JP4877211B2 - Microreactor and manufacturing method thereof - Google Patents

Description

  The present invention relates to a microreactor, and more particularly to a microreactor for advancing a desired reaction with a supported catalyst and a method for producing the same.

Conventionally, a reactor utilizing a catalyst has been used in various fields, and an optimum design is made according to the purpose.
On the other hand, in recent years, attention has been focused on using hydrogen as a fuel because no global warming gas such as carbon dioxide is generated and the energy efficiency is high from the viewpoint of protecting the global environment. In particular, fuel cells are attracting attention because they can directly convert hydrogen into electric power and have high energy conversion efficiency in a cogeneration system that uses generated heat. Up to now, fuel cells have been adopted under special conditions such as space development and marine development, but recently they have been developed for use in automobiles and household distributed power supplies, and fuel cells for portable devices have also been developed. ing.
Miniaturization is indispensable for fuel cells for portable devices, and various attempts have been made to reduce the size of reformers that produce hydrogen gas by steam reforming hydrocarbon fuels. For example, various microreactors have been developed in which a microchannel is formed on a metal substrate, a silicon substrate, a ceramic substrate, etc., and a catalyst is supported in the microchannel.

The microreactor for producing hydrogen used in such a fuel cell has a high steam reforming temperature of the hydrocarbon-based fuel. For example, even the lowest temperature methanol has a temperature of 250 to 300 ° C. For this reason, it is necessary to arrange the reaction part that becomes high temperature in the housing to insulate it from the outside. And the microreactor which uses the vacuum heat insulation with the highest heat insulation efficiency is developed as a heat insulation means using a glass container as a housing | casing and a reaction part and a glass container (patent documents 1, 2). In such a microreactor, the lead wire for electrical connection between the reaction section arranged in the glass container and the outside, and the portion where the raw material supply pipe and the gas discharge pipe penetrate the glass container are sealed with glass. By stopping, the vacuum in the glass container is maintained.
JP 2005-259354 A JP 2007-95359 A

However, if the housing for arranging the reaction part is made of a metal such as stainless steel, considering the difference in thermal expansion between the glass member having a small thermal expansion coefficient and the housing having a large thermal expansion coefficient, In order to ensure glass sealing, the thickness of the housing needs to be 1 mm or more. In this case, when the casing is manufactured by drawing using a metal material, the entire casing has a uniform thickness. Therefore, a thickness of 1 mm or more necessary for the glass sealing is required for the entire casing. There was a problem of increasing the size and weight of the reactor.
On the other hand, it is conceivable that the sealing member is not a glass material, but a material having a thermal expansion coefficient close to that of a metal housing, for example, a brazing material such as solder. Since insulation is required, a glass member must be used, and the above problem cannot be solved.
Moreover, although it is possible to reduce the thickness of the housing by using a metal material having a thermal expansion coefficient close to that of a glass member, for example, 42 alloy (Fe / Ni alloy), this 42 alloy has insufficient corrosion resistance. Therefore, there is a problem that it cannot be put to practical use for a microreactor for hydrogen generation.
The present invention has been made in view of the above circumstances, and a highly reliable microreactor that enables highly efficient catalytic reaction while suppressing the influence of heat to the outside, and such a microreactor. An object of the present invention is to provide a method for easily producing the above.

  In order to achieve such an object, a microreactor of the present invention includes a vacuum housing, a microreactor body disposed in a vacuum sealed cavity in the vacuum housing, and at least one surface of the microreactor body. The microreactor body has a raw material inlet and a gas outlet, and the raw material inlet is connected to the outside of the vacuum casing by a raw material supply pipe penetrating the vacuum casing. The gas exhaust port is connected to the outside of the vacuum casing by a gas exhaust pipe that penetrates the vacuum casing, and the heating element is connected to an external power source via a lead pin that penetrates the vacuum casing. The vacuum casing is made of stainless steel having a thickness in the range of 0.1 to 0.5 mm, and the lead pin, the raw material supply pipe, and the gas discharge pipe penetrate therethrough. A through hole through which the lead pin passes is sealed with a glass member, and the length of the glass member along the length direction of the lead pin. The peripheral part of the through-hole of the vacuum casing is a thick part so that the thickness is in a range of 0.5 to 1.4 mm, and the raw material supply pipe and the gas discharge pipe are penetrated. The through hole was configured to be sealed by welding, brazing, or a resin member.

As another aspect of the present invention, the thick portion is configured to have a width of 1.0 to 2.0 mm around the through hole.
As another aspect of the present invention, the thick part is configured to have a thin part in the peripheral part as compared with the part where the through hole is formed.
As another aspect of the present invention, the microreactor main body includes a joined body in which a set of metal substrates is joined, and a fine groove formed on a joining surface of at least one of the set of metal substrates. A tunnel-shaped flow path, a catalyst supporting layer formed in the tunnel-shaped flow path, and a catalyst supported on the catalyst-supporting layer, wherein the raw material inlet and the gas outlet are the tunnel-shaped flow path The catalyst support layer is configured to be an inorganic oxide film.

As another aspect of the present invention, the microreactor main body includes a joined body in which three or more metal substrates are laminated and joined, a channel formed inside the joined body, and a catalyst formed in the channel. The metal substrate having a support layer and a catalyst supported on the catalyst support layer, and at least the metal substrate not located in the outermost layer has a groove formed in at least one joining surface and a through hole formed in the groove. In addition, the flow path is constituted by the groove and the through hole, the raw material inlet and the gas outlet are communicated with the flow path, and the catalyst support layer is an inorganic oxide coating.
As another aspect of the present invention, a plurality of the groove portions are formed through partition walls.
As another aspect of the present invention, a plurality of through holes are formed in the groove.

  In addition, the microreactor manufacturing method of the present invention includes a vacuum casing, a microreactor body disposed in a vacuum sealed cavity in the vacuum casing, and a heating element positioned on at least one surface of the microreactor body. And a manufacturing method of a microreactor including a casing manufacturing step of manufacturing an opening casing having one opening surface using stainless steel having a thickness of 0.1 to 0.5 mm, and the opening casing A plurality of drilling steps for forming a plurality of through holes for penetrating the raw material supply pipe, the gas discharge pipe and the lead pin on a desired wall surface of the body, and a plurality of stainless steels having a thickness in the range of 0.5 to 1.4 mm A thick portion for producing a lead pin holding thick member by drilling a lead pin through hole in a small piece of lead, and penetrating the lead pin through the through hole and sealing with a glass member A microreactor having a manufacturing process, a raw material inlet and a gas outlet, a raw material supply pipe and a gas outlet connected to the raw material inlet and the gas outlet, and a heating element located on at least one surface A placing step of placing the main body in the opening housing such that the raw material supply pipe and the gas discharge pipe are inserted into the through hole, and welding, brazing, or sealing the through hole with a resin member And joining the lead pin holding thick member to the outer wall surface of the opening housing so that the lead pin is inserted into the corresponding through hole of the opening housing, and the lead pin and the electrode of the heating element, And joining a lid made of stainless steel having a thickness in the range of 0.1 to 0.5 mm to the opening housing so as to close the opening surface, true A vacuum housing manufacturing step of manufacturing a vacuum enclosure constituting a closed cavity, and the like comprising configure.

