Catalytic reactor, method for obtaining a fluid product in said catalytic reactor, and method for producing said catalytic reactor

Abstract

To provide a pipe type catalytic reactor excellent in removal of a reaction heat such that an excessive temperature difference is not generated in a longitudinal direction.SOLUTION: A catalyst reactor has a mechanism comprising a multilayer-structured pipe made of a cylindrical porous layer 1 formed by laminating on a cylindrical nonporous layer 2 and its inside, and having a reaction pipe lumen 3 communicating from a fluid influx port to a fluid exit port side, and having a distribution in a thickness of the porous layer in a range from a fluid influx port side to a fluid exit port side, and a heat transmission medium pipe having a reaction pipe provided with a catalyst carried by the porous layer and a heat transmission medium pipe lumen communicating from a heat transmission medium influx port to a heat transmission medium exit port, and having a mechanism where at the fluid influx port, a liquid-like raw material flows into the reaction pipe lumen; in the reaction pipe lumen, the liquid-like raw material is caused to contact with a catalyst to cause a chemical reaction; and at the fluid exit port, a fluid mixture containing a fluid-like product flows out, and a mechanism in which the reaction pipe is inserted in the heat transmission medium pipe lumen and the heat transmission medium exchanges heat with a fluid in the reaction pipe lumen via a reaction pipe wall.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a catalytic reaction device. A method for obtaining a fluid product in said catalytic reactor, and a method for producing said catalytic reactor About 。 [Background technology]

[0002] Various proposals have been made for catalytic reaction apparatuses for producing fluid products. For example, Patent Document 1 discloses a catalytic gas phase reaction method in which a columnar catalyst for catalytic gas phase reaction is packed in a reaction tube, the columnar catalyst is characterized in that the longitudinal length of the catalyst is longer than the inner diameter of the reaction tube and has at least one through hole in the longitudinal direction, and the columnar catalyst is placed at the inlet end of the catalyst layer in the reaction tube, and then a granular catalyst having a different shape from the catalyst is packed around and / or behind the catalyst to carry out a reaction.

[0003] Patent Document 2 discloses a catalytic reactor for a gas phase reaction containing a cylindrically molded catalytic reaction tube, characterized in that the cylindrically molded catalytic reaction tube is provided with a gradient of catalytic activity in the direction from the inlet to the outlet of the raw material gas of the catalytic reactor.

[0004] Patent Document 3 discloses a hybrid porous pipe having an inner porous alloy sprayed film and a porous ceramic sprayed film laminated on the inner porous alloy sprayed film.

[0005] Patent Document 4 discloses a honeycomb monolith reforming catalyst that produces a hydrogen-containing reformed gas using hydrocarbons, molecular oxygen, and water as raw materials, and is characterized in that the porosity of the catalyst increases from the raw material inlet to the reformed gas outlet.

[0006] Patent Document 5 discloses an exhaust gas treatment device having a pair of porous corrugated plates and porous flat plates carrying an exhaust gas purification catalyst as a basic unit, a molded body in which the corrugated ridgelines of the porous corrugated plates are stacked alternately at right angles, the side of the molded body perpendicular to the corrugated ridgelines is closed, and an inflow path and an outflow path for exhaust gas are formed between the porous corrugated plate and the porous flat plate via the porous flat plate, characterized in that the porosity of the porous corrugated plate is smaller than the porosity of the porous flat plate.

[0007] US Patent No. 5,993,336 discloses a method of reacting one or more reactants in a microchannel in the presence of a graded catalyst to form one or more products, where the graded catalyst appears to have a distribution of catalytically active material such that one or more reactants are exposed to a higher concentration of the catalytically active material in some regions of the catalyst than in other regions of the catalyst. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2017-209632 A [Patent Document 2] JP 2020-124665 A [Patent Document 3] JP 2007-329132 A [Patent Document 4] JP 2005-177624 A [Patent Document 5] JP 2006-198533 A [Patent Document 6] WO 2004 / 37418 A Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a tubular catalytic reaction device that is excellent in removing reaction heat so as to prevent an excessive temperature difference from occurring in the longitudinal direction. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention has been completed, which includes the following aspects.

