JP2014028343A - Method for joining external pipes targeting microreactor, microreactor having junction structure joined by the same method, and bundle and module structure of the latter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for joining external pipes targeting a microreactor, a microreactor having a junction structure joined by the same method, and a bundle or module structure of the microreactor.SOLUTION: The pipe joining method is a joining method for feeding or discharging fluids of reaction raw ingredients or reaction products into or from the reactor providing a joint structure wherein terminal portions of the external pipes are sheathed within pipes of the reactor and wherein the external pipes are connected horizontally or vertically to a group of microchannels arrayed to embody a horizontal plane; the microreactor has a joint structure wherein terminal portions of the external pipes are sheathed within pipes of the reactor and a junction structure wherein the external pipes are connected horizontally or vertically to a group of microchannels arrayed to embody a horizontal plane; the bundle or module structure of the microreactor is constituted by laminating or integrating the microreactors.

Description

  The present invention relates to a method for joining external pipes in a microreactor, a microreactor having a joined structure joined by the method, and an integrated structure thereof, and more specifically, a microreactor having a microchannel, The present invention relates to a joining method in which an external pipe for supplying or discharging reaction raw materials or reaction products is connected to a reactor and joining them together, its joining structure, a microreactor having the joining structure, its bundle, and a module structure It is.

  The present invention constructs a bundle or a module structure in which microreactors are stacked or integrated in multiple stages and a microreactor is a unit that can increase mass transfer / scale up mass transfer in microchannels of the microreactor. It provides new technologies and new products related to the joining technology of external pipes in micro reactors that are important and indispensable.

In recent years, development of a continuous reaction process using a microchannel composed of fine capillaries having a cross-sectional area of around 0.01 cm ² or less has been energetically advanced. The feature of this technology is that it takes advantage of the high specific surface area of the microchannel to improve heat removal efficiency, thereby greatly improving reaction controllability and improving the efficiency of the reaction by improving the mass transfer efficiency. It is in.

  As an example that can greatly improve the controllability of the reaction in a continuous reaction process, direct fluorination reaction using hydrogen in the gas phase and reaction of hydrogen and oxygen can be efficiently performed using a microchannel. A controlled example is known (Non-Patent Document 1).

  For the reaction in the microreactor composed of microchannels, mass transfer in the microchannel is promoted, the reaction efficiency is improved, and the reaction temperature is easily controlled by increasing the specific surface area of the reactor, It is said that the reaction conditions and the selectivity of the reaction that cannot be achieved by the reactor according to the prior art can be achieved. Therefore, in the prior art, most proposals related to the shape, size, etc. of microreactors and macrochannels, and development examples of more suitable or optimal reaction conditions and catalyst use environments in these reactors are as follows: I can hardly find it.

  As an example of production using a microreactor using a catalyst, for example, an epoxy compound production method characterized by epoxidation from an olefin compound and hydrogen peroxide has been proposed (Patent Document 1). Also in this document, the oxidation catalyst used is not particularly limited, and it is said that a known oxidation catalyst can be used.

  In this document, the liquid feeding method for supplying a mixture of an olefin compound and hydrogen peroxide to a microreactor is not particularly limited, and a known method can be adopted. However, for example, the particle size of the catalyst disclosed in the examples is less than 1 micron, and it is expected to cause significant pressure loss in the microreactor. From the viewpoint of stable reaction operation, it is clear that special consideration is necessary for the liquid feeding method.

  As a production example using a microreactor using a catalyst, for example, a method of performing hydrogenation under mild conditions by catalytic hydrogenation of an aldehyde compound or a nitro compound has been proposed (Patent Document 2). Examples of the hydrogenation catalyst used in the present invention include a palladium catalyst, a nickel catalyst, a platinum catalyst, and a ruthenium catalyst.

  In this document, the average particle diameter of the hydrogenation catalyst is preferably about 0.1 to 100 μm, particularly about 1 to 50 μm, and (the average particle diameter of the catalyst) / (the diameter of the flow path) is Although it is considered to be preferably about 0.1 or less, particularly 0.07 or less, there is no disclosure regarding the amount of hydrogen flow, and the effectiveness of hydrogen utilization is a problem from the viewpoint of reaction efficiency.

  A hydrocarbon-containing fluid containing an alkane or alarcan and an oxygen source are passed through a microchannel in which a catalyst is present, and the hydrocarbon-containing fluid and the oxygen source are reacted in the microchannel at a temperature range of 300 to 1000 ° C. Therefore, a technique for generating water and at least one alkene and / or aralkene has been proposed (Patent Document 3).

  Also in this document, the catalytically active substance to be used is not particularly limited, and can include any conventional effective oxidative dehydrogenation catalyst. In particular, there is no disclosure regarding the environment in which the catalyst is used to increase the reaction efficiency. Absent. In addition, the present technology uses a gas phase reaction as a target reaction, and it is not clear whether it can be applied as it is to a gas-liquid mixed phase reaction.

  Next, for the reaction of hydrogen and oxygen, the microreactor is expected to be applied to the production process of hydrogen peroxide. Conventionally, hydrogen peroxide is produced by a production process called the anthraquinone method. Yes. However, it has been pointed out that in this manufacturing process, anthraquinone and organic solvent are sequentially decomposed during the process operation, and this is mixed with hydrogen peroxide as a product to produce impurities. Thus, alternatives to this process for direct reaction processes with hydrogen and oxygen that do not produce such impurities have been studied for many years.

  As an example of applying a microreactor to the anthraquinone method, which is a method of producing hydrogen peroxide that is currently used commercially, for example, by adopting a hydrogenation process, the hydrogenation reactor of the conventional anthraquinone method is used. (Patent Document 4), it is said that the catalyst used in the hydrogenation microreactor may have any size and geometry that fits within the microchannel. .

  However, even in this document, there is no disclosure regarding the environment in which the catalyst is used to enhance the reaction efficiency, and this technology is a fundamental problem of the anthraquinone method, which is the sequential decomposition of anthraquinone and organic solvents. However, it does not solve the contamination of the product hydrogen peroxide.

