JP2003160306A - Hydrogen containing gas generator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen containing gas generator 100 capable of keeping a desulfurizing part 34, a reforming part 36, a converting part 38 and a selective oxidizing part 40 in a suitable temperature respectively without consuming surplus energy in a simple composition. <P>SOLUTION: A plurality of cylindrical bodies are assembled toward the diameter and the axis center I and on their axis center. The cylindrical spaces formed between a plurality of the cylindrical bodies are composed as each part such as 34, 36, 38, 40 and each flow path such as 2, 4, 6, 8, 10, 12, 14, 16, 20 connected to each part. The reforming part 36, the desulfurizing part 34, the converting part 38 and the selective oxidizing part 40 are arranged in the mentioned order along the axis center I of the cylindrical bodies. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a desulfurization treatment section for desulfurizing a hydrocarbon-based raw fuel gas and a desulfurization treatment gas heated by a heating section and supplied from the desulfurization treatment section by steam. A reforming processing part for reforming a reforming treatment gas containing hydrogen gas and carbon monoxide gas, and by converting the carbon monoxide gas in the reforming treatment gas into carbon dioxide gas And a selective oxidation treatment unit for selectively oxidizing the selective shift treatment gas to selectively oxidize carbon monoxide in the shift treatment gas. The present invention relates to a hydrogen-containing gas generator that discharges a selective oxidation treatment gas as a hydrogen-containing gas.

[0002]

2. Description of the Related Art A hydrogen-containing gas generator as described above is
Desulfurization treatment of hydrocarbon-based raw fuel gas in the desulfurization unit,
The desulfurization treatment gas is reformed with steam in the reforming treatment unit to a reforming treatment gas containing hydrogen gas and carbon monoxide gas,
The reforming treatment gas is transformed in the reforming treatment section into carbon dioxide gas by transforming the carbon monoxide gas in the reforming treatment gas into carbon dioxide gas, and the transformation treatment gas is transformed in the selective oxidation treatment section. The selective oxidation treatment is performed by selectively oxidizing carbon monoxide in the treatment gas to generate a hydrogen-rich hydrogen-containing gas having a low carbon monoxide concentration (for example, 10 ppm or less). , Used as a fuel gas for power generation reaction in a fuel cell.

During the operation of the hydrogen-containing gas generator thus constructed, the desulfurization treatment section, the reforming treatment section, the shift conversion treatment section and the selective oxidation treatment section are respectively operated at appropriate temperatures for desulfurization treatment ( Hereinafter, it may be referred to as a desulfurization treatment temperature), a temperature suitable for the reforming treatment (hereinafter, also referred to as a reforming treatment temperature), a temperature suitable for the shift treatment (hereinafter referred to as the shift treatment temperature) In some cases), it is necessary to maintain the temperature suitable for the selective oxidation treatment (hereinafter sometimes referred to as the selective oxidation treatment temperature). Incidentally, for example, the reforming treatment temperature is in the range of 600 to 700 ° C., the desulfurization treatment temperature is in the range of 200 to 350 ° C., and the shift treatment temperature is, for example, 15
The range of 0 to 300 ° C., the selective oxidation treatment temperature is 80 to 120
It is in the range of ° C.

Therefore, the conventional hydrogen-containing gas generator is
In order to operate the desulfurization treatment unit, the reforming treatment unit, the shift conversion treatment unit, and the selective oxidation treatment unit so as to maintain the desulfurization treatment temperature, the reforming treatment temperature, the shift treatment temperature, and the selective oxidation treatment temperature, for example, desulfurization Desulfurization treatment section heating means for heating the treatment section, shift treatment section heating means for heating the shift treatment section, shift treatment section cooling means for cooling the shift treatment section, and selective oxidation treatment section heating means for heating the selective oxidation treatment section And a selective oxidation treatment section cooling means for cooling the selective oxidation treatment section,
To maintain the desulfurization treatment part at the desulfurization treatment temperature, adjust the heating capacity of the desulfurization treatment part heating means, and to maintain the reforming treatment part at the reforming treatment temperature, change the heating capacity of the reforming treatment part heating means. The heating capacity of the shift treatment section heating means and the cooling capacity of the shift treatment section cooling means are adjusted so as to maintain the shift treatment section at the shift treatment temperature, and the selective oxidation treatment section is kept at the selective oxidation treatment temperature. As described above, the heating capacity of the selective oxidation treatment section heating means and the cooling capacity of the selective oxidation treatment section cooling means are adjusted.

