JP2015209348A - Hydrogen production method, hydrogen production apparatus, and reforming reactor for the apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen production technology for achieving steam reforming in the absence of a catalyst in a small facility.SOLUTION: By mixing and contacting a raw material gas Gp1 and steam ST, heated to a temperature causing a reforming reaction, with each other, the reforming reaction can occur without using a catalyst, and cost required for introduction, replacement, and regeneration of a catalyst becomes unnecessary. Since the raw material gas Gp1 and steam ST are independently heated, they can be heated to the temperature causing the reforming reaction with the minimum required amount of heat to the raw material gas Gp1 and steam ST respectively, and the storage of a catalyst becomes unnecessary, so that the size of a facility can be reduced.

Description

  The present invention relates to a hydrogen production method by steam reforming, a hydrogen production apparatus, and a reforming reactor for the apparatus.

Hydrogen is expected not only as important in the chemical industry and oil refining but also as clean energy, and the main use in clean energy is a distributed fuel cell for home use and automobile. (Non-Patent Document 1, page i, top frame)
97% of hydrogen is produced by a thermochemical method, and in particular, the importance of the steam reforming method is increasing because of its economical efficiency and mass productivity. (Non-patent document 1, page i, in the second frame from the top)

The steam reforming method uses a steam reforming reaction in which a hydrocarbon, which is a raw material gas, reacts with steam, and as a result of the reaction, hydrogen and carbon monoxide are generated. Its chemical formula is as shown in formula (1) of FIG.
The carbon monoxide generated in the steam reforming reaction is then converted into carbon dioxide and hydrogen by an aqueous shift reaction that reacts with steam. Its chemical formula is as shown in formula (2) in the figure.
The aqueous shift reaction increases the hydrogen yield. (Non-Patent Document 1, page 7, lines 1-5)

  The hydrogen reforming reaction is an endothermic reaction and is generally “reacted in the presence of a high temperature / catalyst” in the reforming reactor. (Non-Patent Document 1, page i, top frame)

  The catalyst is used for the purpose of lowering the reaction temperature. In Non-Patent Document 1, all of the patents (Patent Documents 1 to 9) that are notable for steam reforming use the catalyst and heat the reforming reactor. Has been. That is, the use of a catalyst and heating of the reforming reactor are common.

In Patent Document 1, an oxidation removal unit is arranged after the reforming / denaturing unit, which is a reforming reactor, to reduce the carbon monoxide concentration. The reforming / denaturing unit has a reforming catalyst layer. The catalyst is heated by a heat source gas (paragraphs “0011” and “0015”).
Note that the application of Patent Document 1 has been withdrawn.

Patent Document 2 arranges a two-stage oxidation part, a selective oxidation part and a partial oxidation part, after the reforming reactor,
The carbon monoxide concentration is reduced, but a reformer, which is a reforming reactor, is filled with a catalyst and heated to a temperature according to the characteristics of the catalyst (paragraph “0015” in the specification).
In addition, the application of Patent Document 2 has been rejected.

Patent Document 3 relates to a steam reforming method in which dimethyl ether and steam are reacted. The reformer, which is a reforming reactor, is filled with a catalyst (paragraph “0009” in the specification), and is heated to 200 ° C. to 250 ° C. It appears to have been heated (paragraph “0011”).
The application of Patent Document 3 is patented as Japanese Patent No. 418175 in a trial against a decision of rejection after a decision of rejection.

In Patent Document 4, a mixture of methanol and water is vaporized to generate a raw fuel gas, and a reforming reaction is caused by the raw fuel gas. At the same time, an oxidation exothermic reaction of methanol occurs to supplement the reaction heat of the reforming reaction. That is, the reformer is heated by an exothermic reaction (paragraph “0086” in the specification). The reformer, which is a reforming reactor, is filled with a catalyst (paragraph “0079”).
The application of Patent Document 4 has been rejected.

In Patent Document 5, the shift reaction part and the CO oxidation part are connected by a CO oxidation part pipe, and combustion gas is supplied into the shift reaction part so that the shift reaction part can be heated from the inside. It is an enhanced one. The reforming reactor is filled with a catalyst and has a built-in main combustion section that compensates for the heat quantity of the endothermic reaction (paragraph “0012” in the specification).
The application of Patent Document 5 has been rejected.

In Patent Document 6, a reforming section (reforming reactor) filled with a reforming catalyst is disposed in a combustion chamber, and a combustion catalyst is disposed in the vicinity of the reforming section via a partition wall. Improved. The reforming section is filled with a reforming catalyst (paragraph “0022” in the specification), and the reforming catalyst is heated and maintained at a constant temperature (paragraph “0029”).
The application of Patent Document 6 has been withdrawn.

