JP5359063B2 - Method for producing cycloalkanone oxime - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a cycloalkanone oxime by using a light-emitting diode as a next generation light source for substituting a discharge lamp sealing-in mercury, sodium, etc., as the light source, in a photo-nitrosation method. <P>SOLUTION: This method for producing the cycloalkanone oxime by performing a photochemical reaction of a cycloalkane with a photo-nitrosating agent by the irradiation of the light is characterized by using the light-emitting diode as the light source, and having a 400 to 760 nm wavelength range for generating the maximum light-emitting energy in a light-emitting energy distribution for the wavelength of the light source. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing cycloalkanone oxime using a light-emitting diode as a light source in the photonitrosation method.

  A photoreaction is also called a photochemical reaction. A chemical reaction in which a molecule, that is, a radical reactant, absorbs energy by light irradiation to make the molecule a high energy level, so-called excited state, and cause the reaction by the excited molecule. Refers to general. According to Non-Patent Document 1, photoreactions include types such as oxidation / reduction reactions by light, substitution / addition reactions by light, etc. Applications include photo industry, copy technology, photovoltaic induction, organic It is known to be used for the synthesis of compounds. In addition, as an unintentional photochemical reaction, photochemical smog and the like belong to the photochemical reaction.

  As described in Patent Document 1 and Non-Patent Document 2, it is known to synthesize cyclohexanone oxime by photochemical reaction as described in Patent Document 1 and Non-Patent Document 2, and the photonitrosation of cycloalkane is also described in Patent Document 2. As you can see, this is now widely known technology.

  All the light sources used for photoreactions used so far enclose mercury, thallium, sodium, and other metals in a vacuum or near-vacuum environment, apply voltage, and irradiate the encapsulated metal with the emitted electron beam. Thus, in most cases, a lamp using light emission by discharge in gas or vapor, for example, a discharge lamp or a fluorescent lamp is used as the light source.

  For example, in Patent Document 1, an effective wavelength is set to 365 nm to 600 nm using a high-pressure mercury lamp as a light source. However, a discharge lamp using this type of mercury also has specific emission energy due to mercury in a wavelength region including ultraviolet light of less than 365 nm. Therefore, as in Patent Document 3 and Patent Document 4, when the light emission energy is in a short wavelength region containing ultraviolet light of less than 350 nm, it is comparable to the dissociation energy of many chemical bonds. A side reaction is promoted, and a tar-like brown film is formed on the light-irradiated surface of the discharge lamp, thereby reducing the yield. Therefore, in order to cut off ultraviolet rays, use of a water-soluble fluorescent agent and ultraviolet cut glass have been proposed.

  In order to reduce the problem of the mercury lamp and increase the luminous efficiency, a thallium lamp showing an effective emission energy at a wavelength of 535 nm and a sodium lamp showing an effective emission energy at a wavelength of 589 nm have been proposed. In Patent Document 5, a sodium lamp is used as a light source to dramatically increase the yield and enable a stable reaction. Further, Patent Document 6 proposes an increase in efficiency in a wavelength region of 600 nm to 700 nm with an industrial effective wavelength of 400 to 700 nm using a high pressure sodium discharge lamp. The peak wavelength in this range can be estimated to be about 580 to 610 nm. However, in order to improve the electrical characteristics and starting of the discharge lamp, the coexistence of mercury is inevitable, and a filter that cuts off ultraviolet rays is necessary. Here, a short wavelength of less than 400 nm is considered to be an unnecessary wavelength because energy is too strong and an unnecessary side reaction is caused.

  Furthermore, the sodium lamp has a specific emission energy peak in a wavelength region including infrared rays having a wavelength of 780 to 840 nm, and the energy intensity thereof is often at a level comparable to the maximum emission energy of the sodium lamp. The dissociation energy of nitrosyl chloride is about 156 J / mol, which is comparable to the emission energy near the wavelength of 760 nm from Einstein's law. Therefore, the light energy is small in the longer wavelength region and the nitrosyl chloride is not dissociated. It doesn't contribute, resulting in a large energy loss. In Patent Document 7, although the theoretical basis is unknown, in the photonitrosation reaction, it is described that a mercury or sodium vapor lamp that emits a wavelength of 500 nm to 700 nm, preferably 565 to 620 nm is preferable. There is no mention of the wavelength of maximum emission energy or the wavelength causing light irradiation loss.

  In the light reaction by the discharge lamp, since a large amount of heat is emitted in the light irradiation direction of the discharge lamp, it is necessary to cool the light irradiation surface of the discharge lamp as in Patent Document 8. Furthermore, the cooling of the discharge lamp alone does not provide sufficient cooling, and the reaction temperature rises due to the remaining radiant heat and reaction heat from the photoreaction, so it is necessary to cool the reactor by providing a jacket outside the photoreaction vessel. In order to suppress the increase in the temperature, a huge cooling area is required, and the photoreaction tank is complicated.

Light-emitting diodes have the advantage of being able to directly convert electrical energy into light using a semiconductor, have been attracting attention in terms of energy saving, long life, etc., suppressing the generation of heat. The history of its development is still short, and red LEDs were commercialized in 1962, and blue, green, and white LEDs were developed around 2000 and commercialized for display and lighting applications. On the other hand, discharge lamps used for photoreactions have very high output and high luminous efficiency. Therefore, in order to obtain the necessary luminous energy, LEDs are not sufficient, and the required number of LEDs becomes enormous. However, it has been considered difficult to apply to a light source of photoreaction due to circuit design, LED heat countermeasures, and cost issues. Furthermore, it is necessary for the reaction to irradiate the reaction solution with uniform light, but the LED is highly directional and it is difficult to obtain the wavelength required for the reaction with high efficiency. Application of reactions to light sources has been considered difficult.
Tokyo Chemical Doujin Chemical Dictionary p457-458 Japan Petroleum Institute Vol.17 No.10 (1974) p72-p76 Japanese Examined Patent Publication No. 39-15976 Japanese Patent Laid-Open No. 10-25279 Japanese Examined Patent Publication No. 39-10336 Japanese Examined Patent Publication No. 39-22959 Japanese Patent Publication No. 44-13498 JP-A-11-265687 JP 2001-509472 A Japanese Examined Patent Publication No. 39-25041

  As described above, when a discharge lamp with mercury or sodium sealed as a light source is used, the effective wavelength of light irradiation in the production of cycloalkanone oxime in the photonitrosation method cuts short wavelengths including ultraviolet rays. From 360 nm to a wavelength of 760 nm, which is comparable to the theoretical dissociation energy of nitrosyl chloride. However, an unnecessary reaction may occur even at a short wavelength of less than 400 nm. Since it is light emission, it is practically considered that the wavelength region of 400 to 620 nm is the mainstream from the viewpoint that it is difficult to emit light having the maximum light emission energy in the wavelength region of 620 to 760 nm. In addition, a discharge lamp encapsulating mercury or sodium has a wide energy distribution with respect to wavelength, is not efficient because there is wasted energy that does not contribute to the reaction in the long wavelength region, and the energy is high in the short wavelength region. As a result of radicalization that does not occur, the generation of impurities and the adhesion of tar-like substances are significant, and there is a problem that measures such as a filter that cuts the short wavelength region are necessary to suppress the occurrence.

  That is, the present invention provides a method for producing cycloalkanone oxime using a light-emitting diode as a next-generation light source as a light source in the photonitrosation method, which is replaced by a discharge lamp lamp in which mercury, sodium or the like is enclosed. Is an issue.

  Therefore, as a result of diligent studies to solve these problems, electrical energy can be changed directly into light as a new light source instead of the conventional discharge, its wavelength band is narrow, and any wavelength and wavelength region Using a light-emitting diode capable of emitting light, photonitrosation was performed, and it was found that cycloalkanone oxime was obtained with high photon yield.

