JP7075490B2 - Photoreactive device and method - Google Patents

Description

The present invention relates to photoreactive devices and methods.

As a photoreactive device that causes a light reaction by irradiation with light, a device that continuously performs a photoreaction is known. This device performs a photoreaction by irradiating the flowing reaction target liquid with light while flowing the reaction target liquid containing the photoreactive compound.

For example, Patent Document 1 describes a device including a micro-reactor, a gas supply unit for supplying a non-raw material gas, and a liquid raw material supply unit for supplying a liquid raw material, and performing a photodecomposition reaction. The microreactor is provided with a photocatalyst layer on the inner surface and includes a microchannel through which a liquid raw material flows. The microchannel is made of a light transmissive material and has a rectangular, circular, elliptical, or polygonal cross section. The microchannel has a channel diameter of 10 to 2000 μm, and the length of the long side / the length of the short side when the cross section is rectangular and the long diameter / short diameter when the cross section is circular are about 1 to 20. It is said that.

The photoreactive device of Patent Document 2 includes a reaction unit in which a porous silicon layer is provided on the inner surface of a microchannel, a feeding means for feeding a raw material liquid into the microchannel, and a light irradiation means for irradiating the porous silicon layer with light. And prepare. The microchannel is a channel having a fine diameter of about several tens to several thousand μm, and it is described that a width of 50 μm to 1000 μm and a depth of 10 μm to 1000 μm are preferable.

Further, in Patent Document 3, a transparent and cylindrical inner container in which a tube is spirally wound, a light source arranged so as not to come into contact with the cylindrical container, and an arrangement between the inner container and the light source. A photoreactor with a cooling tube is described.

Japanese Unexamined Patent Publication No. 2009-23366 Japanese Unexamined Patent Publication No. 2011-161416 Japanese Unexamined Patent Publication No. 2009-21994

In any of the devices of Patent Documents 1 to 3, when the processing amount is increased, the light source is increased and the micro is increased in order to increase the flow rate of the reaction target liquid while ensuring the irradiation time required for the photoreaction. It is necessary to increase the size of the device such as lengthening the flow path or tube. However, since this method increases the pressure loss, there is a limit to the improvement of the processing amount.

Therefore, an object of the present invention is to provide a photoreactive device and a method for improving the processing amount while suppressing the increase in size of the device.

In order to solve the above problems, the present invention comprises a reaction unit, a light source unit, and a light source side temperature control mechanism, and irradiates the reaction target liquid with light while flowing the reaction target liquid containing a photoreactive compound. By doing so, it causes a photoreaction. The reaction unit has a first plate-shaped member that transmits light and a second plate-shaped member that faces the first plate-shaped member with a gap. The reaction section is internally formed with a flat flow path in which a set of facing surfaces is defined by the first plate-shaped member and the second plate-shaped member. The light source unit is arranged on the side opposite to the second plate-shaped member side of the first plate-shaped member, and a plurality of light sources for emitting light are arranged in a plane shape. The light source side temperature control mechanism adjusts the temperature of the reaction unit from the light source unit side. The light source side temperature control mechanism has a third plate-shaped member and a light source side supply unit. The third plate-shaped member is arranged on the light source unit side of the first plate-shaped member in a state of facing the first plate-shaped member with a gap, and transmits light. The light source side supply unit supplies a heat transfer medium between the third plate-shaped member and the first plate-shaped member.

Further, the present invention includes a reaction unit, a light source unit, a light source side temperature control mechanism, and a back surface side temperature control mechanism, and emits light to the reaction target liquid while flowing a reaction target liquid containing a photoreactive compound. By irradiating, it reacts with light. The reaction unit has a first plate-shaped member that transmits light and a second plate-shaped member that faces the first plate-shaped member with a gap. The reaction section is internally formed with a flat flow path in which a set of facing surfaces is defined by the first plate-shaped member and the second plate-shaped member. The light source unit is arranged on the side opposite to the second plate-shaped member side of the first plate-shaped member, and a plurality of light sources for emitting light are arranged in a plane shape. The light source side temperature control mechanism adjusts the temperature of the reaction unit from the light source unit side. The rear temperature control mechanism adjusts the temperature of the reaction unit from the side opposite to the light source unit side, and faces the second plate-shaped member on the opposite side of the first plate-shaped member with a gap from the second plate-shaped member. It has a fourth plate-shaped member arranged in a state, and a back side supply unit that supplies a heat transfer medium between the second plate-shaped member and the fourth plate-shaped member.

The second plate-shaped member preferably reflects light.

The first plate-shaped member and the second plate-shaped member are preferably arranged in an upright posture.

It is preferable that the flat flow path is opened at the lower part of the reaction part as a supply port of the liquid to be reacted and at the upper part of the reaction part as a discharge port.

In the cross section orthogonal to the flow direction of the reaction target liquid in the flat flow path, the ratio obtained by WP / TP is at least 3 when the length in the longitudinal direction is WP and the length in the lateral direction is TP. Is preferable.

It is preferable to provide a back side temperature control mechanism that adjusts the temperature of the reaction unit from the side opposite to the light source unit side.