[0005]

Therefore, in the conventional hydrogen-containing gas generator, the desulfurization treatment section, the reforming treatment section, the shift conversion treatment section and the selective oxidation treatment section are respectively provided with a desulfurization treatment temperature,
In order to maintain the reforming treatment temperature, the shift conversion treatment temperature, and the selective oxidation treatment temperature, the temperature of each of the desulfurization treatment unit, the reforming treatment unit, the shift treatment unit, and the selective oxidation treatment unit is controlled separately, which is complicated. Control was required and improvements were desired.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a desulfurization treatment section, a reforming treatment section, a shift treatment section and a selective oxidation treatment section with a simple structure. Another object of the present invention is to provide a hydrogen-containing gas generator capable of maintaining an appropriate temperature without consuming extra energy.

[0007]

Means for Solving the Problems [Structure 1] A hydrogen-containing gas generator according to the present invention has the following structure.
A plurality of tubular bodies are provided in a radial direction and an axial center and coaxially, and a tubular space formed between the plurality of tubular bodies is used as each of the parts and each flow path connected to each of the parts. Configured, along the axial direction of the tubular body, the modification processing unit,
The desulfurization treatment unit, the shift conversion treatment unit, and the selective oxidation treatment unit are arranged in the order described.

[Operation and Effect] That is, the inventors of the present invention
Among the reforming treatment temperature, the desulfurization treatment temperature, the shift treatment temperature and the selective oxidation treatment temperature, the reforming treatment temperature is the highest, the selective oxidation treatment temperature is the lowest, and the desulfurization treatment temperature and the shift treatment temperature are the same as the reforming treatment temperature. In view of the fact that the temperature is between the selective oxidation treatment temperature, an intensive study was conducted to simplify the structure of the hydrogen-containing gas generator. The reforming treatment section, the desulfurization treatment section, the shift conversion treatment section, and the selective oxidation treatment section are placed between the reforming treatment section that needs to be maintained at the highest temperature and the selective oxidation treatment section that is required to be maintained at the lowest temperature. In addition, the desulfurization processing section and the shift conversion processing section, which need to be maintained at a temperature between the temperature of the reforming processing section and the temperature of the selective oxidation processing section, are located, and adjacent ones can transfer heat. In the state where the reforming treatment section, the desulfurization treatment section, the shift conversion treatment section and the selective oxidation treatment section are provided in such a manner, the heat transfer state between adjacent ones and the selective oxidation treatment section and other tubular bodies are By appropriately setting the heat radiation state from the part to the outside, it is possible to control the reforming processing part to an appropriate temperature without consuming extra energy, and the other processing parts can be controlled individually without controlling the temperature. That it can be maintained at an appropriate temperature I found the door.

Further, in the hydrogen-containing gas generating apparatus of this structure, each processing section can be maintained at an appropriate temperature as described above, and each section and each flow path connected to each section have a plurality of cylinders. Since it is composed of a cylindrical space formed between the cylindrical bodies, it is possible to form a flat cylindrical flow path, which does not need to be specially configured by a pipe material or the like and can be made compact. Therefore, the heat exchange with the space adjacent to the tubular body can be favorably performed. Further, in the case of suppressing the heat radiation to the outside of each flow path or each part, it is sufficient to provide the heat insulating material so as to surround the flow path or the cylindrical body on the outside of the processing unit, so that the volume of the heat insulating material is small. Therefore, expansion of the device due to installation of heat insulating material can be suppressed.

[Structure 2] The hydrogen-containing gas generator according to the present invention has, in addition to the structure of the hydrogen-containing gas generator of Structure 1 described above, a modification in which the reforming gas flows. The space configured as a quality treatment gas flow channel and the space configured as a raw fuel gas flow channel through which the raw fuel gas flows are arranged adjacent to each other via the tubular body, and the reforming is performed. A first process gas heat exchange section for exchanging heat between the process gas and the raw fuel gas is provided.

