Multiple pipe-type reaction vessel

Abstract

To provide a multiple pipe-type reaction vessel excellent in cooling efficiency, and also to provide a multiple pipe-type reaction vessel easy to exchange catalysts to be loaded.SOLUTION: A multiple pipe-type reaction vessel 1 includes: a catalyst loading container 3 configured to allow a reaction gas to flow and to have a catalyst loaded thereto; an inner cooling pipe 5 arranged along a loading direction inside the catalyst loading container 3, and configured to allow a cooling fluid to flow therein to cool the catalyst inside the catalyst loading container 3; and an outer shell container 7 disposed on an outer periphery of the catalyst loading container 3 and configured to allow the cooling fluid to flow inside to cool the catalyst loading container 3 from outside.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a reactor vessel having a catalyst-filled vessel through which a reaction gas flows and which is filled with a catalyst, and in particular to a multi-tube reactor vessel in which the reactor vessel has multiple tubes. [Background technology]

[0002] Catalytic reactions are often exothermic, and as the reactor scale increases, there is a concern that abnormal heat generation within the catalyst bed may cause the reaction to go out of control or damage the catalyst and equipment, so a cooling mechanism is important. For example, Patent Document 1 discloses a method in which a heat transfer tube through which a refrigerant flows is provided in a catalyst packed bed to cool the packed bed.

[0003] In addition, the activity of the catalyst gradually decreases due to poisoning by impurities contained in the raw materials, adhesion of products to the catalyst surface, etc. For this reason, the catalyst packed in the reactor is generally replaced periodically.

[0004] As a method for replacing a catalyst, for example, 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. Moreover, Patent Document 3 discloses a method in which a fluid is fed into a tube filled with a catalyst to flush out the filler. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2003-229147 A [Patent Document 2] Japanese Patent Application Publication No. 10-328555 [Patent Document 3] Japanese Patent Publication No. 60-71036 Summary of the Invention [Problem to be solved by the invention]

[0006] Regarding the cooling mechanism, the method of Patent Document 1 has a problem in that the cooling efficiency is good in 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.

[0007] In addition, in the method of Patent Document 2, the replacement of the catalyst requires the use of a vacuum pump to suck out the catalyst. In addition, since the catalyst is sucked up, the catalyst may fall due to the effect of gravity, making it difficult to recover all of it. Furthermore, in 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.

[0008] Furthermore, the method of Patent Document 3 has a problem in that it requires power to transport the fluid. In addition, when the filler is pushed away, depending on the shape of the container, the filler may be structurally trapped, making it impossible to recover the entire amount.

[0009] 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. [Means for solving the problem]

[0010] (1) The multi-tube reaction vessel of the present invention is characterized in that it comprises 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 around the outer periphery of the catalyst-filled vessel and through which a cooling fluid flows to cool the catalyst-filled vessel from the outside.

[0011] (2) In addition, in the above-mentioned (1), the catalyst-filled container is made of a cylindrical body, and the inner cooling pipe is disposed in the center of the catalyst-filled container.

[0012] (3) Furthermore, in the above-mentioned (1) or (2), the catalyst-filled container has a filling port at an upper end for filling the catalyst and a discharge port at a lower end for discharging the catalyst, and is characterized in that the catalyst can be discharged from the discharge port by gravity.

[0013] (4) Furthermore, in any one of the above (1) to (3), there are multiple sets of the catalyst-filled container and the inner cooling pipe, and the multiple sets are provided in one outer shell container.

[0014] (5) Furthermore, in the above (3), the present invention is characterized in that it comprises a catalyst layer temperature detection unit which detects the temperature inside the catalyst layer filled in the catalyst filled container, a catalyst temperature comparison unit which 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 which determines whether or not catalyst replacement is necessary based on the comparison result of the catalyst temperature comparison unit, and a notification unit which notifies that fact when the catalyst replacement determination unit determines that replacement is necessary.

[0015] (6) In the device described in (5) above, 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.

[0016] (7) In addition, in the above-mentioned (5), 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, and 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.

