JPH04160002A - Method and device for reforming methanol - Google Patents

Abstract

PURPOSE:To reduce the generation of by-product CO gas and to miniaturize the device by setting a cylindrical combustion catalyst in a reaction part, passing a gaseous fuel and air through the catalyst, superheating the mixed vapors of methanol and water with the generated combustion gas and supplying the mixed vapors to the reaction part. CONSTITUTION:A raw gas S consisting of the mixed vapors of methanol and water is passed through a reaction space (e.g. reaction tubes 10,...) packed with a reforming catalyst 17, and the catalyst 17 is externally heated to obtain the hydrogen-rich reformed gas T. The following means are used in this methanol reforming method. Namely, a combustion catalyst 2 is placed close to the reaction space forming material (e.g. reaction tubes 10,...), and a gaseous fuel F and air A are passed through the catalyst 2 and burned. The generated combustion gas O is freely circulated around the materials 10,... to heat the catalyst 17, a superheating pipe 5 for the raw gas S is provided in the passage Q for the combustion gas O, and the raw gas S heated in the superheating pipe 5 is supplied into the reaction spaces 10,....

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a methanol reforming system that uses combustion gas generated by so-called catalytic combustion as a heating source for a reforming catalyst, and is mainly used in the organic and inorganic chemical industries, It is used to produce hydrogen from methanol and water as raw materials in various fields such as the food industry, ceramics, metallurgy, and semiconductor industry, and can also be incorporated into cogeneration systems. It is.

(Prior Art) As a system for obtaining hydrogen-rich reformed gas, a reforming system using natural gas as a raw material has already been put into practical use.

However, when natural gas is used as a raw material, the reforming process requires 80%
Since it requires a high temperature of 00 to 850°C, it takes time to start up the equipment, making it difficult to start up the equipment quickly.

On the other hand, steam reforming of methanol, which uses methanol and water as raw materials to produce hydrogen-rich reformed gas, has a relatively low reforming temperature of 200°C to 300°C, so in the case of natural gas, In comparison, there are advantages in that equipment can be started up quickly and demands from the load side can be easily met.

Therefore, in recent years, methanol reforming equipment has been extensively developed (Japanese Patent Application Laid-open No. 60-258865;
No. 7822, JP-A-64-5901, etc.).

Therefore, in conventional methanol reforming equipment, the vaporization section and reforming section of methanol and water are generally separated, and a furnace for heating the heat medium is often provided separately. ing. This is because if the methanol and water vaporization section and reforming section are separated and a heating medium heating furnace is provided separately, it becomes possible to adopt a so-called heating medium circulation method in which local heating is less likely to occur. This is because, by maintaining the entire area inside the reformer at the optimum reforming reaction temperature, it is possible to improve reforming performance and operational stability.

However, the methanol reforming system configured as described above has the basic drawback that the reforming system becomes complicated and the reformer inevitably becomes larger, and it is impossible to reduce its size. . That is, it is impossible to apply the above configuration to a small methanol/steam reformer (for example, one whose reformed gas generation rate is 50 ONr/h or less) or a compact portable device.

In order to reduce the size of the reformer, a reformer has been developed in which the methanol and water vaporization section and the reforming section are integrated, and the reformer is heated by burner combustion gas.

However, the heating method using burner combustion gas frequently causes local heating in the reforming section due to the flame, and there is a risk of thermal damage to the reaction tube, carbon deposition on the packed reforming catalyst, and deterioration of the reforming catalyst due to sintering. There is. Therefore, special structural measures are required to prevent the occurrence of these inconveniences, resulting in a disadvantage that the structure of the reformer becomes complicated.

Incidentally, the steam reforming reaction of methanol is generally said to proceed via -carbon oxide as an intermediate product, as shown in the following reaction formula.

CH1○H-+GO+2H2...(I)CO+H20
→CO2+H2-(II)CH,OH+H2O-+CO
, +3H, · (III) That is, the steam reforming reaction of methanol is represented by the formula (m), and its elementary reactions are represented by the formulas (I) and (II).

