JP6321946B2 - Catalytic reaction system and catalytic reaction apparatus - Google Patents

Description

  The present invention relates to a catalytic reaction system and a catalytic reaction apparatus suitably used for, for example, a dehydrogenation reaction of an organic hydride or a hydrogenation reaction that is a reversible reaction thereof.

  In the dehydrogenation reaction of a fluid to be treated with endothermic heat, it is necessary to supply heat necessary for the reaction. For example, in a reactor used for organic hydride dehydrogenation, a catalyst device in which a catalyst material is integrally provided on the surface of a heater that generates heat when energized via a carrier is used. The organic hydride dehydrogenation reaction occurs relatively frequently on the upstream surface of the first contacting catalyst body in the flow of the fluid to be treated. Since unreacted organic hydride is released as it is, it is difficult to satisfy the reaction efficiency.

 It is desirable that the above-described reaction of the fluid to be treated be performed uniformly over the entire catalyst body in the flow of the fluid to be treated. However, the reaction is usually partially different depending on the configuration of the apparatus and processing conditions. For example, a catalytic reaction system in which plate-like supports formed in a flat plate shape are arranged in multiple stages, and a heating fluid and a fluid to be treated are separately circulated in each stacking gap, as is often used conventionally. However, unevenness is likely to occur in the heating temperature for each part. Even if the entire catalyst body is heated in the same manner, the endothermic reaction tends to vary depending on the inflow state of the fluid to be treated, and it may be difficult to obtain sufficient treatment efficiency as the temperature decreases. In order to improve such a phenomenon, it is conceivable to arrange a plurality of catalyst bodies in the flow direction of the fluid to be treated. However, in that case, there is a problem that a large temperature difference occurs between the upstream catalyst body and the downstream catalyst body.

  In addition to such inconvenience, if the dehydrogenation reaction is continued, the catalyst material is likely to deteriorate, although there is a difference in degree. The main cause of the deterioration of the catalyst material is considered to be coking caused by carbon in the fluid to be treated adhering to the surface of the catalyst material (for example, Pt). Coking increases as the amount of reaction increases and the temperature of the catalyst material increases. Therefore, if the temperature of the catalyst material is increased more than necessary, the deterioration of the catalyst material is accelerated. On the other hand, when the temperature of the catalyst material is low, the reaction conversion rate tends to decrease. For this purpose, the catalyst material needs to be controlled at an appropriate temperature.

JP 7-192746 A Japanese Patent Laid-Open No. 5-270801 JP-A-4-354544

  The present invention has been devised in view of the above-described problems. For example, a catalytic reaction system and a catalytic reaction apparatus useful for improving the reaction conversion rate of an organic hydride dehydrogenation reaction, extending the life of a catalytic substance, and the like. The main purpose is to provide

  A first invention of the present application is a catalytic reaction system using a catalyst that promotes a chemical reaction of a fluid to be treated, and is disposed in the chamber so that the fluid to be treated flows, and the chamber to be in contact with the fluid to be treated. A catalyst member, and a controller for supplying electric power to the catalyst member, the catalyst member having a plurality of catalyst bodies arranged in multiple stages along the flow direction of the fluid to be treated. The medium includes a heater unit that generates heat when energized, and a carrier carrying a catalyst substance disposed on the surface of the heater unit, and the control device controls the temperatures of the catalyst bodies independently of each other. It is characterized by.

  In the catalyst reaction system according to the first aspect of the present invention, it is preferable that the control device controls the temperature of each catalyst body by adjusting the amount of electricity supplied to each heater section.

  In the catalyst reaction system according to the first aspect of the present invention, it is preferable that the control device supplies different amounts of electricity to the heater units according to a supply state of the fluid to be processed and / or a reaction state of the catalyst body. .

  In the catalytic reaction system according to the first aspect of the present invention, the control device energizes the upstream catalyst body in the flow direction of the fluid to be treated, and uses the radiant heat to thereby apply the downstream catalyst body to the downstream catalyst body. Therefore, it is desirable to add a smaller amount of electricity or to be in a non-energized state.

  In the catalytic reaction system of the first invention, it is desirable that the control device intermittently energizes the heater portions of the catalyst members arranged in the flow direction of the fluid to be processed.

  In the catalytic reaction system according to the first aspect of the invention, the control device detects a functional deterioration of the catalytic material from a change in the amount of electricity and temperature of the heater unit, and a functional deterioration of the catalytic material is detected. It is desirable to include adjustment means for changing the amount of electricity to the catalyst body downstream of the catalyst body.