[0017] (8) In the device described in (5) above, 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.

[0018] (9) In the above (5), the apparatus 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 vessel, 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.

[0019] (10) In the device described in (5) above, 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. Effect of the Invention

[0020] In the present invention, there is provided a catalyst filled container through which a reaction gas flows and which is filled with a catalyst, an inner cooling pipe arranged 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 provided 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, so that the catalyst filled layer can be cooled from both the inside and the outside, resulting in excellent cooling efficiency.

[0021] In addition, the catalyst filling 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 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.

[0022] Furthermore, the system is equipped with a catalyst layer temperature detection unit which detects the temperature inside the catalyst layer filled in the catalyst container, a catalyst temperature comparison unit which inputs the detection information detected by the catalyst layer temperature detection unit 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 judgment unit which judges whether or not catalyst replacement is necessary based on the comparison result of the catalyst temperature comparison unit, and a notification unit which notifies this fact when the catalyst replacement judgment unit judges that replacement is necessary.This makes it possible to replace only catalyst that has deteriorated due to progress in deterioration and whose performance has decreased, without having to replace the entire amount of catalyst, thereby enabling effective use of the catalyst while reducing catalyst costs. [Brief description of the drawings]

[0023] [Figure 1] FIG. 1 is an explanatory diagram of a multi-tube reaction vessel according to a first embodiment of the present invention. [Diagram 2] FIG. 11 is an explanatory diagram of a multi-tube reaction vessel according to a second embodiment of the present invention. [Diagram 3]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. [Figure 4] 4A and 4B are detailed explanatory diagrams of another embodiment shown in FIG. 3, in which FIG. 4(a) shows the catalyst-filled container 3 and the top surface of the lid member 13, FIG. 4(b) shows the state in which the lid member 13 has been removed, and FIG. 4(c) shows the on-off valve 19. [Diagram 5] FIG. 11 is an explanatory diagram of a multi-tube reaction vessel according to a third embodiment. [Figure 6] FIG. 11 is an explanatory view of a multi-tube reaction vessel according to another aspect of the third embodiment. [Figure 7] FIG. 11 is an explanatory view of a multi-tube reaction vessel according to another aspect of the third embodiment. [Figure 8] FIG. 11 is an explanatory diagram of a multi-tube reaction vessel according to a fourth embodiment. [Figure 9] FIG. 13 is an explanatory diagram of a multi-tube reaction vessel according to a fifth embodiment. [Figure 10] FIG. 13 is an explanatory diagram of a multi-tube reaction vessel according to a sixth embodiment. [Figure 11] FIG. 23 is an explanatory diagram of a multi-tube reaction vessel according to another aspect of the sixth embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] [Embodiment 1] The multi-tubular reaction vessel 1 according to the first embodiment includes a catalyst-filled vessel 3, an inner cooling tube 5, and an outer shell vessel 7, as shown in FIG. Each component will be described in detail below.

[0025] <Catalyst filling vessel> The catalyst-filled vessel 3 is a vessel through which the reaction gas flows and into which the catalyst is filled. In this embodiment, as shown in Fig. 1, the vessel is made of a cylindrical body, but the shape 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 packed 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 packed container 3.

[0026] Furthermore, catalyst filling container 3 has at its upper end a filling port 12 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. Additionally, catalyst filling container 3 has at its lower end a discharge port 15 for discharging the catalyst, and the catalyst can be discharged from discharge port 15 by gravity. The exhaust port 15 is provided at the tip of a megaphone-shaped exhaust pipe 17 . A sliding 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. In this way, the filling port 12 and the discharge port 15 are structured to be open only when 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, but may be any shape. Also, the opening and closing valve 19 is not limited to a slide type, but may be a rotary type such as a butterfly valve.

[0027] Because catalyst filling vessel 3 has the above-mentioned structure, catalyst replacement is extremely easy.

[0028] <Inner cooling pipe> 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, forming 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. Note that, as in this example, 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).

[0029] Examples of cooling fluids include, but are not limited to, air, inert gas, water, seawater, ethylene glycol, and the like.

