CN106276794A - Hydrogen-manufacturing reactor - Google Patents

Abstract

The present invention relates to a reactor for generating hydrogen-containing reformed gas from raw materials containing carbon compounds and water, the reactor comprising: a reforming section for generating hydrogen-containing reformed gas by reforming the raw materials; a section for supplying heat to the above-mentioned reforming section by burning the raw material; a carbon monoxide removal reaction section for removing carbon monoxide in hydrogen-containing reformed gas; a heating raw material delivery pipe; and a reforming raw material phase change pipe located in the combustion section, and The raw material is heated, wherein, a first shell, a second shell and a heating raw material conveying pipe are sequentially arranged in a concentric structure from the outside, and the reforming part and the combustion part are respectively composed of the first shell and the second shell. The space between the two shells and the space between the second shell and the heating material delivery pipe are formed independently.

Description

Hydrogen reactor

technical field

The present invention relates to a hydrogen production reactor which reforms carbon compounds into reformed gas containing hydrogen and supplies it to a fuel cell. Specifically, it relates to a hydrogen production reactor for producing hydrogen from carbon compounds by evaporating the raw material gasified in the phase change part of the liquid raw material mixed with carbon compounds and water in a reforming reaction part filled with a catalyst In order to promote the reaction, a combustion reaction part is set on the adjacent flow path separated from the reforming reaction part, and a part of the liquid raw material is induced to carry out combustion reaction on the catalyst, so that the heat generated by the combustion reaction It is supplied to the reforming reaction part as reaction heat.

Background technique

In recent years, as concerns about environmental issues have increased, interest and demand for clean fuels fueled by hydrogen have also increased. As a high-efficiency power generation device, the polymer fuel cell system can be used as a multi-purpose power supply device if it is connected to an appropriate hydrogen gas supply device because it operates at a low temperature and can be quickly started.

The carbon compound containing methanol does not contain sulfur components and has a molecular structure with a high hydrogen/carbon-ratio characteristic. At the same time, it is easy to mix with water and is liquid at normal temperature and normal pressure. stored fuel. As one of methods for producing hydrogen from carbon compounds including methanol, a steam reforming method has been developed and widely used.

In order to carry out the steam reforming reaction from carbon compounds, a gasifier for vaporizing a mixture of liquid carbon compounds and water, a burner for supplying heat to the reforming reactor, and a liquid for combustion are required. A gasifier for fuel gasification requires an additional purifier to remove carbon monoxide when it is supplied to a polymer fuel cell that is susceptible to carbon monoxide image, such as a polymer fuel cell.

The reaction of producing hydrogen from methanol is carried out according to the following reaction formula 1.

[Reaction 1]

CH ₃ OH+H ₂ O=CO ₂ +3H ₂ ΔH=49.4kJ/mol (1)

CH ₃ OH=CO+2H ₂ ΔH=90.5kJ/mol (2)

CO+H ₂ O=CO ₂ +H ₂ ΔH=-41.1kJ/mol (3)

As mentioned above, while the reforming reaction using methanol is carried out according to (1) of the above reaction formula 1, the reaction of (2) is partially produced at high temperature. However, the reactions of (1) and (2) are endothermic reactions, and continuous supply of heat is required to proceed these endothermic reactions, and in order to adjust the reaction rate, it is necessary to simultaneously adjust the temperature of the catalyst causing the reforming reaction.

In addition, when the temperature of the reactor in the above reaction of (2) is too high, the direct decomposition reaction of methanol and the reverse reaction of the above reaction of (3) proceed, and the carbon monoxide concentration in the product becomes high, and when the temperature is too low In the case of condensing water vapor, the reaction rate of the catalyst layer decreases and the conversion capacity of methanol fuel decreases. Therefore, it is necessary to reliably maintain the temperature of the reforming section.

In order to solve such a problem, Korean Patent No. 10-0314829 describes a methanol reformer equipped with double pipes for maintaining the temperature of the reformer at a constant temperature. However, this methanol reformer has disadvantages that the size of the reactor as a whole is large, that the combustion catalyst does not completely contact the side of the reforming catalyst, and that the combustion catalyst is not filled in one tube but dispersedly filled in multiple places. , so that it is difficult to efficiently supply heat to the reformer.

In addition, in the paper J.of Power source, 108(2002) 21-27 of the Pacific North National Laboratory (Pacific North National Laboratory), a small-scale methanol steam reformer using methanol as a combustion fuel and a reforming fuel was described. whole device. However, this small methanol steam reforming device has the following disadvantages: it has a relatively low output power of about 200 mW, and in order to maintain the reaction temperature, a large amount of fuel, that is, methanol, is put into the burner, so that the overall thermal efficiency is very low. 5 to 10%.

Therefore, it is necessary to continuously research and develop a reactor having a high thermal efficiency and a high hydrogen conversion rate while keeping the size of the reactor small.

<Prior art document>

Patent Document: Korean Authorized Patent 10-0314829 (November 2, 2001)

Non-patent literature: Pacific North National Laboratory, J. of Power source, 108(2002) 21-27

Contents of the invention

(1) Technical problems to be solved

The present invention has been made to solve the above-mentioned problems, and its object is to provide a heat exchange type reactor for producing hydrogen from carbon compounds, which can minimize the energy consumption required in the phase change, Simultaneously, the reforming catalyst and the combustion catalyst are filled adjacently through the casing to minimize the heat transfer distance, thereby making it possible to manufacture a small reactor with a simple structure.

In addition, an object of the present invention is to provide a hydrogen production reactor capable of quickly and stably supplying hydrogen gas to a fuel cell for emergency power supply by arranging a portion of the evaporated liquid fuel inside the reactor to quickly start the reactor. .

In addition, an object of the present invention is to provide a hydrogen production reactor that effectively removes carbon monoxide in a hydrogen-rich gas generated from carbon compounds, so that even if it is supplied as fuel to a polymer fuel cell, it does not It will cause deterioration of the fuel cell.

(2) Technical solution

The invention relates to a hydrogen production reactor for producing hydrogen from carbon compounds.

