Apparatus and method for obtaining gaseous product

Abstract

To provide a new apparatus and method for chemically reacting a gaseous raw material in the presence of a catalyst to obtain a gaseous product.SOLUTION: An apparatus for obtaining a gaseous product is provided with a first reaction tube 110 having a first reaction tube inner cavity that communicates from a first gas inflow port to a first gas outflow port, and a first heat transfer medium tube having a first heat transfer medium tube inner cavity that communicates from a first heat transfer medium inflow port 19 to a heat transfer medium outflow port 20, has a catalyst placed in the first reaction tube inner cavity, and includes a second reactor 210 having the same mechanism as a first reactor, and a connecting tube that connects the first gas outflow port and a second gas inflow port to communicate the first reaction tube inner cavity and a second reaction tube inner cavity.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an apparatus for obtaining a gaseous product and a method for obtaining a gaseous product, and more particularly to an apparatus and a method for obtaining a gaseous product by chemically reacting a gaseous feedstock in the presence of a catalyst. [Background technology]

[0002] Various proposals have been made for devices and methods for obtaining gaseous products. For example, Patent Document 1 discloses a generation device including a reaction section that generates a product gas and generated water in which the product gas is dissolved by an exothermic reaction of gaseous reactants, a cooling tower that cools cooling water that removes heat generated by the exothermic reaction, a cooling water circulation system that circulates the cooling water between the reaction section and the cooling tower, and a mixing means that mixes the generated water generated in the reaction section into the cooling water circulation system.

[0003] Patent Document 2 discloses a multi-tube heat exchanger comprising a group of inner tubes (heat transfer tubes) through which a first fluid passes and an outer tube (body) through which a second fluid passes, the group of multiple heat transfer tubes being arranged with both ends held by inlet side and outlet side holding plates located on the first fluid inlet side and the first fluid outlet side, respectively, wherein plate-like or lump-like protrusions are formed at predetermined intervals (predetermined pitch) in the longitudinal direction on the wall surface of the flow passage of each of the heat transfer tubes.

[0004] Patent Document 3 discloses a single-shell open interstage reactor for producing acrylic acid from propylene, comprising, in order of process flow, a) a first shell-and-tube reaction stage including a plurality of reaction tubes, the reaction tubes of the first reaction stage including a first catalyst for oxidizing propylene to produce acrolein, b) an interstage heat exchanger, c) an open interstage region, and d) a second shell-and-tube reaction stage including a plurality of reaction tubes, the reaction tubes of the second reaction stage including a second catalyst for oxidizing acrolein to produce acrylic acid, the reaction tubes of the second reaction stage having a diameter of more than 22.3 mm.

[0005] Patent Document 4 discloses a honeycomb structure having a first fluid circulation section, which is partitioned by ceramic partition walls and penetrates in the axial direction from one end face to the other end face, and has a plurality of cells through which a heating body, which is a first fluid, flows; and a second fluid circulation section, which is partitioned by ceramic partition walls and penetrates in a direction perpendicular to the axial direction, is separated from the first fluid circulation section by the partition walls and is capable of thermal conduction, through which a second fluid flows, receives heat from the first fluid circulation section through the first fluid circulation section, and transmits the heat to a heated body, which is the second fluid, which flows. The cells on the first fluid circulation section side are smaller than the cells on the second fluid circulation section side, and the density of the partition walls is 0.5 to 5 g / cm. 3 The present invention discloses a ceramic heat exchanger comprising a heat exchange element in which the partition walls have a thermal conductivity of 10 to 300 W / mK, and a catalyst is supported on the wall surface of the first fluid circulation portion.

[0006] Patent Document 5 discloses a process for hydrocracking a Fischer-Tropsch synthesis product in a microchannel reactor comprising a plurality of process microchannels, the process microchannels comprising the steps of: flowing a gas containing hydrogen into a plurality of process microchannels at a superficial velocity of at least 0.01 meters per second; flowing a liquid containing a Fischer-Tropsch synthesis product into the plurality of process microchannels, the plurality of process microchannels comprising a hydrocracking catalyst, the liquid forming a film on at least a portion of the hydrogenation catalyst, the gas contacting the liquid, and reacting the hydrogen with the Fischer-Tropsch synthesis product in the presence of the hydrocracking catalyst to form a hydrocracked Fischer-Tropsch synthesis product, the hydrocracked Fischer-Tropsch synthesis product comprising one or more linear aliphatic hydrocarbons having five or more carbon atoms; and removing the hydrocracked Fischer-Tropsch synthesis product from the plurality of process microchannels, the heat being transferred from the plurality of process microchannels to a heat exchanger. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] WO2019 / 082538A1 [Patent Document 2] JP 2002-181468 A [Patent Document 3] JP 2018-111696 A [Patent Document 4] JP 2010-271031 A [Patent Document 5] JP 2017-48397 A [Patent Document 6] JP 2019-172595 A Summary of the Invention [Problem to be solved by the invention]

[0008] It is an object of the present invention to provide a new apparatus and method for chemically reacting a gaseous feedstock in the presence of a catalyst to obtain a gaseous product. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention has been completed, which includes the following aspects.

