WO2024252939A1 - Récipient de réaction multitubulaire - Google Patents

Récipient de réaction multitubulaire Download PDF

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Publication number
WO2024252939A1
WO2024252939A1 PCT/JP2024/018992 JP2024018992W WO2024252939A1 WO 2024252939 A1 WO2024252939 A1 WO 2024252939A1 JP 2024018992 W JP2024018992 W JP 2024018992W WO 2024252939 A1 WO2024252939 A1 WO 2024252939A1
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Prior art keywords
catalyst
temperature
vessel
filled
detection unit
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English (en)
Japanese (ja)
Inventor
治貴 浦部
真 土居
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JFE Engineering Corp
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JFE Engineering Corp
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Priority claimed from JP2023126690A external-priority patent/JP2024177002A/ja
Application filed by JFE Engineering Corp filed Critical JFE Engineering Corp
Publication of WO2024252939A1 publication Critical patent/WO2024252939A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes

Definitions

  • This relates to a reaction vessel equipped with a catalyst-filled vessel through which a reaction gas flows and which is filled with a catalyst, and in particular to a multi-tube reaction vessel in which the reaction vessel has multiple tubes.
  • Patent Document 1 discloses a method in which a heat transfer tube through which a refrigerant flows is provided in a catalyst packed bed, and cooling is performed from the packed bed.
  • the activity of the catalyst gradually decreases due to poisoning from impurities in the raw materials and adhesion of the products to the catalyst surface. For this reason, it is common for the catalyst packed in the reactor to be replaced periodically.
  • Patent Document 2 discloses a technique in which the tip of a double pipe is cut open, a vacuum pump hose is inserted to suck out the filler, and the pipe is refilled and then welded shut.
  • Patent Document 3 discloses a method in which a fluid is fed into a tube filled with a catalyst to flush the filler.
  • JP 2003-229147 A Japanese Patent Application Publication No. 10-328555 Japanese Unexamined Patent Publication No. 60-71036
  • the method of Patent Document 1 has a problem in that the cooling efficiency is good in the areas close to the heat transfer tubes in the packed bed, but is poor in areas away from the heat transfer tubes, such as near the wall of the packed container.
  • the vacuum pump power is used to suck out the catalyst.
  • the catalyst since the catalyst is sucked up, the catalyst may fall due to the effect of gravity, and there is a problem that it is difficult to recover all of it.
  • the container in the method of Patent Document 2, the container must be cut open prior to recovery of the catalyst, and the cut portion must be welded shut after filling, which is problematic in terms of labor and cost.
  • Patent Document 3 also has the problem that it requires power to transport the fluid. Also, when pushing the filler away, depending on the shape of the container, the filler may be trapped structurally, making it impossible to recover the entire amount.
  • the present invention has been made in order to solve the above problems, and a first object of the present invention is to provide a multi-tube reaction vessel having excellent cooling efficiency.
  • a second object of the present invention is to provide a multi-tube reactor in which the catalyst packed therein can be easily replaced.
  • the multi-tube reaction vessel of the present invention is characterized by comprising a catalyst-filled vessel through which a reaction gas flows and which is filled with a catalyst, an inner cooling pipe disposed within the catalyst-filled vessel along the filling direction and through which a cooling fluid flows to cool the catalyst within the catalyst-filled vessel, and an outer shell vessel disposed on the outer periphery of the catalyst-filled vessel and through which a cooling fluid flows to cool the catalyst-filled vessel from the outside.
  • the catalyst-filled container is cylindrical and the inner cooling pipe is arranged in the center of the catalyst-filled container.
  • the catalyst-filled container has a filling port at the upper end for filling the catalyst and a discharge port at the lower end for discharging the catalyst, and is characterized in that the catalyst can be discharged from the discharge port by gravity.
  • the device is characterized by comprising a catalyst layer temperature detection unit that detects the temperature inside the catalyst layer filled in the catalyst-filled container, a catalyst temperature comparison unit that inputs detection information detected by the catalyst layer temperature detection unit and compares the current catalyst temperature based on the detection information with the catalyst undegraded temperature when the catalyst is not degraded, a catalyst replacement determination unit that determines whether or not catalyst replacement is necessary based on the comparison result of the catalyst temperature comparison unit, and a notification unit that notifies the catalyst replacement need when the catalyst replacement determination unit determines that replacement is necessary.
  • the catalyst layer temperature detection unit is characterized in that it is provided at multiple locations from the upstream side to the downstream side of the catalyst layer.
  • a filling port opening and closing member that opens and closes the filling port
  • a discharge port opening and closing member that opens and closes the discharge port
  • an actuator that performs opening and closing operations of the filling port opening and closing member and the discharge port opening and closing member
  • the catalyst replacement determining unit has a function of activating the actuator when it determines that the catalyst needs to be replaced.
