JP2000007303A - Reforming reactor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the hydrogen generation efficiency, the efficiency to decrease the formation of CO as a by-product, etc., by improving the cell density relationship between catalysts in the case of placing a plurality of catalysts having honeycomb structure in the reactor taking consideration of especially the case that the reaction on the catalyst accompanies essentially considerable heat-generation or heat-absorption or the case that the reaction substrate flows into the reactor at a high concentration. SOLUTION: A plurality of catalysts having honeycomb structure and generating hydrogen from a reaction fluid containing an organic compound or carbon monoxide by catalytic reaction are placed in a fluid channel 3 of the objective reforming reactor. At least two catalysts 1, 2 among the plurality of catalysts satisfy the relationship of (the cell density of the upstream-side catalyst)<=(the cell density of the downstream-side catalyst).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a reforming reaction device for generating hydrogen, which can be suitably used for industrial use and on-vehicle use.

[0002]

2. Description of the Related Art In recent years, attention has been paid to cleanliness in electric production, and interest in fuel cells has been increasing. Fuel cells have high power generation efficiency and low carbon dioxide (CO ₂ ) generation, and additionally have carbon monoxide (CO) and nitrogen oxide (N
There is an advantage that generation of harmful gas such as O _x ) can be suppressed. Therefore, recently, an on-site type power generator and a fuel cell for use in a vehicle have been developed. High-purity hydrogen is required to generate electricity from a fuel cell. This hydrogen is mainly composed of hydrocarbons such as butane and propane, alcohols such as methanol, and CO2.
It is produced by a catalytic reaction using these as starting materials.

[0003] The main reaction of hydrogen synthesis is a steam reforming reaction (Steam Reforming) that occurs in the presence of steam and a catalyst. However, in the product gas obtained by the steam reforming reaction, the purity of hydrogen is not high enough to be used for a fuel cell, and CO generated together with hydrogen is applied to a Pt-based electrode used in the fuel cell. To have a toxic effect, CO
The purity of hydrogen is improved by a shift reaction (aqueous conversion reaction) or a selective oxidation reaction of only CO.

As another reaction for generating hydrogen from hydrocarbons or the like, hydrogen or CO is generated by a partial oxidation reaction of hydrocarbons instead of a steam reforming reaction, and the above-described CO shift reaction or CO selective oxidation reaction There is a method of obtaining hydrogen by using Further, another reaction for generating hydrogen from a hydrocarbon or the like includes a decomposition reaction. Specifically, there is a decomposition reaction that generates hydrogen from methanol.

[0005]

Meanwhile, in a reforming reaction apparatus for generating hydrogen using such a reaction, an attempt has been made to use a catalyst having a honeycomb structure. It is preferable to arrange a plurality of catalysts having a honeycomb structure for each role in a fluid flow path, such as a catalyst for a CO shift reaction, a catalyst for a CO selective oxidation reaction, and the like. It is known as one of the configurations. However, there is no known apparatus in which a plurality of catalysts having a honeycomb structure are arranged as described above, in which the relationship of cell density between the catalysts has been sufficiently studied.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a catalyst for a reforming reactor in which a plurality of catalysts having a honeycomb structure are arranged in a fluid flow path. The cell density relationship between the media has been improved, especially considering the case where the reaction occurring in the catalyst body involves a substantial amount of exotherm or endotherm, or the case where the reaction substrate flows into the apparatus at a high concentration. It is an object of the present invention to provide a reforming reactor in which the efficiency of generating hydrogen and the efficiency of reducing CO as a by-product in such cases are improved.

[0007]

According to the present invention, a plurality of catalysts having a honeycomb structure for generating hydrogen by a catalytic reaction from a reaction fluid containing an organic compound or carbon monoxide are arranged in a fluid flow path. Wherein at least any two of the plurality of catalysts satisfy the following relationship: cell density of upstream catalyst <cell density of downstream catalyst. A reforming reaction device is provided.

In the present invention, the “honeycomb structure” refers to a large number of through holes (cells) partitioned by partition walls.
Means a structure having Further, in the present invention, the `` catalyst having a honeycomb structure for generating hydrogen by a catalytic reaction from a reaction fluid containing an organic compound or carbon monoxide '' includes a catalyst having a honeycomb structure, such as a CO shift reaction or a CO selection reaction. It also includes a catalyst body that exhibits a catalytic reaction such as an oxidation reaction that increases the purity of hydrogen generated by a catalytic reaction from a reaction fluid containing an organic compound or carbon monoxide.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A reforming reaction device according to the present invention comprises:
A plurality of catalysts having a honeycomb structure for generating hydrogen by a catalytic reaction from a reaction fluid containing an organic compound or carbon monoxide are arranged in a fluid flow path.