[0010] [1] A first reaction tube having a first gas inlet and a first gas outlet and a first reaction tube lumen communicating from the first gas inlet to the first gas outlet; a first heat transfer medium tube having a first heat transfer medium inlet and a first heat transfer medium outlet, the first heat transfer medium tube having a first heat transfer medium tube lumen communicating from the first heat transfer medium inlet to the first heat transfer medium outlet; The first reaction tube is A first catalyst made of a Ni-based catalyst, a platinum group metal-based catalyst, or other precious metal-based catalyst is placed in the lumen of the first reaction tube; and a mechanism for allowing a gaseous raw material containing carbon dioxide gas and hydrogen gas to flow into a first reaction tube lumen at a first gas inlet, bringing the gaseous raw material into contact with the first catalyst in the first reaction tube lumen to cause a first chemical reaction, and allowing a first gas mixture containing methane obtained by the first chemical reaction to flow out from the first reaction tube lumen at a first gas outlet; The first heat transfer medium tube is a mechanism for allowing the heat transfer medium to flow into the first heat transfer medium tube lumen at a first heat transfer medium inlet and out of the first heat transfer medium tube lumen at a first heat transfer medium outlet; and a first reactor having a mechanism in which a first reaction tube is inserted into a first heat transfer medium tube lumen, and a heat transfer medium in the first heat transfer medium tube lumen exchanges heat with a heat transfer medium in the first reaction tube lumen through a first reaction tube wall; a second reaction tube having a second gas inlet and a second gas outlet and a second reaction tube lumen communicating from the second gas inlet to the second gas outlet; a second heat transfer medium tube having a second heat transfer medium inlet and a second heat transfer medium outlet, the second heat transfer medium tube having a second heat transfer medium tube lumen communicating from the second heat transfer medium inlet to the second heat transfer medium outlet; The second reaction tube is a second catalyst is disposed in the second reactor bore; and a mechanism for allowing a first gas mixture to flow into a second reaction tube lumen at a second gas inlet, for contacting the first gas mixture with a second catalyst in the second reaction tube lumen to cause a second chemical reaction, and for allowing a second gas mixture containing a gaseous product obtained by the second chemical reaction to flow out of the second reaction tube lumen at a second gas outlet; The second heat transfer medium tube is a mechanism for allowing the heat transfer medium to flow into the second heat transfer medium tube lumen at a second heat transfer medium inlet and out of the second heat transfer medium tube lumen at a second heat transfer medium outlet; and a second reactor having a mechanism in which a second reaction tube is inserted into a second heat transfer medium tube bore, and a heat transfer medium in the second heat transfer medium tube bore exchanges heat with a heat transfer medium in the second reaction tube bore through a second reaction tube wall; a connecting tube connecting the first gas flow outlet and the second gas flow inlet to communicate the first reaction tube lumen with the second reaction tube lumen, and having a mechanism for removing by-products from the first gas mixture; 1. An apparatus for obtaining a gaseous product comprising:

[0011] [2] The apparatus for obtaining a gaseous product according to [1], wherein the average residence time in the first reaction tube is shorter than the average residence time in the second reaction tube.

[0012] [3] The apparatus for obtaining a gaseous product according to [1] or [2], wherein the connecting pipe removes water, which is a by-product, from the first gas mixture.

[0013] [4] The apparatus for obtaining a gaseous product according to any one of [1] to [3], wherein the first reaction tube has a heat transfer fin protruding inward from the inner surface of the reaction tube wall. [5] An apparatus for obtaining a gaseous product according to [4], wherein the heat transfer fins are provided only on the portion closer to the first gas inlet.

[0014] [6] The apparatus for obtaining a gaseous product according to any one of [1] to [5], wherein the radial cross section of the first reaction tube has a flat shape. [7] The apparatus for obtaining a gaseous product according to any one of [1] to [6], wherein the radial cross section of the second reaction tube has a flat shape. [8] The apparatus for obtaining a gaseous product according to [6], wherein there are a plurality of first reaction tubes, and the first reaction tubes are arranged so that the longitudinal directions of the first reaction tubes in the flattened shape of their radial cross sections are parallel to each other. [9] The apparatus for obtaining a gaseous product according to [7] or [8], wherein there are a plurality of second reaction tubes, and the second reaction tubes are arranged such that the longitudinal directions of the second reaction tubes in the flattened shape of their radial cross sections are parallel to each other.

