JP5342985B2 - Reactor - Google Patents

Description

  The present invention relates to a reactor, and more particularly to a flow reactor that performs a reaction using a metal catalyst.

  Development of technology for producing hydrogen as a fuel source for fuel cells such as automobiles and various chemical raw materials is underway. In particular, since there is no generation of global warming gas such as carbon dioxide and the energy efficiency is high, technologies relating to hydrogen fuel cells are attracting attention from the viewpoint of protecting the global environment. Recently, hydrogen can be directly converted into electric power, and high energy conversion efficiency is possible in a cogeneration system that uses generated heat. Therefore, development for use in a home-use distributed power source has recently been advanced.

  As a technique for producing hydrogen, a method by reaction reforming using an organic compound such as a petrochemical raw material is known. For example, there is a method of generating a reaction gas containing hydrogen gas and carbon dioxide gas by reacting an alcohol compound with water in the gas phase in the presence of a catalyst such as nickel. Specifically, Patent Documents 1 and 2 disclose a method of generating a water gas that is a mixed gas of hydrogen and carbon monoxide by a decomposition reaction of a polyhydric alcohol such as glycerin and a subsequent water gas shift reaction. . In this technology, a technique that introduces and flows a raw material fluid containing polyhydric alcohol, water, and hydrogen into a reaction field provided with a catalyst is proposed, and a technique for suppressing the generation of soot (carbon) in the reaction process is proposed. Has been.

  On the other hand, as a reaction apparatus that can be used for the steam reforming reaction, a joined body in which two or more metal members are joined at the contact surface is formed, and a tunnel-like flow path connected to the raw material inlet and the gas outlet is formed there. A microreactor is disclosed (see Patent Document 3). A catalyst-carrying layer is formed in the tunnel-like flow path, and a heating element is provided on at least one surface of the joined body via a ceramic insulating layer. According to this reactor, since the two or more metal members are joined and integrated so that the contact surface of the joined body is equal to or less than a predetermined surface roughness, high airtightness at the interface is realized. be able to.

JP 2009-051703 A JP 2009-051704 A Japanese Patent Laid-Open No. 2008-1000016

  Certainly, as disclosed in Patent Document 3, if the abutting surface of the metal member is polished and mirror-finished to improve its bondability, the interface where both abuts is strongly bonded by the fusion. In addition, it exhibits high hermeticity in a high-temperature (for example, 600 ° C.) heating flow reaction such as a steam reforming reaction, and can suitably cope with the production of synthesis gas. However, the metal member fusion-bonded as described above has a very strong bonding force and cannot be decomposed on the contrary, and confirmation and maintenance inside the reaction channel may be extremely difficult. In particular, when the reaction flow path is on the order of micrometers, it becomes difficult to insert a cleaning tool or a cleaning medium therein. For example, when a predetermined metal surface is used as a catalyst surface, it can be used only once. It will be also. If it becomes so, it will become inadequate in terms of manufacturing efficiency, manufacturing cost, etc.

  In view of the above points, the present invention provides a reaction apparatus in which a reaction channel is arranged on a corresponding contact surface of a reactor body formed by contacting two or more metal members. It is possible to easily separate the metal members and to check the state of the inner surface of the reaction channel, verify the product attached thereto, maintain the channel, etc. without complicated operations. For the purpose of provision.

  The above-described problem is a reaction apparatus in which a reactor main body in which two or more metal members are in contact with each other is inserted into a housing, and a reaction channel is formed on the surface in which the metal members are in contact with each other. In addition, the present invention has been solved by a reaction apparatus characterized in that the contacted surface is subjected to anti-fusing treatment.

  In the reaction apparatus of the present invention, a reaction channel is arranged on a corresponding contact surface of a reactor main body formed by contacting two or more metal members, and both metal members are easily separated at the contact surface after the reaction is completed. Thus, confirmation of the state of the inner surface of the reaction channel, verification of the product attached thereto, maintenance of the channel, and the like can be performed without complicated operations.

