Apparatus for obtaining gaseous products and method for obtaining gaseous products

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. More specifically, the present invention relates to an apparatus and a method for chemically reacting a gaseous raw material in the presence of a catalyst to obtain a gaseous product.

Background Art

[0002] Various proposals have been made for an apparatus and a method for obtaining a gaseous product. For example, Patent Document 1 discloses a reaction unit that generates a product gas and generated water in which the product gas is dissolved by an exothermic reaction of a gaseous reactant, 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 unit and the cooling tower, and a mixing means that mixes the generated water generated in the reaction unit into the cooling water circulation system.

[0003] Patent Document 2 discloses a multi-tubular heat exchanger including a group of inner tubes (heat transfer tubes) through which a first fluid passes and an outer tube (cylinder) through which a second fluid passes, wherein a plurality of groups of heat transfer tubes are arranged by being held by introduction-side / discharge-side holding plates that are respectively positioned at both ends thereof on the first fluid introduction side and the first fluid discharge side, and plate-like or tuberous protrusions are formed on the wall surfaces of the flow paths of the respective heat transfer tubes at a predetermined interval (predetermined pitch) in the longitudinal direction.

[0004] Patent Document 3 discloses a single-shell open interstage reactor for producing acrylic acid from propylene, comprising, in process flow order: a) a first shell-and-tube reaction stage comprising a plurality of reaction tubes, wherein the reaction tubes of the first reaction stage comprise 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 comprising a plurality of reaction tubes, wherein the reaction tubes of the second reaction stage comprise a second catalyst for oxidizing acrolein to produce acrylic acid, and the reaction tubes of the second reaction stage have a diameter greater than 22.3 mm.

[0005] Patent Document 4 describes a honeycomb structure comprising a first fluid circulation section having multiple cells through which a first fluid, which is a heating element, flows, separated by ceramic partitions and penetrating axially from one end face to the other; and a second fluid circulation section having cells through which a second fluid flows, separated by ceramic partitions and penetrating in a direction perpendicular to the axial direction, separated from the first fluid circulation section by the partitions and allowing heat conduction, receiving heat from the first fluid flowing through the first fluid circulation section via the partitions, and transferring heat to the heating element, which is the second fluid, flowing through the second fluid, with the cells on the first fluid circulation section side being smaller than the cells on the second fluid circulation section side, and the density of the partitions being 0.5 to 5 g / cm³. 3 The present invention discloses a ceramic heat exchanger comprising a heat exchanger having a thermal conductivity of 10 to 300 W / mK for the partition wall, and in which a catalyst is supported on the wall surface of the first fluid flow section.

[0006] Patent Document 5 discloses a process for hydrocracking a Fischer-Tropsch synthesis product in a microchannel reactor containing a plurality of process microchannels, comprising the steps of: flowing a hydrogen-containing gas through a plurality of process microchannels at an empty tower velocity of at least 0.01 meters per second; flowing a liquid containing a Fischer-Tropsch synthesis product through the plurality of process microchannels, wherein the plurality of process microchannels contain a hydrocracking catalyst, the liquid forms a film on at least a portion of the hydrocracking catalyst, the gas comes into contact with the liquid, and the hydrogen reacts with the Fischer-Tropsch synthesis product in the presence of the hydrocracking catalyst to form a hydrocracking Fischer-Tropsch synthesis product, wherein the hydrocracking Fischer-Tropsch synthesis product contains one or more linear aliphatic hydrocarbons having five or more carbon atoms; and removing the hydrocracking Fischer-Tropsch synthesis product from the plurality of process microchannels, wherein the heat is 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] Japanese Patent Publication No. 2002-181468 [Patent Document 3] Japanese Patent Publication No. 2018-111696 [Patent Document 4] Japanese Patent Publication No. 2010-271031 [Patent Document 5] Japanese Patent Publication No. 2017-48397 [Overview of the project] [Problems that the invention aims to solve]

[0008] The object of the present invention is to provide a novel apparatus and method for obtaining a gaseous product by chemically reacting a gaseous raw material in the presence of a catalyst. [Means for solving the problem]

[0009] In order to solve the above problems, we have completed the present invention, which includes the following forms.

