JP2007252979A - Method for manufacturing compound by micro-reactor, its micro-reactor and distributor for micro-reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and a device for manufacturing a compound which mix and react a plurality a raw material solutions while the interaction of a pipe wall, an intermediate product and a product is cut off, and a mixing time is suppressed. <P>SOLUTION: A method is used which fractionates two or more solutions to a plurality of minute segments and arranges them suitably by using a distributor made by stacking grooved thin layers. The arranged solutions are mixed in the downstream. Further, at the time of mixing, micro-mixing is performed by generating turbulent flow in the solutions flowing in a micro-channel 12 by a turbulent flow generating means 17. The intensity (Re number) of the turbulent flow and a period of time when the turbulent flow occurs are controlled. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a compound by a microreactor for producing a compound by reacting a plurality of solutions in a microchannel, the microreactor, and a shunt for the microreactor. More specifically, the present invention relates to a method for producing a compound for efficiently performing a chemical reaction by subdividing a solution into a plurality of segments and supplying the solution into a microchannel for chemical reaction, and a microreactor and a shunt for the microreactor. .

  In the production and production of chemical compounds, efforts are made every day to improve the chemical reaction reaction control, such as supply of chemical reaction samples, mixing, heat supply for reaction activation, heat removal, and efficient catalytic reaction. ing. Improved reaction control allows for improved production safety, reaction product yield, reaction product purity, and isolation of useful highly active intermediate products.

  Conventionally, a large reaction tank is generally used for chemical reaction. In recent years, as a device for generating fine particles, a device for performing a chemical reaction in a micro flow channel connected to a plurality of solution supply pipes typified by a microreactor or a micromixer has been studied. Research aimed at increasing the efficiency of chemical reactions using these devices and creating new compounds has attracted attention. This micromixer or microreactor causes a chemical reaction by diffusion and mixing of a plurality of fluids in a narrow flow path having an inner diameter on the order of submicrometers to millimeters.

  The object for mixing a plurality of fluids is generally defined as a micromixer. The microreactor is for performing a chemical reaction while diffusing, mixing, or mixing a plurality of fluids. Hereinafter, the microreactor will be described as including a micromixer.

  If the flow path is made smaller, the heat capacity of the liquid in the flow path is reduced, so that heat exchange from other parts constituting the microreactor to the flow path can be performed quickly. Thereby, temperature control of the chemical reaction in the flow path can be easily performed. In addition, the microreactor is highly efficient and can control chemical reactions between the solution phases flowing in the flow path, so it is innovative for chemical synthesis, creation of new compounds, analysis and analysis of various samples, etc. It is highly expected to bring about change.

  Some active chemical reaction control devices perform rapid mixing by mechanically mixing minute regions such as a magnetic stirrer. In the magnetic stirrer, a rod-like or plate-like permanent magnet for stirring is arranged in a container containing a reaction solution. When a driving permanent magnet disposed outside the container is driven by a motor, the stirring permanent magnet is rotated by receiving the magnetic force to stir the reaction solution and promote the reaction.

  Patent Document 1 discloses a method for producing nanoparticles using a microchannel having a particle diameter of 1 μm to 1 mm. Specifically, a precursor-containing solution for forming particles in a microchannel is rapidly heated to the reaction start temperature while being continuously supplied, and the reaction is performed, followed by rapid cooling to produce nanoparticles. It is. In this manufacturing method, the particle size is controlled by controlling the heating temperature and time.

  Patent Document 2 discloses a structure of a microreactor. The fluids A and B are merged from the fluid introduction part into the microchannel of the microreactor, and a complex reaction is performed by molecular diffusion. At this time, in the radial cross section at the inlet of the microchannel, the fluids A and B are divided into a plurality of fluid segments A and B and merged, and these fluid segments A and B are circulated as a laminar flow by molecular diffusion. Mix to allow complex reaction.

  Further, as a chemical reaction control device having no movable part and no power part, there is a static mixer or the like. The static mixer is intended to facilitate mixing by complicating the flow of the mixed liquid flowing in the pipe. In the static mixer, a rectangular plate-like element is twisted and arranged in a pipe, and the flow of the mixed liquid changes every time it passes through the element. For example, the liquid mixture is split as it passes through the element, or is changed from the center of the tube to the wall or from the wall to the center along the twist of the element.

  There is a chaotic mixer as a mixing / reactor using chaotic convection instead of turbulent flow. Patent Document 3 discloses a chaotic mixer. In a static mixer or the like, basically, mixing is performed by alternately laminating a plurality of laminar flows. A chaotic mixer performs mixing by three-dimensionally folding a laminar flow of a plurality of solutions.

The ceramic microreactor of Non-Patent Document 1 generates nanoparticles with two kinds of reaction solutions flowing in a laminar flow. In the zigzag channel of Non-Patent Document 2, two types of solutions are injected to generate nanoparticles.
The microreactor of Non-Patent Document 3 uses a double tube to create a concentric liquid flow and synthesize the particles only in the inner liquid to prevent the synthesized particles from adhering to the tube wall. is doing.
Japanese Patent Publication No. 2003-225900 Japanese Patent Publication No. 2005-262053 Japanese Patent Publication No. 2004-287991 H. Wang et.al., Chem. Comm., Pp. 1462-1463 (2002) Paul JAKenis et.al., Science, vol285, p83-85 (1999) M. Takagi et.al., Chem. Eng. J., 101, 269 (2004)

  In a nanoparticle synthesis reaction in which the reaction proceeds in a time of 1 second or less, that is, a gold nanoparticle synthesis reaction using tannic acid and citric acid as a reducing agent, a crystallization reaction by addition of a poor solvent, etc., mixing is performed. If the reaction proceeds at a non-uniform time, the reaction becomes non-uniform. For this reason, the deposition rate is fast, and it is necessary to mix uniformly in a sufficiently short time compared to the reaction time of the precipitant and the raw material. However, conventionally, in the batch-type synthesis method using a stirring tank or the like as a reactor, when the volume of the container increases, mixing between the solutions can be performed in centimeter order macro mixing, millimeter order meso mixing, or micrometer. Mixing is performed in the order of order micromixing. For this reason, it takes time to mix the solutions.