[0011] [1] A reaction tube comprising a cylindrical non-porous layer and a cylindrical porous layer laminated on the inside thereof, having a fluid inlet and a fluid outlet, a reaction tube lumen communicating from the fluid inlet to the fluid outlet, and a thickness of the porous layer having a distribution in the range from the fluid inlet side to the fluid outlet side. Many Layered pipe and , many A catalyst supported on the porous layer. Multiple Reaction tube and, A reactor and Equipped with The reactor comprises: a heat transfer medium tube having a heat transfer medium inlet and a heat transfer medium outlet, the heat transfer medium tube having a heat transfer medium tube lumen communicating from the heat transfer medium inlet to the heat transfer medium outlet; A mechanism in which a fluid raw material flows into the inner cavity of the reaction tube at a fluid inlet, the fluid raw material is brought into contact with a catalyst in the inner cavity of the reaction tube to cause a chemical reaction, and a fluid mixture containing a fluid product obtained by the chemical reaction flows out from the inner cavity of the reaction tube at a fluid outlet. a mechanism in which a heat transfer medium flows into a heat transfer medium tube lumen at a heat transfer medium inlet and flows out of the first heat transfer medium tube lumen at a heat transfer medium outlet; The reaction tube is inserted into the inner cavity of the heat transfer medium tube, and the heat transfer medium in the inner cavity of the heat transfer medium tube exchanges heat with the inside of the reaction tube through the reaction tube wall. Has The plurality of reaction tubes have plate fins provided so as to protrude outward from the outer surface of the multi-layer structure tube, and adjacent reaction tubes are connected to each other via the plate fins arranged parallel to the longitudinal direction of the multi-layer structure tube. . [2] The porous layer according to [1], wherein the thickness of the porous layer is thicker on the fluid outlet side than on the fluid inlet side, or thicker on the fluid inlet side than on the fluid outlet side. Catalytic Reactor . [3] The method according to [1] or [2], wherein the sum of the thickness of the porous layer and the thickness of the non-porous layer is substantially constant in the range from the fluid inlet side to the fluid outlet side. Catalytic Reactor .

[0012] [4] Each of the multiple reaction tubes is Consists of two or more short reaction tubes, Each of the short reaction tubes is composed of a cylindrical non-porous layer and a cylindrical porous layer laminated on the inside of the non-porous layer, has a fluid inlet and a fluid outlet, and has a short reaction tube lumen communicating from the fluid inlet to the fluid outlet. The multi-layer structure tube is provided with a catalyst supported on the porous layer, The fluid outlet of one reaction tube is connected in series to the fluid inlet of another reaction tube such that the lumen of each reaction tube is in communication with the lumen of the other reaction tube; The thickness of the porous layer of one reaction short tube is substantially different from the thickness of the porous layer of another reaction short tube; The catalytic reaction apparatus according to any one of [1] to [3]. . [5] The method according to any one of [1] to [4], further comprising a plate-shaped porous layer provided in a convex manner from the inner surface of the cylindrical porous layer toward the inner cavity of the reaction tube (or the inner cavity of the short reaction tube). Catalytic Reactor .

[0015] [ 6 〕 One of [1] to [5] In the catalytic reaction apparatus described in Supplying a fluid feedstock into a reactor tube lumen at a fluid inlet; supplying a heat transfer medium to the inner lumen of the heat transfer medium tube at the heat transfer medium inlet, causing the heat transfer medium to flow through the inner lumen of the heat transfer medium tube, and discharging the heat transfer medium from the inner lumen of the heat transfer medium tube at the heat transfer medium outlet, thereby controlling the temperature of the contents in the inner lumen of the reaction tube and carrying out a chemical reaction; Discharging a fluid mixture containing a fluid product obtained by said chemical reaction from the reaction tube lumen at a fluid outlet. Including, A method for obtaining a fluid product.

[0016] [ 7 The fluid raw material contains hydrogen and carbon dioxide, and the fluid product contains carbon monoxide, methanol or methane. 6 〕 The method described in

[0017] [ 8 a multilayer structure plate comprising an annular non-porous layer and an annular porous layer laminated inside the non-porous layer, is formed by irradiating and sintering the spread material powder with a laser or an electron beam so that irradiation of the portion corresponding to the non-porous layer is stronger than irradiation of the portion corresponding to the porous layer, and the multilayer structure tube is obtained, which comprises a cylindrical non-porous layer and a cylindrical porous layer laminated inside the non-porous layer, has a fluid inlet and a fluid outlet, and has a reaction tube lumen communicating from the fluid inlet to the fluid outlet; The method includes supporting a catalyst on a porous layer. The method according to any one of [1] to [5]. Catalytic Reactor Manufacturing method. Effect of the Invention

[0018] In a reaction tube packed with a granular catalyst, the granular catalyst has a lower thermal conductivity than the tube wall, so the efficiency of heat transfer from the granular catalyst located far from the tube wall is low. Also, it is not easy to pack the granular catalyst into a tube with a small inner diameter. On the other hand, the reaction tube of the present invention is excellent in heat removal because the reaction heat can be directly transferred to the non-porous layer laminated on the catalyst-loaded porous layer, and excessive temperature differences (hot spots) are unlikely to occur in the longitudinal direction. In addition, the temperature distribution caused by the chemical reaction can be estimated from the relationship between the target chemical reaction rate and the space velocity, and the thickness of the porous layer in the part that is likely to become high temperature in the estimated temperature distribution can be reduced, thereby reducing the amount of catalyst loaded in that part and suppressing the reaction rate in that part. As a result, it is possible to prevent problems such as catalyst deterioration in hot spots. According to the method for producing a reaction tube of the present invention, even in a tube having a small inner diameter in which it is difficult to pack a granular catalyst, a necessary and sufficient amount of catalyst for a chemical reaction can be easily and uniformly supported. According to the method for producing a reaction tube of the present invention, even if the tube wall is made thin and lightweight to enhance heat transfer, the pressure resistance can be sufficiently ensured. The catalytic reaction apparatus and catalytic reaction method of the present invention can uniformly control the temperature distribution within a predetermined range within a reaction tube, and can stably perform a chemical reaction of a fluid raw material in the presence of a catalyst at a desired pressure over a long period of time to obtain a fluid product. The present invention is 2 The present invention can be preferably used in a chemical reaction for producing methane gas and water by utilizing the above-mentioned reaction. [Brief description of the drawings]

