JP2021175567A - Flow-type photoreaction reactor and flow-type photoreaction apparatus - Google Patents

Abstract

To provide a flow-type photoreactor in which a liquid flow flowing a liquid communication part is suppressed from being disturbed by air.SOLUTION: A flow-type photoreactor 100 characterized in that a reaction case 101 for carrying out a photoreaction while supplying liquid 200 and gas 201 is provided, and inside a reaction case, there is provided a liquid circulation part 104 having at least one channel groove for circulating liquid from upstream to downstream, and a gas circulation part 105 for circulating gas, at the bottom of the upstream end of the liquid circulation portion, there is a liquid supply port 109 for supplying liquid to the channel groove, and a liquid outlet 110 for draining the liquid at the bottom of the downstream end of the liquid circulation part, and on the top and/or bottom of the reaction case, a photo irradiation part 102 that transmits light for performing a photoreaction by irradiating light to the liquid circulation part and the gas circulation part is provided, and a reaction case support table 111 for supporting the reaction case is provided.SELECTED DRAWING: Figure 1

Description

The present invention relates to a flow-type photoreaction reactor and a flow-type photoreactor that cause a photoreaction while flowing a liquid and a gas through a flow path.

Organic photochemical reactions are one of the useful means of organic synthesis, and new reactions using light have been developed and applied to large-scale industrial production. For example, ring closure reactions using molecular oxygen and conversion reactions of methyl groups on the aromatic ring to carboxylic acids have been developed, and as an example of industrial production, cyclohexane nitrosation using nitrosyl chloride to ε-caprolactam In addition, various photoreactors have been developed.
Patent Document 1 discloses a photoreactive device in which one or a plurality of structural units are combined with a combination of an optical plate holding a light emitter and a frame-shaped frame having an internal space as a constituent unit.
Patent Document 2 describes a reaction flow path for advancing a chemical reaction, a supply flow path for supplying a liquid to be reacted to a reaction flow path connected to one end of the reaction flow path, and a reaction flow path of the reaction flow path. A small reactor having an inorganic transparent substrate formed in which a discharge channel for discharging a reacted product is discharged from a reaction channel connected to the other end, and the inorganic transparent substrate has an arcuately curved shape. Is disclosed.
Patent Document 3 includes a reaction case that reacts while flowing a liquid, and a support that tilts and supports the reaction case so that the liquid flows by its own weight, and a flow path for flowing the liquid into the reaction case. A multi-channel flow reactor is disclosed, which includes a liquid flow section having a groove and a gas flow section for flowing a gas so as to be in contact with the flow path groove, and stores the liquid in the liquid supply section and supplies the liquid while overflowing. There is.

In the method of Patent Document 1, the structural unit in which the optical plate and the frame-shaped frame are combined can be disassembled, so that the internal cleaning is easy, and the internal space of the frame-shaped frame has a serpentine tube through which a heat transfer medium flows. Since it is installed, it is easy to change the amount of heat exchange, and because it is composed of parts of the same shape, it is possible to reduce manufacturing costs and maintenance parts costs. However, it is not suitable for gas-liquid reactions.
The method of Patent Document 2 states that a photoreaction can be stably and efficiently performed with a small reactor and a reactor, but when a gas is used, the reaction solution is pushed out of the reactor system by the gas. Since the residence time in the reactor is shortened, the reaction does not proceed sufficiently.
The method of Patent Document 3 secures a space between the liquid flow section and the gas flow section in order to carry out the gas-liquid photoreaction so that the liquid is not pushed out of the system of the reactor by the gas. Although it is an improved photoreactor, it has a structure in which a liquid flows from the liquid storage section by overflow and a gas supply port is provided above the liquid flow section, so the liquid flowing through the liquid flow section flows by the gas. The liquid does not flow constantly because it is disturbed.

JP-A-59-146583 Japanese Unexamined Patent Publication No. 2016-068018 JP-A-2019-209302

Therefore, an object of the present invention is suitable for a gas-liquid reaction (particularly a photoreaction), the reaction proceeds sufficiently, and the flow of the liquid flowing through the liquid flow section is suppressed from being disturbed by the gas. In addition, a reaction case that reacts while flowing a liquid and a gas, a support that tilts and supports the reaction case so that the liquid flows by its own weight, and a light irradiation unit for irradiating the upper surface of the reaction case with light. An object of the present invention is to provide a flow type photoreaction reactor and a flow type photoreactive device, which are provided with a temperature control device for controlling the temperature of the reaction case.

As a result of diligent studies to achieve the above-mentioned problems, the inventors of the present application have found that the above-mentioned problems can be solved by adopting the following means.

As a result of diligent studies to achieve the above object, the inventors of the present application have found that the above problem can be solved by adopting the following means.
The first means comprises a reaction case in which a photoreaction is carried out while supplying a liquid and a gas.
Inside the reaction case, there is a liquid flow section having at least one flow path groove for circulating the liquid from the upstream to the downstream direction, and a gas flow section for circulating the gas.
At the bottom of the upstream end of the liquid flow section, a liquid supply port for supplying the liquid to the flow path groove, and at the bottom of the downstream end of the liquid flow section, a liquid discharge port for discharging the liquid. Have,
It has a gas storage unit A installed inside the reaction case on the upstream side of the upstream end of the liquid supply port.
The upper part of the gas storage part A has a gas supply port for supplying the gas, and the upper part of the downstream end of the gas flow part has a gas discharge port for discharging the gas.
On the upper surface and / or the lower surface of the reaction case, a light irradiation unit that transmits light for irradiating the liquid flow unit and the gas flow unit with light to carry out a photoreaction is provided.
Further, the inclination of the reaction case can be freely adjusted, and the liquid supplied from the liquid supply port to the flow path groove is designed to flow from the upstream side to the downstream direction of the reaction case by its own weight. The above object is achieved by providing a flow type photoreaction reactor provided with a reaction case support base for supporting the reaction case.
The second means is that the reaction case is composed of a substrate, a lid covering the substrate, an upper holding frame that surrounds the substrate and the lid and is gripped from above, and a lower holding frame that is gripped from below.
The light irradiation unit is composed of the lid body.
The flow path groove is formed on the upper surface of the substrate or the upper surface of the lid.
The flow-type photoreactive reactor according to the first means, which has a temperature sensor installation port for installing a temperature sensor for measuring the temperature of the reaction case on a side surface of the lower holding frame parallel to the upstream to downstream directions. By providing the above purpose.
The third means achieves the above object by providing the flow type photoreactive reactor according to the first means or the second means, in which the liquid supply port is installed for each of the flow path grooves. It has been achieved.
The fourth means is the flow type according to any one of the first means to the third means, wherein the liquid flow part is installed in the downstream direction from the gas storage part A having the gas supply port. By providing a photoreactive reactor, the above objectives have been achieved.
The fifth means is the flow type photoreaction reactor according to any one of the first means to the fourth means, wherein the flow path groove is one or is separated into a plurality of lines in the lateral direction. By providing the above-mentioned purpose.
The sixth means is the flow-type photoreaction reactor according to any one of the first to fifth means, wherein the portion of the light-irradiated portion that is not irradiated with light is covered with a light reflector. By providing the above-mentioned purpose.
The seventh means is the flow type according to any one of the first to fifth means, in which a light reflector and a heat insulating material are installed in a portion of the light-irradiated portion that is not irradiated with light. By providing a photoreactive reactor, the above objectives have been achieved.
The eighth means includes the flow type photoreaction reactor, the light source, the upper part of the light irradiation unit provided on the upper surface of the reaction case of the flow type photoreaction reactor, and the upper part of the light irradiation unit according to any one of the first means to the seventh means. / Or a light source support base on which the light source is installed under the light irradiation unit on the lower surface of the reaction case, a liquid composition discharged from the liquid discharge port, and a gas composition discharged from the gas discharge port. The above-mentioned object was achieved by providing a flow-type photoreactive apparatus comprising a storage tank for storing the above-mentioned storage tank, further comprising a medium-flowing unit for circulating a medium for controlling the temperature of the above-mentioned reaction case. It is a thing.
The ninth means is that the light source support can be moved in the vertical and parallel directions with respect to the plane on which the light of the light irradiation unit is irradiated, and the irradiation angle of the light source can be changed. The above object is achieved by providing the flow type photoreactor according to the means.
The tenth means is connected to the downstream end portion of the medium distribution section, and is connected to the medium supply port for supplying the medium to the medium distribution section and the upstream end portion of the medium distribution section. The above object has been achieved by providing the flow type photoreactor according to the eighth means or the ninth means, which has a medium discharge port for discharging the medium flowing through the medium distribution unit. be.
The eleventh means is that the storage tank has a storage tank liquid supply port, a storage tank gas supply port, a storage tank gas outlet, and a storage tank liquid outlet in the lower part near the upper part.
At the gas outlet of the storage tank, a pressurizing device for allowing the inside of the reaction case to be pressurized and performing a photoreaction in a normal pressure system or a pressurizing system, and a gas treatment device for treating the gas composition. The above object is achieved by providing the flow type photoreactor according to any one of the eighth means to the tenth means to which the gas is connected.
In the twelfth means, a second flow type photoreaction reactor having a structure similar to that of the flow type photoreaction reactor is installed between the flow type photoreaction reactor and the storage tank.
Using the flow-type photoreaction reactor and the light source, the liquid composition and the gas composition obtained by carrying out a photoreaction are supplied to the second flow-type photoreaction reactor, and the second flow. The second photoreaction is carried out in a normal pressure system or a pressurized system using a second light source installed in the photoreaction reactor.
The gas supply port of the second flow type photoreaction reactor is connected to the gas discharge port of the flow type photoreaction reactor.
The flow-type light according to any one of the eighth means to the eleventh means, wherein the liquid supply port of the second flow-type photoreaction reactor is connected to the liquid discharge port of the flow-type photoreaction reactor. By providing a reactor, the above object has been achieved.
The thirteenth means comprises a reaction case in which a photoreaction is carried out while supplying a liquid and a gas.
Inside the reaction case, a liquid flow section for circulating the liquid from the upstream to the downstream direction and a gas flow section for circulating the gas are provided.
The upstream end of the gas flow section has a gas supply port for supplying the gas, and the downstream end of the gas flow section has a gas discharge port for discharging the gas.
The upstream end of the liquid flow section has a liquid supply port for supplying the liquid, and the downstream end of the liquid flow section has a liquid discharge port for discharging the liquid.
On the upper surface and / or the lower surface and / or the side surface of the reaction case, a light irradiation unit that transmits light for irradiating the liquid flow unit and the gas flow unit with light to carry out a photoreaction is provided.
Further, the inclination of the reaction case can be freely adjusted, and the liquid supplied from the liquid supply port to the liquid flow section is designed to flow from the upstream to the downstream of the reaction case by its own weight. A single-tube flow-type photoreaction reactor provided with a reaction case support base for supporting the reaction case is installed between the flow-type photoreaction reactor and the storage tank.
Using the flow-type photoreaction reactor and the light source, the liquid composition and the gas composition obtained by carrying out a photoreaction are supplied to the single-tube flow-type photoreaction reactor, and the single tube type photoreaction reactor is supplied. To carry out further photoreactions in atmospheric or pressurized systems using a separate light source installed in a tube-type flow photoreactor.
The gas supply port of the single-tube flow-type photoreaction reactor is connected to the gas discharge port of the flow-type photoreaction reactor.
Any of the eighth to eleventh means, characterized in that the liquid supply port of the single-tube flow-type photoreaction reactor is connected to the liquid discharge port of the flow-type photoreaction reactor. The above object has been achieved by providing the flow type photoreactive device described in the above.