1 is a partially cutaway perspective view schematically showing a flow reactor as an embodiment of the present invention. FIG. It is sectional drawing of the II-II line cross section shown in FIG. It is a disassembled perspective view of the flow reaction apparatus shown in FIG. It is the schematic diagram which showed the cross section of the metal member among the reactor main bodies in the cross section corresponding to FIG. 2 of the flow-type reaction apparatus as another embodiment in this invention, (a) is a square-shaped flow path in a cross section. (B) has a hexagonal channel in cross section. It is the schematic diagram which showed the cross section of the metal member among the reactor main bodies in the cross section corresponding to FIG. 2 of the flow-type reaction apparatus as another embodiment in this invention, (a) is the metal member of one side in a cross section. The side with a semicircular channel is applied, (b) is with a rectangular channel in cross section, and (c) is with a triangular channel in cross section. The contact surface of one metal member is typically shown among the reactor main bodies in the flow-type reaction apparatus as still another embodiment of the present invention, and the flow path is in the middle of one flow path range. (A) is a plan view seen from the contact surface, (b) is a cross-sectional view taken along line BB in (a), and (c) is ( It is CC sectional view taken on the line of a). FIG. 6 schematically shows a contact surface of one metal member of a reactor main body in a flow reactor according to still another embodiment of the present invention, and includes two independent parallel flow paths. It is a schematic diagram of what has ((a) is a top view seen from the contact surface, (b) is a BB sectional drawing of (a)). It is a drawing substitute photograph which shows the microscope image observed with SEM-EDX in the contact surface of the metal material (polishing process, 600 degreeC-10 hours heat processing) produced in Example 1, (a) is an optical microscope image, ( b) is a secondary electron image, and (c) is a reflected electron image. It is the characteristic X-ray spectrum acquired by the SEM-EDX measurement in the contact surface of the metal material (Polishing process, 600 degreeC-10 hours heat processing) produced in Example 1. FIG. It is a drawing substitute photograph which shows the microscope image observed by SEM-EDX in the contact surface of the metal material (polishing process, 600 degreeC-1 hour heat processing) produced in Example 2, (a) is an optical microscope image, ( b) is a secondary electron image, and (c) is a reflected electron image. It is the characteristic X-ray spectrum acquired by the SEM-EDX measurement in the contact surface of the metal material (Polishing process, 600 degreeC-1 hour heat processing) produced in Example 2. FIG. It is a drawing substitute photograph which shows the microscope image observed by SEM-EDX in the contact surface of the metal material (without grinding | polishing process and heat processing) produced by the comparative example, (a) is an optical microscope image, (b) is secondary. An electronic image, (c) is a reflected electron image. It is the characteristic X-ray spectrum acquired by the SEM-EDX measurement in the contact surface of the metal material (without grinding | polishing process and heat processing) produced by the comparative example. It is apparatus explanatory drawing which shows the state which connected the various apparatuses and apparatus which were used for the airtightness test implemented in Example 1. FIG.

  FIG. 1 is a partially cutaway perspective view schematically showing a flow reactor as an embodiment of the present invention, and FIG. 2 is a cross-sectional view taken along the line II-II shown in FIG. It is a disassembled perspective view of the shown flow reaction apparatus.

  In the reaction apparatus 10 of this embodiment, a metal member 12 and a metal member 13 are in contact with each other at their contact surfaces 12a and 13a to form the reactor body 1. The reactor body 1 is sandwiched by support plates 11 and 14 from a direction perpendicular to the contact surface and inserted into the insertion hole 2b of the housing 2 without a gap. In the present invention, the term “without a gap” includes not only a contact with no gap, but also a slight gap in consideration of insertion / extraction during assembly of the reactor and a gap due to processing errors. Although the value of a clearance gap is not specifically limited, For example, 0.1 mm-3.0 mm are preferable, and 0.5 mm-1.0 mm are more preferable. Moreover, even if the reactor main body is inserted alone without a gap, it may be further inserted with no gap through another member such as a support plate. Further, twelve screw holes 2m are provided on the upper surface of the casing 2, and the same number of screws 3 are screwed into the twelve screw holes 2m. The screw is tightened until the tip 3a of the screw comes into contact with the support plate 11, the reactor main body 1 is firmly fixed inside the housing 2, and the reaction apparatus 10 is configured.

In the reactor main body of the present embodiment, the abutment surface 12a of the metal member 12, to 13a, a groove 12n which forms the reaction channel 6 communicating from the inlet _{m 1} to the outlet _{m 2,} 13n are formed respectively (See also FIGS. 2 and 3). Therefore, the contact channels 12a and 13a are brought into contact with the substantially rectangular metal members 12 and 13 to form the reaction channel 6 which is circular in the cross section and linearly extends in the longitudinal direction. Then, in the reactor body 1, the inlet m ₁ and outlet m ₂ of metal members 12 and 13 are formed so as to face is the female screw portion is provided, the joint 4 to the screw hole which the inlet and outlet forms The male screw portion 4a can be screwed and attached. Pipes 5 are connected to the joints, respectively, so that a raw material is sent from the pipe 5 to the inlet m ₁ , a desired reaction is advanced in the reaction flow path 6, and a reaction product is discharged from the outlet m _2. 5 can be recovered.

