JP2021037458A - Photoreaction flow type reactor - Google Patents

Abstract

To provide a photoreaction flow type reactor capable of enhancing uniformity of reaction, in addition, to provide preferably, a photoreaction flow type reactor capable of enhancing uniformity of reaction even when a Reynolds number of a reaction mixture flowing in a reactor part is small.SOLUTION: A photoreaction flow type reactor comprises: a raw material liquid feeding part; a reactor part for circulating a raw material liquid from the raw material liquid feeding part toward an outlet; a light source for irradiating the raw material liquid in the reactor part; and a structure which is detachably stored in the reactor part, and which has a single or repeated structure of a swivel flow generation member or a plate-shaped obstacle.SELECTED DRAWING: Figure 1

Description

The present invention relates to a flow reactor that performs a photoreaction.

The flow reactor is a microflow reactor in which the flow path diameter is increased to the order of millimeters or centimeters, and while maintaining the high-speed mixing, precise temperature controllability, precision residence time controllability, etc. of the microflow reactor. , It is a chemical reaction device with higher operability and increased processing amount than a microflow type reactor, and is composed of a raw material liquid feeding section and a reactor section for reacting raw materials. Compared to batch reactors, flow reactors have been attracting attention in recent years because the entire process can be made more compact, and the reaction can be made faster and more efficient. For example, Patent Document 1 discloses a flow reactor for a photoreaction having a light-transmitting flow path that winds around a light source as a reaction unit.

Japanese Unexamined Patent Publication No. 2007-75682

However, the intensity of light is inversely proportional to the square of the distance from the light source. Therefore, in the flow reactor, the reaction progresses differently between the raw material liquid passing near the outer periphery of the flow path and the raw material liquid passing through the center of the flow path, and the uniformity of the reaction is lowered.
Therefore, an object of the present invention is to provide a flow reactor for a photoreaction capable of increasing the uniformity of the reaction. Another object of the present invention is preferably to provide a flow type reactor for a photoreaction capable of improving the uniformity of the reaction even if the Reynolds number of the reaction solution flowing through the reactor portion is low.

The present invention that has solved the above problems is as follows.
[1] The raw material liquid feeding unit, the reactor unit that distributes the raw material liquid from the raw material liquid feeding unit toward the outlet, the light source that irradiates the raw material liquid in the reactor unit, and the reactor unit are detachably housed in the reactor unit. A flow reactor for photochemical reaction, wherein the structure has a swirling flow generating member or a plate-like obstacle alone or repeatedly.
[2] The flow reactor according to [1], wherein the reactor portion is tubular.
[3] The plate-shaped obstacle has a planar outer shape that is the same as or similar to the cross section of the flow path of the reactor portion, and a flow port for the raw material liquid, and is arranged orthogonal to the flow path of the reactor portion. The flow reactor according to [1] or [2].
[4] The area of at least one of the distribution ports formed in one plate-shaped obstacle is 1% or more with respect to the cross-sectional area of the flow path.
The flow reactor according to [3], wherein the total area of all the flow ports formed in one plate-shaped obstacle is 80% or less with respect to the cross-sectional area of the flow path.
[5] The flow reactor according to any one of [1] to [4], wherein the structure is composed of a plurality of baffle plates installed apart from each other and a rod-shaped member connecting the baffle plates. ..
[6] The flow reactor according to any one of [1] to [5], wherein the light source is provided in the structure.
[7] The flow reactor according to any one of [1] to [6], wherein the light source is provided on the inner wall of the reactor portion.
[8] The flow equation according to any one of [1] to [7], wherein the light source is installed outside the reactor portion and the difference in refractive index between the reactor portion and the raw material liquid is −0.5 or more and +0.5 or less. reactor.

In the present specification, the shortest distance between the raw material liquid and the light source may be referred to as "optical path length".

According to the present invention, since a specific structure is housed in the reactor portion, the reaction progresses differently depending on the place where the raw material liquid passes, such as near the outer periphery or the central portion of the flow path, due to the difference in the optical path length. It can be eliminated and the uniformity of the reaction can be improved. Further, more preferably, according to the present invention, since a specific structure is housed in the reactor portion, the uniformity of the reaction can be improved even if the Reynolds number of the reaction solution flowing through the reactor portion is low. By increasing the uniformity of the reaction, it is possible to improve the yield and reduce impurities produced as a by-product during the reaction.

