JP2012176897A - Hydrogenation desulfurizer-integrated cylindrical steam reformer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogenation desulfurizer-integrated cylindrical steam reformer of a new structure wherein a hydrogenation desulfurizer is integrally attached to a cylindrical steam reformer.SOLUTION: The cylindrical steam reformer includes: a plurality of cylindrical bodies consisting of a first cylindrical body, a second cylindrical body and a third cylindrical body arranged concentrically at intervals in the order of increasing diameter; a burner disposed at a central part in the radial direction of the first cylindrical body; a reforming catalyst layer packed with a reforming catalyst in a gap partitioned in the radial direction by the first cylindrical body and the second cylindrical body; and a CO conversion catalyst layer, which is formed in a gap wherein a passage direction is inverted at one end in the axial direction with respect to the reforming catalyst layer, and a CO removal catalyst layer arranged in order in a gap between the second cylindrical body and the third cylindrical body in a position above the reforming catalyst layer. A heat insulator layer is disposed around the third cylindrical body at a part where the reforming catalyst layer is located in the cylindrical steam reformer. In the hydrogenation desulfurizer, a hydrogenation catalyst layer and a first adsorbent layer are disposed around the heat insulator layer, while a second adsorbent layer is disposed outside the cylindrical steam reformer.

Description

  The present invention relates to a hydrodesulfurizer integrated cylindrical steam reformer, more specifically, (1) a cylindrical steam reformer including a steam reformer for raw fuel, a CO converter and a CO remover, Or (2) a hydrodesulfurizer-integrated cylindrical steam reformer in which a hydrodesulfurizer for removing sulfur compounds in the raw fuel is integrated with a cylindrical steam reformer of the raw fuel .

  Hydrogen, which is a fuel of a fuel cell, for example, a polymer electrolyte fuel cell (PEFC), reforms raw fuel such as hydrocarbons, alcohols, ethers, or mixtures thereof by a steam reforming method or a partial oxidation method. It is manufactured by. Among these, the steam reforming method is a method for generating a hydrogen-rich reformed gas by reforming raw fuel with steam. In the steam reforming method, the raw fuel is converted into a hydrogen-rich reformed gas by a catalytic reaction in a steam reformer.

  In this specification, the fuel supplied to the steam reformer for reforming is referred to as “raw fuel”. Raw fuels include methane, ethane, propane, butane, pentane, city gas, LP gas (liquefied petroleum gas), natural gas, gasoline, kerosene, and other hydrocarbons (including mixtures of two or more hydrocarbons). Although used, alcohols such as methanol and ethers may be mixed therein.

  The steam reformer is generally composed of a combustion part (heating part) in which a combustion catalyst such as burner or platinum is arranged and a reforming part in which a reforming catalyst is arranged. In the reforming section, the raw fuel is reacted with steam to generate hydrogen-rich reformed gas. Since the reaction occurring in the reforming part involves a large endotherm, heat from the outside is necessary for the progress of the reaction, and a temperature of at least about 400 ° C. is necessary. Note that, for example, 680 ° C. is set during steady operation. For this reason, combustion heat (ΔH) generated by combustion of fuel gas with air in the combustion section is supplied to the reforming section. As the reforming catalyst, a Ni-based or Ru-based catalyst is used.

  FIG. 13 is a diagram for explaining an exemplary embodiment from raw fuel processing to PEFC or SOFC. Sulfur compounds such as mercaptans, sulfides, and thiophenes are added to city gas and LP gas (liquefied petroleum gas) as odorants for the purpose of leakage protection. In addition, gasoline, kerosene, and the like contain trace amounts of sulfur compounds that could not be desulfurized by a refining process from crude oil. Since the reforming catalyst is poisoned by these sulfur compounds and causes performance deterioration, it is introduced into a desulfurizer in order to remove those sulfur compounds. Next, steam from a steam generator provided separately is added, mixed and introduced into the steam reformer, and a hydrogen-rich reformed gas is produced by the reforming reaction of the raw fuel with steam in the steam reformer Is done.

The reforming reaction when the raw fuel is methane is represented by “CH ₄ + 2H ₂ O → CO ₂ + 4H ₂ ”. The reformed gas produced contains about 8-15% (capacity%, the same applies to the following%) of carbon monoxide (CO) as a by-product in addition to unreacted methane, unreacted water vapor, carbon dioxide. ing. For this reason, the reformed gas is subjected to a CO converter to remove by-product CO by converting it to carbon dioxide. In the CO converter, a catalyst such as a copper-zinc system or a platinum catalyst is used, but a temperature of about 200 to 250 ° C. is necessary to make the catalyst function. The reaction in the CO converter is represented by “CO + H ₂ O → CO ₂ + H ₂ ”, and unreacted residual steam is utilized in the steam reformer as the steam necessary for this reaction.

  The reformed gas exiting from the CO converter is composed of hydrogen and carbon dioxide gas except for unreacted methane and excess water vapor. Of these, hydrogen is an intended component, but the reformed gas obtained through the CO converter also does not completely remove CO, but contains a trace amount of CO. The CO content in the fuel hydrogen supplied to the PEFC is limited to about 100 ppm (capacity ppm, the same applies to the following ppm), and beyond this, the cell performance is significantly deteriorated, so the CO component can be formed before being introduced into the PEFC. As long as it is necessary to remove.

For this reason, the reformed gas is applied to the CO oxidizer after the CO concentration is lowered to about 1% or less by the CO converter. Here, an oxidant gas such as air is added, and CO is reduced to about 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less by an oxidation reaction of CO (CO + 1 / 2O ₂ = CO ₂ ). The operating temperature of the CO oxidizer is about 100 to 150 ° C. The purified hydrogen is supplied to the fuel electrode of PEFC.

  The above is an example in the case where the fuel cell is a PEFC. However, when the fuel cell is a SOFC, CO is also a fuel, so a CO converter and a CO remover are unnecessary, and a steam reformer Reformed gas containing hydrogen and CO produced in step 1, or reformed containing hydrogen, CO and methane (methane is reformed to hydrogen and CO by a metal such as Ni contained in the SOFC fuel electrode and support substrate) Gas is supplied to the SOFC anode.

  One of the technologies for removing sulfur compounds from raw fuel is a hydrodesulfurization method. In the hydrodesulfurization method, the adsorption capacity of sulfur is as large as [20 wt% -S (= hydrogenation catalyst → adsorption amount as sulfur content by the adsorbent)], so there is no need to replace the adsorbent even during long-term operation. It is possible to stably desulfurize by a chemical reaction.

  However, on the other hand, hydrogen is required for the desulfurization reaction in the hydrodesulfurization system. In addition, heating is necessary from the viewpoint of the operating temperature of the hydrogenation catalyst, and depending on the type of hydrogenation catalyst, a high temperature state of about 200 to 400 ° C. is necessary. FIG. 14 is a diagram for explaining the outline of a hydrodesulfurizer for carrying out the hydrodesulfurization method. 14 (a) to 14 (b), the hydrogenated catalyst layer and the container / heater heater that accommodates each adsorbent layer are shown in cross section.

<Normal configuration of hydrodesulfurizer>
As shown in FIG. 14 (a), a hydrodesulfurizer usually has a hydrogenation catalyst layer that converts a sulfur compound into hydrogen sulfide by hydrogen and an adsorbent layer that adsorbs the generated hydrogen sulfide in a container. Composed of a combination of seed layers. However, in a system that needs to remove a very small amount of sulfur, such as a raw fuel desulfurization system for producing fuel hydrogen such as PEFC, a leak occurs from the first adsorbent layer as shown in FIG. It is composed of three layers including a second adsorbent layer that lowers the slight amount of hydrogen sulfide to be further reduced to a low concentration.