In order to achieve the above object, the present invention adopts the following configuration.
(1) In a method of photochemical reaction of cycloalkane and a photonitrosating agent by light irradiation, a light emitting diode is used as a light source, and the maximum value of the light emission energy is shown in the light emission energy distribution with respect to the wavelength of the light source. A method for producing a cycloalkanone oxime, wherein the wavelength is in the range of 430 nm to 650 nm, and the energy conversion efficiency of the light emitting diode is 10% or more and 75% or less.
(2) In the emission energy distribution with respect to the wavelength of the light source, the emission energy with respect to the wavelength in the shorter wavelength region than 400 nm is 5% or less of the maximum value of the emission energy, and in the longer wavelength region with the wavelength of 760 nm. The method for producing a cycloalkanone oxime according to (1), wherein the emission energy with respect to the wavelength is 5% or less of the maximum value of the emission energy.
(3) Using a plurality of light emitting diodes arranged in a plane along the side surface of the photochemical reactor containing the photoreaction liquid, the photoreaction liquid is irradiated with light through the transmissive photochemical reactor. The method for producing cycloalkanone oxime according to any one of (1) to (2).
(4) The method for producing a cycloalkanone oxime according to any one of (1) to (3), wherein the photoreaction liquid is cooled by immersing a cooler in the photoreaction liquid.
(5) The method for producing a cycloalkanone oxime according to any one of (1) to (4), wherein the cycloalkane is cyclohexane.
(6) The method for producing cycloalkaneoxime according to any one of (1) to (5), wherein the photonitrosating agent is nitrosyl chloride.
(7) The method for producing a cycloalkanone oxime according to any one of (1) to (6), wherein the cycloalkanone oxime is cyclohexanone oxime.

  Note that a light-emitting diode is a semiconductor that emits light when a voltage is applied in the forward direction, and is also referred to as an LED (Light Emitting Diode), and uses an electroluminescence (EL) effect as a light emission principle. .

  As in the present invention, in a photonitrosation reaction in which the radicalization energy (dissociation energy) of a photonitrosating agent is small, by using a light emitting diode that is a light source with a very narrow emission energy distribution, energy in the emission energy distribution with respect to wavelength Loss can be suppressed and cycloalkanone oxime can be produced by photo-nitrosation reaction for any wavelength that was not possible with conventional discharge lamps. No wavelength absorber such as a filter is required. In particular, cycloalkanone oxime can be obtained with a high yield with respect to the photon number in the effective wavelength region of 400 to 760 nm, that is, a high photon yield. In addition, since the heat generation of the light irradiation surface of the light source is very small, it is possible to eliminate the cooling of the light irradiation surface of the light source and further reduce the cooling of the photoreaction liquid. The reaction apparatus can be simplified. Also, from the mechanical strength aspect, glass is used as a light-tight airtight container for discharge lamps, so its strength is low, and it may be damaged due to temperature differences when turning on and off, but since light emitting diodes are compound semiconductors, mechanical strength Since it is strong and covered with a lens such as resin, there is little damage. Even if it is damaged, there is a great advantage that it can be repaired only by changing the damaged light emitting diode or the module in the light emitting diode or the module used in large numbers. In the case of a discharge lamp, it is necessary to replace one, and the cost of the repair can be greatly reduced in that no major repair is required.

  The emission color of light-emitting diodes varies depending on the material used, and unlike lamps such as discharge lamps, it can emit light at any wavelength, from the ultraviolet region to the visible light region and the infrared region. In manufacturing, almost all of the emission energy can be contained only in the wavelength region effective for the photoreaction, and the loss of emission energy can be greatly reduced.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  The light source used in the present invention is a light emitting diode, which is a semiconductor that emits light when a voltage is applied in the forward direction. A light emitting diode is also called LED (Light Emitting Diode), and the light emission principle utilizes the electroluminescence (EL) effect.

  A preferred form of the emission energy distribution with respect to the wavelength of the light emitting diode used in the present invention will be described with reference to FIG. As shown in FIG. 1, the emission energy distribution is a spectrum distribution in which the horizontal axis indicates the wavelength and the vertical axis indicates the emission energy. FIG. 1 is a graph showing a light emission energy distribution of an example of a light emitting diode having a maximum light emission energy in the vicinity of a wavelength of 625 nm.

  As shown in FIG. 1, the maximum value of the light emission energy of the present invention is the maximum value of energy indicated by Emax in the light emission energy distribution with respect to the wavelength.

  In the present invention, in the light emitted from the light emitting diode, the light having a wavelength in the range of 400 nm to 760 nm in the emission energy distribution with respect to the wavelength is used. In order to obtain a high yield of cycloalkanone oxime, 430 nm to 650 nm is preferable. Moreover, 500-650 nm is good from a viewpoint of suppressing further the production | generation of the tar-like substance in a light irradiation surface. Further, when there are two or more peak wavelengths such as a white LED, for example, even if the maximum peak is 400 nm or more and less than 500 nm, the wavelength band can be extended to a long wavelength if the other peak wavelength is 500 nm or more. Therefore, in some cases, the generation of tar-like substances can be suppressed. Furthermore, it is desirable that a photon number higher than the main peak spectrum of a discharge lamp such as a mercury lamp or a sodium lamp is obtained because a high photon number can be obtained with respect to input power at a wavelength of 620 nm to 650 nm. For example, when a wavelength filter such as an ultraviolet cut is used, the maximum value of the emission energy in the distribution may be obtained as the emission energy distribution excluding the cut wavelength band. Energy will be lost.

  In the emission energy distribution with respect to the wavelength of the present invention, in order to suppress loss of emission energy and side reactions, it is preferable to suppress emission at wavelengths shorter than 400 nm and longer than 760 nm as much as possible. That is, in the emission energy distribution with respect to the wavelength of the light source, the emission energy with respect to the wavelength in the shorter wavelength region than the wavelength of 400 nm is preferably 5% or less of the maximum value. Further, it is desirable that the emission energy with respect to the wavelength in the wavelength region longer than the wavelength of 760 nm is 5% or less of the maximum value.

  For example, as shown in FIG. 1, in the energy distribution of the light emitting diode, 5% of the maximum value of the emission energy in a wavelength region shorter than the wavelength of 400 nm and a wavelength region longer than the wavelength of 760 nm, that is, 0.05 Emax or less in FIG. Most of the luminescence energy can be used effectively for the photonitrosation reaction.

  However, for example, FIG. 2 is a graph showing the emission energy distribution of an example of a mercury lamp whose wavelength indicating the maximum value of emission energy is in the range of 400 to 760 nm. According to this, the emission energy distribution is very wide, Furthermore, it has a plurality of peak spectra. Emission that has a wavelength that shows 5% of the maximum value of emission energy with respect to the wavelength in a wavelength region shorter than wavelength 400 nm, that is, emission energy higher than 0.05 Emax in FIG. 2, and cannot use the emitted light for the photonitrosation reaction High efficiency is difficult due to the existence of energy. FIG. 3 is a graph showing a light emission energy distribution of an example of a sodium lamp having a maximum light emission energy wavelength in the range of 400 to 760 nm. According to this graph, the light emission energy distribution is very wide and the wavelength is from 760 nm. In the long wavelength region, there is a wavelength exhibiting a light emission energy higher than 5% of the maximum value of the light emission energy with respect to the wavelength, and there is a light emission energy in which the emitted light cannot be used for the photonitrosation reaction. In the case of a sodium lamp, the maximum value of light emission energy may exist in a longer wavelength region than the wavelength of 760 nm, and the light emission energy in the long wavelength region is very large. Therefore, at a long wavelength, heat generated by infrared rays is large and it is difficult to keep the reaction temperature constant.