FIG. 1 is a schematic cross-sectional view showing an example of the flow reactor of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the reactor portion of the present invention. FIG. 3 is a schematic perspective view showing an example of the structure of the present invention. FIG. 4 is a schematic perspective view showing an example of a plate-shaped obstacle constituting the structure of the present invention. FIG. 5 is a schematic perspective view showing another example of a plate-shaped obstacle constituting the structure of the present invention. FIG. 6A is a schematic plan view showing another example of the structure used for the reactor portion of the present invention, and FIG. 6B is a schematic perspective view of the structure. FIG. 7 is a schematic cross-sectional view showing another example of the reactor portion of the present invention.

Hereinafter, the present invention will be described in more detail with reference to illustrated examples as necessary.
FIG. 1 is a schematic cross-sectional view showing an example of the flow type reactor 10 of the present invention, FIG. 2 is a schematic cross-sectional view of the reactor portion 20 used in the flow type reactor 10 of FIG. 1, and FIG. 3 is a schematic cross-sectional view of this reactor. It is a schematic perspective view of the structure 30 housed in the part 20.

The flow reactor 10 shown in FIG. 1 has a light emitting unit 50, a tubular reactor unit 20 arranged along the light emitting unit 50, and a raw material liquid supply line (raw material feed) connected to the inlet of the reactor unit 20. It has a liquid unit) 11 and a reaction liquid discharge line 12 connected to the outlet of the reactor unit 20. In such a flow type reactor 10, the light from the light emitting unit 50 reaches the inside of the reactor unit 20, so that the raw material liquid is supplied to the reactor unit 20 from the raw material liquid supply line 11 to cause a photoreaction in the reactor unit 20. It is possible to wake it up.

As shown in FIG. 2, the structure 30 is housed in the reactor unit 20. The layered flow of the raw material liquid that is irradiated with light in the reactor section 20 is destroyed by this structure 30, and the raw material liquid that has flowed near the outer periphery of the reactor section is directed toward the center of the reactor section or is flowing through the center of the reactor section. The distance (optical path length) between the raw material liquid in the vicinity of the outer circumference or the center of the flow path and the light emitting part (more accurately, the light source) is randomized, such as the raw material heading toward the outer circumference, and the photoreaction becomes uniform. Can be advanced. Further, the structure 30 of FIG. 2 can be attached to and detached from the reactor portion 20. For example, in the illustrated example, the structure 30 can be made removable by making the inlet side cap 21 or the outlet side cap 22 of the reactor portion removable. It is removable. By making the structure 30 removable, it is possible to replace the structure 30 with a structure 30 having an appropriate shape according to the reaction, and it becomes easy to clean the inside of the reactor portion 20 and the structure 30. In addition to the method using a cap, various known methods can be adopted for attachment / detachment. For example, the structure 30 can be folded, and the structure 30 can be folded and taken in / out from the reactor unit 20 at the time of attachment / detachment. The structure 30 that was folded when it was mounted in the reactor portion 20 may be opened.

More specifically, as shown in FIG. 3, the structure 30 of FIG. 2 has a plate-like obstacle (also an obstruction plate) having a planar outer shape (circular in the illustrated example) substantially the same as the cross section of the flow path 23 of the reactor portion 20. It has one or more (7 in the illustrated example) single or repeating structure (repeated structure in the illustrated example) of 31 (referred to as), and the plate-shaped obstacle 31 is arranged substantially orthogonally to the flow path 23. By doing so, the raw material liquid can be made into a turbulent state. Further, the plate-shaped obstacle 31 has one or more distribution ports 32 for the raw material liquid (one in the illustrated example), and the raw material liquid (or reaction liquid) can be sent toward the downstream side of the reactor. It becomes. Further, the plurality of obstacles 31 are connected by a rod-shaped member 33, and can be easily attached to and detached from the reactor portion 20.

The number of distribution ports 32 included in the baffle plate 31 of the structure 30 is, for example, 1 to 4, preferably 1 to 2, and more preferably 1. The outer shape of the distribution port 32 is not limited to the circular shape as shown in FIG. 3, and various shapes such as an ellipse and a polygon (for example, a quadrangle) can be adopted. Further, for example, as in the plate-shaped obstacle 34 shown in FIG. 4, the distribution port 36 may have a shape in which the circular flow path is blocked by two semicircular plates 35.