The reaction apparatus of the present invention is characterized in that the contact surfaces of two or more metal members forming the reaction flow path are subjected to a fusion prevention treatment in advance. This will be described in detail by taking the flow reaction type apparatus 10 of the above embodiment as an example. In the present embodiment, as described above, the two metal members 12 and 13 are brought into contact with the contact surfaces 12a and 13a, and the grooves 12n and 13n formed on the contact surfaces form the reaction flow path 6. ing. Further, the metal member is inserted into the insertion hole 2 b of the housing and is sandwiched and pressed between the housing 2 and the screw 3 via the support plates 11 and 14. Therefore, the contact surfaces 12a and 13a of the metal member receive a considerable surface pressure and are in close contact with each other. In particular, considering the airtightness that prevents the reaction fluid from leaking out from the reaction flow path, a sufficient sealing property is required. Usually, the contact surface is sufficiently polished and finished in a mirror state, and is subjected to a surface pressure as described above. It is pressed.
In this way, the surface roughness of the contact surface of the metal member is extremely small and is in close contact with a high surface pressure. Further, when subjected to high temperature heating conditions, diffusion bonding of metal on the contact surface proceeds. Thus, both are joined. That is, even if the metal material is not melted, if it is heated or pressurized and held under a predetermined condition, atoms diffuse beyond the contact interface, and a complete or sufficient bonding state is obtained. When melting and partial melting are caused by such diffusion bonding or heating, these members cannot be divided unless the metal is cut or broken. In the present invention, it is referred to as “fusion” including the above-described diffusion bonding and bonding by melting, and also room temperature bonding (typically bonding of clean surfaces of metals in a vacuum state).
On the other hand, according to the present invention, since the anti-fusing treatment is performed on the contact surface of the metal member, the surface is subjected to a mirror surface treatment by polishing or the like, strongly pressed and brought into close contact, Even in a heating environment, the contact surface does not melt and can be easily divided. In other words, in the present invention, the reaction channel formed on the contact surface at the time of the reaction is sufficiently maintained while overcoming the conventional conflicting problem, and after the reaction is completed, special equipment and severe processing are performed. The metal member can be divided at its abutment surface without doing so.

(Metal member)
The material forming the metal members 12 and 13 of the present embodiment is not particularly limited, but it is preferable to use a metal having catalytic activity for the reaction to be used. It is possible to use a metal member having the above catalytically active metal attached to the surface by a surface treatment such as plating, thermal spraying, sputtering or vapor deposition. In consideration of repeated use after the surface has been heated to a high temperature, the material is preferably made of the above catalytically active metal. Although it does not specifically limit as a metal material, if it says as a metal active by a heat | fever distribution | circulation reaction, it will be group 8-12 metal, Preferably group 8 iron, ruthenium, osmium, etc., group 9 cobalt, rhodium, iridium, etc. , Group 10 nickel, palladium, platinum, etc., or alloys thereof. In consideration of use in the steam reforming reaction, nickel having excellent industrial cost, mechanical strength, and formability can be mentioned. Among them, pure nickel having high purity, for example, 99% or more is preferable. In the present invention, the metal material may be a composite that is applied in combination with a material other than a metal, for example, a predetermined inorganic material, as long as the metal material is applied in a range in which the predetermined metal acts as described above.

  In the present embodiment, the shape of the metal member is not particularly limited. However, in consideration of being inserted in the insertion hole of the housing without a gap as shown here, it is preferably a rectangular parallelepiped shape, and two or more metals It is preferable that both of the members have the same shape.

