Patent Application
20170305851
The present invention relates to a photoirradiation device using light-emitting diodes as a light source, a photoreaction method using the photoirradiation device, and a method for producing a lactam by using the photoreaction method.
A photoreaction is also called a photochemical reaction, and indicates the whole of chemical reactions each in which molecules are brought into a state having a high energy level, that is, a so-called excited state by photoirradiation, namely by making a radical reaction initiator absorb energy ascribed to the irradiated light, and the reaction is caused by the excited molecules. The photoreaction includes kinds of oxidation-reduction reaction by light, substitution-addition reaction by light, etc., and it is known that the applications include photo industry, copying technology, induction of photovoltaic power, and in addition, synthesis of organic compounds. Further, as unintentional photochemical reaction, photochemical smog and the like also belong to photochemical reaction.
For example, it is known that cyclohexanone oxime can be synthesized by photochemical reaction, and photonitrosation of cycloalkane is also a widely known technology at the present time.
As light sources for the photoreaction which have been used so far, in most cases, a lamp, in which mercury, thallium, sodium or another metal is enclosed in an environment of vacuum or close to vacuum, voltage is applied, and the emitted electron beam is irradiated to the enclosed metal, and the light emitting ascribed to electric discharge in gas or vapor condition is utilized, for example, a discharge lamp or a fluorescent lamp, is used as the light source.
For example, in case where a high pressure mercury lamp is used as a light source, the effective wavelength is 365 nm to 600 nm. However, in this type of discharge lamp using mercury, specific light emission energy due to mercury exists also in the wavelength region including ultraviolet rays of less than 365 nm. Therefore, for example, in case of having light emission energy in a short wavelength region including ultraviolet rays of less than 350 nm, because it is comparable to the dissociation energy of many chemical bonds, a reaction other than the purpose proceeds and promotes a side reaction, and a brown tar-like deposit is formed on the photoirradiation surface of the discharge lamp, thereby reducing the yield. Therefore, in order to cut the ultraviolet rays, a water-soluble fluorescent agent or a UV-cut glass is used.
In order to reduce such problems in a mercury lamp and improve the luminous efficiency, it is known that a thallium lamp exhibiting light emission energy effective to a wavelength of 535 nm and a sodium lamp exhibiting light emission energy effective to a wavelength of 589 nm are effective. By using a sodium lamp as a light source, the yield is dramatically increased and a stable reaction becomes possible. Further, by using a high-pressure sodium discharge lamp, the industrially effective wavelength is set at 400 to 700 nm, and the efficiency can be increased in the wavelength region of 600 nm to 700 nm. The peak wavelength in this range can be estimated to be about 580 to 610 nm. However, in order to improve the electric properties and starting of the discharge lamp, coexistence of mercury is inevitable, and a filter for cutting ultraviolet rays due to mercury is necessary. In particular, short wavelengths less than 400 nm generated by mercury are unnecessary wavelengths because they have excessive energy and cause unnecessary side reactions.
Furthermore, the sodium lamp has a peculiar light emission energy peak in a wavelength region including infrared rays having a wavelength of 780 to 840 nm, and its energy intensity is frequently comparable to the maximum light emission energy of the sodium lamp. Since the dissociation energy of nitrosyl chloride is about 156 J/mol, which is comparable to the light emission energy at a wavelength near 760 nm according to Einstein's law, the light energy is small in the longer wavelength region and the nitrosyl chloride does not dissociate, and therefore, it does not contribute to a reaction and causes a great energy loss.