  In the production of hydrogen peroxide by the direct reaction process using hydrogen and oxygen, so far, in addition to hydrogen and oxygen, an aqueous solution containing a trace amount of stabilizer for stably recovering hydrogen peroxide, palladium and gold A reaction system comprising a catalyst mainly composed of a noble metal such as has been studied. In this direct reaction process, specifically, hydrogen and oxygen dissolved in water react on a catalyst to generate hydrogen peroxide (Non-patent Document 2).

  In order to realize the direct reaction process industrially, there are some problems from the viewpoint of safety and productivity. First, since hydrogen and oxygen form an explosive gas mixture in a very wide range, it was necessary for the conventional technology to operate under conditions where the hydrogen partial pressure was reduced to 4% or less. Further, since hydrogen peroxide is generated by the reaction of hydrogen and oxygen dissolved in water, it is necessary to improve the dissolution efficiency of each component.

  In order to solve such problems of the direct reaction process, it is considered that a continuous process technology using a microchannel is effective. For example, the present inventors constructed a microreactor by processing a microchannel on silicon, and constructed a microreactor in which a supported palladium catalyst was filled in the microchannel of the microreactor.

  This microreactor is used to produce hydrogen peroxide from a mixed gas of hydrogen and oxygen, in a safe and steady manner, in spite of explosive conditions of hydrogen content of 20% to 50%. It was effective in producing hydrogen. In addition, when the mass transfer from the gas phase to the liquid phase was quantitatively evaluated, it was found that the mass transfer was 10 to 100 times more efficient than the conventional reactor.

  The reason why the gas mixture of hydrogen and oxygen with explosive composition can be handled safely by the micro reactor is that the propagation of explosion was prevented by using the micro channel, and the high efficiency of mass transfer was achieved by the micro channel. This is thought to be because the gas-liquid contact interface was increased by the catalyst having a small particle size filled therein.

  On the other hand, the concentration of the obtained hydrogen peroxide remained as low as 0.2 weight percent, which was due to the problem of gas-liquid introduction into the microreactor from the gas flow visualization experiment. It turned out that (nonpatent literature 3).

  On the other hand, Vanden Bussche et al. Discloses a method for producing hydrogen peroxide after producing hydrogen and oxygen by electrolysis with respect to a method for producing hydrogen peroxide based on microchannels (Patent Document 5). -8). However, in these documents, the details of the reactor are unknown, and the hydrogen peroxide concentration is also unknown.

  Moreover, Tonkovich et al. Disclose the structure of a reactor in detail for a method for producing hydrogen peroxide based on microchannels (Patent Document 9). However, this document does not disclose detailed reaction conditions, and the performance of the reactor is completely unknown.

  Lawal et al. Have proposed a reactor in which a supported palladium catalyst is packed in a SUS tube having an inner diameter of 775 μm, and synthesizes 1.1 wt% hydrogen peroxide at the maximum (Patent Document 10). However, in this reactor, a large excess of hydrogen and oxygen is circulated in order to form a stable gas-liquid multiphase flow, and there is a problem in recycling unreacted gas.

  By the way, in the development of continuous reactors using microchannels, in order to secure the required production volume while ensuring a high degree of controllability of the reaction, for example, microchannels are paralleled in several to ten sequences. It is essential to do. In this case, in order to ensure productivity as expected, it is necessary to uniformly prepare reaction conditions for each microchannel.

  For example, in the method for producing hydrogen peroxide developed by the present inventors (Non-Patent Document 3), although microchannels are arranged in parallel in 10 rows, the gas-liquid to each microchannel is analyzed by flow visualization analysis. It has been found that the multiphase flow varies. This is considered to be the reason why the productivity in the method for producing hydrogen peroxide disclosed in this document is impaired.

  On the other hand, Kitamori et al. Have developed a parallel method by bonding glass reactors (Patent Document 11). However, this method is limited to the liquid phase reaction, and when the degree of parallelization increases, the flow rate of the reaction solution for each microchannel is likely to be different due to drift, which is the production of the reactor. The problem is that it can lead to a decline in sex.

  Tonkovich et al. Have developed a reactor in which microchannels are arranged in parallel, and have shown that fluid can be evenly distributed to each microchannel (Patent Document 12). However, this reactor is disclosed only when a single kind of fluid is circulated, and it is not clear whether it can be applied to a gas-liquid mixed phase reaction such as the production of hydrogen peroxide.

  Wada et al. Have also developed a reactor in which 16 microchannels for performing an ozone oxidation reaction are arranged in parallel. In this reactor, post-type structures are integrated in each microchannel by microfabrication technology. It is shown that a gas-liquid multiphase flow with improved mass transfer is formed (Non-Patent Document 4). However, this reactor has a problem from the viewpoint of accumulation of the catalyst in the microchannel in consideration of application to a solid catalyst reaction, and an equal gas liquid between the 16 channels under the condition where the catalyst is accumulated. It is not clear whether a multiphase flow is formed.

  As another prior art, for example, with respect to a microfluidic system, a reaction microchannel, a plurality of different fluid pressurized liquid containers that pressurize the fluid by reducing fluid foaming, and a microchannel from the container. There has been proposed a microreactor (Patent Document 13) comprising a plurality of displacement pumps arranged downstream of the vessel for sending fluid to the vessel. As shown in FIG. 1, each container is connected to a reaction channel on a chip, which is a microreactor, by a gasket seal via each pump. However, nothing is shown about the specific structure of the gasket seal.

  Furthermore, as another prior art, the present inventors have proposed a fixed bed gas-liquid mixed phase reactor and a gas-liquid mixed phase reaction method using the same (Patent Document 14).

  As a prior art regarding joining means in a microreactor, for example, an interconnect system (Patent Document 15) including a contact pad, a compression screw, and an adapter groove is proposed. Yes. However, this technique shows an example of mechanical fixing by a gasket, and there is a problem that pressure resistance is limited (no 20 atmospheres).

  As another prior art, for example, an apparatus for connecting a fluid conduit to a microfluidic chip, a first structural part such as a sealing aid capable of mechanically connecting the fluid conduit, and a microfluidic chip Proposed is an apparatus (Patent Document 16) comprising a second structure part that can be moved, and having a structure that moves the first structure part and the second structure part back and forth in the vertical direction. Has been. However, this type of apparatus has a problem that the chip is damaged due to excessive screwing by a sealing aid.

