WO2023181860A1 - Reforming apparatus - Google Patents

Abstract

Provided is a reforming apparatus whereby it becomes possible to increase the temperatures of a desulfurizer and a CO converter rapidly during a start-up operation while effectively utilizing an already-existing configuration.　Before the starting of an operation from a non-operation state, an operation control unit M performs a start-up operation for circulating a temperature rising gas through a compressor D, a heat exchanger W for raw material gas heating use, a desulfurizer P, a reforming reaction tube A, the heat exchanger W for raw material gas heating use, a CO converter Q and a water vapor separation unit 19 in such a manner that the temperature rising gas is returned to an upstream-side point in the compressor D through a return passage L10 when the temperature rising gas is discharged from the water vapor separation unit 19. Subsequently, the operation control unit M performs a steady operation, and also performs a water vapor mixing treatment for mixing the temperature rising gas that has passed through the desulfurizer P with water vapor produced by a heat exchanger J for water vapor production use and separating he water vapor from the temperature rising gas in the water vapor separation unit 19 when the temperature of the CO converter Q rises to a preset intermediate temperature, i.e., a temperature at which the dew condensation of water vapor can be avoided, or higher in the start-up operation.

Description

Reforming treatment equipment

The present invention relates to a desulfurizer that desulfurizes raw material gas supplied by a compressor, a reforming reaction tube that produces reformed gas by steam reforming the raw material gas from the desulfurizer, and the reformer. A reformer equipped with a reforming burner that heats a reaction tube, a heat exchanger for heating the raw material gas that heats the raw material gas with the reformed gas from the reformer, and a heat exchanger for heating the raw material gas. Cooling that has a carbon monoxide shift catalyst that converts carbon monoxide contained in the reformed gas from the reformed gas into carbon dioxide to generate a shift gas, and flows cooling water to cool the carbon monoxide shift catalyst. a CO shift converter including a pipe; a heat exchanger for steam generation that heats water for steam generation with the combustion gas of the reforming burner to generate steam to be mixed with the raw material gas after the desulfurization treatment; The present invention relates to a reforming treatment apparatus equipped with a steam separation section that separates steam from gas.

Such a reforming treatment device supplies raw material gas, which is a hydrocarbon gas such as natural gas or naphtha, to a desulfurizer and performs desulfurization treatment, and supplies the raw material gas after the desulfurization treatment to a reforming reaction tube in a mixed state of steam. By doing so, the reformed gas is reformed with a large amount of hydrogen components in a reformer, and the carbon monoxide contained in the reformed gas is converted into carbon dioxide in a CO converter. This results in the production of a metamorphosed gas with a low concentration of carbon monoxide (see, for example, Patent Document 1).

Although a detailed explanation of the CO shift converter is omitted in Patent Document 1, the CO shift converter has a carbon monoxide shift catalyst that converts carbon monoxide contained in reformed gas into carbon dioxide, and The carbon monoxide shift catalyst is configured to include a cooling pipe through which cooling water flows to cool the carbon monoxide shift catalyst (see, for example, Patent Document 2).
In other words, the reaction that converts carbon monoxide into carbon dioxide in the CO converter is an exothermic reaction, so by flowing cooling water through the cooling pipe, the temperature of the CO converter can be adjusted to convert carbon monoxide into carbon dioxide. It will be maintained at a temperature suitable for processing (eg, 180°C to 190°C).

Incidentally, the modified gas generated in the reforming processing equipment is supplied to, for example, a pressure fluctuation adsorption type hydrogen purification equipment, and the hydrogen component is removed by adsorption and removal of miscellaneous gases other than the hydrogen component in the modified gas. A highly concentrated product gas will be produced.

Japanese Patent Application Publication No. 2001-335304 Japanese Patent Application Publication No. 9-268001

In the reforming processing equipment, when starting operation from a stopped state in which the supply of raw material gas and the combustion of the reforming burner are stopped, the supply of raw material gas to the compressor is stopped and the reforming burner is stopped. When the heating gas (e.g., hydrogen) is discharged from the steam separation section while combustion is started in the quality burner, it is returned to the upstream side of the compressor. Start-up operation is performed to raise the temperature of the desulfurizer, reforming tube, and CO shift converter by circulating the flow through the exchanger, desulfurizer, reforming reaction tube, heat exchanger for heating raw material gas, CO shift converter, and steam separation section. After that, steady operation is performed in which the compressor supplies raw material gas to the desulfurizer.

By the way, if the reformer is stopped and the internal flow path of the reformer is filled with hydrogen gas, the hydrogen gas will be used as the temperature raising gas for startup operation. It turns out.
In addition, if the reformer's internal flow path is filled with inert gas (for example, nitrogen gas) when the reformer is stopped and stored, A hydrogen gas purge process is performed in which an inert gas (e.g., nitrogen gas) is discharged outside the equipment while supplying hydrogen gas to the flow path, and then the hydrogen gas filled in the reforming equipment is used as a heating gas. , start-up operation will be performed.

During start-up operation, it is easy to quickly raise the temperature of the reforming tube by combustion in the reforming burner, but the raw material gas supplied to the desulfurizer is heated by the heating gas in the raw gas heating heat exchanger. Although it is heated, it tends to be difficult to quickly raise the temperature of the desulfurizer. Furthermore, although the temperature of the CO shift converter is raised by stopping the flow of cooling water through the cooling pipe and heating the flowing temperature-raising gas, it tends to be difficult to raise the temperature quickly.
In addition, in order to quickly raise the temperature of the desulfurizer and CO transformer, it is possible to install a heater for startup operation, but in this case, the initial cost and running cost will increase significantly, so it is not practical. It's difficult.

The present invention has been made in view of the above-mentioned circumstances, and its purpose is to be able to quickly raise the temperature of the desulfurizer and CO shift converter during start-up operation while effectively utilizing the existing configuration. The object of the present invention is to provide a reforming treatment device.

The reforming processing apparatus of the present invention includes a desulfurizer that desulfurizes raw material gas supplied by a compressor, and a reforming reaction that produces reformed gas by steam reforming the raw material gas from the desulfurizer. a reformer including a reforming burner that heats a tube and the reforming reaction tube; a heat exchanger for heating the raw material gas that heats the raw material gas with the reformed gas from the reformer; and a heat exchanger for heating the raw material gas. A cooling device that includes a carbon monoxide shift catalyst that converts carbon monoxide contained in the reformed gas from the gas heating heat exchanger into carbon dioxide to generate a shifted gas, and that cools the carbon monoxide shift catalyst. A CO shift converter equipped with a cooling pipe for flowing water, and a heat exchanger for steam generation that heats water for steam generation with the combustion gas of the reforming burner to generate steam to be mixed with the raw material gas after the desulfurization treatment. and a steam separation section that separates steam from the transformed gas, the characteristic configuration of which is as follows:
The operation control unit stops the supply of the raw material gas to the compressor when starting the operation from the stopped state in which the supply of the raw material gas and the combustion of the reforming burner are stopped. In a state where the reforming burner is combusted, the temperature increasing gas is discharged from the steam separation section and returned to the upstream side of the compressor through a return path. the desulfurizer, the reforming reaction tube, the CO After performing a start-up operation in which the temperature of the shift converter is raised to a set target state, a steady-state operation is performed in which supply of the source gas to the compressor is started to generate the shift gas, and in the start-up operation, When the temperature of the CO shift converter rises to a set intermediate temperature that can avoid condensation of water vapor, the water vapor generated in the heat exchanger for water vapor generation is added to the heating gas after passing through the desulfurizer. The present invention is characterized in that a steam mixing process is performed in which the steam is mixed and the steam is separated from the temperature-raising gas in the steam separation section.