  • the catalyst layer temperature detection units are provided at a plurality of locations from the upstream side to the downstream side of the catalyst layer, and the device further includes a temperature fluctuation cause determination unit that determines whether a temperature fluctuation in the catalyst layer is caused by catalyst deterioration or a reaction gas fluctuation based on inputs from the plurality of catalyst layer temperature detection units,
  • the catalyst replacement determination unit is characterized in that it makes a catalyst replacement determination when the temperature variation cause determination unit determines that the temperature variation is caused by catalyst deterioration.
  • the present invention further comprises a supply reactant gas property detection unit which detects the temperature, pressure, flow rate, and concentration of the reactant gas supplied to the catalyst-filled container, an undegraded catalyst temperature database which stores the temperature exhibited by an undegraded catalyst for each assumed property of the reactant gas, and an undegraded catalyst temperature estimation unit which estimates the undegraded catalyst temperature for the current reactant gas property based on the undegraded catalyst temperature database and data from the supply reactant gas property detection unit,
  • the catalyst temperature comparison unit is characterized in that it compares the undegraded catalyst temperature estimated by the undegraded catalyst temperature estimation unit with the catalyst temperature detected by the catalyst layer temperature detection unit.
  • the catalyst layer temperature detection unit is provided at a plurality of locations from the upstream side to the downstream side of the catalyst layer, a supply reaction gas property detection unit that detects the temperature, pressure, flow rate, and concentration of the reaction gas supplied to the catalyst-filled container; an exhaust reaction gas property detection unit that detects the temperature, pressure, flow rate, and concentration of the reaction gas exhausted from the catalyst-filled container; A wall surface temperature detection unit that detects the wall surface temperature of the catalyst filled container; A database of physical properties of the catalyst packing container material and catalyst; a catalyst layer temperature distribution estimation unit that estimates an undegraded catalyst temperature at each of the plurality of locations on an undegraded catalyst based on the temperature detection unit, the supply reaction gas property detection unit, the exhaust reaction gas property detection unit, the wall surface temperature detection unit, and the physical property database,
  • the catalyst temperature comparison unit is characterized in that it compares the undegraded catalyst temperature estimated by the catalyst layer temperature estimation unit with the temperature detected by the catalyst layer temperature detection unit.
  • a catalyst-filled container through which a reaction gas flows and which is filled with a catalyst is provided, an inner cooling pipe that is disposed within the catalyst-filled container along the filling direction and through which a cooling fluid flows to cool the catalyst within the catalyst-filled container, and an outer shell container that is disposed on the outer periphery of the catalyst-filled container and through which a cooling fluid flows to cool the catalyst-filled container from the outside.
  • the catalyst filling container has a filling port at the top end for filling the catalyst and a discharge port at the bottom end for discharging the catalyst, and the catalyst can be discharged from the discharge port by gravity, making it easy to discharge and fill the catalyst and improving the efficiency of catalyst replacement work.
  • a catalyst layer temperature detection section that detects the temperature inside the catalyst layer filled in the catalyst filled container
  • a catalyst temperature comparison section that inputs the detection information detected by the catalyst layer temperature detection section and compares the current catalyst temperature based on the detection information with the undegraded catalyst temperature when the catalyst is not degraded
  • a catalyst replacement determination section that determines whether or not catalyst replacement is necessary based on the comparison result of the catalyst temperature comparison section
  • a notification section that notifies the catalyst replacement determination section when it has determined that replacement is necessary
  • FIG. 1 is an explanatory diagram of a multi-tube reaction vessel according to a first embodiment of the present invention.
  • FIG. 11 is an explanatory diagram of a multi-tube reaction vessel according to a second embodiment of the present invention.
  • 6 is an explanatory diagram of another aspect of the catalyst filled vessel and the inner cooling pipe in the first and second embodiments.
  • FIG. 4A and 4B are detailed explanatory diagrams of another embodiment shown in FIG. 3, in which FIG. 4A shows the catalyst-filled container 3 and the top surface of the lid member 13, FIG. 4B shows the state in which the lid member 13 has been removed, and
  • FIG. 4C shows the opening/closing valve 19.
  • FIG. 11 is an explanatory diagram of a multi-tube reaction vessel according to a third embodiment.
  • FIG. 13 is an explanatory diagram of a multi-tube reaction vessel according to another aspect of the third embodiment.
  • FIG. 13 is an explanatory diagram of a multi-tube reaction vessel according to another aspect of the third embodiment.
  • FIG. 13 is an explanatory diagram of a multi-tube reaction vessel according to a fourth embodiment.
  • FIG. 13 is an explanatory diagram of a multi-tube reaction vessel according to a fifth embodiment.
  • FIG. 13 is an explanatory diagram of a multi-tube reaction vessel according to a sixth embodiment.
  • FIG. 23 is an explanatory diagram of a multi-tube reaction vessel according to another aspect of the sixth embodiment.
  • the multi-tube reactor 1 As shown in FIG. 1, the multi-tube reactor 1 according to the first embodiment includes a catalyst-filled vessel 3, an inner cooling tube 5, and an outer shell vessel 7. Each component will be described in detail below.