As another aspect of the present invention, the casing manufacturing step is configured to manufacture an open casing by drawing.
As another aspect of the present invention, the thin piece is configured to have a thin portion in the peripheral portion as compared with a portion where the through hole is formed.
As another aspect of the present invention, the vacuum casing manufacturing process is performed in a vacuum chamber, thereby forming a vacuum sealed cavity in the vacuum casing.
As another aspect of the present invention, in the vacuum casing manufacturing step, after the lid member is joined to the opening casing, the inside of the vacuum casing is made into a vacuum sealed cavity by suction from a suction hole provided in the vacuum casing. Thereafter, the suction hole is sealed.

  In the microreactor of the present invention, the microreactor body is located in the vacuum sealed cavity of the vacuum casing, so that the vacuum sealed cavity can conduct heat from the microreactor body to the outside even when the microreactor body is in a high temperature state. The heat insulation effect of this vacuum-sealed cavity is much higher than when other heat insulating materials are used, and the microreactor (vacuum case) can be used without increasing the size of the vacuum case. ) The outer wall temperature can be set to room temperature to about 50 ° C., and the vacuum housing has a thick portion around the through hole for penetrating the lead pin, and is used for sealing the through hole. Since the length of the glass member to be obtained is in the range of 0.5 to 1.4 mm, the airtightness is reduced due to the difference in thermal expansion between the glass member and the stainless steel constituting the vacuum casing. On the other hand, the other part of the vacuum casing is in the range of 0.1 to 0.5 mm in thickness, so that it is possible to reduce the size and weight. The influence is suppressed and the efficiency of the catalytic reaction is high.

  In the manufacturing method of the present invention, the manufacturing of the opening housing having one opening surface and the manufacturing of the lead pin holding thick member are manufactured in different steps, and the microreactor body is placed in the opening housing, and then the opening is opened. The lead pin holding thick member is joined to the housing, so that the sealing of the lead pin penetrating part is reliably maintained, the influence of heat to the outside is suppressed while being small, and the catalytic reactor is highly efficient. Can be manufactured.

Embodiments of the present invention will be described below with reference to the drawings.
[Microreactor]
FIG. 1 is a perspective view showing an embodiment of the microreactor of the present invention, FIG. 2 is an enlarged longitudinal sectional view taken along line II of the microreactor shown in FIG. 1, and FIG. 3 is shown in FIG. FIG. 1 to 3, a microreactor 1 is disposed in a vacuum casing 2, a microreactor body 4 placed in a vacuum sealed cavity 3 in the vacuum casing 2, and the microreactor body 4. The heating element 7 is provided.

  The vacuum housing 2 is for providing the vacuum sealed cavity 3 around the microreactor body 4 and is made of stainless steel having a thickness in the range of 0.1 to 0.5 mm. If the thickness of the vacuum casing 2 is less than 0.1 mm, the mechanical strength may be insufficient, and if it exceeds 0.5 mm, the effect of reducing the weight of the microreactor 1 cannot be obtained sufficiently. The shape of the vacuum housing 2 is a rectangular parallelepiped shape in the illustrated example, but is not limited thereto. The internal volume and shape of the vacuum casing 2 can be set as appropriate in consideration of the shape and heat insulating action of the microreactor body 4. For example, the thickness of the vacuum sealed cavity 3 (microreactor body 4 and vacuum casing 2) (distance to the inner wall surface 2) can be set to be 1 mm or more, preferably 2 to 15 mm.

The microreactor body 4 has a raw material inlet 29a and a gas outlet 29b. The raw material inlet 29a is connected to the outside of the vacuum casing 2 by a raw material supply pipe 5A, and the gas outlet 29b is vacuumed by a gas outlet pipe 5B. It is connected to the outside of the housing 2. Further, the heating element 7 is disposed in the microreactor body 4 via the insulating film 6, and electrodes 8 and 8 are formed on the heating element 7, and an electrode opening 9a that exposes the electrodes 8 and 8 is formed. , 9 a is provided so as to cover the heating element 7.
The vacuum casing 2 has through holes 12 and 16. Lead pins 14 pass through the two through holes 12 and are sealed with a glass member 13. Further, the two supply holes 5A and the gas discharge pipe 5B pass through the two through holes 16, and are sealed by welding, brazing, or a resin member.

  FIG. 4 is a partially enlarged sectional view of the vicinity of the through hole 12 of the vacuum casing 2 through which the lead pin 14 passes. As shown in FIG. 4, in the present invention, the through hole 12 through which the lead pin 14 passes is sealed with the glass member 13, and the length of the glass member 13 along the length direction of the lead pin 14 is The peripheral part of the through-hole 12 of the vacuum housing 2 is the thick part 11 so as to be in the range of 0.5 to 1.4 mm. The thick portion 11 is for preventing a decrease in airtightness due to a difference in thermal expansion between the glass member 13 used for sealing the through hole 12 and the stainless steel constituting the vacuum housing 2. If the length of the glass member 13 is less than 0.5 mm, the airtightness may be lowered due to the difference in thermal expansion between the stainless steel constituting the vacuum housing 2 and the glass member 13, and 1.5 mm Exceeding this is undesirable because it causes an unnecessary weight increase.

  Such a thick portion 11 can be formed around the through-hole 12 so that the width W is in the range of 1.0 to 2.0 mm, for example. If the width W is less than 1.0 mm, the mechanical strength of the thick portion 11 may be insufficient, and if it exceeds 2.0 mm, an unnecessary weight increase is caused. In the above example, one lead pin 14 passes through one through-hole 12 and the peripheral portion of the through-hole 12 is a thick portion 11. For example, the through-hole 12 is formed into an oval shape, A plurality of lead pins 14 may pass through one through hole 12, and the peripheral portion of the through hole 12 may be an oval thick portion 11. Further, a plurality of through holes 12 may be arranged adjacent to each other, and one lead pin 14 may pass through each through hole 12, and the peripheral portion of the plurality of through holes may be the thick portion 11. In any example, the width W of the thick portion 11 around the through hole 12 is preferably in the above range.

Moreover, although the internal diameter of the through-hole 12 can be suitably set according to the thickness of the lead pin 14 to be used, it can be set so that it may become the range of 0.5-1.5 mm, for example. Moreover, when the through-hole 12 has a long and short internal diameter like the above-mentioned ellipse shape, the short internal diameter can be made into the range of 0.5-1.4 mm. The peripheral shape of the thick portion 11 is a square in the illustrated example, but is not limited to this, and can be set as appropriate, such as a circle, a polygon, a triangle, an ellipse, and a continuous circle.
In this invention, the thick part 11 may have a thin part in a peripheral part compared with the location in which the through-hole 12 is formed. FIG. 5 is a view showing such a thick portion, and this thick portion 11 'has a main body 11a in which a through hole 12 is formed and a thin flange portion 11b formed in the periphery thereof. ing. In this case, the thickness of the main body 11a is appropriately set so that the length of the glass member 13 along the length direction of the lead pin 14 is in the range of 0.5 to 1.4 mm, similarly to the thin portion 11 described above. be able to. Moreover, the thickness of the flange part 11b can be suitably set, for example in the range of 0.2-1.1 mm, and it is preferable that the width W of the main body 11a is the range of 0.5-1.4 mm. Furthermore, the peripheral shape of the main body 11a of the thick portion 11 'and the peripheral shape of the flange portion 11b are not particularly limited, and can be set as appropriate, such as a square, a circle, a polygon, a triangle, an oval, and a continuous circle. it can.