  In the catalytic reaction system of the first invention, the adjustment means may include a power regulator.

  In the catalytic reaction system of the first invention, the fluid to be treated includes hydrogen and an aromatic compound, and the chemical reaction is suitable for generating an organic hydride by a hydrogen addition reaction between hydrogen and an aromatic compound. is there.

  In the catalytic reaction system of the first invention, it is preferable that the fluid to be treated includes atomized methylcyclohexane (MCH) and an accompanying gas, and hydrogen is generated from the fluid to be treated by a dehydrogenation reaction.

  A second invention of the present application is a catalytic reaction apparatus using a catalyst that promotes a chemical reaction of a fluid to be treated, and is disposed in the chamber so that the fluid to be treated flows, and the chamber to be in contact with the fluid to be treated. A catalyst member and a control device for supplying electric power to the catalyst member, the catalyst member having a plurality of catalyst bodies arranged in multiple stages along the flow direction of the fluid to be treated. The medium includes a heater unit that generates heat when energized, and a carrier that supports a catalyst substance disposed on a surface of the heater unit, and the control device controls an energization amount of each catalyst body to the heater unit. The temperature of each catalyst body is formed so as to be controllable independently of each other.

  In the catalyst reaction apparatus according to the second aspect of the invention, the catalyst body is formed by forming a wire in a coil shape, and the wire includes a heater core, a porous alumite layer covering the surface, and the porous And the catalyst material supported in the pores.

  In the catalytic reaction apparatus according to the second aspect of the invention, it is preferable that the catalyst body is arranged in a spiral shape along a reaction chamber provided in the chamber.

  The catalytic reaction system of the present invention includes a chamber through which a fluid to be treated flows, a catalyst member disposed in the chamber so as to be in contact with the fluid to be treated, and a controller for supplying electric power to the catalyst member, The member has a plurality of catalyst bodies arranged in the flow direction of the fluid to be treated, and each catalyst body includes a heater part that generates heat by energization, and a carrier that carries a catalyst substance arranged on the surface of the heater part. The control device controls the temperatures of the respective catalyst bodies independently of each other, for example, so as to improve the reaction conversion rate of the fluid to be treated or to suppress deterioration of the catalyst substance. Can do. Therefore, according to the system of the present invention and the invention by the catalytic reactor embodying the system, the reaction conversion rate of the fluid to be treated can be improved and the life of the catalytic material can be extended.

It is a flowchart of the process using the catalytic reaction system of this invention. It is an assembly perspective view of the principal part of a catalytic reaction device. It is a top view of a catalytic reaction apparatus. It is AA sectional drawing of FIG. It is a block diagram of the catalytic reaction apparatus which concerns on one Embodiment of this invention. It is a schematic diagram which shows an example of a coil-shaped catalyst body. It is sectional drawing which shows an example of a composite coil-shaped catalyst body. It is a graph which shows the relationship between the conversion rate and reaction processing time for demonstrating the effect of a catalytic reaction apparatus.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings.
In this embodiment, for example, an aromatic compound (organic hydride) is used as a fluid to be treated, and a catalytic reaction apparatus (hereinafter referred to as hydrogen generation) that promotes dehydrogenation reaction (endothermic reaction) of the aromatic compound to generate hydrogen, for example. (It is also simply called “reactor”).

  Examples of the fluid to be treated used in this reaction include hydrogenated derivatives of aromatic compounds such as methylcyclohexane (MCH), benzene, and cyclohexane in addition to esters, carboxylic acids, and aldehydes. These are used as gas or atomized gas fluids. The catalytic reaction apparatus 1 of the present embodiment preferably constitutes a hydrogen generation system based on the catalytic reaction of the above compound.

  FIG. 1 is an example showing a processing flow of the hydrogen generation system 20 described above. In this system 20, for example, an organic hydride (for example, methylcyclohexane: MCH) that is a hydrogenated derivative of an aromatic compound (for example, toluene) is used as a fluid to be treated. The system 20 includes, for example, a storage tank 21 that stores MCH, a pump 22 that pumps the MCH in the storage tank 21, a vaporizer 23 that vaporizes the pumped MCH, and a catalytic reaction that is disposed downstream thereof. The apparatus 24 and the cooler 25 which cools the reaction gas produced | generated with the reaction apparatus 24, and enables gas-liquid separation are provided. In this system 20, the gas content in the obtained product is taken out as hydrogen, and the liquid in the tank 28 is taken out as toluene. The taken-out toluene can constitute a circulation type reaction apparatus that returns to MCH using the reverse reaction as necessary.

