JP2021160946A - Modification system - Google Patents

Abstract

To provide a modification system capable of improving start performances of a modification device.SOLUTION: A modification device 2 comprises: a stationary modification catalyst 12 and a start modification catalyst 13 for modifying an ammonia gas and being arranged in a housing 5; and an electric heater 14 for heating the stationary modification catalyst 12. On one end side of the housing 5, there is provided a main introduction part 8 into which the ammonia gas and air are introduced, on the other end side of the housing 5, there is provided a derivation part 10 from which a modification gas is derived. The start modification catalyst 13 is provided closer to the derivation part 10 side relative to the stationary modification catalyst 12, the housing 5 comprises an auxiliary introduction part 11 for introducing air into a space between the stationary modification catalyst 12 and the start modification catalyst 13. A gas supply part 22 has an ammonia gas valve 19 for adjusting a flow rate of an ammonia gas supplied to the main introduction part 8, and a stationary air valve 20 and a start air valve 21 for adjusting a flow rate of air supplied to the main introduction part 8 and the auxiliary introduction part 11.SELECTED DRAWING: Figure 2

Description

The present invention relates to a reforming system.

As a conventional reforming system, for example, the technique described in Patent Document 1 is known. The reforming system described in Patent Document 1 includes a reforming device that supplies fuel, air, and steam to generate hydrogen by a reforming reaction. The reformer includes a honeycomb-type catalyst heater that generates heat by energizing and promotes heat generation by catalytic combustion from the upstream side to the downstream side, a honeycomb catalyst that mainly promotes a partial oxidation reaction, and mainly self-heat. A honeycomb catalyst that promotes the reforming (ATR) reaction is provided.

JP-A-2002-154805

However, the above-mentioned prior art has the following problems. That is, depending on the catalyst material of the honeycomb catalyst, if the temperature of the honeycomb catalyst is low at the time of starting the reformer, the honeycomb catalyst may be in an oxidized state. In this case, if the honeycomb catalyst is not sufficiently reduced, the oxidation reaction of the honeycomb catalyst will not proceed easily when the next reformer is started. Therefore, it takes time for the honeycomb catalyst to start reforming, and the starting performance of the reforming apparatus deteriorates.

An object of the present invention is to provide a reforming system capable of improving the starting performance of a reformer.

The reforming system according to one aspect of the present invention is a reforming device that generates a reforming gas containing hydrogen by reforming the fuel gas by utilizing the heat generated by burning the fuel gas. It includes a gas supply unit that supplies fuel gas and oxidizing gas to the quality equipment, and a control unit that controls the reforming equipment and the gas supply unit. It has a first catalyst and a second catalyst for reforming the gas, and a heater for heating the first catalyst, and a main introduction portion for introducing a fuel gas and an oxidizing gas is provided on one end side of the housing. , The other end side of the housing is provided with a lead-out portion for leading out the reforming gas, the second catalyst is arranged on the lead-out portion side with respect to the first catalyst, and the housing has the first An auxiliary introduction section for introducing an oxidizing gas is further provided between the catalyst and the second catalyst, and the gas supply section is a fuel gas flow rate adjusting section for adjusting the flow rate of the fuel gas supplied to the main introduction section. It has an oxidizing gas flow rate adjusting unit that adjusts the flow rate of the oxidizing gas supplied to the main introduction unit and the auxiliary introduction unit, and the control unit supplies fuel gas to the main introduction unit when the reformer is started. The fuel gas flow rate adjusting unit is controlled so as to supply the oxidizing gas to the auxiliary introduction section, and the oxidizing gas flow rate adjusting section is controlled so as not to supply the oxidizing gas to the main introduction section, and the heater is energized. After the first control process is executed, the fuel gas flow rate adjusting unit is controlled so as to supply the fuel gas to the main introduction unit, and the oxidizing gas is supplied to the main introduction unit. At the same time, the second control process for controlling the oxidizing gas flow rate adjusting unit so as not to supply the oxidizing gas to the auxiliary introduction unit is executed.