In other words, when starting operation from a stopped state in which the supply of raw material gas and the combustion of the reforming burner are stopped, the supply of raw material gas to the compressor is stopped and the combustion of the reforming burner is stopped. When the heating gas is discharged from the steam separation section, it is returned to the upstream side of the compressor through a return path. A start-up operation will be performed in which the gas is circulated through the pipes, the heat exchanger for heating the raw material gas, the CO shift converter, and the steam separation section. In the startup operation, when the temperature of the CO transformer rises above the set intermediate temperature that can avoid condensation of water vapor, water vapor is generated in the heating gas after passing through the desulfurizer in the heat exchanger for water vapor generation. A steam mixing process is performed in which the steam is mixed and the steam is separated from the temperature-raising gas in the steam separation section.

In other words, if dew condensation occurs in the CO shift converter, the carbon monoxide shift catalyst will deteriorate, but if the temperature of the CO shift converter rises above the set intermediate temperature that can avoid water vapor condensation, it will pass through the desulfurizer. The steam generated in the heat exchanger for steam generation is mixed with the heating gas after heating, and a steam mixing process is performed in which the steam is separated from the heating gas in the steam separation section. .

When the steam generated in the steam generation heat exchanger is mixed with the temperature-raising gas that has passed through the desulfurizer, the temperature-raising gas mixed with steam is heated in the reforming burner. After passing through the reforming reaction tube, it flows to the raw material gas heating heat exchanger and the CO shift converter, where the raw material gas is heated and the carbon monoxide shift catalyst of the CO shift converter is heated. It will heat up.
Since the temperature-raising gas mixed with water vapor has a larger amount of heat than the temperature-raising gas alone, the amount of heat required to heat the raw material gas in the raw material gas heating heat exchanger is Also, the amount of heating for heating the carbon monoxide shift catalyst of the CO shift converter increases, and as a result, the temperature of the desulfurizer and the CO shift converter can be quickly raised during start-up operation.

In other words, it is possible to quickly raise the temperature of the CO shift converter during start-up operation while effectively utilizing the existing configuration, that is, the steam generation heat exchanger, etc.

In short, according to the characteristic configuration of the reforming treatment apparatus of the present invention, it is possible to quickly raise the temperature of the desulfurizer and the CO shift converter during start-up operation while effectively utilizing the existing configuration.

A further characteristic configuration of the reforming treatment apparatus of the present invention is that the operation control unit controls the water supply source from the start of the startup operation until the temperature of the CO shift converter rises to the set intermediate temperature or higher. water from the water vapor is supplied to the steam generation heat exchanger, and temperature raising steam generated in the steam generation heat exchanger is supplied to the cooling pipe.

In other words, when starting operation from a stopped state, startup operation is performed as described above, but from the start of startup operation until the temperature of the CO transformer rises above the set intermediate temperature. In other words, until the steam mixing process is performed, water from the water supply source is supplied to the steam generation heat exchanger to generate temperature raising steam, and the temperature raising steam is supplied to the cooling pipe of the CO transformer. do.

Therefore, when starting up, in addition to heating the CO shift converter with the heating gas, it is also possible to heat the CO shift converter with the heating steam supplied to the cooling pipe. During operation, the temperature of the CO shift converter can be quickly raised.
In other words, it is possible to quickly raise the temperature of the CO transformer during start-up operation while effectively utilizing the existing configuration, that is, the steam generation heat exchanger and the cooling pipe of the CO transformer.

By the way, when starting the supply of raw material gas to the compressor and performing steady operation to generate transformed gas, water from the water supply source is supplied as cooling water to the cooling pipe of the CO transformer, and the cooling The water after flowing through the pipe is supplied to the steam generation heat exchanger as water for steam generation.

In short, according to the characteristic configuration of the reforming treatment apparatus of the present invention, it is possible to quickly raise the temperature of the CO shift converter during start-up operation while effectively utilizing the existing configuration.

A further characteristic configuration of the reforming treatment apparatus of the present invention is that the compressor includes an intercooler between a front-stage compression section and a rear-stage compression section,
In the middle of the return path, a main line and a bypass line having a higher passage resistance than the main line are installed in parallel,
A line switching unit is provided that switches between a main line flow state in which the temperature raising gas flows through the main line and a bypass line flow state in which the temperature raising gas flows through the bypass line,
During the start-up operation, the operation control unit maintains the main line flow state and the CO shift converter from the start of the start-up operation until the temperature of the CO shift converter rises to the set intermediate temperature or higher. After the temperature of the vessel rises to the set intermediate temperature or higher, the line switching section is switched to the bypass line flow state while cooling of the intercooler is stopped.

That is, during start-up operation, the line switching section is switched to the main line flow state from the start of start-up operation until the temperature of the CO transformer rises above the set intermediate temperature, and the temperature of the CO transformer remains at the set intermediate temperature. After the temperature rises above the temperature, the line switching section is switched to the bypass line flow state while cooling of the intercooler is stopped.

Therefore, when the state is switched to the bypass line flow state, the pressure of the heating gas flowing to the upstream side of the compressor through the return path decreases, so when the compressor raises the heating gas to the set target pressure. As the amount of compression increases, the heating gas becomes hot, and since the cooling of the intercooler is stopped, the heating gas is circulated in a high temperature state, so water vapor is mixed in. The heating gas becomes hot.

In other words, when the bypass line is switched to the flow state, the circulating flow rate of the heating gas mixed with water vapor decreases, but the heating gas mixed with water vapor becomes high temperature, and the heat exchanger for heating the raw material gas This increases the amount of heat used to heat the raw material gas and the amount of heat used to heat the carbon monoxide shift catalyst of the CO shift converter. It can be heated.

In short, according to the further characteristic configuration of the reforming treatment apparatus of the present invention, the temperature of the desulfurizer and the CO shift converter can be raised more quickly during startup operation.

A further characteristic configuration of the reforming treatment apparatus of the present invention is that the reformer is configured to include a reforming furnace in which a cylindrical side wall is disposed between a ceiling wall and a bottom wall,
The reforming burner is provided at the center of the ceiling wall in a downward combustion state, and the reforming reaction tube is provided around the reforming burner in a position hanging from the ceiling wall,
A discharge part for discharging the combustion gas of the reforming burner is opened at an upper part of the side wall,
A cylindrical outer wall is provided at an outer location of the side wall and is disposed between the ceiling wall and the bottom wall,
The steam generation heat exchanger is arranged in an external space between the side wall and the outer wall,
The present invention is characterized in that an external discharge port is provided at a lower portion of the outer wall to discharge the combustion gas of the reforming burner flowing from the discharge portion through the external space.

That is, a cylindrical outer wall is provided at the outer side of the side wall of the reforming furnace so as to be disposed between the ceiling wall and the bottom wall, and the combustion gas discharged from the discharge section is The fluid flows through the external space between the side wall and the outer wall and is discharged to the outside from the external outlet at the lower part of the outer wall. By covering the furnace with a wall and by allowing the combustion gas to flow through the external space between the side wall and the outer wall, the heat generated by combustion in the burner can be prevented from escaping to the outside of the furnace body. As a result, the combustion amount of the burner can be sufficiently reduced while maintaining the catalyst inside the reforming reaction tube at an appropriate reaction temperature.

Moreover, since the steam generation heat exchanger is placed in the external space between the side wall and the outer wall where combustion gas flows, the steam generation heat exchanger and the reforming furnace must be placed in separate locations. The steam generation heat exchanger and the reforming furnace can be arranged more compactly than in the case where they are arranged in the same manner.