  Since the light emitting diode can emit light emission energy at a wavelength suitable for the target yield and efficiency, it may be optimized by using light emitting diodes of different types and lots.

  In the present invention, the light emission energy distribution can be measured by the method described later. However, the light emission energy distribution in the case of using a plurality of light emitting diodes is the light emitting diode used after measuring the light emission energy distribution of each light emitting diode. It is only necessary that the emission energy distribution aggregated in all quantities is obtained and the wavelength showing the maximum emission energy is 400 nm to 760 nm. When it is clear that a plurality of light emitting diodes to be used are a single lot and the quality is uniform, it is possible to measure and judge any light emitting diode as a simple method. In addition, when using multiple types of light emitting diodes, as a simple method, measure arbitrary light emitting diodes for each of the same quality types, taking into account the quantity of each type, and the light emission energy aggregated in the total number of light emitting diodes used. It is also possible to calculate the distribution.

  Furthermore, in the present invention, in the emission energy distribution with respect to the wavelength of the light source, the emission energy with respect to the wavelength in a wavelength region shorter than the wavelength of 400 nm is 5% or less of the maximum value of the emission energy and more than the wavelength of 760 nm. The emission energy with respect to the wavelength in the long wavelength region is preferably 5% or less of the maximum value of the emission energy. In the case of using a plurality of light emitting diodes, the light emission energy distribution is calculated by using the light emission energy distributions of the respective light emitting diodes, and the light emission energy corresponding to the wavelength in the shorter wavelength region than the wavelength of 400 nm is the light emission energy. It is 5% or less of the maximum value, and the emission energy with respect to the wavelength in the wavelength region longer than the wavelength of 760 nm may be 5% or less of the maximum value of the emission energy. When it is clear that a plurality of light emitting diodes to be used are a single lot and the quality is uniform, it is possible to measure and judge any light emitting diode as a simple method. In addition, when using multiple types of light emitting diodes, as a simple method, measure arbitrary light emitting diodes for each of the same quality types, taking into account the quantity of each type, and the light emission energy aggregated in the total number of light emitting diodes used. It is also possible to calculate the distribution.

  In the present invention, in each kind and / or lot, in the emission energy distribution with respect to the wavelength, the emission energy with respect to the wavelength in a wavelength region shorter than the wavelength of 400 nm is 5% or less of the maximum value of the emission energy, and the wavelength More preferably, the emission energy with respect to the wavelength in the wavelength region longer than 760 nm is 5% or less of the maximum value of the emission energy. Furthermore, in order to carry out the photonitrosation reaction at an effective wavelength, the total emission energy (effective energy) in the wavelength region of 400 to 760 nm is 90% or more with respect to the total emission energy distribution (total emission energy). Preferably, it is 95% or more, more preferably 98% or more. The calculation of the ratio of the effective energy to the total light emission energy is based on the light emission energy distribution of each light emitting diode to be used, and the light emission energy distribution aggregated to the total quantity of light emitting diodes is obtained. This is done by determining the ratio to energy. When using multiple light-emitting diodes of the same type and the same lot that are clearly of uniform quality, use a light-emitting diode with an arbitrary light-emitting energy distribution as a simple method. It is also possible. In addition, when using multiple types of light emitting diodes, such as different types and / or lots, as a simple method, measure any light emitting diode for each type of equal quality, and consider the quantity of each type. It is also possible to calculate and obtain the emission energy distribution aggregated to the total number of light emitting diodes.

  Further, in the present invention, when a plurality of light emitting diodes are used, in the light emission energy distribution with respect to the wavelength in each type and / or lot, the total of the light emission energy in the wavelength region of 400 to 760 nm is obtained. It is desirable that it is 90% or more, preferably 95% or more, and more preferably 98% or more.

  Here, the wavelength region in the emission energy distribution is a region of ultraviolet rays, visible rays, and near infrared rays, and in the present invention, it is an energy spectrum in a region of 300 to 830 nm that can be detected by at least a general emission spectrum measuring instrument. Shall be confirmed.

  Since the irradiation characteristics of the light-emitting diode are affected by the drive current value and temperature, the measurement of the light emission energy distribution is performed under the same drive current and temperature conditions as when light is irradiated by a photochemical reaction. That is, the drive current applied to the light emitting diode to be measured is set to the same drive current value as the average drive current value per light emitting diode applied when light is irradiated by the photochemical reaction, and light is emitted. The temperature of the light emitting diode to be measured is the surface temperature on the back side of the light emitting diode (if the back surface of the light emitting diode is provided with a heat sink, heat sink, heat sink, etc., the surface temperature, the light emitting diode is mounted on the substrate, etc. If it is, the surface temperature of the substrate may be sufficient), but the measurement is performed under the same temperature condition as the average temperature when the light emitting diode is irradiated by the photochemical reaction. Examples of the heat dissipation plate, heat dissipation substrate, heat sink, and the like provided on the back surface of the light emitting diode include those made of aluminum or copper having good thermal conductivity. In the measurement, the light emitting diode to emit light may be radiated by providing a heat sink, a heat radiating board, a heat sink or the like so that the temperature is the same as the reaction condition, or may be cooled in some cases. Since the temperature of the light emitting diode rises due to heat generation during driving, the temperature rise is within 1 ° C., and the measurement time is measured in the range of 10 to 300 ms. The average temperature of the surface temperatures of the heat radiating plate, heat radiating substrate, heat sink, etc. of the light emitting diode is used as the temperature when light is irradiated by the photochemical reaction. The light emission energy distribution is a distribution at a total output for each wavelength of 5 nm or less. Further, the emission energy distribution when it is necessary to measure with high accuracy is preferably a total output for each wavelength of 0.5 to 1 nm. It is preferable to use the center value of the wavelength band of the aggregate output as the wavelength. When the measurement is performed before the photochemical reaction, the measurement is performed using the temperature and driving current value at which the photochemical reaction is to be performed.

  The light-emitting diode used in the present invention preferably has an energy conversion efficiency, that is, a light emission energy integrated value (effective energy) in a wavelength region of 400 to 760 nm with respect to input power per light-emitting diode is 3% or more. Furthermore, 10% or more is preferable for improving the yield. The upper limit is not particularly limited, but the ratio of the photon number extracted to the outside with respect to the number of input electrons, that is, the theoretically 100% performance in the external quantum efficiency, the energy conversion efficiency is 75% as the upper limit. Even if the effect is obtained and the energy conversion efficiency is 60% or less, the calorific value can be suppressed as compared with the discharge lamp, and a sufficient effect can be obtained.

  The energy conversion efficiency is measured by the following method. The measurement is performed under the driving current and temperature conditions in which the emission energy distribution with respect to the wavelength is measured, and the integrated value of the emission energy at each wavelength of 400 to 760 nm is used. For the emission energy of each wavelength, an integrated value (effective energy) of wavelengths 400 to 760 nm is used in the entire emission energy distribution measured by the above method.

  In the present invention, a device for measuring the emission energy is preferably one that can measure the absolute value of the emission energy of each wavelength, and an integrating sphere is used. An integrating sphere having an inner diameter of 3 inches (7.6 cm) or more is used, but when measurement is difficult, a 10 inch (25.4 cm) or more is used. The measurement width of each wavelength is preferably 5 nm or less, and more preferably 0.5 to 1 nm. In the present invention, as described above, measurement is performed based on the light emission energy distribution in the integrating sphere. If this is not appropriate for some reason, light emission energy per unit area irradiated with light, that is, irradiance is used. When irradiance is used, the absolute value of the emission energy of each wavelength is calculated using the total irradiation area at the measurement distance from the light source. For example, in the case of a point light source such as a discharge lamp, it may be calculated as the spherical area at the measurement distance. However, in the case of a light emitting diode, the irradiation direction is the forward direction, so the measured value depends on the measurement position and angle even if the measurement distance is the same. Therefore, with respect to the center of the light source, the irradiance is measured at an angle of 10 ° or less at a fixed measurement distance, and converted into a hemisphere area at the measurement distance using the irradiance at each point. The absolute value of the emission energy at the wavelength is calculated.