According to the present invention, it is suitable for a gas-liquid reaction (particularly a photoreaction), the reaction proceeds sufficiently, and the flow of the liquid flowing through the liquid flow section is suppressed from being disturbed by the gas. A reaction case that reacts while flowing a liquid and a gas, a support that tilts and supports the reaction case so that the liquid flows by its own weight, a light irradiation unit for irradiating the upper surface of the reaction case with light, and the above. A flow type photoreactor and a flow type photoreactive device can be provided, which include a temperature control device for controlling the temperature of the reaction case.

FIG. 1 is a schematic view showing an embodiment of a flow type photoreaction reactor. FIG. 2 is a schematic view showing an embodiment of a liquid flow unit having a flow path groove. FIG. 3 is a schematic diagram showing an embodiment of a light source and a flow type photoreaction reactor. FIG. 4 is a schematic view showing an embodiment of the reaction case. FIG. 5 is a schematic view showing a cross section of a reaction case of a conventional overflow type photoreaction reactor. FIG. 6 is a schematic view showing an embodiment of a flow type photoreaction reactor and a light source. FIG. 7 is a schematic diagram showing an embodiment of a reaction system including a flow type photoreactor. FIG. 8 is a schematic view showing an embodiment of the medium distribution unit. FIG. 9 is a schematic diagram showing an embodiment of a reaction system including two flow type photochemical reactors.

Hereinafter, the present invention will be described in detail.
A first embodiment of the flow type photoreaction reactor 100 shown in FIG. 1 will be specifically described. The reaction case 101 in which the liquid 200 and the gas 201 are reacted while flowing has a light irradiation unit 102 that transmits light for irradiating the upper surface with light to carry out a photoreaction. The light emitted from the light source 302 is applied to the liquid 200 and the gas 201 through the light irradiation unit 102. The light irradiation unit 102 may be provided on the lower surface of the reaction case 101.

Inside the reaction case 101, a liquid flow unit 104 for flowing the liquid 200 and a gas flow unit 105 for flowing the gas 201 are provided. As shown in FIG. 2, the liquid flow section 104 has a flow path groove 103, and the liquid 200 flows through the flow path groove 103. The number of the flow path grooves 103 may be at least one.

As shown in FIG. 1, the reaction case 101 has a liquid supply port 109 that supplies the liquid 200 to the flow path groove 103 from below (bottom) of the upstream end of the liquid flow section 104, and the liquid. It has a liquid discharge port 110 for discharging the liquid composition 202 from the lower part (bottom) of the downstream end of the distribution part. The gas storage unit 106A is located upstream of the upstream end of the liquid supply port 109, the gas storage unit 106B is located downstream of the downstream end of the liquid flow unit 104, and the gas 201 is placed above the gas storage unit 106A. It has a gas supply port 107 for supplying and a gas discharge port 108 for discharging the gas composition 203 above the gas storage unit 106B. The liquid flow unit 104 is installed downstream of the gas storage unit 106A having the gas supply port 107.
Further, the gas 201 may be supplied from the gas discharge port 108 and discharged from the gas supply port 107.

At the lower part of the reaction case 101, preferably, a medium distribution unit 304 for distributing the medium 204 for controlling the temperature of the reaction case 101 is provided, and is connected to the downstream end of the medium distribution unit 304. , A medium supply port 307 that supplies the medium 204 to the medium distribution section 304, and a medium discharge port that is connected to the upstream end of the medium distribution section and discharges the medium 204 that has flowed through the medium distribution section. 308 is provided.

The reaction case 101 is supported by being inclined by the reaction case support base 111. In the reaction case 101, the “upstream” refers to the one having a higher height of the reaction case 101 tilted by the reaction case support table 111. The "downstream" refers to the one having a lower height of the reaction case 101 tilted by the reaction case support base 111.

FIG. 3 schematically shows a light source 302 and a flow type photoreaction reactor 100. As shown in FIG. 3, the inclination angle of the reaction case 101 can be freely changed by adjusting the height of the reaction case support base 111. In FIG. 3, the right side is “upstream” and the left side is “downstream”. The reaction case support base 111 has an upstream vertical frame 122 that supports the upstream end of the reaction case 101, and a downstream vertical frame 123 that supports the downstream end of the reaction case 101.
The upstream vertical frame 122 has a large number of through holes 124 arranged in the vertical direction from the upper end. As a result, the reaction case support base 111 can increase the inclination angle of the reaction case 101 by fixing the reaction case 101 using the through hole 124 at the high position, and uses the through hole 124 at the low position. By fixing the reaction case 101, the inclination angle of the reaction case 101 can be reduced.
The liquid 200 supplied from the liquid supply port 109 to the flow path groove 103 flows from the upstream to the downstream of the reaction case 101 by its own weight.
In FIG. 3, 303 is a light source support and 306 is a fixing bracket. These will be described later.