In short, according to the characteristic configuration of the reforming treatment apparatus of the present invention, it is possible to sufficiently reduce the combustion amount of the burner while maintaining the catalyst inside the reforming reaction tube at an appropriate reaction temperature, and, moreover, The heat exchanger for steam generation and the reforming furnace can be arranged compactly.

A further characteristic configuration of the reforming treatment apparatus of the present invention is that the CO shift converter includes a cylindrical shift furnace body having a reformed gas inlet at one end and a shift gas outlet after the shift treatment at the other end. configured in a form that provides
A columnar filling body is disposed at a radially central location inside the shift furnace main body in a direction from the one end side to the other end side, and in a space outside the filling body inside the shift furnace main body. , the cooling pipe is arranged spirally and filled with the carbon monoxide shift catalyst.

That is, a columnar packing body is arranged at the center in the radial direction inside the cylindrical converter main body, with one end facing toward the other end, and the columnar packing body is placed in the outer space of the packing body inside the converter main body. Since the cooling pipes are arranged in a spiral and are filled with a carbon monoxide shift catalyst, the entire carbon monoxide shift catalyst, which converts carbon monoxide contained in the reformed gas into carbon dioxide, is placed in the cooling pipe. This allows for good cooling to the appropriate temperature.

In other words, if there were no columnar packing bodies, the carbon monoxide shift catalyst would also be filled in the radial center of the cylindrical shift furnace body; The carbon monoxide shift catalyst, which is packed in the center of the radial direction, is located in the center of the cooling pipe, which is arranged spirally inside the converter main body. Although there is a risk that the carbon monoxide shift catalyst cannot be cooled to the appropriate temperature, the presence of the columnar packing body in the radial center of the cylindrical shift reactor body cools the entire carbon monoxide shift catalyst. The tube can be cooled to an appropriate temperature.

Since the entire carbon monoxide shift catalyst can be well cooled to an appropriate temperature using the cooling pipe, the entire reformed gas flowing through the carbon monoxide shift catalyst of the CO shift converter can be successfully shifted. Can be done.

In short, according to the characteristic configuration of the reforming processing apparatus of the present invention, it is possible to perform a good shift processing on the entire reformed gas flowing through the carbon monoxide shift catalyst of the CO shift converter.

FIG. 1 is a schematic configuration diagram of a hydrogen production device. FIG. 3 is a diagram showing a gas flow state during startup operation (first half). FIG. 6 is a diagram showing a gas flow state during startup operation (late stage). Diagram showing the flow state of pure water in start-up operation mode (first half) It is a figure which shows the flow state of pure water in startup operation mode (later period) and steady operation. FIG. 2 is a longitudinal sectional front view showing a CO transformer. FIG. 2 is a longitudinal sectional front view showing a reforming furnace. FIG. 2 is a plan view showing an arrangement of reaction tubes in a reforming furnace. FIG. 2 is a partially omitted vertical sectional front view showing a reforming reaction tube. It is a schematic block diagram of the hydrogen production apparatus of another embodiment. FIG. 7 is a diagram showing a gas flow state during startup operation (first half) of another embodiment. FIG. 7 is a diagram showing a gas flow state during startup operation (late stage) of another embodiment.

[Embodiment]
Embodiments of the present invention will be described below based on the drawings.

(Overall configuration of hydrogen production equipment)
The hydrogen production apparatus 100 will be explained based on FIG. 1. Note that FIG. 1 is an example of a steady operation in which hydrogen purification operation is being performed. Channels that are not in flow are indicated by thin lines. Regarding valves that open and close the flow paths, those in the open state are shown in white, and those in the closed state are shown in black. FIG. 2 shows a state in which the first half of the startup operation is being performed, FIG. 3 shows a state in which the second half of the startup operation is being performed, and FIG. 4 shows the flow state of pure water in the first half of the startup operation mode, as well as the startup operation. The same applies to FIG. 5, which shows the flow state of pure water in the latter half of the mode and the steady operation mode.

The hydrogen production device 100 includes a reforming section R (an example of a reforming processing device), and adsorbs and removes impurities (miscellaneous gas) contained in the converted gas supplied from the reforming section R to increase the hydrogen concentration. A pressure fluctuation adsorption type hydrogen separation unit 20 is provided to purify a product gas having a high content.
The operation control section M is configured to control the operation of the reforming section R and the hydrogen separation section 20.

(Details of modification section)
The reforming section R includes a desulfurizer P that desulfurizes the raw material gas G, which is a hydrocarbon gas supplied under pressure by the compressor D, and a desulfurizer P that desulfurizes the raw material gas G, which is a hydrocarbon-based gas supplied under pressure by the compressor D, and the raw material gas G after desulfurization is supplied in a mixed state of water vapor. a reformer H, and a CO shift converter Q that generates a reformed gas by converting carbon monoxide contained in the reformed gas K (see FIG. 7) generated in the reformer H into carbon dioxide; A heat exchanger W for heating the raw material gas that heats the raw material gas G supplied to the desulfurizer P with the reformed gas K from the reformer H, and generates steam to be mixed with the raw material gas G after the desulfurization treatment. It is equipped with a heat exchanger J for steam generation.
Note that a raw material gas valve V1 for intermittent supply of the raw material gas G and for adjusting the supply amount of the raw material gas G is provided at a location on the upper side of the compressor D.

The raw material gas G that is pressure-fed by the compressor D is supplied to the desulfurizer P through the first flow path L1 and the heat exchanger W for heating the raw material gas. The desulfurizer P is filled with a Ni-Mo-based, ZnO-based, etc. desulfurization catalyst, and is configured to remove sulfur components such as odorants from the raw material gas G using the desulfurization catalyst.
The raw material gas G after desulfurization is supplied to the reformer H through the second flow path L2. The second flow path L2 is supplied with water vapor generated in the steam generation heat exchanger J, and the water vapor is mixed with the raw material gas G flowing through the second flow path L2.

In the reformer H, the reforming reaction tube A (see FIG. 9) is heated by combustion in the reforming burner B, and the raw material gas G mixed with steam is subjected to a steam reforming process. The system is configured to generate quality gas K.
Note that FIG. 1 schematically shows the configuration of the reformer H, and the description of the configuration for supplying combustion air to the reforming burner B is omitted.

A CO shift converter in which carbon monoxide in the reformed gas is reacted with water vapor while the reformed gas K obtained in the reformer H passes through the third flow path L3 and the heat exchanger W for heating raw material gas. Q is supplied. The CO shift converter Q is filled with a carbon monoxide shift catalyst Z (see FIG. 6), and carbon monoxide in the reformed gas is reacted with water vapor to be shift-converted into hydrogen and carbon dioxide.
Through the reaction in the CO shift converter Q, the reformed gas K becomes a reformed gas containing hydrogen, carbon monoxide, carbon dioxide, and methane (hydrogen concentration is 64 to 96% by volume).
Note that the desulfurization reaction in the desulfurizer P is an endothermic reaction, and the CO shift reaction in the CO shift converter Q is an exothermic reaction.

(About the flow of metamorphic gas)
The transformed gas discharged from the CO transformer Q is cooled by exchanging heat with the cooling water in the cooling water heat exchanger 18 while flowing through the fourth flow path L4, and the water vapor is liquefied. Moisture (water vapor) is removed, and then guided to the hydrogen separation section 20 through the fifth flow path L5.
The fifth flow path L5 is provided with a converted gas valve V5 that opens and closes the fifth flow path L5.