The glass member 13 used for sealing the through-hole 12 may be a conventionally known glass member for sealing. For example, a commercially available hermetic glass (for example, ASF powder glass manufactured by Asahi Glass Co., Ltd.) is used as a mold. Glass beads produced by molding can be used.
The lead pin 14 may be made of, for example, Kovar, 42 alloy (Fe / Ni alloy), stainless steel, or the like, and the diameter can be appropriately set within a range of 250 to 1000 μm.

  The material of the raw material supply pipe 5A and the gas discharge pipe 5B may be the same stainless steel as that of the housing 2, and may be the same material as a later-described joined body 22 constituting the microreactor body 4, Different materials may be used. Of course, the housing 2 and the joined body 22 may be made of the same material. Moreover, as welding for sealing the two through-holes 16 which the raw material supply pipe | tube 5A and the gas exhaust pipe 5B penetrate, laser welding and resistance welding can be used, for example. Also, as a brazing material for sealing the through hole 16 by brazing, for example, a conventionally known brazing material such as Sn—Pb solder, Sn—Zn solder, Cd—Zn solder, silver brazing, copper brazing, brass brazing, etc. Materials can be used. Furthermore, in the present invention, since the outer wall temperature of the vacuum casing 2 of the microreactor 1 can be set to room temperature to about 50 ° C., the through hole 16 can be sealed using a resin member, for example, an epoxy resin Resin members such as polyimide resin and acrylic resin can be used.

  FIG. 6 is a perspective view showing an example of the microreactor body 4 constituting the microreactor 1 of the present invention, and FIG. 7 is an enlarged longitudinal sectional view taken along the line III-III of the microreactor body 4 shown in FIG. 6 and 7, the insulating film 6, the heating element 7, the electrodes 8 and 8, and the heating element protection layer 9 are omitted. 6 and 7, the microreactor body 4 includes a metal substrate 24 having a fine groove portion 25 formed on one surface 24a and a metal substrate 26 having a fine groove portion 27 formed on one surface 26a. 25 and the joined body 22 joined so that the fine groove part 27 may oppose. Inside the joined body 22, a tunnel-like flow path 23 composed of opposing fine groove portions 25, 27 is formed, and a catalyst support layer 28 is disposed on the entire inner wall surface of the tunnel-like flow path 23. The catalyst C is supported on the catalyst support layer 28. Further, the tunnel-like flow path 23 communicates with the raw material introduction port 29 a and the gas discharge port 29 b provided on the opposite end surfaces of the joined body 22.

  FIG. 8 is a perspective view showing a state in which the metal substrate 24 and the metal substrate 26 of the microreactor body 4 shown in FIG. 6 are separated from each other. In FIG. 8, the catalyst support layer 28 is omitted. As shown in FIG. 8, the fine groove portions 25 and 27 are formed in a continuous shape while being bent by 180 degrees and meandering. The fine groove portion 25 and the fine groove portion 27 have a pattern shape that is symmetrical with respect to the joint surfaces of the metal substrates 24 and 26. Therefore, by joining the metal substrates 24 and 26, the end 25a of the fine groove 25 is located on the end 27a of the fine groove 27, and the end 25b of the fine groove 25 is located on the end 27b of the fine groove 27. Thus, the fine groove portion 25 and the fine groove portion 27 are completely opposed to each other. As shown in FIG. 6, the end portions of the tunnel-like flow path 23 composed of such fine groove portions 25 and 27 form a raw material introduction port 29a and a gas discharge port 29b. In addition, the shape of the tunnel-shaped flow path 23 of the microreactor body 4 and the positions of the raw material introduction port 29a and the gas discharge port 29b are not limited to the illustrated example. Therefore, the positions of the raw material supply pipe 5A and the gas discharge pipe 5B are not limited to those shown in FIG.

  For the metal substrates 24 and 26 constituting the microreactor body 4, it is possible to select a metal material that allows easy processing of the fine groove portions 25 and 27 that constitute the wall surface of the tunnel-shaped flow path 23 and that can be easily joined. For example, it may be a stainless steel substrate, a copper substrate, an aluminum substrate, a titanium substrate, an iron substrate, an iron alloy substrate, or the like. In the case of a stainless steel substrate, precision processing of the fine groove portions 25 and 27 is easy, and a strong joined body 22 can be obtained by diffusion bonding. Further, in the case of a copper substrate, precise processing of the fine groove portions 25 and 27 is easy, and a strong joined body 22 can be obtained by laser welding, resistance welding, and brazing. The thicknesses of the metal substrates 24 and 26 may be appropriately set in consideration of the size of the microreactor body 4, the heat capacity of the metal used, characteristics such as thermal conductivity, the sizes of the fine groove portions 25 and 27 to be formed, and the like. For example, it can be set in the range of about 50 to 5000 μm.

The fine groove portions 25 and 27 formed in the metal substrates 24 and 26 are not limited to the shape as shown in FIG. 8, and the amount of the catalyst C carried in the fine groove portions 25 and 27 increases, and The flow path where the raw material comes into contact with the catalyst C can have an arbitrary shape.
Further, the shape of the inner wall surface of the fine groove portions 25 and 27 in the cross section perpendicular to the fluid flow direction of the tunnel-shaped flow path 23 is preferably an arc shape, a semicircular shape, or a U shape. The diameter of the tunnel-like channel 23 composed of such fine groove portions 25 and 27 can be set, for example, within a range of about 100 to 2000 μm, and the channel length can be set within a range of about 30 to 300 mm. .

The catalyst support layer 28 is an inorganic oxide film, for example, an alumina (Al ₂ O ₃ ) film, a mullite (Al ₂ O ₃ .2SiO ₂ ) film, a silica (SiO ₂ ) film, a zirconia (ZrO ₂ ) film formed by thermal spraying. ) Film, titania (TiO ₂ ) film, ceria (CeO ₂ ) film, and the like. The thickness of such a catalyst-carrying layer 28 can be appropriately set within a range of about 10 to 50 μm, for example.
The catalyst C can be appropriately selected according to the purpose of use of the microreactor 1. For example, when used for hydrogen production, the catalyst C is a reforming catalyst such as Cu—Zn-based, Pd—Zn-based, Pt, A combustion catalyst such as Pd, NiO, Co ₂ O ₃ , or CuO can be used.

FIG. 9 is a plan view for explaining the heating element 7 constituting the microreactor body 4. As shown in FIGS. 3 and 9, the heating element 7 is formed on the electric insulating layer 6 in a continuous shape while being bent by 180 degrees and meandering, and electrodes 8, 8 are disposed at both ends of the heating element 7. Is arranged.
The electrical insulating layer 6 can be made of, for example, polyimide, ceramics (Al ₂ O ₃ , SiO ₂ ), or the like. Further, the electrical insulating layer 6 may be a metal oxide film formed by anodizing the joined body 22. The thickness of the electrical insulating layer 6 can be appropriately set in consideration of the characteristics of the material to be used, and can be set, for example, in the range of about 0.5 to 150 μm.

The heating element 7 is for supplying heat necessary for the catalytic reaction of the raw material, which is an endothermic reaction, and uses a material such as carbon paste, nichrome (Ni—Cr alloy), W, Mo, Au, or Ti. be able to. As shown in FIG. 9, the shape of the heating element 7 can be, for example, a shape in which a thin wire having a width of about 10 to 200 μm is drawn on the electrical insulating layer 6, but is limited to such a shape. However, it can be set as appropriate.
The current-carrying electrodes 8 and 8 formed on the heating element 7 can be formed using a conductive material such as Au, Ag, Pd, Pd-Ag, etc. Good. As shown in FIGS. 2 and 3, the electrodes 8 and 8 are connected to the lead pins 14 via the wirings 15 and 15.