[0010] [1] A first reaction tube having a first gas inlet and a first gas outlet, and having a first reaction tube lumen connecting the first gas inlet to the first gas outlet, It comprises a first heat transfer medium tube having a first heat transfer medium inlet and a first heat transfer medium outlet, and having a first heat transfer medium tube lumen connecting the first heat transfer medium inlet to the first heat transfer medium outlet, The first reaction tube is, The catalyst is placed in the lumen of the first reaction tube, and The mechanism comprises the following: gaseous raw materials flow into the lumen of the first reaction tube at the first gas inlet, the gaseous raw materials are brought into contact with a catalyst in the lumen of the first reaction tube to undergo a chemical reaction, and the first gas mixture containing the gaseous products obtained from the chemical reaction flows out of the lumen of the first reaction tube at the first gas outlet. The first heat transfer medium tube is The mechanism has such that the heat transfer medium flows into the lumen of the first heat transfer medium tube at the first heat transfer medium inlet, and the heat transfer medium flows out of the lumen of the first heat transfer medium tube at the first heat transfer medium outlet, and A first reactor having a mechanism in which a first reaction tube is inserted into the lumen of a first heat transfer medium tube, and the heat transfer medium in the lumen of the first heat transfer medium tube exchanges heat with the material in the lumen of the first reaction tube via the wall of the first reaction tube, A second reaction tube having a second gas inlet and a second gas outlet, and having a second reaction tube lumen connecting the second gas inlet to the second gas outlet, It comprises a second heat transfer medium tube having a second heat transfer medium inlet and a second heat transfer medium outlet, and a second heat transfer medium tube having a lumen connecting the second heat transfer medium inlet to the second heat transfer medium outlet, The second reaction tube is, The catalyst is placed in the lumen of the second reaction tube, and At the second gas inlet, the first gas mixture flows into the inner cavity of the second reaction tube. In the inner cavity of the second reaction tube, the first gas mixture is brought into contact with a catalyst to cause a chemical reaction. At the second gas outlet, a second gas mixture containing the gaseous product obtained by the chemical reaction flows out from the inner cavity of the second reaction tube. It has a mechanism. The second heat transfer medium tube At the second heat transfer medium inlet, the heat transfer medium flows into the inner cavity of the second heat transfer medium tube. At the second heat transfer medium outlet, the heat transfer medium flows out from the inner cavity of the second heat transfer medium tube. It has a mechanism, and The second reaction tube is inserted into the inner cavity of the second heat transfer medium tube, and the heat transfer medium in the inner cavity of the second heat transfer medium tube exchanges heat with that in the inner cavity of the second reaction tube through the wall of the second reaction tube. A second reactor having a mechanism. It includes a connecting pipe that connects the first gas outlet and the second gas inlet to communicate the inner cavity of the first reaction tube and the inner cavity of the second reaction tube. An apparatus for obtaining a gaseous product.

[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 has a mechanism for removing by-products from the first gas mixture.

[0013] 〔4〕 The gaseous product generating apparatus according to any one of 〔1〕 to 〔3〕, wherein the first reaction tube has heat transfer fins protruding inward from the inner surface of the reaction tube wall. 〔5〕 The 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 is flat. 〔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 is flat. 〔8〕 An apparatus for obtaining a gaseous product according to 〔6〕, wherein there are a plurality of first reaction tubes, and the longitudinal directions in the flat shape of their radial cross-sections are arranged parallel to each other. 〔9〕 An apparatus for obtaining a gaseous product according to 〔7〕 or 〔8〕, wherein there are a plurality of second reaction tubes, and the longitudinal directions in the flat shape of their radial cross-sections are arranged parallel to each other.

[0015] 〔10〕 In an apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔9〕, supplying a gaseous raw material into the lumen of the first reaction tube at the first gas inlet, supplying a heat transfer medium into the lumen of the first heat transfer medium tube at the first heat transfer medium inlet, flowing it through the lumen of the first heat transfer medium tube, and discharging it from the lumen of the first heat transfer medium tube at the first heat transfer medium outlet, thereby performing a chemical reaction while controlling the temperature of the substances in the lumen of the first reaction tube, discharging a first gas mixture containing the gaseous product obtained by the chemical reaction from the lumen of the first reaction tube at the first gas outlet, supplying the first gas mixture into the lumen of the second reaction tube at the second gas inlet, supplying a heat transfer medium into the lumen of the second heat transfer medium tube at the second heat transfer medium inlet, flowing it through the lumen of the second heat transfer medium tube, and discharging it from the lumen of the second heat transfer medium tube at the second heat transfer medium outlet, thereby performing a chemical reaction while controlling the temperature of the substances in the lumen of the second reaction tube, and discharging a second gas mixture containing the gaseous product obtained by the chemical reaction from the lumen of the second reaction tube at the second gas outlet, including a method for obtaining a gaseous product.