[0010] In the reforming reaction apparatus having such a configuration, when the reaction occurring in the catalyst body essentially involves a large amount of heat generation or endotherm, or when the reaction substrate flows into the apparatus at a high concentration, the reaction proceeds upstream. If the cell density of the disposed catalyst body (upstream catalyst body) is too high, that is, if the contact efficiency with the fluid is too good, a sudden change in temperature occurs there, which is not preferable. For example, if the reaction occurring in the catalytic body is a reaction involving a large amount of endotherm, the temperature of the catalytic body may drop at a stretch and drop below the catalytic action temperature. The temperature rises at once, which may degrade the catalyst and the carrier.

On the other hand, a fluid which has been treated with the upstream catalyst and has a reduced concentration of the reaction substrate to some extent is introduced into the catalyst body (downstream catalyst body) disposed on the downstream side, and conversely, the cell density is reduced. It is preferable to increase the value to increase the contact efficiency with the catalyst site. In particular, as for the catalyst bodies arranged adjacent to each other, it is preferable that the downstream catalyst body has a cell density higher than that of the upstream catalyst body because the mixing efficiency of the reaction fluid between the catalyst bodies is improved.

From these viewpoints, the reforming reaction apparatus according to the present invention is characterized in that at least any two catalyst bodies out of the plurality of catalyst bodies having the honeycomb structure are as follows: The relationship was satisfied. Cell density of upstream catalyst body ≤ cell density of downstream catalyst body ...

FIG. 1 is a schematic sectional view showing an embodiment of the reforming reaction device according to the present invention. In FIG. 1, an upstream catalyst body 1 and a downstream catalyst body 2 are arranged in a metallic can body (fluid flow path) 3 to constitute a reforming reaction device. The reaction fluid A flows through the inlet hole 5 and reaches the outlet hole 6 via the upstream catalyst 1 and the downstream catalyst 2. The obtained fluid B containing hydrogen is conveyed to a fuel cell unit disposed downstream of the reforming reaction device. Both the upstream catalyst body 1 and the downstream catalyst body 2 have a honeycomb structure, and their cell densities satisfy the above relationship.

In the embodiment of FIG. 1, two catalysts are arranged in the fluid flow path. However, three or more catalysts may be arranged in the apparatus along the flow direction of the fluid. . In that case, if at least any two of the catalyst bodies satisfy the above relationship, the intended effect can be obtained, but the catalyst body is arranged at the most upstream side of the plurality of catalyst bodies. The catalyst body and at least one of the catalyst bodies disposed downstream thereof satisfy the above relationship, or at least any two adjacent catalyst bodies of the plurality of catalyst bodies are It is preferable that the above relationship is satisfied, and furthermore, the catalyst body arranged at the most upstream side of the plurality of catalyst bodies and the catalyst body arranged adjacent to the downstream side thereof satisfy the above relationship. The effect is great when satisfied. Further, the greatest effect can be expected when the catalyst body arranged at the most upstream side of the plurality of catalyst bodies and all the catalyst bodies arranged at the downstream side satisfy the above relationship. .

In the present invention, in addition to the above-described relationship of cell density, at least any two of the plurality of catalysts having the honeycomb structure have the following relationship. It is preferable to satisfy. Heat capacity of upstream catalyst body ≤ heat capacity of downstream catalyst body ...

In the reforming reaction apparatus in which a plurality of catalyst bodies are arranged as described above, the upstream catalyst body quickly rises to the operating temperature at the time of cold start, and the downstream catalyst body has This is because it is preferable to design the heat capacity of the medium to be equal to or less than the heat capacity of the downstream catalyst body so as not to be a heat sink. Normally, in a reforming reactor for generating hydrogen, the temperature of the fluid itself cannot be expected to rise like exhaust gas from an internal combustion engine, and it is necessary to forcibly obtain the reaction temperature by some means. Such a heat capacity design as described above is more necessary than other catalyst devices.