On the other hand, in the recently developed diffusion mixing by the microreactor, the mixing time is defined by the diffusion rate of the reactive species. The mixing speed by the diffusion of the solution under laminar flow can be obtained using the following Peclet number Pe.
Pe = Dt / L ² (Formula 1)
However, D [m ² / s] is a diffusion coefficient, t [s] is time, and L [m] is a length (tube diameter) for diffusion.

For complete mixing, the condition is that the Peclet number Pe is 1, and the time t is t <L ² / D (Equation 2)
Mix thoroughly in time. The diffusion coefficient D can be roughly calculated by the following Stokes-Einstein equation.
D = kT / (6πηα) (Formula 3)
Where k [J / K] is the Boltzmann constant, T [K] is the absolute temperature, η [Pa · s] is the viscosity coefficient, and α [m] is the particle diameter or molecular diffusion diameter.

In Equation 3, the diffusion coefficient D is inversely proportional to the particle diameter α. For example, the diffusion coefficient D of a molecule having a size of 0.3 nm (particle diameter α =) in water is about 10 ⁻⁹ m ² / s. When (particle diameter α =) 3 nm, the diffusion coefficient D is 10 ⁻¹⁰ m ² / s. From this, the layer width for complete mixing in 2 seconds is 30 μm at 0.3 nm and 10 μm at 3 nm. Therefore, in the case of a low molecule (size of about 0.3 nm), a layer thickness of 30 μm or less is desirable for a reaction that is completed in 10 seconds or less.

  However, even in this case, in the case where the reaction proceeds sufficiently in a few seconds (depending on the type of reaction, for example, about several tens of percent of the final yield), the diffusion length L Must be reduced to the order of a few μm or less. For this reason, when reaction intermediates or reaction products are involved in secondary reactions, or in crystallization reactions where the crystallization speed is sub-second or less, mixing occurs at a point in time, resulting in the formation of multiple products. There is a problem that the particle size distribution is likely to increase or agglomerate.

  Furthermore, in the case of a tubular reactor, when a product, a raw material, a by-product, or the like comes into contact with the wall of the reactor, they may precipitate, preventing continuous operation. However, in the static mixer, the flow pattern in the direction perpendicular to the flow direction can be controlled only one-dimensionally. In addition, the chaotic mixer basically performs a three-dimensional folding of the laminar flow, but because of its complicated structure, it tends to cause partial turbulence especially when the flow velocity is high. Reactant species are likely to contact the reactor wall. Active micromixers are essentially turbulent and difficult to prevent reactants from contacting the reactor walls.

  In the above-described static mixers and the like, the layer interface comes into contact with the wall surface of the container, so the interface caused by the contact of different solutions also comes into contact with the wall surface of the container. When contacting with the wall surface of the container in this way, the product generated by the reaction at the layer interface may adhere to the tube wall or the reaction between this product and the tube wall may occur. Thus, the product produced by the contact of the solution may interact with the wall surface of the container, which may affect the overall reaction.

  On the other hand, in order to break the contact between the tube wall and the reaction solution, there is a method using a two-flow tube (see Non-Patent Document 3). Since this interior is basically laminar, mixing occurs by diffusion. However, in order to shorten the diffusion time, it is necessary to make the reaction solution in the center thinner, so that the production volume decreases, and conversely if the layer of the reaction solution in the center is made thicker in order to improve the production volume , The mixing time becomes longer.

  Furthermore, in the nanoparticle production method of Patent Document 1, when synthesizing nanoparticles, two liquids are mixed in advance, or the sample solution and the reagent solution are forcibly stirred with a nanomaterial stirrer, The product is obtained by heating. In this case, the above interaction often occurs because the inner wall of the tube is in contact with the mixed solution. In addition, even if the inside of the tube is laminar, the flow velocity distribution can be made in the direction perpendicular to the flow due to friction with the wall, so there is a problem that the heating time varies slightly and the particle size distribution of the generated nanoparticles is widened. .

The present invention has been made based on the technical background as described above, and achieves the following objects.
An object of the present invention is to produce a compound by mixing a plurality of raw material solutions while causing the reaction between the tube wall and the intermediate product, the tube wall and the product to be stopped, and suppressing the mixing time, and causing the reaction to occur. A method for producing a compound using a microreactor, the microreactor, and a shunt for the microreactor are provided.

  Another object of the present invention is to provide a method for producing a compound by a microreactor, the microreactor, and a shunt for the microreactor in order to improve the productivity of the product while preventing the product from being deposited on the tube wall.

In order to achieve the above object, the present invention employs the following means.
The method for producing a compound by the microreactor according to the first aspect of the present invention is used in a method for producing a compound by introducing a plurality of types of solutions into a microchannel and reacting them by combining them in a laminar flow to produce a compound. In the cross-section in the flow direction of the solution before the merge, each of the solutions is subdivided into a plurality of segments by a flow divider, the solutions of the adjacent segments are merged in a micro flow path in a laminar flow, and the merge Thereafter, turbulent flow is generated in the solution by turbulent flow generation means, and the solution is micromixed to perform the reaction.

  The method for producing a compound by the microreactor according to the second aspect of the present invention is the method for producing a compound by the microreactor according to the first aspect, wherein the flow rate of the solution is increased by narrowing a cross section in the flow direction of the solution after merging in the laminar flow. The turbulent flow is generated.

  The method for producing a compound by the microreactor according to the third aspect of the present invention is the method for producing a compound by the microreactor according to the first aspect, wherein the turbulence swirls the solution around an axis along which the solution flows. And

  The method for producing a compound by the microreactor according to invention 4 of the present invention is the method for producing a compound by the microreactor according to one invention selected from inventions 1 to 3, wherein the solutions subdivided into the plurality of segments are joined together in a laminar flow. Then, after the molecular diffusion reaction is performed between the adjacent segments, the reaction is performed by micromixing the solution by the turbulent flow generation means.

  The method for producing a compound by the microreactor according to invention 5 of the present invention is the method for producing a compound by the microreactor according to one invention selected from the inventions 1 to 3, wherein the microchannel is heated or cooled in order to control the reaction. It is characterized by doing.