  Patent Document 7 arranges a converter for an aqueous shift reaction along the wall surface of a reformer (reformer reactor) and improves heat efficiency by mutual heat transfer. Is provided with a catalyst layer (paragraph “0011”).

  Patent Document 8 is a hydrogen reforming device for a portable fuel cell and a fuel cell mounted on an electric vehicle, and includes a liquid raw material heating unit, an evaporation unit, a steam superheating unit, a reforming unit (reforming reactor), and a catalytic combustion unit. The shift unit and the heat recovery unit are each laminated in a flat plate shape. A catalyst is disposed in the reforming reaction flow path of the reforming unit, and heat necessary for the reforming reaction is supplied from the heat transfer fluid. (Specification paragraph “0006”).

  Patent Document 9 discloses that a triple cylinder structure of an inner cylinder, an outer cylinder, and an outermost cylinder communicates the bottom of the outer cylinder and the outermost cylinder, uses the inner cylinder as a fire channel, introduces a source gas from the middle cylinder, The inside of the cylinder is a reforming reactor. The reforming reactor is filled with a reforming catalyst (paragraph “0027” in the specification), and thermal energy necessary for the reforming reaction is supplied by a combustion burner (paragraph “0030”).

As described above, in a general steam reforming method, the use of a catalyst and its heating are common, and after introduction into the reforming reactor, the raw material gas and steam are heated. At this time, since heating that compensates for the temperature drop due to the endothermic heat of the reforming reaction is necessary, the inside of the reforming reactor must be maintained at a temperature higher than that required for the reforming reaction.
Although the catalyst itself is expensive, it requires a large running cost such as replacement and regeneration costs. When the reforming reactor is heated, the catalyst is significantly deteriorated.
In addition, when the raw material gas and water vapor are heated in a mixed state in the reforming reactor, the gas in the reforming reactor expands with the generation of hydrogen gas, and is subsequently introduced into the reforming reactor. This is an impediment to introduction of water vapor and raw material gas. This is an obstacle to continuous hydrogen production.

Non-catalytic steam reforming is also performed (Patent Document 10). This is because a heat exchange tube as a reforming reactor is arranged in an exhaust gas duct directly connected to the upper part of the metallurgical furnace. In Invention Example 1 (paragraph “0064” in the specification), the reforming reaction is performed without a catalyst. Is caused.
However, Patent Document 10 is a reforming reaction in an environment where the heat energy is extremely abundant, such as an exhaust gas duct of a metallurgical furnace, and cannot be applied to a small facility such as hydrogen production in a hydrogen station.

  That is, conventionally, a hydrogen production facility using a steam reforming method has a large cost due to the use of a catalyst, and it has been difficult to realize a small facility that does not use a catalyst.

Japanese Unexamined Patent Publication No. 7-12001

JP-A-8-157201

JP-A-9-118501

JP-A-9-315801

JP-A-11-43303

JP-A-11-343101

Japanese Patent No. 3108269

Japanese Patent No. 31296670

Japanese Patent No. 3197095

JP 2011-102658 A

Incorporated Administrative Agency Industrial Property Information / Training Hall Edition / Issued, “2005 Patent Distribution Support Chart, General 20, Hydrogen Production Technology”, March 2006

Tsutsumi Junji et al. “Fuel Cell”, published in March 2007

  The object of the present invention is to overcome the common sense of a general steam reforming method by using and heating the catalyst, and to realize steam reforming without catalyst in a small facility.

  In the method of the present invention according to claim 1, since the raw material gas heated to the temperature at which the reforming reaction occurs and water vapor are mixed and brought into contact with each other, it is possible to cause the reforming reaction without using a catalyst. In addition, the cost required for introduction, replacement, regeneration, etc. of the catalyst is unnecessary. In addition, since the source gas and water vapor are heated separately, they can be heated to the temperature at which the reforming reaction takes place with the minimum amount of heat required for each of the source gas and water vapor, and no catalyst is required. obtain.

  The apparatus of the present invention according to claim 2 heats the steam generated in the boiler to a temperature at which a reforming reaction occurs with a steam heater, heats the source gas to a temperature at which the reforming reaction occurs with a source gas heater, Heated steam and raw material gas are mixed by a reforming reactor to generate a steam reforming reaction, so that it is possible to generate a reforming reaction without using a catalyst. Costs required for reproduction and the like are unnecessary. In addition, since the source gas and water vapor are heated separately, they can be heated to the temperature at which the reforming reaction takes place with the minimum amount of heat required for each of the source gas and water vapor, and no catalyst is required. obtain.