The back surface side temperature control mechanism preferably has a fourth plate-shaped member and a back surface side supply unit. The fourth plate-shaped member is arranged on the opposite side of the second plate-shaped member from the first plate-shaped member in a state of facing the second plate-shaped member with a gap. The back side supply unit supplies a heat transfer medium between the second plate-shaped member and the fourth plate-shaped member.

In the photoreaction method of the present invention, a reaction target liquid containing a photoreactive compound is allowed to flow, and the reaction target liquid is irradiated with light to cause a photoreaction. In the photoreaction method, the reaction target liquid is supplied to the flat flow path provided inside the reaction unit, the reaction target liquid flowing in the flat flow path is irradiated with light, and the light source unit side of the first plate-shaped member is irradiated. , A heat transfer medium is supplied between the third plate-shaped member, which is arranged so as to face the first plate-shaped member with a gap and transmits light, and between the third plate-shaped member and the first plate-shaped member. The temperature of the reaction unit is adjusted from the light source unit side by the light source side temperature control mechanism having the light source side supply unit . In the flat flow path, a set of facing surfaces is defined by a first plate-shaped member that transmits light and a second plate-shaped member that faces the first plate-shaped member with a gap. The light is arranged on the side opposite to the second plate-shaped member side of the first plate-shaped member, and the reaction target liquid is irradiated with the light source unit in which a plurality of light sources for emitting light are arranged in a plane shape. Further, the photochemical reaction method of the present invention comprises a fourth plate-shaped member arranged on the opposite side of the second plate-shaped member from the first plate-shaped member so as to face the second plate-shaped member with a gap. The temperature of the reaction unit is adjusted from the side opposite to the light source unit side by the back side temperature control mechanism having the back side supply unit for supplying the heat transfer medium between the second plate-shaped member and the fourth plate-shaped member. do.

According to the present invention, the processing amount is improved while suppressing the increase in size of the apparatus.

It is a schematic perspective view of a photoreactor. It is a top view of a light source. It is a partial cross-sectional view of a photoreactor, (A) is a cross-sectional view orthogonal to the flow direction of the reaction target liquid, and (B) is a cross-sectional view along the flow direction of the reaction target liquid. It is explanatory drawing of the flat flow path. It is a graph which shows the relationship between the ratio WP / TP and the yield. It is explanatory drawing of the optical reaction apparatus. It is explanatory drawing of another light reaction apparatus. It is explanatory drawing of another light reaction apparatus. It is explanatory drawing of the example of a photoreaction.

In FIG. 1, the photoreactive device 10 according to the embodiment of the present invention irradiates the reaction target liquid 11 with light while flowing the reaction target liquid 11 (see FIG. 3) containing the photoreactive compound. The photoreaction is continuous. The photoreactive device 10 includes a light source unit 13 and a reaction unit 14.

The light source unit 13 is for irradiating the reaction target liquid 11 with light. The light source unit 13 is formed in a plate shape, and one surface 13a is an emission surface for emitting light. Hereinafter, reference numerals 13a are attached to the injection surface. The light source unit 13 is arranged so that the injection surface 13a is parallel to the direction (hereinafter referred to as the flow direction) X through which the reaction target liquid 11 flows. In this example, since the flow direction X is directed upward in the vertical direction, the light source unit 13 is provided in a vertically standing posture (vertical posture) in a state where the injection surface 13a is in the vertical direction. Details of the light source unit 13 will be described later with reference to another drawing. The direction orthogonal to the flow direction X is defined as the width direction Y, and the direction orthogonal to both the flow direction X and the width direction Y is defined as the thickness direction Z.

The reaction unit 14 includes a unit main body 21, a liquid feeding unit 22, a collecting unit 23, and a cooler 24. The unit main body 21 is formed in a substantially rectangular parallelepiped shape, but the shape is not limited to this example. The housing 27 of the unit main body 21 is formed with an opening 27a for guiding the light from the light source unit 13 to the inside. The unit main body 21 is arranged so that the opening 27a faces the light source unit 13. The opening 27a is rectangular, but the shape of the opening is not limited to this example.

Inside the unit main body 21, each flow path of the reaction target liquid 11 and water 28 (see FIG. 3) is formed. The liquid feeding unit 22 and the collecting unit 23 are connected to the unit main body 21, the liquid feeding unit 22 supplies the reaction target liquid 11 to the unit main body 21, and the collecting unit 23 supplies the reaction target liquid 11 that has undergone a photoreaction to the unit. Collect from the main body 21. In this example, since the flow direction X of the reaction target liquid 11 is directed upward in the vertical direction as described above, the liquid feeding unit 22 is the supply port S1 formed in the lower part of the unit main body 21, specifically, the bottom surface of the housing 27. The recovery unit 23 is connected to the upper part of the unit main body 21, specifically, the discharge port D1 (see FIG. 3B) formed on the top surface of the housing 27.

The cooler 24 is connected to the unit main body 21 by pipes L1 to L6. The cooler 24 supplies water 28 to the unit main body 21, collects the water 28 that has passed through the unit main body 21, cools the water 28, and then supplies the water 28 to the unit main body 21 again. As described above, the cooler 24 has a function of a supply unit for supplying water 28 to the unit main body 21, a recovery unit for collecting water from the unit main body 21, and a cooling unit for cooling. As a result, the water 28 circulates between the cooler 24 and the unit main body 21, and the temperature of the reaction target liquid 11 in the unit main body 21 is adjusted by this circulation. Therefore, even if the light continues to be irradiated, the temperature of the unit main body 21 is adjusted. Does not increase, and the photoreaction is more likely to proceed. The details of the reaction unit 14 will be described later with reference to another drawing.