[0015]

[10] An apparatus for obtaining a gaseous product according to any one of [1] to [9], supplying a gaseous source material comprising carbon dioxide gas and hydrogen gas into a lumen of a first reaction tube at a first gas inlet; supplying a heat transfer medium to the first heat transfer medium tube lumen at a first heat transfer medium inlet, flowing the heat transfer medium through the first heat transfer medium tube lumen, and discharging the heat transfer medium from the first heat transfer medium tube lumen at a first heat transfer medium outlet, thereby controlling the temperature of the contents within the first reaction tube lumen and conducting a first chemical reaction; Discharging a first gas mixture comprising methane resulting from said first chemical reaction from a first reaction tube lumen at a first gas outlet; supplying a first gas mixture into a second reactor tube lumen at a second gas inlet; providing a heat transfer medium to the second heat transfer medium tube lumen at a second heat transfer medium inlet, flowing through the second heat transfer medium tube lumen, and discharging the heat transfer medium from the second heat transfer medium tube lumen at a second heat transfer medium outlet, thereby controlling the temperature of the contents of the second reaction tube lumen while conducting a second chemical reaction; and discharging a second gas mixture from the second reaction tube lumen at a second gas outlet, the second gas mixture comprising gaseous products of said second chemical reaction; Including, A method for obtaining a gaseous product.

[0016]

[11] The method according to

[10] , wherein the gaseous product comprises methane.

[12] The method according to

[10] , wherein the gaseous product comprises methanol.

[13] The method according to

[10] , wherein the gaseous product comprises carbon monoxide, acetone or ethylene. Effect of the Invention

[0017] The apparatus and method for obtaining a gaseous product of the present invention can uniformly control the temperature distribution in the reaction tube within a predetermined range, and can prevent problems related to hot spots. The apparatus and method for obtaining a gaseous product of the present invention are preferably used in chemical reactions that generate methane gas and water using CO2. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a diagram showing an example of an apparatus for obtaining a gaseous product of the present invention. [Diagram 2] FIG. 2 is a diagram showing an example of the external appearance of first to fourth reactors. [Diagram 3] FIG. 2 is a view showing an AA cross section of an example of the first to fourth reactors. [Figure 4] FIG. 1 is a view showing a BB cross section of an example of a first reactor. [Diagram 5] FIG. 2 shows a radial cross section of an example of a first reactor. [Figure 6] FIG. 1 is a view showing a B-B cross section of an example of a second reactor. [Figure 7] FIG. 2 shows a radial cross section of an example of a second reactor. [Figure 8] FIG. 1 is a view showing a BB cross section of an example of the third to fourth reactors. [Figure 9] FIG. 4 is a view showing a radial cross section of an example of the third to fourth reactors. [Figure 10] FIG. 2 shows a radial cross section of another example of a reactor. [Figure 11] FIG. 2 shows a radial cross section of another example of a reactor. [Figure 12] FIG. 2 is a diagram showing an example of a reaction tube. [Figure 13] FIG. 13 is a view showing a CC cross section of the reaction tube shown in FIG. [Figure 14] FIG. 13 is a view showing a DD cross section of the reaction tube shown in FIG. [Figure 15] FIG. 13 is a view showing a CC cross section of another example of the reaction tube. [Figure 16] FIG. 13 is a view showing a CC cross section of another example of the reaction tube. [Figure 17] FIG. 13 is a view showing a CC cross section of another example of the reaction tube. [Figure 18] FIG. 13 is a view showing a CC cross section of another example of the reaction tube. [Figure 19] FIG. 13 is a view showing a CC cross section of another example of the reaction tube. [Figure 20] FIG. 13 is a view showing a CC cross section of another example of the reaction tube. [Figure 21] FIG. 2 is a diagram showing the appearance of another example of the main part of the apparatus for obtaining a gaseous product according to the present invention. [Figure 22] FIG. 22 is a diagram showing a longitudinal section of the device shown in FIG. 21. [Diagram 23] FIG. 22 shows another longitudinal section of the device shown in FIG. 21. [Figure 24] FIG. 2 is a vertical cross-sectional view of another example of a reactor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] 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.

[0020] The apparatus 1 for obtaining a gaseous product of the present invention includes a first reactor 110, a second reactor 210, and a connecting pipe. In the apparatus of the present invention, a third reactor 310 may be provided downstream of the second reactor via an additional connecting pipe, and a fourth reactor 410 may be provided downstream of the third reactor via an additional connecting pipe.

[0021] The first reactor 110 has a first reaction tube 112 and a first heat transfer medium tube 113 .

[0022] The first heat transfer medium tube 113 has a first heat transfer medium inlet 116 and a first heat transfer medium outlet 117, and has a first heat transfer medium tube lumen 124 that communicates from the first heat transfer medium inlet to the first heat transfer medium outlet. The radial cross section of the first heat transfer medium tube can be, for example, a circle, an oval, an ellipse, an oval, a rounded rectangle, a rectangle, or the like.