[0030] 1 shows an example in which one inner cooling pipe 5 is arranged in the catalyst filled vessel 3, the present invention is not limited to this, and multiple inner cooling pipes 5 may be arranged in the catalyst filled vessel 3. In this way, the cooling efficiency of 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.

[0031] <Outer shell container> The outer shell vessel 7 is provided on the outer periphery of the catalyst filled vessel 3 and cools the catalyst filled vessel 3 from the outside by passing a cooling fluid through the inside of the outer shell vessel 7. 1, 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.

[0032] In the multi-tubular reaction vessel 1 constructed as above, the catalyst-filled vessel 3 is filled with a catalyst, and a cooling fluid flows through the inner cooling pipe 5 and the outer shell vessel 7. When the reaction gas flows into the catalyst-filled vessel 3, 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.

[0033] In this way, in this embodiment, the heat of the catalytic reaction is cooled from both the inside and the outside, which is very efficient. By making it possible to cool from both the inside and the outside, it is possible to reduce the temperature unevenness of the catalyst and to prevent the occurrence of hot spots (a phenomenon in which a very small part of the packed bed generates abnormal heat).

[0034] In this embodiment, 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 bias. Similarly, 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 bias. However, 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.

[0035] Furthermore, in this embodiment, catalyst filling container 3 is designed so that catalyst introduced through filling port 12 by opening lid member 13 can be discharged from discharge port 15 by gravity without using any power, so that catalyst can be easily discharged by simply opening and closing lid member 13 and opening and closing valve 19. Although discharge is possible by gravity, it is acceptable to assisted this by using a tool such as a scraping stick or wind pressure from a blower or the like to further improve discharge efficiency.

[0036] [Embodiment 2] In embodiment 1, one pair of catalyst filled container 3 and inner cooling pipe 5 is provided for one outer shell container 7, but in the multi-tube reaction vessel 29 of embodiment 2, as shown in Figure 2, multiple pairs of catalyst filled container 3 and inner cooling pipe 5 are provided for one outer shell container 7. In FIG. 2, the same parts as those in FIG. 1 are denoted by the same reference numerals.

[0037] In this embodiment as well, the same effects as those in the first embodiment can be achieved. Furthermore, for example, when the same amount of catalyst as in embodiment 1 shown in FIG. 1 is used in the embodiment shown in FIG. 2, the amount of catalyst filled in each catalyst filled container 3 in the embodiment shown in FIG. 2 is small, and the thickness of the catalyst in the filled state is thin, thereby improving the cooling efficiency from the inside and outside.

[0038] The filling ports 12 and discharge ports 15 of the catalyst filling containers 3 may be connected together. This allows the catalyst to be filled and discharged simultaneously, improving the efficiency of the work when replacing the catalyst.

[0039] In the catalyst filling container 3 of the first and second embodiments, the gas inlet 9 is provided on the lower side and the gas outlet 11 is provided on the upper side, but as shown in FIG. 3, the gas inlet 9 may be provided on the bottom surface and the gas outlet 11 on the top surface. In addition, in 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 vessel 3 to form the inner cooling fluid inlet 21 and the inner cooling fluid outlet 23, respectively. However, as shown in Figure 3, the inner cooling pipe 5 may be configured so that the upper and lower ends are not bent and protrude from the top and bottom surfaces of the catalyst filled vessel 3 to form the inner cooling fluid inlet 21 and the inner cooling fluid outlet 23, respectively.

[0040] In this case, the cover member 13 may be provided with a notch 13a as shown in Fig. 4(b). Also, the on-off valve 19 may be provided with a notch 19a as shown in Figs. 3 and 4(c). In this case, as shown in Fig. 4(a), 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. In this regard, a bottom surface portion of the same shape is provided on the bottom surface of the catalyst filled container 3.