One aspect of the present invention relates to a reactor for generating hydrogen-containing reformed gas from a feedstock comprising carbon compounds and water, the reactor comprising: a reforming section for generating hydrogen-containing gas by reforming the feedstock reformed gas; a combustion section that supplies heat to the reforming section by burning the raw material; a heating raw material delivery pipe; and a reformed raw material phase change tube that is located in the combustion section and heats the raw material, wherein, from the outside A first casing, a second casing and a heating raw material conveying pipe are sequentially arranged in a concentric structure, and the reforming part and the combustion part are separated by the space between the first casing and the second casing and the The space between the second casing and the heating raw material conveying pipe is formed independently.

In this case, the reactor may include: a reforming part, a space between the first case and the second case is filled with a reforming catalyst; and a combustion part, the second case and the second case Combustion catalysts are filled in the separated space of the heating raw material conveying pipe.

Another aspect of the present invention relates to a reactor including: a reforming section for generating hydrogen-containing reformed gas by reforming a raw material containing carbon compounds and water; The whole part supplies heat, wherein, from the inside to the outside, the heating raw material conveying pipe, the first shell and the second shell are sequentially arranged in concentric circles, and the reforming part is separated by the first shell and the second shell. Space is formed, the combustion part is formed by the space separated by the second casing and the heating raw material delivery pipe, and the reforming raw material phase change tube for heating the raw material is included in the interior of the combustion part, and at one end of the reforming part Includes carbon monoxide removal section.

In this case, a reformed material phase change tube surrounding an inner surface of the second casing may be provided at the same height position adjacent to the carbon monoxide removing part.

In addition, the reactor may include: a reforming part, the space between the first casing and the second casing is filled with a reforming catalyst; a carbon monoxide removal part, the end of the reforming part is filled with a carbon monoxide removal catalyst. a catalyst; and a combustion part, the space between the second casing and the heating raw material delivery pipe is filled with a combustion catalyst.

In the present invention, a heater or a combustion catalyst may be further provided inside the heating raw material delivery pipe, the lower end of the heating raw material delivery pipe and the lower end of the second housing are separated from each other to form a first compartment, and The lower end of the second housing and the lower end of the first housing are spaced apart from each other to form a second compartment.

In the present invention, the combustion catalyst can be filled from the lower end of the combustion part, and filled to be separated from the upper end of the combustion part, the inner lower end of the raw material phase change tube and the inner lower end of the heater, The reforming catalyst may be filled from a lower end of the reforming section and spaced apart from an upper end of the reforming section.

In the present invention, the reactor may further be provided with a horizontal isolation plate for isolating the heating material delivery pipe, the first shell, and the second shell from the outside at the upper end of the heating material delivery pipe, and It may be arranged that the heating raw material delivery pipe, the combustion product discharge pipe, the reforming raw material supply pipe and the reforming raw material discharge pipe penetrate through the horizontal partition plate.

In the present invention, the heating raw material supply pipe may be connected to the heating raw material delivery pipe, the combustion product discharge pipe may be connected to the combustion part, and the reforming raw material supply pipe and reforming raw material discharge pipe may be They are respectively connected to one end of the raw material phase change pipe, and the reformed raw material discharge pipe can be connected to the second compartment through a preheating pipe.

In addition, a preheating pipe connected to the reformed raw material discharge pipe may wrap a side surface of the first casing in a coil shape.

In addition, a space not filled with a combustion catalyst in the combustion unit may be provided with a heat transfer net, and the reformer unit may be provided with one or more heat transfer pins.

In the present invention, the combustion catalyst, reforming catalyst or carbon monoxide removal catalyst may comprise a catalyst selected from gold, silver, iron, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, osmium, iridium, palladium, More than one metal of zirconium and lanthanum group metals or their oxides, specifically, the combustion catalyst may contain one selected from platinum, rhodium, ruthenium, osmium, iridium, palladium, gold, silver and copper The above metals or their oxides, the reforming catalyst may comprise copper/ceria/zirconia composite, copper/zinc oxide/alumina composite, copper/ceria/alumina composite and copper /zirconia/alumina composites any one or more composites.

In the present invention, the raw material is stored in the raw material tank, and the raw material may include the heated raw material supplied from the raw material tank to the heating raw material supply pipe and the raw material supplied from the raw material tank to the reformed raw material supply pipe. Reforming raw materials.

Another aspect of the present invention is a hydrogen production method using the hydrogen production reactor, wherein the heating raw material flows through the following steps: a) the heating raw material is transported into the heating raw material delivery pipe through the heating raw material supply pipe; b) through The first compartment is transported from the heating raw material delivery pipe to the combustion part, and reacts with the combustion catalyst filled in the combustion part to carry out catalytic combustion; and c) after the catalytic combustion, the combustion product discharge pipe The combustion product is discharged to the outside of the reactor, and the flow of the reformed raw material includes the following steps: 1) the reformed raw material is transported to the reformed raw material phase change pipe through the reformed raw material supply pipe, and then the phase changes into the gas phase; 2) the phase change The reformed raw material is delivered to the second compartment through the reformed raw material discharge pipe and the preheating pipe; 3) the reformed raw material supplied to the second compartment passes through the reforming section and is filled into the reforming section The reforming catalyst reacts; and 4) the product after the reaction is discharged to the outside of the reactor.

In addition, after the step 3), the present invention may further include a step of passing the carbon monoxide removal catalyst layer of the carbon monoxide removal unit at the end of the reformer unit and performing a selective carbon monoxide removal reaction.

In the present invention, the heating raw material or the reforming raw material may contain 30 to 50% by weight of water and 50 to 70% by weight of carbon compounds, and the reforming catalyst in the step 3) may be maintained at 100°C to 300°C temperature range. Therefore, the preheating pipe may be arranged to be wound downward in contact with the outer periphery of the first casing.

The aspects described above are not limited to the described contents, and include all items that can be easily replaced by those skilled in the art. As an example, a case where a device of another type is used for the purpose of implementing the same technique is included.

(3) Effect of the invention

According to the heat exchange reactor for producing hydrogen from carbon compounds of the present invention, a first shell, a second shell, and a heating raw material delivery pipe are sequentially arranged in a concentric structure from the outside, and each shell and the raw material are transported to each other. The spaces created by the separation of the tubes are respectively filled with combustion catalysts or reforming catalysts, so that the heat generated by catalytic combustion can be easily transferred to the reforming catalysts, and the thermal gradient can be freely adjusted according to the filling conditions of the catalysts.