  As another prior art, for example, a PEEK tube is connected to the surface of a silicon microreactor at the interface of a supply / discharge line of a direct synthesis reactor of hydrogen peroxide from hydrogen and oxygen, and this is bonded by an epoxy resin. Thus, a technique for adding adhesiveness (see Non-Patent Document 3) and FIG. 2) has been proposed. In this technique, the pressure resistance is achieved up to 20 atm. However, since this has only been several hours, it is a problem to maintain the pressure resistance.

  As another prior art, for example, in connection of chip-to-tube and chip-to-chip using solder of a microfluidic device, a technique of connecting a ferrule and a tube to a chip by a bond pad (Non-patent Document 5) , See FIGS. 1 and 3). However, this technique has a problem that the strain is concentrated on the microreactor and the microreactor is damaged.

  As another prior art, for example, in a glass microreactor with a three-phase reaction of gas (hydrogen and oxygen), fluid (reaction solution) and solid (catalyst) for the direct synthesis of hydrogen peroxide, the ferrule is PEEK. Adhesion structure (see Non-Patent Document 6, FIGS. 1 and 3) that is mechanically attached to the tip of the tube and bonded to the opening of the channel formed in the glass plate with a silicon adhesive and mechanical fixing has been proposed. ing. This technology has been demonstrated to show long-term stability at 20 atmospheres, but may cause clogging of the hole by the adhesive, and the piping is perpendicular to the reactor and is too bulky. There is a problem.

  As another prior art, for example, a microreactor having a microchannel equipped with a chip 1, a channel 2, gaskets 10 to 12 for connecting pipes, reagent containers 3 to 6, and pumps 7 to 9 and 13 for supplying the reagent A microfluidic system (see Patent Document 17, FIG. 1) has been proposed. This technique shows a structure in which pipes are joined in parallel to the reactor, and is effective when the chip is small, but there is a problem that the pressure resistance decreases when the chip is large, and the chip becomes large. However, it has been a challenge to develop a technique that does not reduce pressure resistance.

  Therefore, in this technical field, it has been strongly demanded to develop a joining structure with a simple structure, high reliability, and compact as a joining technique for piping in a microreactor.

  As described above, various examples of continuous reaction processes using microchannels composed of minute capillaries and the development of microreactors used in the processes have been reported. In order to mass-produce products on an industrial scale, it is necessary to develop a stacking and modularization technology for microreactors that can connect multiple reactors to increase mass transfer, that is, scale up mass transfer. And important. However, in the case of microreactors, there are still limited development examples of such mass transfer enhancement, that is, mass transfer scale-up technology.

  That is, with the conventional microreactor technology composed of microchannels, for example, it is difficult to cope with industrial production of gas-liquid mixed phase reactions. In this technical field, continuous reaction using microchannels is not possible. Therefore, there has been a strong demand to develop a new technology capable of continuous production and capable of increasing mass transfer / scaling up mass transfer and capable of handling industrial production.

JP 2007-230908 A JP 2006-248972 A PCT / US2003 / 016210 (WO / 2003/106386) PCT / US2006 / 033851 (WO / 2007/027767) US Pat. No. 6,713,036 US Pat. No. 7,115,192 US Pat. No. 7,192,562 US Pat. No. 7,195,747 US Pat. No. 7,029,647 US Patent Publication No. 2006 / 0233695A1 JP 2002-292275 A US Patent Publication No. 2007 / 0246106A1 US Pat. No. 7,858,048 WO2010 / 044271A1 WO2007 / 131925A1 WO2009 / 002152A1 EP1510255B1

Volker Hessel, Stephen Hardt, Holger Loewe, “Chemical Micro Process Engineering-Fundamentals, Modeling and Reactions”, 2004, Publisher; Wiley-VCH Verg. KGaA, Weinheim (ISBN: 3-527-30741-9) Jose M. Campos-Martin et al., “Hydrogen Peroxide Synthesis: An Outlook Beyond the Anthraquinone Process”, Angelwande Chemie International Edition, 45, 6966-69. Tomoya Inoue et al., “Microfabricated Multiphase Reactors for the Direct Synthesis of Hydrogen Peripheral 3 Hydrogen and Oxygen”, Industrih. Yashiro Wada et al., “Flow Distribution and Ozonolisis in Gas-Liquid Multichannel Microreactors”, Industrial and Engineering Chemistry Research, Vol. 36, 80, 42 Edward R.D. Murphy et al., “Solder-based chip-to-tube and chip-to-chip packaging for microfluidic devices,” Lab on a Chip, Vol. 7, 1309-1314 (2007) Tomoya Inoue et al., “Reactor design optimization for direct synthesis of hydrogen peroxide”, Chemical Engineering Journal, 160, 909-914 (2010).

  Under such circumstances, the present inventors, in view of the above-mentioned prior art, can perform a continuous reaction in a microreactor using a microchannel, and can increase mass transfer / scale up mass transfer. As a result of intensive research aimed at developing new technologies that can respond to industrial production, fluid leakage from joints caused by inadequate positioning when joining external piping We have succeeded in developing a technology for joining micro reactor external pipes that can be easily stacked or integrated in multiple stages into a bundle or module structure without the risk of blockage of pipes and pipes. The invention has been completed.

  Compared to conventional reactors, the present invention is free from the risk of fluid leakage from the joints and blockage of the pipes due to inadequate positioning during joining of the external pipes, and the multi-reactor can be easily multistaged. It is an object of the present invention to provide a technique for joining external piping of a microreactor that can be stacked or integrated into a bundle or module structure.

  In the present invention, the external piping connected to the microreactor is connected in a horizontal direction with respect to the microreactor in which the microchannels are arranged in a horizontal plane, and the microreactors are simply and easily stacked in multiple stages. Alternatively, it is an object of the present invention to provide a method for joining external pipes that can be integrated into a bundle or module structure, a joint structure for the pipes, and a microreactor having the joint structure.

  The present invention has a structure in which an external pipe is partially inserted into a microreactor, the pipe is connected to the microreactor in a horizontal or vertical direction, and the joint structure is bonded and fixed with an adhesive. It is an object of the present invention to provide a joint structure by mechanical fixing by a typical fixing method.