The distribution ports formed in the plate-shaped obstacles 31 and 34 may differ in their formation location, size, and the like for each of the plate-shaped obstacles 31 and 34. By arranging the plate-shaped obstacles 31 and 34 having different distribution ports, the mixing efficiency can be further improved.

As shown in FIG. 5, the plate-shaped obstacles 31 and 34 may have a tubular portion 37 attached to the outer periphery thereof. The direction of the plate-shaped obstacles 31 and 34 can be more reliably fixed by the tubular portion 37. When the tubular portion 37 is provided, the rod-shaped member 33 may connect the tubular portions 37 to each other, and the tubular portion 37 is lengthened in the flow path direction to fix the plurality of plate-shaped obstacles 31 to the tubular portion 37. It is also possible to eliminate the need for the rod-shaped member 33.

The area of the distribution ports 32 and 36 per of the plate-shaped obstacles 31 and 34 is, for example, 1% or more, preferably 3% or more, more preferably 5% or more, assuming that the flow path cross-sectional area is 100%. is there. When a plurality of distribution ports are formed in the plate-shaped obstacle, it is sufficient that at least one of them satisfies the above numerical range, and it is more preferable that all the distribution ports satisfy the above numerical range. .. Further, the upper limit of the area of the distribution ports 32 and 36 can be defined by the total area of the distribution ports 32 and 36 formed in one plate-shaped obstacle 31 and 34, and when the flow path cross-sectional area is 100%, the total area ( When there is one distribution port 32, 36, one area) is 80% or less, preferably 50% or less, and more preferably 30% or less.

When the structure 30 has a plurality of plate-shaped obstacles 31 and 34, the intervals between the plate-shaped obstacles 31 and 34 may or may not be constant. Further, the plate-shaped obstacles 31 and 34 may be biased to the upstream side of the reactor portion 20 or may be biased to the downstream side, but are preferably present without bias. The distance between the plate-shaped obstacles 31 and 34 is, for example, 30 to 2000, preferably 100 to 1500, and more preferably 300 to 1000, when the inner diameter of the flow path is 100.

As the structure 30, a structure having a function of mixing the liquid by flowing the liquid through the stationary structure 30 (that is, a static mixer (static mixer)) can be appropriately used, and an obstacle other than the plate-shaped obstacle can be used as appropriate. Can also be used as the structure 30. For example, a static mixer (static mixer) 40 having one or more swirling flow generating members as shown in the plan view of FIG. 6A and the perspective view of FIG. 6B can be mentioned. The structure (static mixer) 40 of FIG. 6 has a first element 41 that swirls the fluid in one direction and a second element 42 that swirls the fluid in the opposite direction in succession. Further, the first and second elements have blade ends (divided ends) 43 and 44 that divide the flow path into two, respectively, and the raw material liquid is divided and swirled in a complicated manner to efficiently distribute the raw material. The liquids can be mixed and the uniformity of the photoreaction can be improved.

In the structure 30 having the swirling flow generating portion (first element 41, second element 42, etc.), it is preferable that the swirling flow generating portions 41, 42 are directly connected without passing through the rod-shaped member 33 or the like. For example, as shown in FIG. 7, it is preferable that the first element 41 and the second element 42 are alternately connected and continuously housed in the reactor unit 20.

The swirling flow generating portions 41 and 42 may be biased to the upstream side of the reactor portion 20 or may be biased to the downstream side, but are preferably present through from the upstream side to the downstream side. The circle-equivalent diameter in the planar shape obtained by projecting the swirling flow generating portions 41 and 42 onto a plane orthogonal to the flow path is, for example, 95% or more, preferably 98% or more of the circle-equivalent diameter of the flow path cross section.

The volume of the structure 30 is, for example, 1 to 80%, preferably 1 to 30%, based on the internal volume of the reactor portion 20. The larger the volume of the structure 30, the higher the uniformity of the reaction, and the smaller the volume of the structure 30, the higher the productivity.

By accommodating the structure 30 in the reactor unit 20, the Reynolds number of the raw material liquid flowing in the reactor unit 20 is as low as, for example, 1 to 30, preferably 1 to 20, and more preferably 1 to 10. However, the same effect as when the number of Ray nozzles is 200 or more can be obtained. The effect to be obtained may be, for example, the same as when the number of ray nozzles is 8000 or less, and in particular, the same as when 2000 or less.