In such a reforming system, when the reformer is started, the fuel gas and the oxidizing gas are supplied into the housing of the reformer, and the heater is energized to heat the first catalyst. .. At this time, the fuel gas is introduced into the housing from the main introduction portion, passes through the first catalyst, and flows to the second catalyst. The oxidizing gas is introduced from the auxiliary introduction portion between the first catalyst and the second catalyst in the housing and flows to the second catalyst. Then, when the temperature of the second catalyst reaches the combustible temperature of the fuel gas due to the oxidation of the second catalyst and the temperature rise, the fuel gas is burned in the second catalyst, and the fuel gas is reformed by the combustion heat. And a reforming gas is generated. The reformed gas generated by the second catalyst is derived from the out-licensing part of the housing. After that, the oxidizing gas is introduced into the housing from the main introduction portion and flows to the first catalyst. At this time, the first catalyst is heated by the heater. Therefore, when the temperature of the first catalyst reaches the combustible temperature of the fuel gas, the fuel gas is burned in the first catalyst, and the fuel gas is reformed by the combustion heat to generate the reformed gas. The reformed gas produced by the first catalyst is led out from the out-licensing part of the housing through the second catalyst. At this time, the hydrogen contained in the reformed gas is used to reduce the second catalyst in the oxidized state. Therefore, when the next reformer is started, the oxidation reaction of the second catalyst is likely to proceed, so that the time until the reforming of the fuel gas is started by the second catalyst is shortened. As a result, the starting performance of the reformer is improved.

The heater may have a heating element that is arranged on the main introduction portion side of the housing with respect to the first catalyst and generates heat when energized. In such a configuration, when the heating element is energized, the fuel gas introduced into the housing is heated by the heating element, and the heat of the heated fuel gas heats the first catalyst. Therefore, the first catalyst can be heated by effectively utilizing the fuel gas.

The reforming system further includes a temperature detection unit that detects the temperature of the first catalyst or the second catalyst, and the control unit receives when the temperature of the first catalyst or the second catalyst detected by the temperature detection unit becomes equal to or higher than the specified temperature. , The second control process may be executed. In such a configuration, when the temperature of the first catalyst or the second catalyst detected by the temperature detection unit becomes equal to or higher than the specified temperature, the location where the oxidizing gas is introduced into the housing by the control unit is changed from the auxiliary introduction unit to the main introduction unit. Can be switched to. Therefore, the control process by the control unit can be simplified.

The auxiliary introduction portion may be provided so as to introduce the oxidizing gas toward the central portion in the direction perpendicular to the arrangement direction of the first catalyst and the second catalyst in the second catalyst. With such a configuration, the oxidizing gas can be introduced uniformly over a wide range of the second catalyst.

The catalyst materials of the first catalyst and the second catalyst may be the same. In such a configuration, it is not necessary to prepare a plurality of types of catalysts having different catalyst materials.

According to the present invention, the starting performance of the reformer can be improved.

It is a schematic block diagram which shows the modification system which concerns on one Embodiment of this invention. It is sectional drawing of the reformer shown in FIG. It is a flowchart which shows the detail of the procedure of the control processing executed by the controller shown in FIG. It is a conceptual diagram which shows the operation of the electric heater, the reforming catalyst for stationary operation, and the reforming catalyst for start-up shown in FIG. 2 together with the introduction location of ammonia gas and air. It is a timing diagram which shows the operation of the reforming system shown in FIG. It is sectional drawing of the reformer as a comparative example.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or equivalent elements are designated by the same reference numerals, and duplicate description will be omitted.

FIG. 1 is a schematic configuration diagram showing a reforming system according to an embodiment of the present invention. In FIG. 1, the reforming system 1 of the present embodiment includes a reforming device 2, an ammonia gas supply source 3, and an air supply source 4.

Reformer 2, by using ammonia gas (NH ₃ gas) the heat generated by burning a fuel gas reforming the ammonia gas to produce a reformed gas containing hydrogen.

The ammonia gas supply source 3 generates ammonia gas. Although not particularly shown, the ammonia gas supply source 3 includes an ammonia tank that stores ammonia in a liquid state and a vaporizer that vaporizes liquid ammonia to generate ammonia gas.

The air supply source 4 generates air, which is an oxidizing gas for burning ammonia gas. As the air supply source 4, for example, a blower or the like is used.

FIG. 2 is a cross-sectional view of the reformer 2. In FIG. 2, the reformer 2 has a cylindrical housing 5. The housing 5 is made of a metal material such as stainless steel, which has corrosion resistance to ammonia gas.