[Effects] That is, the raw fuel gas supplied to the desulfurization processing section has a temperature close to room temperature, for example, and the difference from the temperature of the desulfurization processing section to which the raw fuel gas is supplied is large. The reforming treatment gas discharged from the quality treatment portion has a temperature close to the reforming treatment temperature, for example, and the temperature difference between the reforming treatment gas and the shift treatment portion to which the reforming treatment gas is supplied is large. Therefore, heat exchange is performed between the raw fuel gas supplied to the desulfurization processing section or the desulfurization processing section and the reforming processing gas discharged from the reforming processing section through the tubular body in the first processing gas heat exchange section. Thus, the temperature difference between the raw fuel gas and the desulfurization treatment temperature is preheated without consuming extra energy to preheat the raw fuel gas and without dissipating heat to cool the reforming treatment gas. Can be supplied to the desulfurization processing section in a reduced state, and at the same time, the reforming processing gas can be supplied to the conversion processing section in a state in which the temperature difference from the conversion processing temperature is reduced. Therefore, the respective temperatures of the desulfurization processing section and the shift conversion processing section can be maintained at more appropriate temperatures without consuming extra energy.

[Structure 3] The hydrogen-containing gas generator according to the present invention has, in addition to the structure of the hydrogen-containing gas generator of Structure 2 described above, a shift treatment in which the shift treatment gas flows. The space configured as a gas flow path and the space configured as an upstream side of the first process gas heat exchange section of the raw fuel gas flow path are arranged adjacent to each other via the tubular body. And a second process gas heat exchange section for exchanging heat between the shift process gas and the raw fuel gas.

[Effects] That is, the shift treatment gas discharged from the shift treatment unit has a temperature close to the shift treatment temperature, and the difference from the temperature of the selective oxidation treatment unit to which the shift treatment gas is supplied is different. On the other hand, the raw fuel gas before being supplied to the first process gas heat exchange section has a temperature close to room temperature, and the temperature difference between the raw fuel gas and the desulfurization processing section to which the raw fuel gas is supplied is large. Therefore, by exchanging heat between the shift process gas and the raw fuel gas discharged from the shift process unit through the tubular body in the second process gas heat exchange unit, extra energy is added to preheat the raw fuel gas. It is possible to supply the raw fuel gas to the desulfurization treatment section in a state where the temperature difference from the desulfurization treatment temperature is reduced by preheating the raw fuel gas without consuming the heat and without discarding heat for cooling the shift treatment gas. At the same time, the shift treatment gas can be supplied to the selective oxidation treatment unit in a state where the temperature difference from the selective oxidation treatment unit is reduced by cooling the shift treatment gas. Further, the raw fuel gas flowing through the raw fuel gas flow path is preheated by heat exchange with the shift treatment gas close to the shift treatment temperature in the second process gas heat exchange unit, and then the shift treatment is performed in the first process gas heat exchange unit. It can be preheated by heat exchange with the reforming treatment gas at a temperature higher than the temperature, and can be made to flow into the desulfurization treatment section at about the desulfurization treatment temperature, and the heat of the reforming treatment gas and the shift treatment gas can be effectively used. The raw fuel gas can be preheated. Therefore, the respective temperatures of the desulfurization treatment section and the selective oxidation treatment section can be maintained at more appropriate temperatures without consuming extra energy.

[Structure 4] The hydrogen-containing gas generator according to the present invention has the structure 2 or 3 described above.
In addition to the configuration of the hydrogen-containing gas generator, the space configured as an upstream side of the first process gas heat exchange section of the reforming process gas flow path, and a desulfurization process gas flow through which the desulfurization process gas flows. The space configured as a passage is disposed adjacent to the inside of the desulfurization treatment unit via the tubular body, and performs heat exchange between the reforming treatment gas and the desulfurization treatment gas. It is characterized in that a 3 process gas heat exchange section is provided.

[Effects] That is, the desulfurization treatment gas discharged from the desulfurization treatment portion has a temperature close to the desulfurization treatment temperature, and a difference from the temperature of the reforming treatment portion to which the desulfurization treatment gas is supplied is Large, while discharged from the reforming treatment section
The reforming treatment gas in a state before being supplied to the treatment gas heat exchange unit has a temperature close to the reforming treatment temperature, and has a large temperature difference from the shift treatment unit to which the reforming treatment gas is supplied. Therefore,
The desulfurization treatment gas discharged from the desulfurization treatment unit and the reforming treatment gas discharged from the reforming treatment unit are heat-exchanged with each other through the tubular body in the third treatment gas heat exchange unit, whereby the desulfurization treatment gas is removed. In a state where the temperature difference between the reforming treatment temperature and the desulfurization treatment gas is reduced by preheating the desulfurization treatment gas without consuming extra energy for preheating and without dissipating the heat for cooling the reforming treatment gas. In addition to being able to supply to the reforming treatment section, the reforming treatment gas can be supplied to the transformation treatment section in a state where the reforming treatment gas is cooled to reduce the temperature difference from the transformation treatment temperature. Moreover, since the temperature of the third process gas heat exchange section is within or near the range between the reforming treatment temperature and the desulfurization treatment temperature, the third process gas heat exchange section is subjected to the reforming process. By arranging the inside of the desulfurization processing section adjacent to the processing section, it becomes easy to maintain the temperatures of the desulfurization processing section and the third process gas heat exchange section at proper temperatures. Further, after the reforming treatment gas flowing through the reforming treatment gas channel is cooled by heat exchange with the desulfurization treatment gas close to the desulfurization treatment temperature in the third treatment gas heat exchange unit, the first treatment gas heat exchange unit It can be cooled by heat exchange with the raw fuel gas having a temperature lower than the desulfurization treatment temperature and can be made to flow into the shift conversion treatment section at about the shift treatment temperature, and the heat of the reforming treatment gas can be effectively used. Therefore, it is possible to maintain the respective temperatures of the reforming processing section, the shift conversion processing section, and the desulfurization processing section at more appropriate temperatures without consuming extra energy.

