WO2013047248A1 - Microreactor and method for manufacturing reaction product - Google Patents

Microreactor and method for manufacturing reaction product Download PDF

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Publication number
WO2013047248A1
WO2013047248A1 PCT/JP2012/073698 JP2012073698W WO2013047248A1 WO 2013047248 A1 WO2013047248 A1 WO 2013047248A1 JP 2012073698 W JP2012073698 W JP 2012073698W WO 2013047248 A1 WO2013047248 A1 WO 2013047248A1
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WIPO (PCT)
Prior art keywords
reaction
channel
slag
liquid
gas
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PCT/JP2012/073698
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French (fr)
Japanese (ja)
Inventor
重司 榊原
慎太郎 二上
博之 南
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デクセリアルズ株式会社
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Publication of WO2013047248A1 publication Critical patent/WO2013047248A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/433—Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
    • B01F25/4331—Mixers with bended, curved, coiled, wounded mixing tubes or comprising elements for bending the flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30—Micromixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
    • B01J2219/00792—One or more tube-shaped elements
    • B01J2219/00795—Spiral-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00831—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/0086—Dimensions of the flow channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00867—Microreactors placed in series, on the same or on different supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00891—Feeding or evacuation
    • B01J2219/00894—More than two inlets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00891—Feeding or evacuation
    • B01J2219/00903—Segmented flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00925—Irradiation
    • B01J2219/00934—Electromagnetic waves
    • B01J2219/00936—UV-radiations

Definitions

  • the present invention relates to a microreactor for producing a reaction product at a gas-liquid interface or a liquid-liquid interface and a method for producing a reaction product using the microreactor.
  • an apparatus for causing a chemical reaction at an interface between a gas phase and a liquid phase and between a liquid phase and a liquid phase to obtain a reaction product has been used.
  • a liquid sample 100 is supplied by a pump 101 and a reaction gas 102 is supplied.
  • a slag is formed in which a liquid sample and a reaction gas are alternately and continuously formed, a chemical reaction proceeds at a gas-liquid interface between the liquid sample and the reaction gas, and ultraviolet rays are applied to the slag flowing through the reaction tube 104.
  • Irradiating means such as a high pressure mercury lamp 105 for irradiating.
  • the supply unit 103 controls the pump 101 and the valve 106 so that the liquid sample and the reaction gas are alternately supplied to form a slag.
  • the reaction tube 104 is formed using a glass tube or the like, and is disposed so as to wrap around the outer periphery of the lamp, so that the slag flowing in the tube is irradiated with ultraviolet rays, and the chemical reaction caused thereby proceeds. Configure the road.
  • a flow path for performing a chemical reaction at the gas-liquid interface or the liquid-liquid interface is formed on one chip by using an ultrafine processing technique.
  • Microreactors have been developed.
  • a microreactor 109 shown in FIG. 7 is connected to, for example, a syringe 110 and supplied with a liquid sample, a gas channel 113 connected to a syringe 112 and supplied with a reaction gas, and these liquid channels.
  • the supply flow path 114 in which the liquid sample and the reaction gas are alternately supplied the supply flow path 114 is continuous, and the slag in which the liquid sample and the reaction gas are alternately continuous
  • the reaction channel 115 in which the chemical reaction proceeds at the gas-liquid interface between the liquid sample and the reaction gas is formed on the substrate.
  • a microreactor is required to stably transport slag in a reaction channel that is secured for a long time because a chemical reaction proceeds at a gas-liquid interface between a liquid sample and a reaction gas. That is, as shown in FIG. 9, when the slag is disturbed in the reaction channel and the liquid sample is integrated with the preceding and following liquid samples, the area of the gas-liquid interface is reduced and the reaction is not promoted. For this reason, the microreactor is required to have a long reaction channel and to flow stably without disturbing the slag.
  • the pressure variation in the reaction channel is eliminated as much as possible, and the resistance against the pressure variation is increased even when the pressure variation in the supply channel propagates to the reaction channel.
  • the reaction channel is formed as thin as possible.
  • slugs are formed to be elongated, so that even when pressure fluctuations occur, the pressure can be absorbed by expanding and contracting in the longitudinal direction, and there is no disturbance in the width direction. In other words, the liquid samples moving back and forth are not integrated.
  • reaction flow path is narrowed, the area of the gas-liquid interface between the liquid sample and the reaction gas decreases, and the reaction cannot be promoted efficiently. Moreover, since the flow rate is fast in a narrow flow path, there is a risk of being discharged without sufficient reaction. Furthermore, when two microreactors are connected via the connecting pipe 119, the reaction path is divided and the slag becomes unstable. Therefore, it is necessary to configure a reaction channel in one substrate, but the limited substrate area There was a limit to the length of the reaction channel in the interior.
  • the present invention uses a microreactor capable of efficiently performing a chemical reaction at a gas-liquid interface or a liquid-liquid interface and allowing a slag to flow stably within a limited substrate area, and this microreactor. It aims at providing the manufacturing method of a reaction product.
  • a microreactor according to the present invention is supplied via a supply channel in which fluid samples forming a gas-liquid interface or a liquid-liquid interface are alternately supplied, and the supply channel.
  • a slag forming channel that forms a slag in which the sample is alternately continuous;
  • a reaction channel that is formed wider than the slag forming channel and that irradiates light to advance a chemical reaction at the interface of the sample;
  • a widened portion that is interposed between the slag forming flow channel and the reaction flow channel, one end is continuous with the slag forming flow channel, the other end is continuous with the reaction flow channel, and is gradually widened, and the reaction
  • a discharge channel that discharges the reacted sample continuously from the channel.
  • the reaction product manufacturing method forms a supply step in which fluid samples forming a gas-liquid interface or a liquid-liquid interface are alternately supplied, and a slag in which the supplied samples are alternately continuous.
  • a slag forming step, a reaction step of causing a reaction to proceed at the interface of the sample by irradiating light, and a discharge step of discharging the reacted sample, the slag comprising the slag forming step and the above By flowing through the widened portion where the flow path is gradually widened between the reaction step and the reaction step, the interface of the fluid sample is enlarged in the reaction step as compared with the slag formation step.
  • the widened portion 20 interposed between the reaction channel and the slag forming channel gradually increases the channel width from the slag forming channel to the reaction channel. Therefore, according to the present invention, it is possible to prevent a rapid change in pressure from the slag formation channel to the reaction channel, and to deform the slug shape of a thin and long fluid sample into a thick and short shape without breaking the slag. Thereby, according to this invention, reaction efficiency and a yield can be improved by expanding the cross-sectional area of the interface of a fluid sample in the state where the slag was stabilized, and slowing down the flow velocity of slag.
  • FIG. 1 is a perspective view showing a microreactor according to the present invention.
  • FIG. 2 is a plan view showing a slag forming flow channel and a reaction flow channel that are continuous via the widened portion.
  • FIG. 3 is a plan view showing a reaction channel and a discharge channel.
  • FIG. 4 is a perspective view showing a microreactor having a two-layer structure.
  • FIG. 5 is a plan view showing a configuration in which the rectilinear portion of the reaction channel is continued by the widened portion.
  • FIG. 6 is a diagram showing a configuration of a conventional apparatus for performing a gas-liquid reaction or a liquid-liquid reaction.
  • FIG. 7 is a diagram showing a configuration of a conventional microreactor.
  • FIG. 8 is a diagram showing the configuration of another conventional microreactor.
  • FIG. 9 is a plan view showing a state in which slag is disturbed in a conventional microreactor.
  • a microreactor 1 to which the present invention is applied has a slag formed between a liquid sample 3 and a reaction gas 4 or a slag formed between liquid samples 3 having different properties inside a rectangular substrate 2.
  • a small-diameter flow path is provided, and a chemical reaction proceeds at the gas-liquid interface or liquid-liquid interface of the slag by being irradiated with light rays such as ultraviolet rays from one side.
  • light rays such as ultraviolet rays from one side.
  • the microreactor 1 has different properties and forms slag without mixing. It can also be used when reacting liquid samples 3 to be reacted.
  • the substrate 2 is formed, for example, by bonding two pieces of glass on which each flow path described later is formed. Or the board
  • substrate 2 is formed by bonding the glass by which each flow path was formed on the surface, and the glass used as a top plate.
  • the flow path is formed using a fine processing technique such as etching or grinding.
  • a supply channel 10 that alternately supplies a liquid sample 3 and a reaction gas 4 that form a gas-liquid interface with each other, and a liquid sample 3 and a reaction gas 4 that are supplied via the supply channel 10 alternately.
  • a slag forming channel 11 that forms a continuous slag
  • a reaction channel 12 that is continuous with the slag forming channel 11 and that is irradiated with light, thereby allowing the reaction to proceed at the gas-liquid interface
  • a discharge channel 13 for discharging the reaction product.
  • the supply channel 10 includes a first supply channel 10a to which the liquid sample 3 is supplied, a second supply channel 10b to which the reaction gas 4 is supplied, and the first and second supply channels 10a and 10b merge. And is formed in a substantially Y shape.
  • the first and second supply paths 10a and 10b face outward through openings 15 and 16 formed on the upper surface of the substrate 2, respectively. Further, the combined channel 10 c is continuous with the slag forming channel 11.
  • the first supply channel 10 a is connected to a syringe 17 for injecting the reaction gas 4 through the opening 15, and the reaction gas 4 is injected into the combined channel 10 c at a predetermined pressure according to the operation of the syringe 17.
  • the second supply channel 10b is connected to a syringe 18 for injecting the liquid sample 3 through the opening 16, and the liquid sample 3 is intermittently injected into the combined channel 10c at a predetermined pressure according to the operation of the syringe 18. .
  • the liquid sample 3 and the reaction gas 4 are alternately and continuously supplied by intermittently injecting the liquid sample 3 into the reaction gas 4 flowing in the combined flow path 10 c.
  • the first supply path 10a, the second supply path 10b, and the combined flow path 10c are all formed with the same depth and the same width, for example, with a depth of 0.3 mm and a width of 0.3 mm. .
  • the supply channel 10 is configured so that the pressure received by the reaction gas 4 in the first supply channel 10a and the pressure received by the liquid sample 3 in the second supply channel 10b, and the liquid sample 3 and the reaction gas 4 in the combined channel 10c. The difference from the pressure received is reduced, and the liquid sample 3 and the reaction gas 4 are continuously supplied alternately and stably.
  • the slag forming flow path 11 is formed from the combined flow path 10c toward one side edge in the width direction of the substrate 2, and further, the one side edge is formed in the longitudinal direction.
  • the slag forming channel 11 stably forms and conveys a slag in which the liquid sample 3 and the reaction gas 4 are alternately continued, and is formed narrower than a reaction channel 12 described later.
  • the slag forming flow path 11 is formed with a narrow width, so that the slag is formed long and narrow. Therefore, the slag forming channel 11 can absorb the pressure variation by the expansion and contraction of the slag in the longitudinal direction even when the pressure fluctuation occurs in the supply channel 10, and there is no disturbance in the width direction.
  • the liquid samples 3 moving back and forth via 4 are not integrated.
  • the microreactor 1 sends a long and stable slag to the reaction channel 12 by providing a narrow and long slag forming channel 11 between the supply channel 10 and the reaction channel 12. be able to.
  • the slag formation flow path 11 has the same depth and the same width as the supply flow path 10, for example, is formed in depth 0.3mm and width 0.3mm.
  • the reaction channel 12 is a channel that causes a chemical reaction to proceed at the interface by irradiating the gas-liquid interface of the slag with light such as ultraviolet rays.
  • a plurality of rectilinear portions 12a that advance straight in the longitudinal direction of the substrate 2 are formed in parallel in the width direction, The end portions are continuous by the curved portion 12b, and thereby, the end portions are formed to meander over the entire surface of the substrate 2.