A catalyst may be supported on the structure 30 to carry out a solid-liquid reaction, and from the viewpoint of more efficiently transmitting light, a reaction in which a catalyst is not supported on the structure 30 is preferable. When a catalyst is supported on the structure 30, the refractive index of the structure 30 described later is the refractive index of the structure 30 and the supported catalyst as a weighted average.

The refractive index of the structure 30 is preferably closer to the refractive index of the raw material liquid. The smaller the difference in refractive index, the more the refraction and reflection of light at the interface between the raw material liquid and the structure 30 can be reduced, the less likely the difference in optical path lengths to occur, and the more uniform the photoreaction can be. The difference in refractive index between the structure 30 and the raw material liquid is preferably -0.5 or more and +0.5 or less, more preferably -0.4 or more and +0.4 or less, and further preferably -0.3 or more and +0. It is 0.3 or less. The refractive index is determined by the D line of Na (589.3 nm).
As will be described later, in the present invention, a light source may be provided in the reactor unit 20, and in this case, depending on the installation location of the light source, a structure 30 having no difference in refractive index can be preferably used. is there.

Examples of the material of the structure 30 include quartz, optical glass, fluororesin (Teflon (registered trademark), etc.), fluororubber, silicone rubber, vinylidene fluoride, silicone resin, silicone rubber, acrylic rubber, polypropylene, acrylic resin, and butyl rubber. , Nylon, polyethylene, polystyrene, polyester resin, melamine resin, polymethacrylic acid resin, nitrile rubber, transparent materials such as MBS resin, metal materials such as aluminum and stainless steel, ceramics and the like. When the raw material liquid is a transparent solution, a transparent material having durability against the raw material liquid can be preferably used, and when the refractive index of the raw material liquid is large, it has durability against the raw material liquid and refraction with the raw material liquid. A material having a rate difference of −0.5 or more and +0.5 or less can be preferably used.

In the example of FIG. 1, two tubular reactor units 24 are connected by a tube 13 to form one reactor portion 20, but the number of reactor portions is not particularly limited. For example, if the tube 13 is removed and the raw material liquid supply line and the reaction liquid discharge line are connected to each of the tubular reactor units 24, two reactor portions can be formed. Further, a reactor unit 20 other than the one shown in the drawing may be added to form a mode having three or more reactor units.

When the reactor portion 20 is tubular, the cross-sectional shape of the tubular reactor portion 20 may be elliptical or polygonal (square, hexagon, etc.) as well as circular. Further, if necessary, a planar reactor unit may be used. Further, the tubular reactor portion 20 may be formed of a hollow hard member or a hollow soft member. The tubular reactor portion 20 formed of a hard member is usually linear (rod-shaped), and the tubular reactor portion 20 formed of a soft member may be linear or curved, or spiral. May be good.

When the reactor portion 20 is tubular, the axial length of the tubular reactor portion 20 is, for example, 1 cm or more, preferably 5 cm or more. The upper limit of the axial length of the tubular reactor portion 20 is not particularly limited, but is, for example, 500 m or less, preferably 300 m or less. The length of the tubular reactor portion 20 can be appropriately determined according to the residence time of the reaction solution and the like.

When the reactor portion 20 is tubular, the diameter equivalent to a circle in the cross section of the flow path of the tubular reactor portion 20 is, for example, 0.1 mm or more and 100 mm or less in consideration of light irradiation efficiency, heat removal efficiency, and the like. From the viewpoint of ease of attaching and detaching the structure 30, it is preferably 1 mm or more and 70 mm or less.

When the reactor portion 20 is tubular, the circle-equivalent diameter of the flow path cross section of the tubular reactor portion 20 may be constant over the entire portion to be irradiated with light, in order to control the progress of the photochemical reaction and the heat removal performance. In addition, the diameter corresponding to the circle may be changed once or a plurality of times in the middle of the portion of the tubular reactor portion 20 that receives light irradiation. Further, the circle-equivalent diameter of the cross section of the flow path may be gradually changed, or may be greatly changed at a certain point as a boundary. The size of the structure 30 may be changed according to the equivalent diameter of the circle, the size of the structure 30 may be uniform in the entire reactor portion, and the shaft of the equivalent diameter of the circle of the tubular reactor portion 20. The relationship between the direction change and the structure 30 may be appropriately designed according to the reaction.