[Structure 5] The hydrogen-containing gas generator according to the present invention has the structures 1 to 4 as described in claim 5.
In addition to the configuration of the hydrogen-containing gas generator of any one of the above, the heating unit burns the fuel gas supplied from the fuel gas flow path using the combustion air supplied from the combustion air flow path, A space that is configured as a combustion unit that heats the reforming processing unit and discharges combustion exhaust gas to the combustion exhaust gas flow passage, and that is configured as the space configured as the combustion exhaust gas flow passage and a water flow passage to which water is supplied. And are arranged adjacent to each other via the tubular body, and heat the water flowing through the water flow path by heat exchange with the combustion exhaust gas flowing through the combustion exhaust gas flow path, and are supplied to the reforming processing unit. It is characterized in that a steam generator for generating steam is provided.

[Advantageous Effects] According to the hydrogen-containing gas generating apparatus of this configuration, the heating section is configured as a combustion section for burning the fuel gas, and the steam generating section is provided so that the steam is generated at the steam generating section. The generated water is heated by the combustion exhaust gas discharged from the combustion unit to generate the steam for the reforming process in the reforming unit, so that the steam for the reforming process can be generated without consuming extra energy. Can be generated.

[Structure 6] In addition to the structure of the hydrogen-containing gas generator of Structure 5, the hydrogen-containing gas generator according to the present invention has the structure of the hydrogen-containing gas generator and the fuel gas flow path for combustion as described in claim 6. The space configured as at least one of the air flow paths, the space configured as a downstream side of the steam generation unit of the combustion exhaust gas flow path, is arranged adjacent to each other through the tubular body, It is characterized in that a preheating unit for exchanging heat between at least one of the fuel gas and the combustion air and the combustion exhaust gas is provided.

[Effect] That is, since the temperature of the combustion exhaust gas discharged from the above-described steam generation unit is at least the temperature of the steam, the energy efficiency can be improved if the heat of the combustion exhaust gas can be effectively used. . Therefore,
According to the hydrogen-containing gas generation device of the present configuration, by providing the preheating section, at least one of the fuel gas and the combustion air supplied to the combustion section in the preheating section, and the combustion exhaust gas of the steam temperature or higher By preheating by the heat exchange of 1, the energy can be regenerated and the energy efficiency can be improved.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of a hydrogen-containing gas generator according to the present invention will be described with reference to FIGS. 1 is a vertical cross-sectional view of the hydrogen-containing gas generator, FIG. 2 is a cross-sectional view across the reforming treatment section of the hydrogen-containing gas generator, and FIG. 3 is a process flow of the hydrogen-containing gas generator. It is a block diagram showing.

As shown in FIGS. 1 and 3, the hydrogen-containing gas generator 100 includes a desulfurization processing unit 34 for desulfurizing a hydrocarbon-based raw fuel gas such as a natural gas-based city gas 13A.
The water vapor generation unit 28 that heats the water supplied to the water flow path 16 to generate water vapor, the combustion unit 45 as a heating unit, and the desulfurization treatment gas heated by the combustion unit 45 and supplied from the desulfurization treatment unit 34. A reforming treatment unit 36 that reforms a reforming treatment gas containing hydrogen gas and carbon monoxide gas using the steam generated in the steam generation unit 28, and a reforming treatment gas supplied from the reforming treatment unit 36. A conversion processing unit 38 that performs conversion processing by converting the carbon monoxide gas therein to carbon dioxide gas using steam, and the carbon monoxide gas in the conversion processing gas supplied from the conversion processing unit 38 is supplied from the outside. And a control unit (not shown) for controlling the operation of the hydrogen-containing gas generation apparatus 100, and the like. hand It has been made. The hydrogen-containing gas discharged from the selective oxidation processing unit 40 via the hydrogen-containing gas flow channel 10 has a low carbon monoxide gas concentration (for example, 1
It becomes a hydrogen-containing gas rich in hydrogen (0 ppm or less).