  • both the rectilinear portion 12a and the curved portion 12b are formed with the same depth and the same width, thereby suppressing fluctuations in pressure and enabling stable conveyance without disturbing the slag. That is, the reaction channel 12 can be provided with a rectilinear portion where the pressure fluctuation does not occur by providing the rectilinear portion 12a along the longitudinal direction of the substrate 2, and the curved portion 12b has the same width as the rectilinear portion 12a.
  • the slag can be curved and the direction can be changed while suppressing fluctuations in pressure.
  • the reaction channel 12 is formed wider than the slag forming channel 11.
  • the microreactor 1 increases the gas-liquid contact time and the ultraviolet irradiation time by widening the cross-sectional area of the gas-liquid interface of the slag and slowing the flow rate of the slag, thereby efficiently promoting the gas-liquid reaction. Can do. Therefore, the microreactor 1 can obtain a gas-liquid reaction product with a high yield.
  • the reaction channel 12 and the slag forming channel 11 are connected via the widened portion 20.
  • the widening section 20 is a flow path that gradually widens the width of the flow path from the slag forming flow path 11 to the reaction flow path 12, thereby deforming the liquid sample 3 and the reaction gas 4 thickly and shortly without breaking the slag. is there.
  • the widened portion 20 is formed to have the same width as that of the slag forming channel 11 on one end side and the same width as that of the reaction channel 12 on the other end side, and gradually widens.
  • the widening portion 20 prevents a sudden change in pressure from the slag forming channel 11 to the reaction channel 12, widens the cross-sectional area of the gas-liquid interface while stabilizing the slag, and slows the flow rate of the slag. can do.
  • the widened portion 20 is formed such that one end side has the same depth of 0.3 mm and width 0.3 mm as the slag forming channel 11, and the other end side has the same depth 0.3 mm and width 0 as the reaction channel 12. .5mm.
  • the microreactor 1 has the same depth (0.3 mm) over the supply flow path 10, the slag formation flow path 11, the widened portion 20, and the reaction flow path 12, so that each flow path is controlled only by width control. Can be more easily formed by etching or the like.
  • the widened portion 20 is formed in a curved shape in which the end portions of the slag forming flow channel 11 and the reaction flow channel 12 formed adjacent to each other in parallel in the width direction of the substrate 20 are continuous. That is, the liquid sample 3 and the reaction gas 4 constituting the slag are gradually deformed thicker and shorter while the widened portion 20 is curved.
  • the widened portion 20 is curved from the slag forming channel 11 to the reaction channel 12 to reduce the flow rate of the slag.
  • the widening section 20 gradually widens the slag in a decelerated state, so that the slag is prevented from being disturbed due to pressure fluctuations, the cross-sectional area of the gas-liquid interface is widened in a stable slag, and the slag The flow rate can be reduced.
  • the widened portion 20 is bent at 180 ° in order to make the end portions of the slag forming flow channel 11 and the reaction flow channel 12 formed in parallel to each other continue.
  • slag can be decelerated to the maximum.
  • the slag is depressurized by passing through the widened portion 20 that gradually widens, but at that time, since it is decelerated by the curved shape, rapid fluctuations in pressure are prevented and the front and rear liquid samples 3 are connected to each other. However, it is stably deformed from a thin and long shape to a thick and short shape.
  • the discharge flow path 13 that is continuous with the reaction flow path 12 and discharges the reaction product is approximately 90 ° from the front end of the reaction flow path 12 provided on the other end side in the width direction of the substrate 2. It is formed toward the one end side in the width direction of the substrate 2 through a bent portion 24 that bends to the side. Further, the discharge channel 13 has the other end opposite to the one end continuous with the reaction channel 12 facing outward from the opening 25 formed in the lower surface of the substrate 2. Further, the discharge channel 13 is formed to have the same depth as the reaction channel 12 and narrower than the reaction channel 12, for example, the reaction channel 12 has a depth of 0.3 mm and a width of 0.5 mm. On the other hand, the discharge channel 13 is formed with a depth of 0.3 mm and a width of 0.3 mm.
  • the discharge channel 13 is formed to be narrower than the reaction channel 12, thereby transporting the slag in a stable state and discharging the gas-liquid reaction product from the opening 25. That is, since the discharge flow channel 13 faces outward from the opening 25, the internal pressure is released from the opening 25, so that pressure fluctuation is likely to occur and the slag becomes unstable. When the pressure fluctuation in the discharge channel 13 propagates to the reaction channel 12, the pressure balance in the reaction channel 12 is lost and the liquid samples 3 may be integrated.
  • the microreactor 1 can stably transport slag having a large cross-sectional area at the gas-liquid interface to the end of the reaction channel 12, and the gas-liquid contact time and The irradiation time of ultraviolet rays can be increased.
  • the discharge channel 13 is continuous with the reaction channel 12 via the bent portion 24, the deformation of the slag due to the pressure balance variation from the opening 25 is further prevented from propagating to the reaction channel 12. can do.
  • One end of the bent portion 24 is continuous with the reaction flow path, the other end is continuous with the discharge flow path 13, and is bent so as to gradually become narrower. Therefore, the slag flowing from the reaction flow path 12 to the bent portion 24 flows out to the discharge flow path 13 in a stable state without sudden pressure fluctuation.
  • the microreactor 1 is provided with the discharge flow path 13 narrower than the reaction flow path 12 via the bent portion 24, thereby stabilizing the slag flow in the reaction flow path 12 and improving the efficiency of the gas-liquid reaction, High yields can be achieved.
  • the syringe 17 containing the reaction gas 4 is connected to the first supply path 10a via the opening 15 of the substrate 2, and the syringe 18 containing the liquid sample 3 is supplied to the second supply via the opening 16. Connect to path 10b. Then, by operating the syringe 17, the reaction gas 4 is injected from the first supply path 10 a into the combined flow path 10 c, and by operating the syringe 18, intermittently from the second supply path 10 b to the combined flow path 10 c. The liquid sample 3 is injected into.
  • the supply channel 10 is supplied with the liquid sample 3 and the reaction gas 4 alternately and continuously by intermittently injecting the liquid sample 3 into the reaction gas 4 flowing in the combined channel 10c.
  • a slag flow in which the liquid sample 3 and the reaction gas 4 are alternately continued is formed in the slag formation flow channel 11 continuous with the combined flow channel 10c.
  • the first and second supply channels 10a and 10b, the combined channel 10c, and the slag forming channel 11 of the supply channel 10 all have the same depth (for example, 0.3 mm) and the same width (for example, 0.2 mm). 3 mm), the pressure fluctuation in the flow path is suppressed, and the slag can be stably formed and transported.
  • the channel can be formed only by controlling the width when the channel is formed by etching the substrate 2 or the like.
  • the slag flow that flows through the slag forming channel 11 flows into the reaction channel 12 that is wider than the slag forming channel 11 through the widened portion 20, whereby the shapes of the liquid sample 3 and the reaction gas 4 constituting the slag are changed. It is deformed thick and short. Further, the reaction flow path 12 is irradiated with light rays such as ultraviolet rays from the upper surface side of the substrate 2, and a chemical reaction proceeds at the gas-liquid interface.
  • the liquid sample 3 and the reaction gas 4 in the reaction channel 12 are prevented in a state in which a rapid change in pressure is prevented and the slag flow is stabilized by passing through the widened portion 20 where the channel width gradually increases.
  • the area of the gas-liquid interface can be enlarged.
  • the widened portion 20 is formed in a curved shape, so that the flow path width is gradually widened while the flow rate of the slag is reduced. Accordingly, it is possible to suppress the slag disturbance due to a rapid change in pressure, to expand the cross-sectional area of the gas-liquid interface in a stable state of the slag, and to reduce the flow rate of the slag.
  • the reaction flow path 12 increases the contact area at the gas-liquid interface and the irradiation time of the ultraviolet rays by expanding the contact area at the gas-liquid interface without reducing the slag and reducing the flow rate of the slag, A gas-liquid reaction can be advanced efficiently. Therefore, the microreactor 1 can obtain a gas-liquid reaction product with a high yield.
  • the reaction product generated in the reaction channel 12 flows into the discharge channel 13 and is discharged from the opening 25.
  • the pressure of the discharge channel 13 becomes zero when the opening 25 is opened.
  • the discharge channel 13 is formed to be narrower than the reaction channel 12, the disturbance of the slag due to the pressure variation is suppressed, and the pressure variation is applied to the reaction channel 12. Can be prevented from propagating.
  • the discharge channel 13 is continuous with the reaction channel 12 via the bent portion 24, the propagation of the pressure fluctuation can also be prevented by this.
  • Examples of the gas-liquid reaction using the microreactor 1 include a photo-oxidation reaction of a methyl group on an aromatic ring.
  • this photo-oxidation reaction 4-tert-butyltoluene and oxygen are reacted by irradiating with ultraviolet rays in the presence of a catalytic amount of LiBr to produce 4-tert-butylbenzoic acid in which methyl groups on the aromatic ring are oxidized. It is a gas-liquid reaction.
  • the slag flow composed of 4-tert-butyltoluene and oxygen flows into the reaction channel 12 through the widened portion 20 and is stably deformed from a thin and long shape to a thick and short shape.
  • the slag flow composed of 4-tert-butyltoluene and oxygen has a wide cross-sectional area at the gas-liquid interface, and the flow rate is slowed down, so that the contact time between 4-tert-butyltoluene and oxygen and the ultraviolet rays are reduced.
  • the irradiation time can be increased and the reaction can proceed efficiently. Therefore, the microreactor 1 can obtain 4-tert-butylbenzoic acid in which the methyl group on the aromatic ring is oxidized with a high yield.
  • the maricro reactor 1 can be used for a liquid-liquid reaction between liquid samples that form a slag flow without being mixed with each other because of different properties such as an aqueous system and an oil system.
  • Examples of the liquid-liquid reaction using the microreactor 1 include a photo-oxidation reaction between oxygen water and a liquid sample such as organic esters. Specifically, oxygen water and a liquid sample such as organic esters are respectively supplied from the first and second supply passages 10a and 10b at a predetermined pressure, and the oxygen water and the liquid sample are supplied through the slag formation passage 11. And slag is formed and conveyed alternately.
  • the slag flow comprising oxygen water and a liquid sample is stably deformed from a thin and long shape to a thick and short shape by flowing into the reaction channel 12 via the widened portion 20.
  • the slag flow composed of oxygen water and the liquid sample is irradiated with light in the reaction channel 12 because the cross-sectional area of the liquid-liquid interface is widened and the flow velocity is slow, so that the liquid slag liquid
  • the oxidation reaction proceeds at the interface.
  • liquid-liquid reaction is a photopolymerization reaction using various acrylic monomers and a photopolymerization initiator contained in an aqueous liquid sample.
  • an acrylic monomer such as an acrylate ester and a photopolymerization agent contained in an aqueous liquid sample are supplied from the first and second supply paths 10a and 10b, respectively, at a predetermined pressure to form slag.
  • slag in which acrylic monomers and photopolymerization initiators are alternately continued is formed and conveyed.
  • the slag flow composed of the acrylic monomer and the photopolymerization initiator flows to the reaction flow path 12 through the widened portion 20, so that the cross-sectional area of the liquid-liquid interface similarly increases, and the flow rate becomes slow.
  • light such as ultraviolet rays
  • radicals by the photopolymerization initiator are generated at the liquid-liquid interface of the slag, and the radical polymerization reaction of the acrylic monomer proceeds.
  • the reaction to proceed at the liquid-liquid interface of the slag and polymerizing the surface of the acrylic monomer, it is possible to suppress agglomeration of the separated particles, and then perform the main polymerization. Can do.