In particular, there is an advantage in that the carbon monoxide concentration can be drastically reduced by disposing a carbon monoxide removal unit at one end of the reforming unit, and the system can be used efficiently by transferring the heat generated by the carbon monoxide removal unit to the adjacent heating raw material delivery pipe. While heating, the reaction catalyst in the carbon monoxide removal unit can be used stably for a long period of time.

In addition, the raw material phase change part is arranged inside, and the energy consumption required for phase change is minimized by supplying heat generated by catalytic combustion, and the reactor can be quickly started in a cold state, so it is economical and the reactor can be reduced The size makes it compact.

In addition, in the initial operation, the heating fuel is vaporized by the heater installed inside the heating material delivery pipe, and is supplied to the combustion catalyst together with air, so that the liquid-phase raw material and the combustion catalyst are not in contact. A stable combustion reaction is carried out, and once the combustion reactor is started, the combustion product heats the reforming material phase change tube installed at the upper end of the heating material delivery pipe to vaporize the liquid reforming material supplied to the reforming catalyst. Therefore, there is an advantage that the heating raw material and the reforming raw material can be rapidly vaporized in sequence and supplied to the respective catalyst layers even with a simple structure.

In the case where the heat exchange type reactor of the present invention is connected to a fuel cell, it can be widely used not only in general energy systems using hydrogen as fuel but also as a backup power source or as a substitute for lead storage batteries by virtue of the advantages described above. Terminals, repeaters, etc. located in remote areas where power supply is difficult.

Description of drawings

1 to 6 are diagrams showing a cross-section of a reactor according to an embodiment of the present invention.

Fig. 7 is a diagram showing a cross section of a reactor in which a heating raw material delivery pipe is removed.

8 is a diagram showing a cross section of a horizontal partition plate provided with a heating raw material delivery pipe and a reforming raw material phase change pipe.

9 and 10 are diagrams showing cross-sections of a heating raw material delivery pipe and a reforming raw material phase change pipe.

Fig. 11 is a diagram showing a lower end portion of a reforming material phase change tube composed of double coils.

Fig. 12 is a plan view showing a horizontal insulation panel.

Explanation of reference signs

1: Reactor 2: First shell

3: Second shell 4: Horizontal isolation plate

5: Reforming section 6: Reforming catalyst

7: Combustion part 8: Combustion catalyst

9: Carbon monoxide removal unit 10: Heating raw material delivery pipe

11: Reforming raw material phase change tube 12: Heating raw material supply tube

13: Combustion product discharge pipe 14: Reforming raw material supply pipe

15: Reforming raw material discharge pipe 16: Preheating pipe

17: First Compartment 18: Second Compartment

19: heat transfer net 20: heat transfer pin

21: Flange 22: Buffer

23: Guide punching plate 24: Reformed gas discharge pipe

25: Heater

detailed description

Hereinafter, the reactor for producing hydrogen from carbon compounds according to the present invention will be described in more detail with reference to the drawings and specific examples. However, the following specific example or embodiment is only a reference for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various ways.

In addition, if not otherwise defined, all technical and scientific terms have the same meanings as commonly understood by some of those skilled in the art to which this invention belongs. The terms used in the description of the present invention are used to effectively describe specific examples and are not intended to limit the present invention.

In addition, the drawings described below are provided to fully convey the idea of the present invention to those skilled in the art. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms. In order to clarify the idea of the present invention, the drawings presented below may be enlarged and shown. In addition, the same reference numerals refer to the same constituent members throughout the specification.

In addition, regarding the singular forms used in the specification and claims, if there is no special indication in the text, the singular forms may also include the plural forms.

Regarding the reactor of the present invention, in FIG. 1 , one end of the reactor where the reforming raw material supply pipe is located is referred to as "upper end", and the other end opposite to the upper end is referred to as "lower end". This applies not only to the reactor, but also to the first housing, the second housing and the raw material delivery pipes with the same upper and lower ends as described above.

The term "concentric axis" used in the present invention refers to the axis connecting the center of the figure formed by the first shell, the second shell, and the raw material delivery pipe when the reactor is viewed from the direction in which the raw material flows into the reactor. . At this time, the center of the figure represents the center of gravity, and the first housing, the second housing and the raw material delivery pipe may have the same or different shapes. In addition, based on the direction perpendicular to the concentric axis, the direction opposite to the concentric axis from the first casing, the second casing, and the raw material conveying pipe indicates the inside, and the opposite direction indicates the outside.

The term "raw material" used in the present invention collectively refers to liquid or gaseous substances containing carbon compounds and water, the raw material is stored in a raw material tank, and the raw material may include a raw material supplied from the raw material tank to the heating raw material supply pipe. The "heating raw material" and the "reforming raw material" supplied from the raw material tank to the reforming raw material supply pipe. In addition, the heating raw material and the reforming raw material may have the same or different composition ratios, and the present invention is not limited thereto.

1 to 3 are sectional views of a hydrogen generating reactor according to an embodiment of the present invention. As shown in Figures 1 to 3, the reactor of the present invention has a first shell, a second shell, and a raw material delivery pipe of a concentric structure, and the first shell, the second shell, and the raw material delivery pipe are separated from each other. Open settings. In addition, it is further equipped with reforming raw material phase change tubes inside, so that the transportation of raw materials, phase change, combustion and reforming reactions can be carried out simultaneously in a single reactor.

To describe this in more detail, the reactor 1 is sealed by the first shell 2 and the horizontal partition plate 4, and the inside of the reactor 1 is equipped with the second shell 3, the heating raw material delivery pipe 10 and the reformed raw material Phase change tube 11. In addition, a heating raw material supply pipe 12, a combustion product discharge pipe 13, a reforming raw material supply pipe 14, and a reforming raw material discharge pipe 15 are provided on the horizontal partition plate so as to penetrate the horizontal partition plate 4, so that The reforming raw material or heating raw material is supplied inside, or the product is discharged from the inside of the reactor to the outside after the reaction.

The heating raw material supply pipe 12 is used to transport the heating raw material to the heating raw material delivery pipe 10. The heating raw material can be catalytically combusted by the combustion catalyst 8 laminated in the combustion part, and the product after the catalytic combustion is passed through the combustion chamber. The product discharge pipe 13 discharges to the outside of the reactor.