In the desulfurization processing section 34, for example, 200
At a desulfurization treatment temperature in the range of ˜350 ° C., a desulfurization catalyst hydrogenates a sulfur compound in the raw fuel gas supplied through the raw fuel gas channel 2, and the hydride is adsorbed on zinc oxide to desulfurize. To do. Incidentally, the desulfurization reaction in the desulfurization treatment section 34 is an exothermic reaction. The desulfurization treatment section 34 contains nickel-
A large number of granular molded bodies of hydrodesulfurization catalysts such as molybdenum type and chromium-molybdenum type are filled. Further, the desulfurization processing gas desulfurized in the desulfurization processing unit 34 is discharged to the desulfurization processing gas passage 4.

In the reforming unit 36, when desulfurization gas is supplied from the desulfurization gas passage 4 and natural gas whose main component is methane gas is the raw fuel gas, ruthenium, nickel, platinum, etc. are modified. Due to the catalytic action of the high quality catalyst, for example, at a reforming treatment temperature in the range of 600 to 700 ° C., methane gas and steam undergo a reforming reaction according to the following reaction formula [Chemical formula 1] to produce hydrogen gas and carbon monoxide gas. A reforming treatment gas containing the reforming treatment is performed. Incidentally, the reforming reaction in the reforming processing unit 36 is an endothermic reaction. Further, the reforming catalyst is held by a ceramic porous granular material, and the reforming processing unit 36 is used.
Are filled with a large number of the porous particles. Further, the reforming treatment gas which has been reformed by the reforming treatment section 36 is discharged to the reforming treatment gas passage 6.

[0024]

[Chemical 1]

The combustion section 45 is supplied with off-gas (an example of fuel gas) discharged from the fuel cell G through the off-gas flow passage 12, and is supplied with combustion air supplied to the combustion air flow passage 14. The off gas is burned in a premixed manner by the combustion air, and the reforming treatment unit 36 is heated by the combustion heat. Further, the combustion unit 45 is supplied with a mixture of the fuel gas, which is the city gas 13A, and the combustion air through the mixture passage 47, and burns the mixture at the time of startup or when the amount of off gas is insufficient. The reforming processing temperature of the reforming processing unit 36 is maintained at an appropriate temperature by adjusting the flow rate of the air-fuel mixture and the like. Further, the combustion unit 45 is provided with an igniter 46 that ignites the air-fuel mixture supplied at startup. Further, the combustion exhaust gas discharged from the combustion section 45 is discharged to the outside via the combustion exhaust gas passage 20.

In the shift treatment section 38, the carbon monoxide gas in the reforming treatment gas supplied from the reforming treatment gas passage 6 and the steam supplied from the water passage 16 of the steam generating portion 28, which will be described later, are supplied. , By the catalytic action of the iron oxide or copper-zinc conversion catalyst, for example, under the conversion treatment temperature in the range of 150 to 300 ° C., the conversion reaction is performed according to the following reaction formula [Chemical Formula 2] to convert carbon monoxide gas into carbon dioxide. Transform into gas. Incidentally, the shift reaction in the shift processing unit 38 is an exothermic reaction. The transformation processing section 5 is filled with a large number of granular molded bodies. Further, the shift processing gas subjected to shift processing in the shift processing unit 38 is discharged to the shift processing gas flow path 8.

[0027]

[Chemical 2]

In the selective oxidation treatment section 40, by the catalytic action of the noble metal selective oxidation catalyst such as platinum, ruthenium, rhodium, etc., for example, under the selective oxidation treatment temperature in the range of 80 to 120 ° C., the shift treatment gas passage. The carbon monoxide gas remaining in the conversion treatment gas supplied from 8 is selected by the following reaction formula [Chemical Formula 3] using the selective oxidation air externally supplied to the conversion treatment gas passage 8. Oxidize. Incidentally, the oxidation reaction in the selective oxidation treatment section 40 is an exothermic reaction. The selective oxidation catalyst is held in a ceramic porous granular body, and the selective oxidation treatment section 40 is filled with a large number of the porous granular bodies. Further, the hydrogen-containing gas that has been selectively oxidized by the selective oxidation processing unit 40 is discharged to the hydrogen-containing gas flow channel 10.