  • reaction gas 4 decreases as the reaction proceeds. Therefore, in the slag flow consisting of the reaction product solution and a small amount of the reaction gas 4 downstream of the reaction channel 12, the reaction product solution is reduced. There is a risk of instability, such as linking with the solution before and after.
  • the microreactor 1 may supply an inert gas that does not react with the liquid sample 3, the reaction gas 4, and the reaction product together with the reaction gas 4.
  • an inert gas that does not react with the liquid sample 3, the reaction gas 4, and the reaction product together with the reaction gas 4.
  • the microreactor to which the present invention is applied is not limited to the above-described configuration.
  • the reaction channel 12 may be multilayered in the thickness direction of the substrate 2.
  • the substrate 2 is formed with an upper reaction channel 30, a lower reaction channel 31, and a connection channel 32 that connects the upper and lower reaction channels 30, 31.
  • the upper and lower reaction channels 30, 31 Similar to the reaction channel 12, the upper and lower reaction channels 30, 31 have a plurality of rectilinear portions 30a, 31a that go straight in the longitudinal direction of the substrate 2 in parallel in the width direction and are adjacent to each other. The ends of the rectilinear portions 30 a and 31 a are continuous with each other by the curved portions 30 b and 31 b, thereby forming a meandering over the entire surface of the substrate 2.
  • the upper layer reaction channel 12 is connected to the widened portion 20 at one end, meanders in the upper layer surface of the substrate 2, and is connected at the end on the other end side in the width direction of the substrate 2.
  • the lower reaction channel 31 is continued through the channel 32.
  • One end of the lower reaction channel 31 is continuous with the connection channel, meanders in the lower surface of the substrate 2, and is continued with the discharge channel 13 at the end of one end in the width direction of the substrate 2.
  • the upper and lower reaction channels 30 and 31 are formed so that the rectilinear portions 30a and 31a do not overlap each other, and the upper reaction channel 30 does not block light such as ultraviolet rays irradiated from the upper surface side of the substrate 2.
  • the lower reaction channel 31 can also be irradiated.
  • the channel through which gas-liquid reaction or liquid-liquid reaction proceeds can be lengthened, and the reaction efficiency and yield can be improved in a limited substrate space. Can do.
  • the microreactor to which the present invention is applied is not only between the slag forming channel 11 and the reaction channel 12, but also between the rectilinear portions 12a of the reaction channel 12 via the widened portion 20. May be gradually widened. That is, in the microreactor 1, the channel width is widened through the widened portion 20 from the slag forming flow channel 11 to the reaction flow channel 12, and the widened portion 20 is provided between the plurality of rectilinear portions 12a of the reaction flow channel 12.
  • the reaction channel 12 may be gradually widened by being continued through.
  • the widened portion 20 that connects the plurality of rectilinear portions 12a of the reaction flow path 12 is also curved so that the slag is gradually widened in a decelerated state, so that slag disturbance due to pressure fluctuations is suppressed.
  • the cross-sectional area of the gas-liquid interface can be expanded while the slag is stable, and the flow rate of the slag can be reduced.
  • the microreactor 1 irradiates light such as ultraviolet rays in the reaction channel to advance the gas-liquid reaction or liquid-liquid reaction, but also irradiates the slag forming channel 11, the widened portion 20, or the discharge channel 13.
  • the reaction may be promoted.
  • reaction flow path 1 microreactor, 2 substrate, 3 liquid sample, 4 reaction gas, 10 supply channel, 10a first supply channel, 10b second supply channel, 10c combined channel, 11 slag formation channel, 12 reaction channel, 12a straight line Part, 12b curved part, 13 discharge flow path, 15, 16 opening, 17, 18 syringe, 20 widening part, 24 bending part, 25 opening, 30, 31 reaction flow path

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Abstract

Provided is a microreactor in which the area of the gas-liquid interface is enlarged without the slag being disturbed. This invention has: a supply channel (10) through which fluid samples (3, 4), which form a gas-liquid interface or a liquid-liquid interface with each other, are alternately supplied; a slag-formation channel (11) for forming a slag in which the samples (3, 4) supplied through the supply channel (10) are alternately continuous; a reaction channel (12) formed so as to be wider than the slag-formation channel (11), the reaction channel being irradiated with light, whereby a chemical reaction is caused on the interface between the samples; an expanded width section (20) interposed between the slag-formation channel (11) and the reaction channel (12), one end of the expanded width section being continuous with the slag-formation channel (11), the other end of the expanded width section being continuous with the reaction channel (12), the expanded width section (20) having a width that gradually expands; and a discharge channel (13) for discharging the reacted samples, the discharge channel being continuous from the reaction channel (12).

Description

マイクロリアクタ及び反応生成物の製造方法Microreactor and reaction product manufacturing method
　本発明は、気液界面や液液界面において反応生成物を製造するマイクロリアクタ及び、マイクロリアクタを用いた反応生成物の製造方法に関する。
　本出願は、日本国において２０１１年９月２９日に出願された日本特許出願番号特願２０１１－２１５０９２を基礎として優先権を主張するものであり、この出願は参照されることにより、本出願に援用される。 The present invention relates to a microreactor for producing a reaction product at a gas-liquid interface or a liquid-liquid interface and a method for producing a reaction product using the microreactor.
This application claims priority on the basis of Japanese Patent Application No. 2011-215092 filed on Sep. 29, 2011 in Japan. This application is incorporated herein by reference. Incorporated.
　従来、気相と液相、液相と液相の界面において化学反応を起こし、反応生成物を得る装置が用いられている。気液反応によって所定の化合物を生成する装置としては、例えば図６に示すように、液体試料１００がポンプ１０１によって供給されるとともに、反応気体１０２が供給される供給部１０３と、供給部１０３と連続し、液体試料と反応気体とが交互に連続するスラグが形成され、液体試料と反応気体との気液界面で化学反応が進行する反応管１０４と、反応管１０４を流れるスラグに対して紫外線を照射する高圧水銀ランプ１０５等の照射手段とを備える。 Conventionally, an apparatus for causing a chemical reaction at an interface between a gas phase and a liquid phase and between a liquid phase and a liquid phase to obtain a reaction product has been used. As an apparatus for generating a predetermined compound by gas-liquid reaction, for example, as shown in FIG. 6, a liquid sample 100 is supplied by a pump 101 and a reaction gas 102 is supplied. A slag is formed in which a liquid sample and a reaction gas are alternately and continuously formed, a chemical reaction proceeds at a gas-liquid interface between the liquid sample and the reaction gas, and ultraviolet rays are applied to the slag flowing through the reaction tube 104. Irradiating means such as a high pressure mercury lamp 105 for irradiating.
　供給部１０３は、ポンプ１０１とバルブ１０６とが制御されることにより、液体試料と反応気体とが交互に供給され、スラグが形成される。反応管１０４は、ガラス管などを用いて形成され、ランプの外周を巻回するように配設されることで、管内を流れるスラグに対して紫外線を照射し、これによる化学反応を進行させる流路を構成する。 The supply unit 103 controls the pump 101 and the valve 106 so that the liquid sample and the reaction gas are alternately supplied to form a slag. The reaction tube 104 is formed using a glass tube or the like, and is disposed so as to wrap around the outer periphery of the lamp, so that the slag flowing in the tube is irradiated with ultraviolet rays, and the chemical reaction caused thereby proceeds. Configure the road.
　また、図６に示す装置では大掛かりとなることから、図７に示すように、超微細加工技術を用いることにより、気液界面や液液界面において化学反応を行う流路を１チップ上に構成したマイクロリアクタが開発されている。図７に示すマイクロリアクタ１０９は、例えば、シリンジ１１０に接続され、液体試料が供給される液体流路１１１と、シリンジ１１２に接続され、反応気体が供給される気体流路１１３と、これら液体流路１１１及び気体流路１１３とが合流することにより液体試料と反応気体とが交互に供給される供給流路１１４と、供給流路１１４と連続し、液体試料と反応気体とが交互に連続するスラグが形成されるとともに紫外線照射装置１１６から光線が照射されることにより、液体試料と反応気体との気液界面で化学反応が進行する反応流路１１５とが、基板に形成されている。 Further, since the apparatus shown in FIG. 6 is large-scale, as shown in FIG. 7, a flow path for performing a chemical reaction at the gas-liquid interface or the liquid-liquid interface is formed on one chip by using an ultrafine processing technique. Microreactors have been developed. A microreactor 109 shown in FIG. 7 is connected to, for example, a syringe 110 and supplied with a liquid sample, a gas channel 113 connected to a syringe 112 and supplied with a reaction gas, and these liquid channels. 111 and the gas flow path 113 join together, the supply flow path 114 in which the liquid sample and the reaction gas are alternately supplied, the supply flow path 114 is continuous, and the slag in which the liquid sample and the reaction gas are alternately continuous And the reaction channel 115 in which the chemical reaction proceeds at the gas-liquid interface between the liquid sample and the reaction gas is formed on the substrate.
　このようなマイクロリアクタにおいては、反応流路において液体試料と反応気体とが反応することから、できるだけ長く反応流路を確保することが求められる。そのため、図８に示すように、２つのマイクロリアクタ１１７，１１８を連結管１１９によって連結し、反応流路を長くする構成も提案されている。 In such a microreactor, since the liquid sample and the reaction gas react in the reaction channel, it is required to secure the reaction channel as long as possible. Therefore, as shown in FIG. 8, a configuration in which two microreactors 117 and 118 are connected by a connecting pipe 119 to lengthen a reaction channel has been proposed.
特開２００６－１４２２４２号公報JP 2006-142242 A
　しかし、２つの反応流路を連結管１１９によって連結すると、スラグが不安定となってしまう。マイクロリアクタは、液体試料と反応気体との気液界面で化学反応が進行することから、長く確保された反応流路においてスラグを安定して搬送することが求められる。すなわち、図９に示すように、反応流路内においてスラグが乱れ、液体試料が前後の液体試料と一体化すると、気液界面の面積が減少し、反応が促進されなくなる。このため、マイクロリアクタは、反応流路を長く設けると共に、スラグを乱すことなく安定して流すことが求められる。 However, if the two reaction channels are connected by the connecting pipe 119, the slag becomes unstable. A microreactor is required to stably transport slag in a reaction channel that is secured for a long time because a chemical reaction proceeds at a gas-liquid interface between a liquid sample and a reaction gas. That is, as shown in FIG. 9, when the slag is disturbed in the reaction channel and the liquid sample is integrated with the preceding and following liquid samples, the area of the gas-liquid interface is reduced and the reaction is not promoted. For this reason, the microreactor is required to have a long reaction channel and to flow stably without disturbing the slag.
　ここで、スラグを安定して流すためには、反応流路内における圧力のバラツキをできるだけ無くし、また、供給流路における圧力変動が反応流路に伝搬した場合にも当該圧力変動に対する耐性を上げる必要がある。このため、反応流路は、できるだけ細く形成することが望ましい。流路を細くすることにより、スラグが細長く形成されるため、圧力変動が生じた場合にも長手方向に伸縮することで圧力のバラツキを吸収でき、また幅方向へ乱れがなく、反応気体を介して前後する液体試料同士が一体化することもない。 Here, in order to allow the slag to flow stably, the pressure variation in the reaction channel is eliminated as much as possible, and the resistance against the pressure variation is increased even when the pressure variation in the supply channel propagates to the reaction channel. There is a need. For this reason, it is desirable to form the reaction channel as thin as possible. By narrowing the flow path, slugs are formed to be elongated, so that even when pressure fluctuations occur, the pressure can be absorbed by expanding and contracting in the longitudinal direction, and there is no disturbance in the width direction. In other words, the liquid samples moving back and forth are not integrated.