The pipe L1 connected to the cooler 24 is branched into the pipe L2 and the pipe L3 at the branch portion PS1. The pipe L2 is connected to the light source unit 13 side of the unit main body 21, and the pipe L3 is connected to the side opposite to the light source unit 13 side of the unit main body 21 (hereinafter referred to as the back side). The connection position of the pipe L2 and the pipe L3 is preferably the lower part of the light source unit 13, and this is also the case in this example. The supply port S2 and the supply port S3 (see FIG. 3) formed in the lower part of the housing 27 are connection portions between the pipe L5 and the pipe L6.

Further, the pipe L4 connected to the cooler 24 is branched into the pipe L5 and the pipe L6 at the branch portion PS2. The pipe L5 is connected to the light source unit 13 side of the unit main body 21, and the pipe L6 is connected to the back side of the unit main body 21. The connection position of the pipe L5 and the pipe L6 is preferably the upper part of the light source unit 13, and this is also the case in this example. The discharge port D2 and the supply port D3 (see FIG. 3) formed in the upper part of the housing 27 are connection portions between the pipe L4 and the pipe L5.

As shown in FIG. 2, the light source unit 13 has a plurality of light sources 17 and a support plate 18 that supports these light sources 17. By arranging a plurality of light sources 17 in a planar shape on one surface of the support plate 18, a planar injection surface 13a is formed, and the emission surface 13a of this example is a flat surface. In this example, each light source 17 is embedded in the support plate 18, and each light source 17 and the support plate 18 are flush with each other. However, the mode of installing the light source 17 on the support plate 18 is not limited to this example as long as the injection surface 13a is formed in a planar shape. For example, each light source 17 is provided so as to protrude from the surface of the support plate 18. May be.

The light source 17 is an LED (Light Emitting Diode) in this example, and the plurality of light sources 17 are arranged in a square as shown in FIG. However, the light source is not limited to the LED, and is appropriately selected depending on the photoreactive compound to be photoreacted. The light source may be, for example, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like. The plurality of light sources 17 are not limited to a square array, and may be another regular array such as a matrix array or an irregular arrangement. Further, in FIG. 2, the light source 17 is drawn with 16 columns in the horizontal direction of the paper surface and 15 rows in the vertical direction of the paper surface, but the number of columns and the number of rows of the light source 17 are also used in this example. Not limited. The light source unit 13 includes a controller (not shown) that adjusts the output of each light source 17 when it is on, off, and on, and adjusts the illuminance with respect to the reaction target liquid 11.

The length WE of the region where the light of the emission surface 13a in the width direction Y is emitted (hereinafter referred to as the emission width) is not particularly limited. However, from the viewpoint of securing a larger light receiving region in the reaction unit 14, the length of the opening 27a in the width direction Y (hereinafter referred to as the opening width) W27a (see FIG. 1) may be the same or larger than the opening width W27a. Preferably, in this example, it is made larger than the opening width W27a. In this example, the length from one end to one of the other ends of the plurality of light sources 17 arranged in the width direction Y is defined as the emission width WE.

As shown in FIG. 3, the reaction unit 14 is configured by combining a plate-shaped member for forming a flow path of the reaction target liquid 11 and / or the water 28, a housing 27, and the like. Specifically, the third plate-shaped member 43, the first plate-shaped member 41, the second plate-shaped member 42, and the fourth plate-shaped member 44 are arranged in this order from the light source unit 13 side, and face each other with a gap. It is provided inside the housing 27 in a state parallel to each other and in a vertical posture. If the angle between the facing surfaces is within 0.06 °, it may be regarded as parallel. The first plate-shaped member 41 to the fourth plate-shaped member 44 are for forming a flow path of the reaction target liquid 11 and / or the water 28, so that the reaction target liquid 11 and / or the water 28 leaks out. It is fixed to the inner wall of the housing 27 in a non-existent state. Further, the first plate-shaped member 41 to the fourth plate-shaped member 44 have sufficient strength not to be destroyed by the pressure of the reaction target liquid 11 and / or the water 28.

The first plate-shaped member 41 and the second plate-shaped member 42 are for flowing the reaction target liquid 11 in a planar shape (flat film shape), and together with the housing 27, the reaction unit 47 for reacting the reaction target liquid 11. To configure. The first plate-shaped member 41 and the second plate-shaped member 42 facing each other with a gap are formed to have substantially the same size in the XY plane, and the distance between them is smaller than the length in the width direction Y. As a result, a flat flow path P1 having a flat cross section is formed inside the reaction unit 47 as a flow path of the reaction target liquid 11. Therefore, the flat flow path P1 has a planar shape (planar shape) in which the length WP in the width direction Y (hereinafter referred to as the flow path width) is larger than the length TP in the thickness direction Z (hereinafter referred to as the flow path thickness). It is a flow path. In this way, the first plate-shaped member 41 and the second plate-shaped member 42 define a pair of facing surfaces of the flat flow path P1, and the facing surfaces 41a, 42a and the inner wall surface of the housing 27 are flat. It is the wall surface of the flow path P1.