[0016] 〔11〕 The method according to 〔10〕, wherein the gaseous raw material contains hydrogen gas and carbon dioxide gas, and the gaseous product contains carbon monoxide, methanol or methane.

Advantages of the Invention

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

[0018] [Figure 1] This figure shows an example of an apparatus for obtaining the gaseous product of the present invention. [Figure 2] This figure shows an example of the appearance of reactors 1 through 4. [Figure 3] This is a diagram showing a cross-section AA in an example of reactors 1 through 4. [Figure 4] This is a diagram showing a cross-section of the first reactor in an example. [Figure 5] This figure shows a radial cross-section of an example of the first reactor. [Figure 6] This is a diagram showing a cross-section of a second reactor in an example. [Figure 7] This figure shows a radial cross-section of an example of the second reactor. [Figure 8] This is a diagram showing a cross-section of the BB in an example of the third to fourth reactor. [Figure 9] This figure shows a radial cross-section of an example of the third to fourth reactor. [Figure 10] This figure shows a radial cross-section of another example of a reactor. [Figure 11] This figure shows a radial cross-section of another example of a reactor. [Figure 12] This figure shows an example of a reaction tube. [Figure 13] This figure shows a cross-sectional view of the reaction tube shown in Figure 12. [Figure 14] This figure shows a cross-sectional view of the DD (direct-disc) of the reaction tube shown in Figure 12. [Figure 15] This is a diagram showing a cross-section of a reaction tube in another example. [Figure 16]This is a diagram showing a cross-section of a reaction tube in another example. [Figure 17] This is a diagram showing a cross-section of a reaction tube in another example. [Figure 18] This is a diagram showing a cross-section of a reaction tube in another example. [Figure 19] This is a diagram showing a cross-section of a reaction tube in another example. [Figure 20] This is a diagram showing a cross-section of a reaction tube in another example. [Figure 21] This figure shows the appearance of another example of the main part of the apparatus for obtaining the gaseous product of the present invention. [Figure 22] This figure shows a longitudinal cross-section of the apparatus shown in Figure 21. [Figure 23] This figure shows another longitudinal cross-section of the apparatus shown in Figure 21. [Figure 24] This figure shows a longitudinal cross-section of another example of a reactor. [Modes for carrying out the invention]

[0019] The present invention will be described with reference to the drawings. However, the present invention is not limited to the embodiments shown in the drawings.

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

[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 connects 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, circular, oval, elliptical, oblong, rounded quadrilateral, or quadrilateral.

[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 that connects the first gas inlet to the first gas outlet. The radial cross-section of the first reaction tube can be, for example, circular, oval, elliptical, oblong, rounded quadrilateral, or square, and is preferably flattened. The flattened shape is preferably rectangular (rectangle, rounded rectangle) or oval (oval, oblong, elliptical). The aspect ratio (length in the longitudinal direction / length in the transverse direction) of the flattened shape is preferably 1.2, more preferably 1.5, and even more preferably 2 at the lower limit, and preferably 20, more preferably 10, and even more preferably 5 at the upper limit. In the apparatus of the present invention, it is preferable that there are multiple first reaction tubes 112, and that each first reaction tube is arranged such that the longitudinal directions of the flattened shapes of their radial cross-sections are parallel to each other. Examples of arrangements for the first reaction tube include configurations where multiple first reaction tubes are arranged vertically and horizontally within the lumen of the first heat transfer medium tube, which has a rounded rectangular radial cross-section, as shown in Figures 5, 7, and 9; configurations where the first reaction tubes are arranged vertically in a single row within the lumen of the first heat transfer medium tube, which has a rounded rectangular radial cross-section, as shown in Figure 10; and configurations where the first reaction tubes are arranged within the lumen of the first heat transfer medium tube, which has a circular radial cross-section, as shown in Figure 11.

[0024] The first gas inlet 104 is distinguished from the first heat transfer medium inlet 116 or the first heat transfer medium outlet 117, and gaseous raw materials flow into the lumen of the first reaction tube at the first gas inlet. The distinction between the first gas inlet and the first heat transfer medium inlet or first heat transfer medium outlet can be made, for example, by a plate 25 that holds the gas inlet end of the first reaction tube.