Among them, hydrogenation catalysts are those that react organic hydrogen compounds in raw fuel with hydrogen to change the sulfur content in organic sulfur compounds to hydrogen sulfide. Ni-Mo and Co-Mo catalysts are used. Is done. Due to the hydrogenation catalyst, at a temperature of about 200 ° C. or more and about 200 to 400 ° C., the S content in the organic sulfur compound is replaced with hydrogen and separated, and the separated S content becomes hydrogen sulfide. The adsorbent is an adsorbent composed of ZnO that adsorbs and removes generated hydrogen sulfide. ZnO adsorbs the S content of hydrogen sulfide as ZnS by the reaction: ZnO + H ₂ S → ZnS + H ₂ O.

  Here, when the adsorbent layer has two stages of the first adsorbent layer and the second adsorbent layer, the second adsorbent layer should be an adsorbent that adsorbs residual hydrogen sulfide leaking from the first adsorbent layer. It is not limited to ZnO, and any metal oxide (for example, iron oxide, manganese oxide, etc.) or any other adsorbent having hydrogen sulfide adsorption ability can be used.

  The present invention provides such a hydrodesulfurizer as (1) a cylindrical steam reformer including a steam reformer for a raw fuel, a CO converter and a CO remover, or (2) a cylindrical steam reformer for a raw fuel. In order to keep the hydrodesulfurizer at its target temperature, it is compactly housed in the unit and requires no additional heating means such as an electric heater. An object of the present invention is to provide a hydrodesulfurization unit-integrated cylindrical steam reformer with a new structure that optimizes the installation location.

  JP-A No. 2000-34103, JP-A No. 2006-8459, JP-A No. 2006-111766, etc. have been proposed as those in which a desulfurization unit is integrated with a steam reformer. Is different in content.

JP 2000-34103 A JP 2006-8459 A JP 2006-111766 A

The present invention (1) is a cylindrical steam reformer integrated with a hydrodesulfurizer.
And the cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other in sequence, and a radial central portion of the first cylindrical body. And a reforming catalyst layer in which a reforming catalyst is filled in a gap defined in the radial direction by the first cylinder and the second cylinder,
(B) a CO conversion catalyst layer and a CO removal catalyst layer are sequentially provided in the gap between the second cylinder and the third cylinder above the reforming catalyst layer; and
(C) a cylindrical steam reformer formed by forming the CO shift catalyst layer in a gap in which the flow direction is reversed at one end in the axial direction with the reforming catalyst layer;
(D) In the cylindrical steam reformer, a heat insulating material layer is disposed on an outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrogenation catalyst layer is disposed on the outer periphery of the heat insulating material layer. A hydrodesulfurizer comprising a first adsorbent layer and a second adsorbent layer is arranged.
The present invention (1) is a reference invention.

The present invention (2) is a hydrodesulfurizer integrated cylindrical steam reformer.
And the cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other, and are coaxially arranged inside the first cylindrical body. A reformer in which a reforming catalyst is filled in a radial partition defined by the disposed radiation tube, a burner disposed in a radial center portion of the radiation tube, and the first and second cylinders With a catalyst layer,
(B) a CO conversion catalyst layer and a CO removal catalyst layer are sequentially provided in the gap between the second cylinder and the third cylinder above the reforming catalyst layer; and
(C) a cylindrical steam reformer formed by forming the CO shift catalyst layer in a gap in which the flow direction is reversed at one end in the axial direction with the reforming catalyst layer;
(D) In the cylindrical steam reformer, a heat insulating material layer is disposed on an outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrogenation catalyst layer is disposed on the outer periphery of the heat insulating material layer. A hydrodesulfurizer comprising a first adsorbent layer and a second adsorbent layer is arranged.
The present invention (2) is a reference invention.

The present invention (3) is a hydrodesulfurizer integrated cylindrical steam reformer.
And the cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other in sequence, and a radial central portion of the first cylindrical body. And a reforming catalyst layer in which a reforming catalyst is filled in a gap defined in the radial direction by the first cylinder and the second cylinder,
(B) a CO conversion catalyst layer and a CO removal catalyst layer are sequentially provided in the gap between the second cylinder and the third cylinder above the reforming catalyst layer; and
(C) a cylindrical steam reformer formed by forming the CO shift catalyst layer in a gap in which the flow direction is reversed at one end in the axial direction with the reforming catalyst layer;
(D) In the cylindrical steam reformer, a heat insulating material layer is disposed on an outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrodesulfurizer is disposed on the outer periphery of the heat insulating material layer. Of these, the hydrogenation catalyst layer and the first adsorbent layer are disposed, and the second adsorbent layer is disposed outside the cylindrical steam reformer.
The present invention (3) is an invention related to the divisional application.

The present invention (4) is a hydrodesulfurizer integrated cylindrical steam reformer.
And the cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other, and are coaxially arranged inside the first cylindrical body. A reformer in which a reforming catalyst is filled in a radial partition defined by the disposed radiation tube, a burner disposed in a radial center portion of the radiation tube, and the first and second cylinders With a catalyst layer,
(B) a CO conversion catalyst layer and a CO removal catalyst layer are sequentially provided in the gap between the second cylinder and the third cylinder above the reforming catalyst layer; and
(C) a cylindrical steam reformer formed by forming the CO shift catalyst layer in a gap in which the flow direction is reversed at one end in the axial direction with the reforming catalyst layer;
(D) In the cylindrical steam reformer, a heat insulating material layer is disposed on an outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrodesulfurizer is disposed on the outer periphery of the heat insulating material layer. Of these, the hydrogenation catalyst layer and the first adsorbent layer are disposed, and the second adsorbent layer is disposed outside the cylindrical steam reformer.
The present invention (4) relates to the divisional application.

  The hydrodesulfurizer-integrated cylindrical steam reformer of the present invention (1) to (4) is particularly applied as a hydrodesulfurizer-integrated cylindrical steam reformer for supplying fuel hydrogen to PEFC. be able to.

The present invention (5) is a hydrodesulfurizer integrated cylindrical steam reformer.
And the cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other in sequence, and a radial central portion of the first cylindrical body. A reforming catalyst layer in which a reforming catalyst is filled in a gap partitioned in a radial direction by the first cylinder and the second cylinder,
(B) A cylindrical steam reformer configured such that the reformed gas generated in the reforming catalyst layer is circulated in a gap defined in the radial direction by the second cylinder and the third cylinder. ,
(C) In the cylindrical steam reformer, a heat insulating material layer is disposed on the outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrogenation catalyst layer is disposed on the outer periphery of the heat insulating material layer. A hydrodesulfurizer comprising a first adsorbent layer and a second adsorbent layer is arranged.
The present invention (5) is a reference invention.

The present invention (6) is a hydrodesulfurizer integrated cylindrical steam reformer.
And the cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other, and are coaxially arranged inside the first cylindrical body. A reformer in which a reforming catalyst is filled in a radial partition defined by the disposed radiation tube, a burner disposed in a radial center portion of the radiation tube, and the first and second cylinders With a catalyst layer,
(B) A cylindrical steam reformer configured such that the reformed gas generated in the reforming catalyst layer is circulated in a gap defined in the radial direction by the second cylinder and the third cylinder. ,
(C) In the cylindrical steam reformer, a heat insulating material layer is disposed on the outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrogenation catalyst layer is disposed on the outer periphery of the heat insulating material layer. A hydrodesulfurizer comprising a first adsorbent layer and a second adsorbent layer is arranged.
The present invention (6) is a reference invention.

The present invention (7) is a hydrodesulfurizer integrated cylindrical steam reformer.
And the cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other in sequence, and a radial central portion of the first cylindrical body. A reforming catalyst layer in which a reforming catalyst is filled in a gap partitioned in a radial direction by the first cylinder and the second cylinder,
(B) A cylindrical steam reformer configured such that the reformed gas generated in the reforming catalyst layer is circulated in a gap defined in the radial direction by the second cylinder and the third cylinder. ,
(C) In the cylindrical steam reformer, a heat insulating material layer is disposed on the outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrodesulfurizer is disposed on the outer periphery of the heat insulating material layer. Of these, the hydrogenation catalyst layer and the first adsorbent layer are disposed, and the second adsorbent layer is disposed outside the cylindrical steam reformer.
The present invention (7) is an invention related to the divisional application.

