. To prevent decomposition SNR the surface of the reactor must be made of inert material, or passaged by any known method, for example, Na4P2O7. It is important that the conversion of cyclohexane at any given stage of oxidation did not exceed 1.5 mol.%, preferably, not more than 0.5 mol.%. The residence time of the reaction mixture in the oxidation reactor is 10-120 minutes, preferably 15-30 minutes with increasing number of cycles, the oxidation-decomposition" residence time of the reaction mixture in each individual reactor oxidation decreases.

After oxidation reactor (1), the reaction mixture enters the reactor for the decomposition of cyclohexylpiperazine SNR (2). For decomposition SNR can be used in reactors of different designs, but preferably the decomposition process is conducted in a flow reactor. Reaction conditions, decomposition of the following: temperature of 130-200°C, a pressure of 4 to 15 atmospheres, a contact time of the reaction mixture with the catalyst is 0.3 to 3 minutes as the catalysis of the Torah can be used catalyst, provide under the conditions of the oxidation of cyclohexane selectivity of transformation SNR in KA-oil not less than 95 mol.% at full conversion SNR. As a catalyst it is possible to use the catalyst active component of which is one of the elements or combination of elements taken from the group of Co, Fe, Cu, Ni, Mn, Cr, Re, Os, Ru, Au, Pt, Pd. Catalyst carrier must be resistant to the reaction medium. SiO2, Al2O3, TiO2, MgO, carbon, or any combination thereof may be used as a catalyst carrier. The catalyst in the reactor decay SNR is loaded in the form of granules and/or in the form of a monoblock, and/or woven materials.

It is preferable to decompose SNR to use a gold catalyst, for example, Au/Al2O3or Au/SiO2(in particular, Au/silicalite - SiO2- silicalite with the MFI structure). In this case, the reaction mixture does not require cooling or heating. On gold catalysts for the decomposition process is preferably carried out at a temperature of 160-180°C, the pressure 7-10 bar and a contact time of 0.6-1.2 minutes Conversion SNR should be not less than 90 mol.%, preferably above 99 mol.%.

To ensure the conversion of cyclohexane to KA oil ~3 mol.% with selectivity for the target products is not lower than 92 mol.%, you will need at least three consecutive cycles oxide is s cyclohexane - decomposition SNR". To increase the selectivity of the conversion of cyclohexane in the ketone and alcohol to 96-97 mol.% you will need at least 8-10 cycles "oxidation of cyclohexane decomposition SNR".

Comparison with the prototype (US 6703529) shows that by increasing the number of cycles in the oxidation - decomposition", we win significantly in the total selectivity of the conversion of cyclohexane to cyclohexanone and cyclohexanol. A significant reduction in the formation of by-products will reduce consumption source cyclohexane, to multiple reduction of the resulting acid, and hence the non-volatile residue containing Cr. This not only reduced the cost of extraction of Cr, but also increases the life of the equipment.

The selection of KA-oil from oxidate is carried out by known methods (Msherman, Assadian, Amolde and other Production of cyclohexanone and adipic acid by oxidation of cyclohexane, Moscow, Chemistry, 1967, 240 pages; US 6703529).

The invention is illustrated by the following examples and the drawing.

Example 1

The process of obtaining a mixture of cyclohexanol and cyclohexanone in cyclohexane is carried out by sequential rotation phase oxidation of cyclohexane and stage of decomposition of cyclohexylpiperazine at a temperature of 170°C and a pressure of 8 ATM, using the three follower of the s-cycle oxidation-decomposition". Oxidation lead to capacitive reactor with a stirrer, a decomposition in a flow reactor. The total residence time of the reaction mixture in three series-connected reactors for the oxidation of cyclohexane is about 15 minutes per mol served in the reactor cyclohexane serves 0.1 mol of air. The contact time of the reaction mixture with the catalyst in each reactor decomposition is 1 minutes as a catalyst for the decomposition of cyclohexylpiperazine use 1.5 wt.% Au/SiO2, SiO2- silicalite with the MFI structure. The reaction mixture composition was determined at the outlet of the last reactor of decomposition. Table 1 presents the results. It is seen that three successive cycles of the oxidation-decomposition" provide for the conversion of cyclohexane 3 mol.%, when the selectivity of the conversion of cyclohexane in the ketone and alcohol - 94 mol.%. Cyclohexylpropionic in the reaction products was not found.

Examples 2-3

The oxidation of cyclohexane is carried out analogously to example 1, except that in the process vary the number of consecutive cycles of the oxidation-decomposition". The results are presented in table 1. From the comparison of examples 1-3 shows that the increase in the number of consecutive cycles of the oxidation - decomposition" increases the selectivity of the conversion of cyclohexane to cyclohexanone and cyclohexanol.

Table 1
The influence of the number of cycles of the oxidation-decomposition" on the selectivity of the conversion of cyclohexane to cyclohexanol and cyclohexanone
Example No.The number of cycles "oxidation-decomposition"Total conversion of cyclohexaneThe total selectivity of the conversion of cyclohexane
ketone and alcoholby-products
133.0946
263.1964
3103.2973

Examples 4-5

The oxidation of cyclohexane is carried out analogously to example 3, except that vary the total residence time of the reaction mixture in the oxidation reactors. The results are presented in table 2. It is seen that with increasing time stay the reaction mixture in the reactor oxidation selectivity of conversion of cyclohexane in the ketone and the alcohol drops.