(Reaction channel)
In the reaction apparatus of the present embodiment, the semicircular grooves 12n and 13n are formed in the cross section on the contact surface side of the two metal materials 12 and 13, respectively. A flow path 6 extending linearly is formed. The formation method of this flow path is not specifically limited, For example, machining finishes, such as cutting, grinding, and electrical discharge machining, sandblasting, an etching process, etc. can be employ | adopted suitably. The form of the flow path is not particularly limited to that of the above embodiment, and can be appropriately designed according to the reaction to be used. For example, in the cross-sectional shape of the flow channel, in a cross-section straddling two metal members as shown in FIG. 4, (a) a rectangular flow channel, (b) a hexagonal flow channel, and a polygonal flow channel having an elliptical shape or a hexagonal shape or more. It may be. In addition, a groove is provided on only one of the metal members as shown in FIG. 5, and (a) a semicircular channel, (b) a square channel, (c) a triangular channel, or more than a square in the cross section. It may be a polygonal channel. Further, as a modification of the above, the flow channel configuration viewed from the contact surface side includes a flow channel inlet m ₁ and a flow channel outlet m ₂ as shown in FIG. 6, and the flow channel 6 is changed from the inlet to the flow channel 61. It may be composed of a flow path 63 that enters and is branched into two at the branch point 6p, and then aggregated at the branch point 6p. As in the flow passage 6 comprising a respective two flow paths 6a and the flow path 6b connecting the channel inlet m ₁ and the flow passage outlet m ₂ as shown in FIG. 7 as a further modification, a plurality to one of the abutment surfaces These channels may be formed in a state of being independently parallel. Further, there is no particular problem even if the number of branching and aggregation or independent flow paths is two or more. In addition, a three-dimensional flow path through a through hole may be used in the middle, or a multi-stage reactor main body in which three or more metal members are stacked may be applied. 6 and 7 show only one side of the metal member, a configuration in which another metal member having a flow path of the same or different shape is faced at a corresponding position or a flow path is formed. It has been described that the flow path is formed in a configuration in which no metal member is faced.

  The dimensions of the flow path are not particularly limited, but considering the use as a flow reactor used in the steam reforming reaction, the equivalent circle diameter of the cross section is preferably 0.1 mm to 5.0 mm, preferably 1.0 mm to More preferably, it is 3.0 mm. Although the length of the reaction channel is not particularly limited, it is preferably 10 mm to 300 mm, more preferably 50 mm to 150 mm in consideration of the length suitable for the steam reforming reaction. .

  The catalyst is preferably exposed on the inner surface of the flow path. When the metal material itself is made of a metal having catalytic activity, the metal surface is exposed by forming the reaction flow path by the above-described processing. It functions as a catalyst. On the other hand, when a predetermined metal catalyst layer is formed on the inner surface of the flow path, it can be formed by surface treatment such as plating, thermal spraying, sputtering, and vapor deposition.

(Fuse prevention treatment)
In the reaction apparatus of the present embodiment, the conditions for the anti-fusing treatment on the contact surface of the metal member are not particularly limited, but the metal member is preferably heat-treated in a predetermined atmosphere, and is performed in an oxygen-containing atmosphere. More preferably, it is more preferable to perform the heat treatment in the atmosphere in consideration of the treatment efficiency. Although the heating temperature is not limited to the material metal, for example, when nickel is used as the metal member, the treatment is preferably performed at 100 ° C. to 1000 ° C., more preferably at 500 ° C. to 700 ° C. In addition to the heat treatment, molybdenum, tin, tantalum, chromium, tungsten, titanium, nitrogen, silicon, silica, carbon, alumina, cobalt, etc. are formed by surface treatment such as plating, thermal spraying, sputtering, and vapor deposition. May be.

  In the present embodiment, an inclined oxide film 7 (see the circle in FIG. 2) is formed on the contact surfaces 12a and 13a of the metal materials 12 and 13 by the above-described fusion prevention process. Although the oxygen concentration is not particularly limited, for example, the atomic ratio of the main metal elements is preferably 28 atom% or more, more preferably 30 atom% or more by ESCA measurement described in Examples below. One of the reasons why the present invention has excellent anti-fusing properties as described above is presumed to be that the concentration of the element such as oxygen is increased and a metal structure state different from the metal surface exposed by simply polishing is formed. Is done.

(Polishing)
The polishing method for the contact surface of the metal material is not particularly limited, and a regular method can be adopted. For example, it is finished by machining finishing such as grinding wheel processing, lapping processing, electric discharge processing, or electrolytic processing finishing such as ELID grinding. . The surface roughness of the contact surface after polishing is not particularly limited, but considering airtightness, the center line average roughness (Ra) is preferably in the range of 0.001 μm to 0.100 μm, preferably 0.002 μm to 0 More preferably, it is in the range of 010 μm. Further, the 10-point average roughness (Rz) is preferably 1.0 μm or less, and more preferably 0.1 μm or less.

