Chemical reaction method, chemical reaction device, and manufacturing method

Abstract

To improve a yield of a product.SOLUTION: In a chemical reaction device (100) for carrying out a reaction in which a progress of the reaction in a gas phase that improves a yield of a product is restricted due to chemical equilibrium between a raw material and the product, an integrated value obtained by integrating a product of a distance L between a surface of a catalyst layer (3) in contact with a transmission wall (40) and an external surface of a cooling surface (53), and a height H of the catalyst layer (3) corresponding to the external surface having the distance L, from one end to the other end of the cooling surface (53) in a height direction is 500 mm2 or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a chemical reaction apparatus and a chemical reaction method in which a chemical reaction for obtaining a product from a raw material gas proceeds in a gas phase using a catalyst. [Background technology]

[0002] Patent Document 1 discloses a method and apparatus for synthesizing methanol by reacting a feed gas mainly composed of hydrogen and carbon monoxide or carbon dioxide in the presence of a catalyst. In this method, methanol liquefied on a cooling surface is extracted from the reaction system, and the reaction to produce methanol is allowed to proceed beyond the equilibrium conversion rate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2005-298413 (published on October 27, 2005) Summary of the Invention [Problem to be solved by the invention]

[0004] It is known that in a reaction method in which a reaction proceeds in a gas phase using a catalyst, including a reaction method using a reactor such as that described in Patent Document 1, changing condition parameters such as the pressure in the reaction system, the temperature, and the ratio of the catalyst amount to the raw material supply rate (W / F) contributes to the reaction yield of the product.

[0005] An object of one aspect of the present invention is to provide a chemical reaction method and a chemical reaction apparatus that improves the yield of a product by changing the internal structure of the reaction apparatus without changing the condition parameters. [Means for solving the problem]

[0006] In order to solve the above-mentioned problems, one aspect of the present invention provides a chemical reaction method for promoting a reaction in which a product contains a component having a boiling point higher than that of a component in a raw material gas, and the progress of the reaction in a gas phase is restricted by chemical equilibrium between the raw material and the product, the method comprising: a catalyst layer containing a catalyst for promoting the reaction; a cooling surface disposed at a space apart from the catalyst layer, maintained at a temperature equal to or lower than the dew point of a reaction gas produced by the reaction, and extending in a predetermined direction; and a permeable wall disposed at a boundary between the catalyst layer and the space and allowing the reaction gas to pass therethrough, the permeable wall being provided at the boundary between the catalyst layer and the space, the permeable wall being provided at the boundary between the catalyst layer and the cooling surface, and the height of the catalyst layer corresponding to the cooling surface at that distance, the product being obtained by integrating the product from one end of the cooling surface in the predetermined direction to the other end of the cooling surface, and the product being 500 mm 2 Using the chemical reaction apparatus described above, the raw material gas is supplied to the catalyst layer to cause the chemical reaction to proceed, and a portion of the product produced by the chemical reaction is condensed on the cooling surface and within the space.

[0007] A chemical reaction apparatus according to one aspect of the present invention is a chemical reaction apparatus for carrying out a reaction in which a product contains a component having a boiling point higher than that of a component in a raw material gas, and the progress of the reaction in a gas phase is restricted by chemical equilibrium between the raw material and the product, the chemical reaction apparatus comprising: a catalyst layer to which the raw material gas is supplied and which contains a catalyst that promotes the reaction; a cooling surface disposed at a space apart from the catalyst layer, maintained at a temperature equal to or lower than the dew point of the reactant gas, and extending in a predetermined direction; and a permeable wall disposed at a boundary between the catalyst layer and the space and capable of transmitting the reactant gas produced by the reaction, the permeable wall being provided at the boundary between the catalyst layer and the space, the permeable wall being provided at the boundary between the catalyst layer and the space, and the height of the catalyst layer corresponding to the outer surface having said distance, the integrated value obtained by integrating the product of the distance between the surface of the catalyst layer that contacts the permeable wall and the outer surface of the cooling surface and the height of the catalyst layer corresponding to the outer surface having said distance from one end to the other end of the cooling surface in the predetermined direction is 500 mm 2 As described above, a part of the product is condensed on the cooling surface and in the space.

[0008] A chemical reaction apparatus according to one aspect of the present invention comprises a reaction vessel including at least one multi-layered reaction tube in which a reaction occurs in a gas phase, the reaction containing a component having a boiling point higher than that of a component in a raw material gas, and the progress of the reaction in the gas phase is restricted by chemical equilibrium between the raw material and the product, and each of the at least one reaction tube comprises an inner tube through which a reaction gas produced by the reaction can pass, an outer tube having the inner tube disposed therein, a cooling tube disposed inside the inner tube and extending in a predetermined direction, and a catalyst layer disposed between the inner tube and the outer tube, and the product of the distance between the surface of the catalyst layer in contact with the inner tube and the outer surface of the cooling tube and the height of the catalyst layer corresponding to the outer surface having the distance is integrated from one end to the other end of the cooling tube in the predetermined direction. 2 The temperature of the outer surface of the cooling pipe is maintained at a temperature below the dew point of the reaction gas, and a portion of the product is condensed in the space formed between the cooling pipe and the inner cylinder.

[0009] A chemical reaction apparatus according to one aspect of the present invention comprises a reaction vessel including at least one multi-layered reaction tube in which a reaction occurs in a gas phase, the reaction containing a component having a boiling point higher than that of a component in a raw material gas, and the progress of the reaction in the gas phase is restricted by chemical equilibrium between the raw material and the product, and each of the at least one reaction tube comprises an inner tube through which a reaction gas produced by the reaction can pass, an outer tube having the inner tube disposed therein and extending in a predetermined direction, and a catalyst layer disposed inside the inner tube, wherein the product of the distance between the surface of the catalyst layer in contact with the inner tube and the inner surface of the outer tube and the height of the catalyst layer corresponding to the inner surface having the distance is integrated from one end to the other end of the inner surface in the predetermined direction. 2 The temperature of the inner surface of the outer cylinder is maintained at a temperature below the dew point of the reaction gas, causing a portion of the product to condense in the space formed between the outer cylinder and the inner cylinder.

[0010] A method for producing methanol according to one aspect of the present invention is a method for producing methanol in which a reaction in a gas phase containing a component having a boiling point higher than that of a component in a feed gas proceeds, and the progress of the reaction in the gas phase is restricted by chemical equilibrium between the feed gas and the product, the method comprising: a catalyst layer containing carbon oxides and hydrogen as the feed gas; a cooled surface disposed at a space from the catalyst layer and maintained at a temperature equal to or lower than the dew point of a reaction gas produced by the reaction, the cooled surface extending in a predetermined direction; and a permeable wall disposed at a boundary between the catalyst layer and the space and allowing the reaction gas to pass therethrough, the product of the distance between the surface of the catalyst layer in contact with the permeable wall and the cooled surface and the height of the catalyst layer corresponding to the cooled surface at that distance being integrated from one end to the other end of the cooled surface in the predetermined direction, the product being 500 mm 2 Using the above-described chemical reaction apparatus, the raw material gas is supplied to the catalyst layer to cause the chemical reaction to proceed, and a portion of the reaction gas produced by the chemical reaction is condensed on the cooling surface and within the space. [Effects of the Invention]

[0011] According to one aspect of the present invention, the product yield can be improved by modifying the internal structure of a reactor in which a gas-phase reaction is restricted by the chemical equilibrium between the raw material and the product. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a cross-sectional view of a reaction apparatus according to a first embodiment. [Figure 2] 1 is a partial schematic cross-sectional view of a reaction apparatus according to a first embodiment. [Figure 3] FIG. 10 is a cross-sectional view of a reaction device according to a second embodiment. [Figure 4] FIG. 10 is a cross-sectional view of a reaction tube provided in a reaction apparatus according to a second embodiment. [Figure 5] FIG. 10 is a cross-sectional view of a reaction device according to a third embodiment. [Figure 6] FIG. 10 is a cross-sectional view of a reaction tube included in a reaction apparatus according to a third embodiment. [Figure 7]1 is a graph showing the relationship between distance L and height H for a comparative example and examples 1 to 5. [Figure 8] 1 is a graph showing the relationship between the integrated value of the product of the distance L and the height H and the methanol production rate in Comparative Example and Examples 1 to 5. DETAILED DESCRIPTION OF THE INVENTION

[0013] [Embodiment 1] (Configuration of reaction device 100) An embodiment of the present invention will be described in detail below. FIG. 1 is a cross-sectional view of a reaction apparatus 100 (chemical reaction apparatus) according to embodiment 1, cut along a plane perpendicular to the bottom surface. The reaction apparatus 100 is a chemical reaction apparatus in which a reaction containing a component with a higher boiling point than the main component of the raw material gas 31 as a product proceeds, and the progress of the reaction in the gas phase is restricted by chemical equilibrium between the raw material and the product. Note that the X-axis, Y-axis, and Z-axis in the drawings define directions in the three-dimensional space of each drawing. In this specification, "height" corresponds to the length in the Z-axis direction of the drawing. Hereinafter, in this specification, the X-axis, Y-axis, and Z-axis each represent the same direction.

[0014] In the reaction apparatus 100, the product is condensed and recovered from the reaction vessel, thereby shifting the chemical equilibrium toward the product and allowing the reaction to proceed. In particular, the reaction apparatus 100 is suitable for use as an apparatus for carrying out the chemical reactions shown in the following formulas (1) to (3), in which the raw material gas 31 contains carbon oxides and hydrogen and the product contains methanol.