The measurement distance from the center of the light source is a distance that can be regarded as a point light source, that is, a distance at which the irradiance does not change at an arbitrary angle at a constant distance, and is preferably at least 5 times the light emission length, and more preferably 10 times the light emission length. As a matter of course, the measurement of the light emission energy is performed by measuring a blank without light emission or a reflection entering from another light source.
Energy conversion efficiency (%) = Effective energy (W) / Input power during measurement (W) x 100

Calculation of the energy conversion efficiency in the case of using a plurality of light emitting diodes is obtained as follows from the input power and the effective energy for each light emitting diode to be used.
Energy conversion efficiency (%) = total number of active energy (W) / total number of input power during measurement (W) x 100

  Here, in the case where it is clear that the quality is uniform, such as a single lot, it is possible to use a measured value of any one as a simple method, but different lots and / or different types of light emitting diodes. , Measurement is performed for each lot and / or each type, and the light emitting diodes for each lot and / or each type have the same light emission energy distribution, taking into account the quantity of each type of light emitting diode. The energy conversion efficiency concentrated on the light emitting diode is obtained. Specifically, using the light emission energy distribution of the light emitting diodes for each lot and / or type, the light emission energy distribution aggregated to the total quantity of light emitting diodes used is obtained, and the input energy of the effective energy and the total quantity of light emitting diodes is obtained. Ask more. If the lot or type is unknown, the wavelength (nm), luminous flux (lm), luminous energy (W), photon number (Photon / s), voltage (maximum value of luminous energy at a predetermined or rated driving current Based on the measurement results of at least three items of V), the energy conversion efficiency is obtained by classification according to type. When the quality of the light emitting diodes included in the same classification is uniform, it is possible to measure the integrated value of any one light emitting energy distribution, and to aggregate them considering the quantity.

  An example of a photochemical reaction using the light-emitting diode of the present invention will be described with reference to FIG.

  The light emitting diode 1 which is the light source of the present invention may be any of a general bullet type, surface mount type, chip type, etc., but the temperature of the photoreaction liquid in the photochemical reactor 2 in the light irradiation direction of the light emitting diode 1 In order to suppress the rise, it is desirable to be able to radiate heat from the back surface of the light emitting diode 1.

  The method of light irradiation from the light source may be any as long as it can effectively irradiate a photoreaction liquid composed of a cycloalkane and a photonitrating agent or a reaction product thereof. For example, as shown in FIG. 7, a light source is directly or indirectly immersed in an external irradiation type in which light is applied to the photoreaction liquid from the outside of the photochemical reaction apparatus 2 or inside the photochemical reaction apparatus 2, that is, the photoreaction liquid. There is an internal irradiation type for irradiation. Conventional lamps such as discharge lamps and fluorescent lamps have many spherical or rod-shaped light sources, and internal irradiation has been the mainstream for effective use of light.

  The light-emitting diode 1 is a very small light source, and can be freely arranged using a plurality of light-emitting diodes 1. For example, a module in which a plurality of light-emitting diodes are arranged in units can be combined. There is an advantage that various light irradiation modes can be taken, and it is possible to irradiate a plane, a curved surface, and the like, and it is possible to uniformly emit a light emitting diode having strong directivity. For example, as shown in FIG. 7, a plurality of light emitting diodes 1 are used and arranged in a planar shape along the side surface of the photochemical reactor 2 containing the photoreaction liquid, and light is transmitted through the light-transmitting photochemical reactor 2. By irradiating the reaction solution with light, it is desirable because the photoreaction solution can be irradiated with light uniformly. The material of the side surface of the transmissive photochemical reactor 2 may be any material that has good transmittance of the light emitted from the light emitting diode to be used, and examples thereof include glass, quartz, and transparent resin such as acrylic.

  Further, by arranging the light emitting diodes on the outside of the cylindrical or polygonal rod, an internal irradiation form similar to a discharge lamp can be taken. The cylindrical or polygonal bar is preferably made of a metal material such as aluminum or copper that can dissipate heat. In this case, there is an advantage that the conventional photochemical reaction apparatus does not need to be greatly modified by simply replacing the discharge lamp with the internal irradiation type light emitting diode module without changing the arrangement of the light source and the radiation pattern of the reaction vessel. is there.

  The light emission of the light emitting diode 1 is not particularly limited in temperature, but is affected by the ambient temperature such as the outside air temperature, the temperature of the junction of the light emitting diode, the substrate, the heat sink, or the like. In general, the higher the temperature, the lower the emission energy per unit power. Therefore, it is desirable to suppress the temperature rise, and the lower the temperature, the better if the photonitrosation reaction is possible. The method of suppressing the temperature rise by light emission of the light emitting diode 1 may be allowed to cool as long as the outside air temperature is constant and heat generation of the light emitting diode can be sufficiently suppressed and the temperature rise when the light emitting diode emits light can be suppressed. For example, it is desirable to provide a heat sink 3 made of metal such as aluminum or copper on the back surface of the light-emitting diode 1 and to provide heat radiation and cooling by providing fins or the like in order to improve the contact area with the outside air. In order to facilitate heat dissipation and heat removal of the light emitting diode 1, a metal heat dissipation substrate such as aluminum or copper may be provided on the back surface of the light emitting diode 1. Furthermore, if there is a lot of heat generation and light emission decreases, the light emitting diode can be forcedly cooled. For example, the temperature of the heat sink 3 is 30 ° C. or lower, preferably 20 ° C. or lower. Furthermore, any temperature may be used as long as the photoreaction solution does not freeze, but 0 ° C. or higher is preferable in view of practicality.

  The cycloalkane of the present invention is not particularly limited to the number of carbon atoms, but for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane are preferable. In particular, cyclohexane as a raw material for caprolactam and cyclododecane as a raw material for lauryl lactam are preferable. For example, cycloalkane can be introduced into the photochemical reactor 2 from the cycloalkane introduction line 4. As the photonitrosating agent, for example, nitrosyl chloride or a mixed gas of nitrosyl chloride and hydrogen chloride is preferable. In addition, all of the mixed gas of nitric oxide and chlorine, mixed gas of nitric oxide, chlorine and hydrogen chloride, mixed gas of nitrose gas and chlorine, etc. act as nitrosyl chloride in the photoreaction system. It is not limited to the supply form of the nitrosating agent. Trichloronitrosomethane obtained by photoreaction of nitrosyl chloride and chloroform may be used as a nitrosating agent. For example, the photonitrosating agent can be introduced from the photonitrosating agent introduction line 5. As a result of a photochemical reaction by light irradiation of a light emitting diode using the above cycloalkane and a photonitrosating agent, a cycloalkanone oxime corresponding to the number of carbons of the cycloalkane can be obtained. When the photochemical reaction is carried out in the presence of hydrogen chloride, cycloalkanone oxime becomes its hydrochloride, but it may be in the form of hydrochloride as it is. For example, cyclohexanone oxime can be obtained by photonitrosation reaction with nitrosyl chloride using cyclohexane. The cycloalkanone oxime obtained by the reaction settles in the tank of the photochemical reactor 2 and accumulates as an oily substance. This oil is withdrawn from the reaction product line 10. Unreacted and generated exhaust gas was discharged from the unreacted gas line 9.