  The system 20 is further shown with a combination of MCH supply back pressure and accompanying gas for preventing oxidative degradation of the catalytic material of the reactor 24. For the accompanying gas, for example, hydrogen is used so as to provide a substantially reducing atmosphere.

  FIG. 2 is an exploded perspective view of a main part of the catalytic reaction device 24 of the system of FIG. In FIG. 2, the fluid G to be processed flows from the top to the bottom in the direction of the arrow, and a vaporizer 23 is disposed on the upstream side of the catalytic reaction device 24. The reaction device 24 and the vaporizer 23 are connected via, for example, a joint-shaped flange 30. The vaporizer 23 heats the fluid G to be treated to a predetermined temperature by the heating heater h, and thereby denatures it into a gaseous gas or a spray. The heating conditions are appropriately adjusted depending on the type of the fluid G to be processed and the processing conditions. In the present embodiment, for example, the heating conditions are set to 300 to 400 ° C., and more preferably to 320 to 360 ° C.

  The vaporizer 23 is provided with a nozzle member 26 on the downstream side thereof. The nozzle member 26 and the reaction device 24 are arranged at a certain distance by a flange 30. The nozzle member 26 has a flow passage that gently amplifies toward the downstream side so that the gaseous fluid G to be treated is fed to the catalytic reaction device 24 almost on average. Thereby, the fluid G to be treated is prevented from staying in the nozzle member 26 and the flange 30. When the fluid G to be processed is already gasified, the vaporizer 23 is not necessary, and the vaporizer 23 and the nozzle member 26 are employed as necessary.

  The catalytic reaction device 24 includes, for example, a first unit 24A and a second unit 24B arranged along the flow direction of the fluid G to be processed. In this case, a more efficient reaction apparatus can be provided. However, the catalytic reaction device 24 can be further improved in characteristics by providing more stages. In that case, reactors having different structures can be combined. Conversely, the catalytic reaction device 24 may be composed of a single unit.

  FIG. 3 shows a plan view of each unit 24A, 24B, and FIG. 4 shows a cross-sectional view taken along the line AA. As shown in FIGS. 3 to 4, each unit 24 </ b> A, 24 </ b> B shows a form using a holder 2 </ b> C corresponding to the chamber 2, and a reaction chamber 31 is formed in the holder 2 </ b> C.

  The reaction chamber 31 of this embodiment is provided as, for example, a groove-like space extending in a spiral shape. As a result, the reaction apparatus 24 can be made compact, and the fluid G to be treated is supplied to the reaction chamber 31. A catalyst member 3 is disposed in the reaction chamber 31. If necessary, the catalyst material can also be supported on the inner wall surface 31 </ b> A of the reaction chamber 31. The bottom surface of the reaction chamber 31 is provided with a plurality of discharge ports 34 through which products generated by the catalytic reaction with the catalyst member 3 are discharged out of the system.

  The catalytic reaction device 24 constitutes a series of devices as described above, whereby a more preferable hydrogenation reaction of an aromatic compound or a dehydrogenation reaction of a hydrogenated derivative of the aromatic compound is lined up and accelerated. It can be used as a catalytic reactor. If necessary, it can also be used as an application system for performing such a reversible reaction as needed as a general-purpose type.

  FIG. 5 illustrates the configuration of the catalytic reaction device 24 more specifically. The catalyst reaction device 24 includes the chamber 2, a catalyst member 3 disposed in the chamber 2 so as to be in contact with the fluid G to be processed in the chamber 2, and a control device 4 capable of supplying a predetermined amount of electricity to the catalyst member 3. It is comprised including.

  The shape, structure, and size of the chamber 2 are not particularly limited. The chamber 2 of the present embodiment is formed of, for example, an aluminum block formed to have a size of an outer diameter of 30 to 300 mm and a height of about 20 to 200 mm. The chamber 2 has an inlet 2a to which the fluid G to be processed is supplied, and an outlet 2b to which the processed fluid is discharged on the opposite side. The chamber 2 is connected to a pipe or the like (not shown), and forms a reaction chamber 31 whose interior is substantially maintained in a non-oxidized state isolated from the outside. Thereby, the to-be-processed fluid G gasified by the vaporizer 23 stays in the chamber 2 until it enters from the inlet 2a and is discharged from the outlet 2b.

  The catalyst member 3 includes a plurality of catalyst bodies 3a to 3e arranged in multiple stages along the gas G flow direction (that is, the direction from the upstream side to the downstream side). Accordingly, each of the built-in catalyst bodies 3a to 3e is effectively brought into contact with the fluid G to be processed in the chamber 2, and a target catalytic reaction is performed. In the present embodiment, the five catalyst bodies 3a to 3e are arranged in a substantially adjacent state. The number of catalyst bodies is not limited to this embodiment, and it is sufficient that at least two catalyst bodies are provided.