(Support plate)
In this embodiment, the support plates 11 and 14 are not particularly limited by the coefficient of thermal expansion of the member. For example, stainless steel is preferable because the material is excellent in industrial cost, mechanical strength, and formability. Further, as the thermal expansion coefficient of this material _{(K 2),} it is preferable to use smaller ones _(K 1> K ₂₎ than the thermal expansion coefficient of the material used for the metal member 12,13 _{(K 1).} When the value of the thermal expansion coefficients of typical materials are, for example, illustrates the thermal expansion coefficient at 0 to 100 ° C., nickel ^{(13.3 × 10 -6 /℃),SUS430(10.4×10 -6 /} ℃) a ^{SUS304 (17.3 × 10 -6 /℃),SUS316(15.9×10 -6} / ℃), using SUS430 to the support plate using a nickel metal member in this view of the above relationship It is preferable.

Relationship such thermal expansion coefficient is the same for later-described casing, the thermal expansion coefficient of the housing of the (K _3), the thermal expansion coefficient of the material used for the metal member 12, 13 (K ₁₎ is smaller than It is preferable to use one (K ₁ > K ₃ ). As long as various processes for ensuring airtightness are performed on the contact surface of the metal member as described above, it is not necessary to have a surface pressure more than necessary at that portion. Further, as defined herein, a material having a thermal expansion coefficient larger than the thermal expansion coefficient (K ₁ ) of the metal member is used for the material surrounding the metal member (in this embodiment, the support plate and the casing). The surface pressure at the contact surface of two or more metal members when heated can be moderated moderately, and the effect of preventing fusion at the contact surface can be expected.

  The shape of the support plate is not particularly limited. However, in consideration of compatibility with the metal member and a suitable insertion form into the housing, it is preferable that the metal member has the same shape when viewed in a direction perpendicular to the contact surface. . The thickness is not particularly limited, but is preferably 5 mm to 10 mm. By setting the thickness within this range, it is possible to appropriately hold the material at the time of machining, and to suppress processing distortion due to processing. Moreover, the apparatus can be made compact by not making it thicker than necessary.

(Casing)
Although the material which comprises the housing | casing 2 in this embodiment is not specifically limited, The range of the material used preferably is the same as that of the said support plate. The structure of the housing is a hollow structure provided with an insertion hole 2b. In order to maintain the mechanical strength of the housing and the accuracy of the flatness and parallelism of each inner surface of the insertion hole 2b, by cutting out from the block material An integrated structure with no mounting surface is preferred. The processing method of the insertion hole 2b is not particularly limited, and is finished by, for example, wire cut electric discharge machining. The size of the insertion hole 2b of the housing is preferably determined as appropriate depending on the dimensions of the reactor main body 1 or the support plate to be used, and is the same size as that of the reactor main body 1 held between the support plates, or the insertion / extraction property. In consideration of the above, it may be a dimension provided with a minute clearance. In the present embodiment, two insertion holes 2b are provided, but may be further increased in relation to numbering up of the reaction flow path. Twelve screw holes 2m are provided on the top surface of the housing, and the screws 3 are screwed into these. The screw hole 2m passes through, and the depth of the screw hole 3m is such that the screw tip 3a protrudes somewhat into the insertion hole 2b when the screw 3 is screwed into the deepest position. In other words, it is preferable to use the screw 3 having a screw thread having a length that can be inserted into the screw groove of the screw hole 2m of the housing by being screwed to such a depth. By screwing the screw 3, the screw tip 3 a strongly presses the support plate 11 of the reactor main body 1, and a stable fixing state of the reactor main body can be realized. At this time, it is preferable to adjust the torque for tightening the screw 3 in consideration of the airtightness and the anti-fusing property on the contact surfaces 12a and 13a of the metal member as described above.

(Other)
As the joint 4, a commercially available one can be used as appropriate, and for example, a tube joint, a pipe joint, or the like can be used. In this embodiment, the joint 4 is provided with a male screw portion 4a protruding at the tip thereof, and the female members (entrance, The outlet) is screwed to m ₁ and m ₂ . That is, the thread of the male threaded portion 4a of the joint corresponds to the thread grooves 13m and 12m (see FIG. 3) of the metal member.
As the pipe 5, a commercially available one can be used as appropriate, and for example, a stainless steel pipe, a carbon steel pipe, a copper pipe, a titanium pipe, or the like can be used. The material and the pipe diameter can be appropriately selected according to the kind and supply amount of the raw material compound, the kind and the recovery amount of the product, and the like.