[0019] [Figure 1] FIG. 1 is a cross-sectional view showing an example of a reaction tube of the present invention. [Diagram 2] FIG. 2 is a vertical cross-sectional view of the reaction tube shown in FIG. [Diagram 3] FIG. 2 is a vertical cross-sectional view showing another example of the reaction tube of the present invention. [Figure 4] FIG. 2 is a cross-sectional view showing another example of the reaction tube of the present invention. [Diagram 5] FIG. 2 is a cross-sectional view showing another example of the reaction tube of the present invention. [Figure 6] FIG. 1 is a vertical cross-sectional view showing an example of a reactor of the present invention. [Figure 7] FIG. 2 is a perspective view showing an example of the appearance of the inside of the reactor of the present invention (with the end plate removed). [Figure 8] FIG. 8 is a cross-sectional view of the reactor shown in FIG. [Figure 9] FIG. 1 is a diagram showing an example of a catalytic reaction device of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present invention will be described with reference to the drawings, but the present invention is not limited to the embodiments shown in the drawings.

[0021] The reaction tube of the present invention comprises a multi-layer structure tube and a catalyst.

[0022] The multilayer pipe is composed of a cylindrical non-porous layer 2 and a cylindrical porous layer 1 laminated on the inside thereof. The multilayer pipe has a fluid inlet and a fluid outlet, and has a reaction tube lumen 3 that communicates from the fluid inlet to the fluid outlet. The cross section of the multilayer pipe cut perpendicular to the longitudinal direction can be, for example, a circle, an oval, an ellipse, an oval, a rounded rectangle, a rectangle, etc., and is preferably a circle from the viewpoint of pressure resistance and weight reduction (see, for example, FIG. 1). The inner and outer diameters of the multilayer pipe can be appropriately designed according to the reaction scale, strength, pressure resistance, etc. The inner and outer diameters are values ​​(equivalent diameters) defined by 4A / L, where A is the area of ​​the part where the fluid flows in the cross section perpendicular to the longitudinal direction, and L is the circumferential length (wet perimeter length) where the fluid is in contact with the pipe. The fluid is a liquid, a gas, or a gas-liquid mixture, and is preferably a gas.

[0023] The porous layer is a layer with a structure having many pores. The porous layer preferably has pores (communicating holes) through which a fluid can pass from one side to the other. The porous layer does not need to have all communicating holes, and may have dead-end pores as long as it has a pore volume that allows the fluid to enter. Since the porous layer is a part that serves as a catalyst carrier, it can be appropriately selected from metals, ceramics, etc. depending on the chemical reaction to be carried out in the reaction tube. From the viewpoint of thermal conductivity, the porous layer is preferably made of metal.

[0024] The thickness of the porous layer is distributed in the range from the fluid inlet side to the fluid outlet side. The thickness distribution is preferably, for example, estimated from the relationship between the target chemical reaction rate and the spatial velocity, and the thickness of the porous layer in the part that is likely to become high temperature in the estimated temperature distribution is made thin. More specifically, in a reaction in which the fluid outlet side is more likely to become high temperature than the fluid inlet side, the thickness is made thicker on the fluid inlet side than on the fluid outlet side. Conversely, in a reaction in which the fluid inlet side is more likely to become high temperature than the fluid outlet side, the thickness is made thicker on the fluid outlet side than on the fluid inlet side. The thickness distribution of the porous layer may be a distribution that changes continuously or may be a distribution that changes stepwise. The thickness range of the porous layer is not particularly limited, but is, for example, 0.1 to 2.0 mm.

[0025] The relative density, porosity, open porosity, effective porosity, pore size distribution, etc. of the porous layer can be appropriately set according to the chemical reaction carried out in the reaction tube. For example, the relative density of the porous layer is preferably 20% to 80%. The relative density (density index) is defined by the following formula. Relative density [%] = apparent density / true density x 100 The true density is the density when only the volume occupied by the solid itself is used as the volume for density calculation, and can be calculated by using the density of the metal bulk as the true density or based on the pycnometer method. The apparent density is the density when the volume of the solid itself and internal voids are used as the volume, and can be calculated based on the Archimedes method. The bulk density is the density when the volume of the solid itself, pores, and internal voids are used as the volume, and can be calculated based on a dimensional method using a vernier caliper or micrometer.

[0026] The non-porous layer is a layer having a dense or dense structure that does not substantially have any through holes. The non-porous layer substantially blocks fluids and prevents the fluids from leaking out. The non-porous layer may have voids (internal voids) enclosed within the layer as long as the effects of the present invention are achieved. For example, the non-porous layer preferably has a relative density of 99% or more, most preferably 100%. The non-porous layer can be appropriately selected from those made of metals, ceramics, and the like. From the viewpoint of thermal conductivity, the non-porous layer is preferably made of metal. The thickness of the non-porous layer is not particularly limited, but may be, for example, 0.1 to 2.0 mm. The thickness of the non-porous layer may have a distribution. For example, the sum of the thickness of the porous layer and the thickness of the non-porous layer may be substantially constant in the range from the fluid inlet side to the fluid outlet side. From the standpoint of thermal expansion, the porous layer and the non-porous layer are preferably made of the same material.