The housing 5 is tapered to the main body portion 6, the main introduction portion 8 arranged on the upstream side (one end side) of the main body portion 6 via the tapered portion 7, and the downstream side (the other end side) of the main body portion 6. It has a lead-out portion 10 arranged via the portion 9 and an auxiliary introduction portion 11 attached to the main body portion 6. That is, the main introduction portion 8 is provided on one end side of the housing 5. A lead-out portion 10 is provided on the other end side of the housing 5. An auxiliary introduction section 11 is provided between the main introduction section 8 and the lead-out section 10 in the housing 5.

The main introduction unit 8 introduces ammonia gas and steady air into the main body unit 6. The steady air is air for burning ammonia gas during steady operation after the reformer 2 is activated. The auxiliary introduction unit 11 introduces starting air into the main body unit 6. The starting air is the air for burning the ammonia gas at the time of starting the reformer 2. The lead-out unit 10 derives the reformed gas generated by the reformer 2 from the main body 6.

Inside the housing 5, a steady-state reforming catalyst 12 and a start-up reforming catalyst 13 that reform the ammonia gas by decomposing the ammonia gas into hydrogen are arranged side by side in the axial direction of the housing 5. .. The starting reforming catalyst 13 is arranged on the downstream side (leading unit 10 side) of the steady-state reforming catalyst 12. The steady-state reforming catalyst 12 and the starting-up reforming catalyst 13 have, for example, a honeycomb structure. The steady-state reforming catalyst 12 and the start-up reforming catalyst 13 have an outer peripheral surface having a circular cross section fixed to the main body 6 of the housing 5. The axial length of the steady reforming catalyst 12 is larger than the axial length of the starting reforming catalyst 13.

The steady-state reforming catalyst 12 is a first catalyst that reforms ammonia gas during steady operation of the reforming apparatus 2. The starting reforming catalyst 13 is a second catalyst that reforms ammonia gas when the reforming apparatus 2 is started.

The catalyst materials of the reforming catalyst 12 for stationary use and the reforming catalyst 13 for starting use are the same. As the catalyst material for the steady-state reforming catalyst 12 and the start-up reforming catalyst 13, a metal material capable of oxidizing and raising the temperature at room temperature (for example, about 15 ° C. to 25 ° C.) is used. Examples of such a catalyst material include a cobalt-based catalyst and the like. The cobalt-based catalyst is a catalyst containing cobalt as a main component.

The auxiliary introduction unit 11 is provided in the housing 5 so as to introduce starting air between the steady-state reforming catalyst 12 and the starting reforming catalyst 13 in the housing 5. Specifically, the auxiliary introduction section 11 is provided so as to introduce the start-up air toward the radial center portion of the start-up reforming catalyst 13. The radial direction of the start-up reforming catalyst 13 is the direction perpendicular to the arrangement direction of the steady-state reforming catalyst 12 and the starting reforming catalyst 13, which is the axial direction of the housing 5. The auxiliary introduction portion 11 extends in a direction inclined with respect to the axial direction of the housing 5.

An electric heater 14 for heating the steady-state reforming catalyst 12 is arranged on the upstream side (main introduction portion 8 side) of the steady-state reforming catalyst 12 in the housing 5. The electric heater 14 has a heating element 15 through which ammonia gas passes.

The heating element 15 has, for example, a honeycomb structure. The heating element 15 has an outer peripheral surface having a circular cross section fixed to the main body 6 of the housing 5. The heating element 15 is made of a metal material such as stainless steel, which has corrosion resistance to ammonia gas. The distance between the heating element 15 and the steady-state reforming catalyst 12 is narrower than the distance between the steady-state reforming catalyst 12 and the starting reforming catalyst 13.

The heating element 15 generates heat when energized by a power source (not shown). When the heating element 15 generates heat, the temperature of the heating element 15 itself rises, and the ammonia gas flowing inside the heating element 15 is heated by the heat of the heating element 15. Then, when the heated ammonia gas reaches the steady-state reforming catalyst 12, the heat of the high-temperature ammonia gas is transferred to the steady-state reforming catalyst 12, so that the steady-state reforming catalyst 12 is heated. The starting reforming catalyst 13 arranged on the downstream side of the steady-state reforming catalyst 12 may also be heated by the heat of ammonia gas.

Returning to FIG. 1, the ammonia gas supply source 3 and the reformer 2 are connected via the ammonia gas flow path 16. One end of the ammonia gas flow path 16 is connected to the ammonia gas supply source 3. The other end of the ammonia gas flow path 16 is connected to the main introduction portion 8 of the housing 5. The ammonia gas flow path 16 is a flow path through which ammonia gas flows from the ammonia gas supply source 3 to the main introduction portion 8.