  The reforming reactor in the apparatus of the present invention according to claim 3 comprises a steam introduction pipe into which the heated steam is introduced, a source gas introduction pipe into which the heated source gas is introduced, and the steam introduction pipe A catalyst is used because it has a mixing chamber that mixes and brings the introduced water vapor and the source gas introduced from the source gas introduction pipe into contact with each other, and a lead-out pipe that leads out the gas in the mixing chamber. The reforming reaction can be caused to occur without any cost, and the cost required for introducing, exchanging, and regenerating the catalyst is unnecessary, and the reforming reactor itself does not need to be heated. Therefore, the equipment can be miniaturized.

5. The apparatus according to claim 4, wherein the mixing chamber has a spherical shape with an inner surface opened in one direction, and discharge directions of the source gas introduction pipe and the water vapor introduction pipe are acute with respect to the direction of the opening. The tilt angle is set.
By making the inner surface of the mixing chamber spherical, a shock wave accompanying the reforming reaction collides with, reflects on the inner surface of the mixing chamber, and propagates repeatedly. As a result, the unreacted source gas and water vapor are stirred, and the reforming reaction is promoted.
Further, since the discharge direction of the raw material gas introduction pipe and the water vapor introduction pipe is set to an acute inclination angle with respect to the opening direction, the momentum of the raw material gas and water vapor at the time of discharge is effectively utilized, and the reformed gas and Unreacted gas is smoothly led out from the outlet pipe.

  In the apparatus of the present invention according to claim 5, since the raw material gas introduction pipe and the water vapor introduction pipe are double pipes, one of which is inserted into the other, the raw material gas and water vapor are present in the vicinity from the time of discharge. The contact probability is high.

7. The apparatus according to claim 6, wherein a second mixing chamber is provided between the mixing chamber and the outlet pipe, and a damper for adjusting a flow rate is provided at the opening of the mixing chamber.
Here, since the damper adjusts the discharge amount of the reformed gas and the unreacted gas from the mixing chamber, the damper discharged from the outlet pipe is adjusted according to the balance of the reforming reaction rates in the mixing chamber and the second mixing chamber. The hydrogen concentration of the quality gas, that is, the reforming rate can be maximized.

8. The apparatus according to claim 7, further comprising: a pressure detector that detects the pressure in the mixing chamber; and a control unit that controls the opening of the damper based on the pressure detected by the pressure detector.
As a result, the hydrogen concentration and reforming rate of the reformed gas discharged from the outlet pipe can be automatically optimized.

The reforming reactor in the apparatus of the present invention according to claim 8 includes: a steam introduction pipe into which the heated steam is introduced; a source gas introduction pipe into which the heated source gas is introduced; and the steam introduction pipe A mixing chamber in which the introduced water vapor and the source gas introduced from the source gas introduction pipe are mixed and brought into contact with each other, a lead-out pipe for deriving the reformed gas in the mixing chamber, and a periphery of the mixing chamber An outlet chamber provided in communication with the mixing chamber, wherein the steam introduction pipe and the source gas introduction pipe are arranged such that the introduction direction of the steam and the introduction direction of the source gas introduction are substantially opposite to each other. The derivation chamber is formed along a plane substantially perpendicular to the direction of introduction of the water vapor and the direction of introduction of the raw material gas, and the mixing chamber is filled with non-combustible particles. The raw material gas is mixed in the mixing chamber while flowing around the periphery of the non-combustible particles to generate a reformed gas, and the reformed gas flows radially out of the mixing chamber and is sent to the outlet chamber. The
Thereby, it is possible to cause a reforming reaction without using a catalyst, the cost required for introduction, replacement, regeneration, etc. of the catalyst is unnecessary, and the reforming reactor itself does not need to be heated. Therefore, the equipment can be miniaturized. Further, due to the flow around the non-combustible particles, the frequency of contact with the water vapor and the raw material gas is increased, and the reforming rate is increased.

The apparatus of the present invention according to claim 9, wherein the mixing chamber is provided with a cavity that is not filled with incombustible particles in contact with the lead-out chamber.
Thereby, the reformed gas is smoothly discharged into the outlet chamber, and the residence time in the mixing chamber is shortened. Thereby, the reforming reaction in the mixing chamber is promoted, and the reforming rate is increased.

