Apparatus for obtaining a gaseous product

Abstract

Provided is a new apparatus for obtaining a gaseous product by subjecting a gaseous raw material to a chemical reaction in the presence of a catalyst. 【Solution means】The apparatus for obtaining a gaseous product includes a first reactor 110 having a first reaction tube lumen communicating from a first gas inlet to a first gas outlet, and a first heat transfer medium tube having a first heat transfer medium tube lumen communicating from a first heat transfer medium inlet 19 to a first heat transfer medium outlet 20. A catalyst is placed in the first reaction tube lumen. The apparatus further includes a second reactor 210 having the same mechanism as the first reactor, and a connecting pipe that connects the first gas outlet of the first reactor and the second gas inlet of the second reactor to communicate the first reaction tube lumen and the second reaction tube lumen.

Description

Technical Field

[0001] The present invention relates to an apparatus for obtaining a gaseous product. More specifically, the present invention relates to an apparatus 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 apparatuses for obtaining gaseous products. For example, Patent Document 1 discloses a production apparatus including a reaction section 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 for removing 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 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-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 an introduction-side / discharge-side holding plate positioned at both ends thereof on the first fluid introduction side and the first fluid discharge side, respectively, and plate-shaped or tuberous protrusions are formed on the wall surface of the flow path of each heat transfer tube 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, which includes, in the order of process flow: a) a first shell-and-tube reaction stage including a plurality of reaction tubes, wherein the reaction tubes of the first reaction stage contain 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, wherein the reaction tubes of the second reaction stage contain 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 discloses a ceramic heat exchanger provided with a honeycomb-structured first fluid flow-through portion partitioned by ceramic partitions and axially penetrating from one end face to the other end face, having a plurality of cells through which a heating body, which is a first fluid, flows, and a second fluid flow-through portion partitioned by ceramic partitions and penetrating in a direction orthogonal to the axial direction, thermally conductive through being separated by the first fluid flow-through portion and the partitions, having cells through which a second fluid flows, receiving heat of the first fluid flowing through the first fluid flow-through portion through the partitions, and transferring heat to the heated body, which is the second fluid flowing therethrough, wherein a plurality of the first fluid flow-through portion side cells and the second fluid flow-through portion side cells are alternately formed integrally, the cells on the first fluid flow-through portion side are smaller than the cells on the second fluid flow-through portion side, the density of the partitions is 0.5 to 5 g / cm 3 , and the heat exchanger has a heat conductivity of the partitions of 10 to 300 W / mK, and a catalyst is supported on the wall surface of the first fluid flow-through portion.

[0006] Patent Document 5 discloses a process of flowing a gas containing hydrogen into a plurality of process microchannels at an empty tower velocity of 0.01 meter per second for at least 1 second, flowing a liquid containing Fischer-Tropsch synthesis products into the plurality of process microchannels, the plurality of process microchannels containing a hydrocracking catalyst, the liquid forming a film on at least a part of the hydrocracking catalyst, the gas contacting the liquid, and the hydrogen reacting with the Fischer-Tropsch synthesis products in the presence of the hydrocracking catalyst to form hydrocracked Fischer-Tropsch synthesis products, wherein the hydrocracked Fischer-Tropsch synthesis products contain one or more linear aliphatic hydrocarbons having five or more carbon atoms, and the step of taking out the hydrocracked Fischer-Tropsch synthesis products from the plurality of process microchannels, and the heat moves from the plurality of process microchannels to a heat exchanger, and discloses a process of hydrocracking Fischer-Tropsch synthesis products in a microchannel reactor including the plurality of process microchannels.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0008] An object of the present invention is to provide a new apparatus for obtaining a gaseous product by causing a gaseous raw material to undergo a chemical reaction in the presence of a catalyst.