  • the catalyst-filled vessel 3 is a vessel through which the reaction gas flows and which is filled with a catalyst.
  • the catalyst-filled vessel 3 is made of a cylindrical body, but the shape of the vessel 3 is not particularly limited as long as it is cylindrical.
  • a gas inlet 9 through which reaction gas enters is provided on the lower side of the catalyst filled container 3, and a gas outlet 11 through which reaction gas (which may contain liquid) is discharged is provided on the upper side of the catalyst filled container 3.
  • the catalyst filling container 3 has a filling port 12 at its upper end for filling the catalyst, which is normally closed by an openable and closable lid member 13 as shown in Fig. 1, and which can be opened when filling the catalyst.
  • the catalyst filling container 3 also has a discharge port 15 at its lower end for discharging the catalyst, and the catalyst can be discharged from the discharge port 15 by gravity.
  • the exhaust port 15 is provided at the tip of a megaphone-shaped exhaust pipe 17 .
  • a slide-type on-off valve 19 is provided at the upper end of the discharge pipe 17, and the catalyst can be discharged by sliding the on-off valve 19 in the direction shown by the arrow in the figure.
  • the filling port 12 and the discharge port 15 are structured to be open only during filling and discharging, respectively, and can be closed with a lid or the like under normal circumstances.
  • the shape of the exhaust pipe 17 is not limited to a megaphone shape, and may be any shape.
  • the on-off valve 19 is not limited to a slide type, and may be a rotary type such as a butterfly valve.
  • the catalyst filling container 3 has the above structure, making it extremely easy to replace the catalyst.
  • the inner cooling pipe 5 is disposed in the catalyst filling vessel 3 along the filling direction, and a cooling fluid flows through the inside of the inner cooling pipe 5 to cool the catalyst in the catalyst filling vessel 3 .
  • the inner cooling pipe 5 is disposed in the center of the catalyst filled vessel 3 .
  • the upper and lower ends of the inner cooling pipe 5 are bent laterally and protrude from the catalyst filled vessel 3 to form an inner cooling fluid inlet 21 and an inner cooling fluid outlet 23, respectively. Therefore, the cooling fluid flows from the top to the bottom, counter flowing to the reaction gas flowing from the bottom to the top.
  • the reaction gas and the coolant fluid may flow counter to each other, or they may flow parallel to each other in order to preferentially cool the superheated part (gas inlet part).
  • Cooling fluids include, but are not limited to, air, inert gas, water, seawater, ethylene glycol, etc.
  • the present invention is not limited to this, and a plurality of inner cooling pipes 5 may be arranged in the catalyst filled vessel 3. In this way, the cooling efficiency for cooling the catalyst in the catalyst filled vessel 3 from the inside can be further improved.
  • the multiple inner cooling fluid outlets 23 and the multiple inner cooling fluid inlets 21 may be connected to each other.
  • the outer shell vessel 7 is provided on the outer periphery of the catalyst filled vessel 3 and a cooling fluid flows inside the outer shell vessel 7 to cool the catalyst filled vessel 3 from the outside.
  • the outer shell vessel 7 of this embodiment is a cylinder having a larger diameter than the catalyst-filled vessel 3, and has an outer cooling fluid inlet 25 provided on the upper side and an outer cooling fluid outlet 27 provided on the lower side. Therefore, the flow of the cooling fluid in the outer shell vessel 7 is from top to bottom, similar to the inner cooling pipe 5, and is a counterflow to the reaction gas. Note that the flow directions of the cooling fluid and the reaction gas are not limited to counterflow, and may be parallel.
  • the catalyst-filled vessel 3 is filled with a catalyst, and a cooling fluid flows through the inner cooling tube 5 and the outer shell vessel 7 .
  • reaction heat is generated by the catalytic reaction. This reaction heat is cooled from the inside by the cooling fluid flowing through the inner cooling pipe 5 and from the outside by the cooling fluid flowing through the outer shell vessel 7.
  • the heat of the catalytic reaction is cooled from both the inside and the outside, which is very efficient.
  • the inner cooling pipe 5 is disposed approximately at the center of the catalyst filled container 3, so that cooling can be performed from the inside without any bias.
  • the catalyst filled container 3 is disposed approximately at the center of the outer shell container 7, so that cooling can be performed from the outside without any bias.
  • the present invention is not limited to the arrangement in which the inner cooling pipe 5 is disposed at the center of the catalyst filled vessel 3, nor is it limited to the arrangement in which the catalyst filled vessel 3 is disposed at the center of the outer shell vessel 7.
  • the catalyst filling container 3 is designed so that the catalyst introduced through the filling port 12 can be discharged from the discharge port 15 by opening the lid member 13 and using gravity without using any power, so the catalyst can be easily discharged by simply opening and closing the lid member 13 and the on-off valve 19.
