JP5995322B2 - Reactor for hydrogen generation and control method thereof - Google Patents

Description

  The present invention relates to, for example, a reactor for generating hydrogen in which hydrogen is generated by a catalytic reaction of an aromatic compound and hydrogen conversion efficiency is improved, and a control method thereof.

  In recent years, energy shortage due to global warming and the review of nuclear power generation has been regarded as a problem, and fuel cell systems have attracted attention as new clean energy sources that replace fossil fuels and nuclear power that have been widely used so far. Since this fuel cell system uses hydrogen as fuel and only water is discharged when electricity is generated, there is an increasing expectation for the spread of the clean energy technology with the least environmental impact.

In gasoline automobiles and diesel generators for ships and locomotives, "hydrogen co-firing technology" that adds hydrogen to fuel oil such as gasoline has been proposed. According to this technology, improvement in fuel consumption and reduction in the generation of environmental loads such as CO ₂ , NO _x , and CO are expected. Therefore, in such technological innovation, the trend of demand for hydrogen is increasing.

  On the other hand, since hydrogen is flammable and becomes a causative substance of hydrogen embrittlement for metal materials, there is a problem that it is difficult to store and transport. Therefore, a wide range of measures are necessary for the production, storage, and transportation of hydrogen.

Conventionally, in view of the above problems, hydrogen storage / supply systems that can supply hydrogen with good response as necessary have been studied. As such a system, for example, the following various efforts are being made (see Patent Document 1).
(A) A method for obtaining high-purity hydrogen from a raw material containing hydrogen such as natural gas, propane gas, methanol, etc. by steam reforming or hydrogen separation technology (B) A method for storing and transporting hydrogen by injecting it into a cylinder at high pressure, There are also general methods such as a method of storing and transporting hydrogen by liquefying it at an extremely low temperature, and a storage method using a hydrogen storage alloy.
(C) A method for extracting hydrogen and an aromatic compound from an organic hydride that is an aromatic hydrogenated derivative by a dehydrogenation reaction

  However, in the hydrogen production system of (A) above, in order to effectively obtain a certain amount of hydrogen, it is necessary to increase the size of the modules used and to simultaneously use a plurality of modules. Such a hydrogen production system is hampered in its popularity because the apparatus becomes larger or complicated.

  The storage system using the hydrogen storage alloy (B) described above has problems of limitation of the hydrogen storage amount per unit volume of the alloy used and the response performance of the response speed. Furthermore, since the hydrogen storage alloy is expensive, the storage system has not been sufficiently spread.

  On the other hand, since the dehydrogenation reaction using the organic hydride (C) proceeds reversibly, a hydrogen storage / supply system can be realized by an aromatic compound-organic hydride circulation cycle. Organic hydride is one of the leading technologies that have high energy storage density, can be stored stably for a long time, and can be stored and transported in large quantities using existing infrastructure of petroleum products such as gasoline. Has been.

  As a further improvement of the technique (C), the present applicants formed an alumite layer having fine pores on the outside of the core wire capable of self-heating by energization, and a catalyst material such as platinum was formed in the pores. A supported linear catalyst product is proposed (see Patent Document 2).

  In order to increase the distribution rate of the catalyst per unit volume, the catalyst product is formed of a coil wire carrying a catalyst and is incorporated in a pipe. This catalyst product is arranged in the casing with the spiral axis of the coil wire along the direction in which the fluid to be treated flows. In addition, the coil wire of the catalyst product generates heat by being energized (direct heating method), and the efficiency of hydrogen generation is efficiently increased.

JP 2007-238341 A JP 2011-245475 A

However, the hydrogen generator according to Patent Document 1 is a region for supplying fuel for generating heat necessary for a dehydrogenation reaction, a region having a combustion catalyst used for combustion of the fuel, and the dehydrogenation reaction described above. Since the reactor having a multi-tube structure provided with a region having a dehydrogenation catalyst necessary for the adjoining in the radial direction across the wall, the catalytic reaction efficiency per unit volume is not sufficient, and the size of the apparatus is large. And increase the cost with complicated structure.

The catalyst product of Patent Document 2 improves these drawbacks and can be carried out relatively easily at a low cost. However, in the above catalyst product, from various experimental results, the substantial catalytic reaction is limited to the upstream side of the coil wire, which is the inflow portion of the fluid to be treated, and its effect is small on the downstream side.
Even if a long coil wire is used, it is difficult to obtain a catalytic effect commensurate with it, and there has been a demand for further improvement in reaction efficiency.

  The present invention has been devised in view of the above-described circumstances, and improves the catalytic reaction by improving the defects of the catalyst product using the conventional coil wire, and further increases the flow path space of the housing that accommodates the catalyst product. The main object of the present invention is to provide a hydrogen generation reactor that can be effectively used and a control method thereof.

  The present invention includes a catalyst member that generates high-purity hydrogen from a fluid to be treated by a dehydrogenation reaction, and a housing that houses the catalyst member. The catalyst member includes a core wire made of a metal material, A porous anodized layer formed on the outside and having fine pores on the surface, and a catalyst wire containing a catalyst material supported in the fine pores of the anodized layer, the catalyst wire being continuously coiled A plurality of coil wires arranged in parallel or wound into a plane spiral shape of the coil wires to form a planar element having an apparent plane extending on an arbitrary plane, and a plurality of the elements are formed in the housing It is characterized in that the apparent planes are stacked and arranged in multiple stages so as to intersect each other with respect to the flow direction of the fluid to be treated flowing down.

  The interval between the coiled catalyst wires may be not more than 10 times the equivalent wire diameter d of the catalyst wires and may be not less than a gap through which the fluid to be treated can flow.

  A heat-resistant inorganic cushioning material that can improve the flow dispersibility of the fluid to be treated may be disposed in the gap between each element and the housing.

  The cushioning material may further include a cushioning material disposed so as to cover the most upstream element.

  The buffer material may be composed of any one or more kinds of inorganic fine particles and / or fibers selected from the group consisting of any one of alumina, silicon carbide, silicon nitride, zirconia, and mullite ceramic, quartz, and silica.

  The planar element includes at least a first coil wire having a first coil diameter and a second coil wire having a second coil diameter larger than the first coil diameter and surrounding and enclosing the first coil wire. It may be a composite element including multiple coil wires.

  The coil wires of the composite element are preferably insulated from each other and can be independently energized.