The inclination angle of the reaction case is preferably 1 to 70 degrees, more preferably 2 to 50 degrees, and particularly preferably 3 to 30 degrees with respect to the horizontal plane. If the inclination angle of the reaction case is larger than 70 degrees, the residence time of the liquid flowing in the liquid flow section becomes extremely short, which may cause a decrease in the yield of the photoreaction, which is not preferable. Further, if the inclination angle of the reaction case is smaller than 1 degree, the moving speed of the liquid introduced into the flow path groove from the liquid supply port in the downstream direction becomes slow, so that the liquid is upstream from the liquid supply port. It is not preferable because it may flow in the direction and accumulate in the gas storage unit A.

The liquid 200 flows through the liquid flow section 104, the gas 201 flows through the gas flow section 105, and is between the liquid 200 and the gas 201 by the light emitted from the light source 302 through the light irradiation section 102. The photoreaction proceeds at the above, and the liquid composition 202 and the gas composition 203 are obtained.

The gas supply port 107 for supplying the gas 201 to the gas storage unit 106A is installed above the gas storage unit 106A. When the gas supply port 107 is connected to the gas storage unit 106A at the upstream end of the gas flow unit 105, the gas 201 supplied from the gas supply port 107 is preferably indicated by an arrow in FIG. As described above, the introduction pressure is dispersed at the bottom of the gas storage unit 106A. Here, the gas 201 supplied from the gas supply port 107 may come into contact with the liquid 200 in a state where the introduction pressure is dispersed in the gas storage unit 106A, and the gas supplied from the gas supply port 107 may be in contact with the liquid 200. 201 may be configured to correspond to the side surface or the upper portion of the gas storage unit 106A.

In the flow type photochlorination apparatus 100, in order to relax the blowing pressure of the gas 201 blown from the gas supply port 107 in the gas storage section 106A installed in the gas flow section 105, the gas 201 Even if the blowing pressure is set high, the turbulence of the flow of the liquid 200 flowing through the liquid flow section 104 provided on the downstream side is suppressed. Therefore, a stable reaction can be performed.
The flow velocity of the gas supplied from the gas supply port to the gas flow section can be, for example, 0.3 to 60.0 cm / sec, preferably 10.0 to 60.0 cm / sec. can.

The gas storage section B is optional, but if the downstream gas storage section B is not provided, there is a liquid discharge port near the gas discharge port, but due to the pressure of the supplied gas, liquid and gas from the liquid discharge port. May be extruded and discharged into the storage tank. Preferably, by installing the gas storage unit B to reduce the pressure of the supplied gas, the discharge rate of the liquid and the gas to the storage tank can be reduced, and the reaction can be carried out more effectively. As shown in FIG. 1, when the gas storage section B (106B) is provided, the gas discharge port 108 is preferably provided above the gas storage section B (106B).

Regarding the reaction using the flow reactor, in the conventional example, the liquid and the gas are simultaneously flowed from the upstream, which simplifies the operation. However, since the contact time between the liquid and the gas is short in the upstream, the reaction may be delayed because the gas has not yet dissolved in the liquid. In addition, due to the high concentration of raw materials and gas in the liquid, side reactions may occur. In particular, in a sequential reaction such as a chlorination reaction, a monochloro compound and a monochloro compound react to produce a dichloro compound and a trichloro compound as a by-product.
For this side reaction, when the liquid is flowed from the upstream and the gas is flowed from the downstream, it is preferable to irradiate the light from the downstream to the upstream. Since the gas is flowing on the liquid, the light is irradiated in a state where the gas is absorbed while the liquid is flowing downstream, so that the reaction may be accelerated, and since the reaction is rapid, the side reaction may be suppressed.

The second means will be described with reference to FIG.
The reaction case 101 includes a substrate 112, a lid 113 that covers the substrate 112, an upper holding frame 114 that surrounds and grips the substrate 112 and the lid 113 from above, and a lower holding frame 115 that surrounds and grips the substrate 112 from below. It is composed of. At least one or more flow path grooves 103 are formed on the upper surface of the substrate 112 as a liquid flow section 104 for flowing the liquid 200. The lid 113 serves as a light irradiation unit 102.
The substrate 112 and the lid 113 are hermetically sealed with a sufficient space between them, so that the liquid 200 is not extruded from the reaction case 101 by the pressure of the gas 201. It has become.

The substrate 112 and the lid 113 are preferably materials that are resistant to the liquid 200 and the gas 201 used in the reaction and are inert.
The substrate 112 needs to have enough strength to form the flow path groove 103, and is made of glass, Tempax (registered trademark) glass, Pyrex (registered trademark) glass, Neoceram (registered trademark) glass, quartz glass, fluororesin, and the like. Stainless steel, Hasteroy (registered trademark) steel and the like can be adopted, but Pyrex (registered trademark) glass, quartz glass, stainless steel and Hasteroy (registered trademark) steel are particularly preferable.
The lid 113 can be made of a material that transmits light, and uses glass, Tempax (registered trademark) glass, Pyrex (registered trademark) glass, Neoceram (registered trademark) glass, quartz glass, fluororesin, and the like. However, Pyrex (registered trademark) glass and quartz glass are particularly preferable.

A method of polishing the substrate 112 and the lid 113 to ensure planar smoothness and stacking the substrate 112 and the lid 113 in order to prevent liquid and gas from leaking from the contact surface between the substrate 112 and the lid 113. A method of sandwiching a flexible packing between the lid 113, a method of forming a groove in the substrate 112 and the lid 113, and an O-ring being fitted in the groove can be adopted. It is preferable to sandwich a flexible packing on the surface in contact between the upper holding frame 114 and the lid 113 so that the lid 113 does not crack.
The packing and O-ring are preferably made of an inert material that is resistant to liquids and gases, and is preferably silicone rubber, fluororubber, chloroprene rubber, nitrile rubber, ethylene propylene rubber, tetrafluoroethylene rubber, styrene butadiene rubber, ethylene propylene rubber, etc. A perfluoro elastomer or the like can be used, and it may be appropriately selected from the properties of the liquid 200 and the gas 201 to be used.

The holding frame is composed of the upper holding frame 114 and the lower holding frame 115. The lower holding frame 115 houses the substrate 112 and the lid 113, and the upper holding frame 114 holds the lid 113. It serves to prevent the liquid 200 and the gas 201 from leaking from the reaction case 101 while being suppressed from above.
A plurality of temperature sensor installation ports 116 into which temperature sensors can be inserted are provided on the side surface of the lower holding frame 115 parallel to the upstream to downstream directions, so that the temperature of the reaction case 101 and the temperature rise due to the heat of reaction can be increased. Can be measured.
The material of the holding frame is not particularly limited, but a material having strength for holding the substrate 112 and the lid 113 is preferable, and in particular, metal (steel, stainless steel, aluminum), resin, or the like can be adopted.

In the light irradiation unit 102 provided in the reaction case 101, the longitudinal dimension is preferably 1 to 300 cm, more preferably 5 to 150 cm, and particularly preferably 10 to 100 cm. The lateral dimension is preferably 10 to 70 cm, more preferably 15 to 30 cm, and particularly preferably 15 to 20 cm. If the longitudinal dimension of the light irradiation unit 102 is less than 1 cm and the lateral dimension is less than 10 cm, the light irradiation time for the liquid 200 and the gas 201 flowing in the reaction case 101 becomes short, which causes a decrease in yield.
In the present specification, the flow direction of the liquid 200 from the upstream to the downstream is referred to as a "longitudinal direction", and a direction orthogonal to the longitudinal direction is referred to as a "horizontal direction".

The number of the flow path grooves in the liquid flow section in the reaction case is preferably 1 to 50, more preferably 1 to 20, and particularly preferably 1 to 10. The width of each flow path groove is preferably 1 to 50 mm, more preferably 5 to 30 mm, and particularly preferably 10 to 15 mm. The depth of each flow path groove is preferably 0.1 to 30 mm, more preferably 0.5 to 10 mm, and particularly preferably 1 to 5 mm. If the width of each flow path groove is larger than 50 mm and the depth of each flow path groove is deeper than 30 mm, the liquid flowing in the flow path groove cannot come into contact with the gas, and the reaction remains unreacted. It may be discharged out of the case, which may cause a decrease in yield.
The height of the gas flow section in the reaction case is preferably 1 to 50 mm, more preferably 1 to 20 mm, and particularly preferably 1 to 10 mm. If the height of the gas flow section is larger than 50 mm, the liquid flowing above the gas flow section cannot come into contact with the gas, and the gas may be discharged out of the reaction case without reacting. It may be economically disadvantageous.
The volume of the gas storage portions A and B in the reaction case is preferably 50% or less, more preferably 30% or less, based on the total space volume in the reaction case. When the volumes of the gas storage portions A and B are larger than 50% with respect to the total space volume in the reaction case, the longitudinal dimension of the liquid flow portion becomes short, and the liquid flowing in the flow path groove of the liquid. Since the residence time is shortened, the liquid may be discharged out of the reaction case without reacting, which may cause a decrease in yield. Here, the dimensions of the gas storage unit A and the gas storage unit B may be the same or different from each other.

