The method of producing cyclododecanone or cyclohexanone

 

(57) Abstract:

The inventive product - cyclododecane or cyclohexanone. Reagent 1: the corresponding alcohol. Reaction conditions: dehydration is carried out in the presence of a copper alloy, aluminum, zinc, catalyst, videokniga to 8-50% aluminum. 2 C.p. f-crystals.

The invention relates to an improved process for the preparation of cyclododecanone and cyclohexanone by catalytic dehydrogenation of cyclododecanol and cyclohexanol and can be used in the production of cyclododecanone, cyclohexanone, dodecalactam and caprolactam.

Known methods for producing cyclododecanone and cyclohexanone were mixed copper-containing catalysts. So when getting cyclododecanone dehydration cyclododecanol copper-chromanol the catalyst at temperatures of 200-210oC conversion cyclododecanol is to 97.1-98.2 per cent in selectivity 95,7-98,1% /patent England N 1312086, class C 07 C, 49/27, 1973/ a upon receipt of cyclohexanone by dehydrogenation of cyclohexanol on copper-magnesium catalyst at temperatures 240-280oC conversion is 55,0-66,6% with a selectivity of 99.5% /auth.St. The USSR, N 232231, class C 07 C 49 /30,1977/ /1/.

The disadvantage of the methods is nischay essence is a way of obtaining cycloaliphatic alcohols fused aluminum catalyst is Raney copper. So, at a temperature of 290oC and time of contact less than 15 min on copper Raney received cyclododecanone with a conversion of 97% and a content of cyclododecene 0,02% /Japan patent N 75031145, class C 07 C 49/27, 1975/ /2/.

The disadvantage of this method is that the process is conducted in a reactor with stirrer on powdered catalyst, the reaction product requires stage filter, it is difficult to separate completely the ketone from the catalyst. Shown in patent low cyclododecene is achieved due to the short time of contact, in stationary conditions, this mode is set at high space velocities and leads to mechanical destruction of the catalyst.

Object of the invention is improved method of producing cyclododecanone and cyclohexanone by increasing the mechanical strength of the catalyst and the selectivity of the process.

This task is achieved by the fact that cyclododecane and cyclohexanone is produced by dehydrogenation cyclodecanone and cyclohexanol on aluminum alloy catalyst with partially leached aluminum. The criterion of videochannel alloy is the degree of leaching of aluminum, which is determined by the number of match is Yes) and particle size of 1-3 mm To achieve low levels of leaching (5-15% ) using 3% aqueous solution of caustic soda, adding it to the alloy cooled by flowing water (17oC). To achieve a deeper degree of leaching (30-50%) gradually raising the temperature to 30 to 60oC and for complete leaching (100%) use 25% aqueous solution of alkali, the temperature was raised to 60oC.

Example 1. The degree of leaching of aluminium 5%

Leached and have plenty of alcohol alloy without washing alkali load in the dehydrogenation reactor cyclododecanol, which is a stainless steel tube heated coolant, which continuously from the bottom up fed a liquid cyclododecanol. The catalyst is heated in a current of hydrogen, and then let the reaction product and begin the dehydration.

Digitalout cyclododecanol at a temperature of 260oC and a flow rate of 1 h-1. Get cyclododecanone with a conversion of 92% selectivity of 99.9% of the content of cyclododecene 0,03% After 300 h of operation, the conversion decreased to 90% of the Catalyst was unloaded without reducing the selectivity and mechanical destruction.

Leached alloy is loaded into the dehydrogenation reactor, cyclohex is served cyclohexanol, passed through the evaporator. The catalyst is heated in a current of hydrogen, and then let the reaction product and begin the dehydration.

Digitalout cyclohexanol at a temperature of 250oC and a flow rate of 1 h-1. Get cyclohexanone with a conversion of 42% selectivity 100% cyclohexen and phenol not detected. After 20 hours, the conversion dropped to 13% other parameters unchanged.

Examples 2-6 carried out analogously to example 1, varying the degree of leaching of aluminum. Example 6 (prototype) for dehydrogenation selected intact particles of alloy.

Thus, the proposed method of obtaining cyclododecanone and cyclohexanone partially leached copper alloy, aluminum, zinc allows you to:

to increase the mechanical strength of the catalyst, which is especially seen in the dehydrogenation cyclododecanol, where the process carried out in a gas-liquid environment, predstavljaet increasing demands on the mechanical strength of the catalyst: 500 h operation not lead to the destruction of the catalyst, while fully leached alloy destroyed by 45% after 150 hours of work;

to improve the selectivity of the dehydrogenation cyclododecanol compared to proto,5%

This dehydrogenation cyclododecanol optimal degree of leaching of aluminum is 8-15% and for dehydrogenation of cyclohexanol 30-50% reduction in leaching below these limits leads to a drop in conversion, the increase above the fall selectivity and mechanical strength while maintaining the achieved conversion.

1. The method of producing cyclododecanone or cyclohexanone by catalytic dehydrogenation of the corresponding alcohol in the presence of a copper-containing catalyst, wherein the catalyst used is an alloy of copper, aluminum, zinc, in which the aluminum leached 8 50%

2. The method according to p. 1, characterized in that the dehydrogenation cyclododecanol use alloy in which aluminum is leached 8 15%

3. Way but p. 1, characterized in that the dehydrogenation of cyclohexanol used alloy in which aluminum is leached by 30 to 50%

 

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