　しかし、反応流路を細くすると、液体試料と反応気体との気液界面の面積が減少し、反応を効率よく促進させることができない。また、細い流路においては流速が早いため、十分に反応することなく排出されるおそれもある。さらに、連結管１１９を介して２つのマイクロリアクタを連結すると反応経路が分断されスラグが不安定となることから、一枚の基板内に反応流路を構成する必要があるが、限られた基板面積内において反応流路を細長く取るにも限界があった。 However, if the reaction flow path is narrowed, the area of the gas-liquid interface between the liquid sample and the reaction gas decreases, and the reaction cannot be promoted efficiently. Moreover, since the flow rate is fast in a narrow flow path, there is a risk of being discharged without sufficient reaction. Furthermore, when two microreactors are connected via the connecting pipe 119, the reaction path is divided and the slag becomes unstable. Therefore, it is necessary to configure a reaction channel in one substrate, but the limited substrate area There was a limit to the length of the reaction channel in the interior.
　そこで、本発明は、限られた基板面積内において、気液界面や液液界面における化学反応を効率よく行うことができ、かつスラグを安定して流すことができるマイクロリアクタ及び、このマイクロリアクタを用いた反応生成物の製造方法を提供することを目的とする。 Therefore, the present invention uses a microreactor capable of efficiently performing a chemical reaction at a gas-liquid interface or a liquid-liquid interface and allowing a slag to flow stably within a limited substrate area, and this microreactor. It aims at providing the manufacturing method of a reaction product.
　上述した課題を解決するために、本発明に係るマイクロリアクタは、互いに気液界面又は液液界面を形成する流体試料が交互に供給される供給流路と、上記供給流路を介して供給された上記試料が交互に連続するスラグを形成するスラグ形成流路と、上記スラグ形成流路よりも幅広に形成され、光を照射することにより、上記試料の界面において化学反応を進行させる反応流路と、上記スラグ形成流路と上記反応流路との間に介在し、一端を上記スラグ形成流路と連続され、他端を上記反応流路と連続され、漸次拡幅された拡幅部と、上記反応流路から連続し、反応した試料を排出する排出流路とを有する。 In order to solve the above-described problems, a microreactor according to the present invention is supplied via a supply channel in which fluid samples forming a gas-liquid interface or a liquid-liquid interface are alternately supplied, and the supply channel. A slag forming channel that forms a slag in which the sample is alternately continuous; a reaction channel that is formed wider than the slag forming channel and that irradiates light to advance a chemical reaction at the interface of the sample; A widened portion that is interposed between the slag forming flow channel and the reaction flow channel, one end is continuous with the slag forming flow channel, the other end is continuous with the reaction flow channel, and is gradually widened, and the reaction And a discharge channel that discharges the reacted sample continuously from the channel.
　また、本発明に係る反応生成物の製造方法は、互いに気液界面又は液液界面を形成する流体試料が交互に供給される供給工程と、供給された上記試料が交互に連続するスラグを形成するスラグ形成工程と、光を照射することにより、上記試料の界面において反応を進行させる反応工程と、上記反応した試料を排出する排出工程とを有し、上記スラグは、上記スラグ形成工程と上記反応工程との間に、流路が漸次拡幅された拡幅部を流れることにより、上記反応工程において上記スラグ形成工程よりも上記流体試料の界面が拡大されている。 In addition, the reaction product manufacturing method according to the present invention forms a supply step in which fluid samples forming a gas-liquid interface or a liquid-liquid interface are alternately supplied, and a slag in which the supplied samples are alternately continuous. A slag forming step, a reaction step of causing a reaction to proceed at the interface of the sample by irradiating light, and a discharge step of discharging the reacted sample, the slag comprising the slag forming step and the above By flowing through the widened portion where the flow path is gradually widened between the reaction step and the reaction step, the interface of the fluid sample is enlarged in the reaction step as compared with the slag formation step.
　本発明によれば、反応流路とスラグ形成流路との間に介在する拡幅部２０が、スラグ形成流路から反応流路にかけて漸次、流路幅が広がっていく。したがって、本発明によれば、スラグ形成流路から反応流路にかけて圧力の急激な変動を防止し、スラグを壊すことなく細く長い流体試料のスラグ形状を太く短い形状に変形させることができる。これにより、本発明によれば、スラグを安定した状態で流体試料の界面の断面積を広げ、かつ、スラグの流速を遅くすることで、反応効率、及び収率を向上させることができる。 According to the present invention, the widened portion 20 interposed between the reaction channel and the slag forming channel gradually increases the channel width from the slag forming channel to the reaction channel. Therefore, according to the present invention, it is possible to prevent a rapid change in pressure from the slag formation channel to the reaction channel, and to deform the slug shape of a thin and long fluid sample into a thick and short shape without breaking the slag. Thereby, according to this invention, reaction efficiency and a yield can be improved by expanding the cross-sectional area of the interface of a fluid sample in the state where the slag was stabilized, and slowing down the flow velocity of slag.
図１は、本発明に係るマイクロリアクタを示す斜視図である。FIG. 1 is a perspective view showing a microreactor according to the present invention. 図２は、拡幅部を介して連続するスラグ形成流路及び反応流路を示す平面図である。FIG. 2 is a plan view showing a slag forming flow channel and a reaction flow channel that are continuous via the widened portion. 図３は、反応流路及び排出流路を示す平面図である。FIG. 3 is a plan view showing a reaction channel and a discharge channel. 図４は、２層構造のマイクロリアクタを示す斜視図である。FIG. 4 is a perspective view showing a microreactor having a two-layer structure. 図５は、拡幅部によって反応流路の直進部が連続されている構成を示す平面図である。FIG. 5 is a plan view showing a configuration in which the rectilinear portion of the reaction channel is continued by the widened portion. 図６は、従来の気液反応又は液液反応を行う装置構成を示す図である。FIG. 6 is a diagram showing a configuration of a conventional apparatus for performing a gas-liquid reaction or a liquid-liquid reaction. 図７は、従来のマイクロリアクタの構成を示す図である。FIG. 7 is a diagram showing a configuration of a conventional microreactor. 図８は、従来の他のマイクロリアクタの構成を示す図である。FIG. 8 is a diagram showing the configuration of another conventional microreactor. 図９は、従来のマイクロリアクタにおいて、スラグが乱れている状態を示す平面図である。FIG. 9 is a plan view showing a state in which slag is disturbed in a conventional microreactor.
　以下、本発明が適用されたマイクロリアクタ及び、このマイクロリアクタを用いた反応生成物の製造方法について、図面を参照しながら詳細に説明する。なお、本発明は、以下の実施形態のみに限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々の変更が可能であることは勿論である。また、図面は模式的なものであり、各寸法の比率等は現実のものとは異なることがある。具体的な寸法等は以下の説明を参酌して判断すべきものである。また、図面相互間においても互いの寸法の関係や比率が異なる部分が含まれていることは勿論である。 Hereinafter, a microreactor to which the present invention is applied and a method for producing a reaction product using the microreactor will be described in detail with reference to the drawings. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the present invention. Further, the drawings are schematic, and the ratio of each dimension may be different from the actual one. Specific dimensions should be determined in consideration of the following description. Moreover, it is a matter of course that portions having different dimensional relationships and ratios are included between the drawings.
　本発明が適用されたマイクロリアクタ１は、図１、図２に示すように、矩形状の基板２の内部に、液体試料３と反応気体４とによるスラグ、又は性状の異なる液体試料３同士によるスラグが流される小径流路が設けられるとともに、一面側から紫外線等の光線が照射されることにより、スラグの気液界面又は液液界面において化学反応を進行させるものである。以下では、気液界面又は液液界面を形成する流体試料として、液体試料３及び反応気体４を化学反応させる場合を例に説明するが、マイクロリアクタ１は、性状が異なり混合することなくスラグを形成する液体試料３同士を反応させる場合にも用いることができる。 As shown in FIGS. 1 and 2, a microreactor 1 to which the present invention is applied has a slag formed between a liquid sample 3 and a reaction gas 4 or a slag formed between liquid samples 3 having different properties inside a rectangular substrate 2. In addition, a small-diameter flow path is provided, and a chemical reaction proceeds at the gas-liquid interface or liquid-liquid interface of the slag by being irradiated with light rays such as ultraviolet rays from one side. In the following, a case where the liquid sample 3 and the reaction gas 4 are chemically reacted as a fluid sample forming the gas-liquid interface or the liquid-liquid interface will be described as an example. However, the microreactor 1 has different properties and forms slag without mixing. It can also be used when reacting liquid samples 3 to be reacted.
　基板２は、例えば後述する各流路が形成された２枚のガラスが貼り合わされることにより形成される。あるいは、基板２は、表面に各流路が形成されたガラスと、天板となるガラスが貼り合わされることにより形成される。流路は、エッチングや研削等の微細加工技術を用いて形成される。 The substrate 2 is formed, for example, by bonding two pieces of glass on which each flow path described later is formed. Or the board | substrate 2 is formed by bonding the glass by which each flow path was formed on the surface, and the glass used as a top plate. The flow path is formed using a fine processing technique such as etching or grinding.
　基板２には、互いに気液界面を形成する液体試料３及び反応気体４が交互に供給される供給流路１０と、供給流路１０を介して供給された液体試料３及び反応気体４が交互に連続するスラグを形成するスラグ形成流路１１と、スラグ形成流路１１と連続し、光線が照射されることにより、気液界面において反応を進行させる反応流路１２と、反応流路１２と連続し、反応生成物を排出する排出流路１３とを有する。 On the substrate 2, a supply channel 10 that alternately supplies a liquid sample 3 and a reaction gas 4 that form a gas-liquid interface with each other, and a liquid sample 3 and a reaction gas 4 that are supplied via the supply channel 10 alternately. A slag forming channel 11 that forms a continuous slag, a reaction channel 12 that is continuous with the slag forming channel 11 and that is irradiated with light, thereby allowing the reaction to proceed at the gas-liquid interface; And a discharge channel 13 for discharging the reaction product.
　［供給流路１０］
　供給流路１０は、液体試料３が供給される第１の供給路１０ａと、反応気体４が供給される第２の供給路１０ｂと、これら第１，第２の供給路１０ａ，１０ｂが合流する合流路１０ｃとを備え、略Ｙ字状に形成されている。第１，第２の供給路１０ａ，１０ｂは、それぞれ基板２の上面に形成された開口１５，１６を介して外方に臨まされている。また、合流路１０ｃは、スラグ形成流路１１と連続されている。 [Supply channel 10]
The supply channel 10 includes a first supply channel 10a to which the liquid sample 3 is supplied, a second supply channel 10b to which the reaction gas 4 is supplied, and the first and second supply channels 10a and 10b merge. And is formed in a substantially Y shape. The first and second supply paths 10a and 10b face outward through openings 15 and 16 formed on the upper surface of the substrate 2, respectively. Further, the combined channel 10 c is continuous with the slag forming channel 11.
　第１の供給路１０ａは、開口１５を介して反応気体４を注入するシリンジ１７が連結され、シリンジ１７の操作に応じて所定の圧力で反応気体４が合流路１０ｃに注入される。第２の供給路１０ｂは、開口１６を介して液体試料３を注入するシリンジ１８が連結され、シリンジ１８の操作に応じて所定の圧力で液体試料３が合流路１０ｃに間欠的に注入される。供給流路１０は、合流路１０ｃに流れる反応気体４中に、間欠的に液体試料３が注入されることにより、液体試料３と反応気体４とが交互に連続して供給される。 The first supply channel 10 a is connected to a syringe 17 for injecting the reaction gas 4 through the opening 15, and the reaction gas 4 is injected into the combined channel 10 c at a predetermined pressure according to the operation of the syringe 17. The second supply channel 10b is connected to a syringe 18 for injecting the liquid sample 3 through the opening 16, and the liquid sample 3 is intermittently injected into the combined channel 10c at a predetermined pressure according to the operation of the syringe 18. . In the supply flow path 10, the liquid sample 3 and the reaction gas 4 are alternately and continuously supplied by intermittently injecting the liquid sample 3 into the reaction gas 4 flowing in the combined flow path 10 c.