Since equation (n) showing the conversion reaction of carbon monoxide is an exothermic reaction, the equilibrium shifts to the left under high temperature conditions, and a large amount of -carbon oxide remains. Note that, unlike carbon dioxide, it is necessary to remove this carbon oxide using special purification equipment, and if the amount of carbon monoxide is large, it becomes extremely difficult to completely remove it.

As a result, it is necessary to suppress the amount of -carbon oxide generated as low as possible, and for this purpose, the following countermeasures are required.

b) Adding an excess amount of water equal to or more than the stoichiometrically required amount.

However, considering the energy required to evaporate excess water, there is an economical limit, and a suitable molar ratio of water to methanol is about 1.2 to 3.0.

口 To make the temperature of the catalyst layer high on the upstream side and low on the downstream side.

This is because most of the steam reforming reaction of methanol occurs on the upstream side, and if the temperature on the downstream side is too high, the reaction of formula (II) will proceed in the opposite direction, resulting in an increase in -carbon oxide.

However, in conventional methanol steam reformers of this type, attention is paid only to uniformly heating the entire reaction group in the reformer, and as a result - the rate of carbon oxide by-product is reduced. The problem is that it is relatively expensive.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems in conventional methanol steam reformers of this type, namely, (a) separate vaporization section and reforming section for methanol and water; In a reformer that has a separate heating furnace, it is inevitable that the system becomes complicated and the device becomes larger, and the device cannot be made smaller or more compact. Even if it is integrated, in the case of a configuration in which heating is performed directly by burner combustion gas, there is a high risk of thermal damage to the reaction tube or thermal deterioration of the packed catalyst due to local heating by the flame, and special measures are required to prevent this. (c) Since the downstream side of the catalyst layer is heated to a relatively high temperature like the upstream side, - the by-product rate of carbon oxide is high. -In addition to having a low rate of carbon oxide by-product, it does not cause local heating in the reforming section, and almost eliminates deterioration of the reforming catalyst due to carbon precipitation and sintering8. ,
The present invention provides a methanol reforming method and a methanol reforming device that enable the device to be significantly downsized and compact.

(Means for Solving the Problems) In order to eliminate the drawbacks of the prior art as described above, the present invention has the following features:
■The system is simplified by using a direct heat exchange method with the catalytic combustion gas, ■A cylindrical combustion catalyst is installed in the reaction section to improve combustion characteristics, and ■A superheater is installed to superheat the mixed steam of methanol and water. By arranging them side by side in the reaction section, the device can be made small and compact. Furthermore, the structure is such that the amount of heat transferred to the multiple reaction tubes is almost uniform, and by suppressing the heating downstream of the reaction section, the inside of the reaction section can be reduced. A methanol reforming method that employs a catalytic combustion method that maintains the reforming reaction temperature at an optimal reforming reaction temperature to improve reforming characteristics and suppress carbon monoxide by-products to obtain stable operating performance. It provides quality equipment.

That is, in the present method invention, a raw material gas S consisting of a mixed vapor of methanol and water is passed into a reaction space filled with a reforming reaction catalyst 17, and the reforming reaction catalyst 17 is heated from the outside to produce hydrogen-rich methanol. In a methanol reforming method in which a reformed gas T is obtained, a combustion catalyst 2 is disposed near the material forming the reaction space, and a fuel gas F is supplied to the combustion catalyst 2.
This is combusted through air A, and the generated combustion gas O
is allowed to flow freely into the forming material of the reaction space to heat the reforming reaction catalyst 17, and at the same time, a superheating pipe 5 for the raw material gas S is disposed in the flow path for the combustion gas O, and the material gas S is heated through the superheating pipe 5. The basic structure of the invention is to supply the raw material gas S into the reaction space.