  The catalyst member has an exposed end portion where the surface of the core material is exposed at both ends of the catalyst wire, and can generate heat when energized through the exposed end portion.

  The reactor may further include a vaporizer that vaporizes the fluid to be processed in a gaseous state upstream of the reactor.

  As a method for controlling a reactor for generating hydrogen described in any of the above, it is necessary for an endothermic reaction by adjusting the energization amount of the coil wire of each element of the catalyst member according to the supply amount of the fluid to be treated. And a temperature control process for supplying heat.

The energization amount of the element located on the upstream side of the fluid to be processed is controlled to be larger than the energization amount of the downstream element so that variation in temperature distribution between the elements arranged in multiple stages is reduced. desirable.

  The hydrogen generation reactor described in claim 1 of the present application includes a catalyst member that generates high-purity hydrogen by a dehydrogenation reaction, and a housing that houses the catalyst member. The catalyst member includes a core wire made of a metal material, a porous alumite layer formed on the outside of the core wire and having micropores on the surface, and a catalyst material supported in the micropores of the alumite layer. It consists of a catalyst wire. The catalyst wire is a coil wire continuously wound in a coil shape, and is formed as a planar element having an apparent plane that extends on an arbitrary plane. A plurality of the elements are laminated in a multistage manner in the housing, and the fluid to be processed is supplied in a direction crossing the plane of each element. The fluid contact opportunity is greatly improved, the catalytic reaction can be remarkably enhanced, and the conversion efficiency of hydrogen production is improved as compared with the conventional case.

  Moreover, according to the reactor for hydrogen generation described in claims 2 to 9, the flowability of the fluid to be treated and the contact opportunity with the catalyst substance are further increased, and the conversion efficiency of hydrogen generation is further improved.

  Furthermore, according to the method for controlling a reactor for producing hydrogen described in claims 10 to 11, for example, different energization amounts can be added stepwise in a plurality of elements arranged in multiple stages. For this reason, temperature unevenness of the reaction atmosphere is prevented, and uniform temperature control is possible for the entire reactor by good current heating.

It is a top view which shows an example of the reactor for hydrogen production of this invention. FIG. 2 is a cross-sectional view showing a configuration in which a cushioning material is further arranged between planar elements stacked and arranged in multiple stages in the AA cross-sectional view of FIG. 1. It is a perspective view of a planar element, (A) shows one form which formed the catalyst wire in the shape of a plane spiral, and (B) shows one form constituted by arranging a plurality of coil wires in parallel. It is a side view (partial sectional view) showing the structure of a multiple coil wire. It is sectional drawing of a catalyst wire. It is a microscope picture (160 times) explaining the composite structure of a catalyst wire. It is a microscope picture (500 times) of the cross-sectional direction of the catalyst wire which comprises an alumite layer. It is an enlarged view explaining the porous structure formed in the alumite layer surface. It is a surface enlarged photograph of the porous structure of an alumite layer. It is a composition outline figure showing an example of the whole device explaining a hydrogen generating system. FIG. 11 is a perspective view of an essential part for explaining a mounting structure of a reactor for generating hydrogen in the system of FIG. 10.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
In FIG. 1, as an example of a reactor for generating hydrogen (hereinafter sometimes simply referred to as “reactor”) 1, a surface in which a coil wire of a catalyst wire is wound in a flat spiral shape in a housing 3. A plan view of the reactor with the element-like element is shown. FIG. 2 is a cross-sectional view taken along the line AA. In this embodiment, a cushioning material 10 is further disposed in the gap between the planar element 6 and the housing 3 to improve the flowability of the fluid to be processed.

The reactor 1 includes a catalyst member 2 that generates high-purity hydrogen from a fluid to be treated by a dehydrogenation reaction, and a housing 3 that shields and accommodates the catalyst member 2 from the outside. The reactor 1 is further appropriately incorporated in a pipe (not shown), and this is mounted on the apparatus main body to constitute, for example, a hydrogen production system. In the present invention, the housing 3 and the casing (piping) are separate from each other, the housing 3 is directly coupled to the casing, or the coil wire is directly accommodated in the casing itself. By forming the concave groove, the housing substantially serves as the housing and the housing is also included in the category of the housing.

As shown in FIGS. 1 and 2, the housing 3 is provided with a spiral groove 3 </ b> A having a predetermined depth that is recessed along the size and shape of the catalyst member 2 on one surface side. The catalyst member 2 is disposed in the spiral groove 3A. Thereby, the movement of the catalyst member 2 is prevented, the long coil wire is accommodated in a more compact manner, the energization control is easy, and the temperature distribution is made uniform. In this embodiment, the housing 3 is made of, for example, a block-shaped metal body, and the spiral groove 3A is formed by, for example, cutting.

  The catalyst member 2 includes a long catalyst wire 4 having a catalyst material supported on the surface thereof. For example, as shown in FIGS. 1 to 4, the catalyst member 2 is continuously coiled at a predetermined pitch to form a coil wire 5. The coil wire 5 is, for example, a planar element 6 as shown in FIG. 3A or 3B, whereby the catalyst member 2 is formed.

  FIG. 3 shows a perspective view of a specific external state of the planar element 6, FIG. 3 (A) shows a coil wire 5 wound in a plane spiral shape, and FIG. 3 (B) shows A plurality of linear coil wires 5 are arranged in parallel on a plane. In any form, an apparent plane H extending on one surface is formed. In this case, the contact state between the adjacent coil wires 5 is not limited, and they may be separated by an arbitrary distance as shown in FIG. 3A or may be in contact with each other as shown in FIG. Absent. A specific form is selected in consideration of the size, structure, use conditions, and the like of the housing 3.

  FIG. 5 shows a cross-sectional view of the catalyst wire 4. The catalyst wire 4 includes a core wire 4a made of a metal material, an alumite layer 4c formed directly or through a base aluminum layer 4b of a predetermined thickness on the outside of the core wire 4a, and formed in the alumite layer 4c into the fine holes s. And a supported catalyst substance X. The catalyst wire 4 of this embodiment is described as having a three-layer structure through the aluminum layer 4b so that the formation of the alumite layer 4c is favorably promoted, but the aluminum layer 4b is not necessarily required.

  For example, a long material having a constant cross-sectional shape is used for the catalyst wire 4 in the same manner as a general wire wire. The cross-sectional shape of the catalyst wire 4 is preferably a round wire with a circular cross-section that can be easily molded and can increase the accommodation rate of the catalyst substance X per unit volume. However, the present invention is not limited to this, and the catalyst wire 4 may be formed of, for example, an ellipse, a triangle, a square line, and other various non-circular shapes.