  The method for producing a compound by the microreactor according to invention 6 of the present invention is the method for producing a compound by the microreactor according to one invention selected from the inventions 1 to 3, wherein the turbulent flow has a Re number of 200 or less. To do.

  The method for producing a compound by the microreactor according to the invention 7 is the method for producing a compound by the microreactor according to one invention selected from the inventions 1 to 6, wherein the compound is a nanoparticle having a typical particle length of 1 nm to 100 nm. It is characterized by being.

  The microreactor according to the eighth aspect of the present invention is a microreactor in which a plurality of types of solutions are introduced into a microchannel and combined to react in a laminar flow, and a plurality of sample supply channels for supplying the plurality of types of solutions. (14) and a shunt connected to the sample supply channel (14) for subdividing each of the solutions into a plurality of segments in a cross section in the flow direction of the solution before the merging. 20) for joining the segments, connected to the flow path (16) connected to the flow divider (20), and connected to the flow path after the flow for mixing and reacting the solution A turbulent flow generating means (17, 26, for micro-mixing the solution by generating a turbulent flow in the solution after merging the solution in the micro flow channel (12) and the adjacent segment in a laminar flow 3 , 31) and after the reaction is performed in the microchannel (12), a sample discharge channel (18) connected to the microchannel (12) to discharge the reaction product after the reaction. ).

  The microreactor according to the ninth aspect of the present invention is the microreactor according to the eighth aspect, wherein the merging channel (16) is a merging portion (for constricting the section by reducing the section stepwise in order to increase the flow rate of the merging solution. 16).

  The microreactor according to the tenth aspect of the present invention is the microreactor according to the eighth or ninth aspect, wherein the turbulent flow generation means (17) partially circulates the flow of the solution to stir the solution flowing in the microchannel. It is a baffle plate (26) for damming.

  A microreactor according to an eleventh aspect of the present invention is the microreactor according to the eighth or ninth aspect, wherein the turbulent flow generation means (17) is a fixed helical fixed blade (30) whose axis is the direction in which the solution flows. And

  A microreactor according to a twelfth aspect of the present invention is characterized in that, in the eighth or ninth aspect, the turbulent flow generation means (17) is a rotatable spiral blade (31) whose axis is the direction in which the container flows.

  A microreactor according to a thirteenth aspect of the present invention is the microreactor according to the eighth or ninth aspect, wherein the turbulent flow generation means (17) has a smaller / larger inner diameter of the tube of the microchannel (12). Features.

  A microreactor according to a fourteenth aspect of the present invention is the microreactor according to the eighth or ninth aspect, wherein the turbulent flow generation means (17) is a device that generates ultrasonic waves, and irradiates the micro flow path (12) with the ultrasonic waves, A turbulent flow is generated in the solution.

  The microreactor according to the fifteenth aspect of the present invention is that, in the eighth or ninth aspect, the turbulent flow generation means (17) generates a turbulent flow in the solution by reducing an inner diameter of the discharge end of the merging channel (16). Features.

  The microreactor according to the sixteenth aspect of the present invention is the microreactor according to one aspect selected from the eighth to fifteenth aspects, wherein the temperature of the solution is controlled by heating or cooling in the microchannel (12). And temperature sensor means for measuring the temperature.

  The microreactor according to the seventeenth aspect of the present invention is the microreactor according to the first aspect of the invention selected from the ninth to fourteenth aspects, wherein the segment discharged from the flow divider (20) and introduced into the microchannel (12) includes: It is characterized by being subdivided into 1 mm or less and arranged in parallel.

The microreactor of the invention 18 of the present invention is the microreactor of the invention 8,
A diameter of a cross-sectional area of the microchannel (20) is 1 mm or less after the restriction.

  The flow divider for the microreactor of the invention 19 of the present invention is the microreactor of one invention selected from the inventions 8 to 18, wherein the flow divider (20) is in a cross section in the flow direction of the solution before the merging. , Connected to a plurality of sample supply channels (14) for supplying the plurality of types of solutions, and connected to each of the sample supply channels (14) (21, 22, 51, 52); , Connected to the introduction part (21, 22, 51, 52), changing the direction of flow for each solution and diverting into a plurality of flows, and from the introduction part (21, 22, 51, 52) An intermediate part (23, 24, 53, 54, 55, 56) that is subdivided into a plurality of segments for each type of solution and the intermediate part (23, 24, 53, 54, 55, 56) Of the subdivided solution A discharge section (16, 25, 40, having a discharge hole for mixing the types to mix the solution, and relatively reducing the pressure loss difference between the segments at the introduction section and the intermediate section. 56).

  The microreactor for the microreactor according to the twentieth aspect of the present invention is the shunt for the microreactor according to the nineteenth aspect of the present invention. 16, 25, 40, 56), the thickness in the direction perpendicular to the flow of the segments after being discharged is adjusted.

  The shunt for a microreactor according to a twenty-first aspect of the present invention is the microreactor according to the nineteenth aspect of the present invention, wherein the converging channel (16) has a conical surface whose bottom is connected to the discharge portion and whose apex is connected to the microchannel (12). It is characterized by its shape.

  The method for producing a compound by the microreactor according to inventions 1 to 7 of the present invention is preferably a method for producing nanoparticles. Further, the compound production method using the microreactor may be a method of producing nanoparticles by mixing a nanoparticle raw material dissolved in a good solvent with a poor solvent in a short time.

According to the present invention, the following effects can be obtained.
In the microreactor of the present invention, a reaction solution necessary for producing a compound is subdivided into fine segments and uniformly mixed, and a compound is produced by a contact reaction between different reaction solutions between adjacent segments. In addition, a turbulent flow is generated in the reaction solution flowing in the microreactor to produce a compound by micromixing. Thereby, the reaction solution is micro-mixed and the mixing time can be suppressed, so that the reaction solution can be uniformly mixed.

Moreover, by optimizing the segment by controlling the size and arrangement of the segment, precipitation on the pipe wall was prevented and the production efficiency of the product was improved.
Furthermore, by controlling the size and arrangement of the segments, it became possible to continuously produce nanoparticles with a uniform quality and a finer particle size distribution. Furthermore, since the shunt for the microreactor according to the present invention can be manufactured by an ordinary machining method, it can be mass-produced.