  The reaction apparatus 10 of the present embodiment may be applied to any reaction as long as it exhibits its effects, and can be used without any particular limitation. However, it is particularly preferable to use it for a heating flow reaction, and the reaction is performed by heating the entire reaction apparatus. The flow reaction is preferably performed in a state where the flow path is maintained at a predetermined temperature. The method for heating the reaction apparatus is not particularly limited, but heating may be performed by attaching a heating means such as a sheathed heater, a cartridge heater, or a space heater to the reaction apparatus 10, or the reaction apparatus is installed in a heating furnace for heating. May be. Although it does not specifically limit as heating temperature, What is necessary is just to set according to use object reaction, but when a reaction apparatus is comprised with a metal material, it is preferable to heat to 100 to 1000 degreeC, for example. Examples of the heating flow reaction include a steam reforming reaction using an organic compound. Below, the modification reaction of the polyhydric alcohol which is one of them is illustrated.

  The following chemical reaction formula (1) shows a reaction that proceeds by introducing and flowing a raw material fluid containing a polyhydric alcohol and water into a reaction field where a catalyst coexists. That is, by the decomposition reaction of polyhydric alcohol, the raw material fluid reacts to produce water gas (synthetic gas) that is a mixed gas of hydrogen and carbon monoxide. Usually, along with this reaction, the produced carbon monoxide reacts with water to produce hydrogen secondary by the water gas shift reaction of the following chemical reaction formula (2). As reaction temperature which advances these reactions efficiently, 300 to 1000 degreeC is preferable, for example, and 500 to 700 degreeC is more preferable. An example of a metal catalyst that is particularly preferably used in this reaction is nickel.

  In the above steam reforming reaction, two molecules of the generated carbon monoxide are further bonded to each other to cause a side reaction to generate carbon dioxide and carbon (solid) (chemical reaction formula (3)). As this reaction proceeds, carbon (solid) is produced, which becomes soot and adheres to the inner surface of the reaction vessel.

  The reactor 10 of the present embodiment can also be suitably used for the steam reforming reaction of polyhydric alcohols exemplified above, and can cope with heating at the reaction temperature without any problems. Moreover, after the reaction is completed, the reactor main body 1 can be disassembled easily to expose the internal reaction flow path. For this reason, the reaction flow path of the metal member is easily cleaned to expose the metal surface exhibiting catalytic activity, and appropriate maintenance such as polishing of the contact surface and anti-fusing treatment is performed, and the synthesis gas is rapidly produced again. Can be used for

  According to the reaction apparatus of the said embodiment, it has the advantage that it can adapt also to reaction on high temperature heating conditions, such as about 600 degreeC calculated | required by steam reforming reaction, by selecting a constituent material etc. as needed. At this time, by adopting a structure (self-pressurized structure) in which the pressure generated in the reactor and the casing due to material expansion at high temperature is mutually pressurized (self-pressurized structure), the air tightness at the contact surface of the metal member constituting the reactor body The property can be made extremely high. For this reason, even after the high temperature or high temperature / high pressure reaction, after cooling, the separability at the contact interface of the metal member becomes very good.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not construed as being limited thereto.

Example 1
<Production of reaction apparatus>
The reactor shown in FIG. 1 was prepared by the following procedure. Two materials made of metallic nickel (purity: 99.6% by mass or more) of 10 mm × 15 mm × 115 mm were prepared as metal members. A groove having a semicircular cross section (diameter: 3 mm) extending in the longitudinal direction in the center in the width direction of the metal member was cut by a numerically controlled milling machine and finished by sandblasting. At both ends in the longitudinal direction of the groove, metal members were superposed and held with high accuracy, and screw grooves were simultaneously formed by cutting. The contact surfaces provided with the grooves of the two metal members were each formed by grinding a grinding wheel with a surface grinder and polishing with a lapping machine. As a result of measuring the centerline surface roughness (Ra) and 10-point average roughness (Rz) after polishing by the following measuring method, the centerline average roughness (Ra) is 0.001 μm, 10-point average roughness ( Rz) was 0.007 μm.
(Measurement method of surface roughness)
Using a non-contact type surface shape roughness measuring machine (Ametech Co., Ltd., Talysurf CCI3000 [trade name]), measuring the surface irregularities at a measurement length of 0.35 mm (twice), and the average value of the measurement results The center line average roughness (Ra) and 10-point average roughness (Rz) are obtained from the above.

  Next, the above two metal members were heat-treated at 600 ° C. for 10 hours so that the surface on which the groove was formed was exposed to the air. The result of observing the state of the contact surface of the metal material after the heat treatment with a microscope described in the following SEM-EDX measurement section is shown in FIG. FIG. 8A is an optical microscope image, in which a secondary electron image of a region surrounded by the square is (b) and a reflected electron image is (c). In addition, ESCA measurement and SEM-EDX measurement were performed under the following conditions. The results of the metal composition on the contact surface of the metal material based on these measurement results are collectively shown in Table 1 below. Moreover, the characteristic X-ray spectrum obtained by SEM-EDX measurement is shown in FIG. 9, and the measurement positions (spots 1 to 3) shown in FIG. 8 are enclosed in squares in FIGS. 8B and 8C. It is indicated by a number. In the following Examples and Comparative Examples, microscopic observation and analytical instrument measurement were performed in the same manner as described above.