Light emitting diodes, also abbreviated as LEDs, have the advantage capable of converting electrical energy directly into light using semiconductors, and are attracting attention in terms of suppression of heat generation, energy saving, long life, and the like. Its history of development is still shallow, red LEDs were commercialized in 1962, LEDs such as blue, green and white were developed from around 2000′, and they were commercialized for display and lighting uses. On the other hand, a discharge lamp used for a photoreaction has a very high output and a high luminous efficiency, but if it is attempted to obtain the light emission energy required for a photoreaction equivalent to that of a discharge lamp by LEDs, the required number of LEDs becomes enormous, and it has been considered that it is difficult to apply LEDs as a light source for a photoreaction, because problems in circuit design, LED heat countermeasure and cost remain. Furthermore, it is necessary to irradiate a reaction liquid with uniform light for the photoreaction, but the LED has a strong directivity and it is difficult to obtain the wavelength necessary for the reaction with a high efficiency, and also from this point of view, application of LEDs to the light source of the photoreaction has been considered to be difficult. However, recently, as described in Patent document 1 and Patent document 2, there is an example in which photoreaction by LEDs is carried out using a small reaction apparatus, and moreover, as described in Patent document 2, solution of the problems for enlarging a light-emitting body is being in sight.
However, in the inventions disclosed in these Patent documents 1 and 2, it cannot be said that a structure of a photoirradiation device capable of necessarily and effectively utilizing light linearly emitted from a light emitting diode is proposed. Further, if a photoreaction is aimed, in most case a target liquids is a flammable liquid, physical separation between the photoirradiation device as an ignition source and the target liquid is essential, however, in the inventions disclosed in Patent documents 1 and 2, there is a problem that light is obstructed by reflection by an obstacle for the separation provided in the photoirradiation route, that is, an optically transparent container, and the rate of the light transmission is reduced.
Accordingly, an object of the present invention is to provide a photoirradiation device capable of achieving a desired photoirradiation with a high optical transparency by suppressing reflection of light between a light-emitting diode light source and a target liquid isolated by an optically transparent container, a photoreaction method using the photoirradiation device, and a method for producing a lactam using the photoreaction method.
As a result of earnest investigation to solve the above-described problems, it has been found that by interposing a liquid phase having a specific refractive index in the photoirradiation route from the LED light source provided with an optically transparent container to a target liquid, desirably, by setting the irradiation angle of light from as LED narrow in radiation angle in a specific range with respect to the optically transparent container, the reflection of light at the surface of the optically transparent container, especially, the reflection of light generated when shifting from a high refractive index substance to a low refractive index substance, can be suppressed, and it is possible to efficiently perform the photoirradiation from the LED light source to the target liquid by suppressing energy loss ascribed to dissipation of light energy.
In order to solve the above-described problems, the present invention includes the following constitutions. Namely,
(1) A photoirradiation device using light-emitting diodes as a light source, characterized in that a first optically transparent container for covering a light-emitting body provided with the light-emitting diodes is provided, and on the outside thereof, a liquid phase section formed from a liquid having a refractive index closer to that of the first optically transparent container than that of a gas forming a gas phase section inside the first optically transparent container, and a second optically transparent container for covering the liquid phase section are provide.
(2) The photoirradiation device according to (1), wherein the light emitting diodes are installed such that a center of optical axes of the light emitting diodes is set at 60° or less relatively to a normal line of an inner surface of the first optically transparent container.
(3) The photoirradiation device according to (1) or (2), wherein the liquid forming the liquid phase section is a nonflammable liquid.
(4) The photoirradiation device according to any one of (1) to (3), wherein the liquid forming the liquid phase section is water.
(5) The photoirradiation device according to any one of (1) to (4), wherein the second optically transparent container is disposed at least along an outer circumference of the first optically transparent container.
(6) The photoirradiation device according to any one of (1) to (5), wherein at least one of the first optically transparent container and the second optically transparent container is formed from a material having a refractive index of 1.4 or more.
(7) The photoirradiation device according to any one of (1) to (6), wherein at least one of the first optically transparent container and the second optically transparent container is formed from a glass.
(8) The photoirradiation device according to any one of (1) to (7), wherein the light-emitting body is covered with the gas phase section, and the gas phase section is formed from a gas having an oxygen concentration of 1% or less.
(9) The photoirradiation device according to (8), wherein the gas phase section is formed from an inert gas.