[0023] The first reaction tube 112 has a first gas inlet 104 and a first gas outlet 105, and a first reaction tube lumen 123 communicating from the first gas inlet to the first gas outlet. The radial cross section of the first reaction tube can be, for example, a circle, an egg, an ellipse, an oval, a rounded rectangle, a square, or the like, and is preferably a flat shape. The flat shape is preferably a rectangle (rectangle, rounded rectangle) or an oval (egg, oval, ellipse). The aspect ratio (longitudinal length / shortitudinal length) of the flat shape has a lower limit of preferably 1.2, more preferably 1.5, and even more preferably 2, and an upper limit of preferably 20, more preferably 10, and even more preferably 5. In the apparatus of the present invention, it is preferable that there are a plurality of first reaction tubes 112, and it is preferable that the first reaction tubes are arranged so that the longitudinal directions of the flat shapes of their radial cross sections are parallel to each other. Examples of the arrangement of the first reaction tubes include an arrangement in which the first reaction tubes are vertically and horizontally arranged in a plurality of rows in the inner cavity of the first heat transfer medium tube having a rounded rectangular cross section as shown in Figs. 5, 7 and 9, an arrangement in which the first reaction tubes are vertically arranged in a single row in the inner cavity of the first heat transfer medium tube having a rounded rectangular cross section as shown in Fig. 10, and an arrangement in which the first reaction tubes are arranged in the inner cavity of the first heat transfer medium tube having a circular cross section as shown in Fig. 11.

[0024] The first gas inlet 104 is distinguished from a first heat transfer medium inlet 116 or a first heat transfer medium outlet 117, and the gaseous raw material flows into the inner cavity of the first reaction tube at the first gas inlet. The first gas inlet and the first heat transfer medium inlet or the first heat transfer medium outlet can be distinguished, for example, by a plate 25 that holds the end of the first reaction tube on the gas inlet side.

[0025] Upstream of the first reactor, a device for preparing the gaseous raw material, such as a mixing mechanism for mixing the components constituting the gaseous raw material in a predetermined ratio, a tank for storing the components constituting the gaseous raw material, a compressor 11, a heat exchanger 22, etc., can be installed. When the raw material is in a liquid state such as liquefied carbon dioxide, an evaporator 14 or the like can be provided to safely vaporize it. The components constituting the gaseous raw material include at least hydrogen gas and carbon dioxide gas used in the methanation reaction of carbon dioxide. The inflow amount of the gaseous raw material 8 into the first reaction tube lumen 123 can be appropriately set according to the chemical reaction to be performed in the first reactor.

[0026] The heat transfer medium 19 flows into the first heat transfer medium tube lumen 124 at the first heat transfer medium inlet 116. 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.

[0027] The first heat transfer medium inlet 116 and the first heat transfer medium outlet 117 are not particularly limited in their arrangement, but are preferably arranged as shown in FIG. 5, 7, 9, 10 or 11 so that the heat transfer medium can easily flow in a direction parallel to the longitudinal plane (the wider projection plane of the reaction tube as shown in FIG. 3) in the flat shape of the radial cross section of the first reaction tube. Also, a partition plate 27 as shown in FIG. 24 can be provided to make the heat transfer medium meander so that the heat transfer medium can easily flow in a direction perpendicular to the shorter side plane (the narrower projection plane of the reaction tube as shown in FIG. 4) in the flat shape of the radial cross section of the first reaction tube. Also, a spiral partition plate may be provided to guide the heat transfer medium to flow in a spiral shape along the inner surface of the first heat transfer medium tube wall. The partition plate has a hole through which the reaction tube can pass so as to hold the middle part of the first reaction tube.

[0028] A catalyst is placed in the first reaction tube lumen 123, and the gaseous raw material is brought into contact with the catalyst in the first reaction tube lumen to cause a chemical reaction. The catalyst may be in any shape, such as powder, granules, pellets, flat plate, corrugated plate, corrugated, honeycomb, etc. The catalyst may be loaded or packed in the inner cavity of the first reaction tube, or may be attached to the inner surface of the wall of the first reaction tube.

[0029] The first reaction tube may have a clamping portion protruding inward from the inner surface of the first reaction tube wall in order to stabilize the position of the plate-shaped catalyst when the plate-shaped catalyst is loaded. The shape and number of the clamping portion are not particularly limited, and examples thereof include a clamping portion having projections facing each other as shown in Figures 17 and 18, a clamping portion having projections facing alternately as shown in Figures 15 and 16, and a clamping portion having T-shaped projections facing alternately as shown in Figures 19 and 20. The clamping portion may be made of a material with high thermal conductivity and installed so as to be in contact with the plate-shaped catalyst, so that it can serve as a heat transfer fin 2 described later.

[0030] The catalyst can be appropriately selected depending on the chemical reaction to be carried out in the first reactor. In the methanation reaction of carbon dioxide, 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 / Al2O3, Ru / TiO2, Ni / TiO2, Ru-Ni / TiO2, etc.