  Each of the catalyst bodies 3a to 3e is used as a composite member of a heater section 6 that generates heat when energized and a carrier 8 that supports a catalyst substance 7 disposed on the surface of each heater section 6.

  As the catalyst bodies 3a to 3e, for example, wire-like thin wires are recommended. The fine wire desirably has a wire diameter of 1 mm or less, for example. The thin wire having such a small diameter effectively increases the amount of the catalyst substance supported by increasing the surface area, and can efficiently obtain a catalytic reaction. The heater unit 6 and the carrier 8 are set to meet the requirements.

  The heater unit 6 is preferably made of a material having electrical characteristics capable of self-heating to a predetermined reaction temperature when energized. For example, copper, magnesium, calcium, nickel, cobalt, vanadium, niobium, chromium, titanium, aluminum, It is selected from at least one metal selected from the group of silicon, molybdenum, tungsten and iron, or an alloy thereof.

  On the surface of the heater section 6, there is provided a carrier 8 that supports a catalyst substance in a layered form having a predetermined thickness (for example, about 0.1 to 500 μm, preferably about 5 to 60 μm). The carrier 8 is formed integrally with the heater unit 6 directly or indirectly. The carrier 8 of the present embodiment includes, for example, an alumina layer having a porous structure, and a predetermined catalyst material 7 can be supported in the pores. That is, the alumina layer is formed by forming the porous structure having a large number of micropores on the surface side by the oxidized surface treatment (alumite treatment) of aluminum, and the catalyst material is appropriately supported on the inner wall surface of the micropores. be able to.

In addition to the above, the carrier 8 may have a similar porous surface structure using a metal material such as Ta, Mg, or Ti. The formation of the porous alumina layer can be easily employed as disclosed in, for example, JP-A-2005-171340 and JP-A-2004-107739.

  Various catalyst materials 7 are selected in accordance with the type of the fluid G to be used. Although not particularly limited, the catalyst material 7 is preferably, for example, platinum (including platinum group metals and alloys thereof). In addition to platinum, the catalyst material 7 employs one or more transition metals selected from the group consisting of rhodium, rhenium, nickel, titanium, magnesium, zinc, zirconium, molybdenum, and tungsten. The catalyst material 7 is applied to, for example, a porous carrier 8 and is pressed and penetrated into the pores under pressure.

  The catalyst material 7 and the carrier 8 on which the catalyst material 7 is supported, the processing method and shape thereof are not particularly limited, and various forms can be employed. The catalyst bodies 3a to 3e using the wire-like thin wires have a high capacity of the carrier 8 per unit volume and can support the catalyst material on the increased surface area, thereby promoting the catalytic reaction. Is desirable.

  As a device for enhancing the effect of the catalytic reaction, the catalyst bodies 3a to 3e are preferably used as coil wires wound with a predetermined winding diameter. In particular, as in WO2012 / 090326A1, it is desirable to configure a composite coil wire formed by concentrically inserting a plurality of large and small coil wires having different winding diameters. Furthermore, it is desirable that the coil wire is formed in a planar manner in appearance by being formed in a spiral shape or a meandering shape as in the present embodiment, for example. However, the catalyst bodies 3a to 3e can be implemented in any form other than the above forms.

  FIG. 6 shows, as an example, coiled catalyst bodies 3a to 3e. The catalyst bodies 3a to 3e are provided with a coupler C through a portion 40 where the core material at both ends 40 is exposed. The catalyst bodies 3a to 3e are kept in a spiral shape by being mounted in the spiral reaction chamber 31 of the reaction apparatus of FIG. FIG. 7 shows a configuration of a composite coil wire body in which two types of coil wires having different coil diameters are arranged concentrically.

  In addition to the coil shape, the catalyst bodies 3a to 3e are formed in various forms such as a band shape, a plate shape, or a mesh shape.

  As shown in FIG. 4, a dispersion material 35 is preferably disposed in the reaction chamber 31 in order to disperse the flow of the fluid G to be processed over a wide range. As the dispersion material 35, for example, inorganic powder such as quartz or silica ceramic, fiber material, or porous material is preferably used. As the porous material, for example, a material having a porosity of 40% or more is desirable. Such a dispersing material 35 forms a complicated flow path so as to cover the uppermost catalyst body 3a or in a gap between each of the catalyst bodies 3a to 3e and the reaction chamber 31, and to be processed. It helps to increase the chance of contact between fluid G and the catalytic material.