[0017] Further, particularly when the upstream catalyst generates hydrogen, the fluid flowing into the downstream catalyst contains a higher concentration of hydrogen than the fluid flowing into the upstream catalyst. In order to avoid danger, it is preferable that the temperature is not increased more than necessary. It is preferable that the heat capacity of the downstream catalyst is designed to be equal to or larger than the heat capacity of the upstream catalyst.

Factors that determine the heat capacity of the catalyst body include a catalyst component (mainly a heat-resistant oxide supporting a catalyst metal).
There are various materials such as the material and the amount of the carrier, the material, the structure, and the volume of the carrier, and a catalyst having a desired heat capacity can be produced by using any of these factors alone or in combination.

In the case where the above relationship is further satisfied in addition to the above relationship, the combination of the catalyst body satisfying the above relationship and the combination of the catalyst body satisfying the above relationship are not necessarily the same. However, the same is more preferable.

In the present invention, starting materials for obtaining hydrogen include hydrocarbons such as butane and propane, organic compounds composed of alcohols such as methanol, and carbon monoxide.
A reaction fluid containing (CO) is used. From the viewpoint of transportation of cylinders and pipelines, hydrocarbons are preferable, and in view of handling when mounted on vehicles, alcohol raw materials such as gasoline and methanol that can be loaded with liquids are preferable, but are not limited to these. Not something. CO is also a toxic gas and is not a desirable starting component.

The main reaction in the reforming reaction apparatus of the present invention is a steam reforming reaction that occurs in the presence of steam. In order to obtain high-purity H ₂ , CO as a by-product poisons the electrodes of the fuel cell. Therefore, CO is reduced by CO shift reaction and CO partial oxidation reaction. An example of the reaction using butane is shown below. (1) C ₄ H ₁₀ + 9H ₂ O → 9H ₂ + 4CO steam reforming reaction (2) CO + H ₂ O → CO ₂ + H ₂ CO shift reaction (3) CO + 1 / 2O ₂ → CO ₂ CO Selective oxidation reaction

As another reaction for obtaining hydrogen, there is a method using a partial oxidation reaction instead of the steam reforming reaction. _{(4) C 4 H 10 +} 2O 2 → 4CO + 5H 2 partial oxidation reaction

Following the partial oxidation reaction,
The reactions (2) and (3) are advanced to improve the purity of hydrogen.
The method for obtaining hydrogen from the reaction (1) is called a steam reforming method, and the method for obtaining hydrogen from the reaction (4) is called a partial oxidation method, and the present invention can be applied to any of these methods. Whether to use the steam reforming method or the partial oxidation method is optional,
For vehicle use, attention has been paid to the partial oxidation method for gasoline and the steam reforming method for alcohol such as methanol. Generally, the steam reforming method is easier to obtain high-purity hydrogen at a low temperature and is more efficient.

Further, there are the following two types of reactions for generating hydrogen from methanol. (5) CH ₃ OH → CO + H ₂ decomposition reaction (endothermic) (6) CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ steam reforming reaction (endothermic)

The catalyst components used in these reactions will be described later, but usually different catalyst components are used, and the reaction temperatures are also different. The reactions (1), (5) and (6) are generally endothermic reactions and require temperatures of 500 ° C. or higher. The reactions (2) and (3) are exothermic and proceed at a relatively low temperature of 300 ° C. or lower. The reaction (4) is an exothermic reaction, and also requires a reaction temperature of 500 ° C. or higher. In order to obtain high-purity hydrogen, the above (1) [or (5), (6)], (2), (3) or (4), (2), (3) is usually performed. Each catalyst component is arranged in series in the fluid flow path. In addition, depending on the required hydrogen concentration, a reforming reaction apparatus by the reaction of only (1) [or (5), (6)], or (4) may be used. Causes the reaction of (2) or (3) as necessary.

The catalyst body used in the present invention contains at least any one of the catalyst components having a catalytic action on the above-mentioned steam reforming reaction, partial oxidation reaction or decomposition reaction, CO shift reaction, CO selective oxidation reaction and the like. . Of these, CO
The selective oxidation reaction is for the purpose of reducing CO and is not directly related to hydrogen synthesis, but is important when a high hydrogen concentration is required, and is incorporated in a reforming reaction apparatus. Included in

As the catalyst component, specifically, at least one of the metal elements belonging to groups VB to VIII, IB and IIB in the long-period periodic table and a refractory oxide as main components What contains is preferably used.