  The wire diameter of the catalyst wire 4 is, for example, a fine wire material of 0.05 to 3.0 mm, preferably about 0.1 to 1.5 mm. A wire diameter is shown by the average value of the separation distance measured over the perimeter direction about the arbitrary cross sections of the object wire, for example. However, in the case of the non-circular wire, the wire diameter is represented by an equivalent wire diameter calculated from the area of an arbitrary cross section.

  The core wire 4a of the catalyst wire 4 preferably has electrical characteristics that can generate heat at a predetermined temperature when energized. As such a core wire 4a, for example, stainless steel wire, nickel or nickel alloy wire, chromium or chromium alloy wire, titanium or titanium alloy wire, tungsten or tungsten alloy wire, etc. are desirable. In particular, the core wire 4a is selected to have a characteristic of an electrical resistivity of 5 Ω · cm or more, more preferably 5 to 200 Ω · cm. Particularly, nickel, a nickel alloy wire, and a chromium alloy wire are suitable because they easily generate heat to a use set temperature of, for example, 200 to 600 ° C. by direct energization or electromagnetic induction.

  As an example of the material composition of the core wire 4a, in the nickel alloy wire, for example, mass: Cr: 15-25%, Ni + Co: 55% or more, C: 0.15% or less, Si: 0.5-1. A nickel alloy of JIS-NCH1, NCH2 containing 5% and Mn: 2.5% or less, with the balance being Fe and unavoidable impurities. Similarly, as the nickel material, for example, N200 material of Ni: 99% or more by mass% can be cited. This nickel material is preferable in that the heat generation characteristics are close to those of aluminum and the workability of a small diameter is excellent.

  In the case of a chromium alloy wire, for example, Cr: 15 to 25%, C: 0.10% or less, Si: 1.5% or less, Mn: 1.0% or less, and Al: 2 to 6% in mass%. The chromium alloy by JIS-FCH1 and FCH2 which contains and the remainder is comprised with Fe and an unavoidable impurity can be mentioned.

  In addition to these metals such as nickel and chromium or alloy wires thereof, various metal materials can be used, and can be appropriately selected based on possessed characteristics.

  When the catalyst wire 4 is manufactured, first, an aluminum layer 4b having a predetermined thickness is formed on the surface of the core wire 4a selected from the above metal materials by, for example, plating. The coated wire on which the aluminum layer 4b is formed is made into a porous structure having fine pores s on the outer surface of the aluminum layer 4b after being reduced to a predetermined wire diameter and then subjected to anodizing treatment and firing treatment. An alumite layer 4c is formed. These processing and processing conditions are disclosed in, for example, Japanese Patent Application Laid-Open No. 2-144154 or Japanese Patent Application Laid-Open No. 8-246190.

  The aluminum layer 4b is formed, for example, by coating the core wire 4a by a plating technique or a clad technique, and the core wire 4a itself is made of a metal material containing aluminum and subjected to a precipitation heat treatment at a predetermined temperature. The aluminum element may be deposited in layers on the surface of the core wire 4a.

  Further, in order to form a sufficient alumite layer 4c for supporting the catalyst substance X in the catalyst wire 4, for example, a volume ratio represented by [volume of (alumite layer + aluminum layer) / total volume of catalyst wire]. Is preferably 5 to 70%. When the volume ratio is less than 5%, it is difficult to obtain a uniform and sufficient anodized layer 4c. On the other hand, when the volume ratio exceeds 70%, workability and productivity are deteriorated, and strength is lowered due to heat effects during use. It is easy and a more preferable volume ratio is set in the range of 8 to 65%, more preferably 10 to 60%.

The aluminum layer 4b has a thickness of, for example, 200 μm or less, preferably about 10 to 100 μm. 6 and 7 are examples of enlarged photographs showing a cross section of the catalyst wire 4. FIG. 6 shows a composite state in which an aluminum layer is clad on the core wire 4a, and FIG. 7 shows a state in which the anodized film (alumite layer) of the aluminum layer is formed on the composite wire by anodizing treatment and firing treatment. Has been. It can be seen that the contact interface between the aluminum layer and the alumite layer is well coated without voids.

  The alumite layer 4c can be formed by anodizing treatment and baking treatment of the aluminum layer 4b. For example, as described in the examples of the present application and the above-mentioned publications, an electrochemical treatment in a predetermined electrolytic solution, for example, a temperature of 350 to It is performed by a baking process at about 600 ° C. Although the details of the formation phenomenon of the alumite layer are omitted, γ-alumina having a porous structure in which the micropores formed by the anodizing treatment of the aluminum layer 4b are grown by the subsequent hydrothermal treatment and the firing treatment is formed. Will be.

  An example of the porous structure is shown in FIG. 8 and is a schematic view of a part of the pores s as viewed in the thickness cross-sectional direction. The alumite layer 4c has fine bottomed pores s distributed in a substantially turtle shell shape in the cross-sectional direction, and has a mesoporous porous structure, for example. The pore s has, for example, a fine opening having an inner diameter r of about 10 to 100 nm, preferably 30 to 50 nm, and a depth h of 500 μm or less. The pores s preferably have an aspect ratio (depth h / inner diameter r) adjusted to about 300 to 3000 by the post-treatment such as widening and deep plowing. It is arbitrarily set depending on the conditions of the anodizing treatment.

  FIG. 9 shows an enlarged micrograph of the surface of the alumite layer 4c. As is clear from FIG. 8, it is confirmed that the openings of the pores s are formed almost uniformly on the surface of the alumite layer 4c.

  The alumite layer 4c is an aluminum metal oxide and functions as an electrically non-conductive insulating film. For this reason, even if the catalyst wire 4 contacts with other members (other coil wire 5 or housing 3 etc.) at the time of use, an electrical short circuit is prevented and it can be used without taking special insulation means. In addition, the pores s are very fine and hard, and as shown in FIG. 8, the catalytic substance X is favorably supported on the inner wall surface, so that when the catalyst wire 4 is used, contact with other members and friction And the like, the desorption of the catalyst substance X can be prevented, and the shape change and sealing of the pores s can be prevented.