11. The apparatus according to claim 10, wherein a second mixing chamber is provided between the lead-out chamber and the lead-out pipe, and is slidably fitted on the outer periphery of the water vapor introduction pipe and the source gas introduction pipe in the lead-out chamber. An annular flow control valve is further provided.
Accordingly, the hydrogen concentration of the reformed gas discharged from the outlet pipe, that is, the reforming rate, can be maximized according to the balance of the reforming reaction rates in the mixing chamber and the second mixing chamber.

12. The apparatus according to claim 11, further comprising: a pressure detector that detects the pressure in the mixing chamber; and a controller that controls the opening of the flow rate control valve based on the pressure detected by the pressure detector. It is done.
As a result, the hydrogen concentration and reforming rate of the reformed gas discharged from the outlet pipe can be automatically optimized.

13. The apparatus of the present invention according to claim 12, wherein the reforming reactor introduces the steam introduction pipe into which the heated steam is introduced, a steam introduction valve for adjusting the amount of introduction of steam, and the heated source gas. A raw material gas introduction pipe, a raw material gas introduction valve for adjusting an introduction amount of the raw material gas, the water vapor introduced from the water vapor introduction pipe, and the raw material gas introduced from the raw material gas introduction pipe are mixed. A mixing chamber to be brought into contact with, and a lead-out pipe for leading out the reformed gas in the mixing chamber, one of the water vapor introducing pipe and the raw material gas introducing pipe being inserted into the other, The inside of the introduction pipe is formed in the vicinity of the tip of the inner introduction pipe, and the inner end of the introduction pipe constitutes a part of the water vapor introduction valve and the raw material gas introduction valve.
Thereby, the reforming reactor is small and can be manufactured at low cost.

The apparatus of the present invention according to claim 13 further comprises an expansion wall for adjusting the volume of the mixing chamber according to claim 12.
As a result, the optimum reforming conditions can be set both by adjusting the introduction amount of the raw material gas and water vapor by the water vapor introduction valve and the raw material gas introduction valve and by adjusting the mixing chamber volume.

15. The apparatus according to claim 14, wherein the pressure detector for detecting the pressure in the mixing chamber and the expansion wall are driven based on the pressure detected by the pressure detector, thereby adjusting the volume of the mixing chamber. And a control unit.
As a result, the hydrogen concentration and reforming rate of the reformed gas discharged from the outlet pipe can be automatically optimized.

  The reforming reactor of the present invention according to claim 15 includes a steam introduction pipe into which steam heated to a temperature at which a reforming reaction occurs is introduced, and a raw material into which source gas heated to a temperature at which the reforming reaction occurs is introduced. A gas introduction pipe, a mixing chamber in which the water vapor introduced from the water vapor introduction pipe and the raw material gas introduced from the raw material gas introduction pipe are mixed and brought into contact with each other, and a discharge pipe for deriving the gas in the mixing chamber Therefore, it is possible to generate a reforming reaction without using a catalyst, the cost required for the introduction, replacement, and regeneration of the catalyst is unnecessary, and the reforming reactor itself needs to be heated. There is no. Therefore, the equipment can be miniaturized.

The reforming reactor of the present invention according to claim 16, wherein the mixing chamber has a spherical shape with an inner surface opened in one direction, and the discharge direction of the raw material gas introduction pipe and the steam introduction pipe is relative to the direction of the opening. And an acute inclination angle.
By making the inner surface of the mixing chamber spherical, a shock wave accompanying the reforming reaction collides with, reflects on the inner surface of the mixing chamber, and propagates repeatedly. As a result, the unreacted source gas and water vapor are stirred, and the reforming reaction is promoted.
Further, since the discharge direction of the raw material gas introduction pipe and the water vapor introduction pipe is set to an acute inclination angle with respect to the opening direction, the momentum of the raw material gas and water vapor at the time of discharge is effectively utilized, and the reformed gas and Unreacted gas is smoothly led out from the outlet pipe.

  The reforming reactor of the present invention according to claim 17, wherein the raw material gas introduction pipe and the water vapor introduction pipe are configured as a double pipe in which one is inserted into the other, so that the raw material gas and water vapor are discharged from the time of discharge. Proximity exists and contact probability is high.

The reforming reactor of the present invention according to claim 18, wherein a second mixing chamber is provided between the mixing chamber and the outlet pipe, and a damper for adjusting a flow rate is provided at the opening of the mixing chamber.
Here, since the damper adjusts the discharge amount of the reformed gas and the unreacted gas from the mixing chamber, the damper discharged from the outlet pipe is adjusted according to the balance of the reforming reaction rates in the mixing chamber and the second mixing chamber. The hydrogen concentration of the quality gas, that is, the reforming rate can be maximized.

