The method of producing cycloalkanones c8-c12

 

(57) Abstract:

The invention relates to the production of cycloalkanones C8-C12promising intermediates in the synthesis of lactams, aliphatic dicarboxylic acids, Daminov - monomers for the production of polyamide fibers, plastics and plasticizers new types and other valuable materials. Describes how to obtain cycloalkanones C8-C12the decomposition products of liquid-phase oxidation with molecular oxygen cycloalkanes C8-C12containing the appropriate cycloalkylcarbonyl, at an elevated temperature in the presence of a catalyst based on chromium oxide on the carrier is silica or alumina. The method differs in that the content of the relevant cycloalkylcarbonyl is 10 to 16 wt.% use a catalyst containing 3 to 10 wt.% chromium oxide (II) (chromium oxide). In addition, the promoter using 0.5 - 1 wt.% zinc oxide, the process is carried out for 1 to 2 h at 70 - 90C. effect: obtaining individual cycloalkanones C8-C12high yield.

The invention relates to the production of cycloalkanones C8-C12on the basis of cyclea is in, aliphatic dicarboxylic acids, diamines monomers for the production of polyamide fibers, plastics and plasticizers new types and other valuable materials.

There is information about how to obtain cycloalkanones and cycloalkanones the catalytic decomposition of cycloalkylcarbonyl formed during liquid-phase oxidation of cycloalkanes.

As catalysts for the decomposition of cycloalkylcarbonyl used as homogeneous and heterogeneous with respect to the reaction mixtures catalytic compositions containing the salts or oxides of d-metals with variable valence, such as Co, Mn, Cr, V, Mo, Fe, Cu, Pt. Depending on the composition of the catalytic system and process conditions in the products may contain alcohols and ketones with their personal value.

A method of obtaining mixtures of cyclohexanol and cyclohexanone [U.S. Pat. 4465861 USA, MCI C 07 C 45/53, NCI 568/342. A method of producing mixtures of cyclohexanol and cyclohexanone. Appl. 11.04.83, publ. 14.08.84. RICH, 1985, NP] PA-based decomposition of oxidation products of cyclohexane containing cyclohexylpropionic, at a temperature of 110-130oC in the presence of a catalytic composition containing (A) a the same type as in paragraph A. the Presence of component B provides finding the component in the solution until the end of the reaction. The specified method get a reaction mixture containing cyclohexanol and cyclohexanone in comparable quantities (ratio of alcohol:ketone is(0,8-1,2):1).

Recently in the process of decomposition of hydroperoxides are used heterogeneous catalysts of different composition in combination with different media and different kinds of promoters, which affect the selectivity of the process and composition of the decomposition products of cycloalkylcarbonyl.

In the application [application 0186822 EPO, MKI C 07 C 29/132. Catalyzed by cobalt borate method of decomposition of organic hydroperoxides. Publ. 07.09.86. Fig. countries of the world, 1987, vol. 60, h 1, N 6, S. 27] States that catalyzed by a heterogeneous catalyst consisting of borate cobalt deposited on the titanium dioxide, the process of decomposition of organic hydroperoxides proceeds with high conversion. The residual hydroperoxide is 0.09 to 0.2%. And the main decomposition product is appropriate to the structure of cumene alcohol.

The use of heterogeneous cobalt catalyst containing 10-25% Co in oxide the oxide at 80-120oC [application 3222144 Germany, MKI C 07 C 27/00, C 07 C 35/08, C 07 C 49/403. Method for producing cyclohexanol and cyclohexanone. Appl. 11.06.82, publ. 15.12.83. RICH, 1984, NP] leads to the formation of a mixture of cyclohexanol and cyclohexanone with exit 118% conversion of the hydroperoxide 68%.