  Hereinafter, a method for producing a compound using the microreactor of the present invention, the microreactor, and a shunt for the microreactor will be described with reference to the drawings. FIG. 1 is a schematic diagram showing an entire microreactor 10 according to an embodiment of the present invention. The microreactor 10 divides a compound-generating solution supplied from a plurality of supply pipes 14 into a plurality of segments in a flow divider 20, mixes them in a junction 16, and reacts them in a microchannel 12. Is generated.

  The flow divider 20 has a three-dimensional flow path arrangement, and the inside thereof has a structure in which the solution is divided into a plurality of segments and supplied to the micro flow path 12 by laminar flow or turbulent flow. The flow divider 20 is configured by combining a plurality of flat plates with through holes for flowing a solution and laminating along a flow path, and a three-dimensional flow path is formed. The microreactor 10 also has turbulent flow generation means 17 for generating turbulent flow in the solution flowing through the microchannel 12.

  Hereinafter, the microreactor 10, the current divider 20 of the microreactor 10, the turbulent flow generating means 17 for generating turbulent flow, and the like according to the present embodiment will be described in more detail with reference to the drawings. FIG. 2 is a cross-sectional view showing the structure when the flow divider 20 is cut along a cross section along the flow line of the solution. FIG. 3 is a diagram showing the structure of each layer constituting the flow divider 20.

[Structure of microreactor 10]
As the reactor of the microreactor 10, a reactor having a pipe line and a space of 1 μm to 1 mm is used. For example, in this example, a microchannel 12 having a tube inner diameter of 1 μm to 1 mm is used. As shown in FIG. 1, the microreactor 10 causes a reaction to be performed, a supply pipe 14 for supplying a solution, a flow divider 20 for diverting the supplied solution into a plurality of segments, a confluence 16 for narrowing the solution, and the reaction. And a discharge pipe 18 for taking out the liquid after reaction and the generated particles. The microchannel 12 has turbulent flow generating means 17 for generating turbulent flow in the solution flowing through the microchannel 12.

  The supply pipe 14 is for introducing a solution as a raw material into the microreactor 10, and a plurality of supply pipes 14 are arranged in parallel with each other in order to supply one or a plurality of solutions simultaneously or with a time difference. It is preferable to introduce the solution into the supply pipe 14 at a constant pressure and flow rate. For this purpose, the supply pipe 14 includes a syringe containing a solution, a syringe connector for connecting the syringe to the supply pipe 14, and an injection amount of the solution supplied from the syringe to the supply pipe 14. A pump, a flow rate adjusting valve (not shown) and the like are connected.

  In the present embodiment, two types of solutions (solution A and solution B) are introduced into the microreactor 10 and the reaction is performed. However, depending on the type of product and the control of the reaction, three or more types of solutions are introduced into the microreactor 10 and the reactions of all the solutions or a part of the solutions are supplied simultaneously or with a time difference. Reaction may be performed.

  The flow divider 20 is for diverting the reaction solution into fine segments. The solution A and the solution B are supplied from the supply pipe 14 to the flow divider 20. The solution A and the solution B supplied to the flow divider 20 are divided (divided) into a plurality of flows, that is, segments, and discharged from the flow divider 20. This flow will be described as a segment. The shape of the segment depends on the structure of the flow divider 20 and can be changed by changing the structure of the flow divider 20.

  As shown in FIG. 2, the solution A is divided into two or more segments A. Similarly, solution B is diverted into two or more segments B. When discharged from the flow divider 20, the segment A and the segment B are arranged in a predetermined arrangement. For example, all segments adjacent to segment A can be arranged to be segment B. Segment B is similar. This arrangement is due to the structure of the shunt 20, and the arrangement of the segments A and B can be changed by changing the design of the internal compartment.

  In the present embodiment, as shown in FIG. 3E, the segment A and the segment B are finally arranged alternately. As shown in FIGS. 2 and 3, the current divider 20 includes a plurality of stacked layers, in other words, a partition wall having a predetermined thickness. The shunt 20 has a structure in which plates with a plurality of through holes having a predetermined shape are stacked. These through holes form a three-dimensional flow path for passing the solution.

  FIG. 2 shows a cross-sectional view of the flow divider 20. The shunt 20 is composed of five layers, a first layer 21 to a fifth layer 25, along the flow of the solution. The first layer 21 is for connecting the flow divider 20 to the supply pipe 14 and for introducing the solution from the two supply pipes 14 to the flow divider 20. The first layer 21 is divided into two rooms corresponding to the number of the supply pipes 14 so as to store the solution supplied from the two supply pipes 14 and supply the solution to the second layer 22.

  The second layer 22 to the fourth layer 24 are layers for branching the flow path through which the solution flows and for diverting the solution to each segment. The direction of the flow of the solution supplied from the first layer 21 is changed by the three-dimensional flow path formed from the second layer 22 to the fourth layer 24, and the solution is divided into a plurality of flows. The fifth layer 25 is for discharging the solution divided into the plurality of segments to the joining portion 16. The front end surface of the fifth layer 25 is connected to the bottom surface of the conical junction 16.

  The structure of the first layer 21 to the fifth layer 25 is shown in FIGS. 3 (a) to 3 (e). 3A is a sectional view of the first layer 21, FIG. 3B is a sectional view of the second layer 22, FIG. 3C is a sectional view of the third layer 23, and FIG. d) is a sectional view of the fourth layer 24, and FIG. 3E is a sectional view of the fifth layer 25. The first layer 21 is composed of two triangular triangular holes 21A and triangular holes 21B, which are partitioned through holes. Each of the first layer 21 to the fifth layer 25 has a structure having a plurality of through holes indicated by solid lines, and the dotted lines are imaginary lines. Although the letters “A” and “B” are shown in the holes of each layer, they mean the passages of the solution A and the solution B, respectively.

  The letter “A” means that solution A flows through this hole. The letter “B” means that solution B flows through this hole. Further, in order to facilitate understanding of the flow of the solution in the flow divider 20, in FIG. 3B to FIG. 3E, the holes of the previous layer adjacent to each layer are overlapped by imaginary lines and illustrated by imaginary lines. . For example, the triangular hole 21A and the triangular hole 21B in FIG. 3A are illustrated by imaginary lines in FIG. Similarly, in FIG. 3C to FIG. 3E, when the solution flows into each layer from the previous layer, the holes of the previous layer are illustrated by imaginary lines in each layer.