The reforming reactor of the present invention according to claim 19, wherein a pressure detector for detecting the pressure in the mixing chamber, and a controller for controlling the opening of the damper based on the pressure detected by the pressure detector. Further provided.
As a result, the hydrogen concentration and reforming rate of the reformed gas discharged from the outlet pipe can be automatically optimized.

The reforming reactor of the present invention according to claim 20, wherein the heated steam is introduced from the steam introduction pipe, the source gas introduction pipe into which the heated source gas is introduced, and the steam introduction pipe. The water vapor and the source gas introduced from the source gas introduction pipe are mixed and brought into contact with each other, a lead-out pipe for leading out the reformed gas in the mixing chamber, and a periphery of the mixing chamber. An outlet chamber communicating with the mixing chamber, and the water vapor introduction pipe and the raw material gas introduction pipe are connected to the mixing chamber so that the introduction direction of the water vapor and the introduction direction of the raw material gas are substantially opposed to each other. The lead-out chamber is formed along a plane substantially orthogonal to the direction of introduction of the water vapor and the direction of introduction of the raw material gas, and the mixing chamber is filled with non-combustible particles. Gas mixes in the mixing chamber while flowing around the periphery of the non-combustible particles to generate a reformed gas, and the reformed gas flows radially out of the mixing chamber and is fed to the outlet chamber. .
Thereby, it is possible to cause a reforming reaction without using a catalyst, the cost required for introduction, replacement, regeneration, etc. of the catalyst is unnecessary, and the reforming reactor itself does not need to be heated. Therefore, the equipment can be miniaturized. Further, due to the flow around the non-combustible particles, the frequency of contact with the water vapor and the raw material gas is increased, and the reforming rate is increased.

The reforming reactor of the present invention according to claim 21, wherein the mixing chamber is provided with a cavity not filled with nonflammable particles in contact with the lead-out chamber.
Thereby, the reformed gas is smoothly discharged into the outlet chamber, and the residence time in the mixing chamber is shortened. Thereby, the reforming reaction in the mixing chamber is promoted, and the reforming rate is increased.

23. The reforming reactor of the present invention according to claim 22, wherein a second mixing chamber is provided between the outlet chamber and the outlet tube, and is slidable on the outer periphery of the water vapor inlet tube and the raw material gas inlet tube in the outlet chamber. An annular flow control valve fitted in is further provided.
Accordingly, the hydrogen concentration of the reformed gas discharged from the outlet pipe, that is, the reforming rate, can be maximized according to the balance of the reforming reaction rates in the mixing chamber and the second mixing chamber.

A reforming reactor according to a twenty-third aspect of the present invention is a pressure detector that detects the pressure in the mixing chamber, and a control unit that controls the opening of the flow control valve based on the pressure detected by the pressure detector. And further comprising.
Accordingly, the hydrogen concentration of the reformed gas discharged from the outlet pipe, that is, the reforming rate, can be maximized according to the balance of the reforming reaction rates in the mixing chamber and the second mixing chamber.

25. The reforming reactor of the present invention according to claim 24, wherein a steam introduction pipe into which steam heated to a temperature at which a reforming reaction occurs is introduced, and steam introduced to a temperature at which the reforming reaction occurs controls the amount of introduction. A water vapor introduction valve, a raw material gas introduction pipe into which the heated raw material gas is introduced, a raw material gas introduction valve for adjusting an introduction amount of the raw material gas, the water vapor introduced from the water vapor introduction pipe, and the raw material gas A mixing chamber that mixes and contacts the raw material gas introduced from the introducing pipe, and a lead-out pipe that leads out the reformed gas in the mixing chamber, wherein the water vapor introducing pipe and the raw material gas introducing pipe are either Is inserted in the other, and the mixing chamber is formed in the vicinity of the tip of the inner introduction pipe inside the introduction pipe on the outer side, and the tip of the inner introduction pipe is provided with a water vapor introduction valve and a raw material gas introduction Part of the valve It is.
Thereby, the reforming reactor is small and can be manufactured at low cost.

The reforming reactor of the present invention according to claim 25 further includes an expansion wall for adjusting the volume of the mixing chamber.
As a result, the optimum reforming conditions can be set both by adjusting the introduction amount of the raw material gas and water vapor by the water vapor introduction valve and the raw material gas introduction valve and by adjusting the mixing chamber volume.