  The reaction temperature in the photochemical reaction, that is, the temperature of the photoreaction solution is 30 ° C. or less, preferably 20 ° C. or less. For example, when the light emitting diode 1 is used, the heat generation in the light irradiation direction is reduced, but the reaction temperature rises due to the reaction heat due to the photoreaction, so it is desirable to remove the reaction heat. For example, the cooler 6 is provided in the photoreaction liquid, the cooler 6 is immersed, the cooling water is introduced from the reaction cooling water introduction line 7, and is discharged indirectly from the reaction cooling water discharge line 8. This is desirable. The lower limit is preferably the freezing point or higher from the point of the freezing point of the raw material cycloalkane, and preferably 6.5 ° C or higher if the cycloalkane is cyclohexane.

  In the photochemical reaction by the discharge lamp, a large amount of light irradiation heat is generated in the light irradiation direction, so that cooling on the irradiation surface of the discharge lamp and cooling on the outside of the photochemical reactor 2 are necessary as shown in FIG. However, when the light emitting diode 1 is used, the reaction temperature can be kept constant only by removing the reaction heat, so the cooler 6 can be cooled with a small heat transfer area, and the cooler can be downsized. Therefore, the predetermined reaction temperature can be maintained only by immersing the cooler 6 in the photoreaction liquid and cooling it.

  For example, heat can be removed simply by cooling with a cylindrical cooler 6 as shown in FIG. Further, the photochemical reactor 2 may be cooled by providing a tubular coil, a draft tube, or the like. Although the temperature of cooling water should just maintain a predetermined reaction temperature, Preferably it is 0-30 degreeC, More preferably, it is 5-20 degreeC. The cooling water may be any water as long as it can be cooled, and examples thereof include industrial water, inorganic brine, and organic brine.

  Furthermore, since the cooler 6 can be miniaturized, it is possible to install the cooler 6 at a position where the cooler 6 absorbs light or reflects light to reduce interference with light irradiation. When the light source is irradiated from multiple directions such as both sides and circumference, the cooler 6 is disposed at a position where the distance from the irradiation surface of the light source is farthest, for example, as shown in FIG. The cooler 6 can be arranged to reduce the light irradiation loss.

  The present invention will be specifically described below with reference to examples.

Example 1
Photoreaction Test The photochemical reaction apparatus shown in FIG. 7 was used for the photoreaction test. The photochemical reactor 2 was made of cylindrical glass having an outer diameter of 14 cm. The light-emitting diode 1 as a light source has a maximum energy peak at a wavelength of 454 nm (Royal Blues LXHL-LR3C manufactured by Lumileds, lot number P5KY (here, Bin code of Lumileds is shown)). The same lot was used for all of the light emitting diodes 1. The light emitting diodes 1 are arranged evenly along the outer side surface of the photochemical reactor 2 with the light irradiation surface facing the photochemical reactor 2 side, and light is emitted from the outside of the photochemical reactor 2 through the outer wall glass of the photochemical reactor 2. An external irradiation method for irradiating the reaction solution was used. The arrangement of the light emitting diodes 1 is 24 rows circumferentially and 9 rows vertically in the position below the surface of the photoreaction liquid, and the reaction product accumulates as an oily substance at the bottom of the photochemical reactor 2. The oily substances at the bottom were arranged so that they could not be directly irradiated with light and evenly irradiated to the photoreaction solution. 216 light emitting diodes 1 were used, 36 were connected in series, and the two series were connected in parallel to emit light using three sets of DC power supply devices. The voltage and current of the three sets of DC power supply devices were adjusted so that the drive current values from the respective power supplies were equal. The average drive current value per light emitting diode is 0.5 A / piece, and the total input power to all the light emitting diodes is 376 W.

  Cooling of the reaction heat in the photoreaction is carried out by immersing a cylindrical glass tube having an outer diameter of 5 cm in the center of the photochemical reactor 2 as a cooler 6 in the photoreaction liquid, and in the cooler 6, a reaction cooling water introduction line 7. The cooling water of 6-13 ° C. is continuously supplied, discharged from the reaction cooling water discharge line 8 and indirectly forcibly cooled, and the temperature of the photoreaction liquid, that is, the reaction temperature is 20 ° C. ± 2 ° C. Kept. The average reaction temperature was 20 ° C.

The temperature of the photoreaction liquid is intermediate in the horizontal distance between the outer wall of the photochemical reactor 2 and the outer wall of the cooler 6 and in the vertical distance between the liquid surface of the reaction liquid and the discharge part of the photonitrosating agent introduction line 5. The temperature of the reaction solution was measured at the position of the part. The cooling area of the photoreaction liquid is 381 cm ² as the area where the cooler 6 contacts the photoreaction liquid. When a discharge lamp is used, it is necessary to cool the light irradiation surface because of the heat generation of the discharge lamp, but in the light emitting diode 1, since the heat generation on the light irradiation surface is very low, cooling on the light irradiation surface is not necessary. .

  The light emitting diode 1 is radiated by using an aluminum heat sink on the back surface of the light emitting diode 1 for heat radiation and heat removal. However, when the heat removal is insufficient, the room temperature is lowered, or cold air or cooling water is supplied by an air cooler. Used to remove heat so that the heat sink temperature was 25 ± 5 ° C. The average temperature of the heat sink surface is 25 ° C. The temperature of the surface of the heat sink was measured by measuring the temperature of the light emitting diode side surface of the heat sink provided on the back side of the light emitting diode. The surface temperature was an intermediate part based on the vertical length of the heat sink, and two points were measured continuously with a temperature sensor across the light emitting diodes in the gaps between the arranged light emitting diodes.

  The photochemical reactor 2 was charged with 3 L of cyclohexane (special grade reagent, manufactured by Katayama Chemical Co., Ltd.) from the cycloalkane introduction line 4, the reaction temperature was maintained at 20 ± 2 ° C., and hydrogen chloride (manufactured by Tsurumi Soda Co., Ltd.) gas was supplied at 2000 ml / min. It was supplied from the photonitrosating agent introduction line 5 at a flow rate and continuously blown from the lower part of the photochemical reactor 2. The light emitting diode 1 was turned on after 10 minutes. 10 minutes after the start of lighting, nitrosyl chloride gas (obtained by reacting nitrosylsulfuric acid with hydrogen chloride and then purified by distillation) was mixed with hydrogen chloride gas 2000 ml / min at a flow rate of 200 ml / min to produce a photonitrosating agent. From the introduction line 5, it was continuously blown from the lower part of the photochemical reactor.

  The exhaust gas was discharged from the unreacted gas line 9 and absorbed with water by a scrubber, and the absorbing solution was neutralized with soda ash.

  The photoreaction product cyclohexanone oxime becomes an oily substance, and the oily substance is accumulated at the bottom of the photochemical reactor 2 due to the difference in specific gravity with the unreacted cyclohexane. The oily substance was extracted from the reaction product line 10 every 30 minutes with the start of lighting as the reaction start. The light reaction test was evaluated from an oily substance at 30 to 60 minutes after the start of lighting. Each time the oil was extracted, cyclohexane corresponding to the extracted volume was replenished to keep the level of the photoreaction liquid constant.

  The cyclohexanone oxime was dissolved in an ethanol solution, neutralized with powdered sodium bicarbonate, measured by GC analysis (Shimadzu Corporation, GC-14B), and the concentration of cyclohexanone oxime (wt%) from the calibration curve. ) And the amount (g) of cyclohexanone oxime produced by the reaction was determined from the weight (g) of the oily substance. The GC analysis conditions were: stationary phase liquid Thermo-3000 7%, stationary phase support Chromosorb W-AW (DMCS) 80-100 mesh, column 3.2 mm glass 2.1 m, carrier gas nitrogen 25 ml / min, temperature Is a column thermostat 180 ° C., inlet 240 ° C., the detector is FID, and the internal standard is diphenyl ether.