Means for Solving the Problems

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

[0010] 〔1〕 A first reaction tube having a first gas inlet and a first gas outlet and having a first reaction tube lumen communicating from the first gas inlet to the first gas outlet, and 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 communicating from the first heat transfer medium inlet to the first heat transfer medium outlet, The first reaction tube, has a first catalyst composed of a Ni-based catalyst, a platinum group metal-based catalyst, or another noble metal-based catalyst placed in the first reaction tube lumen, and a gaseous raw material containing carbon dioxide gas and hydrogen gas flows into the first reaction tube lumen at the first gas inlet, the gaseous raw material is brought into contact with the first catalyst in the first reaction tube lumen to cause a first chemical reaction, and a first gas mixture containing methane obtained by the first chemical reaction flows out of the first reaction tube lumen at the first gas outlet, having a mechanism, The first heat transfer medium tube, has a mechanism in which a heat transfer medium flows into the first heat transfer medium tube lumen at the first heat transfer medium inlet and the heat transfer medium flows out of the first heat transfer medium tube lumen at the first heat transfer medium outlet, and the first reaction tube is inserted into the first heat transfer medium tube lumen, and the heat transfer medium in the first heat transfer medium tube lumen exchanges heat with that in the first reaction tube lumen through the first reaction tube wall, a first reactor having a mechanism, A second reaction tube having a second gas inlet and a second gas outlet and having 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 and 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, has a second catalyst placed in the second reaction tube lumen, and a first gas mixture flows into the second reaction tube lumen at the second gas inlet, the first gas mixture is brought into contact with the second catalyst in the second reaction tube lumen to cause a second chemical reaction, and a second gas mixture containing a gaseous product obtained by the second chemical reaction flows out of the second reaction tube lumen at the second gas outlet, having a mechanism, The second heat transfer medium tube, has a mechanism in which a heat transfer medium flows into the second heat transfer medium tube lumen at the second heat transfer medium inlet and the heat transfer medium flows out of the second heat transfer medium tube lumen at the second heat transfer medium outlet, and the second reaction tube is inserted into the second heat transfer medium tube lumen, and the heat transfer medium in the second heat transfer medium tube lumen exchanges heat with that in the second reaction tube lumen through the second reaction tube wall, a second reactor having a mechanism, A connecting pipe having a heat exchanger that connects the first gas outlet and the second gas inlet to communicate the first reaction tube lumen and the second reaction tube lumen, exchanges heat between the first gas mixture and the gaseous raw material, and a mechanism for removing by-products from the first gas mixture, An apparatus for obtaining a gaseous product, including

[0011] 〔2〕 A first reaction tube having a first gas inlet and a first gas outlet and having 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 and 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, Nickel aluminate (NiAl x O y )、Ru / NiAl x O y, a first catalyst composed of Ru / Al2O3, Ru / TiO2, Ni / TiO2, or Ru-Ni / TiO2 is provided, and At the first gas inlet, a gaseous raw material containing carbon dioxide gas and hydrogen gas flows into the inner cavity of the first reaction tube. In the inner cavity of the first reaction tube, the gaseous raw material is brought into contact with the first catalyst to cause a first chemical reaction, and a first gas mixture containing methane obtained from the first chemical reaction flows out from the inner cavity of the first reaction tube at the first gas outlet. It has a mechanism, The first heat transfer medium tube, At the first heat transfer medium inlet, a heat transfer medium flows into the inner cavity of the first heat transfer medium tube, and at the first heat transfer medium outlet, the heat transfer medium flows out from the inner cavity of the first heat transfer medium tube. It has a mechanism, and The first reaction tube is inserted into the inner cavity of the first heat transfer medium tube, and the heat transfer medium in the inner cavity of the first heat transfer medium tube exchanges heat with that in the inner cavity of the first reaction tube through the wall of the first reaction tube. It has a mechanism, a first reactor, A second reaction tube having a second gas inlet and a second gas outlet and having a second reaction tube inner cavity 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 and having a second heat transfer medium tube inner cavity communicating from the second heat transfer medium inlet to the second heat transfer medium outlet, The second reaction tube, A second catalyst is placed in the inner cavity 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 the second catalyst to cause a second chemical reaction, and a second gas mixture containing a gaseous product obtained from the second chemical reaction flows out from the inner cavity of the second reaction tube at the second gas outlet. It has a mechanism, The second heat transfer medium tube, At the second heat transfer medium inlet, a heat transfer medium flows into the inner cavity of the second heat transfer medium tube, and 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. It has a mechanism, a second reactor, A connecting pipe that connects the first gas outlet and the second gas inlet to communicate the lumen of the first reaction tube and the lumen of the second reaction tube, and has a heat exchanger for heat-exchanging the first gas mixture and the gaseous raw material, and a mechanism for removing by-products from the first gas mixture, An apparatus for obtaining a gaseous product, comprising:

[0012] 〔3〕 The heat exchanger for heat-exchanging the first gas mixture and the gaseous raw material is located upstream of the connecting pipe in the flow direction of the first gas mixture flowing through the connecting pipe, relative to the mechanism for removing by-products from the first gas mixture. The apparatus for obtaining a gaseous product according to 〔1〕 or 〔2〕.

[0013] 〔4〕 The average residence time in the first reaction tube is shorter than the average residence time in the second reaction tube. The apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔3〕. 〔5〕 The connecting pipe removes water, which is a by-product, from the first gas mixture. The apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔4〕.

[0014] 〔6〕 The first reaction tube has heat transfer fins protruding inward from the inner surface of the reaction tube wall. The apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔5〕. 〔7〕 The heat transfer fins are provided only in the portion closer to the first gas inlet. The apparatus for obtaining a gaseous product according to 〔6〕. 〔8〕 The radial cross-section of the first reaction tube is flat. The apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔7〕. 〔9〕 The radial cross-section of the second reaction tube is flat. The apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔8〕.

[0015] 〔10〕 There are a plurality of first reaction tubes, and each first reaction tube is arranged such that the longitudinal directions in the flat shape of their radial cross-sections are parallel to each other. The apparatus for obtaining a gaseous product according to 〔8〕.

[0016] 〔11〕 An apparatus for obtaining a gaseous product according to 〔9〕, wherein there are a plurality of second reaction tubes, and each second reaction tube is arranged such that the longitudinal directions in their flat-shaped radial cross-sections are parallel to each other. 〔12〕 An apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔11〕, wherein the first catalyst is in powder form. 〔13〕 An apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔11〕, wherein the first catalyst is in a corrugated plate shape. 〔14〕 An apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔11〕, wherein the first catalyst is in a corrugated shape. 〔15〕 An apparatus for obtaining a gaseous product according to any one of 〔1〕 to 〔11〕, wherein the first catalyst is in a plate shape. 〔16〕 An apparatus for obtaining a gaseous product according to 〔15〕, wherein when the plate-shaped first catalyst is loaded, the first reaction tube has a clamping portion that protrudes inward from the inner surface of the first reaction tube wall to stabilize the position of the first catalyst. 〔17〕 An apparatus for obtaining a gaseous product according to 〔16〕, wherein the protrusions constituting the clamping portion face each other or alternate with each other.

Advantages of the Invention

[0017] The apparatus for obtaining a gaseous product of the present invention can uniformly control the temperature distribution in the reaction tube within a predetermined range and prevent problems related to hot spots. The apparatus for obtaining a gaseous product of the present invention is preferably used in chemical reactions such as generating methane gas and water using CO2.

Brief Description of the Drawings

[0018]

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Embodiments 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 a connecting pipe. In the apparatus of the present invention, a third reactor 310 may be provided via an additional connecting pipe downstream of the second reactor, and a fourth reactor 410 may be provided via an additional connecting pipe downstream of the third reactor.

[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 communicating 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, circular, oval, elliptical, oblong, rounded square, square, etc.