The air supply source 4 and the reformer 2 are connected to each other via air flow paths 17 and 18. One end of the air flow path 17 is connected to the air supply source 4. The other end of the air flow path 17 is connected to the main introduction portion 8 of the housing 5. The air flow path 17 is a flow path through which stationary air flows from the air supply source 4 to the main introduction portion 8. One end of the air flow path 18 is connected to the air flow path 17. The other end of the air flow path 18 is connected to the auxiliary introduction portion 11 of the housing 5. The air flow path 18 is a flow path through which starting air flows from the air supply source 4 to the auxiliary introduction portion 11.

An ammonia gas valve 19 is arranged in the ammonia gas flow path 16. The ammonia gas valve 19 constitutes a fuel gas flow rate adjusting unit that adjusts the flow rate of ammonia gas supplied to the main introduction unit 8 of the housing 5. As the ammonia gas valve 19, an electromagnetic flow rate control valve is used.

A steady-state air valve 20 is arranged in the air flow path 17. The steady-state air valve 20 is a valve that adjusts the flow rate of the steady-state air supplied to the main introduction portion 8 of the housing 5. A start-up air valve 21 is provided in the air flow path 18. The start-up air valve 21 is a valve that adjusts the flow rate of start-up air supplied to the auxiliary introduction portion 11 of the housing 5. The steady-state air valve 20 and the start-up air valve 21 constitute an oxidizing gas flow rate adjusting unit that adjusts the flow rate of air supplied to the main introduction unit 8 and the auxiliary introduction unit 11 of the housing 5. An electromagnetic flow control valve is used as the steady-state air valve 20 and the start-up air valve 21.

Ammonia gas supply source 3, air supply source 4, ammonia gas flow path 16, air flow paths 17, 18, ammonia gas valve 19, stationary air valve 20, starting air valve 21 are provided with ammonia gas and air in the reforming device 2. Consists of a gas supply unit 22 for supplying

A hydrogen utilization device 24 is connected to the reformer 2 via a reformer gas flow path 23. One end of the reformed gas flow path 23 is connected to the lead-out portion 10 of the housing 5. The other end of the reformed gas flow path 23 is connected to the hydrogen utilization device 24. The reformed gas flow path 23 is a flow path through which the reformed gas flows from the reformer 2 to the hydrogen utilization device 24.

The hydrogen utilization device 24 is an apparatus that utilizes hydrogen contained in the reforming gas. Examples of the hydrogen utilization device 24 include a combustion device such as an ammonia engine or an ammonia gas turbine using ammonia as fuel, or a fuel cell that chemically reacts hydrogen with oxygen in the air to generate power.

Further, the reforming system 1 includes a temperature sensor 25 and a controller 26. The temperature sensor 25 is a temperature detection unit that detects the temperature of the starting reforming catalyst 13. The temperature sensor 25 may, for example, detect the temperature of the portion of the housing 5 corresponding to the starting reforming catalyst 13, or may directly detect the temperature of the starting reforming catalyst 13.

The controller 26 includes a CPU, RAM, ROM, an input / output interface, and the like. The controller 26 is a control unit that controls the reformer 2 and the gas supply unit 22. The controller 26 has a first control processing unit 27 and a second control processing unit 28.

The first control processing unit 27 controls the ammonia gas valve 19 so as to supply ammonia gas to the main introduction unit 8 of the housing 5 when the reformer 2 is started, and air is supplied to the auxiliary introduction unit 11 of the housing 5. First control that controls the starting air valve 21 so as to supply the air, controls the stationary air valve 20 so as not to supply air to the main introduction portion 8 of the housing 5, and controls the electric heater 14 to be energized. Execute the process.

After the first control process is executed, the second control processing unit 28 controls the ammonia gas valve 19 so as to supply the ammonia gas to the main introduction unit 8 of the housing 5, and the second control processing unit 28 controls the main introduction unit 8 of the housing 5. A second control process is executed in which the stationary air valve 20 is controlled so as to supply air, and the starting air valve 21 is controlled so as not to supply air to the auxiliary introduction portion 11 of the housing 5.

FIG. 3 is a flowchart showing the details of the procedure of the control process executed by the controller 26. This process is executed when the start of the reformer 2 is instructed by a manual switch or the like. Before the execution of this process, the ammonia gas valve 19, the stationary air valve 20, and the starting air valve 21 are all fully closed.