  As described above, the first layer 21 has two triangular holes 21A and 21B which are triangular spaces, as illustrated in FIG. 3A. The solution A is supplied from the supply pipe 14 to the triangular hole 21A. The solution B is supplied from the supply pipe 14 to the triangular hole 21B. As illustrated in FIG. 3B, the second layer 22 branches from the first layer 21 to the second layer 22 and divides the supplied solution A into three flows. Similarly, the solution B supplied from the triangular hole 21 </ b> B of the first layer 21 is divided into four flows in the second layer 22.

  With only this branch, as shown in FIG. 3B, the solution A and the solution B flow only on one side connected by a rectangular diagonal line. As illustrated in FIG. 3C, the third layer 23 flows by changing the direction of a part of the solution supplied from each hole of the second layer 22 in the lateral direction (direction bent by 90 degrees). As a result, as shown in FIG. 3C, the solution A in the third layer 23 has three elongated flows, and the solution B has four flows. As shown in FIG. 3D, the fourth layer 24 has a plurality of small square holes, and each of the solutions supplied from the holes of the third layer 23 is further divided into a plurality of flows. .

  The fifth layer 25 has a structure in which one or two holes of the fourth layer 24 are collected. As a result, the solution A and the solution B are divided into a plurality of alternately arranged segments. The internal space of the merging portion 16 has a pyramid shape and is connected and fixed to the fifth layer 25 of the flow divider 20. The merging portion 16 is not partitioned on the inside and is composed of one flow path. All the segments discharged from the fifth layer 25 of the flow divider 20 are all supplied to the junction 16.

  The inner diameter of the merging portion 16 becomes narrower as the solution flow becomes downstream, and accordingly, the flow velocity of the solution becomes faster due to the continuity. The rear end of the microchannel 12 is connected to the front end of the junction 16. In the microchannel 12, the reaction between the solution A and the solution B is performed. The front end of the microchannel 12 that is not connected to the merging portion 16 is connected to the discharge pipe 18. The discharge pipe 18 may be a part of the downstream of the microchannel 12. From the discharge pipe 18, the reaction product of the solution A and the solution B and the residual solution are discharged.

  Note that, as described above, the inner diameter of the merging portion 16 may not be a structure that becomes narrower as the flow of the solution becomes downstream. The inner diameter of the merging portion 16 does not necessarily have to be so thin that the solution flow is downstream when it does not significantly affect the reaction. Since the junction 16 is for guiding the solution discharged from the flow divider 20 into the microchannel 12, the inner diameter of the junction 16 is equal to the diameter of the discharge end of the junction 16 and the microchannel 12. It is desirable to have a structure that can smoothly connect the inner diameter.

[Material of microreactor 10]
The material of the microreactor 10 is basically a material that does not adversely affect the operation due to the reaction with the raw material solution and by-products. The following materials are used for the micro channel 12, the flow divider 20, the junction 16, the discharge pipe 18, etc. of the micro reactor 10. For example, metal materials with high chemical resistance such as stainless steel, nickel (Ni) and hastelloy, inorganic materials such as ceramic products such as glass, alumina, mullite and silicon carbide, and polymer materials such as PTFE, PEEK, polyimide and polypropylene Is selected in consideration of the reaction with the raw material solution and the by-products, the pressure and temperature when the microreactor 10 is operated, and the heat conduction.

[Production Method of Shunt 20]
The shunt 20 includes five layers, ie, a first layer 21 to a fifth layer 25 that form a three-dimensional flow path. It is possible to manufacture the first layer 21 to the fifth layer 25 by making holes in flat plates, and stacking the holes to assemble them by bolts, adhesives, welding, diffusion bonding, pressure bonding, and the like. For this reason, mass production is possible at low cost. Furthermore, each layer from the first layer 21 to the fifth layer 25 can be designed independently, and the design change of the shunt 20 can be easily performed. The shunt 20 is
When assembling the first layer 21 to the fifth layer 25, it is preferable that the solution does not flow into the other cells from the joints between the layers or the flow of the solution is not greatly hindered.

[Size of shunt 20]
Here, representative sizes of the constituent parts of the microreactor 10 are shown. Each segment diverted by the flow divider 20 preferably has a diameter of 1 mm or less (see FIG. 3 (e)). That is, the solution supplied from the supply pipe 14 is subdivided into a flow having a circular or rectangular cross section with a side length of 1 mm or less. All of these segmented segments are merged at the merge section 16. Then, the joined solution is contracted by reducing the inner diameter of the joining portion 16. At this time, a narrower width of each segment is desirable for improving the mixing speed, and is particularly preferably 100 μm or less.

  Typical dimensions of the shunt 20 are as follows. The external appearance is a 1 cm square cube, which is divided into six layers as described above. The thickness of each layer is 2 mm. The microreactor 10 is not limited to these sizes, and can be designed and used as necessary.

[Various segment arrangements]
Since the shape of each segment supplied from the flow divider 20 to the merge portion 16 is determined by the design change of the fifth layer 25, various shapes of the shape can be obtained by changing the design of the fifth layer 25 to manufacture the flow divider 20. Can handle segments. For example, the square shape of the fifth layer 25 illustrated in FIG. 3E can be freely changed to a square, a circle, an ellipse, a triangle, and other polygons.

  The cross-sectional arrangement of each segment supplied from the flow divider 20 to the merging portion 16 can be basically changed by changing the design of the first layer 21 to the fifth layer 25. In FIG. 3 (e), the segments of the solution A and the solution B are designed to be alternately arranged. However, it is possible to change the segment to a specific shape. For example, as shown in FIG. 5, a segment having a circular cross section can be used.

[Regarding Turbulent Flow Generation Means 17]
Direct micromixing is performed by creating a turbulent flow in the bundle of solutions in which the segments are arranged. By this micromixing, the mixing time is suppressed and uniform mixing is achieved. As the turbulent flow generation means 17 for generating the turbulent flow, the following means are adopted.