[0027] The transition of the ratio of pores from the porous layer to the non-porous layer may be stepwise or gradational, and the ratio of the thickness of the porous layer to the thickness of the non-porous layer is preferably 1 / 50 to 50 / 1, more preferably 1 / 30 to 10 / 1, and further preferably 1 / 10 to 2 / 1.

[0028] The catalyst is supported on the porous layer. The catalyst can be appropriately selected depending on the chemical reaction to be carried out in the reaction tube. For example, in the methanation reaction of carbon dioxide or carbon monoxide, Ni-based catalysts, platinum group metal-based catalysts, other noble metal-based catalysts, etc. can be used. Specific examples of methanation catalysts include nickel aluminate (NiAl x O y ), Ru / NiAl x O y , Ru / Al 2 O 3 , Ru / TiO 2 , Ni / TiO 2 , Ru-Ni / TiO 2 Examples of CO selective oxidation catalysts include Ru / Al 2 O 3 , Ru / C, Rh porphyrin / C, Co x -Fe 2 O, Co 3 O 4 , Cu / CeO 2 -ZrO 2 , Ni / CeO 2 -ZrO 2 , Co / CeO 2 -ZrO 2 , Fe / CeO 2 -ZrO 2 , Pt / Al 2 O 3 , CuMn 2 O 4 , CuZnO, Pt / SiO 2 ,Pd / Al 2 O 3 , Pt / SnO 2 , Pd / CeO 2 , Pt / TiO 2 , PdCl 2 -CuCl 2 / C, Au / TiO 2 , Au / Fe 2 O 3 Some examples include:

[0029] The method of supporting the catalyst on the porous layer is not particularly limited. For example, the catalyst can be supported by contacting an aqueous solution or dispersion of the components constituting the catalyst (catalyst components) with the porous layer. The aqueous solution or dispersion of the catalyst components can be contacted with the porous layer by a method of immersing a reaction tube equipped with a porous layer in the aqueous solution or dispersion of the catalyst components, a method of passing the aqueous solution or dispersion of the catalyst components through a reaction tube equipped with a porous layer, or the like. After contact, a heat treatment (e.g., drying, calcination, etc.) can be performed as necessary.

[0030] Another embodiment of the reaction tube of the present invention further comprises a plate-shaped porous layer 4 provided in a convex manner from the inner surface of the cylindrical porous layer toward the lumen of the reaction tube (e.g., FIG. 4). The shape of the plate-shaped porous layer is not particularly limited. For example, in another embodiment of the reaction tube of the present invention, the plate-shaped porous layer 5 has a cross shape (e.g., FIG. 5). In another embodiment of the reaction tube of the present invention, the plate-shaped porous layer has a spiral shape. The plate-shaped porous layer contributes to controlling the flow of fluid, increasing the amount of catalyst supported, and increasing the contact area between the fluid and the porous layer.

[0031] Another embodiment of the reaction tube of the present invention further comprises plate fins 11 provided so as to protrude outward from the outer surface of the multi-layer structure tube. The plate fins may be provided so that the plate surfaces are parallel to the longitudinal direction of the multi-layer structure tube, or so that the plate surfaces are spiral, or so that the plate surfaces are non-parallel (for example, perpendicular) to the longitudinal direction of the multi-layer structure tube.

[0032] In another embodiment of the reaction tube of the present invention, the end of a plate fin provided in a convex shape from the outer surface of the multilayer tube toward the outside is connected to the outer surface of another adjacent multilayer tube. For example, as shown in FIG. 8, a plate fin 11 is provided so that the plate surface is parallel to the longitudinal direction of the multilayer tube (reaction tube 10), and the end of the plate fin 11 is connected to the outer surface of the adjacent multilayer tube (reaction tube 10). This makes it possible to suppress the vibration of the reaction tube, control the flow of the heat transfer medium, and promote the release of reaction heat. The mode of connection by the plate fin 11 is not particularly limited, and may be concentric as shown in FIG. 8, radial, or lattice. When the reaction tube 10 is adjacent to the inner surface of the heat transfer medium tube 12, the ends of the plate fins provided in a convex shape from the outer surface of the multi-layer structure tube (reaction tube 10) toward the outside may be connected to the inner surface of the heat transfer medium tube. From the viewpoint of thermal expansion, the plate fins are preferably made of the same material as the reaction tube.

[0033] The plate fins may be plate-shaped without holes or may be plate-shaped with holes. Plate-shaped fins with holes can contribute to controlling the flow of the heat transfer medium, reducing dead space, and increasing the contact area with the heat transfer medium by the holes. The holes are not limited to elliptical and may be of various shapes, and may be provided in appropriate locations depending on the purpose. Furthermore, the plate fins may be made of a non-porous material or may be made of a porous material.

[0034] The catalytic reaction apparatus or gas-phase catalytic reaction apparatus of the present invention comprises a reactor containing the reaction tube of the present invention and a heat transfer medium tube.