In addition, the reformed raw material can be supplied to the reformed raw material phase change pipe 11 through the reformed raw material supply pipe 14 independently from the heated raw material supplied to the heated raw material delivery pipe 10 . At this time, the reformed raw material phase change tube 11 can be in the shape of a coil, and the reformed raw material passing through the reformed raw material phase change tube 11 can be discharged to the outside of the reactor through the reformed raw material discharge pipe 15 and connected to the preheating pipe 16 to It is conveyed into the second compartment 18 at the lower end. The transported reformed raw material is supplied into the second compartment 18 and is converted into hydrogen-rich reformed gas while passing through the reforming catalyst 6 laminated inside the reforming section and discharged to the outside of the reactor.

In the present invention, the first casing 2 and the second casing 3 are made of metal and have concentric axes, and the first casing 2 and the second casing 3 can be arranged apart from each other and form a reforming part 5 . In addition, a reforming catalyst 6 may be filled in the reforming section. That is, as shown in FIG. 2 , the diameter of the first housing 2 is greater than that of the second housing 3 , and the first housing 2 may have a wall to completely isolate the side of the second housing from the outside. way around the shape. In addition, it may be provided so that the reforming catalyst 6 surrounds part of the side surfaces of the second casing.

The reforming part 5 is a part where the reforming raw material is converted into a hydrogen-containing reformed gas through a reforming reaction, and a part of the reforming part 5 can be filled with a reforming catalyst 6. In the reforming part 5 The upper end of the can be formed with a discharge port for discharging the reformed raw material.

In addition, the reactor 1 of the present invention may have a structure in which the lower end of the first shell is separated from the lower end of the second shell to form the second compartment 18 . The second compartment functions as a flow path that receives gaseous reformed fuel and delivers it to the reforming section.

The lower end of the reformer 5 may be provided with a guide punching plate 23 for easy filling of the reforming catalyst 6 . The guide punching plate 23 not only has the function of preventing the reforming catalyst 6 from falling or dispersing to the second compartment 18, but also has the function of separating the reforming part and the second compartment 18. Interval function. In addition, the guide punching plate 23 may have a mesh shape or a hollow shape so that the reforming raw material can easily flow into the reforming section, but the present invention is not limited thereto.

Preferably, the reforming catalyst 6 is filled from the lower end of the reforming section, and is spaced apart from the upper end of the reforming section with the guide punching plate 23 as a reference point. The distance between the reforming catalyst and the reforming section is not limited in the present invention. Preferably, the same distance as the lower end of the reforming section is maintained from the reforming section via a guide. More preferably, the The filling height of the reforming catalyst 6 is higher than that of the combustion catalyst 8 .

In the present invention, the heating raw material delivery pipe 10 may be located inside the second shell 3 and have the same concentric axis as the first shell 2 and the second shell 3 . In addition, the second housing and the heating raw material delivery pipe 10 may be separated from each other to form a combustion part 7 in which a combustion catalyst 8 may be filled.

The combustion part 7 is a part where the heating raw material is combusted through a catalytic combustion reaction and converted into heat energy and combustion products. A part of the combustion part 7 can be filled with a combustion catalyst and heated by the first compartment 17 at the lower end. The feedstock delivery pipe 10 is connected to receive the heated feedstock. In addition, the upper end in contact with the horizontal partition plate 4 may be connected to a combustion product discharge pipe 13 provided through the horizontal partition plate.

As shown in FIGS. 1 to 3 , the combustion catalyst 8 can be filled in different positions and amounts according to the temperature range and temperature gradient of the reformer. As an example, as shown in Figure 2, the filling amount of the combustion catalyst filled to the lower end of the combustion part can be gradually increased by reducing the diameter of the lower end of the heating raw material delivery pipe 10, or as shown in Figure 3, at the lower end of the heating raw material delivery pipe The combustion catalyst is further filled. This is used to compensate for the slow reforming reaction due to the failure of the temperature at the lower end of the reforming section to reach the required temperature. The filling position and filling height can be freely adjusted according to the temperature of the reforming section, and the present invention is not limited thereto.

In addition, a heat conduction net 19 may be further introduced into the combustion part 7 in addition to the combustion catalyst, so as to transfer heat generated by catalytic combustion reaction more efficiently. The heat conduction mesh can be formed by drawing and weaving metals with high thermal conductivity such as gold, silver, copper, aluminum, etc. into a fiber shape. This heat conduction net has the advantage that energy efficiency can be improved by rapidly discharging reaction products generated after catalytic combustion reactions to the outside and transferring heat that cannot be transferred in time to the reforming section.

The heat conduction net 19 may be located in a part of the combustion part that is not filled with a combustion catalyst, preferably, may be located in a part of the combustion part where the raw material phase change tube is located in a manner of surrounding the raw material phase change tube.

The heating raw material conveying pipe 10 plays a role in conveying the heating raw material entering from the outside to the combustion part, and the heating raw material conveying pipe 10 can be made of the same or different material as that of the first shell 2 or the second shell 3 form. In addition, the first compartment 17 may be formed by separating the lower end of the heating raw material delivery pipe and the lower end of the combustion part from the lower end of the second housing.

In the present invention, the reforming raw material phase change tube 11 is introduced to change the reforming raw material from gas phase to liquid phase, as shown in Fig. 1 to Fig. 3 and Fig. 9, the reforming raw material phase The variable pipe 11 can be configured to cover the outer surface of the heating material conveying pipe 10 in a coil shape.

In the present invention, a heater 25 can be further introduced to change the liquid-phase reforming raw material supplied to the reforming raw material phase-change tube 11 into a gas phase. The position of the heater 25 can be set at the upper end of the heating raw material delivery pipe 10, that is, the part where the heating raw material delivery pipe 10 and the heating raw material supply pipe 12 in the heating raw material delivery pipe 10 are connected. parts.

The heater 25 is disposed opposite to the surface of the reforming material phase change tube 11 wound around the heating material delivery tube 10 in a coil shape, so that heat can be efficiently supplied to the reforming material phase change tube 11 .

In the present invention, as shown in FIG. 1 to FIG. 3 and FIG. 12, the horizontal isolation plate 4 is used to isolate the first housing 2, the second housing 3 and the heating raw material delivery pipe 10 from the outside, and heat The raw material supply pipe 12 , the combustion product discharge pipe 13 , the reformed raw material supply pipe 14 and the reformed raw material discharge pipe 15 penetrate the horizontal partition plate 4 in a direction parallel to the concentric axis.

In the present invention, the horizontal separation plate 4 can be bonded through the first shell 2 and the flange 21 . Thereby, it is not necessary to adhere to the second housing 3 or the heating raw material delivery pipe 10 separately, and the assembly time can be shortened.