  The catalyst material X is variously selected according to the purpose of use and the type of fluid to be treated. For example, platinum, rhodium, rhenium, nickel, zirconium, titanium, zinc, magnesium, palladium, ruthenium, iridium, vanadium, osmium, chromium, cobalt, molybdenum or tungsten, or their hydrochloride, nitrate, oxalate and oxyacid salts. It is used, and can be impregnated and supported on alumite clad fine metal wire having a porous surface layer from water or ethanol or methanol solution in a simultaneous or sequential process.

  For example, the catalyst material X made of platinum is preferable because an easy supporting method in which a platinum solution is applied to the alumite layer 4c and press-fitted into the pores s can be adopted. As the platinum solution, for example, hexachloroplatinic (IV) acid hexahydrate, dinitrodiammine platinum (II) nitric acid solution, hexaammine platinum (IV) chloride solution or tetraammine platinum (II) hydrochloride solution is preferably used. . Further, the platinum and / or transition metal salt solution can be supported by a method such as dipping, dropping, coating or spraying in a predetermined temperature range while energizing or electromagnetically heating the fine wire on which the alumite layer 4c is formed. .

In addition to the above methods, metal carbonyl compounds such as Pt (CO) ₂ Cl, Rh ₄ (CO ₁₂ , Ni (CO) ₄ , Re ₂ (CO) ₇ , CpTiCl ₂ (Cp = cyclopentadienyl), Mo (CO ) It can be supported by a chemical vapor deposition method using _6, etc. After supporting, stepwise firing in a temperature range of 250 to 600 ° C. in an oxygen-containing atmosphere, and further in a hydrogen gas atmosphere It is preferable to perform the activation treatment by stepwise raising the temperature in the temperature range of 100 to 450 ° C. The platinum can be obtained by hydrogen activation treatment or reduction treatment with a reducing agent such as hydrazine, sodium formate, or boron hydride. And / or an aluminum clad metal wire catalyst carrying a transition metal can be prepared, and platinum and transition metal anodized clad metal Loading amount for the line, for example a 0.01% to 10% by weight, it is suitably adjusted as needed.

Generally, the alumite layer 4c is hard and brittle, and the coil wire provided with the alumite layer 4c is designed to prevent cracking or peeling due to strong processing such as coil forming, heating expansion or contraction during use. desired. For this reason, the alumite layer 4c is required to be designed in consideration of the coil forming process, for example, the generation stage of the alumite layer 4c. For example, the alumite layer is formed after the coil wire is formed, and, as shown in FIG. 4, the ratio D / d between the winding average diameter D of each coil wire 5 and the equivalent diameter d of the catalyst wire 4 Measures such as adjusting are effective.

The D / d ratio is, for example, preferably set to 3 or more, preferably 3 to 25, more preferably 5 to 22, and still more preferably 7 to 20. Here, the winding average diameter D of the coil wire 5 means a separation dimension between the center points of the catalyst wires 4 facing each other on the coil cross section as shown in FIG. The equivalent diameter d means the diameter of the equivalent circle calculated from the wire diameter of the catalyst wire 4 or the cross-sectional area as described above.

  For example, the coil wire 5 has a winding average diameter D of about 3 to 30 mm and is wound with a predetermined pitch. In this embodiment, the coil wire 5 is continuously wound in a substantially dense winding state over almost the entire length thereof. Is shown.

Here, the winding pitch P of the coil wire indicates the interval between the coil windings, and the interval is not more than 10 times the equivalent wire diameter d of the catalyst wire, and the flow path is not less than the gap through which the fluid to be treated can flow. What is coiled and held, preferably the ratio can be set to about 0.1 to 3 times. By setting such an appropriate winding pitch and coil multiplexing described later, a micro flow path formed between the windings in the planar element is formed. As a result, the contact opportunity between the fluid to be treated and the catalyst is high. The activity is improved. In the present invention, the interval between the coil windings is the dimension when it is constant throughout. However, for example, when the shape of the element is curved as shown in FIG.

In the present invention, the coil wire 5 is formed as a single coil wire by such a single catalyst wire 4, and a plurality of coil wires having different winding diameters are concentrically arranged as shown in FIG. A multiple coil wire inserted through can be used. The multiple coil wire has a first coil wire 5a having a first coil diameter D1, a first coil wire 5a having a second coil diameter D2 larger than the first coil diameter D1 and surrounding the first coil wire 5a. This is a double coil wire including 5a and a second coil wire 5b arranged concentrically.

If necessary, a triple or quadruple coil wire can be used. By such multiplexing, the chance of contact with the fluid to be treated is increased, and the catalyst efficiency can be improved. In that case, in order to optimize the D / d of the coil wire in accordance with the multiplexing, in FIG. 4, the inner first coil wire 5a is a catalyst having a diameter smaller than that of the outer second coil wire. It is preferable to use a wire to extend the life. Furthermore, for example, such a contrivance and adjustment such that the winding direction of the first coil wire 5a and the second coil wire 5b are reversed to prevent the other coil wire from being entangled between the winding pitches. Should be done as needed.

  Further, in such a catalyst member using a multi-layered coil wire, the same or different type of catalyst material X can be provided in each of the inner and outer coil wires 5b, and also in the electric heating when using this For example, the energization amount of the outer second coil wire 5b is set to be higher (or lower) than the inner first coil wire 5a, or only the second coil wire 5b is energized to generate the first coil wire. 5a can also be heated by its radiant heat, and various applications can be made so as to obtain a more efficient catalytic reaction.

  As shown in FIG. 4, exposed ends 4 d where the core wire 4 a is exposed are formed on both ends of the coil wire 5 without being provided with the alumite layer 4 c so as to be suitable for such energization heating, The exposed end 4d is connected to an external power source directly or via the coupler C shown in FIG. 3A. Thereby, each coil wire 5 can be heated by current. This heating method has a high system response and high efficiency. In addition, each coil wire can be individually energized optimally. In this case, the multi-coil wire 5 is supplied with an optimal current set individually for each coil wire, but in this case, it can be connected to a series or parallel circuit.

  The planar element 6 is constituted by the coil wire 5 of the catalyst wire 4 so as to have an apparent plane extending on an arbitrary surface as described above, and the structure, dimensions, and the like are arbitrarily set. One form thereof is shown in FIG. 3A and FIG. 3B, and is used as one spirally curved with one type of coil wire (FIG. 3A) or one in which a plurality of coil wires are arranged in parallel (FIG. 3B).