Table 2
The influence of the total residence time in the reactor of the oxidation on the selectivity of the conversion of cyclohexane in the ketone and alcohol
Example No.The total residence time of the reaction mixture in the oxidation reactorsTotal conversion of cyclohexaneThe selectivity of the conversion of cyclohexane
ketone and alcoholby-products
4305937
550108317

Example 6

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst 2.0% Au/Al2O3.

Example 7

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst 0.8% Cu/SiO2(SiO2- SILIKAL the t with the MFI structure).

Example 8

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst 1.9% Ru/SiO2(SiO2- silicalite with the MFI structure).

Example 9

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst (1.7% Au+1.0% Cu)/SiO2(SiO2- silicalite with the MFI structure).

Example 10

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst 0.7% Fe2O3/SiO2(SiO2- silicalite with the MFI structure) and the contact time of the reaction mixture with the catalyst in each reactor decomposition was 10 minutes

Example 11,

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst (1.5% Au+0.7% Fe2O3)/SiO2(SiO2- silicalite with the MFI structure).

Example 12

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst 0.4% Pd/SiO2(SiO2- silicalite with the MFI structure).

Example 13

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst (2.5% u+0.4% Pd/SiO 2(SiO2- silicalite with the MFI structure).

Example 14

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst 0.6% Au/SiO2(SiO2- fiberglass in the form of fibers).

Example 15

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst 1.6% Au/(SiO2+TiO2) (SiO2+TiO2- titanium-silicate with the MFI structure).

Example 16

The oxidation of cyclohexane is carried out analogously to example 1, except that as the catalyst use of catalyst 1.1% Au/(SiO2) (SiO2- silicalite molded pellets with a diameter of ~1.5 mm, is used as a binding SiO2).

Comparative example 17

The oxidation of cyclohexane is carried out analogously to example 1, except that the sequential chain of transformations remove reactor decay of cyclohexylpiperazine. In this case, the conversion of cyclohexane 2.9 mol.% at the outlet of the last reactor of the oxidation receive the selectivity of the conversion of cyclohexane in the ketone and alcohol - 41 mol.%, in cyclohexylpropionic - 45 mol.%, in by-products - 14 mol.%. It is seen that in this case, in the reaction mixture significantly increases the share of cyclohexylpiperazine and poboc who's products.

Comparative example 18

The oxidation of cyclohexane is carried out analogously to example 6, except that the reaction mixture is released from the last oxidation reactor, placed in a separate container and maintained at a temperature of 170°C in an inert atmosphere until complete decomposition of cyclohexylpiperazine. As a result, when the conversion of cyclohexane 3.1 mol.% the selectivity of the conversion of cyclohexane in the ketone and the alcohol is 73 mol.%, the rest of side products. It is seen that thermal decomposition of cyclohexylpiperazine accompanied by a significant increase in the share of by-products.

Comparative example 19

The oxidation of cyclohexane is carried out analogously to example 6, except that the reaction mixture is released from the last oxidation reactor, is passed at a temperature of 170°C through three series-connected flow reactor with catalyst (1.5 wt.% Au/SiO2, SiO2- silicalite with the MFI structure), similar reactors decomposition in example 1 (the contact time of the reaction mixture with the catalyst in each reactor is 1 min). As a result, at the output during the conversion of cyclohexane 3.2 mol.% the selectivity of its transformation into a ketone and an alcohol is 87 mol.%, the rest of side products.

1. The method of obtaining a mixture of cyclohexanol and cyclohexanone at a heightened pace is the atur and high pressure, characterized in that the process includes a number of consecutive cycles: the oxidation of cyclohexane decomposition of cyclohexylpiperazine, in which the oxidation of cyclohexane and decomposition of cyclohexylpiperazine carried out in a separate series-connected with each other reactors without intermediate separation of the aqueous phase, and in each cycle, the oxidation of cyclohexane is carried out with air or oxygen-containing gas in the liquid phase in the absence of catalyst to the conversion of cyclohexane, not more than 1.5 mol.%, and decomposition formed during oxidation of cyclohexane cyclohexylpiperazine carried out on a heterogeneous catalyst in a separate reactor to a conversion of at least 90 mol.%.

2. The method according to claim 1, characterized in that the temperature and pressure of the oxidation of cyclohexane and decomposition of cyclohexylpiperazine close and are respectively 160-180°C and 7-9 ATM.

3. The method according to claim 1, characterized in that the number of consecutive cycles: the oxidation of cyclohexane decomposition of cyclohexylpiperazine must be at least 2-X.

4. The method according to claim 1, characterized in that the conversion of cyclohexane in each cycle at the stage of oxidation should be not more than 0.5 mol.%.

5. The method according to claim 1, characterized in that the conversion cyclohexylpiperazine each of the Ohm single cycle stage of decomposition must be at least 99 mol.%.