[0015] CO + 2H2 ⇔ CH3OH (1) CO2 + 3H2 ⇔ CH3OH + H2O (2) CO2 + H2 ⇔ CO + H2O (3) When producing methanol through the chemical reactions represented by the above formulas (1) to (3), a catalyst containing copper and zinc can be used as a methanol synthesis catalyst (catalyst 30, described in detail below). Examples of carbon oxides used in this chemical reaction include carbon dioxide and carbon monoxide. In this chemical reaction, a gas containing at least one of carbon dioxide and carbon monoxide and hydrogen can be used as a raw material gas.

[0016] In addition to the methanol synthesis reaction described above, reactor 100 can also be used to perform reactions that produce dimethyl ether or ammonia as products.

[0017] 1, the reaction apparatus 100 includes a reaction vessel 1, a first heat exchange section 22, a catalyst layer 3 in contact with the first heat exchange section 22, a permeable wall 40, and a second heat exchange section 52 disposed across a space 4 from the permeable wall 40. The permeable wall 40 is provided on the catalyst layer 3 on the side opposite to the side where the first heat exchange section 22 is located. The reaction vessel 1 is a pressure-resistant metal vessel made of, for example, stainless steel.

[0018] The first heat exchange section 22 is a heat exchanger composed of the inner wall surface of the reaction vessel 1 and a first heat exchange wall 20, and has a heat transfer surface 23 on the catalyst layer 3 side. A first heat medium region 2 through which a first heat medium 21 flows is formed inside the first heat exchange section 22. The first heat exchange section 22 is formed with a first heat medium supply port 25 for supplying the first heat medium 21 to the first heat medium region 2 and a first heat medium recovery port 26 for discharging the first heat medium 21 from the first heat medium region 2. The first heat exchange wall 20 is made of a material that is impermeable to fluids, and the heat transfer surface 23 of the first heat exchange wall 20 acts as the first heat exchange surface. While the first heat exchange wall 20 is shown as a plate-shaped member in FIG. 1 , its shape is not limited to a plate-like shape. The surface of the first heat exchange wall 20 may be shaped, for example, in a corrugated form. Furthermore, the shape of the first heat exchange section 22 is not limited to the shape shown in FIG. 1, and various shapes such as a multi-tube type or a spiral type can be adopted as long as they improve the efficiency of heat exchange.

[0019] The first heat exchange section 22 can maintain the heat transfer surface 23 at a temperature higher than the dew point of the reaction gas 32 by circulating the first heat medium 21 through the first heat medium region 2. When the reaction occurring in the catalyst layer 3 is an exothermic reaction, the first heat medium 21 acts as a heat medium for cooling the reaction heat generated by the reaction. When the reaction occurring in the catalyst layer 3 is an endothermic reaction, the first heat medium acts as a heat medium for adding heat to the catalyst layer 3 in order to maintain the temperature of the catalyst layer 3 at or above the dew point of the reaction gas 32.

[0020] Here, the "dew point of the reaction gas 32" means the temperature at which condensation begins when the reaction gas 32 is cooled under the conditions where the reaction in the gas phase has reached chemical equilibrium at the temperature and pressure at which the reaction gas 32 exists in the catalyst layer 3.

[0021] The dew point of the reaction gas 32 can be calculated simultaneously with the condensed liquid composition by performing an appropriate vapor-liquid equilibrium calculation using a vapor-liquid equilibrium model, given the vapor phase composition and pressure. For high pressures exceeding 1 MPa, an extended cubic equation of state, such as the Peng-Robinson equation or the Redich-Kwong-Soave equation, can be used as the vapor-liquid equilibrium model.

[0022] The temperature of the heat transfer surface 23 is preferably such that the entire catalyst layer 3 is maintained at a temperature higher than the dew point of the reaction gas 32. By providing the heat transfer surface 23, the reactor 100 can maintain the temperature of the catalyst layer 3 at a temperature suitable for the reaction, thereby improving the efficiency of the reaction. When the product is methanol, for example, high-pressure boiler water at 220 to 265°C (e.g., saturated water at 2.2 MPaG to 5.0 MPaG), molten metal salt (e.g., a mixture of sodium nitrite and potassium nitrate), or heat transfer oil can be used as the first heat transfer medium 21. In this specification, "A to B" means A or higher and B or lower.

[0023] The second heat exchange section 52 is a heat exchanger composed of the inner wall surface of the reaction vessel 1 and a second heat exchange wall 50. A second heat medium region 5 through which a second heat medium 51 flows is formed inside the second heat exchange section 52. The second heat exchange section 52 is provided with a second heat medium supply port 55 for supplying the second heat medium 51 to the second heat medium region 5 and a second heat medium recovery port 56 for discharging the second heat medium 51 from the second heat medium region 5. The second heat exchange wall 50 is made of a material that is impermeable to fluids. The second heat exchange section 52 has a cooling surface 53 on the space 4 side. The cooling surface 53 extends in the Z-axis direction and maintains a temperature below the dew point of the reaction gas 32, thereby cooling the reaction gas 32 in the space 4 and condensing products on the cooling surface 53 and in the space 4. While the second heat exchange wall 50 is shown as a plate-shaped member in FIG. 1 , its shape is not limited to a plate shape. That is, the cooling surface 53 may be formed in a wave shape, etc. Furthermore, the shape of the second heat exchange section 52 is not limited to the shape shown in Fig. 1, and various shapes that improve the efficiency of heat exchange, such as a multi-tube type or a spiral shape, may be adopted.

[0024] The second heat exchange section 52 can maintain the temperature of the cooling surface 53 at or below the dew point of the reaction gas 32 by circulating the second heat medium 51 through the second heat medium region 5. When the product is methanol, the second heat medium 51 can be, for example, low-pressure boiler water at 80 to 150°C (for example, saturated water at -0.05 to 0.4 MPaG), cooling water at -20 to 100°C (for example, methanol water, ethylene glycol water), industrial water, an aqueous ammonia solution, a hydrocarbon compound such as pentane, or a fluorocarbon compound such as 1,1,1,3,3-pentafluoropropane.

[0025] More specifically, when the reaction catalyzed by the catalyst 30 is an exothermic reaction that takes place at a temperature 80°C or more higher than the dew point of the reaction gas 32, it is preferable that the temperature of the first heat medium 21 is 5 to 30°C lower than the average temperature of the catalyst layer 3, and the temperature of the second heat medium 51 is 20°C or more lower than the dew point of the reaction gas 32. Here, the temperatures of the first heat medium and the second heat medium refer to the average of the temperatures at the respective supply ports and recovery ports.

[0026] 1, the first heat medium supply port 25 and the first heat medium recovery port 26, and the second heat medium supply port 55 and the second heat medium recovery port 56 are formed at the bottom and top of the reaction vessel 1. However, it should be understood that these positions can be provided at appropriate positions and with appropriate specifications depending on the pressure of the heat medium used. Furthermore, the supply temperature and supply pressure of the first heat medium 21 and the second heat medium 51 can be set to appropriate values ​​depending on the temperature of the reaction performed in the reaction vessel 1 and the dew point of the reaction gas 32.

[0027] The catalyst layer 3 is filled with a catalyst 30 suitable for the reaction. The catalyst layer 3 contains the catalyst 30 and is the region where the raw material gas 31 comes into contact with the catalyst 30 and the reaction proceeds. For example, a catalyst containing copper and zinc oxide as its main components can be used as the catalyst 30. The space between the catalyst layer 3 and the reaction vessel 1 may be filled with fillers 300. In addition, a support plate (not shown) made of a porous member may be provided at the bottom of the catalyst layer 3 to support the catalyst 30.

[0028] 2 is a partially enlarged cross-sectional view of the reactor 100 according to the first embodiment cut along a plane perpendicular to the bottom surface. FIG. 2 shows an example in which a plurality of protrusions are formed in the Z-axis direction of the cooling surface 53. As shown in FIG. 2, the catalyst layer 3 is formed at a distance L X Height H corresponding to the cooling surface 53 with (x=1, 2, ...) X (x=1, 2, ...) and the distance L X is the distance between the surface of the catalyst layer 3 that contacts the permeable wall 40 and the cooling surface 53. Specifically, the height H1 corresponding to the distance L1, the height H2 corresponding to the distance L2, and the distance L n The height H corresponding to n In this case, the height H of the catalyst layer 3 is X The sum of (H1+H2+ +H n ) In addition, when the surface of the catalyst layer 3 in contact with the permeable wall 40 and the cooling surface 53 are flat in the Z-axis direction, the distance L X is the same distance over the entire cooling surface 53. Therefore, the distance at a given position in this case can be simply expressed as distance L.

[0029] When the catalyst layer 3 is configured as a set of multiple discontinuous catalyst layers as shown in FIG. 2, the height H of the catalyst layer 3 is X The sum of (H1+H2+ +H n ) can be expressed as

[0030] Depending on the filling condition of the catalyst 30, the upper or lower end face of the catalyst layer 3 may not be flat, or the upper and lower end faces may not be parallel. In such cases, in this specification, the height H of the catalyst layer 3 means the height of the catalyst layer 3 at the contact surface with the permeable wall 40. Even when the surface of the catalyst layer 3 that contacts the permeable wall 40 is not flat, the distance L is the same as when the above-mentioned convex portions are formed on the cooling surface 53. X and height H X This stipulates:

[0031] From the viewpoint of the throughput per reactor, the height H X The total of these should preferably be 1,000 mm or more. X The sum of these is preferably 20,000 mm or less.