In this case, in the case of the former curved in a spiral shape, a structure for preventing partial temperature unevenness by preventing the curvature radius R (shown in FIG. 1) from becoming unnecessarily small is also preferable. In this embodiment, as shown in FIG. 1 and others, the curvature radius R of the curved portion is adjusted to be twice or more, preferably about 3 to 20 times the coil diameter D of the coil wire 5, and the spiral Does not extend to the center. Similarly, in the case of the latter parallel arrangement, it is appropriately set depending on the use conditions.

  The housing 3 includes a plurality of planar elements 6 that have a catalytic action and are stacked in multiple stages, and the apparent plane with respect to the flow direction of the fluid to be treated flowing down in the housing. Are arranged in an intersecting direction.

  In the form of FIGS. 1 and 2, upper and lower four planar elements 6 are stacked in the housing 3. The housing 3 has, for example, a cylindrical shape with an outer diameter of about 30 to 200 mm. The housing 3 is used by being further incorporated in the housing. For example, the hydrogen generator is connected to the upper end surface of the housing 3 by screw joining or the like. Composed. In this form, the housing 3 is formed with a spiral groove 3A for accommodating each of the planar elements 6A to 6D in their spiral shape, and a discharge port 3B formed at the groove bottom of the spiral groove 3A. For example, a molded product made of pure aluminum or aluminum alloy is used.

  As a more preferred embodiment, it is also desirable to form the alumite layer on the surface of the housing 3 in the same manner as the catalyst wire 4, and to support the catalyst substance X on the alumite layer, so that the reaction efficiency can be further improved.

  In this way, each of the planar elements 6A to 6D is arranged in multiple layers in the housing so as to intersect, preferably orthogonally cross, the supply direction Z of the fluid to be processed supplied from the upstream side. From the side, for example, it is sprayed and supplied in the form of gas or liquid. As a result, the supplied fluid to be treated flows between the planar elements 6A to 6D, and effectively comes into contact with each catalytic substance X to perform a catalytic reaction.

  In the planar elements 6 </ b> A to 6 </ b> D, for example, about 2 to 10 coil wires 5 are arranged along the spiral groove 3 </ b> A of the housing 3. At this time, if the winding pitch P of the coil wire 5 varies, there may be a difference in partial heat generation temperature due to energization. In order to obtain a more efficient catalytic reaction, it is desirable that the winding pitch P of the coil wire is arranged to be almost uniform.

  As the fluid to be treated, for example, an organic hydride (methylcyclohexane, decalin, etc.) of a hydrogenated derivative of an aromatic compound (eg, dolene, benzene, etc.) that generates high purity hydrogen by its dehydrogenation reaction is used. These organic hydrides are supplied to a vaporizing device that is heated in advance to the boiling point or higher, or an on-surface element that is heated to a reaction temperature simply by a spraying device, and at the same time, an inert gas for discharging reaction products and the like is accompanied by the flow path. The

  For example, when the fluid to be treated is methylcyclohexane, a product containing hydrogen and toluene is obtained by the dehydrogenation reaction of the following formula 1, which is discharged from the discharge port 3B provided in the housing 3. The product is then gas-liquid separated by, for example, a cooling process, and separated into hydrogen and toluene. The chemical change is explained as follows.

  Further, in the present invention, in order to further increase the catalytic reaction efficiency, as shown in the cross-sectional view of FIG. 2, the buffer material 10 is disposed in the gap between the elements 6 to improve the flow dispersibility of the fluid to be treated. Includes things to enhance.

  The buffer material 10 can subdivide the gaps between the elements 6 and the housing 3 to make the flow of the fluid to be treated uniform, and is made of heat-resistant inorganic material such as alumina, silicon carbide, silicon nitride, zirconia, One or more inorganic fine particles and / or fibers selected from either mullite ceramic, quartz, or silica are used. Further, the cushioning material 10 may be formed of a layer having a predetermined thickness so as to cover and enclose the uppermost stream-side planar element.

  The buffer material 10 made of these inorganic compounds is preferable in that it is nonconductive and excellent in heat resistance and does not react with hydrogen. Moreover, since heat conductivity is also low, the heat retention property in the reactor 1 is improved and it contributes to uniform internal temperature.

  The average particle diameter of the fine particles is preferably larger than the spread width (winding pitch P) between the wire rods of the coil wire 5 in contact therewith, for example, about 0.1 to 3 mm. Such a particulate cushioning material 10 freely wraps the coil wire 5 to prevent local intrusion (diffusion) of the fluid to be treated, and flows uniformly to the inside of the coil wire 5, so that the catalyst substance X and The opportunity for contact is increased.

  Similarly, in the case of using a fiber material, for example, a fiber material having a fiber diameter of 1 to 100 μm and a predetermined length is formed in a web shape, a cloth shape, or a knit shape, for example. The buffer material 10 disperses the flow in the complicated flow path of the fluid to be processed, and contributes more effectively to the planar element on the lower layer side.

  Each element 6 housed in the housing 3 is heated by Joule heat determined by its resistance, applied voltage, and time by applying a predetermined amount of electricity between the exposed ends 4d and 4d where the core wire 4a is exposed. To do. The temperature of each element 6A thru | or 6D can be adjusted by applying the predetermined voltage V1-V4 suitably. It is desirable that an independent voltage is applied to each element 6, whereby the temperature of each element stacked in multiple stages can be controlled independently.

  For example, along the element 6 located on the downstream side from the upstream side (hereinafter simply referred to as “upstream side”) in the supply direction Z of the fluid to be treated, It is desirable to set the energization amount to each element in advance in consideration of the rate of temperature rise accompanying the flow of the fluid to be treated. In the reactor of the present invention, the elements 6 are stacked in multiple stages along the flow direction of the fluid to be treated, and independent adjustments can be made, so that such adjustment is possible.

If this point is demonstrated in the example of FIG. 2, the to-be-processed fluid which flows in will absorb heat | fever remarkably in contact with the element 6A of the uppermost stream side, and, thereby, a partial temperature fall will generate | occur | produce. Therefore, it is difficult to obtain a sufficient catalytic reaction in that region, and the production efficiency decreases. In order to supplement this, the energization amount to the upstream element 6 that tends to decrease in temperature is slightly increased in advance. Thus, it is desirable that the set temperatures of the elements 6A to 6D can be adjusted selectively or stepwise from the upstream side to the downstream side of the fluid to be processed. For example, by gradually changing the energization amount from the upstream side, the change in temperature distribution can be minimized as far as the downstream side of the reactor 1. For example, a unit current of 0.3 to 1.0 W / cm ² is applied on the upstream side and 0.6 W / cm ² or less is applied on the downstream side.