  In the microreactor 1 of the present invention as described above, since the microreactor body 4 is located in the vacuum sealed cavity 3 of the vacuum casing 2, the vacuum sealed cavity 3 is maintained even when the microreactor body 4 is in a high temperature state. Effectively cuts off the heat conduction from the microreactor body 4 to the vacuum housing 2, and the heat insulating effect by the vacuum sealed cavity 3 is compared to the case where other heat insulating materials (for example, glass wool, ceramic material, etc.) are used. Therefore, the outer wall temperature of the microreactor 1 (vacuum casing 2) can be set to room temperature to about 50 ° C. without increasing the size of the vacuum casing 2. Further, in the vacuum housing 2, the peripheral portion of the through hole 12 for penetrating the lead pin 14 is the thick portion 11, and the length of the glass member 13 used for sealing the through hole 12 is 0. Since it becomes the range of 5-1.4 mm, the airtight fall by the thermal expansion difference of the glass member 13 and the stainless steel which comprises the vacuum housing | casing 2 is reliably prevented. On the other hand, since the other part of the vacuum casing 2 has a thickness in the range of 0.1 to 0.5 mm, it can be reduced in size and weight.

[Microreactor manufacturing method]
Next, the manufacturing method of the microreactor of this invention is demonstrated.
10 and 11 are process diagrams for explaining the production method of the present invention, and are drawings corresponding to FIG. 3 taking the microreactor 1 shown in FIGS. 1 to 4 as an example.
In the present invention, in the housing production process, an opening housing 2A having one opening surface 2a is produced using stainless steel having a thickness T1 in the range of 0.1 to 0.5 mm. Two through-holes 2b for lead pins, a raw material supply pipe, and a through-hole 2c for gas discharge pipe are formed in desired wall surfaces of the open housing 2A (FIG. 10A). The opening housing 2A can be produced by, for example, drawing, cutting, casting, diffusion bonding, brazing, and the like. The through holes 2b and 2c can be formed by drilling or the like. If the thickness T1 is less than 0.1 mm, the mechanical strength of the opening housing 2A may be insufficient, and if it exceeds 0.5 mm, the effect of reducing the weight of the microreactor 1 can be sufficiently obtained. Absent.

  On the other hand, in addition to the manufacturing of the above-described open housing 2A, in the thick member manufacturing step, a through hole 12 for a lead pin is formed in a small piece 18 made of stainless steel, and the lead pin 14 passes through the through hole 12. Then, the lead pin holding thick member 17 is produced by sealing with the glass member 13 (FIG. 10B). The thin piece 18 to be used has a thickness T2 in the range of 0.5 to 1.4 mm, and the outer shape thereof is not particularly limited, and is circular, rectangular, polygonal, triangular, oval, continuous circular, etc. Can be set as appropriate. If the thickness T2 of the thick piece 18 is less than 0.5 mm, the length of the glass member 13 along the length direction of the lead pin 14 is insufficient, and the thermal expansion between the stainless steel and the glass member 13 at the sealing portion. There is a risk that airtightness may be reduced due to the difference. Moreover, when T2 exceeds 1.4 mm, an unnecessary weight increase is caused in the microreactor, which is not preferable. In addition, although the internal diameter of the through-hole 12 can be suitably set according to the thickness of the lead pin 14 to be used, it can be set so that it may become the range of 0.5-1.5 mm, for example. Moreover, when the through-hole 12 has a long and short internal diameter like an ellipse, for example, a short internal diameter can be made into the range of 0.5-1.5 mm.

In the present invention, as the small-walled piece 18, a portion that is thinner than the portion where the through-hole 12 is formed, for example, a flange portion as shown in FIG. 5 may be used. The lead pin holding thick member 17 using such a thick piece 18 is preferable because the presence of the flange portion facilitates welding to the outer wall surface of the opening housing 2A described later.
In addition to the production of the above-described opening housing 2A and the production of the lead pin holding thick member 17, the material introduction port 29a and the gas discharge port 29b are provided, and the material supply pipe is connected to the material introduction port 29a and the gas discharge port 29b. A microreactor body 4 to which 5A and a gas discharge pipe 5B are connected is manufactured. The microreactor body 4 is provided with a heating element 7 on one surface of the microreactor 4 with an insulating film 6 interposed therebetween. Electrodes 8 and 8 are formed on the heating element 7 so that the electrodes 8 and 8 are exposed. A heating element protective layer 9 having various electrode openings 9 a and 9 a is provided so as to cover the heating element 7. Next, in the placing step, the microreactor body 4 is placed in the open housing 2A so that the raw material supply pipe 5A and the gas discharge pipe 5B are inserted into the through hole 2c, and the through hole 2c is welded. Sealing is performed by brazing or a resin member (FIG. 10C).

  Next, in the joining step, the lead pin holding thick member 17 is joined to the outer wall surface so that the lead pin 14 is inserted into each of the two through holes 2b of the opening housing 2A (FIG. 11A). ). This joining can be performed by, for example, diffusion joining, and the joined thick piece 18 constitutes the thick part 11. In the thick portion 11, the length of the glass member 13 along the length direction of the lead pin 14 is a length corresponding to the thickness T 2 of the thin piece 18. Thereafter, the two lead pins 14 and the electrodes 9 and 9 of the heating element 7 are electrically connected via the wirings 15 and 15.

Next, in the vacuum casing manufacturing step, the lid member 2B made of stainless steel having a thickness in the range of 0.1 to 0.5 mm is joined to the opening casing 2A so as to close the opening surface 2a, Prepares a vacuum casing 2 constituting a vacuum sealed cavity 3 to form a microreactor 1 of the present invention (FIG. 11B). In this vacuum casing manufacturing step, the opening surface 2a of the opening casing 2A is closed with the lid member 2B, and then sucked from a suction port (not shown) provided in the opening casing 2A or the lid member 2B. The inside of the body 2 can be a vacuum-sealed cavity 3, and the suction port can be sealed. Moreover, it is also possible to produce the vacuum casing 2 by closing the opening 2a of the vacuum casing 2 inside the vacuum chamber without providing the suction port.
In addition, embodiment of the above-mentioned microreactor and its manufacturing method is an illustration, and this invention is not limited to these.

Hereinafter, another embodiment of the microreactor body constituting the microreactor of the present invention will be described as an example.
FIG. 12 is a longitudinal sectional view corresponding to FIG. 7 showing another form of the microreactor body constituting the microreactor of the present invention. In FIG. 12, the microreactor body 4A includes a metal substrate 34 having a fine groove 35 formed on one surface 34a, and a metal substrate (cover member) bonded to the surface 34a of the metal substrate 34 so as to cover the fine groove 35. And a joined body 32 composed of 36. Inside the joined body 32, a tunnel-like flow path 33 composed of a fine groove portion 35 and a metal substrate 36 is formed, and a catalyst support layer 38 is disposed on the inner wall surface of the fine groove portion 35. The catalyst C is supported on the support layer 38. In addition, a heating element (not shown) is disposed on at least one surface of the joined body 32 in the same manner as the microreactor body 4 described above.
The fine groove portion 35 of the metal substrate 34 may have a continuous shape while being bent by 180 degrees and meandering like the fine groove portions 25 and 27 shown in FIG. 8, but is not limited thereto. The cross-sectional shape of the fine groove portion 35 may be an arc shape, a semicircular shape, a U shape, or the like. One end of the tunnel-like flow path 33 serves as a raw material introduction port (not shown), and the other opening end serves as a gas discharge port (not shown).