[0032] The permeable wall 40 is provided at the boundary between the catalyst layer 3 and the space 4 and is a member that allows the reaction gas 32 to pass through. The permeable wall 40 is made of a metal member, for example, stainless steel. The permeable wall 40 is made of a material that allows the reaction gas 32 to pass through but does not allow the catalyst 30 to pass through, such as a metal mesh with an appropriate pore size. The reaction gas 32 contains unreacted raw material gas and uncondensed reaction product gas.

[0033] The space 4 is a space formed between the permeable wall 40 and the cooling surface 53. A condensate reservoir 47 capable of storing a product condensed and liquefied on the cooling surface 53 and / or in the vicinity of the cooling surface 53 is formed in the lower part of the space 4, and the condensate 41 is recovered through a condensate recovery port 46 provided in the bottom of the condensate reservoir 47.

[0034] Here, the distance L between the surface of the catalyst layer 3 in contact with the permeable wall 40 and the cooling surface 53 is X It is preferable that the distance L is 0.5 mm or more and 500 mm or less. X When the partial areas of the cooling surface 53 facing the catalyst layer 3 are added together, the range of distance L is preferably realized in an area of ​​80% or more of the vertical length of the total added area, and more preferably realized in an area of ​​95% or more. X The distance L is preferably 0.5 mm or more in order to ensure sufficient space for the condensed droplets to fall by gravity. X If the distance L is less than 0.5 mm, condensation of the product may occur in the catalyst layer 3. X If the distance L is greater than 500 mm, the size of the reaction vessel 1 increases, which may result in various costs increasing and causing economic inconvenience. X is preferably 0.5 mm or more and 500 mm or less.

[0035] (Regarding the integrated value) In the reactor 100 of this embodiment, the distance L between the surface of the catalyst layer 3 that contacts the permeable wall 40 and the cooling surface 53 is X and distance L X The height H of the catalyst layer 3 corresponding to the cooling surface having X The product of these values ​​from one end of the cooling surface 53 to the other in the Z-axis direction is 500 mm 2 That's all.

[0036] In the present invention, the integrated value from one end of the cooling surface 53 to the other end in a predetermined direction is 500 mm 2 That is, at least at one predetermined location, the integrated value from one end of the cooling surface 53 in the Z-axis direction to the other end is 500 mm 2 If the integrated value differs depending on the predetermined position in the X-axis direction, the integrated value integrated from one end of the cooling surface 53 in the Z-axis direction to the other end is 500 mm or more in a region of 50% or more, preferably 80% or more, more preferably 95% or more, and particularly preferably 100% in the X-axis direction.2 It could be.

[0037] The reactor 100 has a cooling surface 53 in the Z-axis direction that is 500 mm thick at least at one predetermined point in the X-axis direction. 2 As a result, the integrated value is 500mm in the 100% area in the X-axis direction. 2 When compared with a reactor with a smaller reaction volume, the reaction yield of the product can be improved even if the condition parameters are the same. The condition parameters include the pressure, temperature, and the ratio of the catalyst amount to the raw material supply rate (W / F) in the reaction system.

[0038] In the above reaction, in which the chemical equilibrium is shifted to the product side by condensing the product and recovering it from the reaction vessel, the overall reaction rate is governed by either the reaction rate of the reaction occurring in the catalyst layer 3, the diffusion rate of the product toward the cooling surface 53, or the condensation rate on the cooling surface 53. X Increasing the distance L is thought to reduce the driving force that shifts the chemical equilibrium toward the product side. X However, the present inventors have modified the internal structure of the reactor 100 so that the integrated value is 500 mm 2 It has been found that by adopting the above structure, the reaction yield of the product can be improved.

[0039] On the other hand, as mentioned above, from an economic point of view, the distance L X is preferably 500 mm or less, and the height H X Since the sum of these is preferably 20,000 mm or less, the above integrated value is 10,000,000 mm 2 It is preferable that the integrated value is 500 mm or less. 2 More than 10,000,000mm 2 By having the following configuration, the reactor 100 and the chemical reaction method using the reactor 100 can improve the reaction yield of the product. In addition, it is possible to provide a reactor 100 and a chemical reaction method that are preferable from an economical point of view.

[0040] (Reaction flow) The raw material gas 31 is supplied from a raw material gas inlet 35 provided at the top of the catalyst layer 3, and the reaction proceeds by contacting the raw material gas 31 with the catalyst 30 packed in the catalyst layer 3. The reaction gas 32 produced by the reaction passes through the permeable wall 40 and advances into the space 4, where it is cooled by the cooling surface 53 to a temperature below the dew point of the reaction gas 32, thereby condensing the product. The condensed and liquefied product falls into the condensate reservoir 47 and is recovered as the condensate 41 via the condensate recovery port 46.

[0041] The reaction gas 32 passing through the permeable wall 40 from the catalyst layer 3 side also contains unreacted raw material gas. However, the main component contained in the unreacted raw material gas is not condensed on the cooling surface 53. Furthermore, since the condensate reservoir 47 is provided in the lower part of the space 4, the unreacted raw material gas is not discharged together with the condensate 41 from the condensate recovery port 46, but returns to the catalyst layer 3 again.

[0042] Here, it is preferable to maintain the gas flow rate passing through the permeable wall 40 within an appropriate range so that the ratio of unreacted raw material gas passing through the space 4 toward the outlet of the catalyst layer 3 does not become excessively high. In order to maintain the gas flow rate within the appropriate range, for example, the porosity of the porous member forming the permeable wall 40 may be adjusted. Alternatively, in order to maintain the gas flow rate within the appropriate range, a member that acts as a resistance to the gas flow may be inserted into the space 4.

[0043] The reaction gas 32 containing the raw materials that did not react in the catalyst layer 3 is recovered from a reaction gas recovery port .

[0044] (Recovery of reaction heat and condensation heat) The first heat medium 21 is supplied from a first heat medium supply port 25 as boiler water at, for example, 2.2 to 5.0 MPaG. In the case of an exothermic reaction, the reaction heat generated in the catalyst layer 3 is heat exchanged via the first heat exchange wall 20 and recovered in the first heat medium 21. The first heat medium 21 passes through a first heat medium recovery port 26 and is recovered in a high-pressure steam separation drum (not shown). Thereafter, the high-pressure steam obtained by gas-liquid separation is used, for example, as a power source for compressing the raw material.

[0045] The second heat medium 51 is supplied from a second heat medium supply port 55 as, for example, boiler water of 0.05 MPaG. The second heat medium 51 recovers heat from the reaction gas 32 to the second heat medium 51 by heat exchange via the second heat exchange wall 50 to reduce the temperature of the reaction gas 32 in the space 4 to below the dew point on the surface of the cooling surface 53. The second heat medium 51 passes through a second heat medium recovery port 56 and is recovered in a low-pressure steam separation drum (not shown). Thereafter, the low-pressure steam obtained by gas-liquid separation is used, for example, as a heat source in a product purification process.

[0046] (Effects of the first embodiment) As described above, the reaction apparatus 100 of the first embodiment is a chemical reaction apparatus in which a reaction containing a component with a higher boiling point than the components in the raw material gas 31 as a product proceeds, and in which the progress of the reaction in the gas phase is restricted by the chemical equilibrium between the raw material and the product. The chemical reaction method of the first embodiment is a method using the reaction apparatus 100. The reaction apparatus 100 includes a catalyst layer 3 to which the raw material gas 31 is supplied and which contains a catalyst 30 that promotes the reaction, a cooling surface 53 that is disposed across a space 4 from the catalyst layer 3 and is maintained at a temperature below the dew point of the reaction gas 32, and extends in a predetermined direction, and a permeable wall 40 that is provided at the boundary between the catalyst layer 3 and the space 4 and allows the reaction gas 32 produced by the reaction to pass through. The distance L between the surface of the catalyst layer 3 that contacts the permeable wall 40 and the cooling surface 53 is X and distance L X The height H of the catalyst layer corresponding to the cooling surface 53 having X The product of these values ​​from one end of the cooling surface 53 to the other in the height direction is 500 mm. 2 The reactor 100 condenses a part of the product on the cooling surface 53 and in the space 4.

[0047] According to the reactor 100 and the chemical reaction method using the reactor 100, by recovering the product as condensate 41 from inside the reaction vessel 1, it is possible to cause the reaction to proceed beyond the equilibrium conversion rate in a reaction system in which the progress of the reaction in the gas phase is restricted by chemical equilibrium.

[0048] In addition, in the reactor 100, at least at one predetermined point in the X-axis direction, the integrated value from one end to the other end of the cooling surface 53 in the Z-axis direction is 500 mm 2 As a result, the reactor 100 and the chemical reaction method using the reactor 100 have a 100% area in the X-axis direction where the integrated value is 500 mm 2 The reaction yield of the product can be improved even when using the same condition parameters as a reactor with less than 1000 kJ / cm2.