  As shown in FIG. 2, the reactor 1 is further provided with temperature measuring means 12 for measuring the temperature in the housing 3. The temperature measuring means 12 is, for example, a thermocouple, and is disposed between the elements 6. The provision of the temperature measuring means 12 makes it possible to control the energization amount of each element 6 more finely. As a result, automatic control of the temperature of the reactor 1 is facilitated.

  FIG. 10 and FIG. 11 show an example of an application form using the reactor 1, and it is used by being incorporated in the dehydrogenation reaction system 20. The system 20 uses, for example, an organic hydride of a hydrogenated derivative of an aromatic compound such as toluene (for example, methylcyclohexane) as a main raw material fluid, and adds hydrogen by a dehydrogenation reaction while adding an accompanying gas to the raw material fluid. Decompose and generate.

  The system 20 includes a storage tank 21 that stores, for example, an organic hydride (for example, methylcyclohexane: MCH) of a hydrogenated derivative of an aromatic compound (for example, toluene) as a fluid to be treated, and a pump 22 that pumps the MCH in the storage tank 21. A vaporizer 23 that vaporizes the MCH pumped by the pump 22, a reactor 24 that is arranged downstream of the vaporizer 23 and separates into an aromatic compound and hydrogen by a dehydrogenation reaction, and the reaction gas is cooled. And a cooler 25 that enables gas / liquid separation. The gas content in the product is taken out as hydrogen, and the liquid is taken out as toluene. In addition, this toluene can be returned to the said raw material methylcyclohexane by making the dehydrogenation reaction of the reverse reaction to the said hydrogenation reaction if necessary.

  In this system 20, the accompanying gas prevents, for example, hydrogen, supply back pressure of MCH and oxidative deterioration of the catalyst material in the reactor 24. The accompanying gas is continuously supplied so that a substantially reducing atmosphere is maintained.

  FIG. 11 is a perspective view of the reactor 24 in the system 20 of FIG. 10 in which the vaporizer 23 is integrally formed. The vaporizer 23 is connected to a pipe 30 through which a fluid to be treated flows, for example, via a joint flange 32.

  For example, the vaporizer 23 heats the fluid to be processed and transforms it into a gaseous state, and includes a heater and the like. The heating conditions are appropriately adjusted according to the type of fluid to be processed and the supply conditions as described above.

  For example, a fluid rectifying plate 26 is provided on the downstream side of the vaporizer 23. The fluid rectifying plate 26 and the reactor 24 are arranged at a certain distance, and gently move toward the downstream side so that the gaseous fluid to be treated is fed to the reactor 24 almost on average. It has an amplifying flow path. Thereby, retention of the gaseous to-be-processed fluid is prevented.

  The supply of the fluid to be treated to the reactor 24 is preferably preliminarily heated to a predetermined temperature to be a vaporized gas as described above, but the fluid to be treated is pressurized and sprayed in a liquid state. Also good. That is, the fluid to be treated may be atomized by a pressurized nozzle or the like and sprayed to the reactor 1. Thus, the vaporizer 23 is used according to the purpose.

The reactor 24 has the same configuration as that described in FIG. That is, spiral-shaped planar elements 6 are arranged in multiple stages in the housing 3. Each element 6 is wired with an external power source 25 (shown in FIG. 10) so as to be heated to a predetermined temperature by energization. A thermocouple as temperature measuring means 12 is disposed between the elements 6 as necessary. The temperature is measured so that the catalytic reaction is appropriately performed.

The dehydrogenation reaction when methylcyclohexane is used as the fluid to be treated is explained by the following chemical reaction. This shows that about three times as much hydrogen is produced.
C ₇ H ₁₄ ⇒ C ₇ H ₈ + 3H ₂ ΔH = 204.8 kJ / mol

Due to the catalytic reaction in the reactor 24, hydrogen can be separated from the fluid to be treated, discharged from the discharge port 3B on the lower surface side of the housing 3, and fed to the next process. In addition, arrangement | positioning and the magnitude | size of the discharge port 3B are set suitably.

As shown in FIG. 10, the treated fluid discharged from the reactor 24 passes through the piping, is cooled by the cooler 27 , and is stored in the storage container 28. At this stage, the treated fluid is separated into gas and liquid. The gas is used as it is as pure hydrogen. Since the liquid forms a precursor solution that becomes toluene of the fluid to be processed by a predetermined hydrogen reaction therein, the liquid is accommodated in the storage container 28. Thereby, circulation recycling is achieved by utilizing the free reversibility of the chemical reaction.

  In this embodiment, a wire catalyst carrying a catalyst substance such as platinum is used for the dehydrogenation reaction of a hydrogenated derivative of an aromatic hydrocarbon or for the hydrogenation reaction. However, the reactors 1 and 24 of the present invention may be used, for example, to perform only a hydrogenation reaction of an aromatic hydrocarbon, or to perform only a dehydrogenation reaction of a hydrogenated derivative (organic hydride). May be used.

  In the following, more preferred embodiments of the present invention will be described. However, the present invention should not be interpreted as being limited to specific examples.

[Test Example 1]
[Manufacture of aluminum clad coil wire]
An aluminum clad wire (wire diameter: 12 mm) in which a nickel wire (purity 99%) having an electric heating function and an aluminum (purity 99.9%) band was encapsulated was made as a base material. The base metal was repeatedly subjected to wire drawing and heat treatment at a temperature of 600 ° C. to obtain a clad fine wire having a wire diameter d of 0.45 mm and an average thickness of the aluminum layer of 30 μm. FIG. 6 shows an enlarged covering state of the cross section of the thin clad wire.

  The clad fine wire was set in a coiling machine to obtain a coil wire having a winding average diameter of 4 mm and a length of 120 mm. The winding width of the coil wire was 0.5 times the wire diameter d. The aluminum layer on the surface did not show defects such as peeling, and had a good coil state.

[Alumite processing of clad fine wire]
Next, the coil wire was anodized under conditions of a 4 wt% oxalic acid aqueous solution at a temperature of 25 to 35 ° C. and a current density of 60 A / m ² . Then, the acid treatment was performed while immersed in the same kind of oxalic acid treatment solution for 6 hours, and the pore size was widened and dried in the atmosphere. Next, after baking at 400 ° C. for about 1 hour, hydration was performed at 80 ° C. or higher for about 2 hours and dried. Thereafter, it was further fired at 500 ° C. for 3 hours to obtain an alumite clad metal fine wire having a porous anodized layer having pores on the surface. FIG. 7 shows an enlarged view of the cross section by a factor of 500, and FIG. 9 further shows a magnified photograph of the outer surface of the microscope.