  The yield (g / kWh) of cyclohexanone oxime was calculated as the amount of cyclohexanone oxime produced (g) with respect to the input power (kWh) per hour.

The photon yield was determined from the number of cyclohexanone oxime determined from the yield of cyclohexanone oxime and the total photon number irradiated during lighting as follows.
Photon yield (%) = {production amount of cyclohexanone oxime per second (g / s) / 113 (molecular weight) × 6.022 × 10 ⁺²³ (Avocado number: pieces / mol)} / {wavelength 400 to 760 nm Total photon number (Photon / s)} × 100
Here, the total photon number will be described in the characteristic evaluation of the light emitting diode.

  The presence or absence of dirt on the light-irradiated surface after the reaction, that is, the tar-like substance was confirmed.

Characteristic Evaluation of Light-Emitting Diodes The emission energy distribution with respect to the wavelength of the light-emitting diodes was measured using a PMA-12 multichannel spectrometer (BTCCD type, C10027-01 type, manufactured by Hamamatsu Photonics) as a detector and an inner diameter of 3 inches (7.6 cm). Using the integrating sphere, the absolute value of the emission energy was measured for each 0.7 nm of the emission energy distribution in the wavelength region of 200 to 950 nm with one light emitting diode. The light-emitting diode was installed on an aluminum heat sink having a length of 4 cm, a width of 7 cm, and a height of 4.5 cm. The heat sink was provided with four fins for heat dissipation. In the evaluation of the characteristics of the light emitting diode, the measurement was performed at the same temperature and driving current as the lighting of the light emitting diode in the light reaction test. The light emission temperature condition was measured when the heat sink was cooled in advance and the heat sink temperature was 25 ° C. The light emission current condition was measured by the average driving current value per light emitting diode in the light reaction test. In the evaluation of the characteristics of the light emitting diode, the characteristics change due to the temperature rise of the light emitting diode when the lighting is performed for a long time. Since the temperature rises due to heat generation when the light emitting diode is driven, the measurement time is measured at 200 ms so that the temperature rise is within 1 ° C. The driving current at the time of measuring the light emission energy distribution is 0.5A.

The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. FIG. 4 shows a relative light emission energy distribution where the maximum value of the light emission energy is 1. As the total emission energy, an integrated value (W) having a wavelength of 300 to 830 nm was used. As the effective energy, an integrated value (W) having a wavelength of 400 to 760 nm was used.
Effective energy (W) = integrated value of emission energy of 400 to 760 nm (W)

The energy conversion efficiency was determined as follows using the effective energy of the luminescence energy distribution data and the input power at the time of luminescence energy measurement.
Energy conversion efficiency (%) = Effective energy (W) / Input power (W) when measuring luminescence energy x 100

  For the total photon number, the photon number of each wavelength was obtained from the emission energy of each wavelength obtained from the emission energy distribution, and the photon number of each wavelength was integrated for each measurement of 0.7 nm in the wavelength range of 400 to 760 nm. The integrated value (Photon / s) was used.

Here, the photon number and the total photon number of each wavelength were obtained as follows.
Emission energy of one photon of each wavelength (J / Photon) = 6.626 × 10 ⁻³⁴ (Planck's constant: J · s) × 2.998 × 10 ⁺⁸ (light velocity: m / s) / wavelength (m)
Photon number of each wavelength (Photon / s) = Emission energy of each wavelength (W) / Emission energy of one photon of each wavelength (J / Photon)

The number of photons per unit energy was determined as follows.
Photon number per unit energy (Photon / J) = Total photon number (Photon / s) / Input power (W) when measuring luminescence energy

  The results are shown in Table 1.

Example 2
A light emitting diode having a maximum energy peak at a wavelength of 463 nm (Blue LXHL-LB3C, lot number Q3JB, manufactured by Lumileds) was used. The average driving current of the light-emitting diode 1 in the photoreaction test was 0.5 A / piece, and the total input power was 352 W. The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. The light emission energy distribution is measured using one light emitting diode, and the drive current is 0.5 A, which is the same as the average drive current of the photoreaction test.

  Other conditions and photoreaction were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3
A light emitting diode having a maximum energy peak at a wavelength of 515 nm (Cyan LXHL-LE3C, lot number T6MC, manufactured by Lumileds) was used. The average driving current of the light-emitting diode 1 in the photoreaction test was 0.5 A / piece, and the total input power was 408 W. The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. The emission energy distribution is measured using one light emitting diode, and the drive current is 0.5 A, which is the same as the average drive current of the photoreaction test.

  Other conditions and photoreaction were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4
A light emitting diode having a maximum energy peak at a wavelength of 528 nm (Green LXHL-LM3C, lot number T4JG, manufactured by Lumileds) was used. The average driving current of the light-emitting diode 1 in the photoreaction test was 0.5 A / piece, and the total input power was 352 W. The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. The light emission energy distribution is measured using one light emitting diode, and the drive current is 0.5 A, which is the same as the average drive current of the photoreaction test.

  Other conditions and photoreaction were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5
A light emitting diode having a maximum energy peak at a wavelength of 591 nm (Amber LXHL-LL3C, lot number E4HA, manufactured by Lumileds) was used. The average driving current of the light-emitting diode 1 in the photoreaction test was 0.6 A / piece, and the total input power was 328 W. The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. The light emission energy distribution is measured using one light emitting diode, and the drive current is 0.6 A, which is the same as the average drive current of the photoreaction test.

  Other conditions and photoreaction were carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 3
A light emitting diode having a maximum energy peak at a wavelength of 624 nm (Red-Orange XHL-LH3C, lot number G2GH manufactured by Lumileds) was used. The average driving current of the light-emitting diode 1 in the photoreaction test was 0.6 A / piece, and the total input power was 320 W. The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. The light emission energy distribution is measured using one light emitting diode, and the drive current is 0.6 A, which is the same as the average drive current of the photoreaction test.

  Other conditions and photoreaction were carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 4
A light emitting diode having a maximum energy peak at a wavelength of 632 nm (Red LXHL-LD3C, lot number G4GR manufactured by Lumileds) was used. The average driving current of the light-emitting diode 1 in the photoreaction test was 0.6 A / piece, and the total input power was 318 W. The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. The light emission energy distribution is measured using one light emitting diode, and the drive current is 0.6 A, which is the same as the average drive current of the photoreaction test.

  Other conditions and photoreaction were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 6
A light emitting diode having a maximum energy peak at a wavelength of 443 nm (White LXHL-LW3C, lot number TV1JW manufactured by Lumileds) was used. The average driving current of the light-emitting diode 1 in the photoreaction test was 0.5 A / piece, and the total input power was 360 W. The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. The light emission energy distribution is measured using one light emitting diode, and the drive current is 0.5 A, which is the same as the average drive current of the photoreaction test.

  Other conditions and photoreaction were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
Photoreaction Test The photochemical reaction apparatus shown in FIG. 8 was used for the photoreaction test. The photochemical reactor 2 was made of cylindrical glass having an outer diameter of 9.5 cm. As a light source, a high-pressure mercury lamp (metal contained in arc tube: Hg) is used as the discharge lamp 11 and has a maximum energy peak at a wavelength of 365 nm (manufactured by Toshiba Lighting & Technology Corp.). The photochemical reactor 2 has a rod-shaped discharge lamp 11 at the center, and the discharge lamp 11 is an internal irradiation method in which light is irradiated by being inserted into a lamp cooler 12 and immersed in a photoreaction liquid. . Lighting was performed by an AC power supply, and the power was adjusted using a ballast, and the input power was 250 W.