A return path L10 for returning the gas discharged from the water vapor separation section 19 to the upstream side of the compressor D, bypassing the PSA device 22, is branched off from the fifth flow path L5.
The return path L10 is provided with a return valve V10 that opens and closes the return path L10.

Although not shown, a return line for desulfurization treatment is provided to return the converted gas from which moisture has been removed in the steam separation section 19 to the upstream side of the compressor D for desulfurization treatment in the desulfurizer P. , and a desulfurization treatment on-off valve that opens and closes this desulfurization treatment return line is provided.
The desulfurization treatment on-off valve is opened during hydrogen purification operation (steady operation) and closed at other times.

Further, at a location upstream of the cooling water heat exchanger 18 in the fourth flow path L4, a pure water supply pump 25 is supplied from a pure water tank 24 (an example of a water supply source) that stores pure water as water for steam generation. A pure water heat exchanger 26 is provided to exchange heat between the supplied pure water and the converted gas.
Furthermore, an exhaust path L12 is branched from the fifth flow path L5 to exhaust the gas flowing through the fifth flow path L5 to the outside. The exhaust path L12 is provided with an exhaust valve V12 that opens and closes the exhaust path L12.

Incidentally, the gas discharged from the steam separation section 19 is transferred upstream of the compressor D using the first flow path L1, the second flow path L2, the third flow path L3, the fourth flow path L4, and the return path L10. The gas is returned to the side via the compressor D, the heat exchanger W for heating raw material gas, the desulfurizer P, the reformer H, the heat exchanger W for heating raw material gas, the CO shift converter Q, and the steam separation section 19. It is configured such that a closed circulation path C for circulating gas can be formed (see FIG. 2).

(Details of hydrogen separation section)
The hydrogen separation unit 20 is a pressure swing adsorption type that separates impurities other than hydrogen (miscellaneous gases) contained in the metamorphosed gas that has been metamorphosed in the CO shift converter Q and purifies the product gas with a high concentration of hydrogen gas. It includes a PSA device 22, a product tank 23 that stores purified product gas, and an off-gas tank 21 that stores off-gas discharged from the PSA device 22.

The PSA device 22 is equipped with a plurality of (three in this embodiment) adsorption towers 20a, 20b, and 20c. Each adsorption tower 20a, 20b, 20c is filled with a combination of zeolite adsorbent, activated carbon, silica gel, etc. as an adsorbent to adsorb miscellaneous gases.
In each of the adsorption towers 20a, 20b, 20c, an adsorption step, a pressure reduction step, a purge step, and a pressure increase step (PSA method process) are executed in different phases in the plurality of adsorption towers 20a, 20b, 20c. The system is configured to purify product gas with a high hydrogen gas concentration.

Although a detailed explanation will be omitted, the above process (PSA method process) is controlled by the operation control unit M to include a plurality of valves (not shown) provided in each flow path connected to the plurality of adsorption towers 20a, 20b, and 20c. ) and are executed sequentially.
Note that FIG. 1 shows a state in which the adsorption tower 20a is performing an adsorption process in which a modified gas is passed through and a product gas is obtained.

The product gas purified by the PSA device 22 is supplied to the product tank 23 through the sixth flow path L6, and the product gas stored in the product tank 23 is stably supplied to the hydrogen usage area.
The sixth flow path L6 is provided with a product gas valve V6 that opens and closes the sixth flow path L6.
The off-gas (miscellaneous gas) after hydrogen has been separated in the PSA device 22 is supplied to the off-gas tank 21 through the seventh flow path L7.
The seventh flow path L7 is provided with an off-gas valve V7 that opens and closes the seventh flow path L7.

Since the off-gas stored in the off-gas tank 21 contains flammable gases such as methane and hydrogen, it is guided to the fuel gas supply section 10 via the off-gas flow path L8, and reformed from the fuel gas supply section 10 as fuel gas. is supplied to burner B for use.
The off-gas flow path L8 is provided with an off-gas return valve V8 that opens and closes the off-gas flow path L8.
Although FIG. 1 only shows the flow of product gas, there are times when delivery of product gas and delivery of off-gas are performed simultaneously to different adsorption towers 20a, 20b, and 20c.

Incidentally, a hydrogen supply path L11 is provided for supplying hydrogen gas from the product tank 23 to the return path L10 in order to perform a hydrogen purge process to be described later.
The hydrogen supply path L11 is provided with a hydrogen gas valve V11 that opens and closes the hydrogen supply path L11.

(Details of hydrogen purification operation)
As shown in FIG. 1, in the hydrogen purification operation (steady operation), the raw material gas G passes through the raw material gas valve V1, is then pressure-fed by the compressor D, flows through the first flow path L1, and then passes through the raw material gas valve V1. It passes through a heating heat exchanger W and is guided to a desulfurizer P where it is desulfurized. Thereafter, the raw material gas G mixed with steam is guided to the reformer H and subjected to steam reforming treatment to generate a reformed gas K. The reformed gas K is transformed in a CO transformer Q, the transformed gas is cooled in a pure water heat exchanger 26 and a cooling water heat exchanger 18, and water vapor (moisture) is removed in a steam separation section 19. After that, the product gas (hydrogen gas) is introduced into the hydrogen separation unit 20 through the fifth flow path L5 and purified.

(Overall configuration of reformer)
As shown in FIG. 7, the reformer H is for reforming a hydrocarbon-based raw material gas G such as natural gas or naphtha into a reformed gas K with a large hydrogen component through steam reforming treatment. The reforming furnace 2 is equipped with a reforming reaction tube A and a reforming burner B for heating the reforming reaction tube A.

The reforming furnace 2 is configured to include a ceiling wall 2U, a bottom wall 2D, and a cylindrical side wall 2S disposed between the ceiling wall 2U and the bottom wall 2D.
A reforming burner B is installed in the center of the ceiling wall 2U of the reformer H in a downward combustion manner, and the combustion gas E of the reforming burner B is discharged to an upper part of the side wall 2S. The discharge section 2E is open.

As shown in FIGS. 7 and 8, a plurality of reforming reaction tubes A are arranged in a manner that they hang down from the ceiling wall 2U of the reformer H and are spaced apart from each other along the periphery of the reforming burner B. It is provided in the form of
In this embodiment, a case where four reforming reaction tubes A are provided as the plurality of reforming reaction tubes A is illustrated, but it may be implemented in a form in which three or five or more reforming reaction tubes A are provided. Good too.

Further, as shown in FIG. 7, a cylindrical outer wall 2G is provided at the outer side of the side wall 2S of the reformer H, and is disposed between the ceiling wall 2U and the bottom wall 2D. ing.
A steam generation heat exchanger J is arranged in the external space F between the side wall 2S and the outer wall 2G, and is arranged to generate steam to be mixed with the raw material gas G supplied to the upper part of the reforming reaction tube A. An external exhaust port 2Z is provided at a lower portion of the outer wall 2G to exhaust the combustion gas E flowing through the external space F from the exhaust portion 2E.

Furthermore, as shown in FIG. 7, an air preheating heat exchanger for preheating the combustion air AR supplied to the reforming burner B is provided between the steam generation heat exchanger J and the outer wall 2G in the external space F. A container N is provided.

(Details of reaction tube part)
As shown in FIG. 9, the reforming reaction tube A includes an outer tube 3 with a closed bottom and an inner tube 4 disposed inside the outer tube 3, with the inner tube 4 having an open bottom. A filling portion filled with granular reforming catalyst S is formed between the outer tube 3 and the inner tube 4 so as to face in the vertical direction.
The upper end portion of the outer tube 3 passes through the ceiling wall 2U of the reformer H and is supported by the ceiling wall 2U, and the upper end portion of the inner tube 4 passes through the upper tube wall 3u of the outer tube 3. In this state, it is supported by the upper wall 3u of the tube.