[0049] In the reaction apparatus 100 and the chemical reaction method using the reaction apparatus 100, the methanol production method using the raw material gas 31 containing carbon oxides and hydrogen and the catalyst 30 being a catalyst for methanol synthesis can improve the reaction yield of methanol.

[0050] [Embodiment 2] Other embodiments of the present invention will be described below. For ease of explanation, the same reference numerals will be used to designate components having the same functions as those described in the first embodiment, and the description thereof will not be repeated.

[0051] Fig. 3 is a cross-sectional view of the reaction apparatus 100A according to the second embodiment, cut along a plane perpendicular to the bottom surface. Fig. 4 is a cross-sectional view of the reaction tube 10A included in the reaction apparatus 100A, cut along a plane perpendicular to the longitudinal axis of the reaction tube 10A. The basic principle of the reaction apparatus 100A is the same as that of the reaction apparatus 100. The reaction apparatus 100A differs from the reaction apparatus 100 in that a cylindrical reaction tube is used in the reaction apparatus 100A.

[0052] Similar to the reactor 100, the reactor 100A can be suitably used as an apparatus for carrying out a chemical reaction in which the raw material gas 31 contains carbon oxides and hydrogen and the product contains methanol. Alternatively, the reactor 100A can be used for carrying out a reaction that produces dimethyl ether or ammonia as a product.

[0053] The following impurities in the source gas 31 are preferably reduced to a level that does not significantly affect methanol production: sulfur compounds and elemental sulfur (e.g., hydrogen sulfide, carbonyl sulfide, carbon disulfide, sulfur oxide, thiophene, methyl thiocyanate), halogen compounds and elemental halogens (e.g., hydrogen chloride, chlorinated hydrocarbons), metal carbonyls (e.g., Fe carbonyl, Ni carbonyl), metal compounds (e.g., metal compounds containing vanadium and alkali metals), nitrogen compounds (e.g., ammonia, amines, nitrogen oxide, nitriles, hydrogen cyanide), liquid and solid substances (e.g., tar, carbon black, soot, ash, metal fines), and unsaturated hydrocarbons. The catalyst 30 is not particularly limited as long as it promotes the reaction, but it may be a catalyst containing Cu or Zn, or may further contain Al, Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si, rare earth elements, Ga, or the like.

[0054] (Reactor 100A) As shown in FIG. 3, the reaction apparatus 100A includes a plurality of reaction tubes 10A extending in the Z-axis direction inside a reaction vessel 1A. The number of reaction tubes 10A provided inside the reaction vessel 1A is not particularly limited as long as it is one or more. Considering the reaction efficiency, it is preferable that the number of reaction tubes 10A is more than one. A raw material gas supply section 37A filled with a raw material gas 31 to be supplied to each reaction tube 10A is formed above the plurality of reaction tubes 10A. A storage section 48A for storing a liquid condensed inside the reaction tube 10A and a gas that has passed through the catalyst layer 3A is formed below the plurality of reaction tubes 10A. A second heat medium recovery section 58A for storing a second heat medium 51 discharged from a second heat exchange section 52A (cooling pipe) described later is formed below the storage section 48A. Further below, a second heat medium supply section 57A is formed to store the second heat medium 51 to be supplied to the second heat exchange section 52A. Each of the above sections is formed by dividing the internal space of the reaction vessel 1A with a metal plate, for example, a stainless steel plate.

[0055] The reaction tube 10A is open to a metal plate 11A located at the upper part of the reaction tube 10A and a metal plate 12A located at the lower part of the reaction tube 10A, and an outer cylinder 20A of the reaction tube 10A and the metal plates 11A and 12A are joined together by welding.

[0056] 2 and 4, the reaction tube 10A includes, in order from the outside, an outer cylinder 20A, a cylindrical catalyst layer 3A in contact with the inner wall surface of the outer cylinder 20A, an inner cylinder 40A provided inside the catalyst layer 3A, and a second heat exchanger 52A (cooling pipe). The second heat exchanger 52A is disposed across a space 4A (first space) from the inner cylinder 40A.

[0057] The first heat exchange section 22A is a heat exchanger that is composed of a part of the inner wall surface of the reaction vessel 1A, the outer wall surface of the outer casing 20A, and metal plates 11A and 12A, and has a heat transfer surface 23A on the catalyst layer 3A side. A first heat medium region 2A that is common to the plurality of reaction tubes 10A is formed inside the first heat exchange section 22A. A first heat medium 21 (heat medium) flows through the first heat medium region 2A. The first heat medium 21 is a heat medium for maintaining the outer casing 20A at a temperature higher than the dew point of the reaction gas 32. The outer casing 20A is made of a material that is impermeable to fluids, and the heat transfer surface 23A of the outer casing 20A acts as a first heat exchange surface.

[0058] The side wall of the reaction vessel 1A is formed with a first heat medium supply port 25A for supplying the first heat medium 21 to the first heat medium region 2A and a first heat medium recovery port 26A for discharging the first heat medium 21 from the first heat medium region 2A. The first heat exchanger 22A circulates the first heat medium 21 through the first heat medium region 2A, thereby maintaining the heat transfer surface 23A at a temperature higher than the dew point of the reaction gas 32. By providing the heat transfer surface 23A, the reaction apparatus 100A can maintain the temperature of the catalyst layer 3A at a temperature suitable for the reaction, thereby improving the reaction efficiency.

[0059] As shown in FIGS. 3 and 4, the second heat exchange section 52A includes a second heat exchange wall 50A and an inner pipe 59A. A second heat medium region 5A is formed between the second heat exchange wall 50A and the inner pipe 59A. The second heat medium region 5A is a region through which the second heat medium 51 flows. The second heat exchange section 52A has a double-pipe structure. The second heat medium 51 in the second heat medium supply section 57A is supplied into the second heat exchange section 52A through the inner pipe 59A. Meanwhile, the flow path between the outer wall surface of the inner pipe and the inner wall surface of the second heat exchange wall 50A communicates with the interior of the second heat medium recovery section 58A. The second heat medium 51 leaving the second heat medium supply section 57A and reaching the upper end of the inner pipe passes through the flow path and is discharged into the second heat medium recovery section 58A through an outlet 54A formed in the upper wall surface of the second heat medium recovery section 58A.

[0060] The second heat exchange wall 50A is made of a material that does not allow fluid to pass through, and the cooling surface 53A (the outer surface of the cooling pipe) of the second heat exchange wall 50A acts as the second heat exchange surface. The second heat exchange section 52A can maintain the temperatures of the second heat exchange wall 50A and the cooling surface 53A at or below the dew point of the reaction gas 32 by circulating the second heat medium 51 through the second heat medium region 5A.

[0061] The catalyst layer 3A is filled with a catalyst 30 suitable for the reaction. The upper end of the reaction tube 10A is covered with a metal cap except for the upper end of the catalyst layer 3A, preventing gas flow. An opening 38A is formed above the catalyst layer 3A, and a raw material gas 31 is supplied to the catalyst layer 3A through the opening 38A. The upper end of the catalyst layer 3A and the opening 38A do not need to be on the same plane, and a filler 300A may be filled between the upper end of the catalyst layer 3A and the opening 38A. An opening 39A is formed below the catalyst layer 3A. The lower end of the catalyst layer 3A and the opening 39A do not need to be on the same plane, and a filler 300A may be filled between the lower end of the catalyst layer 3A and the opening 39A. A support member made of, for example, a metal mesh is provided at the lower end of the catalyst layer 3A, and the support member serves to prevent the catalyst 30 from falling.

[0062] The catalyst layer 3A extends in the Z-axis direction over a distance LA The height H corresponding to the cooling surface 53A having A The distance L A is the distance between the surface of the catalyst layer 3A that contacts the inner cylinder 40A and the cooling surface 53A. When the cooling surface 53A is a curved surface with no irregularities in the Z-axis direction, the length from the upper end to the lower end of the catalyst layer 3A is simply the height H A On the other hand, if the cooling surface 53A has irregularities in the Z-axis direction, the distance L A When the distance L is not constant, the catalyst layer 3A X The height H corresponding to X Specifically, a height H1 corresponding to the distance L1, a height H2 corresponding to the distance L2, and the distance L n The height H corresponding to n In this case, the length from the top end to the bottom end of the catalyst layer 3 is equal to the height H X The sum of (H1+H2+ +H n ) can be expressed as

[0063] distance L X It is preferable that the distance L is 0.5 mm or more and 500 mm or less. X When the partial areas of the cooling surface 53A facing the catalyst layer 3A are added together, it is preferable that this range be realized over an area of ​​80% or more of the vertical length of the total added area, and more preferably over an area of ​​95% or more.

[0064] Height H XThe sum of the lengths is preferably 1,000 mm or more and 20,000 mm or less. If the sum is smaller than 1,000 mm, it is necessary to increase the number of reaction tubes 10A in order to ensure a sufficient catalyst loading amount in the reaction apparatus 100A. Since an increase in the number of reaction tubes 10A leads to an increase in production costs, etc., from an economical point of view, the sum is preferably 1,000 mm or more. If the sum is larger than 20,000 mm, it is necessary to manufacture a very long reaction tube 10A and a tall reaction apparatus 100A. Since such a reaction tube 10A and reaction apparatus 100A leads to an increase in production costs, etc., from an economical point of view, the sum is preferably 20,000 mm or less.

[0065] The inner cylinder 40A is made of a porous member that allows gas to pass therethrough, and allows gas containing products produced in the catalyst layer 3A and unreacted raw materials to pass through to the second heat exchange section 52A side.