As shown in FIG. 3B, the supply port S1 and the discharge port D1 described above are formed between the first plate-shaped member 41 and the second plate-shaped member 42. The supply port S1 and the discharge port D1 are formed in a slit shape extending in the width direction Y, and the opening area (area in the YZ plane) and shape thereof are the area and shape of the cross section of the flat flow path in the YZ plane. It is the same as. As a result, the flow of the reaction target liquid 11 is formed into a shape extending in the width direction Y, guided by the flat flow path P1, and then discharged from the flat flow path P1. In this example, the supply port S1 is formed into a shape extending in the width direction Y of the reaction target liquid 11, but it extends upstream from the supply port S1, that is, on the liquid feeding portion 22 side in the width direction Y. It may be molded into a shape.

The flat flow path P1 surrounded by the first plate-shaped member 41, the second plate-shaped member 42, and the housing 27 is not provided with a partition member for partitioning the flat flow path P1, such as a member extending in the flow direction X. (Not installed). That is, the flat flow path P1 is formed as one space, whereby the reaction target liquid 11 flows inside the reaction portion 47 without being divided in the width direction Y. Compared with the case where the partition member is inside the flat flow path P1, the volume corresponding to the volume of the partition member is secured as the flow region of the reaction target liquid 11, that is, the volumetric efficiency is high. Further, when there is a partition member, there is a decrease in the flow velocity of the reaction target liquid 11 in the vicinity of the partition member, but since the partition member is not installed in the flat flow path P1, there is no decrease in the flow velocity due to the partition member. In this way, a large amount of processing can be secured while suppressing the increase in size of the apparatus.

The first plate-shaped member 41 and the third plate-shaped member 43 arranged on the light source unit 13 side of the flat flow path P1 are formed of a material that transmits light from the light source 17.

The material of the first plate-shaped member 41 and the third plate-shaped member 43 is not particularly limited as long as it transmits light from the light source unit 13. For example, glass, acrylic resin, vinyl chloride and the like can be mentioned. In particular, the first plate-shaped member 41 is made of a material that is not affected by the reaction target liquid, and in this example, both the first plate-shaped member 41 and the third plate-shaped member 43 are made of glass.

Since the light from the light source unit 13 is uniformly irradiated over the entire area in the width direction Y of the flat flow path P1, the flow path width WP of the flat flow path P1 is preferably an opening width W27a or less, and in this example, an opening. It is the same as the width W27a.

The second plate-shaped member 42 is preferably made of a material that is not affected by the reaction target liquid like the first plate-shaped member 41, and is further preferably made of a material that reflects light from the light source unit 13. This is also the case in this example, specifically, it is formed of Hastelloy (registered trademark). The second plate-shaped member 42 may reflect light at least on the facing surface 42a. Therefore, for example, the second plate-shaped member 42 may have a multi-layered structure in the thickness direction Z, and a material that reflects light may be used for the layer forming the facing surface 42a. As such an example, for example, there is an embodiment in which an aluminum foil having a mirror surface is used as the material forming the facing surface 42a. Similarly, it is preferable that the inner surface of the housing 27 that defines the flat flow path P1 is also made of a material that reflects light.

The third plate-shaped member 43 arranged on the light source unit 13 side of the first plate-shaped member 41 and the fourth plate-shaped member 44 arranged on the back surface side of the second plate-shaped member 42 are the above-mentioned cooler 24. Together with (see FIG. 1), it constitutes a temperature control mechanism 48 (see FIG. 1) that regulates the temperature of the reaction unit 47. The third plate-shaped member 43 and the cooler 24 are a light source side temperature control mechanism (hereinafter referred to as a light source side temperature control mechanism) adjusted from the light source unit 13 side. Further, the fourth plate-shaped member 44 and the cooler 24 are a temperature control mechanism on the back side (hereinafter, referred to as a temperature control mechanism on the back side) that is adjusted from the back side.

As described above, in this example, one cooler 24 constitutes both the light source side temperature control mechanism and the back side temperature control mechanism, but the light source side temperature control mechanism and the back side temperature control mechanism are each configured. It may be configured with a separate cooler. Therefore, the mode of the piping connecting the cooler and the unit main body 21 is appropriately changed according to the number of coolers and the like, and the individual coolers are used between the third plate-shaped member 43 and the first plate-shaped member 41. Water 28 is supplied between the fourth plate-shaped member 44 and the second plate-shaped member 42. The cooler 24 may be replaced with a heater (not shown), and the cooler 24 and the heater may be used properly according to the required temperature of the target reaction.