In FIG. 3, when the start of the reformer 2 is first instructed, the controller 26 turns on and controls the power supply of the electric heater 14 to energize the heating element 15 of the electric heater 14 (procedure S101). Subsequently, the controller 26 controls to open the ammonia gas valve 19 and the starting air valve 21 (procedure S102).

Then, ammonia gas and starting air are supplied to the reformer 2. At this time, as shown in FIG. 4A, ammonia gas is introduced into the housing 5 from the main introduction portion 8 of the housing 5, and at the same time, ammonia gas is introduced into the housing 5 from the auxiliary introduction portion 11 of the housing 5. Starting air is introduced. Then, in the starting reforming catalyst 13, ammonia gas is burned, and the ammonia gas is reformed by the combustion heat. Further, the ammonia gas is heated by the electric heater 14, and the steady reforming catalyst 12 is heated by the heat of the ammonia gas.

Subsequently, the controller 26 acquires the detected value of the temperature sensor 25 (procedure S103). Then, the controller 26 determines whether or not the temperature of the starting reforming catalyst 13 is equal to or higher than the specified temperature T1 (see FIG. 5E) based on the detected value of the temperature sensor 25 (procedure S104).

The specified temperature T1 is a temperature corresponding to the temperature at which ammonia gas can be reformed by the steady-state reforming catalyst 12 (reformable temperature), and is determined in advance by experiments or the like. The controller 26 determines that the temperature of the starting reforming catalyst 13 is equal to or higher than the specified temperature T1 when the state in which the temperature of the starting reforming catalyst 13 is equal to or higher than the specified temperature T1 continues for a specified time. May be good. When the controller 26 determines that the temperature of the starting reforming catalyst 13 is not equal to or higher than the specified temperature T1, the controller 26 re-executes the procedure S103.

When the controller 26 determines that the temperature of the starting reforming catalyst 13 is equal to or higher than the specified temperature T1, the controller 26 controls the power supply of the electric heater 14 to be turned off to stop the energization of the heating element 15 of the electric heater 14. Procedure S105). Subsequently, the controller 26 controls to close the starting air valve 21 and controls to open the steady-state air valve 20 (procedure S106).

Then, the supply of the starting air to the reformer 2 is stopped, and the steady-state air is supplied to the reformer 2. At this time, as shown in FIG. 4B, stationary air is introduced into the housing 5 from the main introduction portion 8 of the housing 5. Then, in the steady-state reforming catalyst 12, ammonia gas is burned, and the ammonia gas is reformed by the combustion heat.

Here, the first control processing unit 27 executes the above procedures S101 and S102. The second control processing unit 28 executes the above steps S103 to S106.

In the reforming system 1 as described above, when the reforming device 2 is instructed to start, the power supply of the electric heater 14 is controlled to be turned on, and the ammonia gas valve 19 and the starting air valve 21 are opened. Then, the heating element 15 of the electric heater 14 is energized, and the heating element 15 raises the temperature (see FIG. 5D). Further, ammonia gas and starting air are supplied into the housing 5 of the reformer 2 (see FIGS. 5A and 5B).

Ammonia gas is introduced into the housing 5 from the main introduction portion 8 of the housing 5. Then, the ammonia gas is heated by the heating element 15, and the heat of the warmed ammonia gas is transferred to the steady-state reforming catalyst 12, so that the steady-state reforming catalyst 12 is heated and the temperature rises (FIG. 5 (f). )reference). Then, the ammonia gas passes through the steady reforming catalyst 12 and flows to the starting reforming catalyst 13.

Further, as shown in FIG. 4A, the starting air is introduced into the housing 5 from the auxiliary introduction portion 11 of the housing 5 and flows into the starting reforming catalyst 13. The starting reforming catalyst 13 is oxidized at room temperature to raise the temperature. Then, when the temperature of the starting reforming catalyst 13 reaches a temperature at which ammonia gas can be burned (combustible temperature), the starting reforming catalyst 13 burns the ammonia gas. Specifically, as shown in the following formula, a part of ammonia and oxygen in the air chemically react to generate heat of combustion (exothermic reaction).
NH ₃ + 3/4O ₂ → 1 / 2N ₂ + 3 / 2H ₂ O… (A)