As a metal element effective for a steam reforming reaction, a partial oxidation reaction or a decomposition reaction, it is preferable to use a Group VIII metal as an essential component. Among them, preferred metal elements are Ni, Rh, Ru, Ir, Pd, Pt, Co, and Fe, which are used alone or in combination. VB group V, Nb, VIB group Cr, Mo, W and VIIB
It is preferable to add group Mn, Re, or the like. It is also preferable to add an alkaline earth metal as a carbon deposition inhibitor.
These metals are usually supported on refractory oxides. Thereby, the specific surface area of the catalyst is improved, the activity is improved, and durability to a high reaction temperature is imparted.

As the heat-resistant oxide, Al ₂ O ₃ , SiO ₂ ,
TiO ₂ , ZrO ₂ , MgO or zeolite, SAPO, ALPO, layered compounds, and composite oxides thereof can be used. These heat-resistant oxides usually have a specific surface area of 5 to 300.
Use m ² / g. These heat-resistant oxides and the above-mentioned metal components are synthesized by a known method such as a chemical method such as an immersion method, a coprecipitation method, or a sol-gel method, or a physical mixing method. The specific surface area of the synthesized catalyst is also usually in the range of 5 to 300 m ² / g. When the specific surface area of the catalyst is less than 5 m ² / g, the activity decreases, and when it exceeds 300 m ² / g, the change in characteristics at high temperatures becomes remarkable, resulting in poor durability.

As the heat-resistant oxide, alumina (Al ₂ O
₃ ) can be preferably used because it is relatively inexpensive and exhibits a high specific surface area even at high temperatures. Further, spinel in which magnesia is added to alumina, or magnesia alone or a composite oxide of magnesia, which is a basic carrier, can be used for the purpose of suppressing carbon deposition.

The proportion of the catalyst metal added to the refractory oxide is preferably in the range of 1 to 30% by weight. In the case of precious metal-based metals, the activity is high, so that addition of up to about 10% by weight is sufficient.
It is preferred to be in the range of 0% by weight.

As a suitable catalyst component for the CO shift reaction, Group VIII Fe, Co, Group IB Cu, Group IIB Zn and the like are often used. Show. The metal exhibiting activity at a relatively low temperature is one containing Cu, Zn or both, and by supporting these on a heat-resistant oxide such as the aforementioned alumina, heat resistance can be ensured. In this case, the amount of the metal added to the heat-resistant oxide is preferably in the range of 10 to 50% by weight. When the reaction is performed at a relatively high temperature, spinel itself such as Fe-Cr can be used.

Suitable catalyst components for the CO-selective oxidation reaction include Mn of Group VII, Co of Group VIII and noble metals, Cu and A of Group IB.
A metal such as g, Au or the like can usually be used by being supported on the above-mentioned heat-resistant oxide. It is not necessary to oxidize the generated hydrogen, and Pt or the like having a strong interaction with CO can be used. Also, a hopcalite catalyst can be mentioned as one of the preferable examples.

The catalyst used in the present invention has a honeycomb structure. The catalyst may itself be formed into a honeycomb, or the catalyst may be coated on a honeycomb carrier made of an inert material such as cordierite or mullite. It may be carried and used. Examples of the material of the honeycomb carrier include ceramic materials such as cordierite and mullite, foil-type metal materials made of heat-resistant stainless steel such as Fe-Cr-Al alloy, and a honeycomb structure using powder metallurgy. Preferably, a metal material molded into a metal is used. In addition, the honeycomb carrier is preferably porous in both cases of ceramic and metal from the viewpoint of reducing the heat capacity and improving the catalyst carrying property, and has a porosity of 0.5 to 50. % Is preferable, and 10 to 40% is more preferable.

When the catalyst component is coated and supported on a honeycomb carrier, the thickness is preferably 5 to 100 μm.
When the film thickness is smaller than 5 μm, the activity is reduced, and when the film thickness is larger than 100 μm, the pressure loss is increased. The cell density of the catalyst body is preferably in the range of 4 to 2000 cells per square inch (cpsi), and 50 to 150 cells / square inch (cpsi).
More preferably, it is in the range of 0 cpsi. Cell density of 4 cpsi
When the cell density is less than 2000, the contact efficiency is too low and the action (catalytic reaction) is insufficient. The cross-sectional shape of the cell can take any shape such as a circle, a square, a polygon, and a corrugate.