A porous catalyst support portion T is provided between the outer tube 3 and the inner tube 4 to receive and support the reforming catalyst S.
The catalyst support portion T is formed with a flow hole through which the reformed gas K flowing through between the outer tube 3 and the inner tube 4 flows toward the bottom side of the outer tube 3, and It is supported at the lower end of 4.
Incidentally, in FIG. 9, a perforated plate-like form in which communication holes are formed throughout the catalyst support part T is illustrated, but for example, the communication holes are arranged in a line along the circumferential direction. The catalyst support part T may be formed in a variety of shapes as long as it has a through hole that receives the reforming catalyst S and allows the reformed gas K to flow therethrough, such as a plate-shaped configuration. It can be configured in the form of

As shown in FIGS. 7 and 9, a raw material gas introduction pipe 5a for introducing raw material gas G mixed with water vapor is connected to a portion of the outer tube 3 that protrudes from the ceiling wall 2U of the reformer H. . As shown in FIG. 7, this raw material gas introduction pipe 5a is connected to an annular raw material gas distribution pipe 5b, and a raw material gas pipe 5 for supplying raw material gas G mixed with water vapor is connected to this raw material gas distribution pipe 5b. It is connected.
That is, the raw material gas G mixed with water vapor was supplied from the raw material gas pipe 5 to the annular raw material gas distribution pipe 5b, and the steam was mixed from the circular raw material gas distribution pipe 5b to the plurality of reforming reaction tubes A. It is configured such that raw material gas G is supplied.

Incidentally, as shown in FIG. 7, the raw material gas pipe 5 is supplied with steam generated in the steam generation heat exchanger J as described later, and the raw material gas G and the raw material gas G are supplied through the raw material gas pipe 5. It is supplied to the outer tube 3 in a mixed state with water vapor.

As shown in FIGS. 7 and 9, a discharge pipe 6a for discharging the reformed gas K is connected to a portion of the inner pipe 4 that protrudes from the outer pipe 3. As shown in FIG. 7, the discharge pipe 6a is connected to an annular merging pipe 6b, and a guide pipe 6 for guiding the reformed gas K is connected to the merging pipe 6b.
That is, the reformed gas K is discharged from the reforming reaction tube A through the discharge pipe 6a, and the reformed gas K flows toward the CO shift converter Q through the guide pipe 6 via the annular merging pipe 6b. become.

(Details of heat exchanger for steam generation)
As shown in FIG. 7, the steam generation heat exchanger J is configured such that heat transfer tubes 7 are spirally arranged along the outer periphery of the side wall 2S of the reformer H.
That is, a pure water introduction pipe section 7a for supplying pure water is formed at the lower end of the heat transfer tube 7, and a steam discharge pipe for supplying water vapor to the raw material gas pipe 5 is formed at the upper end of the heat transfer tube 7. A portion 7b is formed.

Therefore, the steam generation heat exchanger J allows the pure water supplied to the pure water introduction pipe section 7a to flow through the inside of the heat transfer pipe 7 heated by the combustion gas flowing in the external space F. , is configured to generate steam, and is configured to supply the generated steam to the raw material gas pipe 5 from the steam discharge pipe section 7b.
Further, a branch pipe 7c is connected to the steam discharge pipe section 7b, which supplies the generated steam to the CO shift converter Q as temperature-raising steam U during the first half of the startup operation to be described later.

(Details of air preheating heat exchanger)
As shown in FIGS. 7 and 8, the air preheating heat exchanger N has a cylindrical shape that allows air to flow between a cylindrical inner wall 8n and a cylindrical outer wall 8g.
An air introduction section 8d for introducing combustion air AR supplied from a blower (not shown) is provided below the air preheating heat exchanger N.
A plurality of air supply pipes 9 connecting the upper part of the air preheating heat exchanger N and the reforming burner B are arranged radially around the reforming burner B, and the reformer It is provided inside the ceiling wall 2U of H.

Therefore, the air preheating heat exchanger N allows the combustion air supplied to the air introduction part 8d to flow between the inner wall 8n and the outer wall 8g, which are heated by the combustion gas flowing in the external space F. , is configured to be heated to a high temperature state, and is configured to supply combustion air heated to a high temperature to the reforming burner B through the air supply pipe 9.

Incidentally, although the detailed configuration of the reforming burner B is omitted, in addition to the air supply pipe 9 being connected to the reforming burner B, a fuel supply pipe 10a connected to the fuel gas supply section 10 is also connected to the reforming burner B. (see FIG. 1) is connected to the fuel gas supply section 10, and is configured to combust the fuel gas supplied from the fuel gas supply section 10 with the combustion air supplied through the air supply pipe 9.

The fuel gas supply unit 10 supplies off gas from the off gas tank 21 (see FIG. 1) as fuel gas, and when there is a shortage of off gas, it supplies raw material gas G as fuel gas. Therefore, the fuel gas supply section 10 is configured to include a supply amount adjustment valve that adjusts the supply amount of the off-gas and the supply amount of the raw material gas G, although a detailed explanation will be omitted.
Further, a blower (not shown) that blows the combustion air AR to the air introduction portion 8d is configured so that the amount of air supplied can be adjusted by adjusting the output.

(Details of CO transformer)
As shown in FIG. 6, the CO shift converter Q has a carbon monoxide shift catalyst Z that converts carbon monoxide contained in the reformed gas K into carbon dioxide, and cools the carbon monoxide shift catalyst Z. A cooling pipe 11 for flowing cooling water is provided.
That is, the CO shift converter Q is configured to include a cylindrical shift furnace main body 12 that includes a reformed gas inlet 12a at one end and a modified gas outlet 12b after the shift conversion process at the other end.
A columnar filling body 13 is disposed at the center in the radial direction of the inside of the shift furnace main body 12 in a state facing from one end side to the other end, and in the outer space of the filling body 13 inside the shift furnace main body 12, A cooling pipe 11 is arranged spirally from one end to the other end, and is filled with a carbon monoxide shift catalyst Z.
The filling body 13 is made of, for example, a cylindrical iron pipe.

To explain further, the converter main body 12 includes a bottomed cylindrical main body portion 12A and a reformed gas receiving portion 12B connected by a flange to the upper part of the main body portion 12A.
The reformed gas receiving portion 12B is configured as a cylindrical portion into which the reformed gas K is introduced through the third flow path L3 and discharges the introduced reformed gas K toward the main body portion 12A.

For example, a porous frame 14 that is formed in a porous shape and has air permeability is placed in the upper part of the interior of the main body portion 12A so as to close the upper end of the filling body 13. Further, a cylindrical gas receiving body 15 forming a plurality of reformed gas inlets 12a in the circumferential direction is connected to the reformed gas receiving portion 12B at a location corresponding to the upper part of the filling body 13, and has a porous lower end portion. It is provided so as to be inserted into the shaped frame 14.
Therefore, the reformed gas K flowing from the reformed gas receiving part 12B to the gas receiving body 15 is discharged from the reformed gas inlet 12a, and the reformed gas K passes through the porous frame 14 to the outer space of the packing body 13. It is configured to flow.

A receiving plate 16 for receiving the carbon monoxide conversion catalyst Z is provided at a lower portion inside the main body portion 12A, and a receiving plate 16 is arranged so that the portion facing the packing body 13 is in a non-porous state and is located outside the packing body 13. The portion is porous and is provided at a location corresponding to the lower end of the filling body 13.
The space below the receiving plate 16 is filled with a metal spherical body 16a, and the metamorphic gas in the space below is discharged from the metamorphic gas outlet 12b to the fourth flow path L4.