[0023] The first reaction tube 112 has a first gas inlet 104 and a first gas outlet 105 and has a first reaction tube inner cavity 123 that communicates from 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 square, square, etc., and is preferably a flat shape. The flat shape is preferably a rectangle (rectangular, rounded rectangle) or an oval (oval, oblong, elliptical). The aspect ratio (length in the longitudinal direction / length in the short transverse direction) of the flat shape has a lower limit that is preferably 1.2, more preferably 1.5, and even more preferably 2, and an upper limit that is preferably 20, more preferably 10, and even more preferably 5. In the device of the present invention, it is preferable that there are a plurality of first reaction tubes 112, and each first reaction tube is preferably arranged such that the longitudinal directions in the flat shape of their radial cross-sections are parallel to each other. Examples of the arrangement of the first reaction tubes include a mode in which a plurality of first reaction tubes are arranged in a vertical and horizontal array in a first heat transfer medium tube inner cavity having a rounded square radial cross-section as shown in FIGS. 5, 7, and 9, a mode in which the first reaction tubes are arranged in a single vertical row in a first heat transfer medium tube inner cavity having a rounded square radial cross-section as shown in FIG. 10, and a mode in which the first reaction tubes are arranged in a first heat transfer medium tube inner cavity having a circular radial cross-section as shown in FIG. 11, etc.

[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 a gaseous raw material flows into the first reaction tube inner cavity at the first gas inlet. The distinction between the first gas inlet and the first heat transfer medium inlet or the first heat transfer medium outlet can be made, 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, devices for preparing gaseous raw materials can be installed, such as a mixing mechanism for mixing the components constituting the gaseous raw materials at a predetermined ratio, a tank for storing the components constituting the gaseous raw materials, a compressor 11, a heat exchanger 22, etc. When the raw material is in a liquid state like liquefied carbon dioxide, an evaporator 14 etc. can be provided for safe vaporization. The components constituting the gaseous raw material at least include hydrogen gas and carbon dioxide gas used in the methanation reaction of carbon dioxide. The inflow rate of the gaseous raw material 8 into the first reaction tube inner cavity 123 can be appropriately set according to the chemical reaction carried out in the first reactor.

[0026] The heat transfer medium 19 flows into the first heat transfer medium tube inner cavity 124 at the first heat transfer medium inlet 116. The heat transfer medium is not particularly limited as long as it does not deteriorate and can maintain fluidity within 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 terphenyl; chlorinated benzenes and polyphenyls such as o-dichlorobenzene and polychlorinated polyphenyl; silicate esters such as tetraallyl silicate; fractionated tars and petroleum such as naphthalene derivatives and mineral oil; nitrates and nitrites (Heat Transfer Salt) 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; etc.

[0027] The positions of the first heat transfer medium inlet 116 and the first heat transfer medium outlet 117 are not particularly limited in their arrangement. However, as shown in FIGS. 5, 7, 9, 10, or 11, they are preferably arranged such that the heat transfer medium easily flows in a direction parallel to the longitudinal plane in the flat shape of the radial cross-section of the first reaction tube (the wider projection plane of the reaction tube as shown in FIG. 3). Further, as shown in FIG. 24, a partition plate 27 can be provided so that the heat transfer medium easily flows in a direction perpendicular to the short-side plane in the flat shape of the radial cross-section of the first reaction tube (the narrower projection plane of the reaction tube as shown in FIG. 4), and the heat transfer medium can be made to flow in a serpentine manner. Also, a helical partition plate may be provided to guide the heat transfer medium to flow helically 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 a gaseous raw material is brought into contact with the catalyst in the first reaction tube lumen to cause a chemical reaction. As the catalyst, those having shapes such as powder, granules, pellets, flat plates, corrugated plates, corrugated, honeycombs, etc. can be appropriately used. The catalyst may be loaded or filled in the first reaction tube lumen, or may be adhered to the inner surface of the first reaction tube wall.