[0025] Upstream of the first reactor, equipment for preparing the gaseous raw material can be installed, such as a mixing mechanism for mixing the components constituting the gaseous raw material in predetermined proportions, a tank for storing the components constituting the gaseous raw material, a compressor 11, a heat exchanger 22, etc. If the raw material is in liquid form, such as liquefied carbon dioxide, an evaporator 14, etc., can be installed to safely vaporize it. The components constituting the gaseous raw material can be appropriately selected according to the chemical reaction carried out in the reactor; for example, the gaseous raw material used in the methane reaction of carbon dioxide contains at least hydrogen gas and carbon dioxide gas. The amount of gaseous raw material 8 flowing into the lumen 123 of the first reaction tube can be appropriately set according to the chemical reaction carried out in the first reactor.

[0026] At the first heat transfer medium inlet 116, the heat transfer medium 19 flows into the lumen 124 of the first heat transfer medium tube. The heat transfer medium is not particularly limited as long as it does not deteriorate and maintains fluidity within the temperature range required for the desired chemical reaction. Specific examples of heat transfer mediums include: polyhydric alcohols such as glycerin and polyglycols; phenols and phenolic ethers such as anisole, diphenyl ether, and phenol; polyphenyls such as terphenyl, chlorinated benzenes and polyphenyls such as o-dichlorobenzene and polychloropolyphenyl; silicic acid esters such as tetraallyl silicate; naphthalene derivatives, fractional distillation tars and petroleum products such as 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 mixtures, and Na-K alloys; and others.

[0027] The arrangement of the first heat transfer medium inlet 116 and the first heat transfer medium outlet 117 is not particularly limited, but it is preferable to arrange them as shown in Figures 5, 7, 9, 10, or 11 so that the heat transfer medium flows easily in a direction parallel to the longitudinal plane of the flattened radial cross-section of the first reaction tube (the wider projection plane of the reaction tube as shown in Figure 3). Alternatively, a partition plate 27 as shown in Figure 24 can be provided to cause the heat transfer medium to meander, so that it flows easily in a direction perpendicular to the short-side plane of the flattened radial cross-section of the first reaction tube (the narrower projection plane of the reaction tube as shown in Figure 4). Furthermore, a helical partition plate may be provided to guide the heat transfer medium to flow in a helical shape along the inner surface of the wall of the first heat transfer medium tube. The partition plate has a hole through which the reaction tube can pass so as to hold the middle section of the first reaction tube.

[0028] A catalyst is placed in the lumen 123 of the first reaction tube, and a gaseous raw material is brought into contact with the catalyst in the lumen of the first reaction tube to carry out a chemical reaction. As a catalyst, various forms such as powder, granules, pellets, flat plates, corrugated plates, honeycomb structures, etc., can be used as appropriate. The catalyst may be loaded or filled into the lumen of the first reaction tube, or it may be attached to the inner surface of the wall of the first reaction tube.

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

[0030] The catalyst can be appropriately selected depending on the chemical reaction carried out in the first reactor. For example, in the methanation reaction of carbon dioxide, Ni-based catalysts, platinum group metal catalysts, other precious metal catalysts, etc., can be used. A specific example of a methanation catalyst is nickel aluminate (NiAl x O y ), Ru / NiAl x O y Examples include Ru / Al2O3, Ru / TiO2, Ni / TiO2, and Ru-Ni / TiO2.

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

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

[0033] The first reaction tube 112 is inserted into the lumen 124 of the first heat transfer medium tube, and has a mechanism for heat exchange between the heat transfer medium 19 in the lumen 124 and the lumen 123 of the first reaction tube via the wall of the first reaction tube. Preferably, the first reaction tube 112 has heat transfer fins 2 that protrude inward from the inner surface of the wall of the first reaction tube. The first reaction tube may also have heat transfer fins that protrude outward from the outer surface of the wall of the reaction tube.

[0034] In general, in tubular reactors, the temperature distribution in the direction of flow in the reaction tube tends to be uneven. Hot spots may also occur in chemical reactions that generate a large amount of heat. It is preferable to suppress the occurrence of hot spots and to make the temperature distribution in the direction of flow in the reaction tube uniform. The heat transfer medium inlet 16 can be positioned close to areas where hot spots are likely to occur, or the lumen of the heat transfer medium tube can be divided by a partition plate, with a heat transfer medium inlet and outlet provided in each of the divided sections, thereby making the temperature of the heat transfer medium flowing through each section of the heat transfer medium tube relatively lower on the side closer to areas where hot spots are likely to occur. In addition, by providing more heat transfer fins near areas where hot spots are likely to occur and increasing the amount of heat transferred in those sections, the temperature distribution in the flow direction of the reaction tube can be made more uniform.