[0041] [Embodiment 3] The catalyst activity generally decreases from the upstream side in the flow of the reaction gas, so even if the overall catalyst yield decreases, the catalyst downstream of the catalyst packed vessel 3 may not be significantly deteriorated. However, in the above-described embodiments 1 and 2, the entire amount of catalyst is replaced when the catalyst is replaced, so that even catalyst that is not significantly deteriorated (i.e., has not reached the end of its replacement life) is also subject to replacement, which poses the problem of insufficient efficient use of the catalyst.

[0042] Therefore, an object of the third embodiment is to provide a multi-tube reaction vessel that allows replacement of a catalyst that has deteriorated (reaching the end of its replacement life). A multi-tube reaction vessel 30 according to this embodiment is shown in Fig. 5. The same parts as those in Fig. 1 are given the same reference numerals and their explanation will be omitted.

[0043] As shown in FIG. 5, the multi-tube reaction vessel 30 according to the third embodiment 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 need for catalyst replacement when the catalyst replacement determination unit 35 determines that replacement is required. Each component will be described in detail below.

[0044] <Catalyst layer temperature detection unit> 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 determined appropriately 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 it is determined that the part where the temperature is being detected needs replacing, the catalyst upstream of that part may be replaced.

[0045] <Catalyst temperature comparison section> 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 it is not degraded. When the reactant gas composition does not change, the temperature that the catalyst exhibits at the beginning of the reaction (initial temperature) may be used as the undegraded catalyst temperature.

[0046] <Catalyst replacement judgment unit> 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.

[0047] <Notification Department> 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.

[0048] When the notification unit 37 notifies the operator that replacement is required, the operator opens the on-off valve 19 to discharge a predetermined amount of catalyst. Since the catalyst is discharged sequentially from the upstream side, the downstream catalyst moves upstream as the upstream catalyst is discharged. This creates a space on the upstream side inside the catalyst filling container 3, and this space is then filled with new catalyst.

[0049] As described above, according to this embodiment, it is possible to replace only the catalyst whose performance has decreased due to deterioration without replacing the entire catalyst, thereby making it possible to effectively utilize the catalyst while reducing catalyst costs.

[0050] In the above example, 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 also 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 Figure 6.

[0051] In this case, it is preferable that 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 whether or not replacement is required for each of the multiple locations where the catalyst temperature detection units are installed.

[0052] In this way, by providing catalyst layer temperature detection units 31 at 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 too frequent, but providing multiple locations allows the decision to replace the catalyst to be changed to a later temperature comparison depending on the situation, enabling flexible operation of the factory.

[0053] In the above example, when 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. However, 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. For example, as shown in FIG. 7, 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.

[0054] In this case, when the on-off valve 19 is opened and the catalyst is discharged from the discharge port 15, 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. Alternatively, the on-off valve 19 may be automatically closed a certain time after the catalyst is opened and discharged from the discharge port 15. Similarly, when the lid member 13 is opened to add catalyst, 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 opening and closing of the on-off valve 19 and the cover member 13 can be applied to the embodiment shown in FIG. 5 and other embodiments described later.

[0055] [Embodiment 4] When the raw material concentration or flow rate of the reaction gas fluctuates, the amount of heat generated by the catalytic reaction also fluctuates accordingly. That is, when the raw material concentration or flow rate is high, the amount of heat generated increases, causing a temperature fluctuation, and when the raw material concentration or flow rate is low, the amount of heat generated decreases, causing a temperature fluctuation. For this reason, simply detecting the temperature inside the catalyst layer makes it impossible to determine, when a temperature fluctuation occurs, whether the temperature fluctuation is due to catalyst deterioration or a reaction gas fluctuation. Therefore, in this embodiment, it is determined that the temperature fluctuation is caused by catalyst deterioration, and in that case, it is determined whether or not the catalyst needs to be replaced. A multi-tube reaction vessel 42 according to this embodiment is shown in Fig. 8. In Fig. 8, the same components as those shown in Fig. 6 are given the same reference numerals and their explanation will be omitted.