In the patent [U.S. Pat. 174247 Netherlands, MKI C 07 C 27/00, B 01 j 23/86. The method of producing cycloalkanones and cycloalkanones decomposition of cycloalkylcarbonyl. Declared 21.10.72, publ. 16.05.84. RICH, 1985, NP] the claimed method of producing cycloalkanones and cycloalkanones decomposition of cycloalkylcarbonyl over heterogeneous catalysts composed of oxides of transition metals. This method is characterized by the fact that the reaction is carried out at a temperature below 160oC (60-100oC) over a catalyst containing copper oxide (II) CuO and chromium oxide (III) - Cr2O3. When using individual copper oxide as a catalyst in the decomposition of cycloalkylcarbonyl high proportion of alcohol - ratio cycloalkanes:cycloalkane (2,1-2,9):1. Supplements of chromium oxide (III) a catalyst containing copper oxide, reduce this ratio to (0,2-0,7): 1. In the case of the use of heterogeneous chromium-copper catalyst to achieve high conversion cycloalkyl, 35/08, 48/30, NCI C 2 C. Method of producing cycloalkanones and cycloalkanones. Publ. 13.12.78. Fig. abroad, 1979, vol. 55, No. 14, S. 57] indicated that cycloalkylcarbonyl decompose at a temperature of 100-150oC in the presence of heterogeneous catalysts based on chromium oxide. When the reaction is proposed reaction mixture is treated with water vapor. The implementation of such a process leads to a mixture of cycloalkanones and cycloalkanones with the yield of the target products 95%, conversion of the hydroperoxide 98-99%.

For further practical use, however, often require individual cycloalkanones and cycloalkanes. At the same time the separation of mixtures of alcohol and ketone individual components by rectification method requires additional material and energy costs.

In this connection, our attention was focused on the search for catalytic systems, providing education mainly cycloalkanones in the decomposition process of cycloalkylcarbonyl.

The closest to the essence of the present invention is indicated in the patent [U.S. Pat. 174343 Netherlands, MKI C 07 C 27/00, B 01 j 23/26. The method of producing cycloalkanones, cycloalkanes the tins and cycloalkanones decomposition of cycloalkylcarbonyl over heterogeneous chromium catalysts. In the catalyst composition comprises an oxide of chromium (III) - Cr2O3or oxide of chromium (VI) - CrO3on the media, which can be used coal, as well as oxides of silicon, aluminum, magnesium, tin, titanium (mass fraction of Cr is greater than 20% (22-36%)), or without media. The use of these heterogeneous catalysts beneficial to obtain mixtures containing predominantly ketone (ratio cycloalkanes: cycloalkane of 0.4: 1). The output of useful products 99-105%. Conversion of hydroperoxide depending on the composition of the catalytic system, the nature of the medium and the degree of loading of the carrier of the catalytically active metal is 33-98%.

The problem solved by the present invention is the obtaining individual cycloalkanones C8-C12with high output.

We propose a method of obtaining cycloalkanones C8-C12decomposition of the corresponding cycloalkylcarbonyl in the presence of a catalyst containing 3-10 wt. % of chromium oxide (II) (chromium oxide) and 0.5-1 wt.% zinc oxide on a carrier - silicon oxide or aluminum oxide. The process is carried out for 1-2 hours at a temperature of 70-90oC.

To use the decomposition products of liquid-phase oxidation recloak cloakingdevice C8-C12unlike cyclohexylpiperazine (C6) are the main product of liquid-phase oxidation of the corresponding cycloalkanes with an average size of the cycle before the conversion cycloalkane 15%. The selectivity of the formation of hydroperoxides in the oxidation process reaches 92-94% [Liquid-phase oxidation of cyclooctane for selective receipt of hydroperoxide / I.e. Timrot, T. N. Antonova, G. N. Koshel, E. M. Zabotkina etc. / Main organic synthesis and petrochemicals.- Yaroslavl, 1989.- Vol. 29.- S. 61-68; Kinetic regularities initiated by liquid-phase oxidation of cycloalkanes / ,N. Koshel, T. N. Antonov, I. I. Glazyrina, etc. / Petrochemicals. - 1981. -T. 21, N 4.-C. 597-601]. Therefore, the products of oxidation of cycloalkanes containing cycloalkylcarbonyl, can be used without pre-treatment processes, leading to the on the basis of cycloalkanones.

Differences of the proposed method from the prototype is the use of a new catalyst and specific process conditions.

The proposed method allows to synthesize individual cycloalkanones C8-C12with the release of 99-100% conversion of the original cycloalkylcarbonyl 97-99%.

Paliaga of cycloalkanones of the decomposition products of the rectification method.