[0066] The space 4A is a space formed between the inner cylinder 40A and the second heat exchange wall 50A. In this embodiment, a condensate liquid circulation pipe (communication pipe) 42A is provided vertically below the space 4A. The condensate liquid circulation pipe 42A is configured to extend the space 4A vertically downward and is made of a material that is impermeable to liquids. More specifically, the condensate liquid circulation pipe 42A forms a space (second space) 6A that is continuous with the space 4A between the condensate liquid circulation pipe 42A and the surface of the second heat exchange section 52A.

[0067] A reservoir 48A is formed below the reaction tube 10A to store the condensate 41 generated in the space 4A and the gas that has passed through the catalyst layer 3A, vertically below the space 4A. The condensate flow pipe 42A is provided inside the reservoir 48A, and the lower end of the condensate flow pipe 42A is positioned so as to be immersed in the condensate 41 stored in the bottom of the reservoir 48A (referred to as a condensate reservoir 47A).

[0068] Furthermore, the upper space (referred to as the gas collection area 49A) inside the storage area 48A stores the uncondensed gas 32A that has passed through the catalyst layer 3A. The uncondensed gas 32A is a gas that is discharged after the reaction gas 32 passes through the catalyst layer 3A without condensing, passes through the gas collection area 49A (storage area 48A), and comes into contact with the condensed liquid storage area (liquid storage area) 47A. The storage area 48A includes an uncondensed gas collection port 36A (exhaust section) that discharges the uncondensed gas 32A stored in the gas collection area 49A. The uncondensed gas collection port 36A is provided at a position vertically above the lower end of the condensed liquid flow pipe 42A.

[0069] Condensate 41, which is a product condensed in space 4A, passes through condensate flow pipe 42A and is discharged to condensate reservoir 47A. Condensate 41 in reservoir 47A is recovered through condensate recovery port 46A provided near the bottom of reservoir 48A. Discharge of fluid from condensate recovery port 46A is controlled so that reaction gas 32 is not recovered from condensate recovery port 46A.

[0070] (Regarding the integrated value) The reactor 100A of this embodiment has a distance L X and height H X The product of these values ​​from one end of the cooling surface 53A to the other in the height direction is 500 mm. 2 In the case where the reaction apparatus 100A is a multi-tube reactor including a plurality of reaction tubes 10A, the integrated value is 500 mm for each reaction tube 10A. 2 That's all.

[0071] In the present invention, the integrated value from one end to the other end of the cooling surface 53A in a predetermined direction is 500 mm 2 That is, at least at one predetermined location, the integrated value from one end to the other end of the cooling surface 53A in the Z-axis direction is 500 mm 2If the integrated value differs depending on a predetermined position in the X-axis direction, the integrated value integrated from one end to the other end of the cooling surface 53A in the Z-axis direction should be 500 mm or more in a region of 50% or more, preferably 80% or more, more preferably 95% or more, and particularly preferably 100% in the X-axis direction. 2 In this embodiment, the X-axis direction means the circumferential direction of the cooling surface 53A having a cylindrical shape.

[0072] The inventors have determined that the integrated value from one end to the other end of the cooling surface 53A in the Z-axis direction at least at one predetermined point in the circumferential direction of the cylindrical cooling surface 53A is 500 mm 2 By satisfying the above, the integrated value is 500 mm in 100% of the circumferential area of ​​the cylindrical cooling surface 53A. 2 It was experimentally found that the reaction yield of the product can be improved compared to a reactor with a smaller capacity than the conventional reactor, even when the condition parameters are the same. The condition parameters include the pressure, temperature, and the ratio of the catalyst amount to the raw material feed rate (W / F) in the reaction system.

[0073] The conventional reactor has an integrated value of 500 mm 2 When the internal structure is changed to satisfy the above, the change can be realized, for example, by increasing the diameter of the inner cylinder 40A without changing the diameter of the outer cylinder 20A. First, consider the case where the filling amount of the catalyst 30 and the density of the catalyst 30 in the catalyst layer 3A (dilution ratio of the catalyst 30) are the same. In this case, if the diameter of the inner cylinder 40A is increased in the reaction tube 10A, the height H of the catalyst layer 3A will increase. X The total sum of the above will also increase. 2 It is possible to realize the above-described reactor 100A. In other words, this modification is a modification for increasing the area of ​​the contact portion between the catalyst layer 3A and the inner cylinder 40A.

[0074] In the above reaction, in which the chemical equilibrium is shifted to the product side by condensing the product and recovering it from the reaction vessel, the overall reaction rate is governed by either the reaction rate of the reaction occurring in the catalyst layer 3, the diffusion rate of the product diffusing toward the cooling surface 53, or the condensation rate on the cooling surface 53. When the overall reaction rate is diffusion-rate-determined, the distance L X Increasing the distance L X However, the present inventors have modified the internal structure of the reactor 100A so that the integrated value is 500 mm 2 It has been experimentally found that by adopting the above structure, the reaction yield of the product can be improved.

[0075] In addition, the above cumulative value is 500 mm 2 Any change to the internal structure that results in the height H X For example, by diluting the catalyst 30 in the catalyst layer 3A, the height H X In order to further increase the integrated value, the diameter of the inner cylinder 40A may be increased and the catalyst 30 may be diluted.

[0076] On the other hand, as mentioned above, from an economic point of view, the distance L X is preferably 500 mm or less, and the height H X Therefore, the total sum of the above is preferably 10,000,000 mm or less. 2 It is preferable that:

[0077] (Reaction flow) The raw material gas 31 is supplied from the raw material gas inlet 35A and supplied to the catalyst layer 3A in the reaction tube 10A through the opening 38A. The raw material gas 31 comes into contact with the catalyst 30 in the catalyst layer 3A, causing a reaction. The reaction gas 32 produced by the reaction passes through the inner tube 40A and advances to the space 4A, where it is cooled by the cooling surface 53A to a temperature below the dew point of the reaction gas 32, causing the product to condense. The condensed and liquefied product passes through the space 4A and the condensate flow pipe 42A and falls into the condensate storage section 47A. The condensate 41 stored in the condensate storage section 47A is recovered through the condensate recovery port 46A.

[0078] The reaction gas 32 passing through the inner cylinder 40A from the catalyst layer 3A side also contains unreacted raw material gas. However, the main components contained in the unreacted raw material gas are not condensed on the cooling surface 53A. In addition, since the lower end of the condensate liquid flow pipe 42A is immersed in the condensate liquid 41 stored in the condensate liquid storage section 47A, the unreacted raw material gas moving inside the condensate liquid flow pipe 42A is prevented from moving by the liquid surface of the condensate liquid 41 and returns to the catalyst layer 3A. A predetermined pressure is applied to the gas recovery area 49A by the injection of the raw material gas 31, and this pressure is also applied to the liquid surface of the condensate liquid 41 in the condensate liquid storage section 47A. Therefore, this liquid surface prevents the unreacted raw material gas from being discharged from the lower end of the condensate liquid flow pipe 42A without returning to the catalyst layer 3A. Here, the liquid height h in the condensate liquid storage section 47A A It is desirable that is maintained within a range that satisfies the following relationship:

[0079] h A =αΔP / ρg 1.0<α<10 h A : Reservoir liquid height [m], ΔP: Pressure loss of the reaction gas passing through the catalyst layer [Pa] ρ: Density of condensate [kg / m 3 ] g: Gravitational acceleration (=9.8[m / s 2 ]), α: Coefficient [-] h AIf this is too small, some of the reaction gas may pass through the space 4A and the condensate reservoir 47A and flow out of the condensate recovery port 46A together with the condensate, which may reduce the efficiency of contact with the catalyst 30. A If is too large, the height of the reaction vessel increases and the pressure in the space 4A becomes greater than the pressure in the catalyst layer 3A, which may hinder the transfer of the product from the catalyst layer 3A to the space 4A.

[0080] Uncondensed gas 32A containing raw materials that did not react in catalyst layer 3A is recovered in gas recovery region 49A and recovered from uncondensed gas recovery port 36A formed in the upper part of reservoir 48A.

[0081] (Recovery of reaction heat and condensation heat) The first heat medium 21 is supplied to the first heat exchange section 22A from the first heat medium supply port 25A. The reaction heat generated in the catalyst layer 3A is heat exchanged via the outer casing 20A and recovered in the first heat medium 21. The first heat medium 21 passes through the first heat medium recovery port 26A and is recovered in a high-pressure steam separation drum (not shown). Thereafter, the high-pressure steam obtained by gas-liquid separation is used, for example, as a power source for compressing the raw material.

[0082] The second heat medium 51 is supplied from the second heat medium supply port 55A to the second heat medium supply section 57A, and then supplied to the second heat exchange section 52A. The second heat medium 51 exchanges heat through the second heat exchange wall 50A to lower the temperature of the reaction gas 32 in the space 4A to below the dew point on the cooling surface 53A, thereby recovering heat from the reaction gas 32. The second heat medium 51 passes through the second heat medium recovery port 56A and is recovered in a low-pressure steam separation drum (not shown). The low-pressure steam obtained by gas-liquid separation is then used, for example, as a heat source in a product purification process.