[0035] One embodiment of the reactor used in the present invention preferably has a plurality of reaction tubes. Each reaction tube is preferably arranged so that its longitudinal direction is parallel to the longitudinal direction of the heat transfer medium tube. In addition, each reaction tube may be connected to another adjacent reaction tube via a plate fin. All of the plurality of reaction tubes may be the reaction tube of the present invention, or a part of them may be the reaction tube of the present invention, but it is preferable that all of them are the reaction tube of the present invention.

[0036] The heat transfer medium pipe 12 is a pipe having a heat transfer medium inlet 16 and a heat transfer medium outlet 17, and a heat transfer medium pipe lumen 13 that communicates from the heat transfer medium inlet to the heat transfer medium outlet. A surface of the heat transfer medium pipe cut perpendicular to the longitudinal direction can be, for example, a circle, an oval, an ellipse, an oval, a rounded rectangle, a rectangle, etc. From the viewpoints of pressure resistance and weight reduction, a circle is preferable.

[0037] The reactor used in the present invention has a mechanism in which a fluid raw material flows into the reaction tube lumen at a fluid inlet, the fluid raw material is brought into contact with a catalyst in the reaction tube lumen to cause a chemical reaction, and a fluid mixture containing a fluid product obtained by the chemical reaction flows out from the reaction tube lumen at a fluid outlet, and a heat transfer medium flows into the heat transfer medium tube lumen at a heat transfer medium inlet, and flows out from the first heat transfer medium tube lumen at a heat transfer medium outlet, and the reaction tube is inserted into the heat transfer medium tube lumen, and the heat transfer medium in the heat transfer medium tube lumen exchanges heat with the heat transfer medium in the reaction tube lumen via the reaction tube wall.

[0038] The fluid inlet 10a is differentiated from the heat transfer medium inlet 16 or the heat transfer medium outlet 17, and the fluid raw material flows into the inner cavity of the reaction tube at the fluid inlet. The fluid inlet and the heat transfer medium inlet or the heat transfer medium outlet can be differentiated, for example, by a plate 25 that holds the end of the reaction tube on the fluid inlet side.

[0039] Upstream of the reactor, a device for preparing the fluid raw material, such as a mixing mechanism for mixing the components constituting the fluid raw material in a predetermined ratio, a tank for storing the components constituting the fluid raw material, a compressor 31, a heat exchanger 32, etc., can be installed. When the raw material is in a liquid state such as liquefied carbon dioxide, a vaporizer 34 or the like can be provided to safely vaporize it. The components constituting the fluid raw material can be appropriately selected depending on the chemical reaction to be performed in the reactor. For example, the fluid raw material used in the methanation reaction of carbon dioxide contains at least hydrogen gas and carbon dioxide gas. The inflow amount of the fluid raw material into the reaction tube lumen can be appropriately set depending on the chemical reaction to be performed in the reactor.

[0040] The heat transfer medium flows into the heat transfer medium tube lumen 13 at the heat transfer medium inlet. The heat transfer medium is not particularly limited as long as it does not change in quality and maintains its fluidity in the temperature range for performing the desired chemical reaction. Specific examples of the heat transfer medium include polyhydric alcohols such as glycerin and polyglycol; phenols and phenolic ethers such as anisole, diphenyl ether, and phenol; polyphenyls such as terphenyls, chlorinated benzenes and polyphenyls such as o-dichlorobenzene and polychloropolyphenyls; silicate esters such as tetraallyl silicate; fractionated tar and petroleum such as naphthalene derivatives and mineral oil; nitrates and nitrites (heat transfer salts) such as sodium nitrate, sodium nitrite, and potassium nitrate; silicones; fluorine compounds; glycols; molten metals and alloys such as Na metal, K metal, Pb metal, Pb-Bi eutectic mixture, and Na-K alloy; and the like. The pressure of the heat transfer medium flowing through the heat transfer medium tube lumen 13 and the pressure of the heat transfer medium flowing through the reaction tube lumen 3 are not particularly limited, but in order to reduce the thickness of the non-porous layer from the viewpoint of heat transfer, it is preferable that the difference between the two pressures is less than the pressure resistance strength of the non-porous layer.

[0041] The heat transfer medium inlet and the heat transfer medium outlet are not particularly limited in their arrangement, but are preferably arranged so that the heat transfer medium can easily flow in a direction perpendicular to the longitudinal direction of the reaction tube. Partition plates can be provided alternately on the left and right sides of the inner surface of the heat transfer medium tube to cause the flow of the heat transfer medium to meander. Also, partition plates can be provided in a spiral shape along the inner surface of the heat transfer medium tube to cause the flow of the heat transfer medium to rotate. The partition plate may have a hole through which the reaction tube can pass so as to hold the middle part of the reaction tube.

[0042] The fluid outlet 10b is differentiated from the heat transfer medium inlet 16 or the heat transfer medium outlet 17, and the fluid mixture including the fluid product flows out from the reaction tube lumen 3 at the fluid outlet. The fluid outlet and the heat transfer medium inlet or the heat transfer medium outlet can be differentiated, for example, by a plate 26 that holds the end of the reaction tube on the fluid outlet side. The heat transfer medium flows out from the heat transfer medium lumen at the heat transfer medium outlet. The flowed out heat transfer medium can be recycled.