(10) The photoirradiation device according to (8) or (9), wherein the gas phase section is formed from nitrogen.
(11) A photoreaction method characterized by using the photoirradiation device according to any one of (1) to (10).
(12) The photoreaction method according to (11), wherein the destination of photoirradiation is a liquid, and the composition of the liquid contains at least a carbon atom.
(13) The photoreaction method according to (12), wherein the liquid as the destination of photoirradiation is a cycloalkane.
(14) The photoreaction method according to (13), wherein a cycloalkanone oxime is produced by performing photoirradiation to the cycloalkane and a photo nitrosating agent.
(15) The photoreaction method according to (14), wherein the cycloalkanone oxime is cyclohexanone oxime or cyclododecanone oxime.
(16) The photoreaction method according to (14) or (15), wherein the photo nitrosating agent is nitrosyl chloride or trichloronitrosomethane.
(17) A method for producing a lactam characterized by using a cycloalkanone oxime produced by the photoreaction method according to any one of (14) to (16).
In the present invention, by interposing the liquid phase section, formed from the liquid having a refractive index closer to that of the first optically transparent container than that of the gas forming the gas phase section inside the first optically transparent container, between the first and second optically transparent containers provided for separating the light emitting body using the LEDs as a light source and the reaction liquid as the target liquid, the reflection of the light irradiated from the LED light source to the target liquid can be efficiently suppressed. Further, if the incident angle of the light to the inner surface of the first optically transparent container is set small, the reflection of the light can be suppressed more efficiently. Thus, the optical transparency can be increased by suppressing the reflection of the light, the optical irradiation to the target liquid can be carried out without accompanying with a great energy loss, and it becomes possible to obtain high reaction yield and reaction amount in the photochemical reaction. In particular, the present invention is extremely useful for the photoreaction for producing cycloalkanone oxime and the production of lactam using the cycloalkanone oxime.
Hereinafter, embodiments of the present invention will be explained referring to figures.
In the present invention, the photoirradiation device is a device which has a light-emitting body emitting light and can irradiate light to an object. The object is, for example, a reaction liquid becoming a raw material as a target liquid of photoreaction.
The light emitting diode is a light emitting diode which emits ultraviolet rays, visible light and infrared rays, and as the light emitting diode 5 to be used, a type selected for the wavelength required for the application of the photoirradiation device 1 can be appropriately selected. The shape and size of the light emitting diode 5 is not particularly limited, and it is possible to use a shape and size depending upon the purpose. Although any of bullet type, mounting type, chip type and the like may be used, one capable of radiating heat from the back side of the light emitting diode 5 is preferable because heat removal is easy. Further, one provided with a heat radiation substrate on the back surface of the light emitting diode 5 is desired because a large heat transfer area can be obtained and the cooling performance is improved.
In the present invention, the light-emitting body means a portion having a surface emitting light in the photoirradiation device. Concretely, for example, a plurality of light emitting diodes 5 are mounted on a planar substrate 12 as shown in
In this case, the shape of the light-emitting body 6 is decided by the shape pf the structural body 13 arranged with the above-described planar substrates 12. However, the shape of the light-emitting body 6 is not particularly restricted, and as the cross-sectional shape, except the above-described star shape, a circular shape, a polygonal shape and the like can be employed. Further, by changing the cross-sectional shape of the light-emitting body 6, the area of the light emitting diode placement surface changes, the possible number of mounted light emitting diodes can be increased and decreased, and the shape can be decided depending upon the purpose.