　ここで、第１の供給路１０ａ、第２の供給路１０ｂ及び合流路１０ｃは、いずれも同一深さ、同一幅で形成され、例えば深さ０．３ｍｍ、幅０．３ｍｍに形成されている。これにより、供給流路１０は、第１の供給路１０ａにおいて反応気体４が受ける圧力や第２の供給路１０ｂにおいて液体試料３が受ける圧力と、合流路１０ｃにおいて液体試料３及び反応気体４が受ける圧力との差が少なくなり、安定して液体試料３と反応気体４とが交互に連続して供給される。 Here, the first supply path 10a, the second supply path 10b, and the combined flow path 10c are all formed with the same depth and the same width, for example, with a depth of 0.3 mm and a width of 0.3 mm. . As a result, the supply channel 10 is configured so that the pressure received by the reaction gas 4 in the first supply channel 10a and the pressure received by the liquid sample 3 in the second supply channel 10b, and the liquid sample 3 and the reaction gas 4 in the combined channel 10c. The difference from the pressure received is reduced, and the liquid sample 3 and the reaction gas 4 are continuously supplied alternately and stably.
　［スラグ形成流路１１］
　スラグ形成流路１１は、合流路１０ｃより基板２の幅方向の一側縁に向かい、さらに当該一側縁を長手方向に亘って形成されている。スラグ形成流路１１は、液体試料３と反応気体４とが交互に連続するスラグを安定して形成、搬送するものであり、後述する反応流路１２よりも幅が細く形成されている。 [Slag forming channel 11]
The slag forming flow path 11 is formed from the combined flow path 10c toward one side edge in the width direction of the substrate 2, and further, the one side edge is formed in the longitudinal direction. The slag forming channel 11 stably forms and conveys a slag in which the liquid sample 3 and the reaction gas 4 are alternately continued, and is formed narrower than a reaction channel 12 described later.
　スラグ形成流路１１は、幅が細く形成されることにより、スラグが細長く形成される。したがって、スラグ形成流路１１は、供給流路１０において圧力変動が生じた場合にも、スラグが長手方向に伸縮することで圧力のバラツキを吸収でき、また幅方向への乱れがなく、反応気体４を介して前後する液体試料３同士が一体化することもない。 The slag forming flow path 11 is formed with a narrow width, so that the slag is formed long and narrow. Therefore, the slag forming channel 11 can absorb the pressure variation by the expansion and contraction of the slag in the longitudinal direction even when the pressure fluctuation occurs in the supply channel 10, and there is no disturbance in the width direction. The liquid samples 3 moving back and forth via 4 are not integrated.
　これにより、マイクロリアクタ１は、供給流路１０と反応流路１２との間に、幅狭でかつ長さを有するスラグ形成流路１１を設けることにより、細長く安定したスラグを反応流路１２に送り出すことができる。なお、スラグ形成流路１１は、供給流路１０と同一の深さ及び同一の幅を有し、例えば深さ０．３ｍｍ、幅０．３ｍｍに形成されている。 As a result, the microreactor 1 sends a long and stable slag to the reaction channel 12 by providing a narrow and long slag forming channel 11 between the supply channel 10 and the reaction channel 12. be able to. In addition, the slag formation flow path 11 has the same depth and the same width as the supply flow path 10, for example, is formed in depth 0.3mm and width 0.3mm.
　［反応流路１２］
　反応流路１２は、スラグの気液界面に紫外線等の光線を照射させることにより、当該界面において化学反応を進行させる流路である。反応流路１２は、反応に供する長さをできるだけ長く確保するために、基板２の長手方向に亘って直進する直進部１２ａが幅方向に亘って平行に複数形成され、隣接する直進部１２ａの端部同士が湾曲部１２ｂによって連続され、これにより、基板２の全面に亘って蛇行するように形成されている。 [Reaction channel 12]
The reaction channel 12 is a channel that causes a chemical reaction to proceed at the interface by irradiating the gas-liquid interface of the slag with light such as ultraviolet rays. In order to secure the reaction channel 12 as long as possible for the reaction, a plurality of rectilinear portions 12a that advance straight in the longitudinal direction of the substrate 2 are formed in parallel in the width direction, The end portions are continuous by the curved portion 12b, and thereby, the end portions are formed to meander over the entire surface of the substrate 2.
　また、反応流路１２は、直進部１２ａ及び湾曲部１２ｂがともに同一深さ、同一幅で形成され、これにより圧力の変動を抑え、スラグが乱れることなく、安定した搬送を可能としている。すなわち、反応流路１２は、直進部１２ａを基板２の長手方向に亘って設けることで、圧力の変動が生じない直進部分を長く設けることができ、かつ湾曲部１２ｂを直進部１２ａと同一幅に形成することで、圧力の変動を抑えながらスラグを湾曲させ、方向転換させることができる。 In the reaction channel 12, both the rectilinear portion 12a and the curved portion 12b are formed with the same depth and the same width, thereby suppressing fluctuations in pressure and enabling stable conveyance without disturbing the slag. That is, the reaction channel 12 can be provided with a rectilinear portion where the pressure fluctuation does not occur by providing the rectilinear portion 12a along the longitudinal direction of the substrate 2, and the curved portion 12b has the same width as the rectilinear portion 12a. By forming the slag, the slag can be curved and the direction can be changed while suppressing fluctuations in pressure.
　この反応流路１２は、スラグ形成流路１１よりも幅広に形成されている。これにより、マイクロリアクタ１は、スラグの気液界面の断面積を広げ、かつ、スラグの流速を遅くすることで気液の接触時間及び紫外線の照射時間を増加させ、気液反応を効率よく進めることができる。したがって、マイクロリアクタ１は、高い収率で気液反応生成物を得ることができる。 The reaction channel 12 is formed wider than the slag forming channel 11. Thereby, the microreactor 1 increases the gas-liquid contact time and the ultraviolet irradiation time by widening the cross-sectional area of the gas-liquid interface of the slag and slowing the flow rate of the slag, thereby efficiently promoting the gas-liquid reaction. Can do. Therefore, the microreactor 1 can obtain a gas-liquid reaction product with a high yield.
　［拡幅部２０］
　反応流路１２とスラグ形成流路１１とは拡幅部２０を介して連続されている。拡幅部２０は、スラグ形成流路１１から反応流路１２にかけて漸次、流路幅を広げていくことで、スラグを壊すことなく液体試料３及び反応気体４の形状を太く短く変形させる流路である。拡幅部２０は、一端側をスラグ形成流路１１と同じ幅に形成され、他端側を反応流路１２と同じ幅に形成され、漸次拡幅する。これにより、拡幅部２０は、スラグ形成流路１１から反応流路１２にかけて圧力の急激な変動を防止し、スラグを安定した状態で気液界面の断面積を広げ、かつ、スラグの流速を遅くすることができる。 [Wide section 20]
The reaction channel 12 and the slag forming channel 11 are connected via the widened portion 20. The widening section 20 is a flow path that gradually widens the width of the flow path from the slag forming flow path 11 to the reaction flow path 12, thereby deforming the liquid sample 3 and the reaction gas 4 thickly and shortly without breaking the slag. is there. The widened portion 20 is formed to have the same width as that of the slag forming channel 11 on one end side and the same width as that of the reaction channel 12 on the other end side, and gradually widens. As a result, the widening portion 20 prevents a sudden change in pressure from the slag forming channel 11 to the reaction channel 12, widens the cross-sectional area of the gas-liquid interface while stabilizing the slag, and slows the flow rate of the slag. can do.
　このような拡幅部２０は、例えば一端側がスラグ形成流路１１と同じ深さ０．３ｍｍ、幅０．３ｍｍに形成され、他端側が、反応流路１２と同じ深さ０．３ｍｍ、幅０．５ｍｍに形成される。このように、マイクロリアクタ１は、供給流路１０、スラグ形成流路１１、拡幅部２０、反応流路１２にかけて同じ深さ（０．３ｍｍ）とすることで、幅の制御のみで、各流路をエッチング等を用いてにより容易に形成できる。 For example, the widened portion 20 is formed such that one end side has the same depth of 0.3 mm and width 0.3 mm as the slag forming channel 11, and the other end side has the same depth 0.3 mm and width 0 as the reaction channel 12. .5mm. As described above, the microreactor 1 has the same depth (0.3 mm) over the supply flow path 10, the slag formation flow path 11, the widened portion 20, and the reaction flow path 12, so that each flow path is controlled only by width control. Can be more easily formed by etching or the like.
　拡幅部２０は、それぞれ基板２０の幅方向に亘って平行に隣接して形成されているスラグ形成流路１１と反応流路１２の各端部を連続させる湾曲形状に形成されている。すなわち、スラグを構成する液体試料３及び反応気体４は、拡幅部２０を湾曲しながら漸次、太く短く変形していく。 The widened portion 20 is formed in a curved shape in which the end portions of the slag forming flow channel 11 and the reaction flow channel 12 formed adjacent to each other in parallel in the width direction of the substrate 20 are continuous. That is, the liquid sample 3 and the reaction gas 4 constituting the slag are gradually deformed thicker and shorter while the widened portion 20 is curved.
　ここで、拡幅部２０は、スラグ形成流路１１から反応流路１２にかけて湾曲することにより、スラグの流速を減速させる。そして、拡幅部２０は、スラグを減速させた状態で漸次拡幅させていくため、圧力の変動によるスラグの乱れを抑え、スラグを安定した状態で気液界面の断面積を広げ、かつ、スラグの流速を遅くすることができる。 Here, the widened portion 20 is curved from the slag forming channel 11 to the reaction channel 12 to reduce the flow rate of the slag. The widening section 20 gradually widens the slag in a decelerated state, so that the slag is prevented from being disturbed due to pressure fluctuations, the cross-sectional area of the gas-liquid interface is widened in a stable slag, and the slag The flow rate can be reduced.
　また、拡幅部２０は、互いに平行に形成されているスラグ形成流路１１と反応流路１２の各端部を連続させるために１８０°に湾曲する。これにより、スラグを最大限減速させることができる。スラグは、漸次拡幅する拡幅部２０を通過することで減圧されるが、その際に、湾曲形状によって減速されるため、圧力の急激な変動が防止され、前後の液体試料３同士が連結することもなく、安定して細く長い形状から太く短い形状へ変形される。 Further, the widened portion 20 is bent at 180 ° in order to make the end portions of the slag forming flow channel 11 and the reaction flow channel 12 formed in parallel to each other continue. Thereby, slag can be decelerated to the maximum. The slag is depressurized by passing through the widened portion 20 that gradually widens, but at that time, since it is decelerated by the curved shape, rapid fluctuations in pressure are prevented and the front and rear liquid samples 3 are connected to each other. However, it is stably deformed from a thin and long shape to a thick and short shape.