The catalyst body may include a plurality of catalyst components having different roles such as a catalyst component for a steam reforming reaction and a catalyst component for a CO shift oxidation reaction. However, since these catalyst components have different reaction temperatures, it is preferable that these catalyst components are separately contained in a plurality of catalyst bodies arranged in the reforming reaction device. In this way, when a heat exchanger for heat recovery, an inlet for auxiliary oxygen necessary for the CO selective oxidation reaction, and the like are arranged in the apparatus, the arrangement can be easily performed. Further, a plurality of catalysts containing the same type of catalyst component may be present in the apparatus. The upstream catalyst body and the downstream catalyst body satisfying the above relationship may contain the same catalyst component or may contain different catalyst components.

[0037]

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Preparation of Catalyst] Catalyst A was prepared in the following procedure.
~ O was produced. The amount of the catalyst component (catalyst metal and Al ₂ O ₃ ) carried per unit volume of the honeycomb carrier was the same for all the catalyst bodies. In addition, since most of the catalyst component is occupied by Al ₂ O ₃ , the heat capacity of the catalyst component coated and supported per unit volume of the honeycomb carrier is almost the same.

(Catalyst A) A commercially available γ-Al ₂ O ₃ having a specific surface area of 200 m ² / g is impregnated with an aqueous solution containing Ru,
After drying, firing was performed at 600 ° C. to obtain a Ru-supported Al ₂ O ₃ powder.
Next, an appropriate amount of water and acetic acid were added to the Ru-supported Al ₂ O ₃ powder, and a supporting slurry was prepared by wet disintegration. The supporting slurry thus obtained was coated on a cordierite honeycomb carrier (Cell density: 400 cells / square inch, volume: 1.0 liter, outer diameter: 93 mmφ, partition wall thickness: 0.15 mm, manufactured by NGK Insulators, Ltd.) (Approximately 6 mil), hexagonal cell), and calcined at 600 ° C. to produce a catalyst body A carrying a catalyst component for a steam reforming reaction.

(Catalyst B) A catalyst component for a steam reforming reaction was supported in the same manner as the catalyst A except that the volume of the honeycomb carrier for coating and supporting the supporting slurry was 0.7 liter. Catalyst B was prepared.

(Catalyst C) A catalyst component for a steam reforming reaction was supported in the same manner as the catalyst A except that the volume of the honeycomb carrier for coating and supporting the supporting slurry was 0.5 liter. Catalyst C was prepared.

(Catalyst D) A catalyst component for a steam reforming reaction was supported in the same manner as the catalyst A except that the volume of the honeycomb carrier for coating and supporting the supporting slurry was 0.3 liter. Catalyst D was prepared.

(Catalyst E) The thickness of the partition wall of the honeycomb carrier for carrying and supporting the slurry for supporting is 0.1 mm (about 4 mi).
A catalyst E carrying a catalyst component for a steam reforming reaction was prepared in the same manner as the catalyst A except for l).

(Catalyst F) A catalyst component for a steam reforming reaction is carried out in the same manner as in the case of the catalyst A except that the cell density of the honeycomb carrier for coating and supporting the supporting slurry is 450 cells / square inch. The prepared catalyst F was produced.

(Catalyst G) A steam carrier was prepared in the same manner as in Catalyst A except that the cell density of the honeycomb carrier for coating and supporting the supporting slurry was 450 cells / square inch and the volume was 0.5 liter. Catalyst G supporting a catalyst component for a catalytic reaction was prepared.

(Catalyst H) The steam reforming was carried out in the same manner as for the catalyst A except that the cell density of the honeycomb carrier for coating and supporting the supporting slurry was 350 cells / square inch and the volume was 0.7 liter. Catalyst H carrying a catalyst component for a catalytic reaction was prepared.

(Catalyst I) A steam reforming was carried out in the same manner as for Catalyst A except that the cell density of the honeycomb carrier for coating and supporting the supporting slurry was 350 cells / square inch and the volume was 0.5 liter. Catalyst I carrying a catalytic component for a catalytic reaction was prepared.

(Catalyst J) The steam reforming was carried out in the same manner as in the case of the catalyst A except that the cell density of the honeycomb carrier for coating and supporting the supporting slurry was 350 cells / in 2 and the volume was 0.3 liter. A catalyst body J on which a catalyst component for a catalytic reaction was supported.