[0029] When a plate-shaped catalyst is loaded, the first reaction tube may have a clamping portion protruding inward from the inner surface of the first reaction tube wall to stabilize the position of the plate-shaped catalyst. The shape and number of the clamping portions are not particularly limited. For example, as shown in FIGS. 17 and 18, the protrusions face each other; as shown in FIGS. 15 and 16, the protrusions face each other alternately; as shown in FIGS. 19 and 20, the T-shaped protrusions face each other alternately, etc. The clamping portion can be made of a material with high thermal conductivity and installed in contact with the plate-shaped catalyst to also serve as the heat transfer fins 2 described later.

[0030] The catalyst can be appropriately selected according to the chemical reaction 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 distinguished from the first heat transfer medium inlet 116 or the first heat transfer medium outlet 117. At the first gas outlet, the first gas mixture 109 containing methane flows out from the inner cavity 123 of the first reaction tube. The distinction between the first gas outlet and the first heat transfer medium inlet or the 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 side of the first gas outlet. At the first heat transfer medium outlet, the heat transfer medium flows out from the inner cavity of the first heat transfer medium tube. The outflowing heat transfer medium can be recycled.

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

[0033] The first reaction tube 112 is inserted into the inner cavity 124 of the first heat transfer medium tube and has a mechanism for heat exchange between the heat transfer medium 19 in the inner cavity 124 of the first heat transfer medium tube and that in the inner cavity 123 of the first reaction tube through the first reaction tube wall. The first reaction tube 112 preferably has heat transfer fins 2 protruding inward from the inner surface of the first reaction tube wall. Further, the first reaction tube can further have heat transfer fins 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 tends to be non-uniform. In a chemical reaction with a large amount of heat generation, hot spots may occur. It is preferable to suppress the generation of hot spots and make the temperature distribution in the flow direction of the reaction tube uniform. The heat transfer medium inlet 16 can be installed at a position close to the part where a hot spot may occur, or the inner cavity of the heat transfer medium tube can be divided by a partition plate, and a heat transfer medium inlet and a heat transfer medium outlet are provided for each of the divided parts, and the temperature of each heat transfer medium flowing through the divided inner cavity of the heat transfer medium tube can be made relatively lower on the side closer to the part where a hot spot may occur. Also, heat transfer fins can be provided in a larger number in the vicinity of the part where a hot spot may occur, and by 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 closer to the gas inlet 4 within the range where the catalyst is placed, or may be provided only in the part closer to the gas outlet 5 within the range where the catalyst is placed, or may be provided in the entire range where the catalyst is placed. In the reaction tube in which heat transfer fins are provided only in the part closer to the gas inlet 4 within the range where the catalyst is placed, FIG. 13 is a view showing a cross-section (C-C cross-section) closer to the gas inlet 4 of the reaction tube 12 filled with granular catalyst, and FIG. 14 is a view showing a cross-section (D-D cross-section) closer to the gas outlet 5 of the reaction tube 12 filled with granular catalyst.

[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 the mechanism 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 second reaction tube lumen at the second gas inlet. The distinction between the second gas inlet and the second heat transfer medium inlet or the second heat transfer medium outlet can be made, for example, by a plate that holds the end of the inlet side 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 brought into contact with the catalyst in the second reaction tube lumen to cause a chemical reaction. The catalyst can be appropriately selected according to the chemical reaction 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 a second gas mixture containing gaseous products flows out of the second reaction tube lumen at the second gas outlet. The heat transfer medium flows out of the second heat transfer medium tube lumen at the second heat transfer medium outlet, respectively. The outflowing heat transfer medium can be recycled. The second gas mixture 209 flowing out at the second gas outlet 205 may contain unreacted gaseous raw materials, gaseous by-products, etc. in addition to the gaseous products. The gaseous product obtained by 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 first reaction tube lumen and the second reaction tube lumen. The connecting pipe preferably has a mechanism for condensing by-products (water in the methanation reaction) contained in the first gas mixture to 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. The average residence time in the reaction tube where there is a risk of hot spot generation can be shortened to suppress hot spot generation. 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 adjustment of the average residence time can be carried out, for example, by making the total volume of the first reaction tube smaller than the total volume of the second reaction tube. The adjustment of the total volume can be carried out, 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, the third heat transfer medium tube, 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 the mechanism described for the first reactor. The connecting pipes for connecting the third reactor and the fourth reactor are the same as the connecting pipes 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. The average residence time in the third reaction tube and / or the fourth reaction tube is preferably longer than the average residence time in the second reaction tube.