(ESCA measurement conditions)
Device: PHI Quantera SXM (ULVAC-PHI) [trade name]
X-ray source: Monochromatic Al Kα (25 W, 15 kV)
Pass Energy: 112eV Step: 0.2eV
Measurement angle: 45 °
Measurement area: 500 × 500 μm

(SEM-EDX measurement conditions)
SEM equipment: S4300SE / N [trade name]
EDX equipment: HORIBA EMAX ENERGY [product name]
Acceleration voltage: 15 kV
X-ray extraction angle: 30 ° X-ray acquisition time: 60 sec

  Thereafter, the metal member is brought into contact with each other so that the fine grooves are opposed to each other, the reactor main body is assembled, and a support member (manufactured by SUS430, vertical x horizontal x length: 5 mm is provided on the opposite side of the groove). X 15 mm x 115 mm). What sandwiched this reactor main body with the support plate was inserted in the insertion hole of the housing | casing (The product made from SUS430, length x width x length: 60 mm x 75 mm x 115 mm). At this time, the insertion hole of the housing had a cross section having the same shape as that of the combination of the reactor main body and the support plate, and these were fixed without gaps in the hole.

  Further, the same number of screws are screwed into the twelve screw holes on the upper surface of the casing, and tightened until the tip of the screw comes into contact with the support plate of the reactor body. The tightening torque per screw is 30 N · m. The reactor body was fixed inside the housing. Next, the joint 4 was screwed into screw holes m1 and m2 formed by facing the threads of two or more metal member ends in the reactor main body, and the pipe 5 was connected to the reactor main body.

<Method for measuring the tightness of the reactor>
Since the pressure of the steam reforming reaction is almost normal pressure, the target value of the channel airtightness in the reactor at 600 ° C. is set to 0.3 MPa by pressurizing the inside of the channel using nitrogen gas, and then The venting stopper was fully closed, and the rate of pressure drop at 0.5 hour was set to 5% or less. In order to perform these airtightness measuring methods, each device was connected as shown in FIG. The nitrogen gas is vented from the nitrogen gas main plug 15 through the valve 16a, the primary pressure regulating valve 17a, the secondary pressure regulating valve 17b, and the valve 16b, and branched at the T-shaped joint 18, one of which is the reactor 10 and the valve 16c. One flowed to the pressure gauge 19 after branching, and the voltage value measured by the pressure gauge was converted by the data collection system 20 and monitored by the personal computer 21. In addition, the stainless steel pipe was used for each connection method of nitrogen gas, and each pipe and each apparatus were connected with the tube joint.

<Method of heating reactor (600 ° C.)>
In order to heat the reactor 10 to the temperature used in the steam reforming reaction, a part of the pipe connected to the reactor 10 was installed in the electric furnace 22 and the temperature in the electric furnace was raised to 600 ° C.

<Airtight test at 600 ° C heating>
After the reactor 2 reached 600 ° C., all valves were opened and nitrogen gas was passed to replace the gas in the flow path and the pipe. Thereafter, the valve 16c is closed, the nitrogen gas pressure is adjusted to 0.3 MPa by the secondary pressure adjusting valve 17b, the valves 16a and 16b are closed, the data collection system is operated, and the pressure value in the reaction channel is reduced to 0.5. Measurements were taken over time. As a result, it was confirmed that the leakage rate was 0.96%, which was a target leakage rate of 5% or less. The results of the leakage rate are shown in Table 2.

<Decomposability after heating at 600 ° C>
Since the reaction time of the steam reforming reaction is scheduled to be 10 hours, after completion of the above airtightness test, 9.5 hours was continuously maintained, and heating was continued at 600 ° C. for a total of 10 hours. Thereafter, the reactor 2 was returned to room temperature (28 ° C.), taken out from the electric furnace 22, and then decomposed in the atmosphere. Disassembly was the reverse of the procedure for assembling the apparatus described above. The reactor main body and the support plate were taken out from the housing, the support plate was removed therefrom, and the metal member was pulled away on the contact surface and separated. At this time, the two metal members were not fused at the contact surfaces at all, and could be quickly separated without applying any force.