The present invention eliminates the blockage of piping accompanying joining, and the piping is connected horizontally to the microreactor, so that the volume excluded around the reactor is reduced and the parallel piping of the reactor is remarkably facilitated. It aims at providing the novel junction structure in a reactor.
Another object of the present invention is to provide a microreactor bundle structure in which microreactors having the above-described bonding structure are stacked in multiple layers.
It is another object of the present invention to provide a microreactor module structure in which the bundle of microreactors described above is modularized.

The present invention for solving the above-described problems comprises the following technical means.
(1) A method of joining a fluid introduction port or a discharge port of a microreactor having a microchannel and an external pipe for supplying or discharging a reaction raw material or a reaction product fluid to the reactor,
The joint of the fluid inlet or outlet of the reactor and the external pipe is a joint structure in which the external pipe is joined by horizontal connection or vertical connection to the microchannel group arranged in a horizontal plane, and A pipe joining method characterized by having a structure in which an end of an external pipe is fitted into an end of a fluid inlet or outlet of a microreactor.
(2) The method for joining pipes according to (1), wherein the end of the external pipe is reinforced by a screw jig and / or a ferrule of a fitting and mechanically fixed.
(3) The method for joining pipes according to (1), wherein the contact surface between the external pipe and the reactor and / or the contact surface between the ferrule and the reactor is bonded with an adhesive and is fixed with the adhesive.
(4) A junction structure of a microreactor having a microchannel and an external pipe for supplying or discharging a reaction raw material or a reaction product fluid to the reactor, wherein the fluid inlet or outlet of the reactor The joint between the outlet and the external pipe has a joint structure in which the external pipe is joined to the microchannel group arranged in a horizontal plane by horizontal connection or vertical connection, and the end of the external pipe is A pipe joining structure characterized by having a structure fitted into an end of a fluid inlet or outlet of a microreactor.
(5) The pipe joining structure according to (4), wherein an end of the external pipe is reinforced by a screw jig and / or a ferrule of a fitting and is mechanically fixed.
(6) The joint structure of the pipe according to (5), wherein the contact surface between the external pipe and the reactor and / or the contact surface between the ferrule and the reactor is bonded by an adhesive and fixed by the adhesive .
(7) The pipe connection structure according to any one of (4) to (6) is provided, and a microreactor and a reaction raw material or a reaction product fluid are supplied to or discharged from the reactor. A microreactor characterized in that the external piping to be piped is joined by horizontal connection or vertical connection.
(8) The microreactor is a fixed bed reactor that performs a gas-liquid mixed phase reaction, and has a piping structure composed of microchannels, and the cross-sectional area of the fixed bed is 0.0001 cm ^{2 to} 0.008 cm ^2. The fixed bed, the vapor phase introduction section, and the liquid phase introduction section, and the fixed bed is filled with a catalyst packing that promotes the formation of a gas-liquid mixed phase. Microreactor.
(9) In the pipe joint structure according to any one of (4) to (6), the external pipe is joined by horizontal connection, and the micro reactor unit connected to the external pipe is multi-staged. A bundle structure of a microreactor characterized in that a bundle is formed by stacking.
(10) In the pipe joint structure according to any one of (4) to (6), the external pipe is joined by horizontal connection, and the microreactor unit connected to the external pipe has multiple stages. A module structure of a microreactor characterized in that it is integrated to constitute a module.

Next, the present invention will be described in more detail.
The present invention provides a pipe joining method, a pipe joining structure, a microreactor having a joint joined by the method, and a bundle or module structure in which the microreactors are stacked or integrated. . According to the pipe joining method of the present invention, in a microreactor having a plurality of microchannels arranged in a plane, an external pipe for introducing or discharging a fluid to or from the microchannel of the reactor is formed in a plane. A pipe joint structure that is connected in a horizontal direction or a vertical direction to a row of a plurality of arranged microchannel groups, and a joint structure in which the tip of the external pipe is partially inserted into a fluid inlet of the microchannel; It is characterized by doing.

  Regarding the pipe connection method of the present invention and the microreactor having the connection part joined by the method, a 16-ch reactor having 16 parallel microchannels for catalyst filling will be specifically described below as an example. explain. 2. Description of the Related Art Conventionally, in a microreactor having a microchannel, an external pipe for introducing a fluid and a pipe joint structure of a joint part between the microchannel are provided as shown in FIG. A pipe joint structure for connecting an external pipe (PEEK tube) from the upper direction, that is, the vertical direction, has been adopted for the reactor).

  As shown in FIG. 13, the prior art of this pipe joint structure is a connection part between the external pipe and the microchannel of the reactor, and the end part of the external pipe is tightened with a screw jig. In general, it is reinforced with a ferrule of the fitting, and a bonding structure in which the contact surface between the ferrule of the fitting and the reactor is bonded and fixed using an adhesive and a mechanical fixing is generally used. there were.

  As described above, in the prior art, the external pipe is a pipe joint by a vertical connection connected from the upper direction to the reactor installed in a planar shape, and therefore the reactors are stacked in multiple stages. Was not expected.

  That is, in such a joint structure of pipes, 1) mechanical strength against external effects such as impact is relatively weak, and therefore, due to imperfections such as alignment during pipe joint, 2) It is difficult to stack multiple reactors in multiple stages, and it is not possible to construct a reactor that realizes mass transfer scale-up. There was a problem that.

  The present invention provides a means for solving the problems of the prior art described above, in a reactor having a plurality of microchannels arranged in a plane, for introducing or discharging a fluid to or from the microchannels of the reactor. Employs a pipe joint structure in which external pipes are connected in a horizontal direction or a vertical direction to a plurality of microchannel groups arranged in a plane, and the tip of the external pipe is connected to a microchannel fluid inlet. It is characterized by having a joint structure partially inserted into the.

  In the present invention, the joining structure is a case where a microchannel of a microreactor having a microchannel and an external pipe for supplying or discharging a reaction raw material or a reaction product fluid to the microchannel of the reactor are joined. It can be adopted as a new pipe joint structure.

  In the present invention, it is important that 1) the end of the external pipe has a joint structure partially inserted into the microreactor, and more preferably 2) the external pipe is connected to the microchannel of the microreactor. 3) It is important that the bonding by the adhesive and the immobilization by the mechanical fixing method are simultaneously used at the time of joining the external pipe and the microreactor. .