The refractive index of the wall portion 25 of the reactor portion 20 is preferably closer to the refractive index of the raw material liquid. The smaller the difference in refractive index, the more the refraction and reflection of light at the interface between the raw material liquid and the reactor portion 20 can be reduced, the less the difference in optical path length occurs, and the more uniform the photoreaction can be. The difference in refractive index between the wall portion 25 of the reactor portion 20 and the raw material liquid is -0.5 or more and +0.5 or less, preferably -0.4 or more and +0.4 or less, and more preferably -0.3 or more. It is +0.3 or less. The refractive index is determined by the D line of Na (589.3 nm).
As will be described later, in the present invention, a light source may be provided in the reactor unit 20, and in this case, a reactor unit 20 having no difference in refractive index can also be used.

A transparent material that is durable against the raw material liquid can be used for the reactor unit 20, and for example, quartz, optical glass, fluororesin (Teflon (registered trademark), etc.), fluororubber, silicone rubber, vinylidene fluoride, silicone resin, etc. Examples thereof include silicone rubber, acrylic rubber, polypropylene, acrylic resin, butyl rubber, nylon, polyethylene, polystyrene, polyester resin, melamine resin, polymethacrylic acid resin, nitrile rubber, MBS resin and the like.

The example of FIG. 1 is an example in which a long-axis (rod-shaped in the illustrated example) light emitting portion 50 is provided outside the tubular reactor portion 20. When the tubular reactor portion 20 is a linear type (rod type), the external long-axis light emitting portion 50 is preferably provided in parallel with the tubular reactor portion 20. When the light emitting unit 50 and the reactor unit 20 are arranged so as to be parallel to each other, reflection and refraction of light at the interface of the reactor unit 20 are less likely to occur, and the amount of irradiation light into the reactor unit 20 can be easily controlled. Further, as shown in FIG. 1, the tubular reactor portion 20 may be irradiated from one side by the external long-axis light emitting portion 50, but an external long-axis light emitting portion (particularly a rod-shaped light emitting portion) 50 may be further added. , The tubular reactor portion 20 may be irradiated from multiple directions.
The shape of the external light emitting unit 50 is not limited to the long axis shape, and an appropriate shape such as a spherical shape can be adopted. The tubular reactor portion 20 may be spirally wound around the outer circumference of the external light emitting portion 50 having an appropriate shape (for example, a cylindrical shape). By spirally winding the flow path around the external light emitting unit, the volume of the reactor unit 20 per unit volume can be increased, and the efficiency of the photochemical reaction and the compactness of the photoreactive device can be made possible.

In the example of FIG. 1, the point light source 51 is a point light source type light emitting unit arranged along the axial direction of the tubular reactor unit 20, but it may be a surface light source type light emitting unit having a planar light source.
Further, it is not necessary to provide the light source in the external light emitting portion, and the light source may be provided in the tubular reactor portion 20. For example, the structure 30 may be provided with a light source, more specifically, the plate-shaped obstacles 31 and 34 may be provided with a light source, or the rod-shaped member 33 or the tubular portion 37 may be provided with a light source. A light source may be provided in the flow generating portions 41 and 42. Further, a light source may be provided on the wall portion 25 of the tubular reactor portion 20. When the light source is provided in the reactor unit 20, the flow type reactor can be made compact. When the light source is provided in the reactor unit 20, it is preferable to cover the light source with a solvent-resistant transparent member so that the reaction solution and the light source do not come into direct contact with each other.

The light source may be evenly present from the upstream to the downstream of the reactor unit 20, may be biased toward the upstream side, or may be present at the downstream side. When the light source is biased to the upstream side, it is preferable that the structure is present at least on the upstream side of the reactor portion 20. When the light source is unevenly distributed on the downstream side, it is preferable that the structure is present at least on the downstream side of the reactor unit 20.

Examples of the light source include mercury lamps, acetylene lamps, electrodeless discharge lamps, HID lamps, low pressure discharge lamps, light emitting diodes (LEDs), fluorescent lamps, cold cathode fluorescent tubes, external electrode fluorescent tubes (EEFL), and electroluminescence. It is preferable to use an artificial light source such as a light, a laser, or a radiated light, but a natural light source may be used. The natural light source may be a focused one or one that cuts light other than a specific wavelength. The light source may be a combination of a plurality of light sources having different wavelengths, intensities, and the like. By having multiple light sources with different wavelengths and intensities, it is possible to select an appropriate wavelength and intensity according to the reaction, and it is also possible to change the wavelength and intensity according to the progress of the reaction. You can also. Further, the light source may be blinked.