  • the catalyst can be discharged by gravity, it is acceptable to use tools such as a scraping rod or wind pressure from a blower to further improve the discharge efficiency.
  • each catalyst filling container 3 may be connected. This allows the catalyst to be filled and discharged simultaneously, improving work efficiency when replacing the catalyst.
  • the gas inlet 9 is provided on the lower side and the gas outlet 11 is provided on the upper side.
  • the gas inlet 9 may be provided on the bottom surface and the gas outlet 11 on the top surface.
  • the inner cooling pipe 5 in embodiments 1 and 2 the upper and lower ends are each bent laterally and protrude from the side of the catalyst filled container 3 to form the inner cooling fluid inlet 21 and the inner cooling fluid outlet 23, respectively.
  • the inner cooling pipe 5 may be configured so that the upper and lower ends do not bend but protrude from the top and bottom surfaces of the catalyst filled container 3 to form the inner cooling fluid inlet 21 and the inner cooling fluid outlet 23, respectively.
  • the cover member 13 may be provided with a notch 13a as shown in Fig. 4(b), and the on-off valve 19 may also be provided with a notch 19a as shown in Figs. 3 and 4(c).
  • a top surface portion 3a (having a shape obtained by excluding the area of the inner cooling fluid inlet 21 from the cutout portion 13a of the lid member 13) that supports the gas exhaust port 11 is provided on the top surface of the catalyst filled container 3.
  • a bottom surface portion of the same shape is provided on the bottom surface of the catalyst filled container 3.
  • the catalyst activity generally decreases from the upstream side in the flow of the reaction gas, so that even if the overall catalyst yield decreases, the catalyst downstream of the catalyst packed vessel 3 may not be significantly deteriorated.
  • the entire amount of catalyst is replaced when the catalyst is replaced, and therefore even catalyst that is not significantly deteriorated (i.e., has not reached the end of its replacement life) is subject to replacement, which poses the problem of insufficient efficient use of the catalyst.
  • an object of the third embodiment is to provide a multi-tube reaction vessel that allows replacement of a catalyst that has deteriorated (has reached the end of its replacement life).
  • a multi-tube reaction vessel 30 according to this embodiment is shown in Fig. 5. Note that the same parts as those in Fig. 1 are given the same reference numerals and their explanations are omitted.
  • the multi-tube reaction vessel 30 includes a catalyst layer temperature detection unit 31 for detecting the temperature inside the catalyst layer filled in the catalyst filled vessel 3, a catalyst temperature comparison unit 33 for inputting detection information detected by the catalyst layer temperature detection unit 31 and comparing the detection information with the undegraded catalyst temperature when the catalyst is not degraded, a catalyst replacement determination unit 35 for determining whether or not the catalyst needs to be replaced based on the comparison result of the catalyst temperature comparison unit 33, and a notification unit 37 for notifying the user when the catalyst replacement determination unit 35 determines that the catalyst needs to be replaced.
  • a catalyst layer temperature detection unit 31 for detecting the temperature inside the catalyst layer filled in the catalyst filled vessel 3
  • a catalyst temperature comparison unit 33 for inputting detection information detected by the catalyst layer temperature detection unit 31 and comparing the detection information with the undegraded catalyst temperature when the catalyst is not degraded
  • a catalyst replacement determination unit 35 for determining whether or not the catalyst needs to be replaced based on the comparison result of the catalyst temperature comparison unit 33
  • a notification unit 37 for notifying the user when the
  • the catalyst layer temperature detection unit 31 detects the temperature inside the catalyst layer filled in the catalyst filled container 3.
  • the part of the catalyst layer where the temperature is detected may be appropriately determined in relation to the amount of catalyst to be replaced at one time. For example, if the amount of catalyst to be replaced at one time is about half of the total amount, the part for detecting the temperature may be located midway from the upstream side to the downstream side of the catalyst filled layer. Since catalyst deterioration progresses from the upstream side, if the part where the temperature is detected is determined to be time for replacement, the catalyst upstream of that part may be replaced.
  • the catalyst temperature comparison unit 33 receives the detection information detected by the catalyst layer temperature detection unit 31 and compares the current catalyst temperature based on the detection information with the undegraded catalyst temperature when the catalyst is not degraded.
  • the undegraded catalyst temperature is the catalyst temperature at which heat is generated by the catalytic reaction when the reactant gas passes through the catalyst when the catalyst is not degraded.
  • the temperature that the catalyst exhibits at the beginning of the reaction may be used as the undegraded catalyst temperature.
  • the catalyst replacement determination unit 35 determines whether or not the catalyst needs to be replaced based on the comparison result of the catalyst temperature comparison unit 33 . As the catalyst deteriorates, the amount of heat generated by the catalytic reaction decreases, and the difference with the undegraded catalyst temperature increases. Therefore, the catalyst replacement determination unit 35 determines that replacement is necessary when the difference between the current catalyst layer temperature and the undegraded catalyst temperature exceeds a preset value.