[0031] The first gas outlet 105 is differentiated from a first heat transfer medium inlet 116 or a first heat transfer medium outlet 117, and a first gas mixture 109 containing methane flows out from a first reaction tube lumen 123 at the first gas outlet. The first gas outlet and the first heat transfer medium inlet or the first heat transfer medium outlet can be differentiated, for example, by a plate 26 that holds the end of the first reaction tube on the first gas outlet side. The heat transfer medium flows out from the first heat transfer medium tube lumen at the first heat transfer medium outlet. The flowed out heat transfer medium can be recycled.

[0032] The first gas mixture 109 flowing out from the first gas outlet 105 may contain, in addition to the product, unreacted gaseous raw material, by-products, etc. The product obtained in the methanation reaction of carbon dioxide is methane, and the by-product is water.

[0033] The first reaction tube 112 is inserted into the first heat transfer medium tube lumen 124, and has a mechanism for heat exchange between the heat transfer medium 19 in the first heat transfer medium tube lumen 124 and the inside of the first reaction tube lumen 123 via the first reaction tube wall. The first reaction tube 112 preferably has a heat transfer fin 2 protruding inward from the inner surface of the first reaction tube wall. In addition, the first reaction tube may further have a heat transfer fin protruding outward from the outer surface of the reaction tube wall.

[0034] 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 preferable 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 16 can be provided 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 near the part where hot spots may occur. Also, by providing more heat transfer 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.

[0035] The heat transfer fins may be provided only in the part of the catalyst placed area close to the gas inlet 4, or only in the part of the catalyst placed area close to the gas outlet 5, or may be provided over the entire catalyst placed area. In a reaction tube in which heat transfer fins are provided only in the part of the catalyst placed area close to the gas inlet 4, Fig. 13 is a diagram showing a cross section (CC cross section) of the reaction tube 12 filled with a granular catalyst on the side close to the gas inlet 4, and Fig. 14 is a diagram showing a cross section (DD cross section) of the reaction tube 12 filled with a granular catalyst on the side close to the gas outlet 5.

[0036] The second reactor 210 has a second reaction tube 212 and a second heat transfer medium tube 213. The second reaction tube and the second heat transfer medium tube are the same as those described for the first reaction tube and the first heat transfer medium tube. The mechanism of the second reactor is the same as that described for the first reactor.

[0037] The second gas inlet 204 is differentiated from the second heat transfer medium inlet 216 or the second heat transfer medium outlet 217, and the first gas mixture 109 flows into the second reaction tube lumen at the second gas inlet. The second gas inlet and the second heat transfer medium inlet or the second heat transfer medium outlet can be differentiated, for example, by a plate that holds the inlet side end of the second reaction tube. The heat transfer medium flows into the second heat transfer medium tube lumen at the second heat transfer medium inlet 216. A catalyst is placed in the second reaction tube lumen, and the first gas mixture is contacted with the catalyst in the second reaction tube lumen to cause a chemical reaction. The catalyst can be appropriately selected depending on the chemical reaction to be performed in the second reactor. The second gas outlet is differentiated from the second heat transfer medium inlet or the second heat transfer medium outlet, and the second gas mixture including the gaseous product flows out from the second reaction tube lumen at the second heat transfer medium outlet. The heat transfer medium flows out from the second heat transfer medium tube lumen at the second heat transfer medium outlet. The flowed out heat transfer medium can be recycled. The second gas mixture 209 flowing out from the second gas outlet 205 may contain, in addition to the gaseous product, unreacted gaseous raw material, gaseous by-products, etc. The gaseous product obtained in the methanation reaction of carbon dioxide is methane, and the by-product is water.

[0038] The connecting pipe connects the first gas outlet and the second gas inlet to communicate the inner cavity of the first reaction tube with the inner cavity of the second reaction tube. The connecting pipe preferably has a mechanism for condensing by-products (water in the case of a methanation reaction) contained in the first gas mixture and removing the by-products from the first gas mixture.

[0039] The average residence time in the first reaction tube and the average residence time in the second reaction tube are not particularly limited. The occurrence of hot spots can be suppressed by shortening the average residence time in a reaction tube where hot spots may occur. In the present invention, it is preferable that the average residence time in the first reaction tube is shorter than the average residence time in the second reaction tube. The average residence time can be adjusted, for example, by making the total volume of the first reaction tube smaller than the total volume of the second reaction tube. The total volume can be adjusted, for example, by changing the number of reaction tubes.

[0040] The third reactor 310 has a third reaction tube 312 and a third heat transfer medium tube 313. The fourth reactor 410 has a fourth reaction tube and a fourth heat transfer medium tube. The third reaction tube and the third heat transfer medium tube and the fourth reaction tube and the fourth heat transfer medium tube are the same as those described for the first reaction tube and the first heat transfer medium tube. The mechanisms of the third reactor and the fourth reactor are the same as those described for the first reactor. The connecting tubes for connecting the third reactor and the fourth reactor are the same as those described for the first reactor and the second reactor. The average residence time in the third reaction tube and / or the fourth reaction tube is not particularly limited. It is preferable that the average residence time in the third reaction tube and / or the fourth reaction tube is longer than the average residence time in the second reaction tube.