The shortest distance (optical path length) from the raw material liquid to the light source is determined according to each part such as the surface layer portion and the deepest portion of the raw material liquid, and is, for example, 0.1 mm to 3 m, preferably 0.1 mm to 30 cm, more preferably 0.1 mm to 30 cm. It is 0.1 mm to 10 cm.

The example of FIG. 1 is an example in which the reactor portion 20 is housed in the jacket 15 and the reaction temperature can be adjusted. The flow reactor has a feature of being excellent in responsiveness to an external temperature, and by using the jacket 15, more accurate temperature control becomes possible. A temperature control facility different from that of the jacket 15 may be used, and for example, a bath whose inside is filled with a temperature control medium may be used. It is not essential to use temperature control equipment such as jacket 15 and bath, but when using temperature control equipment (jacket 15 etc.) and external light emitting unit 50, as shown in FIG. 1, the external light emitting unit 50 is also used. It is preferably housed in a temperature control facility (jacket 15, etc.).

The raw material feeding unit 11 can adopt an appropriate structure depending on the raw material liquid to be sent. For example, when the liquid raw material is used alone as the raw material liquid, the line connecting the raw material liquid storage container and the reactor unit 20 can be used as the raw material liquid feeding unit (raw material liquid supply line) 11. Further, when a mixture of the raw material with another raw material and / or a solvent is used as the raw material liquid, the line connecting the container containing this mixture and the reactor unit 20 is used as the raw material liquid feeding unit (raw material liquid supply line) 11. it can. When a mixture of raw materials with other raw materials and / or a solvent is used as the raw material liquid, a mixer is connected to a supply line corresponding to each of the mixed components, and the raw material liquid prepared by this mixer is supplied as the raw material liquid. It may be supplied from the line 11. Workability is further improved by using a mixed component supply line and a mixer. It is preferable that at least one of the mixed component supply lines is a liquid supply line containing one or more of the raw materials, and the rest is a liquid supply line containing other raw materials and / or a solvent. , It may be a supply line containing a gas raw material.

It is desirable that the raw material liquid feeding unit 11 includes a liquid feeding control unit such as a diaphragm pump and a gear pump. Further, the liquid feed control unit is not limited to the pump, and may be, for example, a raw material liquid storage container in which the internal pressure is increased. The number of liquid feed control units may be the same as the number of various supply lines such as the raw material liquid supply line and the mixed component supply line, and may be less or more than the number of supply lines. Further, by attaching an appropriate pulsation generation mechanism, vibration generator, etc., and causing the raw material liquid to flow or vibrate in the reactor section 20 in the front-rear direction, the raw material liquid and the structure 30 interact with each other to cause a vortex flow. May be formed to improve the mixing property.

A second chemical inflow line may be connected to the reactor unit 20 in the middle thereof, or a branch structure may be inserted in the reactor unit 20, if necessary. When the second chemical inflow line is connected, the reactants generated so far in the reactor section 20 can be reacted with the second chemical solution, and the reactor section 20 can carry out a complicated reaction. When the second chemical solution is a quenching agent, the reaction can be stopped. By inserting the branched structure, a part of the reaction solution can be extracted from the middle.

A measuring device (monitoring device) may be appropriately provided in the flow type reactor 10 for photoreaction, if necessary. For example, a pressure sensor, a temperature sensor, a flow rate sensor, a particle size distribution measurement probe, etc. are appropriately attached to the structures 30 and 40, or branch points are provided at two points in the middle of the reactor portion 20 to form parallel lines connecting the branch points. Then, a pressure sensor, a temperature sensor, a flow rate sensor, a particle size distribution measuring probe, or the like may be appropriately attached to the parallel lines. By installing these measuring devices, more appropriate reaction control becomes possible.

The reaction liquid discharge line 12 of the flow type reactor 10 for photoreaction may be connected to the reaction liquid storage tank, if necessary.
The flow reactor 10 for photoreaction is, for example, an example of a photoreaction operation of a fluid. That is, the present invention also includes the manufacturing equipment having the above-mentioned flow reactor 10 for photoreaction.