The present invention (8) is a hydrodesulfurizer integrated cylindrical steam reformer.
And the cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other, and are coaxially arranged inside the first cylindrical body. A reformer in which a reforming catalyst is filled in a radial partition defined by the disposed radiation tube, a burner disposed in a radial center portion of the radiation tube, and the first and second cylinders With a catalyst layer,
(B) A cylindrical steam reformer configured such that the reformed gas generated in the reforming catalyst layer is circulated in a gap defined in the radial direction by the second cylinder and the third cylinder. ,
(C) In the cylindrical steam reformer, a heat insulating material layer is disposed on the outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrodesulfurizer is disposed on the outer periphery of the heat insulating material layer. Of these, the hydrogenation catalyst layer and the first adsorbent layer are disposed, and the second adsorbent layer is disposed outside the cylindrical steam reformer.
The present invention (8) relates to the divisional application.

  The hydrodesulfurizer-integrated cylindrical steam reformer according to the present invention (5) to (8) particularly includes a hydrodesulfurizer-integrated cylindrical steam reformer for supplying fuel hydrogen to the PEFC, and an SOFC. It can be applied as a hydrodesulfurizer-integrated cylindrical steam reformer for supplying fuel hydrogen and CO.

According to the present invention, the following effects (1) to (8) can be obtained.
(1) A hydrodesulfurizer with a large capacity is made compact by integrating it with a cylindrical steam reformer including a CO converter and a CO remover, and heating means such as a heater for the hydrodesulfurizer are not required. In addition, the hydrodesulfurizer can maintain the required target temperature.
(2) The hydrodesulfurizer with a larger capacity is made compact by integrating it with the cylindrical steam reformer, and the target required for the hydrodesulfurizer without the need for heating means such as a heater for the hydrodesulfurizer. Can be held at temperature.
(3) According to the above (1) to (2), the installation location of the steam reforming system including the hydrodesulfurizer can be optimized.
(4) Conventionally, the reforming catalyst layer having the highest temperature among the cylindrical steam reformers has a thick heat insulating material layer arranged on the outside to suppress heat dissipation, but hydrodesulfurization is performed on the portion of the heat insulating material layer. According to the structure of the present invention in which the apparatus is disposed, the enlargement of the scale of the combined apparatus is prevented when the hydrodesulfurizer is applied to the cylindrical steam reformer without adopting the structure of the present invention. be able to.
(5) According to the structure of the present invention, the hydrodesulfurization unit is located at the highest temperature among the reforming catalyst layers having the highest temperature in the cylindrical steam reformer. The target temperature of the hydrodesulfurizer can be maintained from a relatively early stage at the start. Moreover, from this, the fall of the reforming efficiency by arrange | positioning a hydrodesulfurizer can be prevented.
(6) The heating temperature of the hydrodesulfurizer can be adjusted by arranging a heat insulating material layer around the reforming catalyst layer and arranging a hydrodesulfurizer around it.
(7) In (6) above, the heating temperature of the hydrodesulfurizer can be appropriately controlled by selecting the thickness of the heat insulating material layer disposed around the reforming catalyst layer.
(8) Regarding the cylindrical steam reformer in which the hydrodesulfurizer according to the present invention is disposed, the cylindrical steam reformer in which the hydrodesulfurizer is not disposed without being affected by the layout of the hydrodesulfurizer; Equivalent performance can be demonstrated.

The present inventions (1) to (4) are directed to a cylindrical steam reformer including a CO converter and a CO remover, and the present inventions (5) to (8) are cylinders not including a CO converter and a CO remover. The target is a steam reformer. Below, the aspect of this invention (1)-(4) is demonstrated first, and then the aspect of this invention (5)-(8) is demonstrated. Matters common to the present inventions (1) to (8) are appropriately described in the sections of the aspects of the present invention (1) to (4).
Among the inventions (1) to (8), the inventions (1) to (2) and (5) to (6) are reference inventions, and the inventions (3) to (4) and (7) to (7) to (8) is an invention related to the divisional application.

<Aspects of the present invention (1) to (4)>
The present invention (1) and (3) are applied to a cylindrical steam reformer having no radiation cylinder, and are intended for a cylindrical steam reformer having the following structure (A). The hydrodesulfurizer-integrated cylindrical steam reformer of the present invention (1), (3) is applicable to any cylindrical steam reformer having the structure (A). it can.
(A) It arrange | positions in the radial direction center part of the several cylindrical body which consists of a 1st cylinder with a large diameter sequentially arrange | positioned at intervals, a 2nd cylinder, and a 3rd cylinder, and a 1st cylinder. And a reforming catalyst layer in which a reforming catalyst is filled in a gap defined in the radial direction by the first cylinder and the second cylinder, and a second cylinder at a position above the reforming catalyst layer. And a CO conversion catalyst layer and a CO removal catalyst layer sequentially in the gap between the third cylinders, and the CO conversion catalyst layer is placed in a gap in which the flow path direction is reversed at one end in the axial direction with respect to the reforming catalyst layer. A cylindrical steam reformer formed.

And this invention (1) arrange | positions a heat insulating material layer in the outer periphery in which the said reforming catalyst layer is located among the outer periphery of the said 3rd cylinder in the cylindrical steam reformer which has the structure of the said (A). The hydrogenation catalyst layer, the first adsorbent layer, and the second adsorbent layer of the hydrodesulfurizer are arranged on the outer periphery of the heat insulating material layer.
Further, in the present invention (3), in the cylindrical steam reformer having the structure of (A), a heat insulating material layer is disposed on the outer periphery of the third cylindrical body on which the reforming catalyst layer is located. The hydrogenation catalyst layer and the first adsorbent layer of the hydrodesulfurizer are arranged on the outer periphery of the heat insulating material layer, and the second adsorbent layer is arranged outside the cylindrical steam reformer. It is characterized by.

The present inventions (2) and (4) are applied to a cylindrical steam reformer having a radiation cylinder, and target a cylindrical steam reformer having the following structure (B). The hydrodesulfurizer integrated cylindrical steam reformer of the present invention (2), (4) can be applied to any cylindrical steam reformer having the structure (B). it can.
(B) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other, and are coaxially arranged inside the first cylindrical body. A reformer in which a reforming catalyst is filled in a radial partition defined by the disposed radiation tube, a burner disposed in a radial center portion of the radiation tube, and the first and second cylinders A catalyst layer, and a CO conversion catalyst layer and a CO removal catalyst layer are sequentially provided in the gap between the second cylinder and the third cylinder above the reforming catalyst layer. A cylindrical steam reformer formed in a gap formed by reversing the flow path direction at one end in the axial direction with the catalyst layer.

And this invention (2) arrange | positions a heat insulating material layer in the outer periphery where the said reforming catalyst layer is located among the outer periphery of the said 3rd cylinder in the cylindrical steam reformer which has the structure of the said (B). A hydrodesulfurizer comprising a hydrogenation catalyst layer, a first adsorbent layer and a second adsorbent layer is disposed on the outer periphery of the heat insulating material layer.
Further, in the present invention (4), in the cylindrical steam reformer having the structure (B), a heat insulating material layer is disposed on the outer periphery of the third cylindrical body on which the reforming catalyst layer is located. The hydrogenation catalyst layer and the first adsorbent layer of the hydrodesulfurizer are arranged on the outer periphery of the heat insulating material layer, and the second adsorbent layer is arranged outside the cylindrical steam reformer. It is characterized by.

  Hereinafter, the present invention will be described in order, including the structure of a cylindrical steam reformer to which the present invention is applied, and matters related to the structure.