[0043] The fluid mixture flowing out from the fluid outlet may contain, in addition to the fluid product, unreacted fluid raw material, fluid by-products, etc. For example, the fluid product obtained in the methanation reaction of carbon dioxide is methane, and the fluid by-product is water.

[0044] The reaction tube 10 is inserted into the heat transfer medium tube lumen 13, and the heat transfer medium in the heat transfer medium tube lumen can exchange heat with the fluid in the reaction tube lumen 3 through the non-porous layer and the porous layer of the reaction tube. From the viewpoint of heat exchange efficiency, the reaction tube preferably has a plate-shaped porous layer protruding inward from the inner surface of the reaction tube wall. In addition, the reaction tube preferably has plate fins protruding outward from the outer surface of the reaction tube wall.

[0045] Generally, in a tubular reactor, the temperature distribution in the flow direction of the reaction tube is easily non-uniform. In a chemical reaction that generates a large amount of heat, hot spots may occur. It is desirable to suppress the occurrence of hot spots and to make the temperature distribution in the flow direction of the reaction tube uniform. The heat transfer medium inlet can be located near the part where hot spots may occur, or the heat transfer medium tube lumen can be divided by a partition plate, and a heat transfer medium inlet and a heat transfer medium outlet can be provided for each division, so that the temperature of each heat transfer medium flowing through the divided heat transfer medium tube lumen can be relatively lower on the side closer to the part where hot spots may occur. In addition, by providing more plate fins near the part where hot spots may occur and increasing the amount of heat transfer in that part, the temperature distribution in the flow direction of the reaction tube can be made uniform. The plate fins may be provided only in the part of the catalyst area that is closer to the fluid inlet, or only in the part of the catalyst area that is closer to the fluid outlet, or may be provided throughout the entire catalyst area.

[0046] The catalytic reaction apparatus or gas-phase catalytic reaction apparatus of the present invention is not particularly limited by its manufacturing method. For example, it can be manufactured by preparing a reaction tube, a heat transfer medium tube, and accessories, and assembling them by welding, screwing, or the like.

[0047] Reaction tubes, heat transfer medium tubes, accessories, or reactors having complex shapes can be manufactured by a method that includes forming a three-dimensional object by stacking the cross-sectional shapes based on their 3D data.

[0048] The 3D data may be 3D shape data of a target part. The 3D shape data may be designed using 3D CAD. The 3D data may be, for example, STL (Stereolithography) data obtained by converting the 3D shape data. STL data represents a three-dimensional solid shape as a collection of small triangles (polygons).

[0049] The formation (shaping) of a three-dimensional object by laminating a cross-sectional shape can be performed by the powder bed fusion (PBF) method, the metal deposition method, the fluid extrusion deposition modeling (FDM) method, the liquid metal inkjet method, the binder jet method, a hybrid method in which cutting is performed during lamination modeling by PBF, etc. Of these, the powder bed fusion (PBF) method or the metal deposition method is preferred.

[0050] Powder bed fusion is a method in which material powder is spread out and the part to be shaped is melted and solidified using a laser or electron beam as a heat source. The material powder is spread out and the melting and solidification are repeated to create a shape. After the modeling is complete, the unsolidified powder is removed to extract the model.

[0051] The powder bed fusion method includes a laser beam heat source method and an electron beam heat source method.

[0052] The powder bed laser beam heat source method uses a laser beam to irradiate a spread-out material powder, melting and solidifying it or sintering it to create layered shapes. The laser beam heat source method usually involves melting and solidifying the material in an inert atmosphere such as nitrogen. The laser beam heat source method uses a mirror angle to change the position when irradiating the laser.

[0053] The powder bed / electron beam heat source method converts kinetic energy into heat by irradiating and colliding an electron beam on a spread-out material powder in a high vacuum, melting and solidifying the powder. The electron beam heat source method usually melts and solidifies the powder in a vacuum. The electron beam heat source method changes the direction of the electron beam using a lens with a magnetic field. As a result, the electron beam heat source method allows for high-speed positioning.

[0054] The metal deposition method is a method of forming objects by layering and solidifying molten metal material in a specified location. The metal deposition method does not require the removal of powder after forming is completed.

[0055] Metal deposition methods include a laser beam heat source method using metal powder as the material, and an arc discharge method using alloy wire as the material.

[0056] The metal deposition laser beam heat source method sprays metal powder from a nozzle and simultaneously irradiates it with laser light to supply the metal powder to a molten pool, where it solidifies and forms a shape. A three-dimensional shape is drawn by moving the melting nozzle or stage. By switching the metal powder supply path, dissimilar metals can be formed. The large laser output makes it suitable for high-speed forming.

[0057] The metal deposition arc discharge method melts a metal wire by arc discharge at the tip of the metal wire and layers it to create a shape. The cost of the equipment and materials is relatively low, and high speed modeling is possible.

[0058] After shaping, the product can be heat-treated to relieve stress, improve strength, etc. The conditions for the heat treatment, such as temperature, time, and atmosphere, can be appropriately set depending on the metal material used, etc.