For the metal substrate 34 and the metal substrate (cover member) 36 constituting the microreactor body 4A, the same materials as those of the metal substrates 24 and 26 of the above-described embodiment can be used. In addition, the thickness of the metal substrate 34 can be appropriately set in consideration of the size of the microreactor body 4A, the heat capacity of the metal material to be used, characteristics such as thermal conductivity, the size of the fine groove 35 to be formed, and the like. However, it can set in the range of about 50-5000 micrometers, for example. In addition, the thickness of the metal substrate 36 can be appropriately set in consideration of the material to be used, and can be set, for example, in the range of about 20 to 2000 μm.
The catalyst support layer 38 constituting the microreactor body 4A can be the same as the catalyst support layer 28 of the above-described embodiment.

  FIG. 13 is a perspective view showing another form of the microreactor body constituting the microreactor of the present invention, and FIG. 14 is an enlarged longitudinal sectional view taken along line IV-IV of the microreactor body shown in FIG. FIG. 15 is an enlarged longitudinal sectional view taken along line VV of the microreactor body shown in FIG. 13 to 15, the microreactor body 4B includes a joined body 42 in which five metal substrates 44, 45, 46, 47, and 48 are laminated and joined. A heating element (not shown) is disposed on at least one surface of the joined body 42 as in the case of the microreactor body 4 described above.

  Of the five metal substrates 44, 45, 46, 47, and 48 constituting the joined body 42, the metal substrate 44 that is one of the outermost layers functions as a cover member, and three through holes 44B are formed at predetermined positions. I have. In addition, the three metal substrates 45, 46, 47 that are not located on the outermost layer and the metal substrate 48 on the outermost layer are each provided with three rows of groove portions 45A, 46A, 47A, 48A separated by a partition on one side. In preparation for (on the metal substrate 44 side), through-holes 45B, 46B, 47B, and 48B are provided in the grooves 45A, 46A, 47A, and 48A, respectively. The three rows of groove portions 45A, 46A, 47A, and 48A communicate with each other in the stacking direction through the through holes 45B, 46B, and 47B, respectively. Therefore, three zigzag flow paths 43 extending from the through hole 44B of the metal substrate 44 to the groove 45A → the through hole 45B → the groove 46A → the through hole 46B → the groove 47A → the through hole 47B → the groove 48A → the through hole 48B ( 43A, 43B, 43C).

  Further, as described above, the groove portions 45A, 46A, 47A, 48A of the four metal substrates 45, 46, 47, 48 constituting the three flow paths 43A, 43B, 43C, and the three metal substrates 45, A catalyst support layer 50 is disposed on the inner wall surfaces of the through holes 45 </ b> B, 46 </ b> B and 47 </ b> B of 46 and 47, and the catalyst C is supported on the catalyst support layer 50. The three through holes 44B of the metal substrate 44 are the raw material introduction ports 49a of the three flow paths 43A, 43B, and 43C, and the three through holes 48B of the outermost metal substrate 48 are three. It becomes the gas discharge port 49b of the flow paths 43A, 43B, and 43C.

  FIG. 16 is a perspective view showing a state in which five metal substrates 44, 45, 46, 47, and 48 constituting the microreactor body 4B shown in FIG. 13 are separated from each other. In FIG. 16, the catalyst support layer 50 is omitted. As shown in FIG. 16, three rows of groove portions 45A, 46A, 47A, and 48A are formed on the metal substrates 45, 46, 47, and 48 through partition walls, respectively, and the groove portions 45A, 46A, 47A, and Through holes 45B, 46B, 47B, and 48B are provided at one end of 48A, respectively. In the illustrated example, among the three zigzag flow paths 43, the flow path 43A and the flow path 43C have the same fluid flow direction in the grooves 45A, 46A, 47A, and 48A, and the flow path 43B The direction of flow is reversed.

The five metal substrates 44, 45, 46, 47, and 48 constituting the microreactor body 4B can use the same material as the metal substrates 24 and 26 of the above-described embodiment. Further, the thickness of the metal substrates 45, 46, 47, and 48 is such that the size of the microreactor body 4B, the heat capacity of the metal material to be used, characteristics such as thermal conductivity, and the required groove portions 45A, 46A, 47A, and 48A Although it can set suitably considering a magnitude | size etc., it can set in the range of about 50-5000 micrometers, for example. Further, the thickness of the metal substrate 44 can be appropriately set in consideration of the material to be used, and can be set, for example, in the range of about 20 to 2000 μm.
The catalyst support layer 50 constituting the microreactor body 4B can be the same as the catalyst support layer 28 of the above-described embodiment.

In the microreactor body 4B, the flow direction of the fluid in each of the flow paths 43A, 43B, and 43C is not limited, and the flow direction of the fluid is from the substrate 48 to the substrate 44, contrary to the illustrated example. There may be. In this case, the three raw material inlets 49a and the three gas outlets 49b are reversed. Further, the positions of the three raw material introduction ports 49a and the positions of the three gas discharge ports 49b are not limited to the illustrated example.
Further, the catalyst supporting layer 50 may be disposed on the surface of the metal substrate 44 (the surface exposed to the groove 45A side), and the catalyst C may be supported on the catalyst supporting layer 50. Further, a catalyst supporting layer 50 is also provided on the surface of each metal substrate 45, 46, 47 (the surface exposed to the groove portions 46A, 47A, 48A), and the catalyst C is supported on the catalyst supporting layer 50. Good. Thereby, the loading amount of the catalyst C further increases, and the reaction efficiency and the effective use of the space are improved.

  FIG. 17 is a perspective view showing another form of the microreactor body constituting the microreactor of the present invention, and FIG. 18 is an enlarged vertical sectional view taken along line VI-VI of the microreactor body shown in FIG. 17 and 18, the microreactor body 4C has a joined body 52 in which six metal substrates 54, 55, 56, 57, 58, and 59 are laminated and joined. In addition, a heating element (not shown) is disposed on at least one surface of the joined body 52 as in the case of the microreactor body 4 described above. FIG. 19 is a perspective view showing a state where the six metal substrates 54, 55, 56, 57, 58, 59 constituting the microreactor body 4C shown in FIG. 17 are separated. In FIG. 19, a catalyst support layer 61 described later is omitted.

  Of the six metal substrates 54, 55, 56, 57, 58, 59, the metal substrate 54, which is one of the outermost layers, functions as a cover member, and has three through-holes 54B in a row in the middle. I have. The four metal substrates 55, 56, 57, 58 that are not located on the outermost layer and the metal substrate 59 on the outermost layer are each provided in three rows of groove portions 55A, 56A, 57A, 58A, 59A arranged via partition walls. Is provided on one surface (the metal substrate 54 side). Further, in each of the groove portions 55A, 57A, 59A of the three metal substrates 55, 57, 59, one through hole 55B, 57B, 59B is provided substantially at the center. On the other hand, each of the groove portions 56A, 58A of the two metal substrates 56, 58 is provided with two through holes 56B, 58B, one at each end. The three rows of groove portions 55A, 56A, 57A, 58A, 59A are communicated in the stacking direction via the through holes 55B, 56B, 57B, 58B, respectively. Therefore, from each through hole 54B of the metal substrate 54, the groove 55A → one through hole 55B → the groove 56A → two through holes 56B → the groove 57A → one through hole 57B → the groove 58A → two through holes. Three flow paths 53 (53A, 53B, 53C (the flow path 53A is shown in FIG. 18)) are formed so as to repeat concentration / separation from 58B → groove 59A → one through hole 59B. .