[0083] (Effects of the second embodiment) As described above, the reaction apparatus 100A is equipped with a reaction vessel 1A including at least one multi-layered reaction tube 10A in which a reaction, in which the product contains components with a boiling point higher than that of the raw material gas and the progress of the reaction in the gas phase is restricted by chemical equilibrium between the raw material and the product, proceeds. Each of the at least one reaction tube 10A extends in the Z-axis direction and includes an inner tube 40A through which the reaction gas 32 generated by the reaction can permeate, an outer tube 20A in which the inner tube 40A is provided, a second heat exchanger 52A (cooling tube) provided inside the inner tube 40A, and a catalyst layer 3A provided between the inner tube 40A and the outer tube 20A. The distance L between the surface of the catalyst layer 3A in contact with the inner tube 40A and the cooling surface 53 is X and distance L X The height H of the catalyst layer 3A corresponding to the cooling surface 53 having the X The product of these values ​​is multiplied from one end of the cooling surface 53 to the other in the height direction to reach 500 mm. 2 The temperature of the cooling surface 53 is maintained at a temperature equal to or lower than the dew point of the reaction gas 32, and a part of the product is condensed in the space 4A formed between the second heat exchange section 52A and the inner cylinder 40A.

[0084] According to the reactor 100A configured as described above and the chemical reaction method using the reactor 100A, the reaction can be advanced beyond the equilibrium conversion rate by recovering the product as condensate 41 from within the reactor 100A.

[0085] In addition, in the reactor 100A, at least one predetermined point in the circumferential direction of the cylindrical cooling surface 53A, the integrated value from one end to the other end of the cooling surface 53A in the Z-axis direction is 500 mm 2 As a result, the reactor 100A and the chemical reaction method using the reactor 100A can achieve a temperature of 500 mm2 or higher in a 100% circumferential area of ​​the cylindrical cooling surface 53A. 2 The reaction yield of the product can be improved compared to a reactor having a smaller capacity.

[0086] [Embodiment 3] Another embodiment of the present invention will be described below. As can be seen from Fig. 3, in the second embodiment, a larger amount of the first heat medium 21 for recovering reaction heat can be used compared with the second heat medium 51 for recovering condensation heat. In other words, the reaction apparatus 100A of the second embodiment has an advantageous configuration in a reaction system in which removal of reaction heat is important.

[0087] On the other hand, the reactor 100B of the third embodiment described in detail below has an advantageous configuration in a reaction system in which removal of condensation heat is important. The basic principle of the reactor 100B is the same as that of the reactor 100A.

[0088] Like the reactor 100, the reactor 100B can be suitably used as an apparatus for carrying out a chemical reaction in which the raw material gas 31 contains carbon oxides and hydrogen and the product contains methanol. Additionally, the reactor 100B can also be used for carrying out a reaction that produces dimethyl ether or ammonia as a product.

[0089] Fig. 5 is a cross-sectional view of the reaction apparatus 100B taken along a plane perpendicular to the bottom surface. Fig. 6 is a cross-sectional view of the reaction tube 10B included in the reaction apparatus 100B taken along a plane parallel to and perpendicular to the longitudinal axis of the reaction tube 10B.

[0090] (Reaction Apparatus 100B) As shown in FIGS. 5 and 6, the reaction apparatus 100B includes a plurality of reaction tubes 10B in a reaction vessel 1B. The number of reaction tubes 10B provided in the reaction vessel 1B is not particularly limited as long as it is one or more. Considering the reaction efficiency, it is preferable that the number of reaction tubes 10B is more than one. A raw material gas supply section 37B filled with a raw material gas 31 to be supplied to each reaction tube 10B is formed above the plurality of reaction tubes 10B. A condensed liquid storage section 47B (liquid storage section) for storing a liquid condensed inside the reaction tube 10B is formed below the plurality of reaction tubes 10B. A gas recovery section 48B for storing a gas that has passed through the catalyst layer 3B is formed below the condensed liquid storage section 47B. A first heat medium recovery section 28B for storing a first heat medium 21 discharged from a first heat exchange section 22B (described later) is formed below the gas recovery section 48B. Further below, a first heat medium supply section 27B is formed to store the first heat medium 21 to be supplied to the first heat exchange section 22B. Each of the above sections is formed by dividing the internal space of the reaction vessel 1B with a metal plate, for example, a stainless steel plate.

[0091] The reaction tube 10B comprises, in order from the outside, an outer cylinder 50B, an inner cylinder 40B arranged with a space 4B (first space) separated from the inner wall surface of the outer cylinder 50B, a cylindrical catalyst layer 3B in contact with the inner wall surface of the inner cylinder 40B, and a first heat exchanger 22B (heat source) provided inside the catalyst layer 3B. The catalyst layer 3B has the same material and structure as the catalyst layer 3A. The inner cylinder 40B is a cylinder that allows the reaction gas 32 to permeate, and has the same material and structure as the inner cylinder 40A.

[0092] The second heat exchange section 52B is a heat exchanger constituted by a part of the inner wall surface of the reaction vessel 1A, the outer wall surface of the outer cylinder 50B, and metal plates 11B and 12B. Inside the second heat exchange section 52B, a second heat medium region 5B common to the plurality of reaction tubes 10B is formed. A second heat medium 51 flows through the second heat medium region 5B. The outer cylinder 50B is made of a material that is impermeable to fluids, and a cooling surface 53B of the outer cylinder 50B (the inner surface of the outer cylinder 50B) acts as a second heat exchange surface.

[0093] The side wall of the reaction vessel 1B is formed with a second heat medium supply port 55B for supplying the second heat medium 51 to the second heat medium region 5B and a second heat medium recovery port 56B for discharging the second heat medium 51 from the second heat medium region 5B. The second heat exchanger 52B can maintain the outer casing 50B and the cooling surface 53B at a temperature equal to or lower than the dew point of the reaction gas 32 by circulating the second heat medium 51 through the second heat medium region 5B.

[0094] 5 and 6, the first heat exchange section 22B is a heat exchanger including a first heat exchange wall 20B and an inner pipe 29B, and having a heat transfer surface 23B on the catalyst layer 3B side. A first heat medium region 2B is formed between the first heat exchange wall 20B and the inner pipe 29B. The first heat medium region 2B is a region through which the first heat medium 21 flows.

[0095] The first heat exchange section 22B has a double-pipe structure. The first heat medium 21 in the first heat medium supply section 27B is supplied into the first heat exchange section 22B through an inner pipe 29B. Meanwhile, the flow path between the outer wall surface of the inner pipe 29B and the inner wall surface of the first heat exchange wall 20B communicates with the interior of the first heat medium recovery section 28B. The first heat medium 21 that has passed through the inner pipe 29B passes through the flow path and is discharged into the first heat medium recovery section 28B through an outlet 24B formed in the upper wall surface of the first heat medium recovery section 28B.

[0096] The catalyst layer 3B extends in the Z-axis direction and has a distance L B The height H corresponding to the cooling surface 53B having B The distance L B is the distance between the surface of the catalyst layer 3B that contacts the inner cylinder 40B and the cooling surface 53B. B , distance L X , height H B and the length from the top to the bottom of the catalyst layer 3B (height H X The distance L X It is preferable that the distance L is 0.5 mm or more and 500 mm or less. XWhen the partial areas of the cooling surface 53B facing the catalyst layer 3B are added together, this range is preferably realized in an area of ​​80% or more of the vertical length of the total added area, and more preferably realized in an area of ​​95% or more.

[0097] Space 4B is a space formed between inner cylinder 40B and outer cylinder 50B. In this embodiment, a condensate liquid storage section 47B is provided vertically below space 4B. Furthermore, a condensate liquid circulation pipe 42B (extension pipe) is provided inside condensate liquid storage section 47B so as to extend vertically downward from outer cylinder 50B. The lower end of condensate liquid circulation pipe 42B is positioned so as to be immersed in condensate liquid 41 stored in condensate liquid storage section 47B. Condensate liquid circulation pipe 42B forms a space (second space) 6B inside condensate liquid storage section 47B, which is continuous with space 4B.

[0098] The liquid condensed in the space 4B (condensate 41) passes through the space 6B inside the condensate flow pipe 42B and is stored in the condensate storage section 47B. The condensate 41 stored in the condensate storage section 47B is collected through the condensate recovery port 46B. Here, discharge of the fluid from the condensate recovery port 46B is controlled so that the reaction gas 32 is not collected from the condensate recovery port 46B.

[0099] A gas recovery section 48B (gas storage section) into which gas that has passed through the catalyst layer 3B flows is provided vertically below the catalyst layer 3B. The gas recovery section 48B includes an uncondensed gas recovery port 36B (exhaust section).

[0100] In this way, the condensate storage section 47B and the gas recovery section 48B form separate spaces. Because the condensate storage section 47B forms a closed space with respect to gas, the source gas 31 that descends through the space 4B has nowhere to go and returns to the catalyst layer 3B. This reduces the possibility that the source gas 31 will pass through the space 4B and be discharged to the outside.

[0101] The first heat exchange section 22B passes through the gas recovery section 48B, and the lower end of an inner pipe 29B of the first heat exchange section 22B opens to the internal space of the first heat medium supply section 27B. A flow path between the outer wall surface of the inner pipe 29B and the inner wall surface of the first heat exchange wall 20B communicates with the interior of the first heat medium recovery section 28B. The first heat medium 21 that leaves the first heat medium supply section 27B and reaches the upper end of the inner pipe 29B passes through the flow path and is discharged into the first heat medium recovery section 28B through an outlet 24B formed in the upper wall surface of the first heat medium recovery section 28B.