(Catalyst K) A commercially available γ-Al ₂ O ₃ having a specific surface area of 200 m ² / g is impregnated with an aqueous solution of copper acetate and an aqueous solution of zinc acetate, dried and calcined at 500 ° C.
l ₂ O ₃ powder was obtained. Next, the Cu / Zn-supported Al ₂ O ₃
An appropriate amount of water and acetic acid were added to the powder, and a supporting slurry was prepared by wet disintegration. The supporting slurry thus obtained was applied to a cordierite honeycomb carrier (Cell density: 400 cells / in 2, volume: 1.0 liter, outer diameter: 93 mmφ, partition wall thickness: 0.15 mm, manufactured by NGK Insulators, Ltd.) (About 6mi
l), coated and supported on a hexagonal cell), and calcined at 500 ° C. to prepare a catalyst body K supporting a catalyst component for a CO shift reaction.

(Catalyst L) The thickness of the partition wall of the honeycomb carrier for coating and supporting the supporting slurry is 0.1 mm (about 4 mi).
A catalyst L carrying a catalyst component for a CO shift reaction was produced in the same manner as the catalyst K except for l).

(Catalyst M) A commercially available γ-Al ₂ O ₃ having a specific surface area of 200 m ² / g is impregnated with an aqueous solution of H ₂ PtCl ₅ , dried and calcined at 500 ° C. to obtain Pt-supported Al ₂ O ₃ powder. Obtained. Next, an appropriate amount of water and acetic acid were added to the Pt-supported Al ₂ O ₃ powder, and a supporting slurry was prepared by wet disintegration. The supporting slurry thus obtained was coated on a cordierite honeycomb carrier (Cell density: 400 cells / square inch, volume: 1.0 liter, outer diameter: 93 mmφ, partition wall thickness: 0.15 mm, manufactured by NGK Insulators, Ltd.) (Approximately 6 mils, hexagonal cell), and baked at 500 ° C. to produce a catalyst M carrying a catalyst component for CO selective oxidation reaction.

(Catalyst N) The catalyst component for the selective oxidation of CO is supported in the same manner as the catalyst M except that the cell density of the honeycomb carrier for coating and supporting the supporting slurry is 450 cells / square inch. The prepared catalyst body N was produced.

(Catalyst O) The catalyst component for the CO selective oxidation reaction is supported in the same manner as the catalyst M except that the cell density of the honeycomb support for coating and supporting the supporting slurry is 350 cells / square inch. The prepared catalyst O was produced.

[Configuration of Reforming Reactor] A reforming reactor as shown below was constructed using the catalyst obtained as described above. In addition, in order to clarify the distinction between the symbol indicating the type of the catalyst body and the reference numeral in the figure, in the following description of the apparatus, the reference numeral in the figure is described with parentheses ().

(Apparatus A) As shown in FIG. 2, the catalyst body A (1) is placed in the fluid flow path from the upstream side in the flow direction of the reaction fluid.
0), the catalyst body K (20), and the catalyst body M (22) were arranged in this order to configure the apparatus A. The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst A = catalyst K = catalyst M Heat capacity: catalyst A = catalyst K = catalyst M

(Apparatus B) As shown in FIG. 3, the catalyst I (1) is placed in the fluid flow path from the upstream side in the flow direction of the reaction fluid.
8), catalyst C (12), catalyst K (20), catalyst M (2
The device B was arranged in the order of 2). The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst I <catalyst C = catalyst K = catalyst M Heat capacity: catalyst I <catalyst C <catalyst K = catalyst M

(Apparatus C) As shown in FIG. 4, the catalyst G (1) is placed in the fluid flow path from the upstream side in the flow direction of the reaction fluid.
6), catalyst C (12), catalyst K (20), catalyst M (2
Device C was configured by arranging in the order of 2). The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst G> catalyst C = catalyst K = catalyst M Heat capacity: catalyst G> catalyst C <catalyst K = catalyst M

(Apparatus D) As shown in FIG. 5, the catalyst body A (1) is arranged in the fluid flow path from the upstream side in the flow direction of the reaction fluid.
0), the catalyst body K (20), and the catalyst body N (23) were arranged in this order to configure the device D. The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst A = catalyst K <catalyst N heat capacity: catalyst A = catalyst K <catalyst N