The reforming reactor of the present invention according to claim 26 is a pressure detector for detecting the pressure in the mixing chamber, and the expansion wall is driven based on the pressure detected by the pressure detector, thereby the mixing chamber. Adjust the volume.
As a result, the hydrogen concentration and reforming rate of the reformed gas discharged from the outlet pipe can be automatically optimized.

The block diagram which shows Example 1 of the hydrogen production apparatus which concerns on this invention. The longitudinal cross-sectional view which shows the reforming reactor in FIG. Sectional drawing which follows the 2B arrow line of FIG. 2A. The longitudinal cross-sectional view which shows the double tube | pipe in FIG. 2A. FIG. 3B is a right side view of FIG. 3A. The block diagram which shows the control system in the apparatus of FIG. The flowchart which shows the main control by the control system of FIG. 4A. The flowchart which shows the process (step S4B01) of the preheating setting in FIG. 4B. FIG. 4B is a flowchart showing reforming start / stop processing (step S4B02) in FIG. 4B. The flowchart which shows the process (step S4B03) of waste gas use setting in FIG. 4B. The flowchart which shows the process (step S4B04) of drain water use setting in FIG. 4B. The flowchart which shows the process (step S4B05) of the reforming reaction control in FIG. 4B. The flowchart which shows one Example of the hydrogen manufacturing method which concerns on this invention. The longitudinal cross-sectional view which shows the reforming reactor in Example 2 of the hydrogen production apparatus based on this invention. FIG. 6 is a block diagram illustrating a control system in the apparatus according to the second embodiment. The flowchart which shows the process of the reforming reaction control in the control system of FIG. 7A. The longitudinal cross-sectional view which shows the reforming reactor in Example 3 of the hydrogen production apparatus based on this invention. Sectional drawing which follows the 8B arrow line of FIG. 8A. FIG. 9 is a block diagram showing a control system in Embodiment 3. The flowchart which shows the process of the reforming reaction control in the control system of FIG. 9A. The longitudinal cross-sectional view which shows the reforming reactor in Example 4 of the hydrogen production apparatus based on this invention. FIG. 10 is a block diagram illustrating a control system in the apparatus according to the fourth embodiment. 11B is a flowchart showing preheating setting processing (step S11B01) in the control system of FIG. 11A. 11B is a flowchart showing reforming start / stop processing (step S11B02) in the control system of FIG. 11A. 11B is a flowchart showing the process of the control system reforming reaction control (step S11B05) in FIG. 11A. The longitudinal cross-sectional view which shows the reforming reactor in Example 5 of the hydrogen production apparatus based on this invention. FIG. 10 is a block diagram illustrating a control system in the apparatus according to the fifth embodiment. The flowchart which shows the process of the reforming reaction control in the control system of FIG. 13A. The longitudinal cross-sectional view which shows the reforming reactor in Example 5 of the hydrogen production apparatus based on this invention. Chemical formula of steam reforming reaction and aqueous shift reaction.

[Hydrogen production method]
Next, an embodiment of the hydrogen production method according to the present invention will be described with reference to the drawings.

  As shown in FIG. 5, a raw material gas Gp0, for example, propane gas is desulfurized (process P11), and then heated to a temperature at which a reforming reaction occurs by a raw material gas heater (process P12). On the other hand, water W is heated by a boiler to generate steam ST (process P21), and the generated steam ST is heated to a temperature at which a reforming reaction occurs by a steam heater (process P22).

  The heated raw material gas Gp0 and steam ST are introduced into the reforming reactor, mixed in the reforming reactor, and come into contact with each other. As a result, a reforming reaction (formula (1)) occurs, and a reformed gas Gc0 is generated (process P3).

  Thereafter, the reformed gas Gc0 is introduced into the aqueous shift reactor, and the reformed gas Gc1 having a high hydrogen content is generated by the aqueous shift reaction (formula (2)) (process P4). This increases the hydrogen yield.

  The reformed gas Gc1 is introduced into the steam separator to remove moisture (process P5). And the hydrogen gas Gh from which the water | moisture content was removed is obtained. Moisture is discharged as drain (drain water).

  The heating of the raw material gas Gp0 and the water vapor ST (processes P12 and P22) is performed separately, for example, by using separate heaters, and each heater heats the raw material gas Gp0 and the water vapor ST to temperatures at which the reforming reaction occurs. Only the amount of heat is generated, and the necessary minimum amount of heat is sufficient as compared with the case where the heat absorption of the reforming reaction in the catalyst heating and reforming reactor is compensated as in the prior art.