The third means will be described with reference to FIGS. 1, 2 and 5.
In the flow type photoreaction reactor 400 described in Japanese Patent Application Laid-Open No. 2019-209302 filed by the inventors of the present application, as shown in FIG. 5, a liquid storage unit 402 is provided at the upstream end of the liquid flow unit 401. The liquid 404 is supplied from the liquid supply port 403 installed below the liquid storage unit 402 and simultaneously overflows to the upper ends of a plurality of flow path grooves (not shown) to supply the liquid 404 to the flow path groove. Then, gas is supplied from the gas supply port 405 provided above the liquid flow unit 401 to carry out a photoreaction.
In this method, when the flow rate of the gas is increased, the liquid flowing through the flow path groove directly below the gas supply port 405 is pushed away by the pressure of the supplied gas and moves to the flow path groove in the lateral direction, so that the liquid May not flow evenly in the flow path groove.
As shown in FIG. 1, by supplying the gas 201 from the gas supply port 107 provided above the gas storage unit 106A, the liquid 200 may be pushed away by the pressure of the supplied gas 201. It is suppressed, and as shown in FIG. 2, by installing the liquid supply port 109 below the flow path groove 103, the liquid 200 flowing through the flow path groove 103 can be evenly flowed.
The reaction case in which the liquid is supplied by overflow as in the above-mentioned conventional example is easy to process and the manufacturing cost is low, but the liquid cannot flow evenly in the flow path groove, so that the photoreaction cannot be efficiently carried out. There is a fear. Preferably, if the liquid supply port 109 is provided for each of the flow path grooves 103, the manufacturing cost of the reaction case 101 is high, but the photoreaction can be stably carried out, which is preferable.

The fourth means will be described with reference to FIG.
As described above, if the gas 201 is supplied onto the flow path groove 103, a problem occurs. Therefore, as shown in FIG. 2, by supplying the gas 201 to the gas storage unit 106A, the flow path groove The liquid 200 flowing through the 103 is preferable because it is not affected by the gas 201, flows evenly in the flow path groove 103, and can efficiently carry out a photoreaction.

Regarding the fifth means, when the flow path groove 103 is one, the liquid 200 and the gas 201 do not diffuse in the lateral direction, and the photoreaction can be carried out with a small amount of the liquid 200 and the gas 201. ..
When the flow path grooves 103 are separated into a plurality of channels in the lateral direction as shown in FIG. 2, the production amount of the photoreaction product can be increased.

The sixth means will be described with reference to FIG.
FIG. 6 shows a flow type photoreaction reactor 100 and a light source 302 which are one embodiment of the sixth means. The flow type photoreaction reactor 100 is as described with reference to FIG. 1, but in FIG. 6, the reaction case support base 111, the light irradiation unit 102, and the liquid flow unit 104 are omitted.
As shown in FIG. 6, the light reaction can be efficiently carried out by covering the light irradiation unit 102 with the light reflector 117.
When the light reflecting plate 117 is not installed, the light irradiated to the light irradiation unit 102 passes through the liquid 200 flowing through the flow path groove 103, and is preferably a metal housing that is in contact with the flow path groove 103. The light reflected by the surface escapes from the light irradiation unit 102 to the outside of the reaction case 101.
For example, as shown in FIG. 6, when the light irradiation unit 102 is irradiated with light, the light irradiation unit 102 that is not irradiated with light is covered with the light reflection plate 117, so that the light irradiation unit 102 The transmitted light passes through the liquid 200 flowing through the flow path groove 103 and is reflected by a metal housing surface or the like grounded on the substrate 111, and the reflected light reaches the upper surface of the light irradiation unit 102. ..
The light that reaches the upper surface of the counterlight irradiation unit 102 is reflected by the installed light reflecting plate 117 and again passes through the liquid 200 flowing through the flow path groove 103, so that the light efficiency becomes high and the light reaction efficiency becomes high. The material of the light reflector used in the present invention is not particularly limited, but is limited to a glass mirror, a vinyl chloride reflector, an ethylene carbonate reflector, an aluminum foil, and a metal thin film having a metallic luster (iron, Aluminum, tin, silver foil) can be used.

Regarding the seventh means, in order to increase the reaction rate of the photoreaction, the liquid 200 is often heated and carried out at a temperature of room temperature or higher. Since the surface of the light irradiation unit 102 is in contact with the atmosphere at room temperature, the temperature of the reaction case 101 may drop due to heat dissipation from the surface of the light irradiation unit 102.
As shown in FIG. 6, by installing the heat insulating material 118 on the surface of the light irradiation unit 102 that is not irradiated with light, heat dissipation from the reaction case 101 can be reduced, so that a temperature drop can be prevented and light can be prevented. The reaction temperature of the reaction can be controlled more precisely. Further, the light reflecting plate 117 may be attached to the heat insulating material 118 for use.
The material of the heat insulating material used in the present invention is not particularly limited, but is limited to fiber-based heat insulating materials such as glass wool, rock wool and cellulose fiber, foamed plastic heat insulating materials such as polystyrene foam, polyethylene foam, phenol foam and urethane foam, and wood. Etc. can be used, and a heat insulating material that is resistant to the reaction temperature of the photoreaction may be used as appropriate.

An embodiment of the flow type photoreactive device 301 shown in FIG. 7 will be specifically described with respect to the eighth means.
The flow-type photoreactor 301 includes the flow-type photoreaction reactor 100, a light source 302, and a light source support 303 (not shown, see FIG. 3) on which the light source 302 is installed. The flow-type photoreaction reactor 100 has the reaction case 101, a medium circulation unit 304 for circulating a medium 204 for adjusting the temperature of the reaction case 101, and a liquid composition 202 produced by a photoreaction. And a storage tank 305 for storing the above gas composition 203.
In this reaction system, first, the liquid 200 in the liquid container 121 is introduced into the reaction case 101 from the liquid supply port 109 by the pump 120, and the gas 201 in the gas container 125 is introduced by the float meter 119. While being weighed, it is introduced into the reaction case 101 from the gas supply port 107. On the other hand, light is irradiated from the light source 302 toward the liquid flow section (not shown) in the reaction case 101. Further, the temperature of the reaction case 101 is controlled by the medium 204 that circulates inside by the medium circulation mechanism. In the medium circulation mechanism, the medium 204 (for example, water) having an appropriate temperature in the medium container 126 is supplied from the medium supply port 307 by a pump 127, and the medium 204 circulates in the medium circulation unit 304. It is designed to be returned from the medium discharge port 308. The temperature can be monitored by an appropriately provided temperature measuring point (not shown). Then, in the reaction case 101, the liquid 200 and the gas 201 cause a gas-liquid reaction which is a photoreaction. The liquid composition 202 produced by the reaction is discharged from the liquid discharge port 110 and stored in the storage tank 305 from the storage tank liquid supply port 310.

The ninth means will be described with reference to FIG.
The light source support base 303 is fixed to the upper holding frame 114 (not shown, see FIG. 4) of the reaction case 101 with a fixing metal fitting 306, and has a structure in which the position of the fixing metal fitting 306 can be adjusted. By moving the light source support 303 in the direction perpendicular to the plane (light irradiation surface) irradiated with the light of the light irradiation unit 102 (not shown, see FIG. 4) of the reaction case 101, the light source 302 The intensity of light from can be adjusted. Further, by moving in the direction parallel to the light irradiation surface, the light of the light source 302 can be irradiated to the optimum position of the light irradiation unit 102. Further, since the irradiation angle of the light source 302 with respect to the light irradiation unit 102 can be changed, the light reaction can be efficiently carried out.