(Equipment E) As shown in FIG. 6, the catalyst body A (1)
0), the catalyst body K (20), and the catalyst body O (24) were arranged in this order to configure the apparatus E. The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst A = catalyst K> catalyst O Heat capacity: catalyst A = catalyst K> catalyst O

(Apparatus F) As shown in FIG. 7, the catalyst J (1) is placed in the fluid flow path from the upstream side in the flow direction of the reaction fluid.
9), Catalyst B (11), Catalyst K (20), Catalyst M (2
The device F was configured by arranging in the order of 2). The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst J <catalyst B = catalyst K = catalyst M Heat capacity: catalyst J <catalyst B <catalyst K = catalyst M

(Apparatus G) As shown in FIG. 8, the catalyst body H (1) is placed in the fluid flow path from the upstream side in the flow direction of the reaction fluid.
7), catalyst D (13), catalyst K (20), catalyst M (2
The device G was arranged in the order of 2). The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst H <catalyst D = catalyst K = catalyst M Heat capacity: catalyst H> catalyst D <catalyst K = catalyst M

(Apparatus H) As shown in FIG. 9, the catalyst E (1) is placed in the fluid flow path from the upstream side in the flow direction of the reaction fluid.
4), the catalyst body K (20) and the catalyst body N (23) were arranged in this order to configure the apparatus H. The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst E = catalyst K <catalyst N heat capacity: catalyst E <catalyst K <catalyst N

(Apparatus I) As shown in FIG. 10, the catalyst A
(10), the catalyst L (21), and the catalyst N (23) were arranged in this order to configure the device I. The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst A = catalyst L <catalyst N heat capacity: catalyst A> catalyst L <catalyst N

(Apparatus J) As shown in FIG. 11, the catalyst F
(15), the catalyst body K (20), and the catalyst body O (24) were arranged in this order to configure the apparatus J. The relationship between the cell density and the heat capacity of each catalyst in the apparatus is as follows. Cell density: catalyst F> catalyst K> catalyst O Heat capacity: catalyst F> catalyst K> catalyst O

[Evaluation of Reforming Reactor]: Apparatus A to J
, CH ₃ OH (methanol) and H ₂ O were supplied at a constant flow rate. S / C (Steam Carbon Rat
io) was set to 2.0. The feed was preheated to 600 ° C. before being introduced into the apparatus. In addition, air is supplied between the catalyst body carrying the catalyst component for the CO shift reaction and the catalyst body carrying the catalyst component for the CO selective oxidation reaction in order to supply oxygen necessary for the selective oxidation to the latter. Introduced.

After the apparatus was operated continuously for 100 hours in this way, the operation was stopped once and the apparatus was allowed to cool sufficiently. After cooling, the operation of the apparatus was restarted, and the conversion rate of methanol for 3 minutes (including at the time of cold start) from the start of introduction of the supply source amount was determined. The conversion was calculated by dividing the sum of the number of moles of generated CO and CO _{2 by} the number of moles of supplied methanol. This was used as an index of the hydrogen generation efficiency and is shown in Table 1. On the other hand, the CO emission concentration from the apparatus is used as an index of the CO reduction efficiency of the catalyst body supporting the catalyst component for the CO shift reaction and the catalyst body supporting the catalyst component for the CO selective oxidation reaction. In order to evaluate the rising performance, the measurement was performed 1 minute and 3 minutes after the start of the introduction of the supply source amount, and the measurement results are shown in Table 1.

[0067]

[Table 1]

[0068]

As described above, the reforming reaction apparatus of the present invention particularly relates to the cell density relationship between the catalyst bodies when a plurality of catalyst bodies having a honeycomb structure are arranged in the apparatus. An improvement has been made in consideration of the case where the reaction occurring in the medium is essentially accompanied by a large amount of heat or heat absorption, or the case where the reaction substrate flows into the apparatus at a high concentration. And, according to the present invention, as a result of this improvement,
In such a case, the efficiency of hydrogen generation and the efficiency of reduction of CO as a by-product can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one embodiment of a reforming reaction device according to the present invention.

FIG. 2 is a schematic diagram showing a reforming reaction device used in Examples.

FIG. 3 is a schematic diagram showing a reforming reaction device used in Examples.

FIG. 4 is a schematic view showing a reforming reaction device used in Examples.

FIG. 5 is a schematic diagram showing a reforming reaction device used in Examples.