[0041] A device for separating and purifying the gaseous product, such as a cooler, a condenser, a gas-liquid separator, a membrane separation device, an adsorption separation device, an absorption separation device, a distillation separation device, a cryogenic separation device, etc., may be installed downstream of the second reactor 210 (when a third reactor and / or a fourth reactor are installed, downstream of the last reactor). The unreacted gaseous raw material or water obtained in the separation and purification can be recycled.

[0042] Figures 21 to 23 show another example of the apparatus for obtaining a gaseous product of the present invention. In the apparatus shown in Figure 21, the diameter of the connecting pipe connecting two reactors is the same as the diameter of the reactors. The structure and mechanism of each reactor are the same as those already described.

[0043] The apparatus for obtaining the gaseous product 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, etc.

[0044] Reaction tubes, heat transfer medium tubes, accessories, or reactors having complex shapes can be manufactured by a method that includes forming a single metal three-dimensional object by stacking the cross-sectional shapes based on their 3D data.

[0045] 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).

[0046] The formation (shaping) of a metal 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.

[0047] Powder bed fusion is a method in which metal 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 metal 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.

[0048] The powder bed fusion method includes a laser beam heat source method and an electron beam heat source method.

[0049] The powder bed laser beam heat source method uses a laser beam to irradiate a spread out metal powder material, melting and solidifying it or sintering it to create an additive manufacturing process. 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.

[0050] The powder bed / electron beam heat source method converts kinetic energy into heat by irradiating and colliding an electron beam on a spread-out metal powder material in a high vacuum, and melts the powder. The electron beam heat source method usually melts and solidifies 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.

[0051] 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.

[0052] Metal deposition methods include the laser beam heat source method, which uses metal powder as the material, and the arc discharge method, which uses alloy wire as the material.

[0053] The metal deposition laser beam heat source method sprays metal powder from a nozzle and simultaneously irradiates it with laser light, supplying 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.

[0054] The metal deposition arc discharge method melts metal wires using arc discharge at the tip of the wires and layers them together to create shapes. The cost of the equipment and materials is relatively low, and it allows for high speed modeling.

[0055] 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.

[0056] The method for obtaining a gaseous product of the present invention includes, in the apparatus 1 for obtaining a gaseous product of the present invention, supplying a gaseous raw material 8 to a first reaction tube lumen 123 through a first gas inlet 104, supplying a heat transfer medium to a first heat transfer medium tube lumen 124 through a first heat transfer medium inlet 116, causing the heat transfer medium to flow through the first heat transfer medium tube lumen and discharging the first heat transfer medium tube lumen through a first heat transfer medium outlet 117, thereby carrying out a chemical reaction while controlling the temperature of the contents in the first reaction tube lumen, and discharging methane obtained by the chemical reaction from the first reaction tube lumen through a first gas outlet 105. discharging a first gas mixture 109; supplying the first gas mixture to a second reaction tube lumen 223 at a second gas inlet 204; supplying a heat transfer medium to a second heat transfer medium tube lumen 224 at a second heat transfer medium inlet 216, flowing the heat transfer medium into the second heat transfer medium tube lumen and discharging the second heat transfer medium tube lumen at a second heat transfer medium outlet 217, thereby performing a chemical reaction while controlling the temperature of the contents in the second reaction tube lumen; and discharging a second gas mixture 209 including gaseous products obtained by the chemical reaction from the second reaction tube lumen at a second gas outlet.

[0057] In an apparatus further having a third reactor 310, the method includes supplying the second gas mixture 209 to the third reaction tube lumen 323 at the third gas inlet 304, supplying a heat transfer medium to the third heat transfer medium tube lumen 324 at the third heat transfer medium inlet 316, flowing the heat transfer medium into the third heat transfer medium tube lumen and discharging the third heat transfer medium tube lumen from the third heat transfer medium tube lumen at the third heat transfer medium outlet 317, thereby performing a chemical reaction while controlling the temperature of the contents in the third reaction tube lumen, and discharging the third gas mixture 309 containing gaseous products obtained by the chemical reaction from the third reaction tube lumen at the third gas outlet.

[0058] In an apparatus further having a fourth reactor 410, the method includes supplying the third gas mixture 309 to the fourth reaction tube lumen 423 at the fourth gas inlet 404, supplying a heat transfer medium to the fourth heat transfer medium tube lumen 424 at the fourth heat transfer medium inlet 416, flowing the heat transfer medium into the fourth heat transfer medium tube lumen and discharging the fourth heat transfer medium tube lumen at the fourth heat transfer medium outlet, thereby performing a chemical reaction while controlling the temperature of the contents in the fourth reaction tube lumen, and discharging the fourth gas mixture 409 including gaseous products obtained by the chemical reaction from the fourth reaction tube lumen at the fourth gas outlet 417.