  As shown in FIG. 5, the catalyst reaction device 24 of the present embodiment further includes a power supply unit 10, relay elements 11 a to 11 e, and a relay circuit 9 (9 a to 9 e). The electric power switched by the relay elements 11a to 11e is connected between the catalyst bodies 3a to 3e and the control device 4 so that an independent amount of electricity can be added to each heater unit 6 of the catalyst bodies 3a to 3e. Relay circuits 9 (9a to 9e) for supplying the catalyst bodies 3a to 3e are provided. Thereby, each catalyst body 3a thru | or 3e is each independently controlled by electricity supply and by extension, heating control. For example, a semiconductor, a transistor, or the like is used for the relay elements 11a to 11e, and are switched independently at a predetermined timing by a control signal from the control device 4.

  The catalytic reaction device 24 includes temperature sensors 12a to 12e. Each of the temperature sensors 12a to 12e measures the temperature of each of the catalyst bodies 3a to 3e, and feeds back the detection signal to the control device 4. The control device 4 systematically measures and controls the relationship between the energization amount to the catalyst bodies 3a to 3e and the heat generation temperature. For the measurement management, for example, a power regulator used for temperature management such as a heat treatment furnace can be employed. Based on the difference between the temperature measured by the temperature sensor and the target set temperature, the power regulator appropriately adjusts the output voltage or current to be supplied to the circuit. Thereby, each catalyst body 3a thru | or 3e is controlled to fixed temperature.

  According to the catalyst reaction device 24 of the present embodiment, the control device 4 can independently control the energization amounts to the catalyst bodies 3a to 3e by individually turning on and off the relay elements 11a to 11e. . Thereby, each catalyst body 3a to 3e can be set to an arbitrary temperature, and independent adjustment is possible.

  As a more preferable form of temperature adjustment, the case of the dehydrogenation reaction will be described. In general, the fluid G to be treated has many opportunities to come into contact with the upstream catalyst body 3a. In order to reduce the temperature drop of the upstream catalyst body 3a due to this, a large amount of electricity is added to the catalyst body 3a as a relative thing. On the other hand, the downstream catalyst body 3b is warmed by receiving radiant heat from the upstream catalyst body 3a. Therefore, the energization amount to the downstream side catalyst body 3b can be set to a relatively low amount of electricity or a non-energized state as a relative amount. Thereby, the catalyst bodies 3a to 3e can be adjusted to a constant temperature. The energization amount (voltage or current) to each catalyst body 3a to 3e can be varied depending on, for example, the supply state and concentration of the fluid G to be treated and the reaction state with the catalyst substance. In addition, it is also preferable to change the energization amount at intervals of one to a plurality of intervals for each of the catalyst bodies stacked in multiple stages.

  Since the catalyst bodies 3a to 3e cause an endothermic or exothermic reaction due to a catalytic reaction when used, the reaction state of the catalyst can be observed by managing data on the relationship between the energization amount and the temperature based on this assumption. For example, when the catalyst bodies 3a to 3e are used for a long period of time, the catalytic bodies 3a to 3e may be deteriorated in function due to a coking phenomenon or the like. In this case, the relationship between the energization amount and the heating temperature changes.

  In the present embodiment, the control device 4 measures the relationship between the energization amount and the temperature of each of the catalyst bodies 3a to 3e with time, manages the data, and detects changes, thereby detecting functional deterioration of the catalyst material. The detection means 50 which comprises is provided. Further, the control device 4 includes adjusting means 60 for controlling the heating point to move from the catalyst body whose function has been lowered to the catalyst body on the one-stage downstream side so as to optimize the catalyst reaction, for example. In such an embodiment, a more effective and stable catalytic reaction can be obtained, and the lifetime of the entire apparatus can be extended.

  If necessary, it is desirable to reduce the amount of power applied to the deteriorated catalyst body on the upper stage based on the information that the heating point has been transferred to the downstream catalyst body. Thereby, for example, the coking phenomenon can be suppressed in the upstream catalyst body. Further, it is particularly preferable that the entire apparatus can be run long by programming so that such control is taken over further downstream. Each catalyst body whose function has deteriorated due to the coking phenomenon can be easily recovered by, for example, an air regeneration process in which heating is performed at about 300 to 400 ° C. in an air environment that is separately performed thereafter.