　［排出流路］
　反応流路１２と連続し、反応生成物を排出する排出流路１３は、図３に示すように、基板２の幅方向の他端側に設けられた反応流路１２の先端から略９０°に折れ曲がる折り曲げ部２４を介して、基板２の幅方向の一端側に向かって形成されている。また、排出流路１３は、反応流路１２と連続する一端と反対側の他端が、基板２の下面に形成された開口２５より外方に臨まされている。さらに、排出流路１３は、反応流路１２と同じ深さで、かつ反応流路１２よりも細く形成され、例えば、反応流路１２が深さ０．３ｍｍ、幅０．５ｍｍであるのに対し、排出流路１３は深さ０．３ｍｍ、幅０．３ｍｍに形成されている。 [Discharge flow path]
As shown in FIG. 3, the discharge flow path 13 that is continuous with the reaction flow path 12 and discharges the reaction product is approximately 90 ° from the front end of the reaction flow path 12 provided on the other end side in the width direction of the substrate 2. It is formed toward the one end side in the width direction of the substrate 2 through a bent portion 24 that bends to the side. Further, the discharge channel 13 has the other end opposite to the one end continuous with the reaction channel 12 facing outward from the opening 25 formed in the lower surface of the substrate 2. Further, the discharge channel 13 is formed to have the same depth as the reaction channel 12 and narrower than the reaction channel 12, for example, the reaction channel 12 has a depth of 0.3 mm and a width of 0.5 mm. On the other hand, the discharge channel 13 is formed with a depth of 0.3 mm and a width of 0.3 mm.
　排出流路１３は、反応流路１２よりも細く形成されることにより、スラグを安定した状態で搬送し、開口２５より気液反応生成物を排出することができる。すなわち、排出流路１３は、開口２５より外方に臨まされているため、内部の圧力が開口２５より開放されることから、圧力変動が生じやすくスラグが不安定となる。そして、この排出流路１３の圧力変動が反応流路１２に伝搬すると、反応流路１２においても圧力バランスが崩れ、液体試料３同士が一体化するおそれがある。 The discharge channel 13 is formed to be narrower than the reaction channel 12, thereby transporting the slag in a stable state and discharging the gas-liquid reaction product from the opening 25. That is, since the discharge flow channel 13 faces outward from the opening 25, the internal pressure is released from the opening 25, so that pressure fluctuation is likely to occur and the slag becomes unstable. When the pressure fluctuation in the discharge channel 13 propagates to the reaction channel 12, the pressure balance in the reaction channel 12 is lost and the liquid samples 3 may be integrated.
　そこで、排出流路１３は、反応流路１２よりも細く形成することで、圧力変動を極力抑え、反応流路１２への伝搬を防止することができる。これにより、マイクロリアクタ１は、反応流路１２の最後まで、気液界面の断面積の広いスラグを安定して搬送することができ、かつ、スラグの流速を遅くすることで気液の接触時間及び紫外線の照射時間を増加させることができる。 Therefore, by forming the discharge flow channel 13 to be narrower than the reaction flow channel 12, pressure fluctuation can be suppressed as much as possible and propagation to the reaction flow channel 12 can be prevented. As a result, the microreactor 1 can stably transport slag having a large cross-sectional area at the gas-liquid interface to the end of the reaction channel 12, and the gas-liquid contact time and The irradiation time of ultraviolet rays can be increased.
　また、排出流路１３は、反応流路１２と折り曲げ部２４を介して連続されているため、開口２５からの圧力バランスの変動によるスラグの変形が反応流路１２に伝搬することをさらによく防止することができる。折り曲げ部２４は、一端を反応流路と連続され、他端を排出流路１３と連続され、漸次幅狭となるように湾曲される。したがって、反応流路１２から折り曲げ部２４へ流れるスラグは、圧力の急激な変動もなく、安定した状態で排出流路１３へ流出する。 In addition, since the discharge channel 13 is continuous with the reaction channel 12 via the bent portion 24, the deformation of the slag due to the pressure balance variation from the opening 25 is further prevented from propagating to the reaction channel 12. can do. One end of the bent portion 24 is continuous with the reaction flow path, the other end is continuous with the discharge flow path 13, and is bent so as to gradually become narrower. Therefore, the slag flowing from the reaction flow path 12 to the bent portion 24 flows out to the discharge flow path 13 in a stable state without sudden pressure fluctuation.
　したがって、マイクロリアクタ１は、反応流路１２よりも細い排出流路１３を、折り曲げ部２４を介して設けることにより、反応流路１２におけるスラグ流を安定させ、気液反応の効率を向上させるとともに、高い収率を実現することができる。 Therefore, the microreactor 1 is provided with the discharge flow path 13 narrower than the reaction flow path 12 via the bent portion 24, thereby stabilizing the slag flow in the reaction flow path 12 and improving the efficiency of the gas-liquid reaction, High yields can be achieved.
　［反応生成物の製造工程］
　次いで、マイクロリアクタ１を用いた反応生成物の製造工程について説明する。先ず、反応気体４が収納されたシリンジ１７を、基板２の開口１５を介して第１の供給路１０ａに接続し、液体試料３が収納されたシリンジ１８を開口１６を介して第２の供給路１０ｂに接続する。そして、シリンジ１７を操作することにより、第１の供給路１０ａより合流路１０ｃに反応気体４を注入するとともに、シリンジ１８を操作することにより、第２の供給路１０ｂより合流路１０ｃに間欠的に液体試料３を注入する。 [Production process of reaction product]
Next, a process for producing a reaction product using the microreactor 1 will be described. First, the syringe 17 containing the reaction gas 4 is connected to the first supply path 10a via the opening 15 of the substrate 2, and the syringe 18 containing the liquid sample 3 is supplied to the second supply via the opening 16. Connect to path 10b. Then, by operating the syringe 17, the reaction gas 4 is injected from the first supply path 10 a into the combined flow path 10 c, and by operating the syringe 18, intermittently from the second supply path 10 b to the combined flow path 10 c. The liquid sample 3 is injected into.
　供給流路１０は、合流路１０ｃに流れる反応気体４中に、間欠的に液体試料３が注入されることにより、液体試料３と反応気体４とが交互に連続して供給され、これにより、合流路１０ｃと連続するスラグ形成流路１１には、液体試料３と反応気体４とが交互に連続するスラグ流が形成されていく。 The supply channel 10 is supplied with the liquid sample 3 and the reaction gas 4 alternately and continuously by intermittently injecting the liquid sample 3 into the reaction gas 4 flowing in the combined channel 10c. A slag flow in which the liquid sample 3 and the reaction gas 4 are alternately continued is formed in the slag formation flow channel 11 continuous with the combined flow channel 10c.
　ここで、供給流路１０の第１、第２の供給路１０ａ，１０ｂ、合流路１０ｃ及びスラグ形成流路１１は、いずれも、同一深さ（例えば０．３ｍｍ）、同一幅（例えば０．３ｍｍ）で形成することにより、流路内の圧力変動が抑えられ、スラグを安定して形成、搬送することができる。また、同一深さとすることで、基板２のエッチング等により流路を形成する際にも、幅の制御のみで形成することができる。 Here, the first and second supply channels 10a and 10b, the combined channel 10c, and the slag forming channel 11 of the supply channel 10 all have the same depth (for example, 0.3 mm) and the same width (for example, 0.2 mm). 3 mm), the pressure fluctuation in the flow path is suppressed, and the slag can be stably formed and transported. In addition, by setting the same depth, the channel can be formed only by controlling the width when the channel is formed by etching the substrate 2 or the like.
　スラグ形成流路１１を流れるスラグ流は、拡幅部２０を経てスラグ形成流路１１よりも幅広の反応流路１２に流入し、これにより、スラグを構成する液体試料３及び反応気体４の形状が太く短く変形される。また、反応流路１２には、基板２の上面側から紫外線等の光線が照射され、気液界面において化学反応が進行する。 The slag flow that flows through the slag forming channel 11 flows into the reaction channel 12 that is wider than the slag forming channel 11 through the widened portion 20, whereby the shapes of the liquid sample 3 and the reaction gas 4 constituting the slag are changed. It is deformed thick and short. Further, the reaction flow path 12 is irradiated with light rays such as ultraviolet rays from the upper surface side of the substrate 2, and a chemical reaction proceeds at the gas-liquid interface.
　このとき、マイクロリアクタ１は、流路幅が漸次拡幅する拡幅部２０を経ることにより、圧力の急激な変動が防止され、スラグ流を安定した状態で反応流路１２における液体試料３及び反応気体４の気液界面の面積を拡大することができる。また、マイクロリアクタ１は、拡幅部２０が湾曲形状に形成されることにより、スラグの流速が減速された状態で流路幅が漸次拡幅されていく。したがって、圧力の急激な変動によるスラグの乱れを抑え、スラグを安定した状態で気液界面の断面積を広げ、かつ、スラグの流速を遅くすることができる。 At this time, in the microreactor 1, the liquid sample 3 and the reaction gas 4 in the reaction channel 12 are prevented in a state in which a rapid change in pressure is prevented and the slag flow is stabilized by passing through the widened portion 20 where the channel width gradually increases. The area of the gas-liquid interface can be enlarged. In the microreactor 1, the widened portion 20 is formed in a curved shape, so that the flow path width is gradually widened while the flow rate of the slag is reduced. Accordingly, it is possible to suppress the slag disturbance due to a rapid change in pressure, to expand the cross-sectional area of the gas-liquid interface in a stable state of the slag, and to reduce the flow rate of the slag.
　このように、反応流路１２は、スラグを乱すことなく、気液界面における接触面積を拡大するとともに、スラグの流速を減速することで、気液の接触時間及び紫外線の照射時間を増加させ、気液反応を効率よく進めることができる。したがって、マイクロリアクタ１は、高い収率で気液反応生成物を得ることができる。 Thus, the reaction flow path 12 increases the contact area at the gas-liquid interface and the irradiation time of the ultraviolet rays by expanding the contact area at the gas-liquid interface without reducing the slag and reducing the flow rate of the slag, A gas-liquid reaction can be advanced efficiently. Therefore, the microreactor 1 can obtain a gas-liquid reaction product with a high yield.
　反応流路１２において生成された反応生成物は、排出流路１３に流れ、開口２５より排出される。排出流路１３は、開口２５が開放されることで圧力がゼロとなるが、反応流路１２よりも細く形成されているため、圧力変動によるスラグの乱れを抑え、反応流路１２へ圧力変動が伝搬することを防止することができる。また、排出流路１３は折り曲げ部２４を介して反応流路１２と連続されているため、これによっても圧力変動の伝搬を防止することができる。 The reaction product generated in the reaction channel 12 flows into the discharge channel 13 and is discharged from the opening 25. The pressure of the discharge channel 13 becomes zero when the opening 25 is opened. However, since the discharge channel 13 is formed to be narrower than the reaction channel 12, the disturbance of the slag due to the pressure variation is suppressed, and the pressure variation is applied to the reaction channel 12. Can be prevented from propagating. Further, since the discharge channel 13 is continuous with the reaction channel 12 via the bent portion 24, the propagation of the pressure fluctuation can also be prevented by this.
　［気液反応の具体例］
　次いで、マイクロリアクタ１を用いた反応例について説明する。 [Specific example of gas-liquid reaction]
Next, a reaction example using the microreactor 1 will be described.
　マイクロリアクタ１を用いた気液反応としては、例えば、芳香環上メチル基の光酸化反応が挙げられる。この光酸化反応は、４-tert-ブチルトルエンと酸素とを、触媒量のLiBr存在下において紫外線照射することにより反応させ、芳香環上メチル基が酸化した４-tert-ブチル安息香酸を生成させる気液反応である。 Examples of the gas-liquid reaction using the microreactor 1 include a photo-oxidation reaction of a methyl group on an aromatic ring. In this photo-oxidation reaction, 4-tert-butyltoluene and oxygen are reacted by irradiating with ultraviolet rays in the presence of a catalytic amount of LiBr to produce 4-tert-butylbenzoic acid in which methyl groups on the aromatic ring are oxidized. It is a gas-liquid reaction.