[Catalyst loading adjustment]
Next, the alumite clad fine wire is immersed in a chloroplatinic acid solution dissolved in ethanol using chloroplatinic acid (IV) hexahydrate H ₂ PtCl ₆ 6H ₂ O as a platinum salt as a catalyst substance, Platinum was supported in the porous structure on the surface, and then heated and dried at a predetermined temperature to obtain two types of coil wires (catalyst wires) having different catalyst loadings. These are designated as test specimens A and B, test specimen A has a catalyst loading of 1.0 g Pt / m ² , and test specimen B has 2.5 g Pt / m ² , and the loading is detected from the amount of ions in the solution. Is done.

[Reactor]
Each of the two types of coil wires is prepared four by one, and each type is sequentially placed in an aluminum alloy housing in which a flat spiral groove and a discharge port provided at a predetermined interval are formed as shown in FIG. Incorporated, a total of four layered planar elements were stacked and each element was electrically connected by wiring, and two types of hydrogen generating reactors with different catalyst loadings were obtained.

[performance test]
The performance test of hydrogen generation was performed using methylcyclohexane (MCH) as a fluid to be treated and its dehydrogenation characteristics were good. The hydrogen generation rate and the toluene conversion rate of methylcyclohexane were analyzed and measured by gas chromatography. In the experiment, by adding 300W of electricity to the coil wire of each element, it can be heated to the target temperature of 350 ° C in about 2.5 minutes, and in that state, methylcyclohexane from the pulse type spray nozzle from the upstream side. Is supplied in a hydrogen stream at a flow rate of 150 ml, a spraying time of 0.5 seconds (a single spray amount of 0.39 gr), a spraying interval of 10 and 20 seconds, and the structure of the reactor is shown in FIG.

  The evaluation was performed based on the amount of hydrogen produced by the reaction, methylcyclohexane conversion, and toluene selectivity. As a result, the specimens A and B had a methylcyclohexane conversion of 73.3% and 80.4%, a toluene selectivity of 99%, and an average hydrogen production of 0.36 L / min and 0.41 L / min, respectively. Dehydrogenation characteristics were obtained.

The “methylcyclohexane conversion rate” is a ratio of the amount of the substance that methylcyclohexane of the fluid to be treated is substantially reacted with the catalytic reaction and converted into hydrogen, toluene, etc., and this ratio is high. It means that the reaction efficiency is excellent. The “toluene selectivity” means the content ratio of only the hydrogen and toluene in the reactant, and the higher the ratio, the smaller the amount of secondary products and the better. Any of these can be analyzed by the gas chromatography.

The characteristics of Test Example 1 are that using a single planar element of the coil wire, or using an aluminum plate material by press forming without using a coil wire, and opening a constant dimension at the center. Compared to the characteristics of the corrugated fin-type alumite catalyst body having a platinum catalyst supported on the surface with a chloroplatinic acid solution as in Example 1, using a corrugated-type molded body having holes. The effect is seen. For example, when compared with the conversion ratio of methylcyclohexane, it was confirmed that the corrugated type was 68.2%, whereas the test example 1 was improved to 73-80%. .

[Test Example 2]
[Examples containing quartz fine particles as buffer material]
Next, with respect to the coil wire of the catalyst wire configured in the same manner as in the above test 1, a spiral groove was formed in the same manner as described above using a platinum catalyst carrying amount adjusted to 2.5 g Pt / m ^2. In addition to setting in the housing and interposing a buffer material made of quartz fine particles with an average particle diameter of 0.5 mm between each coil wire, the fluid to be treated is rectified and the chance of contact with the catalyst is improved. It was assumed. Thus, a reactor for generating hydrogen was obtained in which the buffer material was interposed between the four planar elements and laminated.

[performance test]
In the catalyst performance test, methylcyclohexane was used as the fluid to be treated in the same manner as in Test Example 1, and the amount of hydrogen produced, the conversion rate, and the like were determined. As a result, the methylcyclohexane conversion was 90.4%, the toluene selectivity was 99%, and the hydrogen production was 0.47 L / min. This characteristic greatly exceeds the result of Test Example 1, and it is judged that the catalytic reaction efficiency was greatly promoted as an effect of interposing a buffer material.

[Test Example 3]
[Example including quartz fiber as buffer material]
In the reactor of Test Example 2, the same test was performed using a reactor having a buffer material made of quartz fiber having a fiber diameter of 5 μm instead of quartz fine particles. As a result, when the quartz powder was used, substantially the same effect was obtained, and the methylcyclohexane conversion was 90.1%.

[Test Example 4]
[Example of two types of multi-coil wires with quartz cushioning material on one side]
In the same manner as in Test Example 1 above, two types of coil wires having a winding diameter of 7 mm and 4.5 mm were prototyped using a catalyst wire having a diameter of 0.7 mm carrying platinum as a catalyst, and a total of four sets of these were inserted coaxially. The double coil wire was obtained. In addition, the {winding diameter D / wire diameter d} ratio of each coil wire is 9 and 5, and the winding pitch is 0.5 d times.

Each of the double coil wires carries the alumite layer and a predetermined catalyst material, so that the insertion work can be facilitated, and the amount of the catalyst material supported per unit volume is greatly improved, and the double coil wire is easy to handle. . In this way, two sets of multi-stage reactors were prepared for the four sets in an aluminum housing having spiral grooves as in each of the test examples. On one side, ceramic fine particles having an average particle diameter of 0.8 mm used in Test Example 2 were filled as a buffer material between the elements.

  In the catalytic reaction test, methylcyclohexane is supplied from the upstream side through a vaporizer to a reactor in which each element is heated to a predetermined temperature of 350 ° C. by the electrical wiring, and the amount of hydrogen produced is generated accordingly. And methyl cyclohexane conversion and toluene selectivity. The result is shown in Table 1 and can be compared with the same result of the single coil wire with the same buffer material in Test Example 2 together.