The light irradiation angle of the light source 302 used in the present invention is preferably 10 to 90 degrees with respect to the light irradiation surface of the light irradiation unit 102 toward the upstream side in the longitudinal direction of the reaction case 101, preferably 10 to 10 degrees. 60 degrees is more preferable, and 10 to 30 degrees is particularly preferable.
Further, the light irradiation direction of the light source 302 may be directed to the downstream side in the longitudinal direction of the reaction case 101, and the light irradiation angle of the light source 302 in that case is relative to the light irradiation surface of the light irradiation unit 102. 10 to 90 degrees is preferable, 10 to 60 degrees is more preferable, and 10 to 30 degrees is particularly preferable. If the light irradiation angle of the light source 302 is smaller than 10 degrees with respect to the light irradiation surface of the light irradiation unit 102, the liquid 200 and the gas 201 flowing in the reaction case 101 cannot be irradiated with light, and light This is not preferable because it may reduce the yield of the reaction.

The light source used in the present invention is not particularly limited, but a lamp having a wavelength effective for the desired photoreaction may be appropriately used. For example, lamps such as ultraviolet lamps, visible light lamps, infrared lamps, fluorescent lamps, black lights, LED lights, mercury lamps, and xenon lamps can be used.
The lighting method of the light source is not particularly limited, but a starter type, a rabbit start type, an inverter type, a light source electronic ballast, and the like can be used.

Regarding the tenth means, the medium supply port 307 for supplying the medium 204 located at the downstream end of the medium distribution unit 304 and the medium distribution unit 304 located at the upstream end flow from the downstream to the upstream direction. The medium discharge port 308 for discharging the medium 204 is connected (see FIG. 7).
FIG. 8 shows another form of the medium flow section 304, which has a medium flow path 309 inside the medium flow section 304, and the medium flow path 309 is bent into a U shape or the like. In this case, the medium supply port 307 and the medium discharge port 308 can be installed below either the upstream end portion or the downstream end portion of the medium distribution section 304 (that is, the lower surface of the reaction case 101). In this case, since the length of the medium flow passage 309 can be increased, the heat of the medium 204 can be used more effectively.
In this way, the temperature of the reaction case 101 can be controlled and the photoreaction can be carried out at the optimum reaction temperature by flowing the medium 204 whose temperature has been adjusted through the medium distribution unit 304.

The eleventh means will be described with reference to FIG.
The storage tank liquid supply port 310, the storage tank gas supply port 311 and the storage tank gas outlet 312 are provided in the vicinity of the upper part of the storage tank 305, and the storage tank liquid outlet 313 is provided in the lower part of the storage tank 305. The liquid discharge port 110 and the gas discharge port 108 of 100 are connected to the storage tank liquid supply port 310 and the storage tank gas supply port 311, respectively, and the liquid composition 202 discharged from the liquid discharge port 110 and the liquid composition 202. The gas composition 203 discharged from the gas discharge port 108 can be stored in the storage tank 305.
A pipe to which a back pressure device 314 as a pressurizing device for applying pressure in the reaction case 101 is connected to the storage tank gas outlet 312, and the pressure in the storage tank 305 is the back pressure device. When the pressure exceeds the pressure set in 314, the gas composition 203 is discharged from the storage tank 305, so that the pressure in the storage tank 305 can be maintained at the set pressure, and a photoreaction is carried out in the pressure system. can do. The discharged gas composition 203 is sent to the gas processing apparatus 315 for processing and detoxification. Further, the liquid composition 202 stored in the storage tank 305 can be extracted from the liquid composition outlet 313.
As described above, the gas composition 203 and the liquid composition 202 stored in the storage tank 305 can be continuously subjected to a photoreaction while being appropriately extracted from the storage tank 305.

The twelfth means will be described with reference to FIG.
When carrying out a photoreaction using the flow-type photoreactor 301 and the light source 302, the same configuration and function as the flow-type photoreaction reactor 100 is performed between the flow-type photoreaction reactor 100 and the storage tank 305. By connecting the second flow type photoreaction reactor 316 having the above, the efficiency of the photoreaction can be increased.
In this reaction system, first, the liquid 200 in the liquid container 121 is introduced into the reaction case 101 from the liquid supply port 109 by the pump 120, and the gas 201 in the gas container 125 is introduced. It is introduced into the reaction case 101 from the gas supply port 107 while being measured by the float meter 119. On the other hand, light is irradiated from the light source 302 toward the liquid flow section (not shown) in the reaction case 101. Further, the temperature of the reaction case 101 is controlled by the medium 204 that circulates inside by the medium circulation mechanism. In the medium circulation mechanism, the medium 204 (for example, water) having an appropriate temperature in the medium container 126 is supplied from the medium supply port 307 by the pump 127, and the medium circulates in the medium circulation unit 304. , It is designed to be returned from the medium discharge port 308. The temperature can be monitored by an appropriately provided temperature measuring point (not shown). Then, in the reaction case 101, the liquid 200 and the gas 201 cause a gas-liquid reaction which is a photoreaction. The liquid composition 202 produced by the reaction is discharged from the liquid discharge port 110, and the gas composition 203 is discharged from the gas discharge port 108.

The liquid discharge port 110 and the gas discharge port 108 of the flow type photoreaction reactor 100, and the second liquid supply port 317 and the second gas supply port 318 of the second flow type photoreaction reactor 316 are connected, respectively. The liquid composition 202 and the gas composition 203 discharged from the flow-type photoreaction reactor 100 can be supplied to the second flow-type photoreaction reactor 316.
The liquid composition 202 and the gas composition 203 supplied to the second flow type photoreaction reactor 316 are the second liquid flow section (not shown, the liquid of FIG. 1) in the second flow type photoreaction reactor 316. Flowing through the flow section 104) and the second gas flow section (not shown, the same as the gas flow section 105 in FIG. 1), and the light irradiation section (not shown, FIG. 1) of the second flow type photoreaction reactor 316. It can be expected that the light reaction further progresses due to the light emitted from the second light source 321 installed in the light irradiation unit 102).
The second flow type photoreaction reactor 316 has a second medium flow path 322, and the second medium 324 supplied from the second medium supply port 323 flows through the second medium flow path 322 from the downstream to the upstream direction. , The second flow type photoreaction reactor 316 can be adjusted to a set temperature and the photoreaction can be carried out by flowing it through the second medium discharge port 325.

Further, the medium discharge port 308 connected to the medium flow path 304 of the flow type photoreaction reactor 100 and the second medium supply port 323 of the second flow type photoreaction reactor 316 are connected to each other to connect the medium 204. Can be flowed through the second medium flow section 322 of the second flow type photoreaction reactor 316 to control the temperature of the second reaction case 326, and FIG. 9 shows this aspect. In this case, the second medium discharge port 325 and the medium supply port 307 are connected, and the pump 127 connected to the medium container 126 is interposed between them.
If the second liquid discharge port 327 and the second gas discharge port 328 of the second flow type photoreaction reactor 316 are connected to the storage tank liquid supply port 310 and the storage tank gas supply port 311 of the storage tank 305, respectively. The second liquid composition 205 and the second gas composition 206 discharged from the second flow type photoreaction reactor 316 can be stored in the storage tank 305.
A pipe to which a back pressure device 314 for applying pressure is attached to the inside of the reaction case 101 and the inside of the second reaction case 326 is connected to the storage tank gas outlet 312, and the pressure in the storage tank 305 is the above. When the pressure exceeds the pressure set by the back pressure device 314, the second gas composition 206 is discharged from the storage tank 305, so that the pressure in the storage tank 305 can be maintained at the installed pressure. The discharged second gas composition 206 is sent to the gas processing apparatus 315 for processing and detoxification. Further, the second liquid composition 205 stored in the storage tank 305 can be extracted from the liquid composition outlet 313.
In this way, the photoreaction can be continuously carried out while appropriately extracting the second gas composition 206 and the second liquid composition 205 stored in the storage tank 305 from the storage tank 305.