[0035] The heat transfer fins may be provided only in the portion of the catalyst area closest to the gas inlet 4, or only in the portion of the catalyst area closest to the gas outlet 5, or in the entire portion of the catalyst area. In a reaction tube in which heat transfer fins are provided only in the portion of the catalyst area closest to the gas inlet 4, Figure 13 shows a cross-section (CC section) of the reaction tube 12 filled with granular catalyst on the side closest to the gas inlet 4, and Figure 14 shows a cross-section (DD section) of the reaction tube 12 filled with granular catalyst on the side closest 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 distinguished 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 lumen of the second reaction tube at the second gas inlet. The distinction between the second gas inlet and the second heat transfer medium inlet or outlet can be made, for example, by a plate that holds the inlet end of the second reaction tube. The heat transfer medium flows into the lumen of the second heat transfer medium tube at the second heat transfer medium inlet 216. A catalyst is placed in the lumen of the second reaction tube, and the first gas mixture is brought into contact with the catalyst in the lumen of the second reaction tube to cause a chemical reaction. The catalyst can be appropriately selected depending on the chemical reaction to be carried out in the second reactor. The second gas outlet is distinguished from the second heat transfer medium inlet or the second heat transfer medium outlet, and the second gas mixture containing gaseous products flows out from the lumen of the second reaction tube at the second gas outlet. The heat transfer medium flows out from the lumen of the second heat transfer medium tube at the second heat transfer medium outlet. The flowed-out heat transfer medium can be recycled. The second gas mixture 209 discharged from the second gas outlet 205 may contain unreacted gaseous raw materials, gaseous by-products, etc., in addition to the gaseous product. The gaseous product obtained from the methane reaction of carbon dioxide is methane, and the by-product is water.

[0038] The connecting tube connects the first gas outlet and the second gas inlet, thereby connecting the lumen of the first reaction tube and the lumen of the second reaction tube. Preferably, the connecting tube has a mechanism to condense the by-products (water in the case of a methane reaction) contained in the first gas mixture and remove 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. Hot spot formation can be suppressed by shortening the average residence time in the reaction tube where hot spots are likely to occur. In this 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 third heat transfer medium tube, and the fourth reaction tube and fourth heat transfer medium tube are the same as those described for the first reaction tube and first heat transfer medium tube. The mechanisms of the third and fourth reactors are the same as those described for the first reactor. The connecting tubes for connecting the third and fourth reactors are the same as the connecting tubes described for the first and second reactors. The average residence time in the third and / or fourth reaction tubes is not particularly limited. Preferably, the average residence time in the third and / or fourth reaction tubes is longer than the average residence time in the second reaction tube.

[0041] Downstream from the second reactor 210 (or downstream of the last reactor if a third and / or fourth reactor are installed), equipment for separating and purifying the gaseous product may be installed, such as a cooler, condenser, gas-liquid separator, membrane separator, adsorption separator, absorption separator, distillation separator, or cryogenic separator. Unreacted gaseous raw materials or water obtained during separation and purification can be recycled.

[0042] Figures 21-23 show another example of the apparatus for obtaining the gaseous product of the present invention. In the apparatus shown in Figure 21, the diameter of the connecting tube between the 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, or the like.

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

[0045] 3D data can be 3D shape data of the target part. 3D shape data can be designed using 3D CAD. 3D data can also be obtained by converting 3D shape data, for example, STL (Stereolithography) data. STL data represents a three-dimensional solid shape as a collection of small triangles (polygons).

[0046] The formation (fabrication) of three-dimensional metal objects by layering cross-sectional shapes can be carried out using methods such as powder bed fusion (PBF), metal deposition, material extrusion deposition (FDM), liquid metal inkjet, binder jet, and hybrid methods that perform cutting during additive manufacturing using PBF. Of these, powder bed fusion (PBF) or metal deposition is preferred.