[0029]

[Chemical 3]

Then, the hydrogen-containing gas generated by the hydrogen-containing gas generator 100 is supplied to the fuel cell G through the hydrogen-containing gas passage 10. Although detailed description is omitted, the fuel cell G is a solid polymer type having a polymer membrane as an electrolyte, and includes hydrogen in a hydrogen-containing gas supplied from the hydrogen-containing gas generator 100 and a blower (not shown). ) Is configured to generate electricity by an electrochemical reaction with oxygen in the reaction air supplied from (1).

Next, the characteristic structure of the hydrogen-containing gas generator 100 will be described. Hydrogen-containing gas generator 100
As shown in FIG. 1 and FIG. 2, is configured in a multi-cylinder structure having a plurality of cylindrical bodies in the radial direction and the axial center I direction and coaxially, and the cylindrical shapes adjacent to each other in the radial direction. A plurality of cylindrical spaces formed between the bodies are used as the processing units 3 described above.
4, 36, 38, 40 and respective processing units 34, 36, 3
Each flow path 2, 4, 6, 8, 10, 1 connected to 8, 40
2, 14, 16, 20, the combustion unit 45, and the air-fuel mixture passage 47 connected to the combustion unit 45. Further, the hydrogen-containing gas generation device 100 configured as described above does not require a pipe material or the like for forming the flow path, and thus can be made compact. Further, each of the tubular spaces formed between the tubular bodies is partitioned in the direction of the axis I by appropriately providing a circular or ring-shaped partitioning member along a surface crossing the tubular bodies. Further, the tubular spaces adjacent to each other in the radial direction of the tubular body are appropriately provided by providing a gap between the tubular body and the partition member between the tubular spaces,
It is connected as a space to turn back in the gap.

Further, the hydrogen-containing gas generator 100 is
A reforming treatment unit 36, a desulfurization treatment unit 34, a shift conversion treatment unit 38, and a selective oxidation treatment unit 40 are arranged in this order from below along the axis I direction of the tubular body.

That is, in the hydrogen-containing gas generator 100, the reforming processing unit 36, which needs to be maintained at the highest temperature, is arranged directly above the combustion unit 45 arranged at the lowest position, and is maintained at the lowest temperature. Necessary selective oxidation treatment section 40
Are disposed on the uppermost side, and between the reforming treatment section 36 and the selective oxidation treatment section 40, it is necessary to maintain a temperature between the temperature of the reforming treatment section 36 and the temperature of the selective oxidation treatment section 40. The desulfurization processing section 34 and the shift conversion processing section 38 are arranged from the side of the reforming processing section 36 in the order of increasing temperature, and heat can be transferred between the adjacent processing sections via the tubular body. Further, a cylindrical space filled with a heat insulating material and configured as a heat insulating material portion 50 is formed on the outside of the reforming processing portion 36, and further, steam described later is arranged outside the heat insulating material portion 50. A tubular space filled with a heat insulating material and configured as a heat insulating material portion 52 is formed outside the generating unit 28. Further, outside the desulfurization processing section 34 and the shift conversion processing section 38, a cylindrical space is formed which is filled with a heat insulating material and configured as a heat insulating material section 54. The heat insulating parts 50, 52, 54 suppress the heat radiation of the processing parts and the like. Then, the heat transfer state between the respective processing units,
Since the heat radiation state above the selective oxidation processing unit 40 and the heat radiation suppression state of the heat insulating members 50, 52 and 54 are appropriately set, the combustion amount of the combustion unit 45 can be controlled without consuming extra energy. The temperature of the other processing units 34, 38, 40 can be maintained at an appropriate temperature only by adjusting and controlling the reforming processing unit 36 at an appropriate temperature. In addition, fins for promoting heat dissipation in order to promote heat dissipation of the selective oxidation processing unit 40, fans for generating an air flow between the fins, and the like may be provided.

The hydrogen-containing gas generator 100 heats water by heat exchange with the first to third process gas heat exchange parts 22, 24 and 26 for exchanging heat between the process gases and the combustion exhaust gas to generate steam. A steam generator 28 for generating,
A preheating unit 30 for preheating the off gas and the combustion air supplied to the combustion unit 45 by heat exchange with the combustion exhaust gas is provided, and the details of each unit will be described below.