Examples of the reaction solvent that can be used in the flow reactor 10 for photoreaction include an aliphatic hydrocarbon solvent such as n-hexane, cyclohexane, and methylcyclohexane, an aromatic hydrocarbon solvent such as benzene, toluene, and xylene, and diethyl. Ether-based solvents such as ether, diisopropyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, 4-methyltetrahydropyran, methyl-tert-butyl ether, 1,4-dioxane, cyclopentylmethyl ether, methanol, ethanol, n-propanol, isopropanol, n -Alcohol solvents such as butanol, tert-butanol and benzyl alcohol, halogen solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane and chlorobenzene, ester solvents such as ethyl acetate, propyl acetate and butyl acetate, acetone , Methyl ethyl ketone, methyl isobutyl ketone and other ketone solvents, acetonitrile, propionitrile, butyronitrile and other nitrile solvents, N, N-dimethylacetamide, N-methylpiolidone and other amide solvents and the like. These reaction solvents may be used alone or in admixture of two or more.

In the flow reactor 10 for photoreaction, various photoreactions can be carried out, and it can be applied to all reactions generated by light irradiation, such as cis-trans isomerization reaction, rearrangement reaction, cycloaddition reaction, and cleavage reaction. The fluid flowing to the reactor section is not particularly limited, and can be applied to a photoreaction in a solution system, a photoreaction in a gas-liquid system, a photoreaction in a solid-liquid system, and the like.

The temperature of the reactor unit 20 during the reaction is not particularly limited as long as it is below the boiling point of the reaction solvent and above the freezing point, and is preferably −80 ° C. or higher, more preferably −60 ° C. or higher, still more preferably −40 ° C. or higher. It is preferably 200 ° C. or lower, more preferably 180 ° C. or lower.

The flow velocity of the reaction fluid in the reactor section is preferably 2 m / s or less, more preferably 1.5 m / s or less. The irradiation time (residence time) is preferably 180 minutes or less, more preferably 120 minutes or less, and further preferably 60 minutes or less.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.

The Paterno-Buch reaction described in Examples 1 and 2 and Comparative Examples 1 to 3 below was analyzed by a gas chromatography (GC) method, and the yield and the proportion of impurities were calculated.

The Paterno-Buch reaction described in Examples 1 and 2 and Comparative Examples 1 to 3 is a photoreaction that synthesizes oxetane from carbonyl and alkene, as shown by the following chemical formula.

The yield in this reaction was calculated by the following formula.
Yield = (Oxetane concentration in reaction solution) / (Ethyl benzoylate concentration before reaction) x 100
The main by-product in this reaction was benzaldehyde, and the proportion of impurities was calculated by the following formula.
Percentage of impurities = (Benzaldehyde concentration in reaction solution) / (Oxetane concentration in reaction solution) x 100

The GC conditions are as follows.
Equipment used GC2014 (manufactured by SHIMADZU)
GC measurement conditions Column: SUPELCO WAX (manufactured by Sigma-Aldrich Japan Co., Ltd.)
Column length: 30m
Inner diameter: 0.25 mm
Liquid phase film thickness: 0.25 μm
Detector: FID (Flame Ionization Detector)
Carrier gas: He
Gas flow rate: 50 ml / min
Temperature pattern: 50 ° C for 10 minutes hold → 160 ° C (20 ° C / min) → 15 minutes hold Injection amount: 1.0 μl

(Example 1)
Circular circulation with an inner diameter of 5 mm, an axial length of 20 cm, and a refractive index of 1.3 in the reactor portion of a Teflon (registered trademark) tube having the same planar outer shape as the flow path cross section of the reactor portion and an inner diameter of 1.5 mm. Six 1.2 mm-thick SUS316 baffle plates having one mouth were arranged at 3 cm intervals so as to be orthogonal to the flow path of the reactor portion. The six baffle plates are a structure in which two rod-shaped members having a thickness of 1 mm and a length of 20 cm and made of SUS316 are connected to each other. Further, outside the reactor section, a black light fluorescent lamp (10 W) having a central wavelength of 365 nm is used as a light source, and the surface layer section is installed so that the optical path length is 1 mm. It was connected to obtain a flow reactor for photoreaction. The above-mentioned Paterno-Büch reaction was carried out using the obtained flow reactor for photoreaction. A toluene solution (refractive index: 1.5) prepared by mixing 0.01 M ethyl benzoate and 0.02 M 2,3-dimethyl-2-butene was prepared, and the flow rate was 1 ml / min (equivalent to 6.2 Reynolds number). ), The irradiation time was set to 200 seconds, and the liquid was passed through the reactor section. The yield of oxetane after the reaction was 17.2%, and the ratio of the major impurities to oxetane was 14.7%.