Further, the present device invention according to claim (5) includes a cylindrical outer casing 1 provided with a fuel gas inflow nozzle 7 and an exhaust combustion gas outflow nozzle 6, respectively; It is formed by connecting the upper and lower ends of a plurality of reaction tubes 1o through which raw material gas S containing water flows to an upper ring header 12 and a lower ring to a ladder 13, respectively, and is disposed in the outer casing 1. Cylindrical reaction tube wall 3
a cylindrical combustion catalyst 2 disposed in the outer casing 1 concentrically with the cylindrical reaction tube wall 3 and in communication with the fuel gas inflow nozzle 7 ; a combustion gas passage in the outer casing 1 The combustion gas O produced by catalytic combustion of the fuel gas F is configured to include a raw material gas superheating tube 5 disposed inside the raw material gas inlet nozzle 4, which heats the raw material gas S supplied from the raw material gas inflow nozzle 4, and then supplies the raw material gas S to the reaction 4v10. The basic structure of the invention is to allow the heat to flow freely through the reaction tube wall 3 and the superheating tube 5 so as to transfer the amount of heat to the reaction tube 10 with high efficiency.

Further, the present device invention as set forth in claim (10) provides that in the first device invention, the cylindrical reaction tube wall 3 is formed by a double cylinder, and a metal cylinder forming the double cylinder The basic structure of the invention is to use the gap 18.19 as a reaction space filled with a reforming reaction catalyst 17.

(Function) Fuel gas F and air A are supplied into the cylindrical combustion catalyst 2 through the fuel gas inflow nozzle 7, and while passing between the combustion catalysts 2, the fuel gas undergoes so-called catalytic combustion and the combustion gas O is Occur.

The generated combustion gas 0 is guided into the combustion gas passage, circulates while heating the raw gas superheating tube 5 and the reaction tube 10 which is the material forming the reaction space, and is discharged to the outside from the combustion gas outflow nozzle 6. .

Each reaction tube 10 is heated almost uniformly by the radiant heat from the combustion catalyst 2 and the contact heat transfer of the combustion gas ○, and thereby the reforming reaction catalyst 17 filled in the reaction tube 10 is heated. However, the lower part of each reaction tube 10 does not directly face the combustion catalyst 2, and as a result, the lower part of the reaction tube 10 is heated at a relatively lower temperature than the upper part.

On the other hand, the raw material gas S supplied from the raw material gas inflow nozzle 4
is heated while passing through the superheating tube 5, and then is almost uniformly supplied into each reaction tube 10 forming a reaction space. The raw material gas S supplied into each reaction tube 10 is reformed through a so-called steam reforming reaction while flowing while being in contact with the reforming reaction catalyst 17 filled therein, and the generated hydrogen-rich methanol reformer is reformed. The quality gas T is taken out from the outflow nozzle 16.

Note that the lower part of each reaction tube 10 (i.e., the downstream part of the raw material gas S)
As mentioned above, since the upper part is kept at a lower temperature than the upper part, so-called by-product of carbon oxide is reduced.

Further, the extracted methanol reformed gas T is sent to a high-purity hydrogen gas generator (not shown) as required, where it is refined into high-purity hydrogen gas.

(Example) Hereinafter, an example of the present invention will be described in detail based on the drawings.

FIG. 1 is a schematic cross-sectional view of a methanol steam reformer according to the present invention, and FIG. 2 is a cross-sectional view taken along the line AA in FIG.

In Figures 1 and 2, 1 is a closed cylindrical external casing, 2 is a cylindrical combustion catalyst installed concentrically in the center of the external casing 1, and 3 is the external casing 1 and the combustion catalyst. A reaction tube wall 3 stands concentrically between the reaction tube wall 3 and the reaction tube wall 3, and spaces on both sides of the reaction tube wall 3 serve as combustion gas flow paths P and Q.

Further, 4 is an inflow nozzle for the raw material gas S consisting of methanol and water, and 5 is a superheating tube for the raw material gas S consisting of a mixed vapor of methanol and water.

The external casing 1 is made of a steel plate, a heat insulating material, etc., and an outflow nozzle 6 for the combustion gas O is provided on the lower side thereof. Further, at the lower bottom of the outer casing 1, there is further an inflow nozzle 7 for the fuel gas F and air A that communicates with the combustion catalyst 2.