　より具体的に、この気液反応では、先ず、第１の供給路１０ａから酢酸エチルに溶解した４-tert-ブチルトルエンを、第２の供給路１０ｂから酸素を、それぞれ所定の圧力で交互に供給する。供給された４-tert-ブチルトルエンと酸素とは、合流路１０ｃを介して合流し、スラグ形成流路１１において４-tert-ブチルトルエンと酸素とが交互に連続するスラグを形成し、搬送される。 More specifically, in this gas-liquid reaction, first, 4-tert-butyltoluene dissolved in ethyl acetate from the first supply path 10a and oxygen from the second supply path 10b are alternately alternately supplied at a predetermined pressure. Supply. The supplied 4-tert-butyltoluene and oxygen merge through the combined flow path 10c, and in the slag forming flow path 11, 4-tert-butyltoluene and oxygen form a slag in which they are alternately and continuously conveyed. The
　４-tert-ブチルトルエンと酸素とからなるスラグ流は、拡幅部２０を経て反応流路１２に流れることにより、細く長い形状から太く短い形状へ安定的に変形される。これにより、４-tert-ブチルトルエンと酸素とからなるスラグ流は、気液界面の断面積が広がり、かつ、流速が遅くなることで４-tert-ブチルトルエンと酸素との接触時間及び紫外線の照射時間を増加させ、反応を効率よく進めることができる。したがって、マイクロリアクタ１は、高い収率で芳香環上メチル基が酸化した４-tert-ブチル安息香酸を得ることができる。 The slag flow composed of 4-tert-butyltoluene and oxygen flows into the reaction channel 12 through the widened portion 20 and is stably deformed from a thin and long shape to a thick and short shape. As a result, the slag flow composed of 4-tert-butyltoluene and oxygen has a wide cross-sectional area at the gas-liquid interface, and the flow rate is slowed down, so that the contact time between 4-tert-butyltoluene and oxygen and the ultraviolet rays are reduced. The irradiation time can be increased and the reaction can proceed efficiently. Therefore, the microreactor 1 can obtain 4-tert-butylbenzoic acid in which the methyl group on the aromatic ring is oxidized with a high yield.
　［液液反応の具体例］
　また、マリクロリアクタ１は、水系と油系等の性状が異なり互いに混ざり合わず、スラグ流を形成する液体試料同士の液液反応に用いることもできる。 [Specific example of liquid-liquid reaction]
In addition, the maricro reactor 1 can be used for a liquid-liquid reaction between liquid samples that form a slag flow without being mixed with each other because of different properties such as an aqueous system and an oil system.
　マイクロリアクタ１を用いた液液反応としては、例えば、酸素水と有機エステル類等の液体試料とによる光酸化反応を挙げることができる。具体的には、酸素水と有機エステル類等の液体試料とを、それぞれ第１，第２の供給路１０ａ，１０ｂから所定の圧力で供給し、スラグ形成流路１１にて酸素水と液体試料とが交互に連続するスラグを形成させ搬送する。 Examples of the liquid-liquid reaction using the microreactor 1 include a photo-oxidation reaction between oxygen water and a liquid sample such as organic esters. Specifically, oxygen water and a liquid sample such as organic esters are respectively supplied from the first and second supply passages 10a and 10b at a predetermined pressure, and the oxygen water and the liquid sample are supplied through the slag formation passage 11. And slag is formed and conveyed alternately.
　酸素水と液体試料とからなるスラグ流は、拡幅部２０を経て反応流路１２に流れることにより、細く長い形状から太く短い形状へ安定的に変形される。これにより、酸素水と液体試料とからなるスラグ流は、液液界面の断面積が広がり、かつ、流速が遅くなることで、反応流路１２にて光線を照射することにより、スラグの液液界面にて酸化反応を進行させる。このようにして酸素水と液体試料とを液液界面にて反応させることにより、酸素水中に含まれる酸素が有機エステル類を含有する液体試料の表面で反応するようになる。 The slag flow comprising oxygen water and a liquid sample is stably deformed from a thin and long shape to a thick and short shape by flowing into the reaction channel 12 via the widened portion 20. As a result, the slag flow composed of oxygen water and the liquid sample is irradiated with light in the reaction channel 12 because the cross-sectional area of the liquid-liquid interface is widened and the flow velocity is slow, so that the liquid slag liquid The oxidation reaction proceeds at the interface. By reacting oxygen water and the liquid sample at the liquid-liquid interface in this manner, oxygen contained in the oxygen water reacts on the surface of the liquid sample containing organic esters.
　また、液液反応の他の例として、各種のアクリルモノマーと、水系の液体試料に含有させた光重合開始剤とによる光重合反応が挙げられる。この場合においても、アクリル酸エステル等のアクリルモノマーと、水系の液体試料に含有させた光重合剤とを、それぞれ第１，第２の供給路１０ａ，１０ｂから所定の圧力で供給し、スラグ形成流路１１にてアクリルモノマーと光重合開始剤とが交互に連続するスラグを形成させ搬送する。 Another example of the liquid-liquid reaction is a photopolymerization reaction using various acrylic monomers and a photopolymerization initiator contained in an aqueous liquid sample. Also in this case, an acrylic monomer such as an acrylate ester and a photopolymerization agent contained in an aqueous liquid sample are supplied from the first and second supply paths 10a and 10b, respectively, at a predetermined pressure to form slag. In the flow path 11, slag in which acrylic monomers and photopolymerization initiators are alternately continued is formed and conveyed.
　アクリルモノマーと光重合開始剤とからなるスラグ流は、拡幅部２０を経て反応流路１２に流れることにより、同様に液液界面の断面積が広がり、かつ、流速が遅くなることで、反応流路１２にて紫外線等の光線を照射することにより、スラグの液液界面にて光重合開始剤によるラジカルを生成させ、アクリルモノマーのラジカル重合反応を進行させる。このようにしてスラグの液液界面にて反応を進行させ、アクリルモノマーの表面を重合させた後に分取することにより、分取した粒子同士の凝集を抑制することができ、その後本重合させることができる。 The slag flow composed of the acrylic monomer and the photopolymerization initiator flows to the reaction flow path 12 through the widened portion 20, so that the cross-sectional area of the liquid-liquid interface similarly increases, and the flow rate becomes slow. By irradiating light such as ultraviolet rays through the path 12, radicals by the photopolymerization initiator are generated at the liquid-liquid interface of the slag, and the radical polymerization reaction of the acrylic monomer proceeds. In this way, by allowing the reaction to proceed at the liquid-liquid interface of the slag and polymerizing the surface of the acrylic monomer, it is possible to suppress agglomeration of the separated particles, and then perform the main polymerization. Can do.
　また、同様の機構により、例えば、重合開始剤を含有させた水系の溶液と、この媒体に難溶なモノマーと界面活性剤とを含有させた液体試料との光重合によるエマルション化反応にも適用することができる。 In addition, by the same mechanism, for example, it can be applied to an emulsification reaction by photopolymerization of an aqueous solution containing a polymerization initiator and a liquid sample containing a monomer and a surfactant that are hardly soluble in this medium. can do.
　［その他］
　なお、気液反応では、反応が進むにつれて反応気体４が減少するため、反応流路１２の下流では反応生成物の溶液と少量の反応気体４とからなるスラグ流において、反応生成物の溶液が前後の溶液と連結してしまうなど、不安定となるおそれがある。 [Others]
In the gas-liquid reaction, the reaction gas 4 decreases as the reaction proceeds. Therefore, in the slag flow consisting of the reaction product solution and a small amount of the reaction gas 4 downstream of the reaction channel 12, the reaction product solution is reduced. There is a risk of instability, such as linking with the solution before and after.
　そこで、マイクロリアクタ１は、液体試料３、反応気体４及び反応生成物と反応しない不活性ガスを反応気体４とともに供給してもよい。これにより、液体試料３と反応気体４との反応が進行した場合にも、反応生成物の溶液と不活性ガスとからなるスラグが形成される。したがって、反応流路１２の下流においても圧力変動を極力抑えることができ、反応流路内におけるスラグ流の乱れによる液体試料３同士の連結、これによる気液界面の面積減少、反応効率の低下等を防止することができる。 Therefore, the microreactor 1 may supply an inert gas that does not react with the liquid sample 3, the reaction gas 4, and the reaction product together with the reaction gas 4. Thereby, even when the reaction between the liquid sample 3 and the reaction gas 4 proceeds, a slag composed of the reaction product solution and the inert gas is formed. Accordingly, the pressure fluctuation can be suppressed as much as possible downstream of the reaction channel 12, the liquid samples 3 are connected to each other due to the slag flow disturbance in the reaction channel, the area of the gas-liquid interface is thereby reduced, the reaction efficiency is reduced, etc. Can be prevented.
　また、本発明が適用されたマイクロリアクタは、上述した構成に限らず、例えば図４に示すように、反応流路１２が基板２の厚さ方向に亘って多層化されていてもよい。２層構造とした場合、基板２には、上層の反応流路３０と、下層の反応流路３１と、上層及び下層の反応流路３０，３１を連続させる連結流路３２が形成される。上層及び下層の反応流路３０，３１は、上記反応流路１２と同様に、基板２の長手方向に亘って直進する直進部３０ａ，３１ａが幅方向に亘って平行に複数形成され、隣接する直進部３０ａ，３１ａの端部同士が湾曲部３０ｂ，３１ｂによって連続され、これにより、基板２の全面に亘って蛇行するように形成されている。 Further, the microreactor to which the present invention is applied is not limited to the above-described configuration. For example, as shown in FIG. 4, the reaction channel 12 may be multilayered in the thickness direction of the substrate 2. In the case of a two-layer structure, the substrate 2 is formed with an upper reaction channel 30, a lower reaction channel 31, and a connection channel 32 that connects the upper and lower reaction channels 30, 31. Similar to the reaction channel 12, the upper and lower reaction channels 30, 31 have a plurality of rectilinear portions 30a, 31a that go straight in the longitudinal direction of the substrate 2 in parallel in the width direction and are adjacent to each other. The ends of the rectilinear portions 30 a and 31 a are continuous with each other by the curved portions 30 b and 31 b, thereby forming a meandering over the entire surface of the substrate 2.
　上層の反応流路１２は、上記反応流路１２と同様に、一端を拡幅部２０と連続され、基板２の上層面内を蛇行し、基板２の幅方向の他端側の終端にて連結流路３２を介して下層の反応流路３１と連続されている。下層の反応流路３１は、一端を連結流路と連続し、基板２の下層面内を蛇行し、基板２の幅方向一端側の終端にて排出流路１３と連続されている。 Similarly to the reaction channel 12, the upper layer reaction channel 12 is connected to the widened portion 20 at one end, meanders in the upper layer surface of the substrate 2, and is connected at the end on the other end side in the width direction of the substrate 2. The lower reaction channel 31 is continued through the channel 32. One end of the lower reaction channel 31 is continuous with the connection channel, meanders in the lower surface of the substrate 2, and is continued with the discharge channel 13 at the end of one end in the width direction of the substrate 2.
　上層及び下層の反応流路３０，３１は、直進部３０ａ，３１ａが互いに重畳しないように形成され、基板２の上面側から照射される紫外線等の光線を上層の反応流路３０が遮ることなく下層の反応流路３１にも照射可能とされている。 The upper and lower reaction channels 30 and 31 are formed so that the rectilinear portions 30a and 31a do not overlap each other, and the upper reaction channel 30 does not block light such as ultraviolet rays irradiated from the upper surface side of the substrate 2. The lower reaction channel 31 can also be irradiated.
　このように、反応流路を多層化することにより、気液反応や液液反応が進行する流路を長くすることができ、限られた基板スペース内において、反応効率及び収率を向上させることができる。 Thus, by multilayering the reaction channel, the channel through which gas-liquid reaction or liquid-liquid reaction proceeds can be lengthened, and the reaction efficiency and yield can be improved in a limited substrate space. Can do.