The cooling in the photoreaction is performed on the light irradiation surface to remove the heat of irradiation caused by the light irradiation of the discharge lamp in order to reduce the influence on the reaction system due to the high heat generation during the light emission of the discharge lamp 11, and the reaction by the photoreaction. The photoreaction liquid for removing heat and light irradiation heat was cooled. The cooling on the light irradiation surface is performed by immersing a double cylindrical glass tube having an outer tube outer diameter of 5 cm and an inner tube outer diameter of 3 cm as a lamp cooler 12 in the center of the photochemical reactor 2. The lamp can be inserted into the interior of the lamp to cool the discharge lamp 11 side and the photoreaction liquid side. The cooling water was introduced from the lamp cooling water introduction line 13 through the lamp cooling introduction pipe 14 and discharged from the lamp cooling water discharge line 15 to be cooled. Cooling water at 10 ± 2 ° C. was supplied at 5-9 L / min. Cooling area of the lamp cooler 12 is the sum 605 cm ² of the area 381cm ² lamp cooler 12 the area of the inner tube 224Cm ² and the lamp cooler 12 is in contact with the photoactive solution.

Further, for cooling the photoreaction liquid, in order to maintain the photoreaction liquid at 20 ± 2 ° C., a cooling bath 16 is provided outside the photochemical reactor 2, and cooling is performed at 6 to 13 ° C. from the reaction cooling water introduction line 7. Water was continuously supplied and discharged from the reaction cooling water introduction line 8. The average reaction temperature was 20 ° C. The measurement point of the reaction temperature is the same as in Example 1. The cooling area of the photoreaction liquid is 876 cm ² as the area until the cooling water in the cooling bath 16 comes into contact with the outer wall of the photochemical reactor 2 and the level of the liquid surface of the photoreaction liquid.

  Photochemical reactor 2 was charged with 1 L of cyclohexane (special grade reagent, manufactured by Katayama Chemical Co., Ltd.), the reaction temperature of photochemical reactor 2 was maintained at 20 ± 2 ° C., and hydrogen chloride (manufactured by Tsurumi Soda Co., Ltd.) gas was supplied at a flow rate of 1440 ml / min. It was supplied from the photonitrosating agent introduction line 5 and continuously blown from the lower part of the photochemical reactor. The discharge lamp 11 was turned on after 10 minutes. 10 minutes after the start of lighting, nitrosyl chloride gas (obtained by reacting nitrosylsulfuric acid with hydrogen chloride and obtained by distillation purification) was mixed with hydrogen chloride gas 1440 ml / min at a flow rate of 160 ml / min. From the introduction line 5, it was continuously blown from the lower part of the photochemical reactor 2.

  The exhaust gas was discharged from the unreacted gas line 9 and absorbed with water by a scrubber, and the absorbing solution was neutralized with soda ash.

  Other conditions were the same as in Example 1.

Characteristic Evaluation of Discharge Lamp The emission energy distribution with respect to the wavelength of the discharge lamp is difficult to measure with an integrating sphere because the discharge lamp 11 is large with a rod-shaped light source, and was evaluated by measurement with irradiance. Using a spectroscope (Nikon Corporation, G-250) and a photoelectron amplifier tube (Hamamatsu Photonics Corporation, R1509) measured for emission energy of 300 to 830 nm every 5 nm, the wavelength is the center value every 5 nm Was used. The input power is 250W. The measurement distance was 60 cm from the center of the arc tube, and the emission energy distribution by irradiance (W / cm ² ) was measured. The light emission length of the arc tube 17 of the discharge lamp 11 is 6 cm. The measurement irradiation area was a spherical area at a measurement distance as a point light source, but the decrease in the irradiance due to the sealed tube portion and the decrease in the radiation area were corrected by measuring the irradiance at that angle. The emission energy distribution in the wavelength region of 300 to 830 nm is shown in FIG. FIG. 6 shows a relative emission energy distribution with the maximum value of emission energy being 1. As the total emission energy, an integrated value (W) having a wavelength of 300 to 830 nm was used.

The energy conversion efficiency was calculated | required as follows using the effective light emission energy of wavelength 400-760nm of the light emission energy distribution data, and the input electric power at the time of light emission energy measurement.
Effective luminescence energy (W) = integrated value of luminescence energy of 400 to 760 nm (W)
Energy conversion efficiency (%) = Effective luminescence energy (W) / Input power when measuring luminescence energy (W) x 100

  The total photon number is an integrated value obtained by calculating the photon number of each wavelength from the emission energy of each wavelength obtained from the emission energy distribution, and integrating the photon number of each wavelength for each measurement of 5 nm in the wavelength range of 400 to 760 nm. (Photon / s) was used.

Here, the photon number and the total photon number of each wavelength were obtained as follows.
Emission energy of one photon of each wavelength (J / Photon) = 6.626 × 10 ⁻³⁴ (Planck's constant: J · s) × 2.998 × 10 ⁺⁸ (light velocity: m / s) / wavelength (m)
Photon number of each wavelength (Photon / s) = Emission energy of each wavelength (W) / Emission energy of one photon of each wavelength (J / Photon)

The number of photons per unit energy was determined as follows.
Photon number per unit energy (Photon / J) = Total photon number (Photon / s) / Input power (W) when measuring luminescence energy

  Other conditions and photoreaction were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
A fluorescent agent (Whiteex RP, manufactured by Sumitomo Chemical Co., Ltd.) for cutting a wavelength shorter than 400 nm was introduced into the cooling water introduced into the lamp cooler 12 so as to have a concentration of 0.05%. Since the wavelength of less than 400 nm is cut, the wavelength indicating the maximum energy in the emission energy distribution with respect to the wavelength is 435 nm. The emission energy distribution was set to not include a wavelength of less than 400 nm using Comparative Example 1.

  Other conditions were the same as in Comparative Example 1. The results are shown in Table 1.

  In Table 1, short wavelength cut indicates whether or not a short wavelength of less than 400 nm has been cut with a fluorescent agent.

  The maximum wavelength is a wavelength at which the emission energy has a maximum value in the emission energy distribution with a wavelength of 300 to 830 nm.

  The wavelength other than the effective wavelength region is a wavelength in which the emission energy with respect to the wavelength exceeds 5% of the maximum emission energy in the emission energy distribution of the wavelength of 300 to 830 nm, in the shorter wavelength region than the wavelength 400 nm and in the longer wavelength region than the wavelength 760 nm. Indicates the presence or absence of

  The effective energy / total emission energy is a ratio of emission energy (effective energy) integrated with a wavelength of 400 to 760 nm as an effective wavelength with respect to an integrated value (total emission energy) of emission energy in the 300 to 830 nm wavelength region in the emission energy distribution.

  The photon number is the number of photons per unit energy (Photon / J).

  The reaction temperature was shown as an average value as the temperature of the photoreaction solution.

  The oxime yield is the yield (g / kWh) of cyclohexanone oxime per hour of input power.

From the above results, it was found that cyclohexanone oxime was obtained by the photonitrosation reaction using the light emitting diodes according to Examples 1 to 4 . Both yielded higher oxime yields than the high pressure mercury lamps used in Comparative Examples 1 and 2 and the light emitting diodes used in Comparative Examples 3-6 .

From the characteristics of the light emitting diodes, the maximum wavelengths of Examples 1 to 4 are all 400 to 760 nm, and the light emission energy in the effective wavelength region is very high performance of 99.3% or more. This shows that even if the energy conversion efficiency of the light emitting diode is lower than that of the discharge lamp, it is possible to irradiate light with a wavelength that is highly efficient and effective for reaction.