  • the notification unit 37 notifies the user when it is determined by the catalyst replacement determination unit 35 that replacement is required.
  • Specific examples of the notification may include visual notification, such as displaying "replacement required" on a monitor or turning on a lamp, or audio notification, such as sounding an alarm.
  • the operator opens the on-off valve 19 to discharge a predetermined amount of catalyst.
  • the catalyst is discharged sequentially from the upstream side, so that the downstream catalyst moves upstream as the upstream catalyst is discharged. This creates space on the upstream side inside the catalyst filling container 3, and new catalyst is filled into this space.
  • the catalyst layer temperature detection unit 31 was provided at one location in the catalyst layer, but the catalyst layer temperature detection unit 31 may be provided at multiple locations (four locations in this example) from the upstream side to the downstream side of the catalyst layer, as shown in FIG. 6.
  • the packed bed is divided into equal length sections in the flow direction, and the catalyst layer temperature detection unit 31 is provided at the center of each divided section. Further, the catalyst temperature comparison unit 33 compares the current catalyst temperature with the undegraded catalyst temperature for each of the multiple locations where the catalyst layer temperature detection units 31 are installed. The catalyst replacement determination unit 35 determines whether or not catalyst replacement is necessary for each of the multiple locations where the catalyst layer temperature detection units 31 are installed. The notification unit 37 notifies each of the plurality of locations where the catalyst temperature detection units are installed of whether or not replacement is required.
  • catalyst layer temperature detection units 31 in multiple locations, it is possible to know the extent to which the deterioration of the catalyst in the catalyst filling vessel 3 has progressed from the upstream side to the downstream side, and to know the more appropriate timing for catalyst replacement. Also, depending on the reaction conditions, the catalyst may deteriorate faster than expected, and a uniform replacement decision based on a temperature comparison at one location may result in replacement being made too frequently. However, by providing multiple locations, the decision to replace the catalyst can be changed to a later temperature comparison depending on the situation, allowing for more flexible operation of the factory.
  • the catalyst replacement judgment unit 35 determines that replacement is necessary, the operator opens and closes the on-off valve 19 and the lid member 13.
  • the opening and closing operations of the on-off valve 19 and the lid member 13 can also be automated by linking them to the judgment of the catalyst replacement judgment unit 35.
  • a first actuator 39 for opening and closing the on-off valve 19 and a second actuator 41 for opening and closing the cover member 13 may be provided, and the catalyst replacement judgment unit 35 may have the function of activating the first actuator 39 and the second actuator 41 when it judges that catalyst replacement is necessary.
  • a sensor or a level meter for measuring the remaining amount of catalyst may be installed to detect the amount of catalyst discharged, and when a predetermined amount has been discharged, the on-off valve 19 may be closed by the first actuator 39.
  • the on-off valve 19 may be automatically closed a certain time after the catalyst is opened and discharged from the discharge port 15.
  • a sensor or level gauge for measuring the amount added can be installed to detect the amount added, and the addition can be stopped when a predetermined amount has been added.
  • the automation of the opening and closing of the on-off valve 19 and the lid member 13 can be applied to the embodiment shown in FIG. 5 and other embodiments described later.
  • the multi-tube reaction vessel 42 has catalyst layer temperature detection units 31 provided at multiple locations (four locations in this example) from the upstream to downstream side of the catalyst layer, and a temperature fluctuation cause determination unit 43 that determines whether a temperature fluctuation in the catalyst layer is due to catalyst deterioration or reaction gas fluctuation based on the input from the multiple catalyst layer temperature detection units 31, and the catalyst temperature comparison unit 33 performs a temperature comparison when the temperature fluctuation cause determination unit 43 determines that the temperature fluctuation is due to catalyst deterioration.
  • the characteristic configuration of this embodiment will be described below.
  • the temperature fluctuation cause determining unit 43 determines whether the temperature fluctuation of the catalyst layer is caused by catalyst deterioration or by reaction gas fluctuation, based on the inputs from the multiple catalyst layer temperature detectors 31 .
  • the basic principle of the temperature fluctuation cause determination unit 43 is as follows. Since the catalytic reaction starts at the inlet of the catalyst-filled vessel, there is a temperature peak upstream, close to the inlet. When the temperature fluctuation is caused by catalyst deterioration, the temperature fluctuation is as follows. In the case of catalyst deterioration, the activity on the upstream side decreases, causing the temperature of the upstream catalyst layer to drop, while unreacted gas flows downstream, causing the temperature peak to shift downstream. In other words, the temperature peak of the catalyst layer moves from the upstream side to the downstream side.
  • reaction gas fluctuation for example when the amount of reaction gas is reduced, the temperature of the entire catalyst layer decreases, but the temperature peak remains on the upstream side.
  • the cause of the temperature fluctuation can be inferred.
  • the temperature fluctuation is due to catalyst deterioration or reaction gas fluctuation.