[0059] In the method for producing CO (carbon monoxide), methanol or methane, a gas containing CO2 (carbon dioxide) and H2 (hydrogen) is used as a gaseous raw material, and a reduction reaction of CO2 is carried out. The amount of gas containing CO2 and H2 to be introduced can be appropriately set depending on the reaction rate, the volume of the reaction tube lumen, etc. Depending on the ratio of CO2 to H2, the reduction reaction of CO2 proceeds as follows: CO2+ H2→ CO + H2O CO2+ 3H2→ CH3OH + H2O CO2+ 4H2→ CH4+ 2H2O

[0060] The apparatus and method for obtaining a gaseous product of the present invention can be preferably used for C1 chemical synthesis methods other than the method for producing methane from a gas containing CO2 (carbon dioxide) and H2 (hydrogen). Examples of C1 chemical synthesis methods include a method for producing carbon monoxide and hydrogen by reacting methane with water (water vapor), a method for producing carbon monoxide and hydrogen by reacting methane with carbon dioxide, a method for producing carbon dioxide and hydrogen by reacting carbon monoxide with water, a method for producing carbon dioxide and hydrogen by reacting methane with water, a method for producing methane and carbon dioxide by reacting carbon monoxide with hydrogen, a method for producing methanol by reacting carbon monoxide with hydrogen, a method for producing acetone and water by reacting carbon monoxide with hydrogen, and a method for producing carbon monoxide and hydrogen, ethylene and water, or methanol by reacting methane with oxygen.

[0061] In the present invention, the products (CO (carbon monoxide), methanol or methane) obtained by the reduction reaction of CO2 and the unreacted substances (mainly CO2) can be separated and purified. Examples of the separation and purification method 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. The unreacted materials (mainly CO2) and low-concentration methane obtained in the separation and purification of methane can be used as gaseous raw materials in the above-mentioned methane production method.

[0062] 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 the gaseous feedstock in the methane production process.

[0063] 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. [Explanation of symbols]

[0064] 1: Apparatus for obtaining gaseous products 2: Heat transfer fins 3: Granular catalyst 4: Gas inlet 104: First gas inlet 204: Second gas inlet 304: Third gas inlet 404: Fourth gas inlet 5: Gas outlet 105: First gas outlet 205: Second gas outlet 305: Third gas outlet 405: Fourth gas outlet 6: Plate-shaped catalyst (flat plate) 7: Plate-shaped catalyst (corrugated plate) 8: Gaseous raw materials G1: Raw gas LG2: Liquefied raw gas 9: Gas containing gaseous products 109: First gas mixture 209: Second gas mixture 309: Third gas mixture 409: Fourth gas mixture 10: Reactor 110: First reactor 210: Second reactor 310: Third reactor 410: Fourth reactor 11: Compressor 12: Reaction tube 112: First reaction tube 212: Second reaction tube 312: Third reaction tube 412: 4th reaction tube 13: Heat transfer medium tube 113: First heat transfer medium tube 213: Second heat transfer medium tube 313: Third heat transfer medium tube 413: Fourth heat transfer medium tube 14: Evaporator 15:Cooler 16: Heat transfer medium inlet 116: First heat transfer medium inlet 216: Second heat transfer medium inlet 316: Third heat transfer medium inlet 416: Fourth heat transfer medium inlet 17: Heat transfer medium outlet 117: First heat transfer medium outlet 217: Second heat transfer medium outlet 317: Third heat transfer medium outlet 317: Fourth heat transfer medium outlet 18: Gas-liquid separator 19: Heat transfer medium (inlet) 20: Heat transfer medium (outflow) 21: Drain 22: Heat exchanger 23: Reaction tube inner cavity 123: First reaction tube lumen 223: Second reaction tube lumen 323: Third reaction tube inner cavity 423: Fourth reaction tube lumen 24: Heat transfer medium tube bore 124: First heat transfer medium tube bore 224: Second heat transfer medium tube bore 324: Third heat transfer medium tube bore 424: Fourth heat transfer medium tube bore 25:Inflow side retaining plate 26: Outlet side retaining plate 27: Partition