<Aspect of Cylindrical Steam Reformer Having Structure (A)>
The structure (A) is a cylindrical steam reformer that does not include a radiation cylinder, and the present invention (1) and (3) can be applied to any structure that has the structure (A). FIG. 1 is a diagram for explaining an example thereof and shows a longitudinal section. 1 is used together with FIGS. 3 to 4 as a diagram for explaining a feature point of the present invention (1) described later.

  As shown in FIG. 1, the first cylindrical body 1, the second cylindrical body 2, and the third cylindrical body 3, whose diameters are sequentially increased, are arranged at the same center axis and spaced from each other. A fourth cylinder 4 having a diameter larger than that of the third cylinder 3 is disposed on the third cylinder 3. In FIG. 1, an alternate long and short dash line indicates the central axis, and an arrow (↑) indicates the direction of the central axis, that is, the axial direction.

  A burner 6 is disposed inside the first cylindrical body 1. The burner 6 is disposed at the central axis portion and attached via an upper lid / burner mounting base 7. A bottom plate 8 is disposed on the first cylindrical body 1, and the bottom plate 8 is configured in a disc shape with a diameter corresponding to the diameter of the first cylindrical body 1. The combustion gas in the burner 6 flows inside the first cylindrical body 1 as indicated by an arrow, and is spaced from the lower surface of the upper lid / burner mounting base 7 and the partition wall 61 (the partition wall 10 above the CO removal catalyst layer 36 described later). Is disposed between the upper end portion of the first cylindrical body 1 and a partition wall extending from the first cylindrical body 1 to the fourth cylindrical body 4), and is connected to the combustion exhaust gas discharge pipe 11. The combustion exhaust gas is discharged from here.

  Reference numeral 12 denotes a raw fuel supply pipe, to which desulfurized raw fuel is supplied. In the case of FIG. 13, it is the raw fuel that has passed through the desulfurizer. In the space between the first cylindrical body 1 and the second cylindrical body 2, a preheating layer 14 is provided in the upper part, and a reforming catalyst layer 16 is provided in the lower part following the preheating layer 14. A rod 15 such as a round bar or a square bar is spirally arranged inside the preheating layer 14, and a continuous spiral gas passage is formed inside the preheating layer 14. One or more bars 15 may be used. The reforming catalyst of the reforming catalyst layer 16 is supported at its lower end by a support 17 such as a perforated plate or a mesh body.

  The raw fuel supplied from the supply pipe 12 is mixed with water (steam) supplied from the water supply pipe 26, and then introduced into the reforming catalyst layer 16 through the preheating layer 14, and the raw fuel in the mixed gas. As it descends, it is reformed by steam. The reforming reaction in the reforming catalyst layer 16 is an endothermic reaction, and the reforming reaction proceeds by absorbing the combustion heat generated in the burner 6. That is, when the combustion gas in the burner 6 flows through and passes through the inside of the first cylinder 1, the heat of the combustion gas is absorbed by the reforming catalyst layer 16 through the first cylinder 1 and the reforming reaction is performed. Progresses.

  The lower end of the second cylindrical body 2 is spaced from the bottom plate 18 of the third cylindrical body 3, and the reformed gas flow path is between the second cylindrical body 2 and the third cylindrical body 3. 19 is constituted. The bottom plate 18 is formed in a disc shape with a diameter corresponding to the diameter of the third cylindrical body 3. The reformed gas is folded between the lower end of the second cylindrical body 2 and the bottom plate 18 of the third cylindrical body 3 and flows through the flow passage 19 formed between the second cylindrical body 2 and the third cylindrical body 3. A fourth cylindrical body 4 having a diameter larger than that of the third cylindrical body 3 is disposed above the third cylindrical body 3, and a CO shift catalyst layer 22 is provided between the second cylindrical body 2 and the fourth cylindrical body 4. ing. The reformed gas that has flowed through the flow passage 19 is supplied to the CO shift catalyst layer 22 through a large number of holes provided in the support plate 21.

  A plate body 20 is disposed between the upper end portion of the third cylindrical body 3 and the lower end portion of the fourth cylindrical body 4, and a support having a plurality of holes for gas distribution is provided on the plate body 20 at intervals. A plate 21 is arranged. The plate body 20 is a donut-shaped plate body because the portion corresponding to the diameter of the third cylinder 3 is occupied by the third cylinder 3. The support plate 21 is a donut-shaped support plate because a portion corresponding to the diameter of the second cylinder 2 is occupied by the second cylinder 2.

The CO shift catalyst layer 22 is disposed between the support plate 21 and a partition plate 23 (an upper portion of the CO shift catalyst layer 22) having a plurality of holes for gas flow. The partition plate 23 is a donut-shaped partition plate because a portion corresponding to the diameter of the second cylinder 2 is occupied by the second cylinder 2. The support plate 21 and the partition plate 23 may be formed of a mesh body made of metal or the like. In this case, the mesh body of the mesh body serves as a gas flow hole. As described above, the CO shift catalyst layer 22 is provided between the second cylinder 4 and the fourth cylinder 4. In the CO shift catalyst layer 22, the CO shift reaction “CO + H ₂ O → CO ₂ + H ₂ ”. As a result, CO in the reformed gas is transformed into carbon dioxide, and hydrogen is also generated.

  Here, the reformed gas exiting from the CO shift catalyst layer 22 is composed of hydrogen and carbon dioxide except for unreacted raw fuel (such as methane) and excess steam. Of these, hydrogen is used as fuel for the fuel cell, but the reformed gas obtained through the CO conversion catalyst layer 22 is not completely removed, but is less than about 1%, but still contains CO. Yes.

The allowable concentration of CO in the hydrogen supplied to the PEFC is about 10 ppm (ppm = capacity ppm, the same applies hereinafter), and battery performance is significantly deteriorated when exceeding this. Therefore, the reformed gas is supplied to the CO removal catalyst layer 36 after the CO concentration is lowered to about 1% or less by the CO shift catalyst layer 22. In the CO removal catalyst layer 36, an oxidant gas is added, and CO is changed to CO ₂ by a selective oxidation reaction of CO to remove CO, and the CO concentration is reduced to 10 ppm or less, or 5 ppm or less. As the oxidant gas, air, oxygen-enriched air, oxygen, or the like is used. However, since it is usually air, it is hereinafter referred to as air.

  Above the partition plate 23, a partition plate 51 having one communication hole 52 is provided at an interval, and CO removal air is supplied to the space between the partition plate 23 and the partition plate 51 through the air supply pipe 30. Is done. By setting the number of communication holes 52 to one with a predetermined hole diameter, a predetermined passing speed is obtained when the reformed gas and the CO removal air pass through the communication holes 52, and the reformed gas and CO removal air can be mixed well. In other words, the reformed gas and the CO removal air coming out of the CO converter are assembled at the location of the communication hole 52, and then supplied and dispersed in the CO removal catalyst layer.

  The CO removal catalyst layer 36 is disposed at intervals between the second cylinder 2, the cylinder 37 having a larger diameter, and the lower part and the upper part between the second cylinder 2 and the cylinder 37, respectively. It is arranged in a space between a support plate 34 having a plurality of holes 35 and a partition plate 38 having a plurality of holes 39 for gas flow. The support plate 34 and the partition plate 38 are donut-shaped plates because the portion corresponding to the diameter of the second cylinder 2 is occupied by the second cylinder 2.

  Further, a partition plate 54 having a single reformed gas flow hole 55 is arranged at a predetermined interval above the partition plate 51 having the reformed gas flow hole 52, and the partition plate 54 is connected to the upper portion of the partition plate 54. The CO removal catalyst layer 36 is disposed so as to be spaced from each other.