The first optically transparent container 8 is a container covering the light-emitting body 6 and is provided to protect the light-emitting body 6 from the outside. This first optically transparent container 8 may be formed by using a material transmitting light. If a raw material having transmission wavelength selectivity is used for the optically transparent container, it is possible to suppress transmission of unnecessary wavelength light. As the overall shape of the first optically transparent container 8, for example, a test tube type can be exemplified as shown in
The second optically transparent container 10 is a container disposed outside the first optically transparent container 8, and may be formed by using a material transmitting light similarly to the first optically transparent container 8. This material of the second optically transparent container 10 may be the same as or different from that of the first optically transparent container 8. As the shape thereof, for example, a test tube type can be exemplified as shown in
In the present invention, the liquid phase section formed from a liquid closer to the refractive index of the first optically transparent container than that of the gas forming the gas phase section inside the first optically transparent container means a portion formed from a liquid whose difference in refractive index from the first optically transparent container is smaller than that of the above-described gas, and is, for example, a portion formed by being filled with such a liquid. In this liquid phase section, the liquid may be flowed therethrough at all times or it may be enclosed. As shown in
In case where a liquid, for example, water is flowed through the liquid phase section 11, by lowering the temperature of the flowing water, the refractive index of water can be enhanced and the difference in refractive index from the first optically transparent container can be further reduced. Further, except water, a nonflammable liquid and a liquid having a small difference in refractive index from the first optically transparent container can be used depending upon the purpose. Furthermore, depending upon the purpose, a liquid inert to water may be added and used. It is possible to change the refractive index by the addition.
In the present invention, by interposing the above-described liquid phase section 11 between the first optically transparent container 8 and the second optically transparent container 10, the energy loss ascribed to reflection in the irradiation route of the light from the light-emitting body 6 is suppressed.
Using
Surface reflectance R=0.5×{tan(θ1−θ2)/tan(θ1+θ2)}2+{sin(θ1−θ2)/sin(θ1+θ2)}2 (1)
Namely, in case where there is a media interface having a large difference in refractive index on the optical path, loss ascribed to light reflection increases. Accordingly, in the present invention, by interposing the liquid phase section 11 formed from a liquid having a difference in refractive index as small as possible, in the space between the first optically transparent container 8 and the second optically transparent container 10, the light energy loss ascribed to reflection is reduced.
For example, an example of an optical path accompanied by refraction and reflection when the photoirradiation is performed by the photoirradiation device 1 of
Here, the optical axis 21 of the light emitting diodes 5 means an imaginary center line of a light flux emitted from the light emitting diodes 5 mounted on the aforementioned planar substrate. For example, in case where a plurality of light emitting diodes are equidistantly arranged in a planar substrate and light is irradiated, the optical axis becomes a line extending in the direction perpendicular to the planar substrate from the center of gravity of the planar substrate.
The incident angle of light into the container surface is determined by the positional relationship between the light emitting surface on which the light emitting diodes 5 are disposed and the container surface, concretely, the angle formed between the light emitting surface and the container surface. Since the angle formed between the light emitting surface and the container surface is determined by the shape of the structural body 13 in which the light emitting diodes 5 are disposed and the shape of the container, the incident angle can be controlled by adjusting the shapes of the structural body 13 and the container.
According to the aforementioned equation (1), the reflectance of light varies depending on the incident angle, the smaller the incident angle is, the smaller the reflectance is, and the loss of light can be reduced.
The incident angle into the first optically transparent container 8 is preferably 0° or more and 60° or less, and more preferably 0° or more and 45° or less.
Namely, it is preferred that the optical axis of the light-emitting diodes 5 is set at 45° or less relatively to the normal line of the inner surface of the first optically transparent container 8. This is to arrange the light emitting diodes 5 so that the angle formed by the center of the optical axis and the normal line of the surface of the optically transparent container 8, that is, the incident angle of light into the surface of the optically transparent container 8, becomes 45° or less.
Furthermore, it is known that, when light is entered from the side of a high refractive index medium to the side of a low refractive index medium, total reflection, in which all of the incident lights are not transmitted, is caused at a certain incident angle or more. The minimum incident angle causing total reflection is called as a critical angle, and the critical angle is represented by the following equation (2) using the refractive index n1 of the incident side medium and the refractive index n2 of the transmission side medium. Light entered at an incident angle of the critical angle or more is not transmitted but is all reflected at the interface. Therefore, it is important for suppressing the reflection loss to set so that the incident angle does not exceed the critical angle. Here:
Critical angle θc=arcsin(n2/n1) (2)
Thus, effectively transmitting the light irradiated from the light-emitting body 6 to the reaction liquid 3 present outside the two optically transparent containers 8 and 10 can be achieved by filling the space between the first optically transparent container 8 and the second optically transparent container 10 with the medium having a refractive index close to that of the optically transparent container and making the incident angle to the container surface small.