[0047] Powder bed fusion is a method of fabricating objects by spreading metal powder and using a laser or electron beam as a heat source to melt and solidify the area to be fabricated. The object is fabricated by repeatedly spreading the metal powder and melting and solidifying it. After fabrication is complete, the unsolidified powder is removed and the fabricated object is extracted.

[0048] Powder bed fusion methods include laser beam heat source methods and electron beam heat source methods.

[0049] The powder bed laser beam heat source method involves irradiating a spread of metal powder material with a laser beam to melt, solidify, or sinter it, thereby creating an additive manufacturing structure. In the laser beam heat source method, melting and solidification typically occur in an inert atmosphere such as nitrogen. The laser beam heat source method uses mirror angles to adjust the laser irradiation position.

[0050] The powder bed electron beam heat source method works by irradiating a bed of metal powder material with an electron beam in a high vacuum, causing it to collide with the powder. This converts kinetic energy into heat, melting and solidifying the powder in a vacuum. In the electron beam heat source method, the direction of the electron beam is changed using a lens made of a magnetic field. As a result, the electron beam heat source method enables high-speed positioning.

[0051] The metal deposition method is a fabrication method that involves layering and solidifying molten metal material in a predetermined location. The metal deposition method does not require powder removal after the fabrication process is complete.

[0052] Metal deposition methods include laser beam heat source methods using metal powder as the material, and arc discharge methods using alloy wires as the material.

[0053] The metal deposition laser beam heat source method involves spraying metal powder from a nozzle while simultaneously irradiating it with laser light to supply the metal powder to the molten pool, where it solidifies and forms the object. Three-dimensional shapes are created by moving the molten nozzle or stage. By switching the metal powder supply path, it is possible to create objects using different metals. Due to its high laser output, it is suitable for high-speed manufacturing.

[0054] The metal deposition arc discharge method creates a shape by melting a metal wire with an arc discharge at its tip and layering the melted wire. It offers relatively low equipment and material costs, and enables high-speed fabrication.

[0055] After molding, heat treatment can be performed to relieve stress, improve strength, and other purposes. The conditions for heat treatment, such as temperature, time, and atmosphere, can be appropriately set according to the metal material used.

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

[0057] In an apparatus further comprising a third reactor 310, the following steps are taken: supplying a second gas mixture 209 to the lumen 323 of a third reaction tube at a third gas inlet 304; supplying a heat transfer medium to the lumen 324 of a third heat transfer medium tube at a third heat transfer medium inlet 316, allowing it to flow through the lumen and discharge it from the lumen at a third heat transfer medium outlet 317, thereby controlling the temperature of the contents within the lumen of the third reaction tube while carrying out a chemical reaction; and discharging the third gas mixture 309 containing the gaseous products obtained from the chemical reaction from the lumen of the third reaction tube at a third gas outlet.

[0058] In an apparatus further comprising a fourth reactor 410, the following steps are taken: supplying a third gas mixture 309 to the lumen 423 of the fourth reaction tube at a fourth gas inlet 404; supplying a heat transfer medium to the lumen 424 of the fourth heat transfer medium tube at a fourth heat transfer medium inlet 416, allowing it to flow through the lumen and discharge it from the lumen at a fourth heat transfer medium outlet to carry out a chemical reaction while controlling the temperature of the contents within the lumen of the fourth reaction tube; and discharging the fourth gas mixture 409 containing the gaseous products obtained from the chemical reaction from the lumen of the fourth reaction tube at a 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 the reduction reaction of CO2 is carried out. The amount of CO2 and H2-containing gas introduced can be appropriately set according to the reaction rate, the volume of the reaction tube lumen, and other factors. 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 the gaseous product of the present invention can also be preferably used in C1 chemical synthesis methods other than the method for producing CO (carbon monoxide), methanol, or 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 the reaction of methane with water (water vapor), a method for producing carbon monoxide and hydrogen by the reaction of methane with carbon dioxide, a method for producing carbon dioxide and hydrogen by the reaction of carbon monoxide with water, a method for producing carbon dioxide and hydrogen by the reaction of methane with water, a method for producing methane and carbon dioxide by the reaction of carbon monoxide and hydrogen, a method for producing methanol by the reaction of carbon monoxide and hydrogen, a method for producing acetone and water by the reaction of carbon monoxide and hydrogen, and a method for producing carbon monoxide and hydrogen, ethylene and water, or methanol by the reaction of methane with oxygen.

