Process for the producing .epsilon.-caprolactam from the distillation of cyclohexanone oxime

A process for the production of .epsilon.-caprolactum from cyclohexanone oxime by rearrangement in the gaseous phase on a fluid-bed catalyst containing boron oxide, wherein residues from the distillation of cyclohexanone oxime are introduced into the reaction in liquid form, and wherein from 5 to 500 times their quantity of cyclohexanone oxime in vapor form and at least 50 times their quantity of inert gas are present during the reaction.

Cyclohexanone oxime cannot be distilled without the production of residues. 
Considerable quantities of distillation residues, consisting of 
dark-coloured, impure cyclohexanone oxime, are obtained. These residues 
cannot be further purified and are generally discarded. 
One known process for the production of .epsilon.-caprolactam from 
cyclohexanone oxime is based on rearrangement in the gaseous phase in the 
presence of catalysts containing boron oxide. Fluidised bed reactors are 
generally used in large scale production. Gaseous cyclohexanone oxime is 
introduced into the fluidised catalyst bed together with an inert gas, 
such as nitrogen, and optionally steam and the oxime is rearranged into 
.epsilon.-caprolactam at temperatures of 250.degree. to 400.degree.C. 
Impure oxime or the oxime distillation residue cannot be used in this 
process because it cannot be converted into the gaseous phase. 
The present invention provides a process for the production of 
.epsilon.-caprolactam from cyclohexanone oxime by rearrangement in the 
gaseous phase in the presence of a fluidised-bed catalyst containing boron 
oxide, wherein residues from the distillation of cyclohexanone oxime are 
introduced into the reaction in liquid form, and wherein from 5 to 500 
times their quantity of cyclohexanone oxime in gaseous form and at least 
50 times their quantity in inert gas are present during the reaction. 
Providing these conditions are maintained, the cyclohexanone oxime 
distillation residues can be co-rearranged into .epsilon.-caprolactam 
without any danger of caking occurring in the reactor and without any 
reduction in the quality of the resulting .epsilon.-caprolactam. 
The main difference between the cyclohexanone oxime residue and the pure 
cyclohexanone oxime is in colour. Whereas the residue is dark brown to 
black in colour, pure cyclohexanone oxime is colourless to pale yellow.

EXAMPLE 
120 g/h parts by weight of oxime residue, obtained from the distillation of 
1680 kg/h parts by weight of cyclohexanone oxime with 5% of water, were 
sprayed through a nozzle into the lower part of a fluidised bed reactor. 
The fluidised bed reactor contained 52,000 parts by weight of a catalyst 
containing boric acid which is kept in a state of fluidisation by 36,000 
parts by weight of nitrogen and 5751 parts by weight of vaporised oxime. 
The temperature in the reactor was maintained at around 330.degree. C. 
The ratio of vaporised oxime to residual oxime was 48 whilst the ratio of 
inert gas to residual oxime was 300. 
The reaction product leaving the reactor in the gaseous phase was 
condensed. The conversion, based on the cyclohexanone oxime used, amounted 
to 99.9% and the yield to 96%. The catalyst was partly run off at 
intervals and regenerated with air.