  As a result, according to the present invention, in the reaction apparatus in which two or more metal members are brought into contact with each other at the contact surface and a flow path is provided there, while maintaining sufficient airtightness at the contact surface in the heating flow reaction, Moreover, it is predicted that the metal member can be easily divided by preventing fusion at the corresponding contact surface. In addition, it is predicted that the product on the inner surface of the flow channel after the division can be easily confirmed regardless of a special instrument or a detour operation, and can be quickly maintained and reused.

(Example 2)
Measurement with an analytical instrument was performed in the same manner as in Example 1 except that the heat treatment as a fusion prevention treatment was performed for 1 hour. As a result, it was confirmed that more oxide films were formed by performing heat treatment than in the comparative example. The SEM-EDX measurement is shown in FIGS. 10 and 11, and the results of surface elemental analysis by ESCA are shown in Table 1.

(Example 3)
Analysis was performed in the same manner as in Example 2 except that SUS430 was used as a base material, electroless nickel-phosphorus plating (Ni-P) was applied to the surface, and heat treatment was performed for 10 hours as a fusion prevention treatment. Instrument measurements were taken. As a result, it was confirmed that more oxide films were formed by performing heat treatment than in the comparative example. The results of surface elemental analysis by ESCA are shown in Table 1.

(Comparative example)
Except that the heat treatment as a fusion prevention treatment was not performed, the reaction apparatus was prepared, the measurement with an analytical instrument, and the steam reforming reaction were performed in the same manner as in Example 1. As a result, in this comparative example, after completion of the reaction, the metal material was firmly fused on the contact surface, and an impact was applied with a hammer or the like, but it was impossible to divide. The SEM-EDX measurement of the contact surface of the metal material (only the polishing process is performed and the heat treatment is not performed) is shown in FIGS. 12 and 13, and the surface element analysis results by ESCA are shown in Table 1.

(Reference example)
A heat treatment as an anti-fusing treatment was carried out for 10 hours, a reactor was prepared in the same manner as in Example 1, and a gas tightness test at room temperature was conducted in the same manner as above except that the heating temperature was 28 ° C. It was. As a result, since there are many leaks at normal temperature compared with heating at 600 ° C., the reactor 2 using the material adopted in Example 1 had a self-pressurized structure due to material expansion at high temperature. The results of the leakage rate are shown in Table 2.

(Note) The result of SEM-EDX measurement is shown as the average value of each measurement point (spot). Further, the sum of oxygen (O) and nickel (Ni) is shown to be 100%, and other elements are not included. -Means not measured, 0 means the element was not detected.

(Note) The reaction apparatus is the same as that used in Example 1 after performing the reference example, and there are very few problems such as processing errors due to the manufacture of each apparatus.

DESCRIPTION OF SYMBOLS 1 Reactor body 2 Case 3 Screw 4 Joint 5 (5a, 5b) Pipe 6 Flow path 7 Anti-fusing treatment part (oxide film)
DESCRIPTION OF SYMBOLS 10 Reaction apparatus 11, 14 Support plate 12, 13 Metal member 15 Nitrogen gas main plugs 16a, 16b, 16c Valves 17a, 17b Pressure adjusting valve 18 T-shaped joint 19 Pressure gauge 20 Data collection system 21 Personal computer 22 Electric furnace

Claims (6)

A reaction apparatus in which two or more metal members are in contact with each other on their surfaces and inserted into the inside of the housing without any gap, and a reaction channel is formed on the surface with which the metal members are in contact. And, the contact surface is subjected to a fusion prevention treatment, and the reactor body is directly pressed by a plurality of screws through a support plate from a direction orthogonal to the contact surfaces of the two metal members, The casing has a thermal expansion coefficient smaller than the thermal expansion coefficient of the metal member, and the reactor body and the casing are pressurized with each other by the pressure generated by the thermal expansion when the reactor is heated, The reaction apparatus is separated at the contact surface of the metal member after the reaction apparatus is cooled . Reactor according to claim 1 the reaction is carried out under the conditions of heating the reaction channel. The reaction apparatus according to claim 1 or 2 , wherein the reaction is performed under a condition in which the inside of the reaction channel is pressurized. The reaction apparatus according to any one of claims 1 to 3 , wherein the reactor main body is insertable / removable. The reaction apparatus according to any one of claims 1 to 4 , wherein the contact surface of the metal member has airtightness in a contact portion other than the reaction flow path. The anti-blocking treatment, the reactor according to any one of claims 1, wherein it is a process for heating by exposing the contact surface of the metal member in an oxygen-containing atmosphere 5.