FIG. 6 is a schematic view showing a reforming reaction device used in Examples.

FIG. 7 is a schematic view showing a reforming reaction device used in Examples.

FIG. 8 is a schematic diagram showing a reforming reaction device used in Examples.

FIG. 9 is a schematic diagram showing a reforming reaction device used in Examples.

FIG. 10 is a schematic diagram showing a reforming reaction device used in Examples.

FIG. 11 is a schematic view showing a reforming reaction device used in Examples.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Upstream catalyst body, 2 ... Downstream catalyst body, 3 ... Can body, 5 ...
Inlet hole, 6 ... Outlet hole, 10 ... Catalyst A, 11 ... Catalyst B, 12 ... Catalyst C, 13 ... Catalyst D, 14 ... Catalyst E, 15 ... Catalyst F, 16 ... Catalyst G, 17: Catalyst H, 18: Catalyst I, 19: Catalyst J, 20: Catalyst K, 21: Catalyst L, 22: Catalyst M, 23: Catalyst N, 24: Catalyst O

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 35/02 B01J 35/02 P 35/04 301 35/04 301A H01M 8/04 H01M 8/04 Z 8 / 06 8/06 G (72) Inventor Junichi Suzuki 2-56, Suda-cho, Mizuho-ku, Nagoya-shi, Aichi Japan F Co., Ltd. F-term (reference) 4D006 GA47 MB15 MB19 MC02X MC03X PA01 PB19 PB66 PC80 4G040 EA03 EA05 EB23 EB32. BA01 BA16 BA17

Claims (10)

[Claims] 1. A reforming reaction device comprising a plurality of catalysts having a honeycomb structure for generating hydrogen by a catalytic reaction from a reaction fluid containing an organic compound or carbon monoxide in a fluid flow path, A reforming reaction apparatus, wherein at least any two of the plurality of catalyst bodies satisfy a relationship of cell density of upstream catalyst body ≦ cell density of downstream catalyst body. 2. A cell of an upstream catalyst body, wherein at least one of the catalyst body disposed on the most upstream side of the plurality of catalyst bodies and the catalyst body disposed on the downstream side thereof is provided. 2. The reforming reaction apparatus according to claim 1, wherein a relationship of density ≦ cell density of the downstream catalyst body is satisfied. 3. The catalyst body according to claim 1, wherein at least two adjacent catalyst bodies among the plurality of catalyst bodies satisfy a relationship of cell density of upstream catalyst body ≦ cell density of downstream catalyst body. The reforming reactor according to any one of the preceding claims. 4. A catalyst body disposed at the most upstream side of the plurality of catalyst bodies and a catalyst body disposed adjacent to a downstream side thereof, wherein a cell density of the upstream side catalyst body ≦ downstream side 2. The reforming reaction device according to claim 1, wherein the relationship satisfies a relationship of cell density of the catalyst body. 5. The method according to claim 1, wherein the most upstream catalyst body of the plurality of catalyst bodies and all the catalyst bodies located downstream thereof have a cell density of the upstream catalyst body ≦ the downstream catalyst. 2. The reforming reactor according to claim 1, wherein the relationship satisfies the relationship of cell density of the medium. 6. The catalyst according to claim 1, wherein the catalyst has a catalytic component having a catalytic action of any one of a steam reforming reaction, a partial oxidation reaction and a decomposition reaction, and / or a CO shift reaction and / or a CO selective oxidation catalyst reaction. The reforming reaction device according to claim 1, which contains: 7. The catalyst component contains at least one of metal elements belonging to groups VB to VIII, IB and IIB in a long-period periodic table and a heat-resistant oxide as main components. 7. The reforming reactor according to 6. 8. The method according to claim 8, wherein the metal element is a Group VIII metal element,
The reforming reaction apparatus according to claim 7, wherein the reforming reaction apparatus is at least one of V, Cr, Mo, W, Re, IB group metal elements, and Zn metal elements. 9. The heat-resistant oxide is selected from the group consisting of Al ₂ O ₃ , SiO ₂ and TiO.
_2, ZrO _2, MgO or a zeolite, SAPO, ALPO, layered compound and reformer according to claim 7, wherein the complex oxide thereof. 10. The method according to claim 1, wherein at least any two of the plurality of catalyst bodies satisfy a relationship of heat capacity of upstream catalyst body ≦ heat capacity of downstream catalyst body. Reforming reactor.