  The reformed gas circulation holes 52 of the partition plate 51 and the reformed gas circulation holes 55 of the partition plate 54 are arranged so as to be opposed to each other in the circumferential direction, that is, on the opposite side in the circumferential direction. FIG. 1 shows a case where the reformed gas circulation holes 52 and the reformed gas circulation holes 55 are arranged at positions 180 ° opposite to each other in the circumferential direction. The position opposite to the circumferential direction is most preferably a position on the opposite side of 180 ° in the circumferential direction, but may be a position shifted within ± 10 °.

  While the air supplied through the air supply pipe 30 is mixed with the CO-modified reformed gas flowing out from the partition plate 23 having a plurality of gas outlet holes 60 arranged at the upper part of the CO-converting catalyst layer 22, It flows into the gap between the partition plate 51 and the partition plate 54 through the reformed gas flow hole 52 of the partition plate 51. The air and the CO-modified reformed gas reach the reformed gas circulation hole 55 of the partition plate 54 while being further mixed in the gap between the partition plate 51 and the partition plate 54, and pass through the reformed gas circulation hole 55. Then, it flows into the gap between the partition plate 54 and the CO removal catalyst layer 22.

  That is, since the reformed gas circulation hole 55 is disposed on the opposite side in the circumferential direction with respect to the reformed gas circulation hole 52, the reformed gas having undergone air and CO conversion is separated from the partition plate 51 and the partition plate 54. The gas flows from the reformed gas circulation hole 52 toward the reformed gas circulation hole 55 while mixing in the gap between the two. The mixed gas of the air and the CO-modified reformed gas that has flowed into the gap between the partition plate 54 and the CO removal catalyst layer 36 flows into the CO removal catalyst layer 36 from the plurality of holes 35 of the support plate 34.

  In addition, although the direction which has this has the partition plate 51, the mixing with air and reformed gas is promoted more, but since it is not essential, it may not be necessary. Further, when the partition plate 51 is disposed, an air discharge opening of the air supply pipe 30 may be provided between the partition plate 51 and the partition plate 54.

The CO removal catalyst layer 36 is filled with a CO removal catalyst (also referred to as a PROX catalyst). The CO removal reaction is performed by the PROX catalyst, that is, CO is removed by changing CO to CO ₂ by a selective oxidation reaction of CO. Reduce the CO concentration to a few ppm level. The reformed gas from which CO has been removed is discharged from a plurality of holes 39 provided in the partition plate 38, and taken out from the reformed gas take-out pipe 40 through the gap between the partition plate 38 and the partition wall 10.

  Reference numeral 61 denotes a partition wall that is disposed at a distance from the partition wall 10 above the CO removal catalyst layer 36 and extends from the upper end of the first cylinder 1 to the fourth cylinder 4. The partition wall 61 is a donut-shaped plate body because a combustion chamber formed by the burner 6 is formed in a portion corresponding to the diameter of the first cylindrical body 1. Note that the gap between the partition wall 10 and the partition wall 61 is connected to the preheating layer 14. Since the reformed gas take-out pipe 40 is provided through the partition wall 10, the partition wall 61, and the upper lid / burner mounting base 7, the reformed gas is taken out from above.

<Mode of Cylindrical Steam Reformer with Structure (B)>
The structure (B) is a cylindrical steam reformer provided with a radiation cylinder, and the present inventions (2) and (4) are applicable to any structure provided with the structure (B). The structure (A) differs from the structure (A) only in that a radiation cylinder is provided and a structure related thereto is provided. Therefore, here, the radiation cylinder and the structure related thereto will be described. FIG. 2 is a diagram for explaining an example thereof and shows a longitudinal section. 2 is used together with FIGS. 3 to 4 as a diagram for explaining a feature point of the present invention (2) described later.

  As shown in FIG. 2, a cylindrical heat transfer partition wall, that is, a radiation cylinder 5 having a diameter smaller than that of the first cylinder 1 is arranged on the inner side of the first cylinder 1. A burner 6 is arranged on the side. The burner 6 is disposed at the central axis portion and attached via an upper lid / burner mounting base 7. The radiation cylinder 5 is disposed with a gap between the lower end thereof and the bottom plate 8 of the first cylinder 1, the gap formed with this gap, and the radiation cylinder 5 and the first cylinder 1 connected to the gap. And an air gap between them forms an exhaust passage 9 for the combustion gas from the burner 6.

  The bottom plate 8 is formed in a disc shape with a diameter corresponding to the diameter of the first cylindrical body 1. The exhaust passage 9 is disposed at an upper portion of the exhaust passage 9 at a distance from the upper lid of the exhaust passage 9 (the lower surface of the upper lid / burner mounting base 7) and the partition wall 61 (the partition wall 10 above the CO removal catalyst layer 36 described later). The exhaust gas exhaust pipe 11 is connected to the combustion exhaust gas exhaust pipe 11 through a gap between the upper end of one cylindrical body 1 and a partition wall extending from the upper end of the first cylindrical body 4 to the fourth cylindrical body 4. That is, when the combustion gas in the burner 6 passes through the exhaust passage 9 between the radiation cylinder 5 and the first cylindrical body 1, the heat of the combustion gas is passed through the first cylindrical body 1 through the reforming catalyst layer. 16 is absorbed and the reforming reaction proceeds.

  The partition wall 61 is a donut-shaped plate body because the combustion chamber, the radiant cylinder 5, and the exhaust gas passage 9 for the combustion exhaust gas are disposed in a portion corresponding to the diameter of the first cylindrical body 1. A gap between the partition wall 10 and the partition wall 61 is connected to the preheating layer 14.

  The structure other than that having the radiation cylinder 5 and having a structure related thereto is the same as the structure of the above-mentioned (A).

<Aspects of the present invention (1) to (2)>
In the present invention (1), a hydrodesulfurizer is incorporated into the cylindrical steam reformer having the above-described structure (A) as indicated by reference numeral 100 in FIG. That is, in the hydrodesulfurizer 100, the heat insulating material layer 101 is disposed on the outer periphery of the third cylinder 3 in the cylindrical steam reformer on the outer periphery where the reforming catalyst layer 16 is located. It is arranged on the outer periphery.

  In the present invention (2), a hydrodesulfurizer is incorporated into the cylindrical steam reformer having the above-described structure (B) as indicated by reference numeral 100 in FIG. That is, in the hydrodesulfurizer 100, the heat insulating material layer 101 is disposed on the outer periphery of the third cylinder 3 in the cylindrical steam reformer on the outer periphery where the reforming catalyst layer 16 is located. It is arranged on the outer periphery.

  3-4 is the figure which extracted and showed the part of the heat insulating material layer 101 and the hydrodesulfurizer 100 in FIGS. 1-2. 3 is a sectional view, and FIG. 4 is a perspective view thereof. As shown in FIGS. 3 to 4, the hydrodesulfurizer incorporated in the cylindrical steam reformer is cylindrical, and the raw fuel supply unit S1, the hydrogenation catalyst layer X, The first adsorbent layer Y, the second adsorbent layer Z, and the desulfurized raw fuel discharge part S2 are configured.

  S1 is a space for uniformly supplying the raw fuel mixed with hydrogen to the hydrogenation catalyst layer X, and S2 is a space for collecting the desulfurized raw fuel and leading it to the outlet pipe 114. It is referred to as a part or a raw fuel supply part, a discharge part or a desulfurized raw fuel discharge part.

  The heat insulating material layer 101 is between the outer periphery of the portion where the reforming catalyst layer is located in the third cylinder 3 and the inner periphery of the hydrogenation catalyst layer X, the first adsorbent layer Y, and the second adsorbent layer Z. Deploy. In addition, you may arrange | position the heat insulating material layer 101 also between the outer periphery of the 3rd cylinder 3, and supply part S1, and between the outer periphery of the 3rd cylinder 3, and the inner periphery of discharge part S2. 102 is an inner cylinder of the hydrodesulfurizer in contact with the heat insulating material layer 101, 105 is an outer cylinder surrounding the hydrogenation catalyst layer X, 106 is a discharge of the first adsorbent layer Y, the second adsorbent layer Z, and desulfurized raw fuel It is an outer cylinder surrounding part S2.