The third plate-shaped member 43 is arranged so as to face the first plate-shaped member 41 with a gap, so that the water flow path (hereinafter referred to as a water flow path) P2 is provided in the gap between the third plate-shaped member 43 and the flat flow path. It is formed flat like P1. Similarly, the fourth plate-shaped member 44 is arranged so as to face the second plate-shaped member 42 with a gap, so that the water flow path P3 is formed flat in the gap between the four plate-shaped members 44. Through holes are provided in the lower portions of the second plate-shaped member 42, the fourth plate-shaped member 44, and the housing 27 as water supply ports S2 and S3, and the second plate-shaped member 42 and the fourth plate-shaped member 44. Through holes are formed in the upper portions of the housing 27 as outlets D2 and D3 for the water 28, respectively. The water flow path P2 is connected to the supply port S2 and the discharge port D2, and the water flow path P3 is connected to the supply port S3 and the discharge port D3. The water flow path is not limited to this example, and for example, a tube (not shown) may be arranged in contact with the surface of the first plate-shaped member 41 on the light source side, and the inside of the tube may be used as the water flow path.

The housing 27 is also formed with an opening 27b similar to the opening 27a on the back surface side. However, in this example, since the back surface side does not contribute to the irradiation of light, the opening 27b may be omitted, or the fourth plate-shaped member 44 may be integrally formed with the housing 27.

The flow path width WP, flow path thickness TP, and flow path length LP between the water flow path P2 and the water flow path P3 are not particularly limited. However, from the viewpoint of more reliably controlling the temperature inside the reaction unit 47, the flow path width WP and the flow path length LP should be the same as or larger than the flow path width WP and the flow path length LP of the flat flow path P1. Is preferable. In this example, the water flow path P2 and the water flow path P3 are formed to have the same volume, and the flow path width WP is larger than the flat flow path P1 and the flow path length LP is the same as the flat flow path. .. In FIG. 3, in order to avoid complication of the figure, the flow path width WP, the flow path thickness TP, and the flow path length LP are shown only for the flat flow path P1.

The flow path thickness TP of the flat flow path P1 is preferably in the range of 0.1 mm or more and 20 mm or less. The flow path thickness TP of the flat flow path P1 is more preferably in the range of 0.5 mm or more and 10 mm or less, and further preferably in the range of 1 mm or more and 6 mm or less. In this example, the flow path thickness TP of the flat flow path P1 is 6 mm.

The value obtained by dividing the flow path length LP of the flat flow path P1 by the flow path width WP, that is, the ratio obtained by LP / WP is preferably 300 at the maximum. The ratio obtained by LP / WP is more preferably 100 or less at the maximum, and further preferably 50 at the maximum. In this example, it is 32.

Water 28 is an example of a heat transfer medium. Other examples of heat transfer media include ethylene glycol, propylene glycol, silicone oil and the like.

When the facing surface 42a of the second plate-shaped member 42 and the inner wall surface defining the flat flow path P1 of the housing 27 do not reflect light or have a low reflectance, FIG. 4 of the flat flow path P1 is shown in FIG. As shown in the above, the closer to the facing surface 42a and the inner wall surface of the housing 27, the smaller the light irradiation amount (hereinafter referred to as the low irradiation area) AL. That is, in the end portion in the width direction Y, the region farther from the injection surface 13a in the thickness direction Z, the smaller the irradiation amount of light. The length (hereinafter referred to as the low irradiation region width) WL in the width direction Y of the low irradiation region AL is constant when the flow path thickness TP is constant. Therefore, the larger the flow path width WP, the smaller the ratio WL / WP of the low irradiation region width WL to the flow path width WP. Therefore, the reaction target liquid 11 flowing through the flat flow path P1 is irradiated with light at a larger irradiation amount. Therefore, it is preferable. In FIG. 4, for convenience, only a part of the second plate-shaped member 42 and the housing 27 of the unit main body 21 is drawn, and the supply port S1 and the discharge port D1 are not shown.

Further, at each end of the flat flow path P1 in the width direction Y, the reaction target liquid 11 flows under the resistance of the inner wall surface of the housing 27. Therefore, the flow velocity at the end portion in the width direction Y is smaller than that at the central portion between one end portion and the other end portion. Therefore, the smaller the proportion of the region that receives the resistance of the wall surface in the flat flow path P1, the larger the processing amount, and the larger the proportion of the region where the flow velocity is uniform in the width direction Y. The yield of the product is also high.

Therefore, in order to minimize the influence of the above-mentioned low irradiation region width WL and the resistance of the end portion in the width direction Y, the ratio obtained by WP / TP is preferably at least 3, and 10.4 in this example. It is supposed to be. The ratio determined by WP / TP is more preferably in the range of 3 or more and 1000 or less, and further preferably in the range of 5 or more and 750 or less from the viewpoint of more reliably suppressing each of the above effects. It is particularly preferable that it is within the range of 500 or less.

The operation of the above configuration will be described. The reaction target liquid 11 supplied by the liquid feeding unit 22 flows between the first plate-shaped member 41 and the second plate-shaped member 42 of the unit main body 21 with the vertical upward direction as the flow direction X in this example. Since the flat flow path P1 is a planar flow path parallel to the injection surface 13a, the flow of the reaction target liquid 11 is a flat surface (flat film shape) facing the injection surface 13a. Therefore, as compared with the conventional method such as flowing in a tube, the reaction target liquid 11 can be flowed at a larger flow rate while avoiding an increase in the size of the apparatus, so that the reaction target liquid 11 can be treated with a light reaction. The amount will increase. Further, since the light is radiated in a planar manner to the planar flow, the photoreaction proceeds in the entire area of the reaction target liquid 11 while passing through the flat flow path P1, and as a result, the product obtained by the photoreaction occurs. Yield is also improved.