(About the pure water flow state switching section)
As shown in FIG. 5, water (pure water) from the pure water tank 24 (an example of a water supply source) is supplied to the cooling pipe 11 as cooling water, and the water (pure water) after flowing through the cooling pipe 11 As shown in FIG. 4, there is a start-up operation mode (later stage) in which water is supplied as water for steam generation to the heat exchanger J for steam generation, and as shown in FIG. It is configured so that it can be switched to a start-up operation mode (first half) in which the temperature-raising steam U is supplied to the generation heat exchanger J and the temperature-raising steam U is supplied to the cooling pipe 11. . Note that the startup operation mode (late stage) shown in FIG. 5 is the same as the steady operation mode.

To explain further, as shown in FIG. 5, in the steady operation mode and the start-up operation mode (later stage), the first deionized water supplied by the deionized water supply pump 25 is made to flow into the inlet of the cooling pipe 11. A supply path L13 and a second pure water supply path L14 are provided for causing the pure water discharged from the outlet of the cooling pipe 11 to flow into the pure water introduction pipe section 7a of the heat transfer tube 7.

In addition, as shown in FIG. 4, in the start-up operation mode (first half), the pure water flowing through the first pure water supply path L13 is diverted to the pure water introduction pipe section of the heat transfer pipe 7 by bypassing the cooling pipe 11. A third pure water supply path L15, which is made to flow into the pure water supply path L15, is provided so as to branch from the first pure water supply path L13 and merge into the second pure water supply path L14.
In addition, in the start-up operation mode (first half), the steam discharged from the branch pipe 7c branching from the steam discharge pipe section 7b of the heat transfer pipe 7 is made to flow into the inlet section of the cooling pipe 11 as steam U for temperature increase. A flow path L16 is provided to join the first pure water supply path L13.

Furthermore, a steam exhaust path L17 that causes steam discharged from the outlet of the cooling pipe 11 to flow into the pure water tank 24 is provided so as to branch from the second pure water supply path L14. The steam exhaust path L17 is provided with a steam cooling heat exchanger 27 that cools the steam with cooling water and condenses it.
Incidentally, although a detailed explanation will be omitted, the pure water tank 24 is equipped with a pure water device such as an ion exchange type water purifier that purifies the condensed water that returns through the steam exhaust path L17.

Further, a first on-off valve 28 is provided downstream of the branch point of the third pure water supply path L15 in the first pure water supply path L13, and a first on-off valve 28 is provided near the inlet of the cooling pipe 11 in the steam flow path L16. Two on-off valves 29 are provided.
Further, a third on-off valve 30 is provided downstream of the branch point of the steam exhaust path L17 in the second pure water supply path L14, and a fourth on-off valve 31 is provided on the steam exhaust path L17. .

Therefore, by opening the first on-off valve 28 and the third on-off valve 30 and closing the second on-off valve 29 and the fourth on-off valve 31, the mode can be switched to the steady operation mode and the start-up operation mode (late stage). By closing the first on-off valve 28 and the third on-off valve 30 and opening the second on-off valve 29 and the fourth on-off valve 31, it is possible to switch to the startup operation mode (first half).

Incidentally, in this embodiment, the pure water flow state switching unit Y that switches the flow state of pure water from the pure water tank 24 between the steady operation mode, the start-up operation mode (later stage), and the start-up operation mode (early stage) The main parts include the first on-off valve 28, the second on-off valve 29, the third on-off valve 30, and the fourth on-off valve 31.
Further, the first on-off valve 28, the second on-off valve 29, the third on-off valve 30, and the fourth on-off valve 31 are controlled to open and close by the operation control section M.

(Details of stopped operation)
When the hydrogen purification operation is stopped and the production of hydrogen gas is stopped for a long period of time (for example, longer than several days), a hydrogen purge process, a steam discharge process, and a hydrogen filling process are sequentially performed.
That is, when stopping the hydrogen refining operation, first, while the compressor D continues to operate, the mixing (supply) of steam and the heating of the reformer H by the reforming burner B are continued. The raw gas valve V1, the converted gas valve V5, and the return valve V10 are closed, and the hydrogen gas valve V11 and the exhaust valve V12 are opened to perform a hydrogen purge process to supply product gas (hydrogen gas) to the closed circulation path C. conduct.
By this hydrogen purge process, the product gas (hydrogen gas) is made to flow through the closed circulation path C, and the gas remaining in the closed circulation path C is discharged from the exhaust path L12, while the product gas (hydrogen gas) flows inside the closed circulation path C. (hydrogen gas).

Next, while the compressor D continues to operate, the mixing (supply) of steam is stopped, the heating of the reformer H by the reforming burner B is stopped, and the hydrogen gas valve V11 and the exhaust valve V12 are stopped. At the same time, by closing the return valve V10, the product gas (hydrogen gas) filled in the closed circulation path C is made to flow through the closed circulation path C, thereby removing the water vapor inside the closed circulation path C. The water vapor will be discharged.

Thereafter, compressor D is stopped, water vapor mixing (supply) is continued and stopped, heating of reformer H by reforming burner B is continued and stopped, and hydrogen gas valve V11 and exhaust valve V12 are closed. A hydrogen filling process is performed in which the closed circulation path C is closed and the product gas (hydrogen gas) is filled into the inside of the closed circulation path C.
Although not shown, a pressure sensor is provided to detect the internal pressure of the closed circulation path C, and when the internal pressure of the closed circulation path C decreases, the hydrogen gas valve V11 is opened and the product gas ( Hydrogen gas) will be refilled.
Although a detailed explanation will be omitted, when the stop operation is executed, a hydrogen filling process is performed in which product gas (hydrogen gas) is supplied and filled into the adsorption towers 20a, 20b, and 20c of the PSA device 22. will be held.

(About starting operation)
When starting the operation from a stopped state in which the supply of the raw material gas G and the combustion of the reforming burner B are stopped, the operation control unit M performs a startup operation (see FIGS. 2 and 3). After that, a steady operation (FIG. 1) is performed in which supply of the raw material gas G to the compressor D is started to generate a converted gas.

In the start-up operation, with the supply of raw material gas G to compressor D stopped and reforming burner B combusted, temperature-raising gas (hydrogen gas filled in closed circulation path C) is When water vapor is discharged from the separation section 19, it is returned to the upstream side of the compressor D through the return path L10. It is configured to circulate through the heating heat exchanger W, CO shift converter Q, and steam separation section 19 to raise the temperature of the desulfurizer P, reforming reaction tube A, and CO shift converter Q to a set target state.

That is, with the source gas valve V1, the shift gas valve V5, the hydrogen gas valve V11, and the exhaust valve V12 closed, the compressor D starts operating, and the reformer H is started to be heated by the reforming burner B. The temperature of the desulfurizer P, the reforming reaction tube A, and the CO shift converter Q is raised while flowing the product gas (hydrogen gas) as a temperature-raising gas filled through the closed circulation path C. At this time, the internal pressure of the closed circulation path C is increased by opening the hydrogen gas valve V11 and replenishing the product gas (hydrogen gas).

In this embodiment, the start-up operation includes a start-up operation (early stage) until the temperature of the CO transformer Q rises to a set intermediate temperature (for example, 140°C) that can avoid condensation of water vapor, and a start-up operation (early stage) of the CO transformer Q. It consists of a start-up operation (later stage) after the temperature rises to a set intermediate temperature (for example, 140° C.) that can avoid condensation of water vapor.