The following are examples of the implementation of this method, showing the effectiveness of obtaining cycloalkanones C8-C12decomposition of cycloalkylcarbonyl with the same number of carbon atoms in the presence of a heterogeneous catalyst containing chromium oxide (II) (chromium oxide) on the media promoted zinc oxide.

Example 1.

Into a reaction vessel equipped with a thermometer, stirrer, reflux condenser, without pre-processing, load 250 ml of cyclooxygenase (GPCA) cyclooctane obtained by liquid-phase oxidation of cyclooctane and containing 15,7% (0,916 mol/l) GPCA. Added 9.0 g of a catalyst containing, %: 10,0 CrO, 89,0 SiO2, 1,0 ZnO. The reaction mixture is stirred for 60 min at 80oC. After cooling, the solution is separated from the catalyst and analyzed. Conversion of GPCA is 97.6%, the output of cyclooctanone on hydroperoxide decomposed 100%. The method of distillation from the reaction mixture allocate 28 g of cyclooctanone, so Kip. 90-91oC/22 mm RT. Art., so pl. 40,2 of 40.8oC.

Example 2.

Into a reaction vessel equipped with a thermometer, stirrer, reflux condenser, without pre-processing, load 830 ml and containing of 12.4% to 0.72 mol/l) GPCA. Added 42 g of a catalyst containing,%: 8,0 CrO, 91,5 SiO2, 0,5 ZnO. The reaction mass is stirred for 100 min at a temperature of 90oC. After cooling, the solution is separated from the catalyst and analyzed. Conversion of GPCO 99,3%, the output of cyclooctanone laid out on the hydroperoxide is 99.8%. The method of distillation from the reaction mixture allocate 74,6 g cyclooctanone, so Kip. 90-91oC/22 mm RT. Art., so pl. 40,2 of 40.8oC.

Example 3.

Into a reaction vessel equipped with a thermometer, stirrer, reflux condenser, load 260 g of the solution of cyclododecatriene (GPCD) cyclododecane obtained by liquid-phase oxidation of cyclododecane and containing 13,8% (0.69 mol/kg) GPCD. Add 20 g of a catalyst containing, %: 4,5 CrO, 95,0 Al2O3, 0,5 ZnO. The reaction mass is stirred for 120 minutes at a temperature of 90oC. the reaction mixture is dissolved in toluene, separated from the catalyst and analyzed. Conversion GPCD - 98.4% of the output of cyclododecanone laid out on the hydroperoxide of 99.3%. The method of distillation in a distillation column designed for pickup crystallizing substances, allot of 31.8 g of cyclododecanone, so Kip. 141 - 142oC/17 mm RT. Art., so pl. 58-59oC.

The method of producing cycloalkanones8-C12the decomposition products of liquid-phase oxidation with molecular oxygen cycloalkanes WITH8-C12containing the appropriate cycloalkylcarbonyl, at an elevated temperature in the presence of a catalyst based on chromium oxide on the carrier - silicon oxide or aluminum oxide, wherein the content of the relevant cycloalkylcarbonyl is 10 to 16 wt.% use a catalyst containing 3 to 10 wt. % of chromium oxide (II) (chromium oxide) and optionally as a promoter of 0.5 - 1 wt.% zinc oxide, the process is carried out for 1 to 2 h at 70 - 90oC.

 

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FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to production of olefin or diolefin hydrocarbons via dehydrogenation of corresponding paraffinic C3-C5-hydrocarbons carried out in presence of catalyst comprising chromium oxide and alkali metal deposited on composite material including alumina and aluminum wherein percentage of pores larger than 0.1 μm is 10.0-88.5% based on the total volume of open pores equal to 0.10-0.88 cm3/g. Preparation of catalyst involves treatment of carrier with chromium compound solution and solution of modifying metal, preferably sodium or sodium and cerium. Carrier is prepared by from product resulting from thermochemical activation of amorphous hydrargillite depicted by formula Al2O3·nH2O, where 0.25<n<2.0, added to homogenous mass in amount 1.0 to 99.0% using, as additional material, powdered aluminum metal, which is partly oxidized in hydrothermal treatment and calcination stages. Hydrocarbon dehydrogenation process in presence of the above-defined catalyst is also described.

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3 cl, 2 dwg, 4 tbl, 7 ex

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