For example, compared to the case where the tube is spread in a plane in the same volume as the flat flow path P1, the flat flow path P1 has a large volume of the volume occupied by the tube itself, so that a large flow rate is secured accordingly. .. Further, since the resistance of the inner wall of the long tube is not received, the pressure loss is small, a large flow velocity is secured, and the flow velocity of the reaction target liquid 11 in the flat flow path P1 is higher than the flow velocity in the tube. And uniform. Processing in the flat flow path P1 in which the flow path width WP of the flat flow path P1 is 62.5 mm, the flow path thickness TP is 6 mm, and the length (hereinafter referred to as the flow path length) LP in the flow direction X is 2000 mm. When the amount and the treatment amount in a tube (inner diameter of 4 mm, thickness of 1 mm) spread in a plane in the same volume were compared in a state where the reaction rate of the photochemical reaction was almost the same, the former was the latter. It has been confirmed that it is about 2.9 times that of.

Since the first plate-shaped member 41 and the second plate-shaped member 42 are in an upright posture, specifically, a vertical posture, and the reaction target liquid 11 is supplied from the lower part, the air in the flat flow path P1 is discharged. It is easy to be excluded from the exit D1. For example, when the supply of the reaction target liquid 11 is started, the air in the flat flow path P1 is easily released as the liquid level of the reaction target liquid 11 rises, and the reaction target liquid in the flat flow path P1 is easily released. Even if there are bubbles in 11, the bubbles are easy to escape. Therefore, it is possible to suppress the disturbance of the flow of the reaction target liquid due to the mixing of bubbles.

Since the third plate-shaped member 43 and the first plate-shaped member 41 transmit light, the light from the light source unit 13 arranged on the side opposite to the second plate-shaped member 42 side of the first plate-shaped member 41 is emitted. The reaction target liquid 11 passing through the flat flow path P1 is irradiated through the third plate-shaped member 43 exposed at the opening 27a and further, the first plate-shaped member 41. Since the injection surfaces 13a facing each other and the flow of the reaction target liquid 11 are both formed in a planar shape, light is effectively irradiated over the entire reaction target liquid 11, whereby the photoreaction proceeds reliably.

Since the second plate-shaped member 42 reflects light, the light transmitted through the reaction target liquid 11 in the flat flow path P1 is reflected by the facing surface 42a of the second plate-shaped member 42 and is irradiated to the reaction target liquid 11 again. Ru. As a result, the photoreaction is more likely to proceed.

The water 28 whose temperature is controlled by the cooler 24 is guided from the supply ports S2 and S3 to the water flow paths P2 and P3, flows in a planar shape (flat film shape), and then is discharged from the discharge ports D2 and D3. The temperature of the discharged water 28 is adjusted again by the cooler 24. Since the water flow path P2 is formed as a flat flow path like the flat flow path P1, a larger flow rate of the water 28 is secured, so that the reaction portion 47 is cooled more effectively.

Since the third plate-shaped member 43 and the fourth plate-shaped member 44 are in the same vertical posture as the first plate-shaped member 41 and the second plate-shaped member 42, the air in the water flow paths P2 and P3 is discharged from the outlets D2 and D3. Easy to be excluded from. Therefore, the cooling effect is more reliably maintained.

Since the ratio determined by the ratio WP / TP is 3 or more, the photoreaction proceeds more effectively and the desired product can be obtained in a high yield. As shown in FIG. 5, there is a correlation between the ratio WP / TP and the yield. When the ratio WP / TP is close to 0, the yield is extremely low, and the yield gradually increases as the ratio WP / TP increases, and then slightly increases or becomes constant. The ratio WP / TP at which the gradually increasing yield becomes constant is 3. Therefore, it can be said that the ratio WP / TP is preferably 3 or more.

Since the flow path thickness TP of the flat flow path P1 is 1 mm or more, it is possible to process with a lower pressure loss even if the flow rate is large, as compared with the case where the flow rate is less than 1 mm. Further, since the flow path thickness TP of the flat flow path P1 is 20 mm or less, sufficient illuminance to the deepest part of the flat flow path P1 (the place where the distance from the injection surface 13a is the largest) is sufficient as compared with the case where it exceeds 20 mm. Is illuminated with light. Further, since the flat flow path P1 has an LP / WP of 300 or less, it can be processed with a low pressure loss even if the flow rate is large, as compared with the case where the LP / WP exceeds 300.

The above example is a case where the first plate-shaped member 41 and the second plate-shaped member 42 are arranged in a vertical posture, but the posture is not limited to the vertical posture and may be a horizontal posture. However, from the viewpoint of obtaining the above-mentioned air removal effect, an upright posture is preferable to a horizontal posture. Specifically, as shown in FIG. 6, the angle θ (where 0 ° ≤ θ ≤ 180 °, the unit is °) formed by the first plate-shaped member 41 and the horizontal line HL is 0 ° <θ <. It is preferably 180 °, and more preferably 0 ° <θ≤90 °. Since the second plate-shaped member 42 is arranged in parallel with the first plate-shaped member 41, the angle formed by the second plate-shaped member 42 with the horizontal line HL is also the same as the angle θ formed above. Further, the angle formed by each of the third plate-shaped member 43, the fourth plate-shaped member 44, and the emission surface 13a of the light source 17 and the horizontal line HL is the same as the angle θ formed above. As shown in FIG. 6, the formed angle θ is the angle formed by the back surface of the first plate-shaped member 41 and the horizontal line HL.

