Method of producing cycloalkanone oxime

Patent metadata

Field	Value
Publication number	US-9932296-B2
Application number	US-201314409299-A
Country	US
Kind code	B2
Filing date	Mar 29, 2013
Priority date	Jun 27, 2012
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

A method of producing a cycloalkanone oxime by a photochemical reaction of a cycloalkane with a photo nitrosating agent in a liquid by light irradiation includes irradiating the liquid with a light source configured to emit light satisfying conditions that, in an emission energy distribution with respect to wavelength of light, a wavelength providing a maximum value of emission energy is 550 nm to 700 nm and a continuous wavelength range including the wavelength providing the maximum value and outputting energy of or over 5% of the maximum value is equal to or less than 150 nm, wherein a ratio ηE/V of a light irradiation energy ηE out of electric power E input into the light source to a reaction volume V which is a volume of a space for the photochemical reaction of the cycloalkane with the photo nitrosating agent is equal to or greater than 5.5 w/L.

First claim

The invention claimed is:

1. A method of producing a cycloalkanone oxime by a photochemical reaction of a cycloalkane with a photo nitrosating agent in a liquid by light irradiation comprising:
irradiating the liquid with a light emitting diode configured to emit light satisfying conditions that, in an emission energy distribution with respect to wavelength of light, a wavelength providing a maximum value of emission energy is 600 nm to 650 nm and a continuous wavelength range including the wavelength providing the maximum value and outputting energy of or over 5% of the maximum value is equal to or less than 150 nm, wherein
a ratio ηE/V of a light irradiation energy ηE out of electric power E input into the light emitting diode to a reaction volume V which is a volume of a space for the photochemical reaction of the cycloalkane with the photo nitrosating agent is equal to or greater than 5.5 w/L and equal to or less than 15.0 w/L,
the selectivity calculated as a value of a molar amount of production of the cycloalkanone oxime as a numerator relative to a total molar amount of production of the cycloalkanone oxime and impurity generation as a denominator is equal to or greater than 85.1%, wherein
an energy conversion efficiency of the light emitting diode is equal to or higher than 10%, the energy conversion efficiency being an integrated value of emission energy (effective energy) in the wavelength range of 400 to 760 nm with respect to the input electric power per each light emitting diode.

2. The method according to claim 1 ,
wherein the cycloalkane is cyclohexane or cyclododecane, and
the cycloalkanone oxime is cyclohexanone oxime or cyclododecanone oxime.

3. A method of producing a lactam comprising reacting the cycloalkanone oxime produced by the method according to claim 1 .

4. A method of increasing selectivity of a cycloalkanone oxime by a photochemical reaction of a cycloalkane with a photo nitrosating agent in a liquid by light irradiation comprising:
irradiating the liquid with a light emitting diode configured to emit light satisfying conditions that, in an emission energy distribution with respect to wavelength of light, a wavelength providing a maximum value of emission energy is 600 nm to 650 nm and a continuous wavelength range including the wavelength providing the maximum value and outputting energy of or over 5% of the maximum value is equal to or less than 150 nm, wherein a ratio ηE/V of a light irradiation energy ηE out of electric power E input into the light emitting diode to a reaction volume V which is a volume of a space for the photochemical reaction of the cycloalkane with the photo nitrosating agent is equal to or greater than 5.5 w/L and equal to or less than 15.0 w/L, wherein
the selectivity is calculated as a value of a molar amount of production of the cycloalkanone oxime as a numerator relative to a total molar amount of production of the cycloalkanone oxime and impurity generation as a denominator, wherein
an energy conversion efficiency of the light emitting diode is equal to or higher than 10%, the energy conversion efficiency being an integrated value of emission energy (effective energy) in the wavelength range of 400 to 760 nm with respect to the input electric power per each light emitting diode.

Assignees

• Toray Industries

Inventors

• Takahashi Toru
• Nishikawa Yasuyoshi
• Morita Shoji

Classifications

• B01J2219/1203

  Incoherent waves · CPC title

• C07C249/06 Primary

  by nitrosation of hydrocarbons or substituted hydrocarbons · CPC title

• B01J19/122

  Incoherent waves (gamma-radiation B01J19/082) · CPC title

• C07C251/44

  with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring · CPC title