Inlet/outlet ports 8 for the combustion catalyst 2 are provided in the upper part of the outer casing 1, and are normally sealed with a lid 9.

The combustion catalyst 2 is usually made of, for example, a nickel foam carrier on which a small amount of platinum or palladium is supported. In this embodiment, a 0.2% platinum-nickel foam is used as the combustion catalyst 2.

Note that those using palladium have high activity but are easily poisoned, and those using platinum have slightly low activity but are not easily poisoned.

The combustion catalyst 2 is formed into a hollow cylindrical shape using a metal foam, ceramic honeycomb, metal mesh laminate, etc. as a catalyst carrier, and communicates with the fuel gas inflow nozzle 7 as shown in FIG. At least, the combustion catalyst 2 is disposed in the center of the outer casing 1 concentrically therewith.The length of the combustion catalyst 2 formed in a cylindrical shape is longer than the length of the reaction tube 1o, as will be described later. It is formed short,
The raw material gas S is superheated in the downstream region of the reaction tube 10, and -
This prevents carbon oxide from being produced as a by-product.

Combustion tests for various combustible gases were conducted using the 0.2% platinum-nickel foam combustion catalyst 2 used in this example. As a result, one of the least reactive gases is methane gas, whose combustion initiation temperature is approximately 370-380℃.
Met. Also, one of the most reactive substances is hydrogen gas.

Combustion started at room temperature of 20-25°C. Furthermore, common combustible gases are between the above-mentioned methane gas and hydrogen gas, and most of them start burning between 100 and 200°C.

Furthermore, when the 0.2% platinum-nickel foam combustion catalyst 2 is used, methanol gas starts to burn at room temperature, and -
It has been observed that carbon oxide starts to burn at about 80-100°C.

The catalyst carrier is extremely important for holding platinum and palladium and giving it appropriate strength and heat resistance. The catalyst carrier has high porosity, high heat resistance, good catalyst retention, good dispersion of combustion gas, small heat capacity, flexibility, and heat conduction. Alumina fiber, nickel foam, ceramic honeycomb, spherical alumina, etc. are usually used.

In this example, nickel foam is used as the catalyst carrier.

The reaction tube wall 3 is formed into a cylindrical shape and includes a plurality of reaction tubes 10 and a combustion gas flow regulating baffle 11 that connects the reaction tubes 10 with each other. That is, the plurality of reaction tubes 10, which form the reaction space, are arranged concentrically near the outside of the cylindrical combustion catalyst 2.

The upper end of each reaction tube 10 is a ring-shaped upper header 12.
Furthermore, the lower end of each reaction tube 10 is connected to a ring-shaped lower header 13, and the combustion gas regulating baffle 11 forming the reaction tube wall 3 is selected to be slightly shorter than the reaction tube 10. As a result, a combustion gas passage 14 is formed in the upper part of the reaction tube wall 3 through which the combustion gas O flows from the combustion gas passage P to the passage Q.

The superheating tube 5 for the raw material gas S (ie, the mixed vapor of methanol and water) is formed in a coil shape, and is disposed outside the upper part of the cylindrical reaction tube wall 3.

Note that the starting end of the superheating tube 5 is the inflow nozzle 4 for the raw material gas S.
Furthermore, the distal ends of the superheating tubes 5 are respectively connected to the upper ring header 12 via connecting tubes 15.

In Fig. 1, 16 is the reformed gas outlet nozzle provided on the ladder 13 to the lower ring, 17 is the reforming reaction catalyst filled in the reaction tube lo, S is the raw material gas, and T is the hydrogen-rich gas. This is methanol reformed gas.

FIG. 3 is a schematic vertical cross-sectional view of a methanol reformer according to a second embodiment of the present invention, showing the flow direction of the fuel gas F, the flow direction of the combustion gas 0, and the supply position of the raw material gas S (i.e., the superheating pipe 5
(installation position) is reversed from that shown in FIG.