The first process gas heat exchange section 22 has a cylindrical space formed as the reforming process gas flow path 6 and a cylindrical shape formed as the raw fuel gas flow path 2 outside the shift conversion processing section 38. And a space between the reforming process gas flowing through the reforming gas flow channel 6 and the raw fuel gas flowing through the raw fuel gas flow channel 2. Heat exchange. Then, by the first process gas heat exchange section 22,
A state in which the raw fuel gas can be supplied to the desulfurization treatment unit 34 in a state where the temperature difference from the desulfurization treatment temperature is reduced and the reforming treatment gas is cooled to reduce the temperature difference from the shift treatment temperature. Can be supplied to the transformation processing section 38.

The second process gas heat exchange section 24 has a heat insulating material section 5.
Outside of 4, a tubular space configured as the shift process gas flow channel 8 and a tubular space configured as an upstream side of the first process gas heat exchange section 22 of the raw fuel gas flow channel 2 are provided. Heat is exchanged between the shift process gas in which the shift process gas circulates and the raw fuel gas before flowing into the first process gas heat exchange unit 22, which are arranged adjacent to each other via the tubular body. The second process gas heat exchange unit 24 can supply the first process gas heat exchange unit 22 in a state where the raw fuel gas is preheated to reduce the temperature difference from the desulfurization process temperature, and the shift treatment is performed. The gas can be cooled and supplied to the selective oxidation treatment section 40 in a state where the temperature difference from the selective oxidation treatment temperature is reduced.

The third process gas heat exchange section 26 has a cylindrical space inside the desulfurization process section 34, which is configured as an upstream side of the first process gas heat exchange section 22 of the reforming process gas passage 6. A tubular space configured as the desulfurization treatment gas flow path 4 is arranged adjacent to each other via a tubular body, and the reforming treatment gas before flowing into the first treatment gas heat exchange section 22 is provided. Heat exchange is performed with the desulfurization treatment gas flowing through the desulfurization treatment gas passage 4. The third process gas heat exchange unit 26 can supply the desulfurization process gas to the reforming process unit 36 in a state where the desulfurization process gas is preheated to reduce the temperature difference from the reforming process temperature, and the reforming process gas is also supplied. Can be supplied to the shift conversion treatment unit 38 in a state where the temperature difference between the cooling temperature and the shift treatment temperature is reduced.

The water vapor generating section 28 is formed between the heat insulating material section 50 and the heat insulating material section 52 as a cylindrical space formed as the combustion exhaust gas flow path 20 and the water flow path 16 to which water is supplied. A cylindrical space is arranged adjacent to each other with a cylindrical body interposed therebetween, water is heated by heat exchange with combustion exhaust gas to generate steam, and the generated steam is desulfurized gas passage 4 Supply to. The steam generator 28 can generate steam to be supplied to the reforming processor 36 without consuming extra energy.

The preheating section 30 has a cylindrical space formed outside the heat insulating material section 52 as the off-gas flow path 12 and the combustion air flow path 14, and a downstream side of the steam generation section 28 in the combustion exhaust gas flow path 20. And a cylindrical space configured as described above are arranged adjacent to each other via a cylindrical body, and by heat exchange with the relatively high temperature combustion exhaust gas discharged from the steam generation unit 28, the combustion space 45 is formed. Preheat the supplied offgas and combustion air. The preheating unit 30 can regenerate the energy of the combustion exhaust gas and improve the energy efficiency.

Further, as shown in FIG. 2, the off-gas flow passage 12 and the combustion air flow passage 14 form one cylindrical space with two surfaces forming an angle of 120 ° at the axis I:
2 (off-gas channel 12: combustion air channel 14). Then, by forming both the off-gas flow channel 12 and the combustion air flow channel 14 in one cylindrical space adjacent to the combustion exhaust gas flow channel 20 in this way,
Both off-gas and combustion air can be better preheated with flue gas.

Further, the preheating section 30 includes the combustion exhaust gas passage 20.
A cylindrical space configured as a water flow path 16 through which water before being supplied to the steam generating unit 28 flows is disposed inside the inside of the steam generating unit 28, and the water supplied to the steam generating unit 28 is heated with combustion exhaust gas. It can be preheated to some extent by replacement.

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a hydrogen-containing gas generator.

FIG. 2 is a transverse cross-sectional view across the reforming processing unit of the hydrogen-containing gas generation device.