First turbulent flow generating means By changing the size of the inner diameter of the tube of the micro flow path 12, the linear velocity (m / s) of the fluid is adjusted to generate turbulent flow. Since the strength of the turbulent flow basically depends on the Re number, the mixing of the solution can be controlled by controlling it. The Re number can be calculated from the inner diameter of the microchannel 12 and the viscosity of the solution. By repeating the operation of increasing or decreasing the inner diameter of the microchannel 12, it is possible to generate turbulent flow. When the Re number is as low as 200 or less (Re <200), the turbulent flow is suppressed and the solution becomes the original laminar flow. In this way, it is possible to generate a turbulent flow only in a part of the microchannel 12.

Second Turbulent Flow Generation Means As shown in FIG. 4, devices such as a baffle plate 26 and an impeller are arranged in the microchannel 12. When the solution flowing through the microchannel 12 passes through these devices, the laminar flow of the solution is locally turbulent and becomes a turbulent flow. Similarly to the above, when the Re number is as low as 200 or less (Re <200), the turbulent flow becomes the original laminar flow, and the turbulent flow is generated only in a part of the microchannel 12. The cross-sectional view of FIG. 4A shows an outline in which the baffle plate 26 is installed as the turbulent flow generation means 17 in the microchannel 12. FIG. 4B shows a cross-sectional view taken along the line AA in FIG. A region 27 indicates a portion where turbulent flow occurs in the microchannel 12. When the solution is downstream from this region 27, it becomes a laminar flow.

Third Turbulent Flow Generation Unit FIG. 5 is a cross-sectional view of the microchannel 12 showing the third turbulent flow generation unit. A spiral fixed blade 30 is fixedly arranged in the microchannel 12. The center line of the spiral fixed wing 30 is disposed at a position that coincides with the center line of the microchannel 12. The spiral fixed wing 30 is made by spirally twisting a sheet metal material. Mixing is promoted while the mixed solution A and solution B sent from the merging portion 16 are spirally twisted and sent along the blade by the fixed spiral blade 30.

Fourth Turbulent Flow Generation Means FIGS. 6A and 6B are examples in which a rotating propeller is arranged in the microchannel 12. In recent years, machining of fine metals, synthetic resins, and the like has become possible, and a rotating propeller mechanism that is a micro device that rotates within the microchannel 12 can be manufactured. A propeller 31 having two blades is rotatably supported by a bearing 32. The bearing 32 is fixed in the microchannel 12 by a support member 33. Therefore, when the solution flows, the propeller 31 starts to rotate and stirs the solution.

Fifth turbulent flow generation means The microchannel 12 is irradiated with ultrasonic waves, and the solution flowing through the microchannel 12 is disturbed to generate turbulent flow.

Sixth turbulent flow generation means The inner diameter of the discharge end of the mixing unit 16 is reduced to a small extent until turbulent flow is generated in the solution. The discharge end of the above-described mixing unit 16 is squeezed so that each segment is 0.1 mm or less, but squeezes until it becomes thinner than that to generate turbulent flow.

Seventh Turbulent Flow Generation Unit The solution discharged from the mixing unit 16 is introduced into the microchannel 12 forming a spiral shape or a curve. The solution flows into the microchannel 12 and immediately generates a turbulent flow at a spiral or curve.

Eighth turbulent flow generating means The above first to seventh turbulent flow generating means are used repeatedly or in combination. When the Re number is low, the turbulent flow immediately becomes a laminar flow, so that the solution further undergoes molecular diffusion and the reaction takes place. When one of the first to seventh turbulent flow generating means is repeated or combined, turbulent flow is partially generated in the solution, micromixing is performed, and then reaction is performed by molecular diffusion and then turbulent again. A flow is generated and the reaction is carried out by micromixing. As a result, the reaction in the reactor becomes uniform, the amount of by-products produced decreases, and the size of the produced particles becomes uniform.

  Between the mixing unit 16 and the turbulent flow generation means 17 installed in the microchannel 12, the solution flowing through the microchannel 12 is reacted while causing molecular diffusion between the segments. The reaction can be controlled by changing the distance between the mixing unit 16 and the turbulent flow generation means 17. Shortening this distance and micromixing by turbulence as short a distance as possible after the segments are mixed results in a product of single size particles.

[About the strength of turbulence]
By controlling the strength of the turbulent flow defined by the Re number, both the mixing speed and the suppression of adhesion to the tube wall are achieved.

[Heating / Cooling]
The microreactor 10 can arrange | position a heat exchange board as needed and can prevent generation | occurrence | production of temperature distribution. In addition, the reaction solution can be heated or cooled by arranging the microchannel 12 in a liquid such as an oil bath at a predetermined temperature.

[Nanoparticles]
The microphone reactor 10 of the present embodiment can be adapted to a reaction that generates nanoparticles having a particle diameter of 1 nm to 100 nm. To produce these nanoparticles, crystallization reaction in a poor solvent, synthesis of gold nanoparticles using tannic acid and citric acid as a reducing agent and protective material, and rapid heating after heating the reaction solution to the reaction temperature The synthesis of semiconductor nanoparticles mixed in

[Other Embodiments]
Hereinafter, another embodiment of the present invention will be described. The other embodiments of the present invention are basically the same as the embodiments of the present invention, and only different portions will be described.

[Adjustment of pressure loss]
FIG. 10 shows an outline of another embodiment of the flow divider 20. 10 is the same as that of the current divider 20 in FIG. 3 except for the following points. The second layer 22 in FIG. 10B has 5 holes for the solution A to flow. Accordingly, holes for the solution A are also provided in FIGS. 10 (c), 10 (d), and 10 (e). In FIG. 10, the distribution of the solution passing through each hole can be adjusted by appropriately adjusting the size of the hole. That is, the larger the size of the hole, the smaller the pressure loss when passing through the hole, so that the amount of solution passing through the hole increases.

  It is also possible to adjust the pressure loss by providing a layer for reducing the size of the holes after the fourth layer 24. For example, the layer 40 illustrated in FIG. 10F is provided after the fifth layer 25. In the layer 40, it is desirable to make the hole size smaller than the hole in FIG. 10 (d) so that the overall pressure loss does not become too large (no problem in operation). This makes it possible to relatively reduce the difference in pressure loss between the segments, which occurs in FIGS. 10 (a) to 10 (d).