Then, when the temperature of the starting reforming catalyst 13 reaches the reformable temperature due to the heat of combustion, the starting reforming catalyst 13 reforms the ammonia gas. Specifically, as shown in the following formula, a decomposition reaction of ammonia occurs (endothermic reaction), and a reformed gas in a hydrogen-rich state is generated. The reformed gas is led out from the lead-out unit 10 of the housing 5 and is supplied to the hydrogen utilization device 24.
NH ₃ → 3 / 2H ₂ + 1 / 2N ₂ … (B)

Then, after the temperature of the starting reforming catalyst 13 reaches the specified temperature T1, the flow rate of hydrogen generated by the starting reforming catalyst 13 becomes a constant value (see FIG. 5 (g)). Further, the power supply of the electric heater 14 is controlled to be OFF, the starting air valve 21 is closed, and the steady-state air valve 20 is opened.

Then, the energization of the heating element 15 of the electric heater 14 is stopped, and the temperature of the heating element 15 is lowered (see FIG. 5D). Further, the supply of start-up air into the reformer 2 housing 5 is stopped (see FIG. 5B), and the steady-state air is supplied into the reformer 2 housing 5. (See FIG. 5 (c)).

As shown in FIG. 4B, the starting air is introduced into the housing 5 from the main introduction portion 8 of the housing 5 and flows into the steady-state reforming catalyst 12. Then, in the steady-state reforming catalyst 12, ammonia gas is burned as in the above equations (A) and (B), and the ammonia gas is reformed by the heat of combustion. At this time, since the steady-state reforming catalyst 12 is sufficiently warmed to a reformable temperature by the electric heater 14, it is difficult to oxidize. In addition, combustion and reformation of ammonia gas are started almost at the same time.

The reforming gas generated by the steady-state reforming catalyst 12 passes through the starting reforming catalyst 13, is led out from the lead-out unit 10 of the housing 5, and is supplied to the hydrogen utilization device 24. At this time, since the high-temperature hydrogen gas and ammonia gas contained in the reforming gas flow through the starting reforming catalyst 13, the starting reforming catalyst 13 in the oxidized state is reduced by the hydrogen gas and the ammonia gas.

FIG. 6 is a cross-sectional view of a reformer as a comparative example. In FIG. 6, in the reforming apparatus 50 of this comparative example, the reforming catalyst 51 is arranged on the downstream side of the electric heater 14 in the housing 5. The catalyst material of the reforming catalyst 51 is a metal material such as a cobalt-based catalyst that can be oxidized at room temperature. The housing 5 is not provided with the auxiliary introduction portion 11.

When ammonia gas and air are introduced into the housing 5 when the reformer 50 is started, the reforming catalyst 51 burns the ammonia gas, and the combustion heat reforms the ammonia gas. At this time, the reforming catalyst 51 oxidizes at room temperature. Therefore, the reforming catalyst 51 tends to be in an oxidized state until the temperature of the reforming catalyst 51 reaches the combustible temperature of ammonia gas. When the reforming catalyst 51 is in an oxidized state, the oxidation reaction of the reforming catalyst 51 is difficult to proceed when the next reforming apparatus 50 is started, so that it takes time for the temperature of the reforming catalyst 51 to reach the reformable temperature. It takes. As a result, the starting performance of the reformer 50 deteriorates.

In response to such a problem, in the present embodiment, when the reformer 2 is started, ammonia gas and air are supplied into the housing 5 of the reformer 2, and the electric heater 14 is energized. The steady-state reforming catalyst 12 is heated. At this time, the ammonia gas is introduced into the housing 5 from the main introduction portion 8 of the housing 5, passes through the steady-state reforming catalyst 12, and flows to the starting reforming catalyst 13. Air is introduced from the auxiliary introduction portion 11 of the housing 5 between the steady-state reforming catalyst 12 and the starting reforming catalyst 13 in the housing 5, and flows to the starting reforming catalyst 13. Then, when the temperature of the starting reforming catalyst 13 reaches the combustible temperature of the ammonia gas due to the oxidation of the starting reforming catalyst 13 and raising the temperature, the ammonia gas is burned in the starting reforming catalyst 13. Ammonia gas is reformed by the heat of combustion, and reformed gas is generated. The reforming gas generated by the starting reforming catalyst 13 is led out from the lead-out unit 10 of the housing 5. After that, the air is introduced into the housing 5 from the main introduction portion 8 of the housing 5 and flows to the steady reforming catalyst 12. At this time, the steady reforming catalyst 12 is heated by the electric heater 14. Therefore, when the temperature of the steady-state reforming catalyst 12 reaches the combustible temperature of the ammonia gas, the ammonia gas is burned in the steady-state reforming catalyst 12, and the ammonia gas is reformed by the combustion heat and reformed. Gas is produced. The reforming gas generated by the steady-state reforming catalyst 12 is led out from the lead-out unit 10 of the housing 5 through the starting reforming catalyst 13. At this time, the hydrogen contained in the reforming gas is used to reduce the starting reforming catalyst 13 in the oxidized state. Therefore, when the next reformer 2 is started, the oxidation reaction of the starting reforming catalyst 13 is likely to proceed, so that the time until the reforming of ammonia gas is started by the starting reforming catalyst 13 is shortened. .. As a result, the starting performance of the reformer 2 is improved.