[0041] Downstream of the second reactor 210 (downstream of the last reactor when the third reactor and / or the fourth reactor is installed), a device for separating and purifying the gaseous product, for example, 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. The unreacted gaseous raw material or water obtained in the separation and purification can be recycled.

[0042] Figs. 21 to 23 show another example of the device for obtaining the gaseous product of the present invention. In the device shown in Fig. 21, the thickness of the connecting pipe connecting between the two reactors is the same as the thickness of the reactor. The structure and mechanism of each reactor are the same as those already described.

[0043] The device for obtaining the gaseous product of the present invention is not particularly limited by its manufacturing method. For example, the reaction tube, the heat transfer medium tube, and the accessories can be prepared respectively, and they can be manufactured by 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 including forming them as a single-piece metal solid by stacking their cross-sectional shapes based on their 3D data.

[0045] The 3D data may be 3D shape data of the target part. The 3D shape data can be designed with 3DCAD. 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 (modeling) of a three-dimensional metal object by laminating cross-sectional shapes can be performed by methods such as the powder bed fusion (PBF) method, the metal deposition method, the fused deposition of materials (FDM) method, the liquid metal inkjet method, the binder jet method, and a hybrid method that performs cutting during laminated modeling by PBF. Among these, the powder bed fusion (PBF) method or the metal deposition method is preferred.

[0047] The powder bed fusion method is a method of spreading metal powder and melting and solidifying the part to be modeled with a laser or electron beam serving as a heat source. Modeling is performed by repeatedly spreading the metal powder and melting and solidifying it. After the modeling is completed, the un-solidified powder is removed and the modeled object is taken out.

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

[0049] The powder bed - laser beam heat source method irradiates the spread metal powder material with a laser beam to perform laminated modeling by melting, solidifying, or sintering. In the laser beam heat source method, melting and solidification are usually performed in an inert atmosphere such as nitrogen. The laser beam heat source method performs positioning when irradiating the laser by changing the angle of the mirror.

[0050] In the powder bed electron beam heat source method, an electron beam is irradiated and collided with a laid metal powder material in a high vacuum, converting kinetic energy into heat to melt the powder. The electron beam heat source method usually undergoes melting and solidification in a vacuum. The electron beam heat source method changes the direction of the electron beam using a lens by a magnetic field. As a result, the electron beam heat source method enables high-speed positioning.

[0051] The metal deposition method is a method of forming by laminating and solidifying a molten metal material at a predetermined location. The metal deposition method does not require the operation of removing powder after shaping.

[0052] The metal deposition method includes a laser beam heat source method using metal powder as a material, an arc discharge method using an alloy wire as a material, and the like.

[0053] In the metal deposition laser beam heat source method, metal powder is supplied to a melting pool and solidified by irradiating laser light while injecting metal powder from a nozzle to perform shaping. A three-dimensional shape is drawn by moving the melting nozzle or the stage. By switching the supply path of the metal powder, shaping of different metals can be achieved. Since the laser output is large, it is suitable for high-speed shaping.

[0054] In the metal deposition arc discharge method, an arc discharge at the tip of a metal wire melts the metal wire, and shaping is performed by laminating this. The equipment price and material cost are relatively low, and high-speed shaping can be achieved.