Furthermore, FIG. 4 is a schematic cross-sectional view of an apparatus according to a third embodiment of the present invention, and the structure of the reaction space is slightly different from that of the first embodiment. That is, in this embodiment, the reaction space is formed of two cylinders 18 and 19 arranged concentrically, and the reforming reaction catalyst 17 is filled between the cylinders 18 and 19. has been done.

Furthermore, it goes without saying that the exhaust gas passage 14 is formed in the upper part of the cylindrical body 18.19 that forms the reaction space.

Next, the operation of the methanol steam reformer according to the present invention will be explained based on a first embodiment.

The raw material gas S is a mixed vapor of methanol and water (for example, 1
00° C. to 150° C.) is introduced into the raw material gas superheating tube 5 from the raw material gas inflow nozzle 4 and heated by the combustion gas 0. Mixed superheated steam from superheating tube 5 (e.g. 200~3
50'C) is introduced into the upper ring header 12 and then distributed approximately evenly into the plurality of reaction tubes 10.

While this raw material gas S flows through each reaction tube 10 filled with the reforming reaction catalyst 17 to the lower ring toward the ladder 13, the reforming reaction progresses, and the reformed gas exits from the reformed gas outlet nozzle 16 rich in hydrogen. The reformed gas 1 is taken out as a reformed gas 1, and is supplied to a high-purity hydrogen generator (not shown) or the like.

Since this methanol steam reforming reaction is an endothermic reaction, it is necessary to heat the reaction tube 10 from outside.

In the present invention, combustion gas ○ generated by catalytic combustion of fuel gas F is used as the heating source. The fuel gas F may be a part of the obtained hydrogen-rich reformed gas or the hydrogen purification section (
For example, off-gas extracted from PSA) or hamethanol or a mixture thereof is used. still,
In the embodiment shown in FIG. 1, a portion of the obtained hydrogen-rich reformed gas T is utilized as the fuel gas F.

The fuel gas F and air A are introduced into the reformer through the inflow nozzle 7, and are combusted while flowing from the inner cylinder to the outer cylinder of the hollow cylindrical combustion catalyst 2, and the generated combustion gas 0 is It flows into the combustion gas passage P.

The combustion gas O that has entered the combustion gas passage P is regulated by the reaction tube wall 3 consisting of the reaction tube 10 and the combustion gas flow regulating baffle 11, and flows upward in the exhaust gas passage P, until the upper baffle 11 is chipped. The combustion gas turns into the combustion gas passage Q through the combustion gas passage 14, and while flowing through the passage Q from top to bottom, heat is applied to the superheating tube 5 and the reaction tube 10 disposed in the passage Q. It is exhausted from the outflow nozzle 6.

In the present invention, the combustion gas O for heating required for the reforming reaction is generated by a catalytic combustion method, and the following are characteristics of the catalytic combustion method.

(a) Since the combustion catalyst 2 is used, the combustion speed of the fuel gas F is fast and the combustion efficiency is high.

(b) Since it is flameless combustion, stable combustion can be obtained without locally raising high temperatures.

(c) If a highly active catalyst is used, the oxidation reaction will proceed at a much lower temperature than the ignition temperature without a catalyst.
The generation of so-called thermal NOx is extremely reduced.

(d) Effective heat transfer properties can be obtained by utilizing infrared radiation from the catalyst surface.

(e) Complete combustion is possible even with lean fuel that is outside the flammability limit in the case of no catalyst.

In addition, in the present invention, in order to utilize each of the above features of the catalytic combustion method more effectively, the cylindrical combustion catalyst 2 is provided in the inner cylindrical portion of the reaction tube wall 3.
The infrared radiation from the surface of the reaction tube 10 can be effectively used, and the heat transfer can be carried out effectively, and the amount of heat transferred to each reaction tube 10 can be made almost uniform without causing local high temperatures at all.