Claims

1. a first reaction tube having a first gas inlet and a first gas outlet and a first reaction tube lumen communicating from the first gas inlet to the first gas outlet; a first heat transfer medium tube having a first heat transfer medium inlet and a first heat transfer medium outlet, the first heat transfer medium tube having a first heat transfer medium tube lumen communicating from the first heat transfer medium inlet to the first heat transfer medium outlet; The first reaction tube is A first catalyst made of a Ni-based catalyst, a platinum group metal-based catalyst, or other precious metal-based catalyst is placed in the lumen of the first reaction tube; and a mechanism for allowing a gaseous raw material containing carbon dioxide gas and hydrogen gas to flow into a first reaction tube lumen at a first gas inlet, bringing the gaseous raw material into contact with the first catalyst in the first reaction tube lumen to cause a first chemical reaction, and allowing a first gas mixture containing methane obtained by the first chemical reaction to flow out from the first reaction tube lumen at a first gas outlet; The first heat transfer medium tube is a mechanism for allowing the heat transfer medium to flow into the first heat transfer medium tube lumen at a first heat transfer medium inlet and out of the first heat transfer medium tube lumen at a first heat transfer medium outlet; and a first reactor having a mechanism in which a first reaction tube is inserted into a first heat transfer medium tube lumen, and a heat transfer medium in the first heat transfer medium tube lumen exchanges heat with a heat transfer medium in the first reaction tube lumen through a first reaction tube wall; a second reaction tube having a second gas inlet and a second gas outlet and a second reaction tube lumen communicating from the second gas inlet to the second gas outlet; a second heat transfer medium tube having a second heat transfer medium inlet and a second heat transfer medium outlet, the second heat transfer medium tube having a second heat transfer medium tube lumen communicating from the second heat transfer medium inlet to the second heat transfer medium outlet; The second reaction tube is a second catalyst is disposed in the second reactor bore; and a mechanism for allowing a first gas mixture to flow into a second reaction tube lumen at a second gas inlet, for contacting the first gas mixture with a second catalyst in the second reaction tube lumen to cause a second chemical reaction, and for allowing a second gas mixture containing a gaseous product obtained by the second chemical reaction to flow out of the second reaction tube lumen at a second gas outlet; The second heat transfer medium tube is a mechanism for allowing the heat transfer medium to flow into the second heat transfer medium tube lumen at a second heat transfer medium inlet and out of the second heat transfer medium tube lumen at a second heat transfer medium outlet; and a second reactor having a mechanism in which a second reaction tube is inserted into a second heat transfer medium tube bore, and a heat transfer medium in the second heat transfer medium tube bore exchanges heat with a heat transfer medium in the second reaction tube bore through a second reaction tube wall; a connecting pipe connecting the first gas flow outlet and the second gas flow inlet to communicate the first reaction tube lumen with the second reaction tube lumen, the connecting pipe having a mechanism for removing by-products from the first gas mixture; 1. An apparatus for obtaining a gaseous product comprising:

2. 2. The apparatus for obtaining a gaseous product according to claim 1, wherein the average residence time in the first reaction tube is shorter than the average residence time in the second reaction tube.

3. 3. The apparatus for obtaining a gaseous product according to claim 1 or 2, wherein the connecting pipe removes by-product water from the first gas mixture.

4. 4. The apparatus for obtaining a gaseous product according to claim 1, wherein the first reaction tube has heat transfer fins protruding inward from the inner surface of the reaction tube wall.

5. 5. The apparatus for obtaining a gaseous product according to claim 4, wherein the heat transfer fins are provided only on a portion close to the first gas inlet.

6. 6. The apparatus for obtaining a gaseous product according to claim 1, wherein the radial cross section of the first reaction tube is flattened.

7. 7. The apparatus for obtaining a gaseous product according to claim 1, wherein the radial cross section of the second reaction tube is flattened.

8. 7. The apparatus for obtaining a gaseous product according to claim 6, wherein there are a plurality of first reaction tubes, and each of the first reaction tubes is arranged such that the longitudinal directions of the first reaction tubes in the flat shape of their radial cross sections are parallel to each other.

9. 9. The apparatus for obtaining a gaseous product according to claim 7 or 8, wherein there are a plurality of second reaction tubes, and the second reaction tubes are arranged such that their longitudinal directions in the flat shape of their radial cross sections are parallel to each other.

10. A device for obtaining a gaseous product according to any one of claims 1 to 9, supplying a gaseous source material comprising carbon dioxide gas and hydrogen gas into a lumen of a first reaction tube at a first gas inlet; supplying a heat transfer medium to the first heat transfer medium tube lumen at a first heat transfer medium inlet, flowing the heat transfer medium through the first heat transfer medium tube lumen, and discharging the heat transfer medium from the first heat transfer medium tube lumen at a first heat transfer medium outlet, thereby controlling the temperature of the contents within the first reaction tube lumen and conducting a first chemical reaction; Discharging a first gas mixture comprising methane resulting from said first chemical reaction from a first reaction tube lumen at a first gas outlet; supplying a first gas mixture into a second reactor tube lumen at a second gas inlet; providing a heat transfer medium to the second heat transfer medium tube lumen at a second heat transfer medium inlet, flowing through the second heat transfer medium tube lumen, and discharging the heat transfer medium from the second heat transfer medium tube lumen at a second heat transfer medium outlet, thereby controlling the temperature of the contents of the second reaction tube lumen while conducting a second chemical reaction; and discharging a second gas mixture from the second reaction tube lumen at a second gas outlet, the second gas mixture comprising gaseous products of said second chemical reaction; Including, A method for obtaining a gaseous product.

11. The method of claim 10, wherein the gaseous product comprises methane.

12. The method of claim 10, wherein the gaseous products comprise methanol.

13. 11. The method of claim 10, wherein the gaseous products comprise carbon monoxide, acetone, or ethylene.

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