  That is, the present invention is characterized by having a joining structure in which the end of the external pipe is partially inserted into the end of the pipe of the microreactor, and at that time, the end of the external pipe is Reinforced by a screw jig and / or a fitting ferrule and mechanically fixed, and contact between the external piping and the reactor and / or the end of the external piping and the reactor piping Part or all of the surface is bonded to an adhesive and is fixed by the adhesive.

  Thus, in the present invention, for example, the connection between the microchannel of the reactor and the external pipe that supplies or discharges the fluid to the microchannel of the reactor is, for example, a pipe connection structure by horizontal connection. 1) Positioning at the time of pipe connection is simple and easy. 2) There is no risk of fluid leakage from the joint or piping blockage caused by inadequate positioning at the time of pipe connection. 3) Since external piping does not become an obstacle, it is easy to stack or stack a plurality of reactors in multiple stages. 4) It is simple and easy to bundle or modularize microreactors. It is possible to construct and provide bundled or modular microreactor bundles or module structures that realize mass transfer scale-up, Superiority say can be obtained.

  In the present invention, a material such as a metal plate, a silicon plate, or a glass plate is used as a material for the microreactor. Then, using the MEMS (Micro Electro Mechanical System) technology, the grooves of the fixed bed, the gas phase introduction unit, the liquid phase introduction unit, the discharge unit, and the like are applied to the surface of the plate of those materials. A microreactor having a microchannel can be manufactured by joining the grooved plates to form microchannels such as a fixed bed, a gas phase inlet, a liquid phase inlet, and a discharger. .

  In this case, as a groove processing method using the above-described MEMS technology, for example, plasma etching, chemical etching, and drilling can be exemplified. Moreover, as a technique for joining the grooved plates, for example, heat fusion and anodic joining (in the case of joining silicon and soda glass) can be exemplified.

Next, an application example in which the microreactor of the present invention is applied to a specific chemical reaction will be described. In the present invention, for example, a gas-liquid mixed phase reaction method for performing a gas-liquid mixed phase reaction using a fixed bed reactor is described. Illustrated. In this gas-liquid mixed phase reaction, for example, the gas phase linear velocity is 0.01 m / s to 10 m / s, and the liquid phase linear velocity is 10 ⁻⁵ m / s to 10 ⁻² m / s. The gas-liquid mixed phase reaction can be performed by setting and operating the reactor.

  Regarding the arrangement of the fixed bed, the gas phase introduction part and the liquid phase introduction part in the microreactor, the gas phase introduction part and the liquid phase introduction part are arranged in the gas phase and the liquid phase with respect to the fixed bed of the fixed bed reactor. It is preferable to be located in a portion closer to the upstream of the microchannel. Further, the gas phase introduction part and the liquid phase introduction part are not limited to one place with respect to the fixed bed, and may be provided at a plurality of places.

  The arrangement form of the fixed bed, the gas phase introduction section, the liquid phase introduction section, and the discharge section and the specific configuration of the arrangement location can be arbitrarily designed according to the type of reaction, the purpose of use, and the like. In addition, regarding the shape of the groove and the specific structure of the structure corresponding to the fixed bed, the gas phase introduction part, the liquid phase introduction part, and the discharge part, in the range of the shape and structure of the channel adopted as the microchannel, Can be designed arbitrarily.

  The fixed bed of the microreactor can be filled with a catalyst for the reaction according to the target reaction. For example, in a microreactor intended to produce hydrogen peroxide using hydrogen and oxygen, a catalyst having noble metal fine particles supported on its fixed bed, preferably, for example, palladium, gold, platinum A catalyst containing at least one of the above can be charged.

  The microreactor of the present invention can be suitably used in the case of a mixed phase reaction of a gas phase and a liquid phase, and in particular, as a reaction when a catalyst is packed in a fixed bed, a hydrogenation reaction or an oxygen oxidation reaction is performed. In some cases, it can be suitably used. Although the liquid phase component depends on the reaction, it may contain a reaction substrate. When the reaction substrate is a solid, the reaction substrate may be dissolved in a solvent and circulated.

  When the microreactor of the present invention is used for the production of hydrogen peroxide, the gas phase component contains hydrogen and oxygen, but may contain other gas phase components such as nitrogen, and The main component of the liquid phase component is preferably water and / or methanol. Water and alcohol, preferably water and methanol, may be mixed in any proportion, and may contain stabilizers and other additives to keep hydrogen peroxide stable in the water. It is also possible to make it appropriate.

  In the microreactor of the present invention, for example, a gas phase flow and a liquid phase flow are supplied from a single gas phase introduction unit and a liquid phase introduction unit to a fixed bed having microchannels. In this case, depending on the type of reaction and the purpose of use, a plurality of gas phase inlets and liquid phase inlets are provided for a fixed bed having microchannels, and a plurality of gas phase inlets and liquid phase inlets are provided. Thus, it is also possible to appropriately configure so that the gas phase flow and the liquid phase flow are respectively introduced into the fixed bed.

  In the mixed phase reaction of the gas phase and the liquid phase, the packing such as a catalyst packed in the fixed bed is specifically designed by arbitrarily designing the particle size, form, and packing method of the packing, It is important to promote the formation of the gas-liquid mixed phase flow. The specific configuration of the packing by the packing can be arbitrarily designed according to the type of reaction, the type of gas phase and liquid phase to be used, and the purpose of use of the reactor. As a specific type of the packing, an appropriate catalyst corresponding to the type of reaction can be used as long as it can be packed in a fixed bed.

  In the present invention, the gas-liquid mixed phase reaction condition is not a state where the gas phase flow and the liquid phase flow form a mixed phase, or a state where the mixed phase is not sufficiently mixed without being sufficiently mixed, and is supplied to the fixed bed. This means that the gas phase flow and the liquid phase flow are well mixed with a packing such as a catalyst, so that a mixed phase is formed and the gas-liquid mixed phase reaction is suitably performed. Yes.

  In the microreactor of the present invention, the gas phase to be reacted is introduced from the gas inlet of the gas phase introduction part into the microchannel of the fixed bed, and the reaction is conducted from the reaction solution inlet of the liquid phase introduction part. The provided liquid phase is introduced into a fixed bed microchannel. Further, the gas phase and the liquid phase are divided into the gas phase distribution unit, the gas phase introduction unit for the fixed bed, the liquid phase distribution unit, and the liquid phase introduction unit for the fixed bed by the branch structure of the microchannel. Then, the gas phase and the liquid phase are brought into contact with each other in a fixed bed microchannel having the above-mentioned packing.