When performing startup operation, the outlet pressure of the compressor D is adjusted to the target pressure (for example, 0.8 MPa), and the internal pressure of the closed circulation path C is maintained at a high pressure state.
By the way, the set target conditions include, for example, the temperature of the reforming catalyst S is 720°C or higher, the inlet temperature of the reforming reaction tube A is 200°C or higher, the lower temperature of the desulfurizer P is 210°C or higher, and the CO shift converter Q This is a state in which the temperature at the lower part of the cylinder is 170°C or higher.

In the start-up operation (first half), as shown in FIG. While circulating the water back to the side, the pure water flow state switching unit Y is switched to the start-up operation mode (first half) (see FIG. 4).
That is, the pure water from the pure water tank 24 is supplied to the steam generation heat exchanger J, and the temperature raising steam U generated in the steam generation heat exchanger J is supplied to the cooling pipe 11 of the CO transformer Q. configured to supply.

In the startup operation (later stage), as shown in FIG. While circulating the water back to the side, the pure water flow state switching unit Y is switched to the start-up operation mode (later stage) (see FIG. 5).
Therefore, the steam generated in the steam generating heat exchanger J is mixed with the heating gas after passing through the desulfurizer P, and the steam is separated from the heating gas in the steam separation section 19. A blending process is configured to be performed.

Thereafter, when the temperature of the desulfurizer P, reformer H, and CO shift converter Q rises to the set target state, the operation control section M switches the pure water flow state switching section Y to the steady operation mode and controls the source gas G The supply of gas will be started and steady operation will be performed to generate converted gas.
That is, the source gas valve V1 and the converted gas valve V5 are opened, and the return valve V10 is closed to generate the converted gas and supply the converted gas to the PSA device 22.
Although a detailed explanation will be omitted, after restarting the operation, the PSA device 22 exhausts the purified product gas until the hydrogen concentration of the purified product gas becomes equal to or higher than the set value. When the value exceeds the set value, the purified product gas is stored in the product tank 23.

(Details of standby operation)
Incidentally, when the hydrogen refining operation is temporarily stopped and the production of hydrogen gas is temporarily stopped (for example, for several hours), a standby operation is performed.
That is, the operation control unit M passes the product gas (hydrogen gas) filled in the closed circulation path C to the compressor while the reformer H is continued to be heated by the reforming burner B. A standby operation is performed in which the CO is circulated through the desulfurizer P, the reformer H, and the CO shift converter Q.

To explain, when transitioning from hydrogen refining operation to standby operation, first, while compressor D continues to operate, water vapor is mixed (supplied) and reformer H is heated by reforming burner B. While continuing, the raw gas valve V1, the converted gas valve V5, and the return valve V10 are closed, and the hydrogen gas valve V11 and the exhaust valve V12 are opened to supply the product gas (hydrogen gas) to the closed circulation path C. Hydrogen purge treatment will be performed.
By this hydrogen purge process, the product gas (hydrogen gas) is made to flow through the closed circulation path C, and the gas remaining in the closed circulation path C is discharged from the exhaust path L12, while the product gas (hydrogen gas) flows inside the closed circulation path C. (hydrogen gas).

Thereafter, while the compressor D continues to operate and the reformer H continues to be heated by the reforming burner B, the mixing (supply) of steam is stopped, and the hydrogen gas valve V11 and the exhaust gas are turned off. By closing the valve V12 and opening the return valve V10, a standby operation is performed in which the product gas (hydrogen gas) filled in the closed circulation path C is circulated through the closed circulation path C.

Although a detailed explanation is omitted, when standby operation is executed, a hydrogen displacement process is performed in which product gas (hydrogen gas) is supplied and filled into the adsorption towers 20a, 20b, and 20c of the PSA device 22. will be held.

When transitioning from standby operation to hydrogen refining operation, first, the compressor D is continuously operated, and the reformer H is continued to be heated by the reforming burner B, and water vapor is mixed (supplied). ), the source gas valve V1 and the converted gas valve V5 are opened, and the return valve V10 is closed to supply the converted gas to the PSA device 22.
Although a detailed explanation will be omitted, after restarting the operation, the PSA device 22 exhausts the purified product gas until the hydrogen concentration of the purified product gas becomes equal to or higher than the set value. When the value exceeds the set value, the purified product gas is stored in the product tank 23.

[Another embodiment]
Next, another embodiment will be described. This another embodiment shows a different form of the startup operation of the above embodiment, and in order to omit redundant explanation, it has a different configuration from the above embodiment. However, the description of the same configuration as the above embodiment will be omitted.

As shown in FIG. 10, the compressor D is configured to include an intercooler 34 between a first stage compression section 33A and a second stage compression section 33B.
The intercooler 34 is provided with a cooling water stop valve 35 for stopping the flow of the cooling water. Therefore, the intercooler 34 is configured to be able to be switched between a cooling operation state and a cooling stopped state by opening and closing the cooling water stop valve 35.

In the middle of the return path L10, a main line Lm and a bypass line Lb having a higher passage resistance than the main line Lm are arranged side by side. A line switching unit 36 is provided that switches between a main line flow state in which the temperature raising gas flows through the main line Lm and a bypass line flow state in which the temperature raising gas flows through the bypass line Lb.

That is, the main line Lm is provided with a main line on-off valve 36a that opens and closes the main line Lm, and the bypass line Lb is provided with a bypass line on-off valve that opens and closes the bypass line Lb and provides passage resistance in the open state. 36b is provided.
Therefore, by opening the main line on-off valve 36a and closing the bypass line on-off valve 36b, the main line flow state is established, and by closing the main line on-off valve 36a and opening the bypass line on-off valve 36b, the bypass line flow state is established. The state is configured to appear.

Then, during the start-up operation (early period), from when the operation control unit M starts the start-up operation until the temperature of the CO transformer Q rises above the set intermediate temperature (for example, 140° C.), As shown in Fig. 11, in the main line flow state and in the start-up operation (later stage) after the temperature of the CO transformer Q has risen to the set intermediate temperature (for example, 140°C) or higher, as shown in Fig. 12. Thus, the line switching unit 36 is configured to switch the bypass line to the flow state while the cooling of the intercooler 34 is stopped.

When performing startup operation, the operation control unit M controls the operation of the compressor D so that the outlet pressure of the compressor D becomes the target pressure (for example, 0.8 MPa), and the inside of the closed circulation path C is The pressure will be maintained at high pressure. That is, the compressor D, for example, pressurizes the received gas to an intermediate pressure of the target pressure in the first stage compression section 33A, and increases the pressure to the target pressure in the second stage compression section 33B.
In the bypass line flow state, the pressure of the temperature-raising gas received by the compressor D is lower than in the main line flow state, so the compression amount of the temperature-raising gas in the first-stage compression section 33A and the second-stage compression section 33B is In the bypass line flow state, the temperature is higher than in the main line flow state, and the temperature of the heating gas becomes higher in the bypass line flow state than in the main line flow state.
Moreover, in the bypass line flow state, the intercooler 34 is switched to a state in which cooling is stopped, so that the temperature of the heating gas becomes even higher.

(About the pure water flow state switching section)
As shown in FIGS. 10 and 12, during steady operation and startup operation (later stage), water (pure water) from the pure water tank 24 (an example of a water supply source) is supplied to the cooling pipe 11 as cooling water, The water (pure water) flowing through the cooling pipe 11 is supplied as water for steam generation to the heat exchanger J for steam generation, and the generated steam is transferred to the gas (raw material gas, rising water) flowing through the second flow path L2. It is configured to be mixed with hot gas).