[0055] After shaping, heat treatment can be performed for stress relaxation, strength improvement, etc. Conditions such as temperature, time, and atmosphere in heat treatment can be appropriately set according to the metal material used, etc.

[0056] The method for obtaining the gaseous product of the present invention is as follows: in the apparatus 1 for obtaining the gaseous product of the present invention, a gaseous raw material 8 is supplied to the first reaction tube lumen 123 through the first gas inlet 104, a heat transfer medium is supplied to the first heat transfer medium tube lumen 124 through the first heat transfer medium inlet 116, and while flowing through the first heat transfer medium tube lumen and discharging it from the first heat transfer medium outlet 117, a chemical reaction is carried out while controlling the temperature of the substances in the first reaction tube lumen, discharging a first gas mixture 109 containing methane obtained by the chemical reaction from the first reaction tube lumen through the first gas outlet 105, supplying the first gas mixture to the second reaction tube lumen 223 through the second gas inlet 204, supplying a heat transfer medium to the second heat transfer medium tube lumen 224 through the second heat transfer medium inlet 216, and while flowing through the second heat transfer medium tube lumen and discharging it from the second heat transfer medium outlet 217, a chemical reaction is carried out while controlling the temperature of the substances in the second reaction tube lumen, and discharging a second gas mixture 209 containing the gaseous product obtained by the chemical reaction from the second reaction tube lumen through the second gas outlet.

[0057] In an apparatus further having a third reactor 310, supplying the second gas mixture 209 to the third reaction tube lumen 323 through the third gas inlet 304, supplying a heat transfer medium to the third heat transfer medium tube lumen 324 through the third heat transfer medium inlet 316, and while flowing through the third heat transfer medium tube lumen and discharging it from the third heat transfer medium outlet 317, a chemical reaction is carried out while controlling the temperature of the substances in the third reaction tube lumen, and discharging a third gas mixture 309 containing the gaseous product obtained by the chemical reaction from the third reaction tube lumen through the third gas outlet 305.

[0058] In an apparatus further having a fourth reactor 410, a third gas mixture 309 is supplied to a fourth reaction tube inner cavity 423 at a fourth gas inlet 404, a heat transfer medium is supplied to a fourth heat transfer medium tube inner cavity 424 at a fourth heat transfer medium inlet 416, the heat transfer medium is caused to flow through the fourth heat transfer medium tube inner cavity and discharged from the fourth heat transfer medium tube inner cavity at a fourth heat transfer medium outlet 417, thereby performing a chemical reaction while controlling the temperature of the contents in the fourth reaction tube inner cavity, and discharging a fourth gas mixture 409 containing a gaseous product obtained by the chemical reaction from the fourth reaction tube inner cavity at a fourth gas outlet 405.

[0059] In a 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 the gas containing CO2 and H2 to be introduced can be appropriately set according to the reaction rate, the capacity of the reaction tube inner cavity, etc. Depending on the ratio of CO2 and H2, the reduction reaction of CO2 proceeds as follows. CO2 + H2 → CO + H2O CO2 + 3H2 → CH3OH + H2O CO2 + 4H2 → CH4 + 2H2O

[0060] The apparatus 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 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 (steam), 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, a method for producing carbon monoxide and hydrogen, ethylene and water, or methanol by reacting methane with oxygen, and the like.

[0061] In the present invention, products (CO (carbon monoxide), methanol or methane) and unreacted substances (mainly CO2) obtained by the reduction reaction of CO2 can be separated and purified. Examples of the separation and purification method include a membrane separation method, an adsorption separation method, an absorption separation method, a distillation separation method, a cryogenic separation method, etc. In the separation and purification of methane, the membrane separation method is preferable from the viewpoints of separation selectivity, separation rate, and inexpensive and compact equipment. The unreacted substances (mainly CO2) and low-concentration methane obtained in the separation and purification of methane can be used as gaseous raw materials in the above-described methane production method.