FIG. 3 is a block diagram showing a processing flow of a hydrogen-containing gas generator.

[Explanation of symbols]

2 Raw fuel gas flow path 4 Desulfurization gas passage 6 Reforming gas channel 8 Metamorphic processing gas flow path 10 Hydrogen-containing gas flow path 12 Off-gas flow path 14 Combustion air flow path 16 water channels 20 Combustion exhaust gas passage 22 First process gas heat exchange section 24 Second process gas heat exchange section 26 Third Process Gas Heat Exchange Section 28 Steam generator 30 preheating section 34 Desulfurization unit 36 Modification processing unit 38 Transformation Processing Department 40 Selective oxidation treatment section 45 Combustion part (heating part) 46 Igniter 47 mixture channel 50 Thermal insulation part 52 Thermal insulation 54 Thermal insulation part 100 Hydrogen-containing gas generator G fuel cell

Continued front page    F-term (reference) 4G040 EA03 EA06 EB01 EB03 EB12                       EB24 EB31 EB32 EB42 EB44                 5H027 AA02 BA01 BA16 BA17

Claims (6)

[Claims] 1. A desulfurization processing section for desulfurizing a hydrocarbon-based raw fuel gas, and a desulfurization processing gas heated by a heating section and supplied from the desulfurization processing section by means of steam as hydrogen gas and carbon monoxide. A reforming treatment part for reforming into a reforming treatment gas containing a gas, and a transformation treatment gas by transforming the carbon monoxide gas in the reforming treatment gas into carbon dioxide gas. And a selective oxidation treatment unit that selectively oxidizes the transformation treatment gas into the selective oxidation treatment gas by selectively oxidizing carbon monoxide in the transformation treatment gas, wherein the selective oxidation treatment gas is hydrogen. A hydrogen-containing gas generator for discharging as a contained gas, comprising a plurality of tubular bodies in a radial direction and an axial center and coaxially, and a tubular space formed between the plurality of tubular bodies. , Each part and each part It is configured as each flow path to be connected, and along the axial direction of the tubular body, the reforming treatment unit, the desulfurization treatment unit, the shift conversion treatment unit, and the selective oxidation treatment unit are arranged in the order described. A hydrogen-containing gas generation device characterized by being provided. 2. The tubular structure includes the space configured as a reformed gas flow channel through which the reformed gas flows and the space configured as a raw fuel gas flow channel through which the raw fuel gas flows. The hydrogen-containing gas generation device according to claim 1, further comprising a first process gas heat exchange section that is disposed adjacent to each other with the body interposed therebetween and that performs heat exchange between the reformed process gas and the raw fuel gas. . 3. The space configured as a shift processing gas flow path through which the shift processing gas flows, and the space configured as an upstream side of the first process gas heat exchange section of the raw fuel gas flow path. The hydrogen according to claim 2, further comprising a second process gas heat exchange section that is disposed adjacent to each other through the tubular body and that performs heat exchange between the shift process gas and the raw fuel gas. Inclusion gas generator. 4. The space configured as an upstream side of the first process gas heat exchange section of the reforming process gas channel, and the space configured as a desulfurization process gas channel through which the desulfurization process gas flows. And a third processing gas heat exchange section that is disposed inside the desulfurization processing section so as to be adjacent to each other with the tubular body interposed therebetween and that performs heat exchange between the reforming processing gas and the desulfurization processing gas. The hydrogen-containing gas generator according to claim 2 or 3, which is provided. 5. A combustion exhaust gas flow, wherein the heating section burns the fuel gas supplied from the fuel gas channel using the combustion air supplied from the combustion air channel to heat the reforming section. Is configured as a combustion unit that discharges combustion exhaust gas to a passage, and the space configured as the combustion exhaust gas flow passage and the space configured as a water flow passage to which water is supplied are adjacent to each other via the tubular body. And a water vapor generation unit that heats water flowing through the water flow passage by heat exchange with combustion exhaust gas flowing through the combustion exhaust gas flow passage to generate water vapor that is supplied to the reforming processing unit. The hydrogen-containing gas generator according to any one of claims 1 to 4. 6. The space configured as at least one of the fuel gas flow channel and the combustion air flow channel is a space configured downstream of the steam generation unit in the combustion exhaust gas flow channel, The hydrogen-containing gas according to claim 5, further comprising a preheating unit that is disposed adjacent to each other via a tubular body and that performs heat exchange between at least one of the fuel gas and the combustion air and the combustion exhaust gas. Generator.