  FIG. 8 shows an example of the change over time of the reaction based on the example as an example of the effect. That is, when the function of the most upstream catalyst body deteriorates (in this example, the time S1 when the conversion rate becomes b% or less), the energization point is shifted to the next downstream catalyst body. Thereby, the fall of the conversion rate is suppressed. Further, when the function of the downstream catalyst body deteriorates (in this example, the time S2 when the conversion rate becomes b% or less), the energization point is shifted to the next downstream catalyst body. Thereby, the fall of the conversion rate is suppressed again. At the stage where the energization point reaches the most downstream, the reactor 24 can be air regenerated to restore its function. By such a method, it is possible to extend the life.

  By having the adjusting means 60 as described above, for example, the conversion rate of methylcyclohexane and the selectivity of toluene can be improved. Further, since the reactor 24 of the present embodiment can recover its function, it is effectively employed in a catalyst device for hydrogenation reaction or dehydrogenation reaction. It can also provide long life. “Methylcyclohexane conversion” is the ratio of the amount of the substance that methylcyclohexane in the fluid to be treated substantially reacted with the catalytic reaction and converted into hydrogen, toluene, etc. It becomes a thing of a reaction state. Therefore, the higher this ratio, the better the reaction efficiency. “Toluene selectivity” is the content ratio of only the hydrogen and toluene in the reactant, and the higher the ratio, the better the less secondary products. Any of these can be analyzed by the gas chromatography.

  The above explanation is mainly about the case where hydrogen is generated by the dehydrogenation reaction accompanied by the endothermic phenomenon of the fluid to be treated. In the following examples, the present invention will be described in more detail, but the present invention is not limited to such examples.

[Production of catalyst body]
As shown in FIGS. 6 and 7, the catalyst body of the embodiment of the present invention uses a pure Ni wire 41 of Ni 95 wt% or more as a heater material, and clad an aluminum band 42 for supporting the catalyst substance X on the surface thereof. A clad composite material was used as a starting material, and the wire was thinned to a finished wire diameter of 0.70 mm while performing cold wire drawing and heat treatment to obtain a composite wire 43. The composite rate of the aluminum layer of the composite wire 43 was 60%, and the Ni wire 41 was almost concentrically covered with the aluminum layer.

  Next, the composite wire 43 was set in a commercially available coil winding machine, and coil wires 44A and 44B having a coil average diameter of 7 mm and 4 mm and a length of about 250 mm were manufactured. The ratio (D / d) between the wire diameter d of each coil wire and the average coil winding diameter D was adjusted to 7 to 15 times.

  Each of the coil wires 44A and 44B is subjected to a calcination treatment at a temperature of 300 to 600 ° C. for about 1 hour and a hydration treatment with warm water after an alumite layer is formed on the surface of the aluminum layer by anodizing treatment. It was conducted. As a result, the coil wires 44A and 44B have a layered structure having a uniform thickness of 10 to 30 μm on the surface of the aluminum layer and a γ-alumina based porous structure having fine pores (pore diameter 10 to 200 nm). The carrier was provided. The specific configuration, processing conditions, and the like are in line with the above-mentioned WO2012-090326.

  Next, after the platinum catalyst material is supported in the porous pores of the coil wires 44A and 44B by the impregnation method, the two types of large and small coil wires 44A and 44B are fitted to each other, as shown in FIG. Thus, a composite coil-shaped catalyst body 3 was obtained.

[Incorporation into catalytic reactor]
A plurality of composite coil-shaped catalyst bodies 3 were assembled in a multi-stage (four stages in this embodiment) in order along the spiral reaction chamber of the chamber 2. Both ends 40 of the catalyst body 3 were connected to the control device 4 via the coupler C.

A temperature sensor 12 is further connected to each of the catalyst bodies 3a to 3d. In this example, a dispersion material 35 made of non-conductive quartz powder was further disposed in the gap between the reaction chambers 31.
[Dehydrogenation test]

In this test, the fluid to be treated was fed to the catalytic reaction device to perform a dehydrogenation reaction. The fluid to be treated was cyclomethylhexane (MCH), which was supplied in the form of atomized gas at a rate of 4 ml / min. Controller 2.2 to the catalyst body most upstream (A / dm ^2), the amount of electricity to each supply of 2.0 to catalyst on the downstream side (A / dm ^2), or each catalyst body 3a 3d was controlled to a set temperature of 340 ° C. Furthermore, the amount of electricity was adjusted so that the measured values of each temperature sensor were almost uniform.

  As a result of continuous 200 hours test, the hydrogen production amount was 0.4 (L / min), and the conversion rate was 90.6%. Compared to the case where only one composite coil wire catalyst is used, this performance improves the hydrogen production by 0.3 (L / min) and the conversion rate by about 8%. As a proof of the nature, it was greatly expected to expand.