  Next, after forming a gas-liquid mixed phase and performing a gas-liquid mixed phase reaction, the reaction product is discharged from a discharge port of a discharge unit provided on the fixed bed and collected. The microreactor may be manufactured by joining internal pipes, or by processing a material that is stable to various reaction conditions such as a metal plate, a silicon plate, and a glass plate, Alternatively, the reactor may be manufactured as an integrally processed reactor.

In the present invention, although the operating conditions used in the reactor of the present invention vary greatly depending on the intended reaction, this microreactor is basically a pressure loss when a liquid phase is circulated in a gas-liquid mixed phase reaction. In order to keep the liquid phase circulating at a linear velocity of 10 ⁻² m / s or less, while keeping the fixed bed wet with the liquid phase, a line of 10 ⁻⁵ m / s or more is considered. It is preferable that the liquid phase flow depending on the speed.

  Similarly, in a gas-liquid mixed phase reaction, gas phase circulation at a linear velocity exceeding 10 m / s is not preferable and stable in consideration of drying of the fixed bed and pressure loss applied to the gas phase introduction pipe during gas phase circulation. From the viewpoint of forming a gas-liquid mixed phase flow, it is preferable to flow the gas phase through the fixed bed at a linear velocity of 0.01 m / s or more.

  In the present invention, in a reactor having a plurality of microchannels arranged in a horizontal plane, external piping for introducing or discharging a fluid to or from the microchannel of the reactor is provided in the plurality of horizontal channels arranged in the horizontal plane. The pipe structure is connected to the rows of the microchannel groups by horizontal connection or vertical connection. In this case, the joint structure is such that the tip of the external pipe is partially inserted into the fluid inlet of the microchannel. This is very important. By partially fitting the piping into the fluid introduction port, the external piping and the microreactor are mechanically aligned, thereby obtaining an advantage that the piping is not blocked due to joining.

  Although the above-mentioned joining structure eliminates blockage of the piping, this is important as it leads to an improvement in the operability of the microreactor. Further, the external piping is connected to the rows of microchannels arranged in a horizontal plane by horizontal connection, so that the volume of non-free space around the microreactor can be reduced. Thus, by stacking the microreactor units in multiple stages, it becomes possible to parallelize the microreactor units while minimizing the volume of the non-free space of each microreactor.

  The joint structure of the external pipe includes a bundle structure of a microreactor in which a plurality of the microreactors are stacked and stacked, and an element for constructing a module structure of the microreactor by integrating the bundles into a module It is essential as a technology.

  As a joining structure in which the tip of the external pipe is joined by being partially inserted into the fluid inlet or outlet of the microchannel of the microreactor, for example, with respect to the diameter of the microchannel, the fluid in the microchannel An example is a structure in which the diameter of the pipe of the introduction port or the discharge port is increased so as to match the diameter of the external pipe, and the distal end portion of the external pipe is inserted into the portion, and is fitted and joined. However, the present invention is not limited to this, and the pipe diameter of the inlet or outlet of the microchannel fluid and the pipe diameter of the tip of the external pipe have a structure in which the external pipe is partially inserted into the microreactor. It can be arbitrarily designed as long as it has.

  In the method of connecting the external pipe to the micro reactor by vertical connection as in the prior art, the tip of the external pipe is joined by being partially inserted into the micro reactor. However, it is difficult to implement because the microchannel is unavoidably blocked by fitting or fitting into the microchannel excessively or due to defects. However, in the pipe joining method according to the horizontal connection of the present invention, even if the tip of the external pipe is excessively fitted into the micro flow path, the direction of the external pipe and the direction of the micro flow path are the same in the horizontal direction. Since the microchannel is not blocked, it is possible to implement a joint structure in which the tip of the external pipe is partially fitted into the microreactor.

  In the present invention, when a bundle is formed by stacking microreactor units having a plurality of microchannels in a multi-stage, since a difference in height is generated for each reactor as a whole when arranged in the vertical direction, basically, It is preferable to arrange them horizontally so that there is no difference in height between reactors. In addition, the arrangement structure of the microreactor units is a manifold in which a fluid introduction or discharge port is installed in each microreactor unit and a fluid supply or discharge means in each unit can be shared. It is important to install (manifold), to make the supply or discharge conditions of the fluid in each unit common, and to match the reaction conditions in each unit.

  In the present invention, the microchannel arrangement method in the microreactor unit, that is, the number of channels constituting the microchannel row, the number of channel groups constituting the microchannel row group, and the piping constituting the channels The pipe diameter, the pipe diameter of the inlet or outlet of the channel, and the shape and structure thereof can be arbitrarily designed according to the type and purpose of the reaction. In particular, the pipe diameter of the fluid inlet or outlet of each microreactor is configured to be larger than the pipe diameter of the channel body so as to match the pipe diameter of the external pipe, and the tip of the external pipe Is preferably designed to be partially inserted. In this case, the degree of insertion for inserting the distal end portion of the external pipe, that is, for example, the dimension of the distal end portion where the distal end portion of the multi-part piping is inserted so as to overlap with the micro flow path is arbitrarily determined in the implementation. In this case, it is only necessary that the external pipe and the microchannel be joined in a stable state. For example, it is arbitrarily set within a range of 2 to 5 times the inner diameter of the microchannel. By taking the dimensions, it is possible to further stabilize the bonding between the external pipe and the micro flow path.