In the above example, the second plate-shaped member 42 that reflects the light from the light source unit 13, that is, the irradiation light is used, but the second plate-shaped member that transmits the light may be used. The unit main body 61 of FIG. 7 includes a second plate-shaped member 62 that transmits irradiation light instead of the second plate-shaped member 42. In FIG. 7, the same members and the like as in the above-mentioned example are designated by the same reference numerals, and the description thereof will be omitted.

The second plate-shaped member 62 of this example is made of glass like the first plate-shaped member 41 and the third plate-shaped member 43. Further, the unit main body 61 is provided with a reflector for reflecting the irradiation light on the back surface side of the second plate-shaped member 62, thereby improving the irradiation amount of the reaction target liquid 11 flowing through the flat flow path P1. In addition, instead of the reflector, for example, the above-mentioned aluminum foil or the like may be used. In this case, since the fourth plate-shaped member 44 is provided with a gap from the back surface of the reflector 63, a gap is also provided between the fourth plate-shaped member 44 and the second plate-shaped member 62 via the reflector 63. Become. In this way, the fourth plate-shaped member 44 forms a water flow path P3 with the second plate-shaped member 62 via the reflector 63.

Each of the above examples is an example of irradiating the flat flow path P1 with light from one direction, but the light may be irradiated from a plurality of directions. For example, there is also a mode of irradiating light from the back side. The photoreactive device 70 shown in FIG. 8 includes a unit main body 71 instead of the unit main body 21, and also includes two light source units 13A and 13B. Since each of the light source units 13A and 13B is the same as the light source unit 13, the description thereof is omitted. In the following description, when these two light source units are not distinguished, they are referred to as a light source unit 13. Further, in FIG. 8, the same members and the like as in the above-mentioned example are designated by the same reference numerals, and the description thereof will be omitted.

The unit main body 71 includes the above-mentioned second plate-shaped member 62 in place of the second plate-shaped member 42 in the unit main body 21, and includes a fourth plate-shaped member 74 in place of the fourth plate-shaped member 44. In this example, in addition to the opening 27a of the housing 27, the opening 27b is also used as an opening for guiding light to the flat flow path P1. The unit body 71, the light source unit 13A, and the light source unit 13B are arranged so that the light source unit 13A and the opening 27a face each other and the light source unit 13B and the opening 27b face each other.

The fourth plate-shaped member 74 of this example is made of glass like the first plate-shaped member 41 and the third plate-shaped member 43. Other configurations of the fourth plate-shaped member 74 are the same as those of the fourth plate-shaped member 44. The fourth plate-shaped member 74 faces the second plate-shaped member 62 with a gap, similarly to the fourth plate-shaped member 44 facing the second plate-shaped member 42 with a gap. As a result, the water flow path P3 is formed flat by the second plate-shaped member 62 and the fourth plate-shaped member 74.

Since the amount of light irradiation is twice that of each of the above examples, the flow path thickness TP of the flat flow path P1 of this example is 0.2 mm, which is twice that of each of the above examples, from the viewpoint of the progress of the photoreaction. It may be within the range of 40 mm or less.

The above photoreactor can be used for various photoreactions. Examples of photoreactions include halogenation, reduction, cyclization, cross-coupling, trifluoromethylation and the like.

As an example of halogenation, the photoreaction shown in FIG. 9 can be mentioned as an example. In this reaction, first, o-tolunitrile as a photoreactive compound is dissolved in acetonitrile as a solvent together with N-bromosuccinimide (NBS) as a reagent to prepare a reaction target liquid 11. The reaction target liquid 11 is irradiated with light having a wavelength of 365 nm by an LED while adjusting the temperature to 20 ° C. By using the photoreactor 10, α-bromo-o-tolunitrile as a reaction product can be obtained in a yield of 81%.

10 Optical reactor 11 Reaction target liquid 13 Light source unit 13a Injection surface 14 Reaction unit 17 Light source 18 Support plate 21, 61, 71 Unit body 22 Liquid supply unit 23 Recovery unit 24 Cooler 27 Housing 27a Opening 28 Water 41 First plate Members 42, 62 2nd plate-shaped member 43 3rd plate-shaped member 44,74 4th plate-shaped member 47 Reaction part 48 Temperature control mechanism 63 Reflector AL Low irradiation area D1 to D3 Discharge port LP Flow path length P1 Flat flow path P2, P3 Water flow path S1 to S3 Supply port TP Flow path thickness W27a Opening width WE Injection width WP Flow path width X Flow direction Y Width direction Z Thickness direction

Claims (10)