[0102] (Regarding the integrated value) The reactor 100B of this embodiment has a distance L X , height H X The product of these values ​​from one end to the other end of the cooling surface 53B in the height direction is 500 mm. 2 In the case where the reaction apparatus 100B is a multi-tube reactor including a plurality of reaction tubes 10B, the integrated value is 500 mm for each reaction tube 10B. 2 That's all.

[0103] In the present invention, the integrated value from one end to the other end of the cooling surface 53B in a predetermined direction is 500 mm 2 That is, at least at one predetermined location, the integrated value from one end to the other end of the cooling surface 53B in the Z-axis direction is 500 mm 2 If the integrated value differs depending on a predetermined position in the X-axis direction, the integrated value from one end to the other end of the cooling surface 53B in the Z-axis direction should be 500 mm or more in a region of 50% or more, preferably 80% or more, more preferably 95% or more, and particularly preferably 100% in the X-axis direction. 2 In this embodiment, the X-axis direction means the circumferential direction of the cooling surface 53B having a cylindrical shape.

[0104] The conventional reactor was designed with an integrated value of 500 mm 2When the internal structure is changed to satisfy the above, the change can be realized, for example, by reducing the diameter of the inner tube 40B. First, consider the case where the filling amount of the catalyst 30 and the density of the catalyst 30 in the catalyst layer 3B (dilution ratio of the catalyst 30) are the same. In this case, if the diameter of the inner tube 40B is reduced in the reaction tube 10B, the height H of the catalyst layer 3B will be reduced. X The total sum of the above will also increase. 2 The reactor 100B described above can be realized. In other words, this modification is a modification that increases the area of ​​the contact portion between the catalyst layer 3B and the inner cylinder 40B.

[0105] In addition, the above cumulative value is 500 mm 2 Such a change in the internal structure can also be achieved by, for example, diluting the catalyst 30 in the catalyst layer 3B. To further increase the integrated value, the diameter of the inner cylinder 40A may be increased and the catalyst 30 may be diluted.

[0106] On the other hand, as mentioned above, from an economic point of view, the distance L X is preferably 500 mm or less, and the height H X Therefore, the total sum of the above is preferably 10,000,000 mm or less. 2 It is preferable that:

[0107] (Reaction flow) The raw material gas 31 is supplied from the raw material gas inlet 35B and supplied to the catalyst layer 3B in the reaction tube 10B through the opening 38B. The raw material gas 31 comes into contact with the catalyst 30 in the catalyst layer 3B, causing a reaction to proceed. The reaction gas 32 produced by the reaction passes through the inner cylinder 40B and advances to the space 4B, where it is cooled to a temperature below the dew point of the reaction gas 32 on the inner wall surface (second heat exchange surface) of the outer cylinder 50B, thereby condensing the product. The condensed and liquefied product passes through the space 4B and falls into the condensate reservoir 47B. The condensate 41 stored in the condensate reservoir 47B is recovered through the condensate recovery port 46B.

[0108] The reaction gas 32 passing through the inner cylinder 40B from the catalyst layer 3B side toward the outer cylinder 50B also contains unreacted raw material gas. However, the main components contained in the unreacted raw material gas are not condensed in the outer cylinder 50B. Furthermore, since the condensate storage section 47B forms a closed space with respect to gas, the unreacted raw material gas that descends into the space 4B has nowhere to go, is hindered by the liquid level of the condensate 41, and returns to the catalyst layer 3B. Here, the liquid height h in the condensate storage section 47B B It is desirable that is maintained within a range that satisfies the following relationship:

[0109] h B =αΔP / ρg 1.0<α<10 h B : Reservoir liquid height [m], ΔP: Pressure loss of the reaction gas passing through the catalyst layer [Pa] ρ: Density of condensate [kg / m 3 ] g: Gravitational acceleration (=9.8[m / s 2 ]), α: Coefficient [-] h B If this is too small, a portion of the reaction gas 32 passes through the space 4B and the condensate reservoir 47B and flows out of the condensate recovery port 46B together with the condensate, which may reduce the efficiency of contact with the catalyst 30. B If is too large, the height of the reaction vessel increases and the pressure in the space 4B becomes greater than the pressure in the catalyst layer 3B, which may hinder the mass transfer of the product from the catalyst layer 3B to the space 4B.

[0110] Uncondensed gas 32B containing raw materials that do not react in catalyst layer 3B and fall through catalyst layer 3B is recovered in gas recovery section 48B and recovered from uncondensed gas recovery port 36B formed in gas recovery section 48B.

[0111] (Recovery of reaction heat and condensation heat) The first heat medium 21 is supplied from the first heat medium supply port 25B to the first heat medium supply section 27B, and then supplied to the first heat exchange section 22B. The reaction heat generated in the catalyst layer 3B is heat exchanged via the first heat exchange wall 20B and recovered in the first heat medium 21. The first heat medium 21 passes through the first heat medium recovery port 26B and is recovered in a high-pressure steam separation drum (not shown). Thereafter, the high-pressure steam obtained by gas-liquid separation is used, for example, as a power source for compressing the raw material.

[0112] The second heat medium 51 is supplied from the second heat medium supply port 55B to the second heat exchanger 52B. The second heat medium 51 exchanges heat through the outer cylinder 50B to lower the temperature of the reaction gas 32 in the space 4B to below the dew point, thereby recovering heat from the reaction gas 32. The second heat medium 51 passes through the second heat medium recovery port 56B and is recovered in a low-pressure steam separation drum (not shown). Thereafter, the low-pressure steam obtained by gas-liquid separation is used, for example, as a heat source in a product purification process.

[0113] (Effects of the third embodiment) As described above, the reaction apparatus 100B is provided with a reaction vessel 1B including at least one multi-structured reaction tube 10B in which a reaction containing a product component with a boiling point higher than that of the raw material gas 31 and in which a reaction in the gas phase proceeds under the constraint of chemical equilibrium between the raw material and the product proceeds. Each of the at least one reaction tube 10B extends in the Z-axis direction and includes an inner tube 40B through which the reaction gas 32 produced by the reaction can pass, an outer tube 50B in which the inner tube 40B is provided, and a catalyst layer 3B provided inside the inner tube 40B. The distance L between the surface of the catalyst layer 3B in contact with the inner tube 40B and the cooling surface 53B is X and distance L X The height H of the catalyst layer 3B corresponding to the cooling surface 53B having the X The integrated value obtained by integrating the product of these values ​​from one end to the other end of the cooling surface 53B in the Z-axis direction is 500 mm 2 The temperature of the cooling surface 53B of the outer cylinder 50B is maintained at a temperature equal to or lower than the dew point of the reaction gas 32, and a portion of the product is condensed in the space 4 formed between the outer cylinder 50B and the inner cylinder 40B.

[0114] According to the reactor 100B configured as described above and the chemical reaction method using the reactor 100B, the reaction can be advanced beyond the equilibrium conversion rate by recovering the product as condensate 41 from the reactor 100B.

[0115] In addition, in the reaction apparatus 100B, at least one predetermined point in the circumferential direction of the cylindrical cooling surface 53B, the integrated value from one end to the other end of the cooling surface 53B in the Z-axis direction is 500 mm 2 As a result, the reactor 100B and the chemical reaction method using the reactor 100B can achieve a temperature of 500 mm2 or higher in a 100% circumferential area of ​​the cylindrical cooling surface 53B. 2 The reaction yield of the product can be improved even when using the same condition parameters as a reactor with less than 1000 kJ / cm2.

[0116] (Comparative Example and Examples 1 to 5) (Demonstration test) In this demonstration test, in order to investigate the relationship between the above-mentioned integrated value and the methanol production rate, a methanol synthesis reaction was carried out using the reaction apparatus 100A described in the second embodiment. 2 The examples implemented with an internal configuration where the distance L is less than 1 / 2 are referred to as Comparative Examples. Table 1 shows the internal configuration conditions and the results obtained for the Comparative Examples and Examples 1 to 5. Figure 7 shows the distance L A and height H A 8 is a graph showing the relationship between the above-mentioned integrated value and the methanol production rate in the comparative example and examples 1 to 5. The condition parameters common to the comparative example and examples 1 to 5 in this verification test are as follows:

[0117] Raw material flow rate...115[Ncc / min] Raw material gas composition: H2 72%, CO2 24%, N24% Catalyst: "Copper-based methanol synthesis catalyst" purchased from Alfa Aesar Catalyst loading amount...122[g] Ratio of catalyst amount to raw material feed rate (W / F) 412 [g / (mol / h)] Pressure: 0.85 [MPaG] Reaction temperature: 240°C Cooling water temperature...-10[℃] The conditions for the comparative example and each example are shown in Table 1 below. [Table 1] Examples 1 and 3 are examples in which the integrated value is increased by increasing the height H by diluting the catalyst 30 compared to the comparative example. Example 2 is an example in which the integrated value is increased by increasing the distance L compared to Example 1. Examples 4 and 5 are examples in which the integrated value is further increased by increasing the distance L and increasing the height H by diluting the catalyst 30 compared to Example 1.