  • the temperature fluctuation cause determination unit 43 determines whether the temperature peak is at the most upstream side or has moved downstream based on the input from the multiple catalyst layer temperature detection units 31, and if the temperature peak is at the most upstream side, it determines that there is a reaction gas fluctuation, and if the temperature peak has moved downstream, it determines that there is catalyst deterioration.
  • the catalyst replacement determination unit 35 makes a replacement determination when the temperature fluctuation cause determination unit 43 determines that the temperature fluctuation is due to catalyst deterioration.
  • catalyst deterioration can be appropriately determined even when there is a reaction gas fluctuation.
  • this embodiment is a multi-tube reaction vessel 44 that can handle cases where the properties of the reaction gas change, and an example of a specific configuration is as shown in Figure 9.
  • Figure 9 the same parts as in Figure 5 are given the same reference numerals and their explanations are omitted.
  • the multi-tube reaction vessel 44 of this embodiment is equipped with a supplied reaction gas property detection unit 45 that detects the temperature, pressure, flow rate, and concentration of the reaction gas supplied to the catalyst filled vessel 3, an undegraded catalyst temperature database 47 that stores the temperatures exhibited by undegraded catalysts for each expected reaction gas property, an undegraded catalyst temperature estimation unit 49 that estimates the undegraded catalyst temperature for the current reaction gas properties based on data from the undegraded catalyst temperature database 47 and the supplied reaction gas property detection unit 45, a catalyst replacement judgment unit 35, and an alarm unit 37. Then, the catalyst temperature comparison unit 33 compares the undegraded catalyst temperature estimated by the undegraded catalyst temperature estimation unit 49 with the catalyst temperature detected by the catalyst layer temperature detection unit 31 .
  • the supplied reactant gas property detection unit 45 detects the temperature, pressure, flow rate, and concentration of the reactant gas supplied to the catalyst filled container 3.
  • the detection timing may be, for example, every day, every half day, every hour, every minute, etc., depending on the frequency of fluctuation.
  • the undegraded catalyst temperature database 47 stores the temperature of an undegraded catalyst for each expected property of the reactant gas. It may be expected that any one or all of the temperature, pressure, flow rate, and concentration of the reactant gas supplied to the catalyst filled container 3 will fluctuate. In this case, the catalyst temperature (undegraded temperature) when a reactant gas of expected properties is supplied to an undegraded catalyst is detected in advance, and the undegraded catalyst temperature database 47 is created by associating the catalyst temperature with the properties of the reactant gas and storing it as a database.
  • the undegraded catalyst temperature estimation unit 49 estimates the undegraded catalyst temperature under the current reactant gas properties based on the undegraded catalyst temperature database 47 and data from the supplied reactant gas property detection unit 45 . More specifically, the current properties of the reactant gas are identified based on the temperature, pressure, flow rate, and concentration input from the supply reactant gas property detection unit 45, and the identified properties are stored in the undegraded catalyst temperature database 47. The undegraded temperature of the catalyst is estimated.
  • catalyst deterioration can be appropriately determined even when the properties of the reaction gas fluctuate.
  • an undegraded catalyst temperature database 47 that stores the temperatures of an undegraded catalyst for each expected property of the reactant gas. Therefore, it is necessary to create the undegraded catalyst temperature database 47 by conducting experiments in advance for each expected property fluctuation of the reactant gas supplied to the multi-tube reaction vessel 44. Therefore, the multi-tube reaction vessel 50 of the present embodiment is designed to be able to deal with fluctuations in the properties of the reaction gas without performing such work.
  • a multi-tube reaction vessel 50 according to this embodiment is shown in Fig. 10. In Fig. 10, the same parts as those in Fig. 9 are given the same reference numerals and the description thereof will be omitted.
  • the multi-tube reaction vessel 30 includes a catalyst layer temperature detection unit 31, a supply reaction gas property detection unit 45, an exhaust reaction gas property detection unit 51, a wall surface temperature detection unit 53, a catalyst packing vessel material/catalyst property database 55, a catalyst layer temperature distribution estimation unit 57, a catalyst temperature comparison unit 33, a catalyst replacement determination unit 35, and an alarm unit 37.
  • the catalyst layer temperature detection units 31 are provided at a plurality of locations (four locations in this example) from the upstream side to the downstream side of the catalyst layer.
  • the supplied reactant gas property detection unit 45 detects the temperature, pressure, flow rate, and concentration of the reactant gas supplied to the catalyst filling vessel 3 .
  • the exhausted reaction gas property detection unit 51 detects the temperature, pressure, flow rate, and concentration of the reaction gas exhausted from the catalyst filled container 3 .
  • the wall surface temperature detection unit 53 detects the wall surface temperature of the catalyst filled container 3 .