Further, the groove portions 55A, 56A, 57A, 58A, 59A of the five metal substrates 55, 56, 57, 58, 59 constituting the three flow paths 53A, 53B, 53C and the four metal substrates. A catalyst support layer 61 is disposed on the inner wall surfaces of the through holes 55B, 56B, 57B, and 58B of the 55, 56, 57, and 58, and the catalyst C is supported on the catalyst support layer 61. The three through holes 54B of the metal substrate 54 are the raw material introduction ports 60a of the three flow paths 53A, 53B, and 53C, and the three through holes 59B of the outermost metal substrate 59 are three. The gas discharge ports 60b of the flow paths 53A, 53B, and 53C are provided.
For the six metal substrates 54, 55, 56, 57, 58, 59 constituting the microreactor body 4C, the same material as that of the metal substrates 24, 26 of the above-described embodiment can be used. Further, the thickness of the metal substrates 55, 56, 57, 58, 59 is such that the size of the microreactor body 4C, the heat capacity of the metal material to be used, the characteristics such as the thermal conductivity, the required groove portions 55A, 56A, 57A, Although it can set suitably in consideration of the size of 58A, 59A, etc., it can set in the range of about 50-5000 micrometers, for example. In addition, the thickness of the metal substrate 54 can be appropriately set in consideration of the material to be used, and can be set, for example, in the range of about 20 to 2000 μm.

The catalyst support layer 61 constituting the microreactor body 4C can be the same as the catalyst support layer 28 of the above-described embodiment.
In the above-described microreactor body 4C, the flow direction of the fluid in each of the flow paths 53A, 53B, and 53C is not limited, and the flow direction of the fluid is from the substrate 59 to the substrate 54, contrary to the illustrated example. There may be. In this case, the three raw material introduction ports 60a and the three gas discharge ports 60b are reversed. Further, the positions of the three raw material introduction ports 60a and the positions of the three gas discharge ports 60b are not limited to the illustrated example.
Further, a catalyst supporting layer 61 may be disposed on the surface of the metal substrate 54 (the surface exposed to the groove 55A side), and the catalyst C may be supported on the catalyst supporting layer 61, and each metal substrate 55, The catalyst support layer 61 may be disposed on the surfaces of the surfaces 56, 57, and 58 (the surfaces exposed to the grooves 56A, 57A, 58A, and 59A), and the catalyst C may be supported on the catalyst support layer 61. Thereby, the loading amount of the catalyst C further increases, and the reaction efficiency and the effective use of the space are improved.

  FIG. 20 is a longitudinal sectional view corresponding to FIGS. 14 and 18 showing another embodiment of the microreactor body constituting the microreactor of the present invention. In FIG. 20, the microreactor body 4D has a joined body 72 in which five metal substrates 74, 75, 76, 77, 78 are laminated and joined. A heating element (not shown) is disposed on at least one surface of the joined body 72 in the same manner as the microreactor body 4 described above. FIG. 21 is a perspective view showing a state in which the five metal substrates 74, 75, 76, 77, 78 constituting the microreactor body 4D shown in FIG. 20 are separated. In FIG. 21, a catalyst support layer 80 described later is omitted.

  Of the five metal substrates 74, 75, 76, 77, 78, the metal substrate 74, which is one of the outermost layers, functions as a cover member and straddles six groove portions 75A of the metal substrate 75 described later. One groove portion 74A and one through hole 74B are provided substantially at the center. In addition, the three metal substrates 75, 76, 77 not located in the outermost layer are each provided with six groove portions 75A, 76A, 77A on one surface (the metal substrate 74 side). On the other hand, the outermost metal substrate 78 has one groove portion 78A corresponding to the groove portion 74A of the metal substrate 74 on one surface (the metal substrate 74 side). Further, through holes 75B, 76B, and 77B are provided in the groove portions 75A, 76A, and 77A of the three metal substrates 75, 76, and 77, respectively. The groove 78A of the metal substrate 78 is provided with one through hole 78B. And each groove part 75A, 76A, 77A, 78A is connected in the lamination direction via the some through-hole 75B, 76B, 77B, respectively. Therefore, after entering the groove 74A from one through hole 74B of the metal substrate 74, six independent leads from the groove 75A → the through hole 75B → the groove 76A → the through hole 76B → the groove 77A → the through hole 77B → the groove 78A. A flow path 73 is formed.

Further, each of the groove portions 75A, 76A, 77A, 78A of the four metal substrates 75, 76, 77, 78 constituting the six independent flow paths 73 and the three metal substrates 75, 76, 77 are provided. A catalyst support layer 80 is disposed on the inner wall surfaces of the through holes 75B, 76B, and 77B, and the catalyst C is supported on the catalyst support layer 80. One through hole 74B of the metal substrate 74 is a raw material introduction port 79a of the flow path 73, and one through hole 78B of the outermost metal substrate 78 is a gas exhaust port 79b of the flow path 73. ing.
For the five metal substrates 74, 75, 76, 77, 78 constituting the microreactor body 4D, the same material as that of the metal substrates 24, 26 of the above-described embodiment can be used. The thickness of the metal substrate 75, 76, 77, 78 is the size of the microreactor body 4D, the heat capacity of the metal material to be used, characteristics such as thermal conductivity, and the required groove portions 75A, 76A, 77A, 78A. Although it can set suitably considering a magnitude | size etc., it can set in the range of about 50-5000 micrometers, for example. In addition, the thickness of the metal substrate 74 can be appropriately set in consideration of the material used, the required size of the groove 74A, and the like, and can be set, for example, in the range of about 50 to 2000 μm.

The catalyst support layer 80 constituting the microreactor body 4D can be the same as the catalyst support layer 28 of the above-described embodiment.
Also in the microreactor body 4D described above, the flow direction of the fluid in the flow path 73 is not limited, and the flow direction of the fluid may be from the substrate 78 to the substrate 74, contrary to the illustrated example. . In this case, the raw material inlet 79a and the gas outlet 79b are reversed. Further, the position of the raw material inlet 79a and the position of the gas outlet 79b are not limited to the illustrated example.

Further, the catalyst support layer 80 may be disposed in the groove 74A of the metal substrate 74, and the catalyst C may be supported on the catalyst support layer 80. Further, the surface of each metal substrate 75, 76, 77 (the grooves 76A, 77A). , 78 </ b> A) may also be provided with a catalyst support layer 80, and the catalyst C may be supported on the catalyst support layer 80. Thereby, the loading amount of the catalyst C further increases, and the reaction efficiency and the effective use of the space are improved.
20 and 21, there are six independent flow paths 73. By increasing the number of grooves 75A, 76A, and 77A formed in the metal substrates 75, 76, and 77, the number of the grooves 75A, 76A, and 77A is further increased. Multiple flow paths may be formed.

Next, the present invention will be described in more detail by showing more specific examples.
[Case manufacturing process]
Using a SUS316L substrate having a thickness of 0.3 mm, an open casing having a rectangular parallelepiped having an internal rule of 35 mm × 35 mm × 4.1 mm and having a 35 mm × 35 mm surface as an opening was produced by drawing.