[0118] As shown in FIG. 8, the integrated value is 500 mm in the 100% circumferential area of ​​the cylindrical cooling surface. 2 Compared with the comparative example where the integrated value is less than 500 mm 2 It can be seen that the methanol production rate was improved in all of the above Examples. Furthermore, it can be seen from Figure 7 that the higher the integrated value, the more improved the methanol production rate.

[0119] In other words, even if the condition parameters are the same, the integrated value is 2 It was demonstrated that by changing the internal structure as described above, the yield of the product can be improved.

[0120] (Other Examples) The following Examples 6 and 7 are within the scope of the present invention, although the condition parameters differ from those of Examples 1 to 5. Examples 6 and 7 are examples in which the integrated value is larger than those of Examples 1 to 5.

[0121] Example 6 The condition parameters for Example 6 are as follows: raw material flow rate: 1,000 [Ncc / min], raw material gas composition: H2 71%, CO2 25%, N24%, catalyst: "Copper-based methanol synthesis catalyst" purchased from Alfa Aesar, catalyst loading: 1,746 [g], catalyst dilution ratio: 1.0 [fold], ratio of catalyst amount to raw material supply rate (W / F): 679 [g / (mol / h)], pressure: 0.85 [MPaG], reaction temperature: 200 [°C], cooling water temperature: -10 [°C], distance L: 7.8 [mm], height H: 1,500 [mm], cumulative value: 11,700 [mm 2 The methanol production rate in Example 6 was 87.3%.

[0122] Example 7 The condition parameters for Example 7 are as follows: raw material flow rate: 1,000 [Ncc / min], raw material gas composition: H2 71%, CO2 25%, N24%, catalyst: "Copper-based methanol synthesis catalyst" purchased from Alfa Aesar, catalyst loading: 2580 [g], catalyst dilution ratio: 1.0 [fold], ratio of catalyst amount to raw material supply rate (W / F): 1003 [g / (mol / h)], pressure: 0.85 [MPaG], reaction temperature: 200 [°C], cooling water temperature: -10 [°C], distance L: 3.8 [mm], height H: 1,500 [mm], cumulative value: 5,700 [mm 2 The methanol production rate in Example 7 was 88.1%. [Explanation of symbols]

[0123] 1, 1A, 1B... Reaction vessel 3, 3A, 3B...Catalyst layer 4, 4A, 4B...space 10A, 10B...Reaction tube 20A....Outer cylinder 23, 23A, 23B... Heat transfer surface 30. Catalyst 31. Raw material gas 32. Reactive gas 40...Transparent wall 40A, 40B...Inner cylinder 50B....Outer cylinder 53, 53A, 53B cooling surface 100, 100A, 100B...Reactor 300, 300A, 300B...filling

Claims

1. A chemical reaction method in which a reaction containing a component having a boiling point higher than that of a component in a raw material gas is carried out in a gas phase, and the progress of the reaction in the gas phase is restricted by chemical equilibrium between the raw material and the product, comprising: a catalyst layer containing a catalyst that promotes the reaction; a cooling surface that is disposed apart from the catalyst layer, is maintained at a temperature equal to or lower than the dew point of the reaction gas produced by the reaction, and extends in a predetermined direction; a permeable wall that is provided at the boundary between the catalyst layer and the space and that allows the reaction gas to pass through; The product of the distance between the surface of the catalyst layer that is in contact with the permeable wall and the cooling surface and the height of the catalyst layer corresponding to the cooling surface having that distance is multiplied from one end to the other end of the cooling surface in the predetermined direction to 500 mm. ２ Using the above chemical reaction apparatus, supplying the raw material gas to the catalyst layer to cause a chemical reaction to proceed; A chemical reaction method, comprising condensing a portion of the product produced by the chemical reaction on the cooling surface and within the space.

2. 2. The chemical reaction method according to claim 1, wherein the source gas contains carbon oxides and hydrogen, and the product contains methanol.

3. The integrated value is 10,000,000 mm ２ The chemical reaction method according to claim 1 or 2, wherein:

4. A chemical reaction apparatus for carrying out a reaction in which a product contains a component having a boiling point higher than that of a component in a raw material gas, and the progress of the reaction in a gas phase is restricted by chemical equilibrium between the raw material and the product, a catalyst layer to which the raw material gas is supplied and which contains a catalyst that promotes the reaction; a cooling surface that is disposed apart from the catalyst layer, is maintained at a temperature equal to or lower than the dew point of the reaction gas, and extends in a predetermined direction; a permeable wall provided at the boundary between the catalyst layer and the space, which allows permeation of a reaction gas produced by the reaction, The integrated value obtained by integrating the product of the distance between the surface of the catalyst layer in contact with the permeable wall and the outer surface of the cooling surface and the height of the catalyst layer corresponding to the outer surface having that distance from one end to the other end of the cooling surface in the predetermined direction is 500 mm ２ That's all, A chemical reaction device in which a portion of a product is condensed on the cooled surface and within the space.

5. 5. The chemical reaction device according to claim 4, wherein the feed gas contains carbon oxides and hydrogen, and the product contains methanol.

6. The integrated value is 10,000,000 mm ２ 6. The chemical reaction device according to claim 4 or 5, wherein:

7. 7. The chemical reaction device according to claim 4, further comprising a heat transfer surface, which is maintained at a temperature higher than that of the cooling surface, on the opposite side of the catalyst from the permeable wall.

8. 8. The chemical reaction device according to claim 5, wherein the distance is 0.5 mm or more and 500 mm or less, and the height of the catalyst layer is 1,000 mm or more and 20,000 mm or less.

9. a reaction vessel including at least one reaction tube with a multi-layer structure in which a reaction occurs inside, the reaction containing a component in a product having a boiling point higher than that of a component in a raw material gas, the reaction being restricted in a gas phase by chemical equilibrium between the raw material and the product; Each of the at least one reaction tube comprises: an inner cylinder that allows permeation of the reaction gas generated by the reaction; an outer cylinder having the inner cylinder provided therein; a cooling pipe provided inside the inner cylinder and extending in a predetermined direction; a catalyst layer provided between the inner cylinder and the outer cylinder, The product of the distance between the surface of the catalyst layer that contacts the inner cylinder and the outer surface of the cooling pipe and the height of the catalyst layer corresponding to the outer surface having that distance is multiplied from one end to the other end of the cooling pipe in the predetermined direction to 500 mm. ２ That's all, the temperature of the outer surface of the cooling pipe is maintained at a temperature equal to or lower than the dew point of the reaction gas; A chemical reaction device in which a portion of the product is condensed in a space formed between the cooling pipe and the inner cylinder.

10. The integrated value is 10,000,000 mm ２ 10. The chemical reactor of claim 9, wherein:

11. 11. The chemical reaction apparatus according to claim 9, further comprising a heat transfer medium provided in a space defined by the inner wall of the reaction vessel and the outer wall of the reaction tube.

12. 12. The chemical reaction device according to claim 9, wherein the distance is 0.5 mm or more and 500 mm or less, and the height of the catalyst layer is 1,000 mm or more and 20,000 mm or less.

13. a reaction vessel including at least one reaction tube with a multi-layer structure in which a reaction occurs inside, the reaction containing a component in a product having a boiling point higher than that of a component in a raw material gas, the reaction being restricted in a gas phase by chemical equilibrium between the raw material and the product; Each of the at least one reaction tube comprises: an inner cylinder that allows permeation of the reaction gas generated by the reaction; an outer cylinder having the inner cylinder disposed therein and extending in a predetermined direction; a catalyst layer provided inside the inner cylinder, The product of the distance between the surface of the catalyst layer that contacts the inner cylinder and the inner surface of the outer cylinder and the height of the catalyst layer corresponding to the inner surface having that distance is multiplied from one end to the other end of the inner surface in the predetermined direction to 500 mm ２ That's all, the temperature of the inner surface of the outer cylinder is maintained at a temperature equal to or lower than the dew point of the reaction gas; A chemical reaction device in which a portion of the product is condensed in a space formed between the outer cylinder and the inner cylinder.

14. The integrated value is 10,000,000 mm ２ 14. The chemical reactor of claim 13, wherein:

15. The chemical reaction device according to claim 13 or 14, further comprising a heat source inside the catalyst layer.

16. 16. The chemical reaction device according to claim 13, wherein the distance is 0.5 mm or more and 500 mm or less, and the height of the catalyst layer is 1,000 mm or more and 20,000 mm or less.

17. A method for producing methanol in which a reaction in a gas phase containing a component having a boiling point higher than that of a component in a feed gas is carried out and the progress of the reaction in the gas phase is restricted by chemical equilibrium between the feed gas and the product, The raw material gas contains carbon oxide and hydrogen, a catalyst layer containing a catalyst for methanol synthesis; a cooling surface that is disposed apart from the catalyst layer, is maintained at a temperature equal to or lower than the dew point of the reaction gas produced by the reaction, and extends in a predetermined direction; a permeable wall that is provided at the boundary between the catalyst layer and the space and that allows the reaction gas to pass through; The product of the distance between the surface of the catalyst layer that is in contact with the permeable wall and the cooling surface and the height of the catalyst layer corresponding to the cooling surface having that distance is multiplied from one end to the other end of the cooling surface in the predetermined direction to 500 mm. ２ Using the above chemical reaction apparatus, supplying the raw material gas to the catalyst layer to cause a chemical reaction to proceed; a part of the reaction gas produced by the chemical reaction is condensed on the cooling surface and in the space.

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