  Further, since the raw material gas Gp0 and the steam ST heated to the temperature at which the reforming reaction occurs are brought into contact, it is possible to cause the reforming reaction without using a catalyst, and for the introduction, replacement, regeneration, etc. of the catalyst. No cost is required. The equipment is downsized by saving the amount of heat from the heater and eliminating the need for catalyst storage.

  Since the source gas Gp0 and the steam ST are separately heated and the reforming reaction is caused only by the mixing and contact, there is no possibility of unexpected hydrogen generation before the mixing and the safety is high.

[Hydrogen production equipment]
Next, Example 1 of the hydrogen production apparatus according to the present invention will be described with reference to the drawings.

[overall structure]
As shown in FIG. 1, the hydrogen production apparatus includes a tank (propane gas tank) 100 filled with a raw material gas Gp0, for example, propane gas, and the tank 100 is connected to a desulfurization apparatus 104 via a valve 102 and a heat exchanger 117. ing. A raw material gas heater 108 is connected to the subsequent stage of the desulfurization apparatus 104 via a heat exchanger 115. The desulfurization apparatus 104 desulfurizes the raw material gas Gp0, and the desulfurized raw material gas Gp1 is heated by the heat exchanger 115 and further heated by the heater 108 to a temperature at which the reforming reaction occurs. A reforming reactor 112 is connected to the subsequent stage of the heater 108, and the raw material gas Gp 1 heated to a temperature at which the reforming reaction occurs is sent to the reforming reactor 112.

  A steam heater 110 is connected to the reforming reactor 112 in parallel with the heater 108, and the boiler 106 is connected to the heater 110 via a heat exchanger 116. The boiler 106 generates water vapor ST by heating water W and drain water WD described later. After the steam ST is heated by the heat exchanger 116, the steam ST is further heated by the heater 110 to a temperature at which the reforming reaction occurs, and is supplied to the reforming reactor 112.

  The raw material gas Gp1 and the steam ST heated to the temperature at which the reforming reaction occurs are mixed in the reforming reactor 112 and come into contact with each other. As a result, a reforming reaction (formula (1)) occurs, and a reformed gas Gc0 is generated.

A pipe line extending from the boiler 106 to the heat exchanger 116 is provided with a flow meter 138 and a valve 134. The flow meter 138 can measure the flow rate of the steam ST supplied to the reforming reactor 112, and the valve The flow rate of water vapor ST delivered by 134 can be adjusted.
The pipe from the desulfurization device 104 to the heat exchanger 115 is provided with a flow meter 140 and a valve 136. The flow meter 140 can measure the flow rate of the raw material gas Gp1 fed to the reforming reactor 112. The flow rate of the raw material gas Gp1 fed by the valve 136 can be adjusted.

In the subsequent stage of the reforming reactor 112, heat exchangers 115 and 116 and a carbon filter 142 are passed through.
An aqueous shift reactor 114 is connected, and a steam / water separator 118 is connected to the subsequent stage of the aqueous shift reactor 114 via a heat exchanger 117. A PSA (Pressure Swing Adsorption) device 119 is connected to the subsequent stage of the steam separator 118.
The aqueous shift reactor 114 causes the aqueous shift reaction (formula (2)) to occur in the reformed gas Gc0 to generate the reformed gas Gc1 having a high hydrogen content.
The carbon filter 142 is generated in the heater 108 and the reforming reactor 112, removes soot mixed in the reformed gas Gc0, and sends the purified reformed gas Gc0 to the aqueous shift reactor 114.
In the subsequent stage of the aqueous shift reactor 114, the reformed gas Gc1 is cooled by the heat exchanger 117 and then introduced into the steam separator 118, where moisture is separated and removed.
In the subsequent stage of the steam separator 118, the PSA device uses the difference in the adsorption characteristics of the adsorbent to the gas to alternately repeat the pressurization and depressurization operations from the reformed gas Gc1 to the target gas ( Hydrogen) is continuously separated.
The hydrogen yield in the reformed gas Gc1 is increased by a series of treatments by the aqueous shift reactor 114, the heat exchanger 117, the steam separator 118, and the PSA device 119.

Since the raw material gas Gp1 and the steam ST fed to the reforming reactor 112 are heated to a temperature at which the reforming reaction occurs, the reformed gas Gc0 is at a high temperature (for example, 750 ° C.), and the heat exchangers 115 and 116 are heated. Can effectively heat the raw material gas Gp1 and the steam ST before being introduced into the heaters 108 and 110 by the high-temperature reformed gas Gc0, respectively.
Since the source gas Gp0 is supplied from the tank 100, it is usually at a low temperature, and the heat exchanger 117 can effectively cool the reformed gas Gc1 after the aqueous shift reaction.