In the present invention, the heating supply pipe 12 can be connected to the heating raw material delivery pipe 10, the combustion product discharge pipe 13 can be connected to the combustion part 7, and the reforming raw material supply pipe 14 and the reforming raw material The discharge pipe 15 can be respectively connected with one end and the other end of the reformed raw material phase change pipe 11 . Since each tube is connected to the inside of the reactor, the heating raw material, the reforming raw material, and the product after the reaction can be guided to be efficiently supplied and discharged.

In addition, in order to more effectively adjust the temperature gradient of the reforming section according to the reforming raw material, the present invention connects the reforming raw material discharge pipe 15 to the preheating pipe 16, and the preheating pipe 16 can wrap the reforming pipe in a coil shape. The side (outer wall) of the part 5. It guides heat exchange by wrapping the preheating pipe 16 on the outer wall of a position where overheating is likely to occur in the reforming section, thereby making it possible to adjust the temperature gradient of the reforming section.

In the present invention, if the preheating pipe 16 can achieve the purpose of transferring heat by covering the side of the reforming part 5, then there is no limitation on the winding position, the number of turns, etc., and the preheating pipe 16 can also be It is wound directly in contact with the reforming part 5 or wound at a distance from the reforming part 5 .

In addition, as shown in FIG. 8 , the reforming section of the reactor 1 of the present invention may further include heat transfer pins 20 to further improve thermal efficiency by uniformly transferring heat in the reforming section as a whole. The present invention does not limit the position, shape, size, material, etc. of the heat transfer pin, but preferably, it can be arranged to connect the first housing and the second shell through the heat transfer pin in a way that does not hinder the flow of the reforming material. The second shell, the heat transfer pin can be made of the same material as that of the first shell and the second shell.

In the description of the above drawings, it is described that the reforming part 5 is formed by the space separated by the first casing and the second casing, and the interior is filled with the reforming catalyst 6, and the combustion part 7 passes through the second casing and the heating The raw material conveying pipe is formed with a separate space, and the inside is filled with the combustion catalyst 8, but the reforming section and the combustion section may be installed in exchange for positions. That is, the reforming part may be formed through the space separated by the second shell and the heating raw material delivery pipe, and located inside the reactor, and the combustion part may pass through the space between the first shell and the second shell formed, and connected to the outside of the reactor with the first shell as the boundary. This can be adjusted according to the type of carbon compound contained in the raw material, the type of reforming or combustion catalyst and supporting metal, the calorific value generated during combustion, etc., but the present invention is not limited thereto.

4 to 6 are cross-sectional views of a hydrogen generating reactor according to another embodiment of the present invention. In the following description, contents overlapping with those described in FIGS. 1 to 3 described above may be omitted.

As shown in FIGS. 4 to 6 , the reactor of the present invention is characterized in that it has a carbon monoxide removal section downstream of the reforming section, and the carbon monoxide removal section is used for reforming raw material supplied into the second compartment 18 and passed through After the reforming catalyst 6 laminated inside the reforming section 5 is simultaneously converted into hydrogen-rich reformed gas, contained carbon monoxide is removed. That is, it is characterized in that a carbon monoxide removal unit 9 that is phase-changed into a hydrogen-rich gas while the reformed raw material passes through the reforming catalyst is further included in the aforementioned reactor of FIGS. 1 to 3 The back-end removes carbon monoxide from the hydrogen-rich gas.

The carbon monoxide removal unit 9 includes a catalyst capable of removing carbon monoxide. The method for removing carbon monoxide is not particularly limited, preferably, a selective methanation reaction as shown in Reaction Formula 2 below can be implemented.

[Reaction 2]

CO+3H ₂ →CH ₄ +H ₂ O (heat generation, carbon monoxide methanation) (4)

CO ₂ +4H ₂ →CH ₄ +2H ₂ O (heat generation, methanation of carbon dioxide) (5)

CO ₂ +H ₂ →CO+H ₂ O (endothermic, reverse water gas shift reaction) (6)

In the above reaction formula 2, (4) represents a main reaction which methanates carbon monoxide and generates heat in the catalyst layer due to the reaction. In contrast, (5) and (6) represent side reactions, and in the case of (6), reverse water gas shift reactions can be produced by endothermic reactions. As a result, considerable heat of reaction can be generated in the carbon monoxide removal unit to increase the temperature of the catalyst layer, and at the same time, the side reactions (5) and (6) proceed, which may reduce the methanation conversion rate and selectivity of carbon monoxide.

In particular, as shown in FIGS. 10 and 11, the reforming material phase change tube 11 of the reactor including the carbon monoxide removal unit 9 is connected by a double coil, that is, a primary coil (inside) and a secondary coil (outside). The raw material phase change tube 11 has a shape in which the secondary coil surrounds the outer peripheral surface of the primary coil. At this time, the secondary coil, which is a part of the reforming raw material phase change tube 11, surrounds the heating raw material delivery pipe 10, and surrounds the inner surface of the second case 3 at a position facing the carbon monoxide removal unit 9 via the second case. , so as to be adjacent to the carbon monoxide removal unit 9 , whereby the heat generated by the carbon monoxide removal unit 9 can be transferred to the reforming raw material phase change tube 11 . That is, by locating the carbon monoxide removal unit 9 at a position similar in height to the portion where the reforming material phase change tube 11 is formed, the exothermic reaction generated by the latent heat of the reforming material phase change tube 11 can be selectively The methanation reaction has a certain temperature range, which is more advantageous in terms of ease of thermal gradient adjustment in the carbon monoxide removal section and stability of the reaction catalyst. This can maintain a constant temperature to prevent side reactions or catalyst damage caused by excessively high temperature of the reaction catalyst in the carbon monoxide removal unit 9 .

Preferably, the catalyst layer of the carbon monoxide removing part may have a temperature range of 200 to 300°C. When the above-mentioned range is satisfied, the methanation conversion efficiency of carbon monoxide is high, and the reaction catalyst in the carbon monoxide removal unit 9 can be stably used for a long period of time.