In the twelfth means, as described above, by connecting a plurality of flow-type photoreactor reactors of the present invention in series, it is possible to carry out quantitatively satisfactory industrial production. When the gas composition after the reaction of the first flow-type photoreaction reactor of the present invention is introduced into the second flow-type photoreaction reactor of the present invention, for example, when a photochlorination reaction is carried out, One Cl of Cl ₂ (chlorine) becomes a chlorine radical and chlorinated the raw material, and the other Cl deprives the raw material of hydrogen and becomes hydrogen chloride (HCl), so the volume of the gas does not change and two units The gas supply pressure to the eyes is the same as that of the first unit. Therefore, since the second flow type photoreaction reactor also has a gas storage unit, the reaction can be carried out more efficiently.

In the thirteenth means, similarly to the twelfth means, the photoreaction using the flow type photoreactor 301 and the light source 302 shown in FIG. 9 is carried out, but with the flow type photoreaction reactor 100. A single-tube flow-type photoreactive reactor is connected between the storage tanks 305. In this case as well, the efficiency of the photoreaction can be increased.

The single-tube flow-type photoreaction reactor is provided with a reaction case for carrying out a photoreaction while supplying a liquid and a gas, and a liquid flow for circulating the liquid from upstream to downstream inside the reaction case. It has a section and a gas flow section for circulating the gas. Then, the upstream end of the gas flow section has a gas supply port for supplying the gas, and the downstream end of the gas flow section has a gas discharge port for discharging the gas. The upstream end of the liquid flow section has a liquid supply port for supplying the liquid, and the downstream end of the liquid flow section has a liquid discharge port for discharging the liquid. The upper surface and / or the lower surface and / or the side surface of the reaction case has a light irradiation unit that transmits light for irradiating the liquid flow unit and the gas flow unit with light to carry out a photoreaction.
Further, the inclination of the reaction case can be freely adjusted, and the liquid supplied from the liquid supply port to the liquid flow section is designed to flow from the upstream side to the downstream direction of the reaction case by its own weight. , A reaction case support stand for supporting the reaction case is provided.

In the thirteenth means, the liquid discharge port 110 and the gas discharge port 108 of the flow type photoreaction reactor 100, and the liquid supply port and the gas supply port of the single-tube type flow type photoreaction reactor are provided. By connecting them to each other, the liquid composition 202 and the gas composition 203 discharged from the flow-type photoreaction reactor 100 are supplied to the single-tube flow-type photoreaction reactor.
The liquid composition 202 and the gas composition 203 supplied to the single-tube flow-type photoreaction reactor flow through the liquid flow section and the gas flow section in the single-tube flow-type photoreaction reactor. , It can be expected that the light reaction further progresses by the light emitted from the light source installed in the light irradiation section of the single-tube flow type photoreaction reactor.
The single-tube flow-type photoreaction reactor preferably has a medium flow path for adjusting the temperatures of the liquid flow section and the gas flow path section of the reaction case to a set temperature. It is preferable that the medium flow path is provided with a medium supply port and a medium discharge port. The medium supplied from the medium supply port flows from the downstream to the upstream direction through the medium flow path and flows to the medium discharge port, so that the single-tube flow-type photoreaction reactor is adjusted to a set temperature. , It is preferable to carry out a photoreaction.

Further, the medium discharge port 308 connected to the medium flow path 304 of the flow type photoreaction reactor 100 and the medium supply port of the single tube type flow type photoreaction reactor are connected to connect the medium 204 to the single tube type photoreaction reactor 100. It is also possible to control the temperature of the reaction case by flowing it through the medium flow section of the tube-type flow-type photoreaction reactor. In this case, the medium discharge port of the single-tube flow type photoreaction reactor and the medium supply port 307 are connected, and a pump 127 (see FIG. 9) connected to the medium container 126 is interposed between them. Is preferable.

The method of storing the liquid composition and the gas composition discharged from the liquid discharge port and the gas discharge port of the single-tube flow type photoreaction reactor in the storage tank and the subsequent treatment have been described in the twelfth means. The same method as in can be applied. Further, in the thirteenth means, the same method and means as described in the twelfth means can be applied to the method and means for adjusting the reaction pressure.
In this way, the photoreaction can be continuously carried out while appropriately extracting the second gas composition 206 and the second liquid composition 205 stored in the storage tank 305 from the storage tank 305.

In the thirteenth means, a two-stage reaction can be carried out at low cost by using a single-tube flow-type photoreaction reactor. In a single-tube flow-type photoreaction reactor, since there is only one flow path, the liquid is not expelled to another flow path even if it does not have a gas storage part. Further, since the liquid that has passed through the flow-type photoreaction reactor of the present invention first contains a large amount of gas, the reaction can be promoted even if a single-tube flow-type photoreaction reactor is used.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the Examples.

Using a flow-type photoreaction reactor having five flow path grooves and an LED-UV lamp (wavelength = 365 nm, output = 300 W), a photoreaction of ethylene carbonate with chlorine gas was carried out at normal pressure.
The angle of the support base is adjusted so that the angle of the reaction case is tilted at 5 degrees with respect to the horizontal plane, and 90 ° C. water is circulated in the medium flow section provided on the lower surface of the reaction case to obtain the temperature of the holding frame. A thermocouple thermometer was installed at the sensor installation port to measure the temperature of the reaction case.
The length of the reaction case in the longitudinal direction is 64 cm, the length in the lateral direction is 10 cm, the length in the longitudinal direction of the light irradiation section and the gas flow section is 62 cm, the length in the lateral direction is 8 cm, and the length in the longitudinal direction of the liquid flow section. The length was 60 cm, the length in the lateral direction was 8 cm, and the length of the space created by the substrate and the lid was 0.5 cm.
A gas storage unit A was installed on the upstream side of the liquid flow unit, and a gas storage unit B was installed on the downstream side of the liquid flow unit. The total volume of the gas reservoir was 5.5% by volume with respect to the total space volume in the reaction case.
From a height of 5.0 cm above the light irradiation surface, in the downstream direction, centering on a part of the light irradiation part installed on the upper surface of the reaction case, which is 1/3 of the length from the upstream end of the reaction case. A flow-type photoreaction was performed by irradiating light with an inclination of 20 degrees.
When the temperature of the reaction case reached 85 ° C., ethylene carbonate heated to 60 ° C. was continuously supplied from the liquid supply port at a rate of 10.4 g (118 mmol) / min using a diaphragm pump.
The residence time of ethylene carbonate (time to reach the liquid discharge port from the liquid supply port) was about 20 seconds.
Five minutes after the start of supply, after the flow rate of ethylene carbonate became stable, chlorine gas was continuously introduced into the reaction case at a rate of 10.3 g (145 mmol) / minute from the gas supply port installed in the gas storage section. Introduced in. The flow rate of chlorine gas flowing through the gas flow section was 13.5 cm / sec, and the flow rate of chlorine gas with respect to ethylene carbonate was 1.23 mol equivalent.
The liquid composition and the gas composition obtained by the flow type photoreaction were stored in a storage tank. The gas composition in the storage tank was discharged from the storage tank gas discharge port at the upper part of the storage tank, and was absorbed by an aqueous sodium hydroxide solution for treatment.
Approximately 10 minutes after the start of light irradiation, the liquid composition was collected for about 1 minute from the liquid composition outlet installed at the bottom of the storage tank. The collected liquid composition was analyzed using gas chromatography (GC). The conversion rate of ethylene carbonate was 53.7%, and the production ratio of monochloroethylene carbonate and dichloroethylene carbonate was 83.3%: 16.7%. The% here was calculated by the GC area percentage. The chlorine gas consumption rate was 43.5%. The chlorine gas consumption rate was calculated according to the formula (conversion amount of ethylene carbonate mol / chlorine gas introduction amount mol) × 100.