In a photoreactive device that causes a photoreaction by irradiating the reaction target liquid with light while flowing a reaction target liquid containing a photoreactive compound.
It has a first plate-shaped member that transmits light and a second plate-shaped member that faces the first plate-shaped member with a gap, and a set of the first plate-shaped member and the second plate-shaped member. A reaction part in which a flat flow path in which the facing surfaces of the light is defined is formed inside,
A light source unit arranged on the side opposite to the second plate-shaped member side of the first plate-shaped member and having a plurality of light sources for emitting the light arranged in a plane shape.
A light source side temperature control mechanism that adjusts the temperature of the reaction unit from the light source unit side ,
Equipped with
The light source side temperature control mechanism is
A third plate-shaped member that is arranged on the light source unit side of the first plate-shaped member so as to face the first plate-shaped member with a gap and that transmits the light.
A light source side supply unit that supplies a heat transfer medium between the third plate-shaped member and the first plate-shaped member,
Photoreactive device with. In a photoreactive device that causes a photoreaction by irradiating the reaction target liquid with light while flowing a reaction target liquid containing a photoreactive compound.
It has a first plate-shaped member that transmits light and a second plate-shaped member that faces the first plate-shaped member with a gap, and a set of the first plate-shaped member and the second plate-shaped member. A reaction part in which a flat flow path in which the facing surfaces of the light is defined is formed inside,
A light source unit arranged on the side opposite to the second plate-shaped member side of the first plate-shaped member and having a plurality of light sources for emitting the light arranged in a plane shape.
A light source side temperature control mechanism that adjusts the temperature of the reaction unit from the light source unit side ,
A rear temperature control mechanism that adjusts the temperature of the reaction unit from the side opposite to the light source unit side,
Equipped with
The back side temperature control mechanism is
A fourth plate-shaped member arranged on the opposite side of the second plate-shaped member from the first plate-shaped member so as to face the second plate-shaped member with a gap.
A back side supply unit that supplies a heat transfer medium between the second plate-shaped member and the fourth plate-shaped member,
Photoreactive device with. The photoreactive device according to claim 1 or 2, wherein the second plate-shaped member reflects the light. The photoreactive device according to any one of claims 1 to 3, wherein the first plate-shaped member and the second plate-shaped member are arranged in an upright posture. The photoreactive device according to claim 4, wherein the flat flow path is opened as a supply port for the liquid to be reacted at the lower part of the reaction section and as a discharge port at the upper part of the reaction section. In the cross section of the flat flow path orthogonal to the flow direction of the reaction target liquid, when the length in the longitudinal direction is WP and the length in the lateral direction is TP, the ratio obtained by WP / TP is at least 3. The photoreactor according to any one of claims 1 to 5. The photoreactive device according to claim 1 , further comprising a backside temperature control mechanism that adjusts the temperature of the reaction unit from the side opposite to the light source unit side. The back side temperature control mechanism is
A fourth plate-shaped member arranged on the opposite side of the second plate-shaped member from the first plate-shaped member so as to face the second plate-shaped member with a gap.
A back side supply unit that supplies a heat transfer medium between the second plate-shaped member and the fourth plate-shaped member,
The photoreactor according to claim 7. In a photoreaction method in which a reaction target liquid containing a photoreactive compound is allowed to flow and the reaction target liquid is irradiated with light to cause a photoreaction.
A reaction unit including a flat flow path in which a set of facing surfaces is defined by a first plate-shaped member that transmits light and a second plate-shaped member that faces the first plate-shaped member with a gap. The reaction target liquid is supplied to the flat flow path, and the reaction target liquid is supplied.
A plurality of light sources that are arranged on the side of the first plate-shaped member opposite to the second plate-shaped member side of the reaction target liquid flowing in the flat flow path and emit the light are planar. The light is irradiated by the arranged light source unit,
A third plate-shaped member arranged on the light source unit side of the first plate-shaped member in a state of facing the first plate-shaped member with a gap and transmitting the light, and the third plate-shaped member. A light reaction method for adjusting the temperature of the reaction unit from the light source unit side by a light source side temperature control mechanism having a light source side supply unit for supplying a heat transfer medium between the first plate-shaped member . In a photoreaction method in which a reaction target liquid containing a photoreactive compound is allowed to flow and the reaction target liquid is irradiated with light to cause a photoreaction.
A reaction unit including a flat flow path in which a set of facing surfaces is defined by a first plate-shaped member that transmits light and a second plate-shaped member that faces the first plate-shaped member with a gap. The reaction target liquid is supplied to the flat flow path, and the reaction target liquid is supplied.
A plurality of light sources that are arranged on the side of the first plate-shaped member opposite to the second plate-shaped member side of the reaction target liquid flowing in the flat flow path and emit the light are planar. The light is irradiated by the arranged light source unit,
Adjust the temperature of the reaction unit from the light source unit side,
It is a back side temperature control mechanism that adjusts the temperature of the reaction unit from the side opposite to the light source unit side, and the second plate-shaped member is on the side opposite to the first plate-shaped member of the second plate-shaped member. The back surface having a fourth plate-shaped member arranged so as to face the member with a gap, and a back surface side supply unit for supplying a heat transfer medium between the second plate-shaped member and the fourth plate-shaped member. A light reaction method in which the temperature of the reaction unit is adjusted from the side opposite to the light source unit side by a side temperature control mechanism .

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