  • the catalyst filling container material/catalyst physical property database 55 stores the material of the catalyst filling container 3 and the physical property values of the catalyst. Specifically, C bed : heat capacity of the packed bed, q react : molar heat of reaction, M bed : catalyst loading, k: reaction rate constant, a1: reaction order, a2: reaction order, h: heat transfer coefficient, U: packed bed heat transfer coefficient, cp: gas specific heat, ⁇ : gas density, ⁇ : conversion coefficient from molar flow rate to volumetric flow rate (e.g., 22.4 for mol/s to L/s (standard conditions)).
  • the catalyst layer temperature distribution estimation unit 57 estimates the undegraded temperature at each of a plurality of locations of the undegraded catalyst based on the exhaust reaction gas property detection unit 51, the wall surface temperature detection unit 53, and the physical property database.
  • the non-deterioration temperature can be estimated by solving the following heat balance equation at each position where the catalyst layer temperature detection unit 31 is installed.
  • T pred T 0 +Q all /C bed
  • T 0 Temperature of the catalyst bed at the reference time
  • Q all Heat gain of the packed bed
  • C bed Heat capacity of the packed bed
  • Q all Q r + Q w + Q in - Q out - Q gas
  • Qr Total reaction heat
  • Qw Heat from the wall
  • Qin Heat from upstream
  • Qout Heat to downstream
  • Qgas Heat gained by gas
  • P 1 P 0 ⁇ C 1
  • P 2 P 0 ⁇ C 2
  • k Reaction rate constant
  • P 1 Component 1 partial pressure a1 : Reaction rate
  • U Packed bed heat transfer coefficient
  • Q out U ⁇ (T 0 -T down )
  • T down downstream layer temperature at the reference time (if the layer of interest is the downstream end, set separately)
  • Q gas cp ⁇ F ⁇ t ⁇ (T 0 -T up )
  • cp gas specific heat
  • ⁇ gas density
  • F gas volumetric flow rate
  • F F 0 +r ⁇ M bed ⁇ t ⁇
  • F 0 Inlet gas volumetric flow rate
  • ⁇ Conversion coefficient from molar flow rate to volumetric flow rate (e.g., 22.4 for mol/s to L/s)
  • C bed packed bed heat capacity
  • q react molar reaction heat
  • M bed catalyst filling amount
  • k reaction rate constant
  • a1 reaction order
  • a2 reaction order
  • h heat transfer coefficient
  • U packed bed heat transfer coefficient
  • cp gas specific heat
  • ⁇ gas density
  • ⁇ molar flow rate
  • T0 catalyst layer temperature at the reference time is obtained from the catalyst layer temperature detection unit
  • P0 total pressure is obtained from the gradient of Pgi of the supply reaction gas properties detection unit and Pgo of the exhaust reaction gas properties detection unit
  • Tw wall temperature is obtained from the wall temperature detection unit
  • Tup upstream layer temperature at the reference time is obtained from catalyst layer temperature detection unit Tc1
  • Tdown downstream layer temperature at the reference time is obtained from catalyst layer temperature detection unit Tc4
  • F0 inlet gas volumetric flow rate is obtained from the supply reaction gas properties detection unit.
  • the catalyst temperature comparison unit 33 compares the catalyst temperature estimated by the catalyst layer temperature estimation unit with the temperature detected by the catalyst layer temperature detection unit 31 .
  • the catalyst replacement determination unit and the notification unit are the same as those shown in Figures 8 and 9.
  • catalyst degradation can be appropriately determined even when the properties of the reaction gas fluctuate. Moreover, there is no need to create a non-degraded catalyst temperature database 47 in advance through experiments, etc.
  • a first actuator 39 that opens and closes the on-off valve 19 and a second actuator 41 that opens and closes the lid member 13 are provided, and the catalyst replacement determination unit 35 has the function of activating the first actuator 39 and the second actuator 41 when it determines that catalyst replacement is necessary.
  • Multi-tube reaction vessel (Embodiment 1) Reference Signs List 3 Catalyst-filled vessel 3a Top surface 5 Inner cooling pipe 7 Outer vessel 9 Gas inlet 11 Gas outlet 12 Filling port 13 Lid member 13a Cutout 15 Outlet 17 Outlet pipe 19 Opening/closing valve 19a Cutout 21 Inner cooling fluid inlet 23 Inner cooling fluid outlet 25 Outer cooling fluid inlet 27 Inner cooling fluid outlet 29 Multi-tube reaction vessel (Embodiment 2) 30 Multi-tube reaction vessel (Embodiment 3) 31 Catalyst layer temperature detection unit 33 Catalyst temperature comparison unit 35 Catalyst replacement determination unit 37 Notification unit 39 First actuator 41 Second actuator 42 Multi-tube reaction vessel (Embodiment 4) 43 Temperature fluctuation cause determination unit 44 Multi-tube reaction vessel (Embodiment 5) 45 Supply reaction gas property detection unit 47 Undegraded catalyst temperature database 49 Undegraded catalyst temperature estimation unit 50 Multi-tube reaction vessel (Embodiment 6) 51 Exhaust reaction gas property detection unit 53 Wall surface temperature detection unit 55 Catalys

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

Les objectifs de la présente invention sont d'obtenir un récipient de réaction multitubulaire ayant une excellente efficacité de refroidissement et d'obtenir un récipient de réaction multitubulaire dans lequel un catalyseur emballé peut être facilement remplacé.　Un récipient de réaction multitubulaire (1) selon la présente invention est caractérisé en ce qu'il comprend : un récipient d'emballage de catalyseur (3) dans lequel un gaz de réaction s'écoule et dans lequel un catalyseur est emballé ; un tuyau de refroidissement interne (5) qui est situé à l'intérieur du récipient d'emballage de catalyseur (3) le long de la direction d'emballage et dans lequel un fluide de refroidissement s'écoule pour refroidir le catalyseur à l'intérieur du récipient d'emballage de catalyseur (3) ; et un récipient d'enveloppe externe (7) qui est situé autour de la périphérie externe du récipient d'emballage de catalyseur (3) et dans lequel un fluide de refroidissement s'écoule pour refroidir le récipient d'emballage de catalyseur (3) depuis l'extérieur.