As can be seen from this result, it is recognized that the volume ratio of the catalyst is improved by the multi-structure coil wire according to the present invention, and each result is increased accordingly. Furthermore, it can be seen that further improvement can be achieved by arranging a cushioning material between the elements.
[Test Example 5]
[Example of controlling the energization of multiple coil wires]

  In the reactor obtained in Test Example 4, the electrical wiring and energization of each coil wire are configured to be temperature controlled independently, the energization amount of the outer second coil wire is 0 to 20 A, and the inner first coil wire. The energization amount was set to 0 to 10 A, and the energization amount of the outer coil of each laminated element was controlled to be adjusted to be larger than the energization amount of the inner coil.

As a result, the catalyst temperature during the dehydrogenation reaction was extremely small in variation in the temperature distribution of each element from the upper stage to the lower stage despite the endothermic reaction, and the reaction maintained at about 350 ° C. was possible. By performing such energization control of each element, the conversion rate could be increased to 94.0%, and a great improvement effect was seen.
[Test Example 6]
[Example of changing the amount of electricity in each stacked element when the element arrangement is a parallel placement type]

  In the same manner as in Test Example 1, a nickel composite wire having a wire diameter of 0.45 mm and a surface clad with an aluminum layer of 30 μm was used, and this was wound at an average winding diameter of 4 mm and a pitch of 0.8 d. A coiled wire was obtained. Then, this coil wire is anodized according to each of the above test examples, and further fired at a predetermined temperature to form a porous anodized layer having micropores on the outermost surface of the aluminum layer on the surface. Similarly, a coil wire carrying platinum was used.

The obtained five coil wires are arranged in parallel in close contact with each other on an aluminum housing base member to form a planar element whose upper surface extends substantially in a planar shape. A number of outlets are formed on the bottom surface of the housing, and each element is configured. Each of the coil wires has an exposed end portion on the tip side as an electrical wiring, and a planar element is obtained that is fixed so as not to move by the housing member.

  This planar element was made into 1 set, and this was piled up a total of 4 steps | paragraphs in the depth direction in the housing | casing made from SUS, and the reactor was comprised. In this reactor, the fluid to be treated is supplied from the upstream side orthogonal to the plane of the element. In this test, the electric power supplied to each element is 0 to 20 A in the energization amount of the coil wire in each stage. Zone control was performed by adjusting.

  As described above, by controlling the energization amount of the coil wire at each stage, it is possible to prevent a temperature drop due to the endothermic reaction of the fluid to be processed. As a result, it was confirmed that the entire volume in which the coil wire exists can be utilized, and that it is effective even in an element in which the coil wire is arranged in parallel on the surface.

  The present invention arranges catalyst-supported planar elements that are arranged in multiple stages along the flow direction of the fluid to be treated as a hydrogen production reactor, and can improve the hydrogen production efficiency per unit area. In particular, it is widely used for various applications including automobiles and ships using hydrogen as fuel.

1 Reactor 2 Catalyst Member 3 Housing 4 Wire Catalyst 4a Core Wire 4b Aluminum Layer 4c Anodized Layer 5 Coil Wire 6 Buffer Material X Catalyst Material

Claims (11)

A catalyst member that generates high-purity hydrogen from a fluid to be treated by a dehydrogenation reaction, and a housing that houses the catalyst member;
The catalyst member includes a core wire made of a metal material, a porous alumite layer formed on the outside of the core wire and having micropores on the surface, and a catalyst material supported in the micropores of the alumite layer Made of wire,
The catalyst wire, by its continuous winding of the flat spiral shape of the plurality of parallel arrangement or the coil wire of the coiled coil wire, formed as a planar element having an apparent plane extending over the flat surface is, and a plurality of said elements, with respect to the flow direction of the fluid to be treated flowing down inside the housing, Ri Na said apparent plane is stacked in multiple stages in the direction intersecting each
A hydrogen-producing reactor, characterized in that a heat-resistant inorganic buffer material that improves the flow dispersibility of the fluid to be treated is disposed in the gap between each element and the housing . The reactor for hydrogen generation according to claim 1, wherein the buffer material is further packed and disposed so as to cover the element on the most upstream side . The buffer material is composed of any one or more kinds of inorganic fine particles and / or fibers selected from the group consisting of any one of alumina, silicon carbide, silicon nitride, zirconia, and mullite ceramic, quartz, and silica. The reactor for hydrogen production according to claim 1 or 2. A catalyst member that generates high-purity hydrogen from a fluid to be treated by a dehydrogenation reaction, and a housing that houses the catalyst member;
The catalyst member includes a core wire made of a metal material, a porous alumite layer formed on the outside of the core wire and having micropores on the surface, and a catalyst material supported in the micropores of the alumite layer Made of wire,
The catalyst wire is formed as a planar element having an apparent plane extending on a plane by arranging a plurality of continuously coiled coil wires in parallel or winding the coil wires into a plane spiral shape. ,And
A plurality of the elements are stacked in multiple stages in directions in which the apparent planes intersect each other with respect to the flow direction of the fluid to be processed flowing down in the housing,
The hydrogen generating reactor, wherein the housing includes a concave groove in which the coil wire is accommodated . The reactor for hydrogen generation according to any one of claims 1 to 4, wherein a discharge port through which a fluid to be treated passes is provided at a groove bottom of the concave groove .   The planar element includes at least a first coil wire having a first coil diameter and a second coil wire having a second coil diameter larger than the first coil diameter and surrounding and enclosing the first coil wire. The reactor for hydrogen generation according to any one of claims 1 to 5, wherein the reactor is a composite element including multiple coil wires.   The reactor for hydrogen generation according to claim 6, wherein the coil wires of the composite element are insulated from each other and can be independently energized.   8. The catalyst member according to any one of claims 1 to 7, wherein the catalyst member has an exposed end portion where the surface of the core material is exposed at both ends of the catalyst wire, and generates heat when energized through the exposed end portion. A reactor for producing hydrogen according to claim 1.   The reactor for hydrogen generation according to any one of claims 1 to 8, wherein a vaporizer for vaporizing the fluid to be processed in a gaseous state is further arranged upstream of the reactor. A method for controlling a reactor for hydrogen generation according to any one of claims 1 to 9,
A temperature control step of supplying heat necessary for an endothermic reaction by adjusting an energization amount of the coil wire of each element of the catalyst member according to a supply amount of the fluid to be treated; Reactor control method. The energization amount of the element located on the upstream side of the fluid to be processed is controlled to be larger than the energization amount of the downstream element so that variation in temperature distribution between the elements arranged in multiple stages is reduced. The method for controlling a reactor for producing hydrogen according to claim 10.