In the present invention, it is preferred to use a liquid which forms the liquid phase section 11 as the above-described medium having a refractive index close to that of the optically transparent container. Where, in the present invention, a nonflammable liquid means a liquid that does not correspond to a dangerous substance specified by the Fire Services Act and is a liquid that transmits light. Concretely, exemplified are ethylene glycol 50% aqueous solution, silicone oil, water and the like.
The difference in refractive index between the liquid forming the liquid phase section 11 and the first optically transparent container 8 is preferably smaller than the difference in refractive index between the optically transparent container and air, and the liquid forming the liquid phase section 11 may be one in which the refractive index is adjusted by dissolving a soluble substance in water such as one in which sugar or the like is dissolved in water or one an aqueous glycerin solution. Further, since the refractive index varies depending upon temperature, the refractive index may be adjusted by adjusting the temperature.
Further, by adding a substance which absorbs light having a specific wavelength to the above-described liquid, light of a specific wavelength unnecessary for the reaction may be removed.
In the present invention, it is preferred that at least one of the first and second optically transparent containers is formed from a material having a refractive index of 1.4 or more. As such a material, any of an organic material typically represented by a resin or an inorganic material typically represented by a glass may be employed. More concretely, acrylic resin, methacrylic resin, polycarbonate, polystyrene, polyvinyl chloride, polyester, borosilicate glass, soda-lime-silica glass, lead glass and the like can be exemplified.
The refractive index of a nonflammable liquid such as water filled in the liquid phase section is generally smaller than the refractive index of the optically transparent solid. In particular, since a material that reduces the difference in refractive index from the liquid phase section is preferred, for forming the optically transparent container, it is more preferred to use borosilicate glass having a low refractive index among optically transparent solids and having high pressure resistance and chemical stability.
A material which absorbs light having a specific wavelength may be used for the first and second optically transparent containers. By making the containers absorb the wavelength unnecessary for photoreaction, only the wavelength necessary for photoreaction can be transmitted to the reaction liquid.
In the present invention, the phrase “the light-emitting body 6 is covered with the gas phase section 9” means a state where the space between the light-emitting body 6 and the first optically transparent container 8 is filled with gas.
In case where the above-described gas phase section 9 contains oxygen, it causes oxidation deterioration of electronic components such as the light emitting diodes 5. Therefore, in order to lengthen the lifetime of the light-emitting body 6, it is desired that the gas has an oxygen concentration of 2% or less, more preferably 1.5% or less.
As the gas forming the gas phase section 9, an inert gas can be used, and rare gases such as helium, neon, argon, krypton and xenon can be exemplified, but it is preferred to use nitrogen as an inert gas which can be easily and inexpensively obtained. With respect to this gas phase section 9, the gas may be constantly flown or may be in an enclosed condition.
In the present invention, the destination of the photoirradiation may be a liquid which contains carbon atoms. Namely, the photoirradiation device according to the present invention can be used as a light source for photoreaction, and at least one destination of the photoirradiation may be a raw material system composed of a liquid. The liquid served as a raw material is not particularly restricted as long as it is a liquid containing carbon atoms, and for example, hydrocarbons such as alkane and cycloalkane can be exemplified.
In the present invention, although the cycloalkane is not particularly limited in the number of carbon atoms, for example, preferred are cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane. In particular, cyclohexane as a raw material of 8-caprolactam and cyclododecane as a raw material of co-lauryllactam are preferred.