[0061] In this invention, the products obtained by the reduction reaction of CO2 (CO (carbon monoxide), methanol, or methane) and unreacted products (mainly CO2) can be separated and purified. Examples of separation and purification methods include membrane separation, adsorption separation, absorption separation, distillation separation, and cryogenic separation. For the separation and purification of methane, membrane separation is preferred from the viewpoint of separation selectivity, separation speed, and inexpensive and compact equipment. The unreacted material (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, the methane obtained through separation and purification can be supplied as fuel to a gas turbine. This gas turbine can then generate electricity. Since combustion exhaust gas from a gas turbine typically contains carbon dioxide, it can be used as a gaseous raw material in the above-mentioned methane production method.

[0063] This invention can be used in various chemical reactions. It is useful in utilizing hydrogen produced by the electrolysis of water, utilizing carbon dioxide produced by the respiration of humans and animals or by the combustion of fuels, producing water, or producing methane as a fuel. This invention can also be used in space stations, spacecraft, rockets, and the like. [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 sheet) 8: Gaseous raw materials G1: Raw gas LG2: Liquefied raw material 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: Fourth 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 (inflow) 20: Heat transfer medium (leakage) 21: Drain 22: Heat exchanger 23: Lumen of the reaction tube 123: Lumen of the first reaction tube 223: Luminous tube of the second reaction tube 323: Luminus of the third reaction tube 423: Lumen of the fourth reaction tube 24: Luminous tube of the heat transfer medium 124: Luminous tube of the first heat transfer medium 224: Luminous tube of the second heat transfer medium 324: Luminous tube of the third heat transfer medium 424: Luminous tube of the fourth heat transfer medium 25:Inflow side retaining plate 26: Outlet side retaining plate 27: Partition plate

Claims

1. It includes a first reactor, a second reactor, and connecting tubes. The first reactor is A first reaction tube having a first gas inlet and a first gas outlet, and having a first reaction tube lumen connecting the first gas inlet to the first gas outlet, It comprises a first heat transfer medium tube having a first heat transfer medium inlet and a first heat transfer medium outlet, and having a first heat transfer medium tube lumen connecting the first heat transfer medium inlet to the first heat transfer medium outlet, The second reactor is A second reaction tube having a second gas inlet and a second gas outlet, and having a second reaction tube lumen connecting the second gas inlet to the second gas outlet, It comprises a second heat transfer medium tube having a second heat transfer medium inlet and a second heat transfer medium outlet, and a second heat transfer medium tube having a lumen connecting the second heat transfer medium inlet to the second heat transfer medium outlet, The first reaction tube is, A methanation catalyst for the methane reaction of carbon dioxide is placed in the lumen of the first reaction tube, and The mechanism comprises the following: gaseous raw materials flow into the lumen of the first reaction tube at the first gas inlet; the gaseous raw materials are brought into contact with a methanation catalyst for the methane reaction of carbon dioxide in the lumen of the first reaction tube to undergo a chemical reaction; and the first gas mixture containing the gaseous products obtained from the chemical reaction flows out of the lumen of the first reaction tube at the first gas outlet. The first heat transfer medium tube is The mechanism has such that the heat transfer medium flows into the lumen of the first heat transfer medium tube at the first heat transfer medium inlet, and the heat transfer medium flows out of the lumen of the first heat transfer medium tube at the first heat transfer medium outlet, and The first reaction tube is inserted into the lumen of the first heat transfer medium tube, and the heat transfer medium in the lumen of the first heat transfer medium tube exchanges heat with the material in the lumen of the first reaction tube via the wall of the first reaction tube, The connecting pipe is, It has a connecting tube lumen that connects the first gas outlet and the second gas inlet, thereby connecting the lumen of the first reaction tube and the lumen of the second reaction tube, and The system has a mechanism in which the first gas mixture flows into the lumen of the connecting pipe at the first gas outlet, by-products are removed from the first gas mixture in the lumen of the connecting pipe to obtain the remainder of the first gas mixture, and the remainder of the first gas mixture flows out of the lumen of the connecting pipe at the second gas inlet. The second reaction tube is, A methanation catalyst for the methane reaction of carbon dioxide is placed in the lumen of the second reaction tube, and The mechanism is such that at the second gas inlet, only the remainder of the first gas mixture flows into the lumen of the second reaction tube, where the remainder of the first gas mixture is brought into contact with a methanation catalyst for the methane reaction of carbon dioxide to undergo a chemical reaction, and at the second gas outlet, the second gas mixture, including the gaseous product obtained from the chemical reaction, flows out of the lumen of the second reaction tube. The second heat transfer medium tube is The mechanism has such that the heat transfer medium flows into the lumen of the second heat transfer medium tube at the second heat transfer medium inlet, and the heat transfer medium flows out of the lumen of the second heat transfer medium tube at the second heat transfer medium outlet, The second reaction tube is inserted into the lumen of the second heat transfer medium tube, and the heat transfer medium in the lumen of the second heat transfer medium tube exchanges heat with the material in the lumen of the second reaction tube via the wall of the second reaction tube, and It has a mechanism that ensures the average residence time in the first reaction tube is shorter than the average residence time in the second reaction tube. The gaseous raw material contains at least hydrogen gas and carbon dioxide gas. The gaseous product is methane, and the by-product is water. The heat transfer medium is one that can maintain fluidity without deterioration within the temperature range required for the methane reaction of carbon dioxide, and is selected from among polyhydric alcohols, phenols, phenolic ethers, polyphenyls, chlorinated benzenes, chlorinated polyphenyls, silicate esters, naphthalene derivatives, mineral oils, fractional distillation tars, petroleum products, nitrates, nitrites, silicones, fluorine compounds, glycols, molten metals, or molten alloys. A device for obtaining gaseous products using carbon dioxide.