  The raw fuel supply unit S <b> 1 includes the outer periphery and the lower end plate 103, the cylindrical partition wall 104, and the porous plate 108 of the third cylinder 3. Among them, a raw fuel introduction pipe 112 mixed with hydrogen is arranged in the plate body 103. Hydrogen is mixed with the raw fuel flowing through the introduction pipe 112 through the hydrogen supply pipe 113. The desulfurized raw fuel discharge part S <b> 2 includes the outer periphery of the third cylinder 3, the upper lid 107, the cylindrical partition wall 106, and the porous plate 111. Although the outer cylinder 105 surrounding the hydrogenation catalyst layer X is inclined, a structure without an inclination may be used like the outer cylinder 106.

  A porous plate 108 is disposed between the raw fuel supply unit S1 and the hydrogenation catalyst layer X, a porous plate 109 is disposed between the hydrogenation catalyst layer X and the first adsorbent layer Y, and the first adsorbent. The porous plate 110 is disposed between the layer Y and the second adsorbent layer Z, the porous plate 111 is disposed at the upper end portion of the second adsorbent layer Z, and the upper lid 107 is placed at an interval above the porous plate 111. Deploy. The perforated plates 108, 109, and 110 serve to partition each layer and distribute and distribute the raw fuel.

  Among them, a desulfurized raw fuel outlet pipe 114 is disposed on the upper lid 107. As described above, the hydrogen supply pipe 113 is arranged in the raw fuel introduction pipe 112, and hydrogen for supplying the sulfur compound in the raw fuel to hydrogen sulfide is supplied by the hydrogenation catalyst layer X. As the supply hydrogen, after the hydrogen production in the cylindrical steam reformer is started, the hydrogen produced in the cylindrical steam reformer can be used.

  The raw fuel containing hydrogen sulfide generated in the hydrogenation catalyst layer X flows into the first adsorbent through the porous plate 109. In the first adsorbent, hydrogen sulfide in the raw fuel is adsorbed and removed. The raw fuel that has passed through the first adsorbent flows into the second adsorbent through the perforated plate 110. The second adsorbent adsorbs and removes a slight amount of hydrogen sulfide leaking from the first adsorbent, thereby reducing the hydrogen sulfide to a lower concentration.

<Reason for disposing the heat insulating material layer 101>
Here, in the hydrodesulfurizer integrated cylindrical steam reformer of the present invention, the hydrodesulfurizer 100 is disposed on the outer periphery of the third cylinder 3 via the heat insulating material layer 101, that is, the third cylinder. It is essential to arrange the heat insulating material layer 101 between the outer periphery of the body 3 and the hydrodesulfurizer 100. As such, the arrangement of the heat insulating material layer 101 is an important configuration in the present invention. Hereinafter, the reason will be described based on actual measurement examples.

  FIG. 5 shows each part in the steady operation in the case where the hydrodesulfurizer is arranged “with the heat insulating material layer 101 interposed” on the outer periphery of the third cylinder 3 on the outer periphery where the reforming catalyst layer 16 is located. It is the figure which showed the measured value of the temperature of. In this actual measurement example, in FIG. 5, glass wool [thermal conductivity: 0.03 W / mK (400 ° C.)] was disposed as a heat insulating material layer 101 with a thickness of 5 mm.

  As shown in FIG. 5, when the heat insulating material layer 101 is arranged, 214.6 ° C. at the inlet portion of the hydrogenation catalyst layer, 352.0 ° C. inside the inlet portion of the first adsorbent layer, and 309. Of the inlet portion of the second adsorbent layer, 58.6 ° C. shows 398.6 ° C. on the inside and 342.3 ° C. on the outside. FIG. 5 also shows measured temperatures at two locations, upper and lower, in the reforming catalyst layer 16 where the hydrodesulfurizer is located.

  As described above, when the hydrodesulfurizer is arranged “with the heat insulating material layer 101 interposed” on the outer periphery of the third cylinder 3 in the cylindrical steam reformer on the outer periphery where the reforming catalyst layer 16 is located. In the hydrodesulfurizer, any of the hydrogenation catalyst layer, the first adsorbent layer, and the second adsorbent layer has a temperature within the operating temperature (about 200 to 400 ° C.), and fully exhibits its desulfurization performance. Can be made.

  In the present invention, the kind of the heat insulating material is not particularly limited, and appropriate materials such as glass wool (glass cotton), slag wool, magnesium carbonate powder, magnesium oxide powder, and other various refractories can be used. And the heating temperature of the hydrodesulfurizer arrange | positioned around it can be appropriately controlled by selecting the thickness of these heat insulating materials.

<Aspects of the present invention (3) to (4)>
The present invention (3) is a cylindrical steam reformer having the structure of (A) described above, and in the cylindrical steam reformer, heat insulation is provided on the outer periphery of the third cylindrical body where the reforming catalyst layer is located. The material layer 101 is arranged, the hydrogenation catalyst layer and the first adsorbent layer of the hydrodesulfurizer are arranged on the outer periphery of the heat insulating material layer 101, and the second adsorbent layer is disposed outside the cylindrical steam reformer. It is characterized by being arranged.
The aspect of the present invention (3) is an aspect of the invention related to the divisional application.

The present invention (4) is the cylindrical steam reformer having the structure of (B) described above, and in the cylindrical steam reformer, heat insulation is provided on the outer periphery of the third cylindrical body where the reforming catalyst layer is located. The material layer 101 is arranged, the hydrogenation catalyst layer and the first adsorbent layer of the hydrodesulfurizer are arranged on the outer periphery of the heat insulating material layer 101, and the second adsorbent layer is disposed outside the cylindrical steam reformer. It is characterized by being arranged.
The aspect of the present invention (4) is an aspect of the invention related to the divisional application.

  6-8 is a figure explaining the aspect of this invention (3)-(4). Among them, FIG. 8 shows the portions of the heat insulating material layer 101 and the hydrodesulfurizer (consisting of the hydrogenation catalyst layer X, the first adsorbent layer Y, and the second adsorbent layer Z) in FIGS. In the figure, it is shown as a cross-sectional view. As shown in FIGS. 6 to 8, the hydrogenation catalyst layer X and the first adsorbent layer Y in the hydrodesulfurizer are incorporated into the cylindrical steam reformer via the heat insulating material layer 101, and the second adsorbent layer Z is cylindrical. Placed outside the steam reformer.

  6-8, the part which incorporated the hydrogenation catalyst layer X and the 1st adsorbent layer Y in the cylindrical steam reformer is shown with the code | symbol 120. In FIG. The hydrogenation catalyst layer X and the first adsorbent layer Y are cylindrical, and the raw fuel supply unit S1, the hydrogenation catalyst layer X, the first adsorbent layer Y, the first adsorbent layer Y mixed with hydrogen in order from the bottom to the top. It is constituted by a raw fuel discharge part S3 that has passed through one adsorbent layer Y.

  The heat insulating material layer 101 is disposed between the outer periphery of the third cylinder 3 and the inner periphery of the hydrogenation catalyst layer X and the first adsorbent layer Y. In addition, you may arrange | position the heat insulating material layer 101 also between the outer periphery of the 3rd cylinder 3, and supply part S1, and between the outer periphery of the 3rd cylinder 3, and the inner periphery of discharge part S3. 102 is an inner cylinder of the hydrogenation catalyst layer X and the first adsorbent layer Y in contact with the heat insulating material layer 101, 105 is an outer cylinder surrounding the hydrogenation catalyst layer X, and 106 is a discharge section for the first adsorbent layer Y and raw fuel. It is an outer cylinder surrounding S3. Although the outer cylinder 105 is shown in an inclined manner in FIGS. 6 to 8, the outer cylinder 105 may have a structure without an inclination like the outer cylinder 106.