[Utilization of inert solvent]
In order to improve productivity while preventing precipitation on the tube wall, the arrangement of segments is optimized. For example, an inert solvent (or a precipitant solvent) is placed on the outer periphery of the solution flowing in the tube of the microchannel 12 (see FIG. 7), and the raw material and the precipitating agent are alternately arranged in a checkered pattern inside. Place them in combination. FIG. 7 shows a cross-sectional view of the microchannel 12, in which the outside of the circle 28 is the inert solvent C and the inside of the circle 28 is the solutions A and B. The thickness of the outer inert layer can be controlled by the structure of the shunt 20. That is, the inert solvent C is supplied to the flow divider 20 separately from the reaction solutions A and B, and the inert solvent segment outside the segments A and B of the solutions A and B when discharged from the flow divider 20. C is arranged.

[Reaction temperature control]
The reaction temperature can be controlled by installing an appropriate heat exchanger in the middle of (or before contacting) the plurality of raw material solutions and the solvent. Upstream from the flow divider 20, a method is used in which heat is exchanged by a commonly used method such as heating with a heat transfer heater, a heat medium, a heat exchanger, or the like, and then poured into the flow divider 20. Since the micro flow path 12 is narrower downstream than the flow divider 20, a method of circulating the micro flow path 12 through an oil bath set at an appropriate temperature is used.

  Further, all the segments that exit the flow divider 20 are merged by the merge unit 16, and are again divided into two or more by the second flow divider 34, and are supplied to the respective microchannels 35. 35 can be temperature controlled by a heat exchanger 36. In this case, the structure of the second shunt 34 is appropriately designed (see FIG. 8).

[Other configuration of the shunt 20]
FIG. 9 is a diagram showing the structure of each layer constituting the flow divider 20. The shunt 20 includes six layers from the first layer 51 to the sixth layer 56. The structure of the first layer 51 to the sixth layer 56 is shown in FIGS. 9 (a) to 9 (f). The first layer 51 includes two triangular triangular holes 21A and triangular holes 21B that are partitioned through holes. Each of the first layer 51 to the sixth layer 56 has a structure having a plurality of through holes indicated by solid lines, and the dotted lines are imaginary lines. Although the letters “A” and “B” are shown in the holes of each layer, they mean the passages of the solution A and the solution B, respectively.

  The letter “A” means that solution A flows through this hole. The letter “B” means that solution B flows through this hole. Further, in order to facilitate understanding of the flow of the solution in the flow divider 20, in FIG. 9B to FIG. 9F, the holes of the previous layer adjacent to each layer are overlapped by imaginary lines and illustrated by imaginary lines. . As illustrated in FIG. 9A, the first layer 51 includes two triangular holes 51 a and 51 b that are triangular spaces.

  The solution A is supplied from the supply pipe 14 to the triangular hole 51a. The solution B is supplied from the supply pipe 14 to the triangular hole 51b. As shown in FIG. 9B, the second layer 52 branches from the first layer 51 to the second layer 52 and divides the supplied solution A into five flows. Similarly, the solution B supplied from the triangular hole 51 b of the first layer 51 is divided into four flows in the second layer 52. With only this branch, as shown in FIG. 9B, the solution A and the solution B flow only on one side connected by a rectangular diagonal line.

  As illustrated in FIG. 9C, the third layer 53 flows by changing the direction of a part of the solution supplied from each hole of the second layer 52 in the lateral direction (direction bent by 90 degrees). As a result, as shown in FIG. 9C, the solution A in the third layer 53 becomes five elongated flows, and the solution B becomes four flows. The fourth layer 54 is illustrated in FIG. The fifth layer 55 is illustrated in FIG. The fourth layer 54 and the fifth layer 55 increase or decrease the flow of the solutions A and B.

  Further, the solutions A and B are joined and shunted. The sixth layer 56 has a structure in which the solution flowing through the holes of the fifth layer 55 is divided into one or more. As a result, the solution A and the solution B are divided into a plurality of segments. The internal space of the junction 16 is connected and fixed to the sixth layer 56 of the flow divider 20. The merging portion 16 is not partitioned on the inside and is composed of one flow path. All segments discharged from the sixth layer 56 of the flow divider 20 are all supplied to the junction 16.

  The present invention is preferably used in the field of new material development, biotechnology, and medical fields.

FIG. 1 is a diagram illustrating an outline of a microreactor 10 according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing the structure of the flow divider 20 of the microreactor 10. FIGS. 3A to 3E are schematic views of the layers constituting the flow divider 20. 3A is a sectional view taken along the line aa in FIG. 2, FIG. 3B is a sectional view taken along the line bb in FIG. 2, and FIG. 3C is a sectional view taken along the line cc in FIG. FIG. 3 (d) is a sectional view taken along the line dd in FIG. 2, FIG. 3 (e) is a sectional view taken along the line ee in FIG. 2, and FIG. 3 (f) is another embodiment. It is sectional drawing of the layer for adjusting the pressure loss of a form. FIG. 4 is a cross-sectional view showing an outline of the baffle plate installed in the microreactor, FIG. 4 (a) is a cross-sectional view of the microchannel 12, and FIG. 4 (b) is a cross-sectional view of the baffle plate 26. . FIG. 5 is a cross-sectional view showing an example in which fixed spiral blades are arranged in the microreactor. FIG. 6 is a cross-sectional view showing an example in which a rotating propeller is arranged in the microreactor. FIG. 7 is a diagram illustrating an example in which an inert solvent is used in a microreactor according to another embodiment of the present invention. FIG. 8 is a diagram illustrating an outline of a microreactor according to another embodiment of the present invention. FIGS. 9A to 9F are schematic views of each layer constituting the flow divider 20. FIGS. 10A to 10F are schematic views of each layer constituting the flow shunt 20 according to another embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Microreactor 12, 35 ... Micro flow path 14 ... Supply pipe 16 ... Merging part 17 ... Turbulence generating means 18 ... Discharge pipe 20 ... Current divider 21, 51 ... 1st layer 22, 52 ... 2nd layer 23, 53 ... 3rd layer 24, 54 ... 4th layer 25, 55 ... 5th layer 26 ... Baffle plate 30 ... Fixed spiral blade 31 ... Propeller 33 ... Support member 32 ... Bearing 36 ... Heat exchanger 34 ... 2nd shunt 56 ... 1st 6 layers