Using the above-described cycloalkane and photo nitrosating agent, cycloalkanone oxime is obtained by photochemical reaction due to the photo irradiation of light emitting diodes. As the photo nitrosating agent, for example, nitrosyl chloride or a mixed gas of nitrosyl chloride and hydrogen chloride is preferable. Besides, since any of the mixed gas of nitric monoxide and chlorine, the mixed gas of nitric monoxide, chlorine and hydrogen chloride, the mixed gas of nitrose gas and chlorine, etc. acts as nitrosyl chloride in the photoreaction system, it is not limited to these supply forms of the nitrosating agent. Further, trichloronitrosomethane obtained by photochemical reaction of nitrosyl chloride and chloroform may be used as a nitrosating agent. When the photochemical reaction is carried out in the presence of hydrogen chloride, the cycloalkanone oxime becomes its hydrochloride, but it may be in the form of hydrochloride as it is.
By the above-described photoreaction, it is possible to obtain cycloalkanone oxime which depends upon the carbon number of the cycloalkane. For example, cyclohexanone oxime is obtained by photo nitrosating reaction with nitrosyl chloride using cyclohexane. Further, cyclododecanone oxime is obtained by photo nitrosating reaction with nitrosyl chloride using cyclododecane.
<Method for Producing Lactam>
A photochemical reaction is carried out using the photoirradiation device according to the present invention, and a lactam is obtained by Beckmann rearrangement of the obtained cycloalkanone oxime. For example, in the reaction of Beckmann rearrangement of cyclohexanone oxime, ε-caprolactam is obtained as shown by the following reaction formula [Chemical formula 1]. Further, ω-laurolactam is obtained in the reaction of Beckmann rearrangement of cyclododecanone oxime.
Hereinafter, the present invention will be explained in more detail with reference to Examples.
For the light emitting body using light emitting diodes as a light source, borosilicate glass with a refractive index of 1.49 was used for the first optically transparent container, the gas phase section was formed from N2, and water was placed in the liquid phase section covering the first optically transparent container, and the transmittance of light (optical transparency) from the first optically transparent container to the liquid phase section, in case where the incident angle from the first optically transparent container to the interface between the container outer surface and the liquid phase section was changed, was calculated. As the results are shown in Table 1, high transmittance was obtained. In case where water was placed in the liquid phase section, total reflection occurred at an incident angle of 70 degrees or more (Reference Example 1).
Transmittance was calculated in the same manner as in Example 1 other than a condition where N2 was filled in the liquid phase section. The results are shown in Table 1. The transmittance became lower as compared with the case where water was placed in the liquid phase section. In case where N2 was filled in the liquid phase section, total reflection occurred at an incident angle of 50 degrees or more (Reference Comparative Example 1).
Further, in case where water is placed in the liquid phase section, the critical angle at which total reflection occurs becomes larger than the case where N2 is filled, and therefore, it is possible to use light more effectively.
With respect to the light emitting body using light emitting diodes as a light source, N2 was used for the gas phase section covering the light emitting diodes, and borosilicate glass with a refractive index of 1.49 was used for the first optically transparent container. The incident angle of the light on the optical axis of the light emitting diodes from the gas phase section to the inner surface of the first optically transparent container was set at 10°, and the transmittance of light from the gas phase section to the first optically transparent container was calculated. The results are shown in Table 2.
The optical transparency (transmittance of light) was calculated in the same manner as in Example 2 other than a condition where the incident angle was changed from 20° to 80°. The results are shown in Table 2.
The photoirradiation device according to the present invention is applicable to any field in which efficient photoirradiation is desired, and in particular, it is suitable to a photoreaction method using the photoirradiation device and a method for producing a lactam using the photoreaction method.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-208067 | Oct 2014 | JP | national |
This is the U.S. National Phase application of PCT/JP2015/076415, filed Sep. 17, 2015, which claims priority to Japanese Patent Application No. 2014-208067, filed Oct. 9, 2014, the disclosures of each of these applications being incorporated herein by reference in their entireties for all purposes.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2015/076415 | 9/17/2015 | WO | 00 |