  The raw fuel supply unit S <b> 1 includes the outer periphery and the lower end plate 103, the outer cylinder 104, and the porous plate 108 of the third cylinder 3. Among them, an introduction pipe 112 for raw fuel mixed with hydrogen is arranged in the plate body 103. The raw fuel discharge part S3 is constituted by the outer periphery of the third cylinder 3, the plate 107 at the upper end, the outer cylinder 106, and the porous plate 110.

  Further, the second adsorbent layer Z disposed outside the cylindrical steam reformer is housed and configured in a container 121 therefor. Since the second adsorbent layer Z is disposed outside the cylindrical steam reformer, its shape is not limited and can be configured in various shapes. The arrangement location can also be arranged at an appropriate location. Since the second adsorbent layer is arranged outside the cylindrical steam reformer, the temperature is lower than that of the first adsorbent layer, and the temperature is determined depending on the arrangement location, etc. As the second adsorbent, ZnO However, the hydrogen sulfide adsorbent effective at such temperatures such as various metal oxides can be appropriately selected and used. These points are the same also about the other aspect which arrange | positions the 2nd adsorbent layer mentioned later outside a cylindrical steam reformer.

  The container 121 includes a raw fuel supply unit S4 that has passed through the first adsorbent layer Y, a second adsorbent layer Z, and a desulfurized raw fuel discharge unit S5 that has passed through the second adsorbent layer Z. Reference numerals 122 to 123 are perforated plates in which the second adsorbent layer Z is arranged between them to partition the supply unit S4 and the discharge unit S5.

  The raw fuel containing hydrogen sulfide that has passed through the hydrogenation catalyst layer X flows into the first adsorbent through the porous plate 109. In the first adsorbent, hydrogen sulfide in the raw fuel is adsorbed and removed. The raw fuel that has passed through the first adsorbent is introduced into the second adsorbent layer Z via the supply section S4 of the container 121 via the discharge section S3 and the conduit 114. The second adsorbent Z adsorbs and removes a slight amount of hydrogen sulfide leaking from the first adsorbent Y, thereby reducing the hydrogen sulfide to a lower concentration. The desulfurized raw fuel is supplied to the desulfurized raw fuel introduction pipe 12 to the cylindrical steam reformer via the discharge part S5.

<Mode Common to the Present Inventions (5) and (7)>
The present invention (5) and (7) are applied to a cylindrical steam reformer having no radiation cylinder, and are intended for a cylindrical steam reformer having the following structure (C). The hydrodesulfurizer integrated cylindrical steam reformer of the present invention (5), (7) can be applied to any cylindrical steam reformer having the structure (C). it can.
(C) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other in order, and a radial center portion of the first cylindrical body. And a reforming catalyst layer filled with a reforming catalyst in a gap defined in the radial direction by the first cylinder and the second cylinder, and the reformed gas generated in the reforming catalyst layer A cylindrical steam reformer configured to be circulated in a gap defined by two cylinders and a third cylinder in a radial direction.

And this invention (5) arrange | positions a heat insulating material layer in the outer periphery where the said reforming catalyst layer is located among the outer periphery of the said 3rd cylinder in the cylindrical steam reformer which has the structure of the said (C). A hydrodesulfurizer comprising a hydrogenation catalyst layer, a first adsorbent layer and a second adsorbent layer is disposed on the outer periphery of the heat insulating material layer.
Further, in the present invention (7), in the cylindrical steam reformer having the structure (C), a heat insulating material layer is disposed on the outer periphery of the third cylindrical body where the reforming catalyst layer is located. The hydrogenation catalyst layer and the first adsorbent layer of the hydrodesulfurizer are disposed on the outer periphery of the heat insulating material layer, and the second adsorbent layer is disposed outside the cylindrical steam reformer. And

<Mode Common to Present Inventions (6) and (8)>
The present invention (6) and (8) are applied to a cylindrical steam reformer having a radiation cylinder, and are intended for a cylindrical steam reformer having the following structure (D). The hydrodesulfurizer integrated cylindrical steam reformer of the present invention (6), (8) can be applied to any cylindrical steam reformer having the structure (D). it can.
(D) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body and a third cylindrical body, which are arranged concentrically and spaced apart from each other, and are coaxially arranged inside the first cylindrical body. A reformer in which a reforming catalyst is filled in a radial partition defined by the disposed radiation tube, a burner disposed in a radial center portion of the radiation tube, and the first and second cylinders A cylindrical steam reformer comprising a catalyst layer, wherein the reformed gas generated in the reforming catalyst layer is circulated by being reversed into a gap defined in the radial direction by the second and third cylinders. .

And this invention (6) arrange | positions a heat insulating material layer in the outer periphery in which the reforming catalyst layer is located among the outer periphery of the said 3rd cylinder in the cylindrical steam reformer which has the structure of the said (D), A hydrodesulfurizer comprising a hydrogenation catalyst layer, a first adsorbent layer, and a second adsorbent layer is disposed on the outer periphery of the heat insulating material layer.
Moreover, this invention (8) arrange | positions a heat insulating material layer in the outer periphery in which the reforming catalyst layer is located among the outer periphery of the said 3rd cylinder in the cylindrical steam reformer which has the structure of the said (D), The hydrogenation catalyst layer and the first adsorbent layer of the hydrodesulfurizer are arranged on the outer periphery of the heat insulating material layer, and the second adsorbent layer is arranged outside the cylindrical steam reformer. To do.

<Aspect of the present invention (5)>
FIG. 9 is a diagram for explaining an aspect of the present invention (5). In the present invention (5), a hydrodesulfurizer is incorporated into the cylindrical steam reformer having the structure (C) as indicated by reference numeral 100 in FIG. That is, among the outer circumferences of the third cylinder 3 in the cylindrical steam reformer, the heat insulating material layer 101 is arranged on the outer circumference where the reforming catalyst layer 16 is located, and the hydrodesulfurizer is placed on the outer circumference of the heat insulating material layer 101. The hydrogenation catalyst layer X, the first adsorbent layer Y, and the second adsorbent layer Z are arranged.

<Aspect of the present invention (6)>
FIG. 10 is a diagram for explaining an aspect of the present invention (6). In the present invention (6), a hydrodesulfurizer is incorporated into the cylindrical steam reformer having the structure of (D) as indicated by reference numeral 100 in FIG. That is, among the outer circumferences of the third cylinder 3 in the cylindrical steam reformer, the heat insulating material layer 101 is arranged on the outer circumference where the reforming catalyst layer 16 is located, and the hydrodesulfurizer is placed on the outer circumference of the heat insulating material layer 101. The hydrogenation catalyst layer X, the first adsorbent layer Y, and the second adsorbent layer Z are arranged.

  In the present inventions (5) to (6), a raw fuel supply unit S1 mixed with hydrogen, a hydrogenation catalyst layer X, a first adsorbent layer Y, a second adsorbent layer Z, and a desulfurized raw fuel discharge unit S2 About the structure of these, it is the same as that of the above-mentioned this invention (1)-(2) and the structure of FIGS.

<Aspect of the present invention (7)>
FIG. 11 is a diagram for explaining an aspect of the present invention (7). In the present invention (7), a hydrodesulfurizer is incorporated into the cylindrical steam reformer having the above-described structure (C) as indicated by reference numerals 120 and 121 in FIG. That is, in the hydrodesulfurizer, the hydrogenation catalyst layer X and the first adsorbent layer Y are incorporated into the cylindrical steam reformer via the heat insulating material layer 101, and the second adsorbent layer Z is incorporated into the cylindrical steam reformer. Place outside of.
The aspect of the present invention (7) is an aspect of the invention related to the split application.