Further, in the present embodiment, when the heating element 15 of the electric heater 14 is energized, the ammonia gas introduced into the housing 5 is heated by the heating element 15, and the heat of the warmed ammonia gas is used for steady use. The quality catalyst 12 is heated. Therefore, the steady-state reforming catalyst 12 can be heated by effectively utilizing the ammonia gas.

Further, in the present embodiment, when the temperature of the starting reforming catalyst 13 detected by the temperature sensor 25 becomes equal to or higher than the specified temperature, the air is introduced into the housing 5 by the controller 26 from the auxiliary introduction unit 11. It is switched to the part 8. Therefore, the control process by the controller 26 can be simplified.

Further, in the present embodiment, the auxiliary introduction portion 11 of the housing 5 is provided so as to introduce air toward the radial center portion of the starting reforming catalyst 13. Therefore, air can be introduced uniformly into a wide range of the starting reforming catalyst 13.

Further, in the present embodiment, since the catalyst materials of the steady-state reforming catalyst 12 and the starting reforming catalyst 13 are the same, it is not necessary to prepare a plurality of types of reforming catalysts having different catalyst materials.

The present invention is not limited to the above embodiment. For example, in the above embodiment, when the temperature of the starting reforming catalyst 13 detected by the temperature sensor 25 becomes the specified temperature T1 or higher, the second control processing by the second control processing unit 28 is executed. It is not limited to any form. The temperature sensor 25 detects the temperature of the steady-state reforming catalyst 12, and when the temperature of the steady-state reforming catalyst 12 becomes equal to or higher than the specified temperature, the second control processing unit 28 may execute the second control process. In this case, the temperature sensor 25 may detect, for example, the temperature of the portion of the housing 5 corresponding to the steady-state reforming catalyst 12, or may directly detect the temperature of the steady-state reforming catalyst 12. ..

Further, the temperature sensor 25 does not have to be used, and the temperature of the steady-state reforming catalyst 12 or the starting reforming catalyst 13 is estimated based on, for example, the flow rate of ammonia gas, the flow rate of air, the time, and the room temperature. May be good.

Further, in the above embodiment, the ammonia gas is heated by the electric heater 14, and the heat of the ammonia gas is transferred to the steady-state reforming catalyst 12, so that the steady-state reforming catalyst 12 is heated. The form is not limited to this, and for example, a heater that directly heats the steady-state reforming catalyst 12 may be used.

Further, in the above embodiment, the auxiliary introduction portion 11 of the housing 5 is inclined with respect to the axial direction of the housing 5 so as to introduce air toward the radial center portion of the starting reforming catalyst 13. Although it is provided so as to extend, it is not particularly limited to such a form. If air is introduced between the steady-state reforming catalyst 12 and the starting reforming catalyst 13 in the housing 5, the auxiliary introduction unit 11 extends in a direction perpendicular to the axial direction of the housing 5. It may be provided as follows. Further, the auxiliary introduction unit 11 may be provided so as to introduce air toward a position deviated from the radial center portion of the starting reforming catalyst 13.

Further, in the above embodiment, the ammonia gas flow path 16 is provided with an ammonia gas valve 19 which is a fuel gas flow rate adjusting unit, and the air flow paths 17 and 18 are provided with steady-state air which is an oxidizing gas flow rate adjusting unit. The valve 20 and the starting air valve 21 are respectively arranged, but the fuel gas flow rate adjusting unit and the oxidizing gas flow rate adjusting unit are not particularly limited to such a form. For example, a three-way valve type flow rate adjusting valve for adjusting the distribution ratio of the flow rate of the air flowing to the main introduction section 8 and the auxiliary introduction section 11 of the housing 5 is provided at the confluence of the air flow paths 17 and 18. May be good. In this case, one three-way valve type flow rate adjusting valve constitutes the oxidizing gas flow rate adjusting section. Further, the fuel gas flow rate adjusting unit and the oxidizing gas flow rate adjusting unit may be a compressor, a pump, or the like.