The reactor of Fig. 4 to Fig. 6 is the same as the aforementioned reactor of Fig. 1 to Fig. 3, the first casing 2 and the second casing 3 are made of metal material, and have concentric shafts, the first casing 2 and the second casing The bodies 3 are separated from each other to form a reforming part 5, and a discharge port for discharging the reformed raw material may be formed at the upper end of the reforming part 5. However, the figures show that the reforming catalyst 6 filled in the reforming unit 5 is located at the same position as the reforming unit 5 , but it is not limited thereto. It should be understood that the reforming catalyst 6 is filled in the reforming unit 5 . In addition, the end of the reformer 5 is connected to a carbon monoxide removal unit 9 .

In the present invention, the reforming catalyst 6 may comprise metals selected from gold, silver, iron, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, osmium, iridium, palladium, zirconium and lanthanum group metals more than one metal or their oxides. Specifically, the reforming catalyst 6 may include copper/ceria/zirconia composites, copper/zinc oxide/alumina composites, copper/ceria/alumina composites, and copper/zirconia/zirconia composites. Any one or more composites among aluminum composites.

In more detail, a composite synthesized by coprecipitation in a weight ratio of copper:zinc:aluminum oxide in a weight ratio of 3 to 5:3 to 5:1 to 3 may be used, but not limited thereto.

In the present invention, the combustion catalyst 8 may comprise metals selected from gold, silver, iron, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, osmium, iridium, palladium, zirconium and lanthanum group metals More than one metal or their oxides, preferably, can be selected from such as platinum (platinum), rhodium (rhodium), ruthenium (ruthenium), osmium (osmium), iridium (iridium) and palladium (palladium) etc. Platinum group elements, gold, silver, copper or a mixture of two or more of them.

In addition, the combustion catalyst 8 can be used by being supported in a carrier. The carrier may be one or more selected from the group consisting of alumina, α-alumina, zirconia (ZrO ₂ ), silica (silica; SiO ₂ ), or a mixture of two or more of them. In addition, physical properties such as particle shape and size of the carrier are not limited, and can be freely adjusted and used within the range not hindering the purpose of the present invention.

In addition, the combustion catalyst 8 can adjust the carrying amount of metal or metal oxide according to the temperature gradient of the reforming section. That is, when the temperature required for the reaction cannot be ensured by measuring the temperature of the reforming section after the catalytic combustion reaction, the loading capacity of the metal or metal oxide of the combustion catalyst can be increased, and by The lower temperature part is concentratedly filled with the combustion catalyst with a larger loading capacity to adjust the temperature required by the reforming reaction.

In the present invention, preferably, the carbon monoxide removal catalyst provided in the carbon monoxide removal unit 9 may contain a catalyst selected from gold, silver, iron, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, One or more metals of osmium, iridium, palladium, zirconium and lanthanum group metals or their oxides, but not limited thereto.

Hereinafter, the present invention will be described in more detail on the basis of fluid movement paths.

The heated feedstock is flowed by steps comprising:

a) conveying to the heating raw material delivery pipe 10 through the heating raw material supply pipe 12;

b) conveying from the heating raw material delivery pipe 10 to the combustion part 7 through the first compartment 17, reacting with the combustion catalyst 8 filled in the combustion part, and performing catalytic combustion; and

c) discharge the combustion product to the outside of the reactor 1 through the combustion product discharge pipe 13 after the catalytic combustion,

The reformate feedstock is flowed by steps comprising:

1) The reforming raw material is transported to the reforming raw material phase change pipe through the reforming raw material supply pipe, and then the phase changes to the gas phase;

2) The phase-changed reformed feedstock is transported to the second compartment through the reformed feedstock discharge pipe and the preheating pipe;

3) the reforming material supplied into the second compartment passes through the reforming section and reacts with the reforming catalyst filled in the reforming section; and

4) The product after the reaction is discharged to the outside of the reactor.

In addition, after the above step 3), the present invention may further include the step of passing through the carbon monoxide removal catalyst layer of the carbon monoxide removal unit at the end of the reforming unit and implementing a selective carbon monoxide removal reaction, and discharging the product after the carbon monoxide removal reaction to the outside of the reactor.

Specifically, first, the reformed raw material and the heated raw material are stored in a raw material tank (not shown), and each raw material may have the same or different composition. The raw material may contain 30 to 50% by weight of water and 50 to 70% by weight of carbon compounds, and the content of the carbon compounds can be freely changed according to the composition of the catalyst, the temperature gradient adjustment conditions of the reforming section, and the like.

In the present invention, the carbon compound may include alcohols, aldehydes, ketones, esters, etc. used in the field as organic synthetic materials, solvents, detergents, etc., and the alcohols may include ethanol and butanol other than methanol. Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde, and ketones such as acetone, methyl ethyl ketone, and pentanone can also be used as low-order alcohols. However, as the amount of carbon in the carbon compound increases, impurities such as carbon deposits due to reforming also increase, requiring precise adjustment of the operating temperature, so methanol can also be preferably used.

The water is usually used as a solvent, so that pure water can be used, and in order to save energy and increase the speed of the reaction, it can also go through a preheating process. In the present invention, as in steps a) and b), first, the heating fuel is delivered to the heating material delivery pipe 10 through the heating material supply pipe 12, and injected into the reactor 1, and the heating after injection The raw material can be delivered to the combustion part 7 via the heated raw material delivery pipe 10 , the first compartment 17 . That is, when the heating material passes through the heating material conveying pipe 10, it enters from the upper end to the lower end, and when passing through the first compartment 17 and passing through the combustion part 7, it can proceed from the lower end of the combustion part to the upper end.

The catalytic combustion is an oxidation reaction generated by heating fuel to recombine on the surface layer of the catalyst for adsorption, movement, and reaction, and has the advantage of being able to stably carry out the combustion reaction at a lower temperature due to lower active energy. In addition, due to the high combustion efficiency, the products after the reaction can be decomposed into non-toxic and odorless carbon dioxide and oxygen, so there is no need for secondary treatment such as wastewater treatment, and the increase in the thermalization rate of the combustion catalyst can be suppressed.

The heating fuel after the reaction is converted into carbon dioxide and water, and is discharged to the outside of the reactor through the combustion product discharge pipe 13 as in step c) above.

In the present invention, the reformed raw material may go through the following steps: first, 1) transport the reformed raw material to the raw material phase change pipe 11 through the reformed raw material supply pipe 14, and then, 2) change the phase of the reformed raw material to gas phase.