PCT/JP2024/018992 2023-06-09 2024-05-23 Récipient de réaction multitubulaire Pending WO2024252939A1 (fr)

Applications Claiming Priority (4)

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JP2023095196 2023-06-09
JP2023-095196 2023-06-09
JP2023126690A JP2024177002A (ja) 2023-06-09 2023-08-03 多重管式反応容器
JP2023-126690 2023-08-03

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WO2024252939A1 true WO2024252939A1 (fr) 2024-12-12

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS516289B1 (fr) * 1969-04-25 1976-02-26
JPS5567327A (en) * 1978-11-06 1980-05-21 Kernforschungsanlage Juelich Tube reactor for catalyst process
JPS58180920A (ja) * 1982-03-29 1983-10-22 ザ・バブコツク・アンド・ウイルコツクス・カンパニー 化学反応器におけるホツトスポツトおよびコ−ルドスポツト検出方法および装置
JPS60147226A (ja) * 1984-01-06 1985-08-03 Mitsubishi Heavy Ind Ltd 触媒充填管式固気接触反応装置の運転方法
JPS61287435A (ja) * 1985-06-11 1986-12-17 Ishikawajima Harima Heavy Ind Co Ltd 触媒反応装置
JPS6320029A (ja) * 1986-07-15 1988-01-27 Mitsubishi Heavy Ind Ltd 反応器
JPS6384630A (ja) * 1986-09-29 1988-04-15 Nippon Steel Corp 水素の発生を伴う反応を行わせるために用いる熱交換器型反応装置
JPS63151350A (ja) * 1986-11-21 1988-06-23 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー 発熱性および吸熱性触媒反応のための反応器
JPH10277383A (ja) * 1997-04-02 1998-10-20 Mitsubishi Heavy Ind Ltd 反応器
JP2013154310A (ja) * 2012-01-31 2013-08-15 Ihi Corp 多管式反応器
JP2016168570A (ja) * 2015-03-13 2016-09-23 東ソー株式会社 触媒寿命解析装置を備えた触媒反応製造システム
JP2021159910A (ja) * 2020-03-31 2021-10-11 横河電機株式会社 反応解析装置、反応解析システム、および反応解析方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS516289B1 (fr) * 1969-04-25 1976-02-26
JPS5567327A (en) * 1978-11-06 1980-05-21 Kernforschungsanlage Juelich Tube reactor for catalyst process
JPS58180920A (ja) * 1982-03-29 1983-10-22 ザ・バブコツク・アンド・ウイルコツクス・カンパニー 化学反応器におけるホツトスポツトおよびコ−ルドスポツト検出方法および装置
JPS60147226A (ja) * 1984-01-06 1985-08-03 Mitsubishi Heavy Ind Ltd 触媒充填管式固気接触反応装置の運転方法
JPS61287435A (ja) * 1985-06-11 1986-12-17 Ishikawajima Harima Heavy Ind Co Ltd 触媒反応装置
JPS6320029A (ja) * 1986-07-15 1988-01-27 Mitsubishi Heavy Ind Ltd 反応器
JPS6384630A (ja) * 1986-09-29 1988-04-15 Nippon Steel Corp 水素の発生を伴う反応を行わせるために用いる熱交換器型反応装置
JPS63151350A (ja) * 1986-11-21 1988-06-23 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー 発熱性および吸熱性触媒反応のための反応器
JPH10277383A (ja) * 1997-04-02 1998-10-20 Mitsubishi Heavy Ind Ltd 反応器
JP2013154310A (ja) * 2012-01-31 2013-08-15 Ihi Corp 多管式反応器
JP2016168570A (ja) * 2015-03-13 2016-09-23 東ソー株式会社 触媒寿命解析装置を備えた触媒反応製造システム
JP2021159910A (ja) * 2020-03-31 2021-10-11 横河電機株式会社 反応解析装置、反応解析システム、および反応解析方法

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