2. The apparatus according to claim 1, wherein the first reaction tube has heat transfer fins protruding inward from the inner surface of the reaction tube wall.

3. The apparatus according to claim 2, wherein the heat transfer fins are provided only on the portion closest to the first gas inlet.

4. An apparatus for obtaining a gaseous product according to any one of claims 1 to 3, wherein the radial cross-section of the first reaction tube is flattened.

5. The apparatus according to any one of claims 1 to 4, wherein the radial cross-section of the second reaction tube is flattened.

6. The apparatus according to claim 4, wherein there are multiple first reaction tubes, and each first reaction tube is arranged such that the longitudinal directions of the flattened radial cross-sections of the tubes are parallel to each other.

7. The apparatus according to claim 5 or 6, wherein there are multiple second reaction tubes, and each second reaction tube is arranged such that the longitudinal directions of the flattened radial cross-sections of the tubes are parallel to each other.

8. In the apparatus according to any one of claims 1 to 7, The process involves supplying a gaseous raw material into the lumen of the first reaction tube at the first gas inlet, and supplying a heat transfer medium into the lumen of the first heat transfer medium tube at the first heat transfer medium inlet, allowing it to flow through the lumen of the first heat transfer medium tube, and then discharging it from the lumen of the first heat transfer medium tube at the first heat transfer medium outlet, thereby controlling the temperature of the contents within the lumen of the first reaction tube while carrying out a chemical reaction. The first gas mixture containing the gaseous product obtained from the chemical reaction is discharged from the lumen of the first reaction tube at the first gas outlet and supplied to the lumen of the connecting tube. By-products are removed from the first gas mixture in the lumen of the connecting pipe to obtain the remainder of the first gas mixture. The chemical reaction is carried out while controlling the temperature of the contents inside the second reaction tube lumen by discharging only the remainder of the first gas mixture from the connecting tube lumen at the second gas inlet and supplying it to the second reaction tube lumen, and by supplying the heat transfer medium to the second heat transfer medium tube lumen at the second heat transfer medium inlet, allowing it to flow through the second heat transfer medium tube lumen, and discharging it from the second heat transfer medium tube lumen at the second heat transfer medium outlet. The second gas mixture containing the gaseous product obtained from the chemical reaction is discharged from the lumen of the second reaction tube at the second gas outlet, and The average residence time in the first reaction tube should be shorter than the average residence time in the second reaction tube. Includes, The gaseous raw material contains at least hydrogen gas and carbon dioxide gas. The gaseous product is methane, and the by-product is water. The heat transfer medium is one that can maintain fluidity without deterioration within the temperature range required for the methane reaction of carbon dioxide, and is selected from among polyhydric alcohols, phenols, phenolic ethers, polyphenyls, chlorinated benzenes, chlorinated polyphenyls, silicate esters, naphthalene derivatives, mineral oils, fractional distillation tars, petroleum products, nitrates, nitrites, silicones, fluorine compounds, glycols, molten metals, or molten alloys. A method for obtaining gaseous products using carbon dioxide.

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