In addition, as shown in FIG. 11, in the start-up operation (first half), water (pure water) from the pure water tank 24 (an example of a water supply source) is supplied to the steam generation heat exchanger J, and then the steam is cooled. The pure water is returned to the pure water tank 24 via a heat exchanger 27. In other words, the steam discharged from the steam discharge pipe section 7b of the steam generation heat exchanger J is liquefied in the steam cooling heat exchanger 27 and returned to the pure water tank 24.

Incidentally, in the start-up operation (first half) in this other embodiment, similarly to the start-up operation (first half) in the above embodiment, the temperature-raising steam U generated in the steam cooling heat exchanger 27 is transferred to the CO shift converter Q. It may also be implemented in a form where it flows into the inlet of the cooling pipe 11.

[Other alternative embodiments]
(1) In the above embodiment and the above alternative embodiment, when the hydrogen purification operation is stopped and the production of hydrogen gas is stopped for a long period of time, the hydrogen purge process, the steam discharge process, and the hydrogen filling process are sequentially executed. Although the configuration is illustrated, in the water vapor discharge treatment, instead of the product gas (hydrogen gas), an inert gas (nitrogen gas, etc.) stored in an inert gas storage cylinder (for example, a nitrogen cylinder, etc.) is used in the closed circulation path C. In the hydrogen filling process, the closed circulation path C may be filled with an inert gas (nitrogen gas, etc.).
That is, instead of the hydrogen filling process, an inert gas filling process may be performed in which inert gas (nitrogen gas, etc.) is filled.

In this way, when filling the closed circuit C with an inert gas (nitrogen gas, etc.), when starting up the closed circuit C, first, while supplying the product gas (hydrogen gas) to the closed circuit C, An inert gas discharge process is performed to discharge the inert gas (nitrogen gas, etc.) filled in the circulation path C from the closed circulation path C, and then a startup operation is performed.

(2) In the above embodiment and the above other embodiment, the reformer H having a plurality of reforming reaction tubes A is illustrated, but the reformer H having a single reforming reaction tube A may also be used. The present invention is applicable.

(3) In the embodiments and other embodiments described above, the reformer H includes the steam generation heat exchanger J and the air preheating heat exchanger N, but the steam generation heat exchanger J and the air preheating heat exchanger The air preheating heat exchanger N may be formed at a location different from the reformer H.

(4) In the above-mentioned embodiment and the above-mentioned other embodiment, the case where the hydrogen separation unit 20 is provided for separating hydrogen gas from the converted gas from the reforming unit R is illustrated, but the converted gas is used as the product gas. The modified gas may be used as it is, such as by being supplied to an engine.

Note that the configurations disclosed in the above embodiments (including other embodiments, the same applies hereinafter) can be applied in combination with the configurations disclosed in other embodiments as long as there is no contradiction, and The embodiments disclosed in this specification are illustrative, and the embodiments of the present invention are not limited thereto, and can be modified as appropriate without departing from the purpose of the present invention.

2 Reforming furnace 2U Ceiling wall 2D Bottom wall 2S Side wall 2E Discharge section 2G Outer wall 11 Cooling pipe 12 Shift furnace main body 12a Reformed gas inlet 12b Shift gas outlet 13 Filling body 24 Water supply source 33A First stage compression section 33B Second stage compression section 34 Intercooler A Reforming reaction tube B Reforming burner D Compressor G Raw material gas H Reformer J Heat exchanger for steam generation K Reformed gas Lm Main line Lb Bypass line Q CO shift converter W Heat exchange for heating raw material gas Equipment Z Carbon monoxide shift catalyst

Claims (5)

1. A desulfurizer that desulfurizes the raw material gas supplied by the compressor, a reforming reaction tube that generates reformed gas by steam reforming the raw material gas from the desulfurizer, and heating the reforming reaction tube. a reformer equipped with a reforming burner for heating the raw material gas, a heat exchanger for heating the raw material gas that heats the raw material gas with the reformed gas from the reformer; A CO that has a carbon monoxide shift catalyst that converts carbon monoxide contained in reformed gas into carbon dioxide to generate a shifted gas, and is equipped with a cooling pipe that flows cooling water to cool the carbon monoxide shift catalyst. a shift converter, a steam generation heat exchanger that heats steam generation water with combustion gas of the reforming burner to generate steam to be mixed with the raw material gas after the desulfurization treatment, and a steam generation heat exchanger that generates steam from the shift gas. A reforming treatment device equipped with a steam separation section for separating,
   The operation control unit stops the supply of the raw material gas to the compressor when starting the operation from the stopped state in which the supply of the raw material gas and the combustion of the reforming burner are stopped. In a state where the reforming burner is combusted, the temperature increasing gas is discharged from the steam separation section and returned to the upstream side of the compressor through a return path. the desulfurizer, the reforming reaction tube, the CO After performing a start-up operation in which the temperature of the shift converter is raised to a set target state, a steady-state operation is performed in which supply of the source gas to the compressor is started to generate the shift gas, and in the start-up operation, When the temperature of the CO shift converter rises to a set intermediate temperature that can avoid condensation of water vapor, the water vapor generated in the heat exchanger for water vapor generation is added to the heating gas after passing through the desulfurizer. A reforming processing apparatus that performs a steam mixing process of mixing and separating steam from the temperature-raising gas in the steam separation section.
2. The operation control unit supplies water from the water supply source to the steam generation heat exchanger from the start of the startup operation until the temperature of the CO shift converter rises to the set intermediate temperature or higher. 2. The reforming treatment apparatus according to claim 1, wherein the temperature-raising steam generated in the steam generation heat exchanger is supplied to the cooling pipe.
3. The compressor includes an intercooler between a front compression section and a rear compression section,
   In the middle of the return path, a main line and a bypass line having a higher passage resistance than the main line are installed in parallel,
   A line switching unit is provided that switches between a main line flow state in which the temperature raising gas flows through the main line and a bypass line flow state in which the temperature raising gas flows through the bypass line,
   During the start-up operation, the operation control unit maintains the main line flow state and the CO shift converter from the start of the start-up operation until the temperature of the CO shift converter rises to the set intermediate temperature or higher. The reformer according to claim 1 or 2, wherein the line switching unit is switched to the bypass line flow state with cooling of the intercooler stopped after the temperature of the vessel rises to the set intermediate temperature or higher. Processing equipment.
4. The reformer is configured to include a reforming furnace in which a cylindrical side wall is disposed between a ceiling wall and a bottom wall,
   The reforming burner is provided at the center of the ceiling wall in a downward combustion state, and the reforming reaction tube is provided around the reforming burner in a position hanging from the ceiling wall,
   A discharge part for discharging the combustion gas of the reforming burner is opened at an upper part of the side wall,
   A cylindrical outer wall is provided at an outer location of the side wall and is disposed between the ceiling wall and the bottom wall,
   The steam generation heat exchanger is arranged in an external space between the side wall and the outer wall,
   The reforming process according to claim 1 or 2, wherein an external discharge port is provided at a lower part of the outer wall to discharge the combustion gas of the reforming burner flowing from the discharge part through the external space. Device.
5. The CO shift converter is configured to include a cylindrical shift furnace body having a reformed gas inlet at one end and a shift gas outlet after the shift treatment at the other end,
   A columnar filling body is disposed at a radially central location inside the shift furnace main body in a direction from the one end side to the other end side, and in a space outside the filling body inside the shift furnace main body. 3. The reforming treatment apparatus according to claim 1, wherein the cooling pipe is arranged in a spiral shape and is filled with the carbon monoxide shift catalyst.

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