  Since the light emitting diode can efficiently emit light in the wavelength range of 400 to 760 nm necessary for the photoreaction, an oxime yield higher than that of the high pressure mercury lamp can be obtained in an embodiment in which the energy conversion efficiency as the light source performance is lower than that of the high pressure mercury lamp. It was. Further, even in Examples where the photon number, which is an important factor for the yield of the photoreaction, is lower than that of the high-pressure mercury lamp, the photon yield can be increased in the light emitting diode, and thus a high oxime yield was obtained.

From Examples 1 to 4 , in the photoreaction using a light emitting diode, the higher the energy conversion efficiency and / or the photon number, the higher the oxime yield tends to be obtained. In Examples 1 to 4 , the energy conversion efficiency is 10% to 75%, and a high oxime yield is obtained. A photon number of 2 × 10 ⁺¹⁷ (Photon / J) or higher provides a high oxime yield.

From the wavelength of the light emitting diode, in Examples 3 and 4 , cyclohexanone oxime could be sufficiently obtained even when the wavelength showing the maximum energy that could not be realized by the discharge lamp so far was 600 nm or more. This is because, from Einstein's law, the number of photons per unit emission energy, that is, the number of photons with the same energy conversion efficiency increases as the wavelength increases, so a high yield can be expected if photonitrosation in the long wavelength region is possible. It is shown that.

Light-emitting diodes can not only efficiently emit light in the effective wavelength region, but also can arrange the light-emitting diodes in a planar shape and evenly irradiate the photoreaction solution, so the photon yield is higher than that of high-pressure mercury lamps that emit locally. (Examples 1 to 4 ) were obtained.

Also in the light reaction cooling, the light emitting diodes of Examples 1 to 4 generate little heat in the light irradiation direction, and therefore the light reaction solution may be cooled, and the cooling area can be reduced to half or less of Comparative Examples 1 and 2. In the high pressure mercury lamps of Comparative Examples 1 and 2, it is necessary to further cool the irradiation surface of the discharge lamp, and the cooling area is large. Further, in the examples of the present invention, cooling outside the reactor, which was necessary in the case of Comparative Examples 1 and 2, can be reduced. Moreover, the cooling energy used for cooling the light irradiation surface required for the discharge lamp can also be used for cooling the light emitting diode.

  Comparative Examples 1 and 2 use a high-pressure mercury lamp, which is a kind of discharge lamp. However, as in Comparative Example 1, the yield of cyclohexanone oxime is low at a short wavelength having a maximum energy of 365 nm. Further, since the short wavelength of 400 nm or less is not cut, a large amount of contamination occurs on the light irradiation surface, resulting in light transmission loss and low oxime yield. In Comparative Example 2, by cutting the wavelength of 400 nm or less with the fluorescent agent, the contamination on the light irradiation surface can be reduced and the oxime yield is increased. However, the reduction of the contamination is not complete, and transmission loss of the fluorescent agent also occurs.

In the light emitting diode as in Examples 3 to 4 , there is no contamination on the light irradiation surface even if the short wavelength is not cut. That is, there is no contamination of the light irradiation surface at the maximum wavelength of 500 to 650 nm. In Examples 1 and 2, although the contamination on the light irradiation surface was less than that in Comparative Example 1, the results showed the contamination on the light irradiation surface at a relatively short wavelength. However, these results in a better oxime yield than Comparative Examples 1 and 2, and the influence on the reaction due to contamination on the light irradiation surface is less than that of the discharge lamp. This is also an advantage that the light emitting diode can irradiate the surface, and the light emission energy per unit irradiation area can be reduced.

  Light-emitting diodes, which are friendly to the global environment, are expected to be the next-generation light source due to their energy saving, long life, etc., enable photochemical reactions, especially photonitrosation reactions. As a result, light-emitting diodes are attracting attention as a substitute for lamps for display applications and lighting applications. However, since they can be applied to photochemical reactions, new applications and possibilities of light-emitting diodes are greatly expanded. Further, the production using photochemical reaction, and its application range is not limited to these. For example, in the production of caprolactam and lauryl lactam, particularly in the production of caprolactam from cyclohexanenonoxime by the photonitrosation method, a light emitting diode is used. By applying it, it is possible to efficiently use the luminescence energy for the photonitrosation reaction, and it is possible to reduce the environmental load, save energy, and extend the service life.

FIG. 1 is a graph showing a light emission energy distribution of an example of a light emitting diode having a maximum light emission energy in the vicinity of a wavelength of 625 nm. FIG. 2 is a graph showing a light emission energy distribution of an example of a discharge lamp in which the wavelength indicating the maximum value of light emission energy is in the range of 400 to 760 nm. FIG. 3 is a graph showing a light emission energy distribution of an example of a discharge lamp in which the wavelength indicating the maximum value of light emission energy is in the range of 400 to 760 nm. FIG. 4 is a relative light emission energy distribution with respect to the wavelength of each light emitting diode used in Examples 1-2 and Comparative Examples 3-4 . Figure 5 is a relative emission energy distribution with respect to the wavelength of the light emitting diodes used in Examples 3-4 and Comparative Examples 5-6. FIG. 6 is a relative emission energy distribution with respect to the wavelength of the high-pressure mercury lamp used in Comparative Examples 1 and 2 . FIG. 7 is an example of a photochemical reaction using the light-emitting diode of the present invention. FIG. 8 is an example of a photochemical reaction using the discharge lamp of the comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Light emitting diode 2 Photochemical reactor 3 Heat sink 4 Cycloalkane introduction line 5 Photo nitrosating agent introduction line 6 Cooler 7 Reaction cooling water introduction line 8 Reaction cooling water discharge line 9 Unreacted gas line 10 Reaction product line 11 Discharge lamp 12 Lamp cooler 13 Lamp cooling water introduction line 14 Lamp cooling introduction pipe 15 Lamp cooling water discharge line 16 Cooling bus 17 Arc tube

Claims (7)

In a method of photochemical reaction of cycloalkane and a photonitrosating agent by light irradiation, a light emitting diode is used as a light source, and a wavelength indicating a maximum value of light emission energy in a light emission energy distribution with respect to the wavelength of the light source is 430 nm. A method for producing a cycloalkanone oxime, which is used in the range of ˜650 nm and the energy conversion efficiency of the light emitting diode is 10% or more and 75% or less. In the emission energy distribution with respect to the wavelength of the light source, the emission energy with respect to the wavelength in the shorter wavelength region than the wavelength of 400 nm is 5% or less of the maximum value of the emission energy, and with respect to the wavelength in the longer wavelength region with the wavelength of 760 nm. The process for producing cycloalkanone oxime according to claim 1, wherein the emission energy is 5% or less of the maximum value of the emission energy. The light reaction solution is irradiated with light through a transmissive photochemical reactor using a plurality of light emitting diodes arranged in a plane along the side surface of the photochemical reactor containing the photoreaction solution. The manufacturing method of the cycloalkanone oxime in any one of 1-2. The method for producing cycloalkanone oxime according to any one of 1 to 3, wherein a photocooling solution is cooled by immersing a cooler in the photoreaction solution. The method for producing a cycloalkanone oxime according to any one of claims 1 to 4, wherein the cycloalkane is cyclohexane. The method for producing cycloalkane oxime according to any one of claims 1 to 5, wherein the photonitrosating agent is nitrosyl chloride. The said cycloalkanone oxime is cyclohexanone oxime, The manufacturing method of the cycloalkanone oxime in any one of Claims 1-6 characterized by the above-mentioned.

Images