6. The method according to claim 1, characterized in that as the catalyst for the decomposition of cyclohexylpiperazine use a catalyst containing as an active ingredient one of the elements, or any combination of elements selected from the group of Co, Fe, Cu, Ni, Mn, Cr, Re, Os, Ru, Au, Pt, Pd supported on a carrier.

7. The method according to claim 6, characterized in that as the carrier heterogeneous catalyst decomposition using SiO2, Al2About3, Tio2, MgO, carbon, or any combination thereof.

8. The method according to claim 6, characterized in that as the catalyst for the decomposition used is preferably a catalyst containing as the active component of gold Au supported on a carrier.

9. The method according to claim 6, characterized in that the catalyst decomposition is used in the form of granules, and/or in the form of mono-and/or textile materials.



 

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14 cl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: H-form of ultrastable dealuminated Y-zeolites HUSY with SiO2/Al2O3 ratio within 5 to 120 is used as catalyst. As a rule, zeolites are combined with a binding agent represented by aluminum oxide, silicon oxide or their mix. Usually the catalyst is preliminarily activated by calcination in air at 300-600°C, while the method is implemented at 20-100°C. As a rule, cumol hydroperoxide concentration in the raw mix varies within 3 to 80%, and acetone, cumol, phenol or their mix with various component ratio are used as solvent.

EFFECT: increased process selectivity in relatively mild conditions.

7 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method includes two-stage acid-catalysed decompounding of cumene hydroperoxide in series reactors under heat resulted in simultaneous generation dicumene peroxide in the first stage followed with its decompounding in reaction medium environment in the second stage. Thus any catalytic agent is not used; it is prepared in separate reactor immediately prior to introduce to the first reactor of cumene hydroperoxide decompounding by mixing sulphuric acid with phenol in ratio 2:1 to 1:1000 and keeping produced mixture at temperature 20-80°C within 1-600 minutes.

EFFECT: method allows for considerable yield reduction of hydroxyacetone.

4 cl, 7 tbl, 6 ex

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

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

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

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic decomposition of organic hydroperoxides representing important compounds on organic synthesis. Decomposition of cycloalkyl hydroperoxides comprising from 6 to 12 carbon atoms results to formation a mixture of corresponding alcohols and ketones. Process is carried out in the presence of a solvent (alkane, halogen-containing hydrocarbon) at temperature from 20°C to 200°C. Catalyst comprises ruthenium as a catalytically active metal added to a solid carrier chosen from the following group: carbon prepared by pyrolysis of acetylene and metal oxides chosen from the group comprising zirconium, aluminum, lanthanum and manganese. The amount of catalyst expressed as the mole percents of ruthenium to the amount of moles of hydroperoxide to be decomposed is from 0.0001% to 20%. Preferably, the catalyst comprises one additional rare-earth element as a component of alloy. The carrier represents, as a rule, metal oxide with high specific surface above 10 m2/g but preferably, above 100 m2/g that is resistant against oxidation. The hydroperoxide concentration is in the range from 1 to 80 wt.-% with respect to the solution mass. Preferably, hydroperoxide represents cyclohexyl, cyclododecyl, tetraline, ethyl benzene or pinane hydroperoxide and hydrocarbon used in preparing the parent hydroperoxide is used as a solvent. Invention provides the development of the modified catalyst enhancing conversion and selectivity in decomposition of hydroperoxides.

EFFECT: improved method for decomposition.

8 cl, 24 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing phenol and acetone by acid-catalyzed cleavage of cumyl hydroperoxide. Method involves preliminary heating the reaction mixture to temperature above 100°C and then for thermal treatment of product heat in exothermic reaction is used, mainly the cleavage reaction of cumyl hydroperoxide that presents in the concentration from 5 to 10 wt.-%. The preferable residual content of dicumyl hydroxide in thermally treated product is 0.01-0.05 wt.-%. Stages in cleavage of cumyl hydroperoxide and the following thermal treatment can be carried out in a single reactor with two zones among that one zone is fitted with a device for heat removing and another zone has a feature of the flow-type pipe. Reactor is equipped by a device for circulation of part of product from thermal treatment zone to a feeding line for decomposition of product. Method provides improving energetic indices of process due to optimal consumption of heat energy in maintaining high selectivity of the decomposition process.

EFFECT: improved preparing method.

15 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: device for multistage cyclohexane oxidation is made in form of a cascade consisting of at least two reactors 1 and 2. Reactors 1 and 2 are fitted with connecting pipes 3 and 4 for inlet of cyclohexane and the reaction mixture. Air is let into the reactors through connecting pipes 7 and 8 which are fitted with multistage distributors - air bubblers 9 and 10. The reaction mixture comes out of the devices through bottom connecting pipes 11 and 12. Connecting pipe 11 is joined to pipe 13 for feeding the mixture into the second oxidation stage. An intermediate collector 14 is fitted into pipe 13 before the connecting pipe 4 of the reactor 2, where the intermediate collector has a flow control valve 15. The intermediate collector 14 is fitted with an overflow pipe 16.

EFFECT: more efficient synthesis of cyclohexanone and cyclohexanol.

7 cl, 4 dwg

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