[0056] 8, a multi-tube reaction vessel 42 according to this embodiment is provided with catalyst layer temperature detection units 31 at multiple locations (four locations in this example) from the upstream side to the downstream side of the catalyst layer, and includes a temperature fluctuation cause determination unit 43 that determines whether a temperature fluctuation in the catalyst layer is caused by catalyst deterioration or reactant gas fluctuation based on the input of the multiple catalyst layer temperature detection units 31, and the catalyst temperature comparison unit 33 performs temperature comparison when the temperature fluctuation cause determination unit 43 determines that the temperature fluctuation is caused by catalyst deterioration. The characteristic configuration of this embodiment will be described below.

[0057] <Temperature fluctuation cause determination unit> The temperature fluctuation cause determining unit 43 determines, based on the inputs from the multiple catalyst layer temperature detectors 31, whether the temperature fluctuation in the catalyst layer is caused by catalyst deterioration or by reaction gas fluctuation. 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.

[0058] On the other hand, in the case of 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. By distinguishing between these, the cause of the temperature fluctuation can be inferred. In other words, by referring to both the temperature drop at the catalyst bed position to be replaced and the temperature peak position over the entire packed bed, it is possible to determine whether the temperature fluctuation is due to catalyst deterioration or reaction gas fluctuation.

[0059] 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 multiple catalyst layer temperature detection units 31, and determines that the cause is a reaction gas fluctuation if the temperature peak is at the most upstream side, and that the cause is catalyst deterioration if the temperature peak has moved downstream.

[0060] The catalyst replacement determination unit 35 makes a catalyst replacement determination when the temperature fluctuation cause determination unit 43 determines that the temperature fluctuation is caused by catalyst deterioration.

[0061] According to this embodiment, even when there is a reaction gas fluctuation, the deterioration of the catalyst can be appropriately determined.

[0062] [Embodiment 5] When the properties of the reaction gas (temperature, pressure, flow rate, concentration) change, the catalyst temperature also changes, so in order to accurately judge catalyst deterioration, it is necessary to make the judgment based on the state of the reaction gas properties. Therefore, 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. In Figure 9, the same parts as in Figure 5 are given the same reference numerals and the explanation will be omitted.

[0063] 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, a non-degraded catalyst temperature database 47 that stores the temperatures exhibited by undegraded catalysts for each expected reaction gas property, a non-degraded catalyst temperature estimation unit 49 that estimates the non-degraded catalyst temperature for the current reaction gas properties based on data from the non-degraded 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 .

[0064] <Supply reaction gas property detection unit> 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.

[0065] <Non-deteriorating catalyst temperature database> 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 detected catalyst temperature with the property of the reactant gas and storing it in a database.

[0066] <Non-deterioration catalyst temperature estimation section> 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 undegraded temperature of the catalyst with the identified properties is estimated by referring to the undegraded catalyst temperature database 47.

[0067] According to this embodiment, even when the properties of the reaction gas vary, the deterioration of the catalyst can be appropriately determined.

[0068] [Embodiment 6] In the fifth embodiment, when the properties of the reactant gas fluctuate, an undegraded catalyst temperature database 47 is required 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 of 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.

[0069] The multi-tube reaction vessel 30 according to this embodiment 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 filling container material / catalyst property database 55, a catalyst layer temperature distribution estimation unit 57, a catalyst temperature comparison unit 33, a catalyst replacement judgment unit 35, and an alarm unit 37.

[0070] <Catalyst layer temperature detection unit> 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.

[0071] <Supply reaction gas property detection unit> 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 vessel 3 .

[0072] <Exhaust reaction gas property detection unit> The discharged reaction gas property detection unit 51 detects the temperature, pressure, flow rate, and concentration of the reaction gas discharged from the catalyst filled container 3 .

[0073] <Wall surface temperature detection unit> The wall surface temperature detection unit 53 detects the wall surface temperature of the catalyst filled container 3 .

[0074] <Catalyst packing container materials and catalyst properties database> 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 :Filled bed heat capacity, q react : Molar reaction heat, M bed: catalyst loading 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, ρ: gas density, α: conversion coefficient from molar flow rate to volumetric flow rate (e.g., 22.4 for mol / s to L / s (standard conditions)), etc.