Reference example 1

Photoreaction of ethylene carbonate with chlorine gas using a single-tube Pyrex® glass flow photoreaction reactor with a single channel groove and an LED-UV lamp (wavelength = 365 nm output = 42 W) Was carried out at normal pressure.
By adjusting the angle of the support base so that the angle of the reaction case is tilted at 20 degrees with respect to the horizontal plane, and by circulating water at 90 ° C. to the medium flow section provided in the reaction case, the reaction case The temperature was adjusted to 80 ° C.
The reaction case is a double tube, the inner tube is the distribution section where liquid and gas flow, and the outer tube is the medium distribution section. The length of the flow section in the longitudinal direction is 60 cm and the inner diameter is 1 cm. Liquid is supplied from the liquid supply port provided at the upstream end in the longitudinal direction, and gas is supplied from the gas supply port provided above the upstream end in the longitudinal direction. Was supplied, the liquid was discharged from the liquid discharge port provided at the downstream end in the longitudinal direction, and the gas was discharged from the gas discharge port provided above the downstream end in the longitudinal direction. The length of the light irradiation section and the liquid flow section in the longitudinal direction was 60 cm, and the length of the gas flow section was 50 cm.
A photoreaction was carried out by irradiating the entire surface of the light-irradiated portion at the bottom of the reaction case with light perpendicularly to the light-irradiated portion from a position 1 cm below the light-irradiated portion.
Ethylene carbonate heated to 60 ° C. was continuously supplied from the liquid supply port using a diaphragm pump at a rate of 0.13 g (1.48 mmol) / min. The residence time of ethylene carbonate (time to reach the liquid discharge port from the liquid supply port) was about 10 seconds.
Five minutes after the start of supply, after the flow rate of ethylene carbonate became stable, chlorine gas was introduced into the reaction case at a rate of 0.11 g (1.54 mmol) / minute from the gas supply port installed in the gas storage section. Introduced continuously. The flow rate of chlorine gas flowing through the gas flow section was 1.5 cm / sec, and the flow rate of chlorine gas with respect to ethylene carbonate was 1.04 mol equivalent.
The liquid composition and the gas composition obtained by the flow type photoreaction were stored in a Pyrex (registered trademark) glass storage tank. The gas composition in the storage tank was discharged from the storage tank gas discharge port at the upper part of the storage tank, and was absorbed by an aqueous sodium hydroxide solution for treatment.
Approximately 10 minutes after the start of light irradiation, the liquid composition was collected for about 1 minute from the liquid composition outlet installed at the bottom of the storage tank. The collected liquid composition was analyzed using gas chromatography (GC).
The conversion rate of ethylene carbonate was 45.3%, the production ratio of monochloroethylene carbonate and dichloroethylene carbonate was 92%: 8%, and the consumption rate of chlorine gas was 43.3%.

The same apparatus as in Example 1 was used except that a pressure gauge was installed in the upper part of the storage tank, a back pressure valve was installed in the pipe from the storage tank gas discharge port, and the pressure in the reaction case was set to 0.2 MPa (cage pressure). A photoreaction was carried out.
Example 1 except that ethylene carbonate was supplied at 9.9 g (0.113 mmol) / minute from the liquid supply port and chlorine gas was supplied at 7.1 g (0.100 mmol) / minute from the gas supply port. The photoreaction was carried out in the same manner as in.
The conversion rate of ethylene carbonate was 47.8%, and the production ratio of monochloroethylene carbonate and dichloroethylene carbonate was 84.5%: 7.2%.

A photoreaction was carried out in the same manner as in Example 1 except that the light-irradiated portion not irradiated with light was covered with a light-reflecting plate made of polycarbonate.
The conversion rate of ethylene carbonate was 59.5%, and the production ratio of monochloroethylene carbonate and dichloroethylene carbonate was 83.7%: 16.3%.

A photoreaction was carried out in the same manner as in Example 1 except that the light-irradiated portion not irradiated with light was covered with a light-reflecting plate made of polycarbonate attached to polyurethane foam as a heat insulating material. The conversion rate of ethylene carbonate was 64.7%, and the production ratio of monochloroethylene carbonate and dichloroethylene carbonate was 86.1%: 13.9%.

The flow-type photoreactor (reactor 1) and LED-UV lamp (wavelength = 365 nm, output = 300 W) used in Example 1 and the Pyrex® glass flow-type photoreactor used in Reference Example 1 (registered trademark). Using a reactor 2) and an LED-UV lamp (wavelength = 365 nm output = 42 W), a photoreaction of ethylene carbonate with chlorine gas was carried out at normal pressure.
The liquid discharge port of the reactor 1 and the liquid supply port of the reactor 2, the gas discharge port of the reactor 1 and the gas discharge port of the reactor 2, the medium discharge port of the reactor 1 and the medium supply port of the reactor 2 are connected to each other, and the reactor 2 is connected. The liquid discharge port and the storage tank liquid supply port, and the gas discharge port of the reactor 2 and the storage tank gas supply port were connected, respectively.
The angle of the support base is adjusted so that the angle of the reaction case of the reactor 1 is tilted to 5 degrees and the angle of the reaction case of the reactor 2 is tilted to 17.5 degrees with respect to the horizontal plane. Water at 87 ° C is circulated in the medium circulation section provided on the lower surface, and the circulated water circulates in the medium circulation section of the reactor 2, and a thermocouple thermometer is installed at the temperature sensor installation port of the holding frame to form a reaction case. The temperature was measured.
From a height of 5 cm above the light irradiation surface, centering on the part of the light irradiation unit installed on the upper surface of the reaction case of reactor 1 at a length of 1/3 from the downstream end of the reaction case of reactor 1. Using an LED-UV lamp (wavelength = 365 nm, output = 300 W) at an inclination of 20 degrees in the upstream direction, irradiate the entire surface of the light-irradiated portion at the bottom of the reaction case of the reactor 2 with light. A light reaction was carried out by irradiating light with an LED-UV lamp (wavelength = 365 nm output = 42 W) perpendicularly to the light-irradiated part 1 cm below the part.
When the temperature of the reaction cases of reactors 1 and 2 reached 80 ° C., ethylene carbonate heated to 80 ° C. was continuously supplied from the liquid supply port at a rate of 6.6 g (75 mmol) / min using a diaphragm pump. .. Five minutes after the start of supply, after the flow rate of ethylene carbonate became stable, chlorine gas was supplied at a rate of 5.4 g (76 mmol) / minute from the gas supply port of Reactor 1 installed in the gas storage of Reactor 1. It was continuously introduced into the reaction case of the reactor 1.
The liquid composition and the gas composition obtained by the flow-type photoreaction of the reactor 1 are supplied to the reaction case of the reactor 2 from the liquid supply port of the reactor 2 and the gas supply port of the reactor 2, and are LED-UV lamps (wavelength =). Using 365 nm output = 42 W), a photoreaction was carried out by irradiating light, and the liquid composition of Reactor 2 and the gas composition of Reactor 2 were stored in a storage tank. The gas composition in the storage tank was discharged from the storage tank gas discharge port at the upper part of the storage tank, and was absorbed by an aqueous sodium hydroxide solution for treatment.
Approximately 10 minutes after the start of light irradiation, the liquid composition of Reactor 2 was collected for about 1 minute from the liquid composition outlet installed at the bottom of the storage tank. The collected liquid composition was analyzed using gas chromatography (GC). The conversion rate of ethylene carbonate was 58.3%, and the production ratio of monochloroethylene carbonate and dichloroethylene carbonate was 86.8%: 12.9%. The chlorine gas consumption rate was 46.0%.

Comparative Example 1

Chlorine gas of ethylene carbonate using a flow-type photoreactive reactor consisting of a Pyrex (registered trademark) glass substrate, a lid, and a holding frame made of SUS304, and an LED-UV lamp (wavelength = 365 nm, output = 42 W). The photoreaction was carried out at normal pressure.
The flow-type photoreaction reactor has a liquid supply port and a liquid discharge port, and has a light irradiation portion having a length = 11.5 cm and a width = 7.8 cm on the upper surface, and the dimensions of the substrate are length =. It had a width of 14 cm, a width of 9 cm, a width of 2 mm, a depth of 1 mm, and a total length of 300 cm.
A mixer made of PCTFE was attached immediately before the inlet of the liquid supply port, and ethylene carbonate and chlorine gas were mixed by the mixer and then supplied into the above-mentioned flow type photoreaction reactor.
The flow type photoreaction reactor was installed on a hot plate, the temperature of the substrate was heated to 65 ° C., and the LED-UV lamp was installed so as to cover the entire surface of the light irradiation portion, and the light was irradiated.
A diaphragm pump was used to supply ethylene carbonate heated to 60 ° C. at a rate of 0.066 g (0.75 mmol) / min, and a Cofflock flow meter was used to supply 15 ml (0.77 mmol) of chlorine gas. Feeding at a rate of / min, the flow rate of chlorine gas relative to ethylene carbonate was 1.03 mol equivalence.
Five minutes after the start of supply, the liquid composition discharged from the liquid discharge port was collected for about 1 minute. The collected liquid composition was analyzed using gas chromatography (GC). The conversion rate of ethylene carbonate was 27.1%, and the production ratio of monochloroethylene carbonate and dichloroethylene carbonate was 82.8%: 17.2%.