Claims (21)

In a production method using a microreactor in which a plurality of types of solutions are introduced into a microchannel and combined with each other in a laminar flow to produce a compound,
In the cross section in the flow direction of the solution before the merge, each of the solutions is subdivided into a plurality of segments by a flow divider,
Laminating the solution of adjacent segments in a microchannel in a laminar flow;
After the merging, a turbulent flow is generated in the solution by a turbulent flow generating means, and the solution is micromixed to perform the reaction. A method for producing a compound using a microreactor. In the manufacturing method of the compound by the microreactor of Claim 1,
A method for producing a compound using a microreactor, wherein the turbulent flow is generated by narrowing a cross section in the flow direction of the solution after joining in the laminar flow to increase the flow rate of the solution. In the manufacturing method of the compound by the microreactor of Claim 1,
The turbulent flow is a method for producing a compound by a microreactor, wherein the solution is swirled around an axis line through which the solution flows. In the manufacturing method of the compound by the microreactor of Claim 1 selected from Claim 1 to 3,
After the solution subdivided into the plurality of segments is joined together in a laminar flow, a molecular diffusion reaction is performed between the adjacent segments, and then the solution is micromixed by the turbulent flow generation means to perform the reaction A method for producing a compound using a microreactor, wherein In the manufacturing method of the compound by the microreactor of Claim 1 selected from Claim 1 to 3,
In order to control the reaction, the microchannel is heated or cooled. A method for producing a compound using a microreactor. In the manufacturing method of the compound by the microreactor of Claim 1 selected from Claim 1 to 3,
The turbulent flow has a Re number of 200 or less. A method for producing a compound using a microreactor. In the manufacturing method of the compound by the microreactor of 1 selected from 1 to 6,
The compound is a nanoparticle having a typical particle length of 1 nm to 100 nm. A method for producing a compound using a microreactor. In a microreactor that introduces multiple types of solutions into a microchannel and reacts them by joining them in a laminar flow,
A plurality of sample supply channels (14) for supplying the plurality of types of solutions;
A flow divider (20) connected to the sample supply channel (14) for subdividing each of the solutions into a plurality of segments in a cross-section in the flow direction of the solution before the merging;
A merging channel (16) connected to a flow divider (20) for merging the segments;
A microchannel (12) connected to the channel after the merging, for mixing and reacting the solution;
Turbulent flow generating means (17, 26, 30, 31) for generating a turbulent flow in the solution and micro-mixing the solution after joining the solutions of the adjacent segments in a laminar flow; and A sample discharge channel (18) connected to the microchannel (12) for discharging the reaction product after the reaction after the reaction is performed in the microchannel (12). A microreactor. The microreactor according to claim 8, wherein
The merging flow path (16) includes a merging portion (16) for narrowing and narrowing the cross section stepwise in order to increase the flow rate of the merged solution. The microreactor according to claim 8 or 9,
The turbulent flow generation means (17) is a baffle plate (26) for partially blocking the flow of the solution to stir the solution flowing in the microchannel. . In claim 8 or 9,
The microreactor characterized in that the turbulent flow generation means (17) is a fixed spiral fixed blade (30) whose axis is the direction in which the solution flows. In claim 8 or 9,
The microreactor characterized in that the turbulent flow generation means (17) is a rotatable spiral blade (31) whose axis is the direction in which the container flows. In claim 8 or 9,
The microreactor characterized in that the turbulent flow generation means (17) has a smaller or larger inner diameter of the tube of the microchannel (12). In claim 8 or 9,
The turbulent flow generation means (17) is a device that generates ultrasonic waves,
A microreactor characterized by irradiating the microchannel (12) with the ultrasonic wave to generate turbulent flow in the solution. In claim 8 or 9,
The microreactor characterized in that the turbulent flow generating means (17) generates a turbulent flow in the solution by reducing an inner diameter of a discharge end of the confluence channel (16). 16. A microreactor according to claim 1 selected from among claims 8 to 15.
Temperature control means for controlling the temperature of the solution by heating or cooling in the microchannel (12);
And a temperature sensor means for measuring the temperature. 15. A microreactor according to claim 1 selected from among claims 9 to 14.
The microreactor characterized in that the segments discharged from the flow divider (20) and introduced into the microchannel (12) are subdivided into 1 mm or less and arranged in parallel. The microreactor according to claim 8, wherein
The diameter of the cross-sectional area of the microchannel (20) is 1 mm or less after the restriction. 19. A microreactor according to claim 1 selected from among claims 8 to 18.
The shunt (20)
Before the merging, in the cross section in the solution flow direction, the solution is connected to a plurality of sample supply channels (14) for supplying the plurality of types of solutions, and is connected to each of the sample supply channels (14). Introduction part (21, 22, 51, 52),
The solution from the introduction part (21, 22, 51, 52) is connected to the introduction part (21, 22, 51, 52), changes the flow direction for each solution, and is divided into a plurality of flows. An intermediate portion (23, 24, 53, 54, 55, 56) that is subdivided into a plurality of segments for each type, and
Each type of the solution discharged and subdivided from the intermediate part (23, 24, 53, 54, 55, 56) is joined to mix the solution, and each of the introduction part and the intermediate part is mixed. A shunt for a microreactor comprising a discharge section (16, 25, 40, 56) having a discharge hole for relatively reducing a pressure loss difference generated between segments. 20. A flow divider for a microreactor according to claim 19, wherein the discharge is made from the discharge part (16, 25, 40, 56) by adjusting the size of the hole, adjusting the pressure loss, and adjusting the segment flow rate. A shunt for a microreactor characterized by adjusting a thickness in a direction perpendicular to the flow of segments after being formed. The microreactor according to claim 19, wherein
The confluence channel (16) has a conical shape having a bottom surface connected to a discharge portion and a vertex connected to the micro channel (12).

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