[0075] <Catalyst layer temperature distribution estimation section> 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 temperature without deterioration can be estimated by solving the following heat balance equation at each position where the catalyst layer temperature detection unit 31 is installed. [Temperature of catalyst layer after time Δt] = [Temperature of catalyst layer at reference time] + [Heat received by catalyst layer during time Δt] / [Heat capacity of catalyst layer] [Heat received by the catalyst layer] = [Reaction heat generated by the catalytic reaction] + [Heat flowing in from the boundary of the region] + [Heat brought in by the inflowing gas] - [Heat removed by the outflowing gas] The desired [temperature of the catalyst layer after time Δt] is T pred Then, the specific calculation formula is as follows:

[0076] T pred =T0+Q all / C bed Here, T pred : predicted temperature (= packed bed temperature after Δt time), Δt: calculation time T0: Catalyst layer temperature at the reference time Q all : Heat gain from packed bed C bed :Filled bed heat capacity Q all =Q r +Q w +Q in -Q out -Q gas Here, Q r : Total reaction heat Q w : Heat from the wall Q in : Heat from upstream Q out : Heat to downstream Q gas : Heat gain from gas Q r =q react ×r×M bed ×Δt r=k×P1 a1 ×P2 a2 (For two-component reactions) P1 = P0 x C1, P2 = P0 x C2 Here, q react : Molar reaction heat r: Molar reaction rate M bed :Catalyst loading amount k: reaction rate constant P1: Component 1 partial pressure a1: reaction order P2: Component 2 partial pressure a2: reaction order P0: Total pressure C1: Component 1 concentration C2: Component 2 concentration Q w =h×(T0-T w ) Where, h: heat transfer coefficient T w :Wall temperature Q in =U×(T up -T0) Here, T up : Upper layer temperature at the reference time (if the layer of interest is at the upper end, set separately*) *Approximately the wall temperature, for example. The same applies to the downstream end. U: Heat transfer coefficient of packed bed Q out =U×(T0-T down ) Here, T down : Downstream temperature at the reference time (if the layer of interest is the downstream end, set separately) Q gas =cp×ρ×F×Δt×(T0-T up ) Where, cp: gas specific heat ρ: Gas density F: Gas volume flow rate F = F0 + r × Mbed ×Δt×α Where, F0: inlet gas volume flow rate α: Conversion factor from molar flow rate to volumetric flow rate (e.g., 22.4 for mol / s to L / s)

[0077] In the above calculation, the catalyst packing container material and catalyst physical property database 55 is referred to. bed :Filled bed heat capacity, q react : Molar reaction heat, M bed : catalyst loading 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, ρ: gas density, α: molar flow rate. In addition, T0: catalyst layer temperature at the reference time is obtained from the catalyst layer temperature detector, P0: total pressure is obtained from the gradient of Pgi of the supply reaction gas property detector and Pgo of the exhaust reaction gas property detector, C1: component 1 concentration and C2: component 2 concentration are obtained from the gradient of Cgi of the supply reaction gas property detector and Cgo of the exhaust reaction gas property detector, T w :The wall temperature is measured from the wall temperature detector, T up The upstream layer temperature at the reference time is the catalyst layer temperature detection part T c1 From T down The downstream layer temperature at the reference time is the catalyst layer temperature detection part T c4 and F0: inlet gas volumetric flow rate is obtained from the supply reactant gas property detector.

[0078] <Catalyst temperature comparison section> 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 .

[0079] The catalyst replacement determination unit and the notification unit are similar to those shown in FIGS.

[0080] According to this embodiment, even when the properties of the reaction gas vary, the deterioration of the catalyst can be appropriately determined. Moreover, there is no need to create the undegraded catalyst temperature database 47 in advance through experiments or the like.