The present invention has the following effects.
(1) A junction between a reactor having a microchannel and an external pipe for supplying or discharging a reaction raw material or a reaction product fluid to the reactor is a horizontal connection or a vertical connection, and the external pipe It is possible to provide a method for joining pipes having a joint structure in which the tip of each part is inserted into a fluid inlet of a microchannel, and a joint structure for the pipes.
(2) It is possible to provide a microreactor having a pipe joint by horizontal connection suitable for bundling or modularizing.
(3) A bundle or a module structure constructed by stacking or modularizing micro reactors by connecting the reactor and external piping by pipe joining by horizontal connection can be provided.
(4) There is no risk of fluid leakage from the joint or blockage of the pipe due to imperfections in the joint caused by positioning at the time of pipe joining as seen in the pipe joining method according to the prior art.
(5) Using the above microchannel, it is possible to perform a gas-liquid mixed phase reaction stably and constantly, increasing the efficiency of mass transfer from the gas phase to the liquid phase and increasing the scale of mass transfer. A new microreactor can be provided.
(6) The microreactors can be paralleled, stacked, or integrated to provide a new microreactor bundle or module structure with enhanced productivity.
(7) By using the reactor comprising the microchannel of the present invention, for example, a gas mixture containing explosive composition of hydrogen and oxygen can be safely scaled up while controlling the flow rate and mass transfer. It is possible to provide a microreactor that can be handled easily.

The microreactor of Example 1 produced by microfabricating glass is shown. The tip structure of piping connected to the microreactor produced in Example 1 is shown. The connection structure of the micro reactor produced in Example 1 and the piping shown in FIG. 2 is shown. The example of the jig | tool which fixes the micro reactor produced by the comparative example 1 and piping is shown. An example in which a wedge lock ferrule is fixed to a polyether ether ketone (PEEK) tube of a pipe when the pipe is connected to the micro reactor manufactured in Comparative Example 1 is shown. The example of the microreactor produced in Example 2 is shown. The connection structure of the micro reactor of Example 2 and piping is shown. The example of the microreactor produced in Example 3 is shown. A joining structure is shown in which the end of the external pipe is partially inserted into the fluid inlet or outlet of the microreactor unit and joined by horizontal connection. The example of the micro reactor produced by the comparative example 2 is shown. The example of the connection structure of the microreactor produced in Example 3 and piping is shown. The example which fixed the microreactor and piping of Example 3 using the jig is shown.

  EXAMPLES Next, although an Example and a comparative example are shown and this invention is demonstrated concretely, the following examples and comparative examples do not limit the scope of the present invention at all.

  In this example, a microreactor was fabricated using glass microfabrication. FIG. 1 shows a schematic diagram thereof. The size of the microreactor is 70 mm in length, 30 mm in width, and 2.5 mm in thickness. As openings, a reaction solution inlet, a hydrogen inlet gas 1 inlet, an oxygen inlet gas 2 inlet, a reaction fluid outlet, and a catalyst inlet The catalyst inlet (closed during the reaction) was formed. The diameter of the opening was 1.7 mm. The micro reaction vessel was filled with a titania-supported palladium catalyst having titania fine particles having an average diameter of 60 microns as a carrier.

  On the other hand, a 1/16 inch Swagelok ferrule was fixed to a polyether ether ketone (PEEK) tube having an outer diameter of 1/16 inch (FIG. 2). Using this pipe, the pipe and the microreactor were joined (FIG. 3). In joining, a part of the pipe was fitted into the reactor through the opening, and the gap between the pipe and the opening of the microreactor and the gap between the ferrule and the opening of the reactor were embedded with silylated urethane. Furthermore, the microreactor and the piping were fixed using a jig.

  The fixed microreactor was set in a reaction evaluation apparatus, and hydrogen, oxygen, and a reaction solution were circulated to carry out the reaction. At this time, the pressure at the gas 2 inlet as the oxygen inlet was 1.1 MPa, and the outlet pressure was 0.95 MPa.

Comparative Example 1
In the microreactor as schematically shown in FIG. 1, an opening having a diameter of 1 mm was manufactured. On the other hand, a 1/16 inch Swagelok ferrule was fixed to a polyether ether ketone (PEEK) tube having an outer diameter of 1/16 inch as shown in FIG. Using this pipe, the pipe and the microreactor were joined as shown in FIG. In joining, the gap between the ferrule and the opening of the microreactor was embedded with silylated urethane. Furthermore, the microreactor and the piping were fixed using a jig.

  The fixed microreactor was set in a reaction evaluation apparatus, and hydrogen, oxygen, and a reaction solution were circulated to carry out the reaction. At this time, when the pressure at the outlet became 0.95 MPa, the pressure at the gas 2 inlet as the oxygen inlet exceeded 1.5 MPa, and a tendency to further increase was seen, so the reaction could not be performed. . When the piping was removed from the microreactor, it was found that the opening was blocked with silylated urethane.

  In this example, a microreactor was fabricated using glass microfabrication. FIG. 6 shows a schematic diagram thereof. The size of the microreactor is 70 mm in length, 60 mm in width, and 4.5 mm in thickness. As openings, the reaction solution inlet, the hydrogen inlet gas 1 inlet, the oxygen inlet gas 2 inlet, the reaction fluid outlet, and the catalyst introduction A mouth catalyst inlet (closed during reaction) was formed. At this time, all the openings were side surfaces of the microreactor, and the openings were rectangular with a length of 2 mm and a width of 2 mm.

  On the other hand, a 1/16 inch Swagelok ferrule was fixed to a polyether ether ketone (PEEK) tube having an outer diameter of 1/16 inch as shown in FIG. Using this pipe, the pipe and the microreactor were joined (FIG. 7). In joining, the gap between the opening of the pipe and the microreactor was embedded with silylated urethane.

  Furthermore, the microreactor and the piping were fixed using a jig. The jig size at this time was 95 mm in length, 108 mm in width, and 6 mm in thickness. By combining the microreactor and the jig, it was possible to install 16 microreactors in a space having a length of 100 mm, a width of 110 mm, and a height of 100 mm. The flow rate of the reaction solution per microreactor was 10 g / h. This corresponded to a circulation rate of 160 g / h.

  In this example, a microreactor was fabricated using glass microfabrication. FIG. 8 shows a schematic diagram thereof. The size of the microreactor is 70 mm in length, 60 mm in width, and 4.5 mm in thickness. As openings, reaction solution inlet, hydrogen inlet gas 1 inlet, oxygen inlet gas 2 inlet, reaction fluid outlet, and catalyst introduction A mouth catalyst inlet (closed during reaction) was formed. At this time, the catalyst inlet of the catalyst inlet was made on the front of the microreactor, and all other openings were made on the side of the microreactor. The catalyst inlet of the catalyst inlet is a circle with a diameter of 1 mm, and the other openings are rectangular with a length of 2 mm and a width of 2 mm.