In the present invention, the reforming raw material may be supplied in a liquid phase, but it may also be supplied in a gas phase depending on the process and the structure of the reactor. More specifically, ① after supplying in a liquid phase, heat with the heater 25 to undergo a phase change inside the reactor, or ② perform a phase change before injecting into the reactor 1, and then supply to the reactor. Alternatively, although it is supplied to the reactor in a liquid phase, it is also possible to ③ supply the heating raw material to the reactor first, and receive heat by catalytic combustion to perform a phase change inside the reactor.

Preferably, the operation of the heater 25 is stopped to save energy in case the initial catalytic combustion reaction is carried out inside the reactor. This is because, as described above, the liquid-phase reforming catalyst is naturally gasified while passing through the raw material image converter 11 by continuously supplying heat to the reactor through the catalytic combustion reaction.

The reformed raw material after phase change is discharged to the outside of the reactor through the reformed raw material discharge pipe 15 , and then moves into the second compartment 18 through the preheating pipe 16 . At this time, as described above, the temperature gradient of the reforming section can be adjusted by winding the outside of the reforming section (5) in a coil shape with the preheating pipe 16 .

The reformed raw material moved into the second compartment can flow into the reforming section 5 via the guide punching plate 23, and perform the above-mentioned 4) step. In the reforming section, the reforming raw material can be converted into hydrogen, carbon dioxide, carbon monoxide, methane, and the like by the reforming catalyst 6 .

The reaction between the reforming raw material and the reforming catalyst 6 is carried out according to the following reaction formula 1. (2) of the reaction formula 1 is a direct decomposition reaction of methanol, which can be locally generated at high temperature.

[Reaction 1]

CH ₃ OH+H ₂ O=CO ₂ +3H ₂ ΔH=49.4kJ/mol (1)

CH ₃ OH=CO+2H ₂ ΔH=90.5kJ/mol (2)

CO+H ₂ O=CO ₂ +H ₂ ΔH=-41.1kJ/mol (3)

In the above 4) step, the temperature of the reforming catalyst laminated in the reforming section 5 may be 100°C to 300°C. When the temperature is lower than 100°C, the energy required for the reforming reaction cannot be fully obtained, so the conversion rate of carbon monoxide into hydrogen is greatly reduced. Carbon monoxide is removed, and thermal denaturation of the reforming catalyst may be sharply generated.

The product after the reforming reaction can be supplied to the fuel cell after removing carbon monoxide before being discharged to the outside through the reforming product gas discharge pipe 24 . At this time, preferably, the carbon monoxide concentration in the reformed gas from which carbon monoxide has been removed is 10 ppm or less.

Specifically, as a method for removing carbon monoxide contained in the product, the following method can be used: using a selective carbon monoxide oxidation reaction or a selective carbon monoxide methanation reaction that produces the reaction shown in Reaction Formula 3 or Reaction Formula 4, to make Carbon monoxide is converted to carbon dioxide or methanol.

[reaction formula 3]

CO+1/2O ₂ →CO ₂

The above reaction formula 3 is that air is supplied to supply oxygen to react with carbon monoxide, and an efficient carbon monoxide oxidation reaction is induced by uniform mixing of reformed gas and air. Therefore, the structure of the channel for carrying out the selective oxidation reaction is complicated and difficult to maintain.

Therefore, preferably, a carbon monoxide removal catalyst may be further included in the carbon monoxide removal unit, so that the selective carbon monoxide methanation reaction shown in Reaction Formula 4 can be implemented. However, the present invention is not limited to said selective carbon monoxide methanation reaction.

[Reaction 4]

CO+3H ₂ →CH ₄ +H ₂ O

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are merely examples to illustrate the present invention in detail, and the present invention is not limited thereto.

Example 1

The reforming part is filled with a copper (Cu) component catalyst made in the shape of a tray with an average diameter of 1.5mm as a reforming catalyst, and the combustion part is filled with platinum (Pt) made in the shape of a ceramic honeycomb. )catalyst. The preheating pipe uses a 1/8-inch pipe, and winds the outside of the reforming section into a coil shape at equal intervals according to the height, so that the vaporized reforming raw material is further preheated by the heat supplied by the reforming section on the outer wall.

As a raw material, a liquid fuel prepared by mixing 60% by weight of methanol and 40% by weight of distilled water on a mass basis was used. In addition, the same liquid fuel is used for the heating raw material and the reforming raw material. As a reforming raw material, the liquid fuel was supplied at 7.8 g/min. The heating raw material is supplied at a flow rate of 2.9g/min. For combustion, the Air is supplied at the same time as the flow rate, so as to adjust the maximum temperature of the catalyst layer in the reforming section to be kept below 280°C. At this time, the composition of the reformed product was analyzed with a gas chromatograph, and is described in Table 1. The composition in parentheses is the calculated value of the equilibrium composition at reaction temperature 250 degreeC. The methanol conversion rate calculated according to the carbon amount conservation formula reaches 96%, and the calculated hydrogen production flow rate is 0.52Nm ³ /h.

[Table 1]

Example 2

The reforming part is filled with a copper (Cu) component catalyst manufactured in the shape of a tray with an average diameter of 1.5 mm as a reforming catalyst, and the combustion part is filled with platinum (Cu) made in a ceramic honeycomb shape. Pt) catalyst. The preheating pipe uses a 1/8-inch pipe, and winds the outside of the reforming section into a coil shape at equal intervals according to the height, so that the vaporized reforming raw material is further preheated by the heat supplied by the reforming section on the outer wall. In addition, a catalyst composed of ruthenium (Ru) produced in a tray shape with an average diameter of 1.5 mm was filled in the carbon monoxide removal unit at the end of the reformer unit.

As a raw material, a liquid fuel prepared by mixing 60% by weight of methanol and 40% by weight of distilled water on a mass basis was used. In addition, the same liquid fuel is used for the heating raw material and the reforming raw material. As a reforming raw material, the liquid fuel was supplied at 7.8 g/min. The heating raw material is supplied at a flow rate of 2.9g/min. For combustion, the Air is supplied at the same time as the flow rate, so as to adjust the maximum temperature of the catalyst layer in the reforming section to be kept below 280°C. At this time, the composition of the reformed product was analyzed with a gas chromatograph and is listed in Table 2. The content of carbon monoxide is below 10ppm, the conversion rate of methanol calculated according to the carbon amount conservation formula reaches over 95%, and the calculated hydrogen production flow rate is 0.50Nm ³ /h.