[0081] In order to automatically open and close the on-off valve 19 and the cover member 13, as shown in FIG. 11, 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 should be provided, and the catalyst replacement judgment unit 35 should have the function of activating the first actuator 39 and the second actuator 41 when it is determined that catalyst replacement is necessary. [Explanation of symbols]

[0082] 1. Multi-tube reaction vessel (embodiment 1) 3 Catalyst filling vessel 3a Top section 5 Inner cooling tube 7 Outer shell container 9 Gas inlet 11 Gas exhaust port 12 Filling port 13 Cover member 13a Notch 15 Outlet 17 Discharge pipe 19. On-off valve 19a Notch 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 section 35 Catalyst replacement judgment unit 37 Notification Department 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 section 47 Undegraded Catalyst Temperature Database 49 Non-degraded catalyst temperature estimation section 50 Multi-tube reaction vessel (embodiment 6) 51 Exhaust reactive gas property detection unit 53 Wall temperature detector 55 Catalyst Packing Containers and Catalyst Properties Database 57 Catalyst layer temperature distribution estimation section

Claims

1. A multi-tube reaction vessel 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 a filling direction and through which a cooling fluid flows to cool the catalyst within the catalyst-filled vessel; and an outer shell vessel disposed around the outer periphery of the catalyst-filled vessel and through which a cooling fluid flows to cool the catalyst from the outside.

2. 2. The multi-tube reactor according to claim 1, wherein the catalyst-filled vessel is made of a cylindrical body and the inner cooling tube is disposed at the center of the catalyst-filled vessel.

3. 3. The multi-tube reactor according to claim 1, wherein the catalyst-filled vessel has a filling port at an upper end thereof for filling with a catalyst, and a discharge port at a lower end thereof for discharging the catalyst, and the catalyst can be discharged from the discharge port by gravity.

4. 3. The multi-tube reaction vessel according to claim 1, further comprising a plurality of pairs of the catalyst-filled vessel and the inner cooling tube, the plurality of pairs being provided in one outer shell vessel.

5. 4. The multi-tube reaction vessel according to claim 3, further comprising a plurality of sets of the catalyst-filled vessel and the inner cooling tube, the plurality of sets being provided in one outer shell vessel.

6. 4. The multi-tube reaction vessel according to claim 3, further comprising: a catalyst layer temperature detection unit which detects a temperature inside the catalyst layer filled in the catalyst-filled vessel; a catalyst temperature comparison unit which receives detection information detected by the catalyst layer temperature detection unit and compares a current catalyst temperature based on the detection information with a catalyst non-deteriorated temperature when the catalyst is not deteriorated; a catalyst replacement determination unit which determines whether or not catalyst replacement is necessary based on a comparison result of the catalyst temperature comparison unit; and a notification unit which notifies the necessity of catalyst replacement when it is determined by the catalyst replacement determination unit.

7. 7. The multi-tube reactor according to claim 6, wherein the catalyst layer temperature detection units are provided at a plurality of positions from the upstream side to the downstream side of the catalyst layer.

8. a filling port opening / closing member that opens and closes the filling port, a discharge port opening / closing member that opens and closes the discharge port, and an actuator that performs an opening / closing operation of the filling port opening / closing member and the discharge port opening / closing member, 7. The multi-tube reaction vessel according to claim 6, wherein the catalyst replacement determining unit has a function of activating the actuator when it determines that the catalyst needs to be replaced.

9. 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 catalyst layer 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; 7. The multi-tube reaction vessel according to claim 6, wherein the catalyst replacement determining unit determines whether or not the catalyst should be replaced when the temperature fluctuation cause determining unit determines that the temperature fluctuation is caused by catalyst deterioration.

10. a supply reactant gas property detection unit that detects the temperature, pressure, flow rate, and concentration of the reactant gas supplied to the catalyst-filled vessel; an undegraded catalyst temperature database that stores the temperature exhibited by an undegraded catalyst for each assumed property of the reactant gas; and an undegraded catalyst temperature estimation unit that 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, 7. The multi-tube reaction vessel according to claim 6, wherein the catalyst temperature comparison unit 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.

11. 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, 7. The multi-tube reactor according to claim 6, wherein the catalyst temperature comparison unit compares the undegraded catalyst temperature estimated by the catalyst layer temperature estimation unit with the temperature detected by the catalyst layer temperature detection unit.

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