[0062] In addition, the methane obtained by separation and purification can be supplied as fuel to a gas turbine. Electricity can be generated by this gas turbine. Since the combustion exhaust gas from the gas turbine usually contains carbon dioxide, this can be used as a gaseous raw material in the above-described methane production method.

[0063] The present invention can be used in various chemical reactions. The present invention is useful in the utilization of hydrogen generated by electrolysis of water or the like, the utilization of carbon dioxide generated by respiration of humans or animals or combustion of fuels or the like, the production of water, or the production of methane as a fuel or the like. The present invention can also be used in a space station, a spacecraft, a rocket, or the like.

Explanation of Reference Numerals

[0064] 1: Device for obtaining gaseous product 2: Heat transfer fin 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 catalyst (flat plate) 7: Plate catalyst (corrugated plate) 8: Gaseous raw material G1: Raw material gas LG2: Liquefied raw material gas 9: Gas containing gaseous product 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 417: Fourth heat transfer medium outlet 18: Gas-liquid separator 19: Heat transfer medium (inflow) 20: Heat transfer medium (outflow) 21: Drain 22: Heat exchanger 23: Inner cavity of reaction tube 123: Inner cavity of the first reaction tube 223: Inner cavity of the second reaction tube 323: Inner cavity of the third reaction tube 423: Inner cavity of the fourth reaction tube 24: Inner cavity of heat transfer medium tube 124: Inner cavity of the first heat transfer medium tube 224: Inner cavity of the second heat transfer medium tube 324: Inner cavity of the third heat transfer medium tube 424: Inner cavity of the fourth heat transfer medium tube 25: Inflow side retaining plate 26: Outflow side retaining plate 27: Partition plate

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 heat exchanger for exchanging heat between the first gas mixture and the gaseous raw material, and a mechanism for removing by-products from the first gas mixture; 1. An apparatus for obtaining a gaseous product comprising:

2. 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 The first reaction tube was filled with nickel aluminate (NiAl ｘ O ｙ ), Ru / NiAl ｘ O ｙ , Ru / Al ２ O ３ , Ru / TiO ２ , Ni / TiO ２ , or Ru-Ni / TiO ２ a first catalyst comprising: 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 heat exchanger for exchanging heat between the first gas mixture and the gaseous raw material, and a mechanism for removing by-products from the first gas mixture; 1. An apparatus for obtaining a gaseous product comprising:

3. 3. The apparatus for obtaining a gaseous product according to claim 1 or 2, wherein a heat exchanger for exchanging heat between the first gas mixture and the gaseous raw material is located upstream of the connecting pipe in the flow direction of the first gas mixture flowing through the connecting pipe relative to the mechanism for removing by-products from the first gas mixture.

4. 4. 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.

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

6. 6. 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.

7. 7. The apparatus for obtaining a gaseous product according to claim 6, wherein the heat transfer fins are provided only on a portion close to the first gas inlet.

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

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

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

11. 10. The apparatus for obtaining a gaseous product according to claim 9, 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.

12. The apparatus for obtaining a gaseous product according to any one of claims 1 to 11, wherein the first catalyst is a powder.

13. The apparatus for obtaining a gaseous product according to any one of claims 1 to 11, wherein the first catalyst is in the form of a corrugated plate.

14. An apparatus for obtaining a gaseous product according to any one of claims 1 to 11, wherein said first catalyst is in a corrugated shape.

15. The apparatus for obtaining a gaseous product according to any one of claims 1 to 11, wherein the first catalyst is in the form of a plate.

16. 16. The apparatus for obtaining a gaseous product according to claim 15, wherein the first reaction tube has a clamping portion protruding inward from an inner surface of the first reaction tube wall in order to stabilize the position of the first catalyst when the first catalyst is loaded in a plate shape.

17. 17. The device for obtaining a gaseous product according to claim 16, wherein the protrusions constituting the clamping portion are arranged to face each other or to face each other in a staggered manner.

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