(Example 2)
As a light source, an LED (20 W) having a central wavelength of 365 nm was installed instead of the black light, and the same flow reactor for photoreaction as in Example 1 was used, and the same reaction solution as in Example 1 was used under the same conditions. The liquid was passed through (equivalent to a Reynolds number of 6.2), and the above-mentioned Paterno-Büch reaction was carried out. The yield of oxetane after the reaction was 29.9%, and the ratio of major impurities to oxetane was 30.4%.

(Comparative Example 1)
The above-mentioned Paterno-Buch reaction was carried out using the same flow-type reactor for photoreaction as in Example 1 except that the structure was not housed in the reactor section. When the same reaction solution as in Example 1 was passed under the same conditions (Reynolds number 6.2), the yield of oxetane after the reaction was 14.6%, and the ratio of major impurities to oxetane was 20.0%. It was.

(Comparative Example 2)
Using the same reactor and reaction solution as in Comparative Example 1, the flow rate was set to 68 ml / min (Reynolds number 424), and the above Paterno was circulated so that the irradiation time per unit volume was equivalent to that in Comparative Example 1. -When the Buch reaction was carried out, the yield of oxetane after the reaction was 18.9%, and the ratio of the major impurities to oxetane was 24.8%.

(Comparative Example 3)
The above-mentioned Paterno-Buch reaction was carried out using the same flow-type reactor for photoreaction as in Example 2 except that the structure was not housed in the reactor section. When the same reaction solution as in Example 1 was passed under the same conditions (Reynolds number 6.2), the yield of oxetane after the reaction was 25.2%, and the ratio of major impurities to oxetane was 40.3%. It was.

The flow reactor for photoreaction can be used for the photoreaction of various substances.

10 Flow reactor 11 Raw material liquid supply section (raw material liquid supply line)
12 Reaction liquid discharge line 13 Tube 15 Jacket 20 Reactor part 21 Inlet side cap 22 Outlet side cap 23 Flow path 24 Tubular reactor unit 25 Wall part 30 Structure 31, 34 Plate-shaped obstacle 32, 36 Raw material liquid distribution port 33 Rod-shaped Member 35 Semicircle 37 Cylinder 40 Static mixer (structure)
41 1st element 42 2nd element 43, 44 Divided end 50 Light emitting part 51 Light source

Claims (8)

A structure that is detachably housed in the raw material feeding section, a reactor section that circulates the raw material liquid from the raw material feeding section toward an outlet, a light source that irradiates the raw material liquid in the reactor section, and the reactor section. A flow reactor for photochemical reaction, wherein the structure has a swirling flow generating member or a plate-like obstacle alone or repeatedly. The flow reactor according to claim 1, wherein the reactor portion is tubular. Claim that the plate-shaped obstacle has a planar outer shape that is the same as or similar to the cross section of the flow path of the reactor portion, and a flow port of the raw material liquid, and is arranged orthogonal to the flow path of the reactor portion. The flow reactor according to 1 or 2. The area of at least one of the distribution ports formed in one plate-shaped obstacle is 1% or more with respect to the cross-sectional area of the flow path.
The flow reactor according to claim 3, wherein the total area of all the flow ports formed in one plate-shaped obstacle is 80% or less with respect to the cross-sectional area of the flow path. The flow reactor according to any one of claims 1 to 4, wherein the structure is composed of a plurality of baffle plates installed apart from each other and a rod-shaped member connecting the baffle plates. The flow reactor according to any one of claims 1 to 5, wherein the light source is provided in the structure. The flow reactor according to any one of claims 1 to 6, wherein the light source is provided on the inner wall of the reactor portion. The flow reactor according to any one of claims 1 to 7, wherein the light source is installed outside the reactor unit, and the difference in refractive index between the reactor unit and the raw material liquid is −0.5 or more and +0.5 or less.

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