[0059] A specific embodiment of the method for producing a reaction tube of the present invention includes irradiating and sintering a spread material powder with a laser or an electron beam so that the irradiation of the portion corresponding to the non-porous layer is stronger than the irradiation of the portion corresponding to the porous layer, thereby forming a multilayer structure plate consisting of a ring-shaped non-porous layer and a ring-shaped porous layer laminated inside the ring-shaped non-porous layer, and repeating this process to obtain a multilayer structure tube consisting of a cylindrical non-porous layer and a cylindrical porous layer laminated inside the cylindrical non-porous layer, having a fluid inlet and a fluid outlet, and having a reaction tube lumen communicating from the fluid inlet to the fluid outlet, and supporting a catalyst on the porous layer. As the material powder, powder of a metal; powder of an inorganic compound such as an oxide, carbide, nitride, or boride, etc. can be used.

[0060] The method for obtaining a fluid product of the present invention includes, in the catalytic reaction apparatus of the present invention, supplying a fluid raw material to a reaction tube lumen at a fluid inlet, supplying a heat transfer medium to the heat transfer medium tube lumen at the heat transfer medium inlet, causing the heat transfer medium to flow into the heat transfer medium tube lumen and discharging it from the heat transfer medium tube lumen at a heat transfer medium outlet, thereby performing a chemical reaction while controlling the temperature of the contents in the reaction tube lumen, and discharging a fluid mixture containing the fluid product obtained by the chemical reaction from the reaction tube lumen at a fluid outlet.

[0061] In a method for producing CO (carbon monoxide), methanol or methane, the fluid raw material is CO 2 (carbon dioxide) and H 2 Uses gas containing hydrogen and CO 2 The reduction reaction is carried out. Inflow CO 2 and H 2 The amount of the gas containing the above gas can be appropriately set depending on the reaction rate, the volume of the reaction tube inner cavity, etc. CO 2 and H 2 Depending on the ratio of CO 2 The reduction reaction proceeds as follows: CO 2 + H 2 → CO + H 2 O CO 2 + 3H 2 → CH 3 OH + H 2 O CO 2 + 4H 2 → CH 4 + 2H 2 O

[0062] The catalytic reactor and the method for obtaining a fluid product of the present invention are 2 (carbon dioxide) and H 2It can also be preferably used for C1 chemical synthesis methods other than the method of producing CO (carbon monoxide), methanol or methane from a gas containing (hydrogen). Examples of C1 chemical synthesis methods include a method of producing carbon monoxide and hydrogen by reacting methane with water (water vapor), a method of producing carbon monoxide and hydrogen by reacting methane with carbon dioxide, a method of producing carbon dioxide and hydrogen by reacting carbon monoxide with water, a method of producing carbon dioxide and hydrogen by reacting methane with water, a method of producing methane and carbon dioxide by reacting carbon monoxide with hydrogen, a method of producing methanol by reacting carbon monoxide with hydrogen, a method of producing acetone and water by reacting carbon monoxide with hydrogen, and a method of producing carbon monoxide and hydrogen, ethylene and water, or methanol by reacting methane with oxygen.

[0063] In the present invention, CO 2 The products (CO (carbon monoxide), methanol or methane) obtained by the reduction reaction of and the unreacted substances (mainly CO 2 ) can be separated and purified. Examples of separation and purification methods include membrane separation, adsorption separation, absorption separation, distillation separation, and cryogenic separation. In the separation and purification of methane, the membrane separation method is preferred from the viewpoints of separation selectivity, separation speed, and inexpensive and compact equipment. Unreacted products (mainly CO 2 ) and low-concentration methane can be used as a fluid raw material in the above-mentioned methane production method. Carbon monoxide is toxic to the human body, so it is preferable to treat it so that the carbon monoxide concentration is 30 ppm or less. Methods for lowering the carbon monoxide concentration include, for example, converting carbon monoxide to methane by a CO methanation reaction, converting carbon monoxide to carbon dioxide by a CO selective oxidation reaction, and adsorbing or absorbing carbon dioxide using an adsorbent or absorbent.

[0064] Furthermore, methane obtained by separation and purification can be supplied as fuel to a gas turbine, which can generate electricity. The combustion exhaust gas from a gas turbine typically contains carbon dioxide and can be used as a fluid feedstock in the above-mentioned methane production process.

[0065] The present invention can be used in various chemical reactions. The present invention is useful in utilizing hydrogen produced by electrolysis of water, utilizing carbon dioxide produced by human or animal respiration or by combustion of fuel, producing water, or producing methane as a fuel. The present invention can also be used in space stations, spacecraft, rockets, etc.