Four more holder units containing the four-stage coiled catalyst bodies used in Example 1 were prepared, and a catalyst reaction apparatus in which a total of 16 stages of catalyst bodies were arranged by stacking each unit in series was prototyped. Then, the same dehydrogenation test as in Example 1 was performed. As for energization to each catalyst body, 2 (A / dm ² ) is added only to the most upstream (first stage) and third stage catalyst bodies in each unit, and the second and fourth stages. About the catalyst body, in order to receive the radiant heat of the catalyst body of the 1st step | stage and the 3rd step | paragraph which adjoin substantially arrange | position, it was made into the non-energized state. As a result of the continuous dehydrogenation reaction for 24 hours, the hydrogen production amount was 8 (L / min), and the conversion rate was 99.2%.

The multistage unit type catalyst reaction apparatus of Example 2 was subjected to a life extension test by adjusting the energization method. The test is set so that the energization amount is gradually decreased from the upstream side for each unit as in Example 2, and 2 (A / dm ² ) is added in the upper stage. In this state, while the data analysis of the relationship between the energization amount of each catalyst body, the exothermic temperature, and the amount of hydrogen generated over time, the relationship gradually decreases, and the relationship is initially shown in FIG. The time when the value falls below 70% of the value is regarded as the expiration date of the catalyst body, and the amount of electricity is transferred by switching the point of energization to the second catalyst body at the next stage, and the switching operation is automated by the power regulator. . In this way, by sequentially shifting the energization to each of the accommodated catalyst bodies, as a result, it was possible to sufficiently cope with continuous use for 3000 hours.

A 20 # plain weave mesh sheet was formed using the aluminum-coated composite wire having a wire diameter of 0.45 mm obtained by the method of Example 1. In this mesh sheet, an anodized layer is formed on the surface of the composite wire by anodizing treatment in an oxalic acid solution, and thereafter an average pore diameter of 100 nm and an aspect ratio are obtained by baking treatment and hydration treatment at 500 ° C. for 1 hour. 400 fine holes were formed on almost the entire surface. Then, a catalyst body was prototyped by loading platinum catalyst particles at 1.8 gpt / μm ² in the fine pores on the surface of the mesh sheet.

Next, 10 catalyst bodies made of mesh sheets were laminated in multiple stages at regular intervals. Each sheet was subjected to a dehydrogenation test using MCH as a fluid to be processed while flowing a current in the range of 3.0 to 3.5 (A / dm ² ). In the test, the temperature was measured with a temperature sensor arranged between each mesh sheet in the same manner as in Example 1, and the power was adjusted so that the temperature of each catalyst body was 350 ° C. As a result of the continuous test for 200 hours, the hydrogen production amount was 1.4 (L / min), and the conversion rate was 93%. From this result, it was confirmed that even if the catalyst bodies have different forms, sufficient availability can be expected by arranging them in multiple stages and adjusting the heating temperature appropriately.

  Using a Ni-Cr alloy nichrome wire 1.2 mmφ as the core material of the linear catalyst body, clad an aluminum metal film with a thickness of 0.2 mm on the surface, and the outer diameter by the same small diameter processing as in Example 1. A 0.3 mm aluminum clad composite wire was created. The composite ratio of the aluminum exterior material in the small diameter state was 50%. From this composite wire, a close-contact coil wire was prepared so that the ratio D / d between the coil average diameter D and the wire diameter d was 5. The coil wire is anodized using a 4% oxalic acid solution to form an alumite layer having fine pores on the surface, and a catalyst material of platinum fine particles is supported in the pores to form a linear wire. A catalyst body was obtained.

  Next, six of the above-described catalyst bodies having a length of 230 mm were placed on an aluminum chamber with a discharge port, and a plate-shaped catalyst unit was prototyped by wiring the ends of the catalyst bodies in parallel. The surface of the uppermost coiled catalyst body was further covered with quartz powder having a particle size of 80 μm so that the fluid to be treated was well dispersed and contacted with the catalyst body. Then, five plate-like catalyst units were stacked in the chamber to constitute a reactor, and hydrogen was generated by a dehydrogenation reaction using methylcyclohexane as a fluid to be treated in the same manner as described above.

  Energization of the catalyst unit is performed only for the upstream most upstream (first stage) and its downstream (second stage), and the downstream side uses the radiant heat of the upstream catalyst body. In this way, it was performed without energization. As a result, the hydrogen production amount was 0.5 (L / min), and the hydrogenation rate was 93%.