[Table 2]

The preferred embodiments of the present invention have been described above, but the present invention can include various changes, changes and equivalents, and can be appropriately modified by making changes to the above-mentioned embodiments. Therefore, the above description does not limit the scope of the present invention determined based on the scope of the claims.

Claims (25)

1. a reactor, including: reforming section, the raw material comprising carbon compound and water by reformation generates hydrogeneous reformation Gas；And combustion section, by the described raw material of burning to reforming section supply heat, wherein,

It is disposed with heating feed line, the first housing and the second housing with concentric structure from interior,

Described reforming section is formed by the space that is separated by of the first housing and the second housing, and described combustion section is by the second housing and adds pyrogen The space that is separated by of material conveying tube is formed,

The inside of described combustion section includes the reformer feed phase transition tube heating raw material.

Reactor the most according to claim 1, wherein,

Described reactor includes: reforming section, being separated by space of described first housing and described second housing is filled with reformation and urges Agent；And combustion section, described second housing and being separated by space of described heating feed line are filled with combustion catalyst.

Reactor the most according to claim 1, wherein,

One end of described reforming section also includes carbon monoxide removal portion.

Reactor the most according to claim 3, it is characterised in that

It is provided with in the second housing at and adjoining position relative with described carbon monoxide removal portion across the second housing The reformer feed phase transition tube of side.

Reactor the most according to claim 3, wherein,

Described reactor includes the carbon monoxide removal portion being filled with carbon monoxide removal catalyst at the end of reforming section.

Reactor the most according to claim 1, wherein,

Heater or combustion catalyst is also included in the inside of described heating feed line.

Reactor the most according to claim 1, wherein,

The lower end of the lower end of described heating feed line and described second housing is spaced from each other and forms the first compartment, and described the The lower end of two housings is spaced from each other with the lower end of described first housing and forms the second compartment.

Reactor the most according to claim 1, wherein,

It is also equipped with described heating feed line, described first housing and described general in the upper end of described heating feed line The horizontal division board that second housing is isolated from the outside.

Reactor the most according to claim 8, wherein,

Described horizontal division board is set to add hot charge supply pipe, combustion products discharge pipe, reformer feed supply pipe and reform Raw material discharge pipe runs through described horizontal division board.

Reactor the most according to claim 9, wherein,

The described hot charge supply pipe that adds is connected with heating feed line, and described combustion products discharge pipe is connected with combustion section, Described reformer feed supply pipe and reformer feed discharge pipe are connected with one end and the other end of reformer feed phase transition tube respectively.

11. reactors according to claim 10, wherein,

Described reformer feed discharge pipe is connected with described second compartment.

12. reactors according to claim 9, wherein,

Described reformer feed discharge pipe is connected with preheating pipe, and described preheating pipe is coated with the outside of the first housing with coil shape Face.

13. reactors according to claim 1, wherein,

The part being filled with reforming catalyst in the lateral surface of described first housing is also equipped with more than one temperature sensor.

14. reactors according to claim 1, wherein,

The space being not filled by combustion catalyst in described combustion section is also equipped with thermal conductive network.

15. reactors according to claim 1, wherein,

Described reforming section is also equipped with more than one transfer pin of heat.

16. reactors according to claim 2, wherein,

Described combustion catalyst or reforming catalyst comprise selected from gold, silver, ferrum, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, More than one metal in osmium, iridium, palladium, zirconium and lanthanum race metal or their oxide.

17. reactors according to claim 16, wherein,

Described combustion catalyst comprise more than one the metal in platinum, rhodium, ruthenium, osmium, iridium, palladium, gold, silver and copper or they Oxide.

18. reactors according to claim 16, wherein,

Described reforming catalyst comprises selected from copper/cerium oxide/zirconia composite, copper/zinc oxide/alumina complex, copper/oxygen Change the complex that any one in cerium/alumina composite and copper/zirconium oxide/alumina composite is above.

19. reactors according to claim 5, wherein,

Described carbon monoxide removal catalyst comprise selected from gold, silver, ferrum, cobalt, nickel, copper, manganese, aluminum, zinc, titanium, hafnium, rhodium, ruthenium, osmium, More than one metal in iridium, palladium, zirconium and lanthanum race metal or their oxide.

20. according to the reactor described in any one in claim 1 to 19, wherein,

Described raw material is stored in head tank, and described raw material comprises and adds hot charge supply pipe to described from the supply of described head tank Add hot charge and from described head tank supply to described reformer feed supply pipe reformer feed.

21. 1 kinds of raw material reforming methods utilizing hydrogen-manufacturing reactor, it is the hydrogen manufacturing utilizing the reactor described in claim 20 Method, wherein,

Add hot charge to flow by comprising the following steps:

A) add hot charge and be delivered to heat in feed line by adding hot charge supply pipe；

B) be delivered to combustion section from described heating feed line by the first compartment, and be filled in described combustion section Combustion catalyst reacts and carries out catalysis burning；And

C) by combustion products discharge pipe, combustion products is expelled to outside reactor after catalysis burning,

Reformer feed flows by comprising the following steps:

1) reformer feed becomes gas phase after being delivered in reformer feed phase transition tube by reformer feed supply pipe mutually；

2) reformer feed of phase transformation is delivered in the second compartment by reformer feed discharge pipe and preheating pipe；

3) supply to the reformer feed in described second compartment by reforming section and with the reforming catalyst being filled in reforming section React；And

4) product after reaction being terminated is expelled to outside reactor.

The 22. raw material reforming methods utilizing hydrogen-manufacturing reactor according to claim 21, wherein,

Described heating fuel or fuel reforming comprise water and the carbon compound of 50 to 70 weight % of 30 to 50 weight %.

The 23. raw material reforming methods utilizing hydrogen-manufacturing reactor according to claim 21, wherein,

Described 3) in step, described reforming catalyst has the temperature range of 100 DEG C to 300 DEG C.

The 24. raw material reforming methods utilizing hydrogen-manufacturing reactor according to claim 21, wherein,

Described 3) after step, it is additionally included in the reforming section end carbon monoxide removal catalyst by carbon monoxide removal portion Layer also implements the selective step removing reaction.

The 25. raw material reforming methods utilizing hydrogen-manufacturing reactor according to claim 24, wherein,

Described 4) in step, described in state carbon monoxide removal catalyst layer there is the temperature range of 200 DEG C to 300 DEG C.