100 Flow type photoreaction reactor; 101 reaction case; 102 light irradiation unit; 103 flow channel groove; 104 liquid flow unit; 105 gas flow unit; 106A, 106B gas storage unit; 107 gas supply port; 108 gas discharge port; 109 liquid Supply port; 110 Liquid discharge port; 111 Reaction case support base; 112 Substrate; 113 Lid; 114 Upper holding frame; 115 Lower holding frame; 116 Temperature sensor installation port; 117 Light reflector; 118 Insulation material; 119 Float meter; 120 Pump; 121 Liquid Container; 122 Upstream Vertical Frame; 123 Downstream Vertical Frame; 124 Through Hole; 125 Gas Container; 126 Medium Container; 127 Pump 200 Liquid; 201 Gas; 202 Liquid Composition; 203 Gas Composition; 204 Medium; 205 Second liquid composition; 206 Second gas composition 301 Flow type photoreactor; 302 Light source; 303 Light source support; 304 Medium distribution section; 305 Storage tank; 306 Fixing bracket; 307 Medium supply port; 308 Medium discharge port; 309 Medium flow passage; 310 Storage tank liquid supply unit; 311 Storage tank gas supply unit; 312 Storage tank gas outlet; 313 Storage tank liquid outlet; 314 Back pressure device; 315 Gas treatment device; 316 Second flow type photoreaction reactor; 317th (Ii) Liquid supply port; 318 Second gas supply port; 321 Second light source; 322 Second medium distribution unit; 323 Second medium supply port; 324 Second medium; 325 Second medium discharge port; 326 Second reaction case; 327 Second liquid discharge port; 328 Second gas discharge port 400 Conventional flow type photoreaction reactor; 401 Liquid flow part; 402 Liquid storage part; 403 Liquid supply port; 404 Liquid; 405 Gas supply port

Claims (13)

Equipped with a reaction case that carries out a photoreaction while supplying liquid and gas
Inside the reaction case, there is a liquid flow section having at least one flow path groove for circulating the liquid from the upstream to the downstream direction, and a gas flow section for circulating the gas.
At the bottom of the upstream end of the liquid flow section, a liquid supply port for supplying the liquid to the flow path groove, and at the bottom of the downstream end of the liquid flow section, a liquid discharge port for discharging the liquid. Have,
It has a gas storage unit A installed inside the reaction case on the upstream side of the upstream end of the liquid supply port.
The upper part of the gas storage part A has a gas supply port for supplying the gas, and the upper part of the downstream end of the gas flow part has a gas discharge port for discharging the gas.
On the upper surface and / or the lower surface of the reaction case, a light irradiation unit that transmits light for irradiating the liquid flow unit and the gas flow unit with light to carry out a photoreaction is provided.
Further, the inclination of the reaction case can be freely adjusted, and the liquid supplied from the liquid supply port to the flow path groove is designed to flow from the upstream side to the downstream direction of the reaction case by its own weight. The reaction case is provided with a reaction case support base for supporting the reaction case.
Flow type photoreactive reactor. The reaction case is composed of a substrate, a lid covering the substrate, an upper holding frame that surrounds the substrate and the lid and is gripped from above, and a lower holding frame that is gripped from below.
The light irradiation unit is composed of the lid body.
The flow path groove is formed on the upper surface of the substrate or the upper surface of the lid.
A temperature sensor installation port for installing a temperature sensor for measuring the temperature of the reaction case is provided on a side surface of the lower holding frame parallel to the upstream to downstream directions.
The flow type photoreactive reactor according to claim 1. The liquid supply port is provided for each of the flow path grooves.
The flow type photoreactive reactor according to claim 1 or 2. The liquid flow unit is installed in a direction downstream of the gas storage unit A having the gas supply port.
The flow type photoreaction reactor according to any one of claims 1 to 3. The flow path groove is one, or is separated into a plurality of grooves in the lateral direction.
The flow type photoreaction reactor according to any one of claims 1 to 4. A portion of the light-irradiated portion that is not irradiated with light is covered with a light-reflecting plate.
The flow type photoreaction reactor according to any one of claims 1 to 5. A light reflector and a heat insulating material are installed in a portion of the light-irradiated portion that is not irradiated with light.
The flow type photoreaction reactor according to any one of claims 1 to 5. The flow type photoreactive reactor according to any one of claims 1 to 7.
light source,
A light source support for installing the light source and / or the liquid on the upper surface of the light irradiation unit on the upper surface of the reaction case of the flow type photoreaction reactor and / or on the lower part of the light irradiation unit on the lower surface of the reaction case. A storage tank for storing the liquid composition discharged from the discharge port and the gas composition discharged from the gas discharge port is provided.
The reaction case is further characterized by having a medium distribution unit for distributing a medium for controlling the temperature of the reaction case.
Flow type photoreactor. The light source support can be moved in the vertical direction and the parallel direction with respect to the plane on which the light of the light irradiation unit is irradiated, and the irradiation angle of the light source can be changed.
The flow type photoreactor according to claim 8. A medium supply port connected to the downstream end of the medium distribution section and supplying the medium to the medium distribution section,
It is connected to an upstream end portion of the medium distribution section, and has a medium discharge port for discharging the medium flowing through the medium distribution section.
The flow type photoreactor according to claim 8 or 9. The storage tank has a storage tank liquid supply port, a storage tank gas supply port, a storage tank gas outlet, and a storage tank liquid outlet at the bottom near the upper part.
At the storage tank gas outlet, a pressurizing device for allowing the inside of the reaction case to be pressurized and performing a photoreaction in a normal pressure system or a pressurizing system, and a gas treatment device for treating the gas composition. Is connected,
The flow type photoreactor according to any one of claims 8 to 10. A second flow type photoreaction reactor having a structure similar to that of the flow type photoreaction reactor is installed between the flow type photoreaction reactor and the storage tank.
The liquid composition and the gas composition obtained by carrying out a photoreaction using the flow type photoreaction reactor and the light source are supplied to the second flow type photoreaction reactor, and the second flow. The second photoreaction is carried out in a normal pressure system or a pressurized system using a second light source installed in the optical reaction reactor.
The gas supply port of the second flow type photoreaction reactor is connected to the gas discharge port of the flow type photoreaction reactor.
The liquid supply port of the second flow type photoreaction reactor is connected to the liquid discharge port of the flow type photoreaction reactor.
The flow type photoreactor according to any one of claims 8 to 11. Equipped with a reaction case that carries out a photoreaction while supplying liquid and gas
Inside the reaction case, a liquid flow section for circulating the liquid from the upstream to the downstream direction and a gas flow section for circulating the gas are provided.
The upstream end of the gas flow section has a gas supply port for supplying the gas, and the downstream end of the gas flow section has a gas discharge port for discharging the gas.
The upstream end of the liquid flow section has a liquid supply port for supplying the liquid, and the downstream end of the liquid flow section has a liquid discharge port for discharging the liquid.
On the upper surface and / or the lower surface and / or the side surface of the reaction case, a light irradiation unit that transmits light for irradiating the liquid flow unit and the gas flow unit with light to carry out a photoreaction is provided.
Further, the inclination of the reaction case can be freely adjusted, and the liquid supplied from the liquid supply port to the liquid flow section is designed to flow from the upstream to the downstream of the reaction case by its own weight. A single-tube flow-type photoreaction reactor provided with a reaction case support base for supporting the reaction case is installed between the flow-type photoreaction reactor and the storage tank.
Using the flow-type photoreaction reactor and the light source, the liquid composition and the gas composition obtained by carrying out a photoreaction are supplied to the single-tube flow-type photoreaction reactor, and the single tube type photoreaction reactor is supplied. To carry out further photoreactions in atmospheric or pressurized systems using a separate light source installed in a tube-type flow photoreactor.
The gas supply port of the single-tube flow-type photoreaction reactor is connected to the gas discharge port of the flow-type photoreaction reactor.
The liquid supply port of the single-tube flow-type photoreaction reactor is connected to the liquid discharge port of the flow-type photoreaction reactor.
The flow type photoreactor according to any one of claims 8 to 11.

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