[Punching process]
One circular through-hole (diameter 2.0 mm) for inserting the raw material supply pipe into one 35 mm × 4.1 mm wall surface of the above-mentioned open housing, and a circular through-hole for inserting wiring ( 1.5 mm in diameter), and a circular through hole (diameter 2.0 mm) for inserting a gas discharge pipe into a 35 mm × 4.1 mm wall facing this wall, and a wiring 1 circular through hole (diameter 1.5 μm) was drilled. This through hole was drilled. Moreover, in order to close said opening part, the cover material of 34 mm x 34 mm was produced, and the circular suction opening (diameter 1.0mm) was formed in this cover material.

[Thick member manufacturing process]
A circular through hole (diameter 1.5 mm) for inserting a lead pin is drilled in SUS316L with a thickness of 1.0 mm using a drilling process, and SUS316L is cut by wire discharge so that this through hole is at the center. A thick piece (3.0 mm × 3.0 mm) was prepared. Next, a lead pin (material: Kovar) having a diameter of 1.0 mm is inserted into the above through hole, and the through hole is sealed using a glass member (ASF700G manufactured by Asahi Glass Co., Ltd.) to produce a lead pin holding thick member. did.

[Placement process]
First, a microreactor body was produced as follows.
A SUS316L substrate (25 mm × 25 mm) having a thickness of 1 mm is prepared as a metal substrate, and a photosensitive resist material (OFPR manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied to both surfaces of the SUS316L substrate by a dipping method (film thickness 7 μm (when dry)) )did. Next, a photomask having a shape in which stripe-shaped light-shielding portions having a width of 1500 μm were alternately projected from the left and right (projection length 20 mm) on the resist coating film on the side where the fine groove portions of the SUS316L substrate were to be formed. Also, a SUS316L substrate similar to that described above was prepared, a photosensitive resist material was applied in the same manner, and a photomask was placed on the resist coating film on the side where the fine groove portion of the SUS316L substrate was to be formed. This photomask is symmetrical with the above photomask with respect to the SUS316L substrate surface.

Next, the resist coating film was exposed through a photomask for each of the above set of SUS316L substrates, and developed using a sodium hydrogen carbonate solution. As a result, a resist pattern in which stripe-shaped openings having a width of 500 μm are arranged at a pitch of 2000 μm on one surface of each SUS316L substrate and adjacent stripe-shaped openings are alternately continued at the end portions thereof. Been formed.
Next, using the resist pattern as a mask, the SUS316L substrate was etched (for 3 minutes) under the following conditions.
(Etching conditions)
・ Temperature: 50 ℃
・ Etching solution (ferric chloride solution) Specific gravity concentration: 45 Baume (° B'e)

As a result, a pair of SUS316L substrates has stripe-shaped fine grooves having a width of 1000 μm, a depth of 650 μm, and a length of 20 mm formed on one surface thereof at a pitch of 2000 μm, and alternately at the ends of adjacent fine grooves. A fine groove (flow path length: 220 mm) having a continuous shape (a shape meandering and continuous while being folded back by 180 degrees as shown in FIG. 8) was formed. The shape of the inner wall surface in a cross section perpendicular to the fluid flow direction of the fine groove portion was substantially semicircular.
As described above, alumina spraying was performed by a plasma spray method on the fine groove forming surface of the pair of SUS316L substrates on which the fine groove was formed. Next, the resist pattern was removed using a sodium hydroxide solution and washed with water. By removing the resist pattern, an unnecessary alumina sprayed film was lifted off, and a catalyst support layer (thickness 30 μm) was formed in the fine groove.

Subsequently, the above-mentioned set of SUS316L substrates was diffusion bonded under the following conditions so that the fine groove portions were opposed to each other to produce a joined body. In this bonding, alignment was performed so that the fine groove portions of one set of substrates completely face each other. As a result, a tunnel-like flow path in which the raw material introduction port and the gas discharge port exist on the opposing end surfaces of the joined body was formed in the joined body.
(Diffusion bonding conditions)
-Atmosphere: in vacuum-Joining temperature: 1000 ° C
-Joining time: 12 hours

Next, the catalyst suspension having the following composition is filled in the flow path of the joined body and allowed to stand (15 minutes). Thereafter, the catalyst suspension is removed and subjected to a dry reduction treatment at 120 ° C. for 3 hours. The catalyst was supported on the entire surface of the flow path.
(Composition of catalyst suspension)
・ Al: 5.4 wt%
Cu: 2.6% by weight
Zn: 2.8% by weight
・ Si binder (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.)
… 5.0 wt%
・ Water… the rest

Next, a polyimide precursor solution (Photo Nice manufactured by Toray Industries, Inc.) as an insulating film coating solution is printed on one SUS316L substrate constituting the joined body by screen printing and cured at 350 ° C. to obtain a thickness. A 20 μm insulating film was formed. Next, a heating element paste having the following composition was printed on the insulating film by screen printing and cured at 200 ° C. to form a heating element. The formed heating element had a shape with a line width of 100 μm and drawn around at a line interval of 100 μm so as to be turned 180 ° as shown in FIG.
(Composition of paste for heating element)
Carbon powder: 20 parts by weight Fine powder silica: 25 parts by weight Xylene phenol resin: 36 parts by weight Butyl carbitol: 19 parts by weight

In addition, electrodes (0.5 mm × 0.5 mm) were formed at predetermined two locations of the heating element by screen printing using an electrode paste having the following composition.
(Composition of electrode paste)
Silver-plated copper powder: 90 parts by weight Phenolic resin: 6.5 parts by weight Butyl carbitol: 3.5 parts by weight Next, the following composition is used to expose the two electrodes formed on the heating element. Using the protective layer paste, a heating element protective layer (thickness 20 μm) was formed on the heating element by screen printing.
(Composition of protective layer paste)
Resin content concentration: 30 parts by weight Silica filler: 10 parts by weight Lactone solvent (penta-4-lactone): 60 parts by weight

As a result, a microreactor body (outer dimensions 25 mm × 25 mm × about 2.1 mm) was produced.
Next, the raw material supply pipe and the gas discharge pipe are connected to the raw material introduction port and the gas discharge port of the microreactor main body, respectively, and the raw material supply pipe and the gas discharge pipe are inserted into the through holes, The microreactor body was placed in an open housing. And the through-hole which the raw material supply pipe and the gas exhaust pipe penetrated was sealed by brazing.

[Jointing process]
Two of the above lead pin holding thick members were joined to the outer wall surface by diffusion bonding so that the lead pins were inserted into the two through holes of the open housing. Next, the two lead pins located inside the open housing and the electrode of the heating element were connected by a gold wire.

[Vacuum enclosure manufacturing process]
The lid material was diffusion bonded to the opening of the open housing and closed to form a vacuum housing. The conditions for diffusion bonding were the same as those for the diffusion bonding described above. In this state, the inner wall of the housing and the microreactor main body were not in contact with each other through a space having a width of 1 to 5 mm.
Next, suction was performed from the suction port so that the inside of the vacuum casing had a degree of vacuum of 10 ⁻² Pa, and then the suction port was sealed by welding to form a vacuum sealed cavity.
Thereby, the microreactor of the present invention could be obtained.

  INDUSTRIAL APPLICABILITY The present invention can be used for applications in which a desired reaction is advanced by a supported catalyst, such as hydrogen production including reactions such as methanol reforming and carbon monoxide oxidation removal.