<Aspect of the present invention (8)>
FIG. 12 is a diagram for explaining an aspect of the present invention (8). In the present invention (8), a hydrodesulfurizer is incorporated into the cylindrical steam reformer having the above-mentioned structure (D) as indicated by reference numerals 120 and 121 in FIG. That is, in the hydrodesulfurizer, the hydrogenation catalyst layer X and the first adsorbent layer Y are incorporated into the cylindrical steam reformer via the heat insulating material layer 101, and the second adsorbent layer Z is incorporated into the cylindrical steam reformer. Place outside of.
The aspect of the present invention (8) is an aspect of the invention related to the divisional application.

  Raw fuel supply unit S1 mixed with hydrogen, hydrogenation catalyst layer X, first adsorbent layer Y, raw fuel discharge unit S3, raw fuel supply unit S4 after passing through the first adsorbent layer Y, second adsorbent The configurations of the layer Z, the desulfurized raw fuel discharge section S5 and the like that have passed through the second adsorbent layer Z are the same as the configurations of the present inventions (3) to (4) and FIGS.

  The reformed gas produced by the hydrodesulfurizer integrated cylindrical steam reformer of the present invention (5) to (8) can be used as fuel for SOFC. Further, hydrogen purified by passing the reformed gas through a CO shift catalyst and a CO removal catalyst can be used as a fuel for PEFC.

The figure explaining an example of the cylindrical steam reformer which is not provided with a radiation cylinder, and the aspect of this invention (1) The figure explaining an example of a cylindrical steam reformer provided with a radiation pipe, and the mode of the present invention (2) The figure which extracted and showed the part of the hydrodesulfurizer and the heat insulating material layer among FIGS. The perspective view of the part which took out the part of the hydrodesulfurizer and the heat insulating material layer among FIGS. In a hydrodesulfurizer-integrated cylindrical steam reformer, steady operation when a hydrodesulfurizer is disposed “with a heat insulating material layer” on the outer periphery of the third cylindrical body where the reforming catalyst layer is located. A figure showing the measured temperature during operation The figure explaining the aspect of this invention (3)-(4) The figure explaining the aspect of this invention (3)-(4) The figure explaining the aspect of this invention (3)-(4) The figure explaining the aspect of this invention (5) The figure explaining the aspect of this invention (6) The figure explaining the aspect of this invention (7) The figure explaining the aspect of this invention (8) The figure explaining the example of the form from processing of raw fuel to PEFC and SOFC Diagram explaining the outline of a hydrodesulfurizer that implements the hydrodesulfurization method

DESCRIPTION OF SYMBOLS 1 1st cylindrical body 2 2nd cylindrical body 3 3rd cylindrical body 4 4th cylindrical body 5 Radiation tube 6 Burner 7 Upper cover and burner mounting base 8 Bottom plate 9 Exhaust passage of combustion exhaust gas 10 Bulkhead (upper cover of preheating layer 14 described later)
11 Combustion exhaust gas discharge port 12 Raw fuel supply pipe 22 CO conversion catalyst layer 26 Water supply pipe 36 CO removal catalyst layer 30 Air supply pipe 40 Reformed gas take-out pipe (outlet pipe)
51, 54 Partition plate 52, 55 One reformed gas flow hole 61 Partition 100 Hydrodesulfurizer 101 Heat insulating material layer 102 Inner cylinder of hydrodesulfurizer in contact with heat insulating material layer 103 Plate body at lower end portion 104 Cylindrical partition wall 105 outer cylinder surrounding the hydrogenation catalyst layer X 106 first adsorbent layer Y, second adsorbent layer Z, outer cylinder surrounding the desulfurized raw fuel discharge header S2 107 plate 108, 109, 111, 122, 123 Perforated plate 112 Raw fuel introduction pipe 113 Hydrogen supply pipe 114 Desulfurized raw fuel outlet pipe 120 Portion in which hydrogenation catalyst layer X and first adsorbent layer Y are incorporated in a cylindrical steam reformer 121 of the cylindrical steam reformer Container for second adsorbent layer Z arranged outside

Claims (4)

A hydrodesulfurizer integrated cylindrical steam reformer,
Cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other in sequence, and a radial central portion of the first cylindrical body. And a reforming catalyst layer in which a reforming catalyst is filled in a gap defined in the radial direction by the first cylinder and the second cylinder,
(B) a CO conversion catalyst layer and a CO removal catalyst layer are sequentially provided in the gap between the second cylinder and the third cylinder above the reforming catalyst layer; and
(C) a cylindrical steam reformer formed by forming the CO shift catalyst layer in a gap in which the flow direction is reversed at one end in the axial direction with the reforming catalyst layer;
(D) In the cylindrical steam reformer, a heat insulating material layer is disposed on an outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrodesulfurizer is disposed on the outer periphery of the heat insulating material layer. Of these, a hydrodesulfurizer-integrated cylindrical water vapor comprising a hydrogenation catalyst layer, a first adsorbent layer, and a second adsorbent layer disposed outside the cylindrical water vapor reformer. Reformer. A hydrodesulfurizer integrated cylindrical steam reformer,
Cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other, and are coaxially arranged inside the first cylindrical body. A reformer in which a reforming catalyst is filled in a radial partition defined by the disposed radiation tube, a burner disposed in a radial center portion of the radiation tube, and the first and second cylinders With a catalyst layer,
(B) a CO conversion catalyst layer and a CO removal catalyst layer are sequentially provided in the gap between the second cylinder and the third cylinder above the reforming catalyst layer; and
(C) a cylindrical steam reformer formed by forming the CO shift catalyst layer in a gap in which the flow direction is reversed at one end in the axial direction with the reforming catalyst layer;
(D) In the cylindrical steam reformer, a heat insulating material layer is disposed on an outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrodesulfurizer is disposed on the outer periphery of the heat insulating material layer. Of these, a hydrodesulfurizer-integrated cylindrical water vapor comprising a hydrogenation catalyst layer, a first adsorbent layer, and a second adsorbent layer disposed outside the cylindrical water vapor reformer. Reformer. A hydrodesulfurizer integrated cylindrical steam reformer,
Cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other in sequence, and a radial central portion of the first cylindrical body. A reforming catalyst layer in which a reforming catalyst is filled in a gap partitioned in a radial direction by the first cylinder and the second cylinder,
(B) A cylindrical steam reformer configured such that the reformed gas generated in the reforming catalyst layer is circulated in a gap defined in the radial direction by the second cylinder and the third cylinder. ,
(C) In the cylindrical steam reformer, a heat insulating material layer is disposed on the outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrodesulfurizer is disposed on the outer periphery of the heat insulating material layer. Of these, the hydrodesulfurizer-integrated cylindrical water vapor is characterized in that a hydrogenation catalyst layer and a first adsorbent layer are disposed, and a second adsorbent layer is disposed outside the cylindrical water vapor reformer. Reformer. A hydrodesulfurizer integrated cylindrical steam reformer,
Cylindrical steam reformer
(A) A plurality of cylindrical bodies composed of a first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other, and are coaxially arranged inside the first cylindrical body. A reformer in which a reforming catalyst is filled in a radial partition defined by the disposed radiation tube, a burner disposed in a radial center portion of the radiation tube, and the first and second cylinders With a catalyst layer,
(B) A cylindrical steam reformer configured such that the reformed gas generated in the reforming catalyst layer is circulated in a gap defined in the radial direction by the second cylinder and the third cylinder. ,
(C) In the cylindrical steam reformer, a heat insulating material layer is disposed on the outer periphery of the third cylindrical body where the reforming catalyst layer is located, and a hydrodesulfurizer is disposed on the outer periphery of the heat insulating material layer. Of these, a hydrodesulfurizer-integrated cylindrical water vapor comprising a hydrogenation catalyst layer, a first adsorbent layer, and a second adsorbent layer disposed outside the cylindrical water vapor reformer. Reformer.

Images