　また、本発明が適用されたマイクロリアクタは、図５に示すように、スラグ形成流路１１と反応流路１２との間のみならず、反応流路１２の直進部１２ａ間を拡幅部２０を介して漸次拡幅していってもよい。すなわち、マイクロリアクタ１は、スラグ形成流路１１から反応流路１２にかけて拡幅部２０を介することにより流路幅が拡幅されるとともに、反応流路１２の複数の直進部１２ａの間を拡幅部２０を介して連続させることにより、反応流路１２を漸次拡幅していってもよい。 In addition, as shown in FIG. 5, the microreactor to which the present invention is applied is not only between the slag forming channel 11 and the reaction channel 12, but also between the rectilinear portions 12a of the reaction channel 12 via the widened portion 20. May be gradually widened. That is, in the microreactor 1, the channel width is widened through the widened portion 20 from the slag forming flow channel 11 to the reaction flow channel 12, and the widened portion 20 is provided between the plurality of rectilinear portions 12a of the reaction flow channel 12. The reaction channel 12 may be gradually widened by being continued through.
　反応流路１２の複数の直進部１２ａの間を連結する拡幅部２０も、湾曲形状とすることにより、スラグを減速させた状態で漸次拡幅させていくため、圧力の変動によるスラグの乱れを抑え、スラグを安定した状態で気液界面の断面積を広げ、かつ、スラグの流速を遅くすることができる。 The widened portion 20 that connects the plurality of rectilinear portions 12a of the reaction flow path 12 is also curved so that the slag is gradually widened in a decelerated state, so that slag disturbance due to pressure fluctuations is suppressed. The cross-sectional area of the gas-liquid interface can be expanded while the slag is stable, and the flow rate of the slag can be reduced.
　また、マイクロリアクタ１は、反応流路において紫外線等の光線を照射し、気液反応や液液反応を進行させるが、スラグ形成流路１１、拡幅部２０又は排出流路１３においても光線を照射することで、反応を促進させてもよい。 In addition, the microreactor 1 irradiates light such as ultraviolet rays in the reaction channel to advance the gas-liquid reaction or liquid-liquid reaction, but also irradiates the slag forming channel 11, the widened portion 20, or the discharge channel 13. Thus, the reaction may be promoted.
１　マイクロリアクタ、２　基板、３　液体試料、４　反応気体、１０　供給流路、１０ａ　第１の供給路、１０ｂ　第２の供給路、１０ｃ　合流路、１１　スラグ形成流路、１２　反応流路、１２ａ　直進部、１２ｂ　湾曲部、１３　排出流路、１５，１６　開口、１７，１８　シリンジ、２０　拡幅部、２４　折り曲げ部、２５　開口、３０，３１　反応流路 1 microreactor, 2 substrate, 3 liquid sample, 4 reaction gas, 10 supply channel, 10a first supply channel, 10b second supply channel, 10c combined channel, 11 slag formation channel, 12 reaction channel, 12a straight line Part, 12b curved part, 13 discharge flow path, 15, 16 opening, 17, 18 syringe, 20 widening part, 24 bending part, 25 opening, 30, 31 reaction flow path

Claims (11)

  1. 　互いに気液界面又は液液界面を形成する流体試料が交互に供給される供給流路と、
    　上記供給流路を介して供給された上記試料が交互に連続するスラグを形成するスラグ形成流路と、
    　上記スラグ形成流路よりも幅広に形成され、光を照射することにより、上記試料の界面において化学反応を進行させる反応流路と、
    　上記スラグ形成流路と上記反応流路との間に介在し、一端を上記スラグ形成流路と連続され、他端を上記反応流路と連続され、漸次拡幅された拡幅部と、
    　上記反応流路から連続し、反応した試料を排出する排出流路とを有するマイクロリアクタ。     A supply flow path in which fluid samples forming a gas-liquid interface or a liquid-liquid interface are alternately supplied;
    A slag forming flow path for forming a slag in which the sample supplied through the supply flow path is alternately continuous; and
    A reaction channel that is formed wider than the slag forming channel and that causes a chemical reaction to proceed at the interface of the sample by irradiating light; and
    A widened portion interposed between the slag forming flow channel and the reaction flow channel, one end being continuous with the slag forming flow channel, the other end being continuous with the reaction flow channel, and gradually widened;
    A microreactor having a discharge channel that discharges the reacted sample continuously from the reaction channel.
  2. 　上記拡幅部は、湾曲している請求項１記載のマイクロリアクタ。 The microreactor according to claim 1, wherein the widened portion is curved.
  3. 　上記供給流路は、気液界面又は液液界面を形成する一方の上記流体試料が供給される第１の供給路と、気液界面又は液液界面を形成する他方の上記流体試料が供給される第２の供給路と、上記一方の流体試料及び他方の流体試料とが合流する合流路とを有し、
    　上記第１、第２の供給路及び上記合流路は、いずれも同一径である請求項２記載のマイクロリアクタ。     The supply channel is supplied with a first supply channel through which one of the fluid samples forming a gas-liquid interface or a liquid-liquid interface is supplied, and the other fluid sample forming a gas-liquid interface or a liquid-liquid interface. A second supply channel, and a merge channel in which the one fluid sample and the other fluid sample merge,
    The microreactor according to claim 2, wherein the first and second supply paths and the combined flow path have the same diameter.
  4. 　上記スラグ形成流路においても光を照射する請求項２又は請求項３記載のマイクロリアクタ。 The microreactor according to claim 2 or 3, wherein light is irradiated also in the slag forming flow path.
  5. 　上記反応流路は、基板の同一面内に形成され、互いに平行に形成された複数の直進部と、上記直進部間に設けられ、隣接する上記直進部を連続させる湾曲部とを有する請求項２～請求項４のいずれか１項に記載のマイクロリアクタ。 The reaction channel has a plurality of rectilinear portions formed in the same plane of the substrate and formed in parallel to each other, and a curved portion provided between the rectilinear portions and continuing the adjacent rectilinear portions. The microreactor according to any one of claims 2 to 4.
  6. 　上記反応流路は、基板の厚さ方向に亘って多層化されている請求項５記載のマイクロリアクタ。 The microreactor according to claim 5, wherein the reaction flow path is multilayered over the thickness direction of the substrate.
  7. 　上記反応流路は、上記拡幅部を介して漸次拡幅されていく請求項２～請求項６のいずれか１項に記載のマイクロリアクタ。 The microreactor according to any one of claims 2 to 6, wherein the reaction channel is gradually widened through the widened portion.
  8. 　上記排出流路は、上記反応流路よりも幅狭に形成され、漸次幅狭に形成された折り曲げ部を介して上記反応流路と連続されている請求項２～請求項７のいずれか１項に記載のマイクロリアクタ。 8. The discharge channel according to claim 2, wherein the discharge channel is formed narrower than the reaction channel, and is continuous with the reaction channel via a bent portion formed gradually narrower. The microreactor according to item.
  9. 　互いに気液界面又は液液界面を形成する流体試料が交互に供給される供給工程と、
    　供給された上記試料が交互に連続するスラグを形成するスラグ形成工程と、
    　光を照射することにより、上記試料の界面において反応を進行させる反応工程と、
    　上記反応した試料を排出する排出工程とを有し、
    　上記スラグは、上記スラグ形成工程と上記反応工程との間に、流路が漸次拡幅された拡幅部を流れることにより、上記反応工程において上記スラグ形成工程よりも上記流体試料の界面が拡大されている反応生成物の製造方法。     A supply process in which fluid samples forming a gas-liquid interface or a liquid-liquid interface are alternately supplied;
    A slag forming step of forming a slag in which the supplied sample is alternately continuous; and
    A reaction step of causing the reaction to proceed at the interface of the sample by irradiating with light;
    A discharge step of discharging the reacted sample,
    The slag flows between the slag formation step and the reaction step through a widened portion where the flow path is gradually widened, so that the interface of the fluid sample is expanded in the reaction step as compared to the slag formation step. A method for producing a reaction product.
  10. 　上記拡幅部は、湾曲している請求項９記載の反応生成物の製造方法。 The method for producing a reaction product according to claim 9, wherein the widened portion is curved.
  11. 　上記供給工程で、流体試料及び反応生成物と反応しない不活性の気体を供給する請求項１０記載の反応生成物の製造方法。 11. The method for producing a reaction product according to claim 10, wherein an inert gas that does not react with the fluid sample and the reaction product is supplied in the supplying step.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109647303A (en) * 2018-12-11 2019-04-19 浙江工业大学 Perfluorinated sulfonic resin/copper manganese compound fibrillation micro passage reaction preparation method and application
TWI701075B (en) * 2015-05-29 2020-08-11 日商昭榮化學工業股份有限公司 Method for producing nanoparticles
CN112206727A (en) * 2019-07-10 2021-01-12 中国石油化工股份有限公司 Micro-channel gas-liquid reaction device, gas-liquid reaction strengthening method and adipic acid preparation method
WO2021189639A1 (en) * 2020-03-25 2021-09-30 南京延长反应技术研究院有限公司 Enhanced reaction system and process for propylene hydration catalyzed by ionic liquid

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6086250B2 (en) * 2014-04-25 2017-03-01 大陽日酸株式会社 Gas-liquid reaction method and aminosilane production method
JP6406959B2 (en) * 2014-09-30 2018-10-17 デクセリアルズ株式会社 Small reactor and reactor
CN107413405A (en) * 2017-06-09 2017-12-01 吴振嘉 Prevent the micro-fluid reactor of fluid countercurrent current

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998002237A1 (en) * 1996-07-15 1998-01-22 Kemgas Limited Production of powders
JP2006504512A (en) * 2002-05-09 2006-02-09 ザ ユニバーシティー オブ シカゴ Apparatus and method for transport and reaction by pressure driven plug
JP2007268491A (en) * 2006-03-31 2007-10-18 Fujifilm Corp Micro device and catalytic reaction method using the same
JP2008238313A (en) * 2007-03-27 2008-10-09 Fuji Xerox Co Ltd Micro flow passage device and manufacturing method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1398077A1 (en) * 2002-09-16 2004-03-17 Corning Incorporated Method and microfluidic reaction for photocatalysis
JP2006142242A (en) * 2004-11-22 2006-06-08 Olympus Corp Device for controlling micromotion of liquid
JP5030222B2 (en) * 2006-09-08 2012-09-19 国立大学法人東京工業大学 Photocatalytic microreactor
US8367976B2 (en) * 2008-03-21 2013-02-05 Lawrence Livermore National Security, Llc Laser heating of aqueous samples on a micro-optical-electro-mechanical system

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998002237A1 (en) * 1996-07-15 1998-01-22 Kemgas Limited Production of powders
JP2006504512A (en) * 2002-05-09 2006-02-09 ザ ユニバーシティー オブ シカゴ Apparatus and method for transport and reaction by pressure driven plug
JP2007268491A (en) * 2006-03-31 2007-10-18 Fujifilm Corp Micro device and catalytic reaction method using the same
JP2008238313A (en) * 2007-03-27 2008-10-09 Fuji Xerox Co Ltd Micro flow passage device and manufacturing method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI701075B (en) * 2015-05-29 2020-08-11 日商昭榮化學工業股份有限公司 Method for producing nanoparticles
CN109647303A (en) * 2018-12-11 2019-04-19 浙江工业大学 Perfluorinated sulfonic resin/copper manganese compound fibrillation micro passage reaction preparation method and application
CN112206727A (en) * 2019-07-10 2021-01-12 中国石油化工股份有限公司 Micro-channel gas-liquid reaction device, gas-liquid reaction strengthening method and adipic acid preparation method
CN112206727B (en) * 2019-07-10 2024-01-05 中国石油化工股份有限公司 Microchannel gas-liquid reaction device and method for strengthening gas-liquid reaction and method for preparing adipic acid
WO2021189639A1 (en) * 2020-03-25 2021-09-30 南京延长反应技术研究院有限公司 Enhanced reaction system and process for propylene hydration catalyzed by ionic liquid

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