It is a perspective view which shows one Embodiment of the microreactor of this invention. It is an expanded longitudinal cross-sectional view in the II line of the microreactor shown by FIG. FIG. 2 is an enlarged longitudinal sectional view taken along line II-II of the microreactor shown in FIG. It is a partial expanded sectional view of the through-hole vicinity of the vacuum housing which the lead pin has penetrated. It is a partial expanded sectional view which shows the other aspect of the through-hole vicinity of the vacuum housing which the lead pin has penetrated. It is a perspective view which shows an example of the microreactor main body which comprises the microreactor of this invention. It is an expanded longitudinal cross-sectional view in the III-III line of the microreactor main body shown by FIG. It is a perspective view which shows the state which spaced apart the metal substrate which comprises the microreactor main body shown by FIG. It is a top view for demonstrating the heat generating body which comprises a microreactor main body. It is process drawing for demonstrating the manufacturing method of the microreactor of this invention. It is process drawing for demonstrating the manufacturing method of the microreactor of this invention. It is a longitudinal cross-sectional view equivalent to FIG. 7 which shows the other form of the microreactor main body which comprises this invention. It is a perspective view which shows the other form of the microreactor main body which comprises this invention. It is an expanded vertical sectional view in the IV-IV line of the microreactor main body shown by FIG. FIG. 15 is an enlarged longitudinal sectional view taken along line VV of the microreactor body shown in FIG. 13. FIG. 14 is a perspective view showing a state in which five metal substrates constituting the microreactor main body shown in FIG. 13 are separated from each other. It is a perspective view which shows the other form of the microreactor main body which comprises this invention. It is an expanded longitudinal cross-sectional view in the VI-VI line of the microreactor main body shown by FIG. FIG. 18 is a perspective view showing a state in which six metal substrates constituting the microreactor main body shown in FIG. 17 are separated from each other. It is a longitudinal cross-sectional view equivalent to FIG. 14 which shows the other form of the microreactor main body which comprises this invention. FIG. 21 is a perspective view showing a state in which five metal substrates constituting the microreactor main body shown in FIG. 20 are separated from each other.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Microreactor 2 ... Vacuum housing 2A ... Opening housing 3 ... Vacuum sealed cavity 4, 4A, 4B, 4C, 4D ... Microreactor main body 5A ... Raw material supply pipe 5B ... Gas discharge pipe 7 ... Heating element 11, 11 ' ... Thick part 12, 16 ... Through hole 13 ... Glass member 14 ... Lead pin 17 ... Lead pin holding thick member 18 ... Thick piece 22,42,52,72 ... Joint body 23,33 ... Tunnel flow path 25,27 35 ... fine groove 28, 38, 50, 61, 80 ... catalyst support layer 29a, 49a, 60a, 79a ... raw material inlet 29b, 49b, 60b, 79b ... gas outlet C ... catalyst

Claims (12)

In a microreactor comprising a vacuum casing, a microreactor body disposed in a vacuum sealed cavity in the vacuum casing, and a heating element located on at least one surface of the microreactor body,
The microreactor body has a raw material inlet and a gas outlet, the raw material inlet is connected to the outside of the vacuum casing by a raw material supply pipe penetrating the vacuum casing, and the gas outlet is connected to the vacuum casing. Connected to the outside of the vacuum housing by a gas exhaust pipe penetrating the body,
The heating element can be connected to an external power source through a lead pin that penetrates the vacuum casing,
The vacuum casing is made of stainless steel having a thickness in the range of 0.1 to 0.5 mm, and has a plurality of through holes through which the lead pin, the raw material supply pipe, and the gas discharge pipe pass. The through hole through which the lead pin passes is sealed with a glass member, and the length of the glass member along the length direction of the lead pin is in the range of 0.5 to 1.4 mm. Further, the peripheral portion of the through hole of the vacuum casing is a thick portion, and the through hole through which the raw material supply pipe and the gas discharge pipe pass is welded, brazed, or sealed with a resin member A microreactor characterized by being made.   2. The microreactor according to claim 1, wherein the thick portion is formed in a range of a width of 1.0 to 2.0 mm around the through hole.   The microreactor according to claim 1 or 2, wherein the thick part has a thin part in a peripheral part as compared with a part where the through hole is formed.   The microreactor body includes a joined body in which a set of metal substrates is joined, and a tunnel-like flow path configured by a fine groove formed on a joining surface of at least one metal substrate of the set of metal substrates, A catalyst-carrying layer formed in the tunnel-like flow path; and a catalyst carried by the catalyst-carrying layer, wherein the raw material inlet and the gas discharge port communicate with the tunnel-like flow path, and the catalyst-carrying layer The microreactor according to any one of claims 1 to 3, wherein is an inorganic oxide film.   The microreactor body includes a joined body in which three or more metal substrates are laminated and joined, a flow path formed inside the joined body, a catalyst support layer formed in the flow path, and the catalyst support layer. And the metal substrate that is not located at least in the outermost layer has a groove formed in at least one of the joining surfaces, and a through hole formed in the groove, and the groove and the through hole The flow path is constituted by the above, the raw material inlet and the gas outlet are in communication with the flow path, and the catalyst support layer is an inorganic oxide coating. A microreactor according to claim 1.   The microreactor according to claim 5, wherein a plurality of the groove portions are formed via a partition wall.   The microreactor according to claim 5 or 6, wherein there are a plurality of through holes formed in the groove. In a method of manufacturing a microreactor comprising a vacuum casing, a microreactor body disposed in a vacuum sealed cavity in the vacuum casing, and a heating element located on at least one surface of the microreactor body,
Using a stainless steel having a thickness in the range of 0.1 to 0.5 mm, a housing manufacturing process for manufacturing an open housing having one opening surface,
A drilling step of forming a plurality of through holes for penetrating the raw material supply pipe, the gas discharge pipe and the lead pin on a desired wall surface of the open housing;
By punching through holes for lead pins in a plurality of small pieces made of stainless steel having a thickness in the range of 0.5 to 1.4 mm, and penetrating the lead pins into the through holes and sealing with glass members , A thick member production process for producing a lead pin holding thick member;
A microreactor body having a raw material inlet and a gas outlet, a raw material supply pipe and a gas outlet connected to the raw material inlet and the gas outlet, and a heating element located on at least one surface, A raw material supply pipe and a gas discharge pipe are placed in the opening housing so as to be inserted into the through hole, and the through hole is welded, brazed, or sealed with a resin member,
The lead pin holding thick member is joined to the outer wall surface of the opening housing so that the lead pin is inserted into the corresponding through hole of the opening housing, and the lead pin and the electrode of the heating element are electrically connected. A joining process to connect to each other,
A lid made of stainless steel having a thickness in the range of 0.1 to 0.5 mm is joined to the open housing so as to close the open surface, and a vacuum housing whose inside constitutes a vacuum sealed cavity A manufacturing method of a microreactor comprising: a vacuum casing manufacturing step to be manufactured.   9. The method of manufacturing a microreactor according to claim 8, wherein, in the housing manufacturing step, an open housing is manufactured by drawing.   10. The method of manufacturing a microreactor according to claim 8, wherein the thin piece has a thin portion in a peripheral portion as compared with a portion where the through-hole is formed.   The method for manufacturing a microreactor according to any one of claims 8 to 10, wherein the vacuum casing is made into a vacuum sealed cavity by performing the vacuum casing manufacturing step in a vacuum chamber.   In the vacuum casing manufacturing step, after the lid member is joined to the opening casing, the inside of the vacuum casing is made into a vacuum sealed cavity by sucking from a suction hole provided in the vacuum casing, and then the suction hole is sealed The method for producing a microreactor according to any one of claims 8 to 10, wherein:

Images