[0066] The present invention can be applied to various chemical engineering devices such as instrumentation, pipes, tanks, towers, etc., so long as they have the above-mentioned characteristics. Furthermore, those skilled in the art will understand that modifications, substitutions, additions, and omissions are also included within the scope of the present invention, provided they do not deviate from the gist of the present invention. [Explanation of symbols]

[0067] 1: Cylindrical porous layer 2: Cylindrical non-porous layer 3: Reaction tube inner cavity 4, 5, 6: Plate-shaped porous layer 10: Reaction tube 10a: Reactor fluid inlet 10b: Reactor tube fluid outlet 11: Plate fin 12: Heat transfer medium tube 16: Heat transfer medium inlet 17: Heat transfer medium outlet 13: Heat transfer medium tube bore 20: Reactor 9a: Reactor fluid inlet 9b: Reactor fluid outlet 25:Fluid inlet side retaining plate 26:Fluid outlet side retaining plate 30: Catalytic reactor 31: Compressor 32: Heat exchanger 34: Carburetor 35: Heat exchanger 38: Gas-liquid separator 21:Liquid outflow pipe 39: Gas outflow pipe

Claims

1. a multi-layer structure tube comprising a cylindrical non-porous layer and a cylindrical porous layer laminated on the inner side of the cylindrical non-porous layer, the multi-layer structure tube having a fluid inlet and a fluid outlet, a reaction tube lumen communicating from the fluid inlet to the fluid outlet, the porous layer having a thickness distribution in the range from the fluid inlet side to the fluid outlet side, and a catalyst supported on the porous layer; A reactor and Equipped with The reactor comprises: a heat transfer medium tube having a heat transfer medium inlet and a heat transfer medium outlet, the heat transfer medium tube having a heat transfer medium tube lumen communicating from the heat transfer medium inlet to the heat transfer medium outlet; A mechanism in which a fluid raw material flows into the inner cavity of the reaction tube at a fluid inlet, the fluid raw material is brought into contact with a catalyst in the inner cavity of the reaction tube to cause a chemical reaction, and a fluid mixture containing a fluid product obtained by the chemical reaction flows out from the inner cavity of the reaction tube at a fluid outlet. a mechanism in which a heat transfer medium flows into a heat transfer medium tube lumen at a heat transfer medium inlet and flows out of the first heat transfer medium tube lumen at a heat transfer medium outlet; The reaction tube is inserted into the inner cavity of the heat transfer medium tube, and the heat transfer medium in the inner cavity of the heat transfer medium tube exchanges heat with the inside of the reaction tube through the reaction tube wall. Has The plurality of reaction tubes have plate fins provided so as to protrude outward from the outer surface of the multi-layer structure tube, and adjacent reaction tubes are connected to each other via the plate fins arranged parallel to the longitudinal direction of the multi-layer structure tube.

2. 2. The catalytic reaction device according to claim 1, wherein the porous layer is thicker on the fluid outlet side than on the fluid inlet side, or thicker on the fluid inlet side than on the fluid outlet side.

3. 3. The catalytic reaction device according to claim 1, wherein the sum of the thickness of the porous layer and the thickness of the non-porous layer is substantially constant in the range from the fluid inlet side to the fluid outlet side.

4. Each of the plurality of reaction tubes comprises two or more short reaction tubes, Each of the short reaction tubes is composed of a cylindrical non-porous layer and a cylindrical porous layer laminated on the inside of the non-porous layer, has a fluid inlet and a fluid outlet, and has a short reaction tube lumen communicating from the fluid inlet to the fluid outlet. The multi-layer structure tube is provided with a catalyst supported on the porous layer, The fluid outlet of one reaction tube is connected in series to the fluid inlet of another reaction tube such that the lumen of each reaction tube is in communication with the lumen of the other reaction tube; 4. The catalytic reaction device according to claim 1, wherein the thickness of the porous layer of one short reaction tube is substantially different from the thickness of the porous layer of another short reaction tube.

5. 5. The catalytic reaction apparatus according to claim 1, further comprising a plate-shaped porous layer provided so as to protrude from the inner surface of the cylindrical porous layer toward the inner cavity of the reaction tube.

6. In the catalytic reaction device according to any one of claims 1 to 5, supplying a fluid feedstock into a reactor tube lumen at a fluid inlet; supplying a heat transfer medium to the inner lumen of the heat transfer medium tube at the heat transfer medium inlet, causing the heat transfer medium to flow through the inner lumen of the heat transfer medium tube, and discharging the heat transfer medium from the inner lumen of the heat transfer medium tube at the heat transfer medium outlet, thereby controlling the temperature of the contents in the inner lumen of the reaction tube and carrying out a chemical reaction; Discharging a fluid mixture containing a fluid product obtained by said chemical reaction from the reaction tube lumen at a fluid outlet. Including, A method for obtaining a fluid product.

7. 7. The method of claim 6, wherein the fluid feed comprises hydrogen and carbon dioxide and the fluid product comprises carbon monoxide, methanol or methane.

8. a multilayer structure tube is obtained which is made of a cylindrical non-porous layer and a cylindrical porous layer laminated on the inside thereof, has a fluid inlet and a fluid outlet, and has a reaction tube lumen communicating from the fluid inlet to the fluid outlet, by repeatedly irradiating the spread material powder with a laser or an electron beam so that irradiation of the portion corresponding to the non-porous layer is stronger than irradiation of the portion corresponding to the porous layer, thereby forming a multilayer structure plate consisting of an annular non-porous layer and an annular porous layer laminated on the inside thereof, and The method includes supporting a catalyst on a porous layer. A method for producing a catalytic reaction device according to any one of claims 1 to 5.

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