  On the other hand, a 1/16 inch Swagelok ferrule was fixed to a polyether ether ketone (PEEK) tube having an outer diameter of 1/16 inch as shown in FIG. Using this pipe, the pipe and the microreactor were joined (FIG. 9). In FIG. 11, the example of the connection structure of a micro reactor and piping is shown. In joining, the gap between the opening of the pipe and the microreactor was embedded with silylated urethane.

  Furthermore, the microreactor and the piping were fixed using a jig. The jig size at this time was 95 mm long, 108 mm wide, and 10 mm thick. FIG. 12 shows an example in which a microreactor and piping are fixed using a jig. By combining the microreactor and the jig, it was possible to install ten microreactors in a space having a length of 100 mm, a width of 110 mm, and a height of 100 mm. The reaction solution flow rate per microreactor was set to 10 g / h. This corresponded to a flow rate of 100 g / h.

Comparative Example 2
A microreactor of the type shown schematically in FIG. 10 was fabricated using glass microfabrication. The size of the microreactor is 70 mm in length, 60 mm in width, and 4.5 mm in thickness. As openings, reaction solution inlet, hydrogen inlet gas 1 inlet, oxygen inlet gas 2 inlet, reaction fluid outlet, and catalyst introduction A mouth catalyst inlet was formed. At this time, all openings were made on the top surface of the microreactor. All openings were circular with a diameter of 1 mm.

  On the other hand, a 1/16 inch Swagelok ferrule was fixed to a polyether ether ketone (PEEK) tube having an outer diameter of 1/16 inch as shown in FIG. Using this pipe, the pipe and the microreactor were joined as shown in FIG. In joining, the gap between the opening of the pipe and the microreactor was embedded with silylated urethane.

  Furthermore, the microreactor and the piping were fixed using a jig. The jig size at this time was 95 mm in length, 108 mm in width, and 10 mm in thickness. However, since the piping was fixed as shown in FIG. 5, it was necessary to allow a further 15 mm in the thickness direction. By combining the microreactor and jig, it was possible to install four reactors in a space of 100 mm length, 110 mm width, and 100 mm height. The reaction solution flow rate per microreactor was set to 10 g / h. This corresponded to a flow rate of 40 g / h.

  As described in detail above, the present invention relates to a method for joining pipes and a microreactor having a joint joined by the method, and a microreactor having a microchannel and the microreactor. It is possible to provide a method of joining a pipe with a horizontal connection or a vertical connection as a joint with an external pipe that supplies or discharges a reaction raw material or reaction product fluid, and a joint structure of the pipe. It is possible to provide a microreactor having pipe joints with directional connections. Further, the present invention can provide a bundle or a module structure constructed by connecting a microreactor and an external pipe by pipe connection by horizontal connection and stacking or modularizing the microreactor. There is no fear of leakage of fluid from the joint or blockage of the pipe due to imperfection of the joint caused by positioning at the time of pipe joining, as seen in the pipe joining method by technology. In the present invention, it is possible to perform a gas-liquid mixed phase reaction stably and constantly using the above microreactor, increase the efficiency of mass transfer from the gas phase to the liquid phase, and scale of mass transfer A new microreactor that can be improved can be provided. The microreactor can be paralleled, stacked, or integrated to provide a new microreactor bundle or module structure with enhanced productivity. By using the microreactor of the present invention, for example, a micro gas that can safely handle a gas mixture containing hydrogen and oxygen having an explosive composition by controlling the flow rate and scaling up mass transfer. A reactor can be provided.

Claims (10)

A method of joining a fluid inlet or outlet of a microreactor having a microchannel and an external pipe for supplying or discharging a reaction raw material or reaction product fluid to the reactor,
The joint of the fluid inlet or outlet of the reactor and the external pipe is a joint structure in which the external pipe is joined by horizontal connection or vertical connection to the microchannel group arranged in a horizontal plane, and A pipe joining method characterized by having a structure in which an end of an external pipe is fitted into an end of a fluid inlet or outlet of a microreactor.   The method for joining pipes according to claim 1, wherein an end of the external pipe is reinforced by a screw jig and / or a ferrule of a fitting and mechanically fixed.   The joining method of piping of Claim 1 which adheres the contact surface of external piping and a reactor, and / or the contact surface of a ferrule and a reactor with an adhesive agent, and fixes with this adhesive agent.   A junction structure of a microreactor having a microchannel and an external pipe for supplying or discharging a reaction raw material or a reaction product fluid to the reactor, wherein the reactor fluid inlet or outlet is connected to the outside The joint with the pipe has a joint structure in which the external pipe is joined to the microchannel group arranged in a horizontal plane by horizontal connection or vertical connection, and the end of the external pipe has a micro reaction. A pipe joining structure characterized by having a structure fitted into an end portion of a fluid inlet or outlet of a vessel.   The pipe joining structure according to claim 4, wherein an end of the external pipe is reinforced by a screw jig and / or a ferrule of a fitting and is mechanically fixed.   The joint structure for piping according to claim 5, wherein a contact surface between the external pipe and the reactor and / or a contact surface between the ferrule and the reactor is bonded by an adhesive and fixed by the adhesive.   A pipe junction structure according to any one of claims 4 to 6, wherein the microreactor and an external pipe for supplying or discharging a reaction raw material or a reaction product fluid to the reactor are horizontal. A microreactor characterized in that the pipe is joined by directional connection or vertical connection. The microreactor is a fixed bed reactor that performs a gas-liquid mixed phase reaction, has a piping structure composed of microchannels, and the cross-sectional area of the fixed bed is 0.0001 cm ^{2 to} 0.008 cm ² . The microreactor according to claim 7, comprising the fixed bed, a gas phase introduction section, and a liquid phase introduction section, wherein the fixed bed is filled with a catalyst packing that promotes formation of a gas-liquid mixed phase. .   The pipe joint structure according to any one of claims 4 to 6, wherein the external pipe is joined by horizontal connection, and the microreactor units connected to the external pipe are stacked in multiple stages to form a bundle. A microreactor bundle structure characterized by   7. The piping joining structure according to claim 4, wherein the external piping is joined by horizontal connection, and the microreactor units connected to the external piping are integrated in multiple stages to form a module. A microreactor module structure characterized by