Further, in the above embodiment, the housing 5 has a cylindrical shape, but the shape is not particularly limited, and for example, the housing 5 may have a square cylindrical shape.

Further, in the above embodiment, the catalyst materials of the steady-state reforming catalyst 12 and the start-up reforming catalyst 13 are the same, but the present invention is not particularly limited to that form, and the steady-state modification catalyst 12 and the start-up reforming catalyst 13 are not particularly limited. The catalyst material may be different.

Further, in the above embodiment, ammonia gas is used as the fuel gas, but the present invention can also be applied to a reforming system using a hydrocarbon gas or the like as the fuel gas.

Further, in the above embodiment, air is used as the oxidizing gas, but the present invention can also be applied to a reforming system using oxygen as the oxidizing gas.

1 ... reforming system, 2 ... reforming device, 5 ... housing, 8 ... main introduction part, 10 ... out-licensing part, 11 ... auxiliary introduction part, 12 ... steady-state reforming catalyst (first catalyst), 13 ... start For reforming catalyst (second catalyst), 14 ... electric heater (heater), 15 ... heating element, 19 ... ammonia gas valve (fuel gas flow rate adjusting section), 20 ... stationary air valve (oxidizing gas flow rate adjusting section), 21 ... Starting air valve (oxidizing gas flow rate adjusting unit), 22 ... Gas supply unit, 25 ... Temperature sensor (temperature detection unit), 26 ... Controller (control unit).

Claims (5)

A reformer that produces a reformed gas containing hydrogen by reforming the fuel gas using the heat generated by burning the fuel gas.
A gas supply unit that supplies the fuel gas and the oxidizing gas to the reformer,
It is provided with the reformer and a control unit that controls the gas supply unit.
The reformer
With the housing
A first catalyst and a second catalyst arranged in the housing and reforming the fuel gas,
It has a heater that heats the first catalyst.
A main introduction portion for introducing the fuel gas and the oxidizing gas is provided on one end side of the housing.
On the other end side of the housing, a lead-out portion for leading out the reformed gas is provided.
The second catalyst is arranged closer to the lead-out unit than the first catalyst.
The housing is further provided with an auxiliary introduction section for introducing the oxidizing gas between the first catalyst and the second catalyst.
The gas supply unit
A fuel gas flow rate adjusting unit that adjusts the flow rate of the fuel gas supplied to the main introduction unit, and a fuel gas flow rate adjusting unit.
It has an oxidizing gas flow rate adjusting unit that adjusts the flow rate of the oxidizing gas supplied to the main introduction unit and the auxiliary introduction unit.
The control unit
When the reformer is started, the fuel gas flow rate adjusting unit is controlled so as to supply the fuel gas to the main introduction unit, the oxidizing gas is supplied to the auxiliary introduction unit, and the main introduction unit is supplied with the oxidizing gas. The first control process of controlling the oxidizing gas flow rate adjusting unit so as not to supply the oxidizing gas and controlling the heater to be energized is executed.
After the first control process is executed, the fuel gas flow rate adjusting unit is controlled so as to supply the fuel gas to the main introduction unit, the oxidizing gas is supplied to the main introduction unit, and the auxiliary introduction is performed. A reforming system that executes a second control process for controlling the oxidizing gas flow rate adjusting unit so as not to supply the oxidizing gas to the unit. The reforming system according to claim 1, wherein the heater is arranged on the main introduction portion side of the first catalyst in the housing and has a heating element that generates heat when energized. A temperature detection unit for detecting the temperature of the first catalyst or the second catalyst is further provided.
The reforming system according to claim 1 or 2, wherein the control unit executes the second control process when the temperature of the first catalyst or the second catalyst detected by the temperature detection unit becomes equal to or higher than a specified temperature. The auxiliary introduction unit is provided so as to introduce the oxidizing gas toward the central portion in the direction perpendicular to the arrangement direction of the first catalyst and the second catalyst in the second catalyst. The reforming system according to any one of 3. The reforming system according to any one of claims 1 to 4, wherein the catalyst materials of the first catalyst and the second catalyst are the same.

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