(Effect of the invention) In the present invention, the cylindrical combustion catalyst 2 is arranged concentrically inside the material forming the cylindrical reaction space through which the raw material gas S flows and filled with the reforming reaction catalyst 17. At the same time, since the combustion gas 0 after flowing through the combustion catalyst 2 is made to flow along the reaction space forming material, the heat held by the fuel gas F is effectively transferred to the reaction space forming material. This makes it possible to significantly downsize the device, and the amount of heat transferred to the forming materials of the reaction space is almost uniform, allowing for a more efficient design of the reforming reaction in terms of catalyst loading. This makes it possible to completely prevent deterioration of the reforming catalyst 17 due to carbon precipitation and sintering.

In addition, in the present invention, cylindrical combustion catalysts 2 are arranged concentrically within the cylindrical reaction tube wall 3 forming one reaction space.
Since the length dimension is made shorter than the reaction tube wall 3, and the heating of the reaction space on the downstream side is suppressed, the carbon monoxide landscape generated during the reforming reaction is reduced, and its by-product rate is reduced. descend.

Furthermore, in the present invention, a superheating tube 5 for superheating the mixed steam of methanol and water is disposed in the combustion gas passage in the outer casing 1, and a direct heat exchange method with the combustion gas O is adopted. Compared to the conventional heat transfer oil circulation method, the system can be simplified and equipment costs can be significantly reduced.

As described above, the present invention has excellent practical effects in terms of downsizing and compactness of the apparatus, improvement of thermal efficiency, improvement of reforming efficiency, etc.

[Brief explanation of the drawing]

FIG. 1 is a schematic vertical cross-sectional view of a methanol reforming apparatus according to a first embodiment of the present invention, and FIG. 2 is a cross-sectional view taken along line AA in FIG. 1. FIG. 3 is a schematic vertical cross-sectional view of an apparatus according to a second embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of an apparatus according to a third embodiment of the present invention. 1 External casing 2 Combustion catalyst 3 Reaction tube wall 4 Raw material gas inflow nozzle 5 Raw material gas overheating tube 6 Combustion gas outflow nozzle 7 Fuel gas inflow nozzle 8 Combustion catalyst inlet/outlet port 9 Cover body 10 Reaction tube 11 Combustion gas flow regulating baffle 12 Upper ring Header 13 Lower ring header 14 Combustion gas passage 15 Connecting pipe 16 Reformed gas outflow nozzle 17 Reforming reaction catalyst 18.19 Gold IA cylinder P, Q Smoking gas passage O Combustion gas S Raw material gas (methanol/water mixture Steam) T Methanol reformed gas F Fuel gas A Air Patent applicant Takuma Research Institute Co., Ltd. Figure 2 Figure 3, Figure 4

Claims (10)