  The present invention provides a catalyst reaction system for generating hydrogen and a catalyst reaction apparatus therefor, in which catalyst bodies configured to be controllable so that independent heating temperatures can be set along the flow direction of the fluid to be treated are stacked in multiple stages. In addition to increasing the efficiency of hydrogen generation per unit area, the application range by any heating operation according to the purpose of use is widened.For example, hydrogen fueled automobiles, ships, hydrogen stations, etc. It can be widely used for various purposes.

24 catalytic reaction device 2 chamber 3a, 3b, 3c, 3d, 3e catalyst body 4 control device 6 heater unit 7 catalyst material 8 carrier 9a, 9b, 9c, 9d, 9e relay circuit 10 power supply unit 11a, 11b, 11c, 11d, 11e Relay element 12a, 12b, 12c, 12d, 12e Temperature sensor

Claims (10)

A catalytic reaction system using a catalyst that promotes a chemical reaction of a fluid to be treated,
A chamber through which the fluid to be treated flows;
A catalyst member disposed in the chamber so as to be in contact with the fluid to be treated;
A controller for supplying electric power to the catalyst member,
The catalyst member has a plurality of catalyst bodies arranged in multiple stages along the flow direction of the fluid to be treated,
Each of the catalyst bodies has a heater portion that generates heat when energized, and a carrier that supports a catalyst material disposed on the surface of the heater portion,
The control device controls the temperature of each catalyst body independently of each other , and energizes a catalyst body on the upstream side in the flow direction of the fluid to be treated among the plurality of catalyst bodies. A lesser amount of electricity than the upstream catalyst body is added to the downstream catalyst body in the flow direction of the processing fluid, or a non-energized state is established.
The control device further includes:
Detection means for detecting functional deterioration of the catalytic material from changes in the amount of electricity and temperature of the heater section;
An adjustment means for increasing the amount of electricity to the catalyst body downstream of the catalyst body in which the function deterioration of the catalyst material is detected, when the function deterioration is detected,
Catalytic reaction system.   2. The catalytic reaction system according to claim 1, wherein the control device controls the temperature of each catalyst body by adjusting an amount of electricity supplied to each heater unit.   3. The catalytic reaction system according to claim 1, wherein the control device supplies different amounts of electricity to the heater units according to a supply state of the fluid to be processed and / or a reaction state of the catalyst body. The catalytic reaction system according to any one of claims 1 to 3, wherein the control device intermittently energizes heater portions of the catalyst members arranged in a flow direction of the fluid to be treated. The catalytic reaction system according to claim 1, wherein the adjusting means includes a power regulator. The treated fluid contains hydrogen and an aromatic compound,
The catalytic reaction system according to any one of claims 1 to 5, wherein the chemical reaction generates an organic hydride by a hydrogenation reaction between hydrogen and an aromatic compound. The catalytic reaction system according to claim 6, wherein the fluid to be treated includes atomized methylcyclohexane (MCH) and an accompanying gas, and generates hydrogen from the fluid to be treated by a dehydrogenation reaction. A catalytic reaction apparatus using a catalyst for promoting a chemical reaction of a fluid to be treated,
A chamber through which the fluid to be treated flows;
A catalyst member disposed in the chamber so as to be in contact with the fluid to be treated;
A controller for supplying electric power to the catalyst member,
The catalyst member has a plurality of catalyst bodies arranged in multiple stages along the flow direction of the fluid to be treated,
Each of the catalyst bodies has a heater portion that generates heat when energized, and a carrier that supports a catalyst material disposed on the surface of the heater portion,
The control device is configured to control the energization amount of each catalyst body to the heater unit so that the temperature of each catalyst body can be controlled independently of each other, and among the plurality of catalyst bodies, Energize the upstream catalyst body in the flow direction of the fluid to be treated, and add a smaller quantity of electricity to the downstream catalyst body in the flow direction of the fluid to be treated than the upstream catalyst body, or Turn off the power,
The control device further includes:
Detection means for detecting functional deterioration of the catalytic material from changes in the amount of electricity and temperature of the heater section;
An adjustment means for increasing the amount of electricity to the catalyst body downstream of the catalyst body in which the function deterioration of the catalyst material is detected, when the function deterioration is detected,
Catalytic reactor. In the catalyst body, a wire is formed in a coil shape. The wire includes a heater core, a porous anodized layer covering the surface of the heater, and the catalyst supported in the porous pores. The catalytic reaction apparatus according to claim 8, comprising a substance. The catalytic reaction apparatus according to claim 8 or 9, wherein the catalyst body is arranged in a spiral shape along a reaction chamber provided in the chamber.

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