[Claims] (1) Raw material gas (S
) is passed through a reaction space filled with a reforming reaction catalyst (17), and the reforming reaction catalyst (17) is heated from the outside to obtain a hydrogen-rich methanol reformed gas (T). In the method, a combustion catalyst (2) is disposed near the material forming the reaction space, and fuel gas (F) and air (A) are passed through the combustion catalyst (2) to combust it. The combustion gas (O) is made to flow freely into the forming material of the reaction space to heat the reforming reaction catalyst (17), and a superheating pipe ( 5), and the heated raw material gas (S) is supplied into the reaction space through the superheating tube (5). (2) According to claim (1), the reaction space forming material is heated by the combustion gas (O) so that the downstream part of the raw material gas (S) is at a lower temperature than the upstream part. The method for modifying methanol described. (3) Methanol reformed gas (from which fuel gas (F) was generated)
The methanol reforming method according to claim 1, wherein the methanol reforming method is formed as a mixture of one or more of T), off-gas from a hydrogen purification section of a high-purity hydrogen generator, and methanol. (4) Combustion catalyst (2) as one of platinum-alumina, palladium-alumina, platinum and palladium-alumina, platinum-nickel foam, palladium-nickel foam, platinum and palladium-nickel foam. The methanol reforming method according to claim (1). (5) A cylindrical outer casing (1) each equipped with a fuel gas inflow nozzle (7) and a combustion gas outflow nozzle (6); a raw material gas filled with a reforming reaction catalyst (17) and containing methanol and water; (S) is formed by connecting each upper end and each lower end of a plurality of reaction tubes (10) to an upper ring header (12) and a lower ring header (13), respectively, and inside the outer casing (1). The cylindrical reaction tube wall (3
); the cylindrical reaction tube wall (3) into the outer casing (1);
) and a cylindrical combustion catalyst (2) disposed concentrically with the fuel gas inflow nozzle (7) and in communication with the fuel gas inflow nozzle (7); A raw material gas superheating tube (5) that heats the raw material gas (S) supplied from the gas inflow nozzle (4) and then supplies it into the reaction tube (10).
The combustion gas (O) produced by catalytic combustion of the fuel gas (F) is transferred to the reaction tube wall (3) and the superheating tube (
5) A methanol reforming device characterized in that the amount of heat is transferred to the reaction tube (10) with high efficiency by freely contacting the methanol reforming device. (6) The length of the cylindrical combustion catalyst (2) is made shorter than the length of the cylindrical reaction tube wall (3), so that the downstream portion of the reaction tube wall (3) of the raw material gas (S) The methanol reformer according to claim 5, wherein the methanol reformer is configured not to face the combustion catalyst (2). (7) The fuel gas (F) is made into a mixture of one or more of the generated methanol reformed gas (T), the off-gas from the hydrogen purification section of the high-purity hydrogen generator, and methanol, and the combustion Claim (5) wherein the catalyst (2) is any one of platinum-alumina, palladium-alumina, platinum and palladium-alumina, platinum-nickel foam, palladium-nickel foam, platinum and palladium-nickel foam. The methanol reformer described. (8) Connect the fuel gas inflow nozzle (7) to the outer casing (1
), a combustion gas outlet nozzle (6) is formed in the lower side of the outer casing (1), and a superheating pipe (5) is formed in the lower side of the outer casing (1).
), and connect the end of the superheating tube (5) to the upper ring header (12), and connect the reformed gas outlet nozzle (13) to the lower ring header (13).
16), furthermore, a plurality of reaction tubes (10) are connected to each other by a combustion gas flow regulating baffle (11), and a combustion gas flow path (14) is formed in the upper part of the reaction tube wall (3). The methanol reforming apparatus according to claim (5). (9) Connect the fuel gas inflow nozzle (7) to the outer casing (1
), combustion gas outflow nozzles (6) are formed on the upper side of the outer casing (1), and superheating pipes (5) are formed on the upper side of the outer casing (1).
) is connected to the tip of the raw material gas inflow nozzle (4), and the end of the superheating tube (5) is connected to the lower ring header (13), and the upper ring header (12) is provided with a reformed gas outflow nozzle (16). Claim (1) further characterized in that the plurality of reaction tubes (10) are connected to each other by a combustion gas flow regulating baffle (11) and a combustion gas flow path (14) is formed in the lower part of the reaction tube wall (3). 5) The methanol reformer according to item 5). (10) A cylindrical outer casing (1) equipped with a fuel gas inflow nozzle (7) and a combustion gas outflow nozzle (6); a raw material gas (1) filled with a reforming reaction catalyst (17) and containing methanol and water; S) is formed by connecting an upper ring header (12) and a lower ring header (13) to an upper opening and a lower opening of a double cylinder body forming a space through which S) flows, and into the outer casing (1). The wall of the cylindrical reaction tube (
3) and; the cylindrical reaction tube wall (
3) and a cylindrical combustion catalyst (2) disposed concentrically with the fuel gas inflow nozzle (7) and in communication with the fuel gas inflow nozzle (7); A raw material gas superheating pipe (5) that heats the raw material gas (S) supplied from the raw material gas inflow nozzle (4) and then supplies it into the double cylinder body.
The combustion gas (O) generated by catalytic combustion of the fuel gas (F) is transferred to the reaction tube wall (3) and the superheating tube (5).
A methanol reforming device characterized by highly efficient heat transfer to a reaction tube by allowing free contact with the methanol.