One or more hydrogen gas tanks 122 and one or more waste gas tanks 124 are connected to the subsequent stage of the PSA device 119, and the hydrogen gas tank 122 is filled with high-quality hydrogen gas Gh from which moisture has been removed. In addition, components having a higher specific gravity than hydrogen gas, such as unreacted source gas and water, contained in the hydrogen gas Gh are filled and stored in the waste gas tank 124. The waste gas WG can be used as fuel for the boiler 106.
The steam / water separator 118 is provided with a drain discharger 120, and the separated water can be appropriately discharged as drain water WD. If the liquid level gauge 126 is provided in the steam separator 118 and the drain discharger 120 is controlled by the output of the liquid level gauge 126, the drain water WD can be automatically discharged. The drain water WD is supplied to the boiler 106 together with the water W as a raw material of the water vapor ST, and is effectively used.

  Pressure gauges 130 and 132 are provided in the hydrogen gas tank 122 and the waste gas tank 124, respectively, and the storage amounts of the hydrogen gas Gh and the waste gas WG can be measured.

A propane gas tank 100 is connected to the boiler 106 via a valve 127, and a waste gas tank 124 is connected via a valve 128. The raw material gas Gp0 or the waste gas WG can be selectively used as fuel. By utilizing the waste gas WG as a fuel, the hydrogen production cost can be reduced.
Although the waste gas WG is not stored in the initial operation of the hydrogen production apparatus, at this time, the raw material gas Gp0 can be diverted to the fuel of the boiler 106. Further, when the waste gas WG is consumed and is not sufficient for the operation of the boiler 106, the raw material gas Gp0 can be used again. That is, smooth operation can be ensured while minimizing fuel costs for the boiler 106.

The heaters 108 and 110 need to be able to heat the raw material gas Gp1 and the steam ST to a reforming temperature, for example, a high temperature of, for example, 1000 ° C. A better reforming reaction has occurred in the electric heater.
[Reforming reactor]

  As shown in FIGS. 2A and 2B, the reforming reactor 112 includes a spherical shell-shaped mixing chamber 204 that is opened (opening 205) in one direction (rightward in FIG. 2A). A heavy tube 203 is attached. The double pipe 203 is configured by inserting a water vapor introduction pipe 200 for introducing water vapor ST into a raw material gas introduction pipe 202 for introducing the raw material gas Gp1. The discharge direction of each double tube 203 is directed to the spherical shell center So of the mixing chamber 204 and has an acute inclination angle θ with respect to the direction of the opening 205 (different angles in FIG. Simplified.) Is set.

A reforming reaction is caused by the raw material gas Gp1 and the steam ST discharged into the mixing chamber 204, and a reformed gas Gc0 is generated. At this time, since the raw material gas introduction pipe 202 and the water vapor introduction pipe 200 are made into the double pipe 203, the raw material gas Gp1 and the water vapor ST exist close to each other from the time of discharge, and the contact probability is high. Further, since the discharge direction from the double pipe 203 is toward the center So, the contact probability between the source gas Gp1 and the water vapor ST is increased.
The internal / external relationship between the source gas introduction pipe 202 and the water vapor introduction pipe 200 in the double pipe 203 is not limited to the above, and the inside and outside may be reversed. Further, the double pipe may not be adopted, and both may be separately attached to the mixing chamber 204.

  The supply amounts of the raw material gas Gp1 and the water vapor ST to the respective double pipes 203 are adjusted by valves 136 and 134, respectively. The water vapor introduction pipe 200 and the raw material gas introduction pipe 202 in each double pipe 203 are provided with a water vapor introduction valve. 230 and a raw material gas introduction valve 220 are respectively mounted. In FIG. 2A, the valves 220 and 230 are displayed only for one double pipe 203, and the display is omitted for the other double pipes. The valves 220 and 230 are opened and closed to adjust the number of double pipes 203 that supply the raw material gas Gp1 and the steam ST to the reforming reactor 112, thereby adjusting the feed amounts of the raw material gas Gp1 and the steam ST. obtain.

The volume of the reformed gas Gc0 generated is larger than that of the discharged raw material gas Gp1 and water vapor ST, and a shock wave is generated due to rapid gas expansion. The shock wave collides with the spherical inner surface of the mixing chamber 204, is reflected, and propagates repeatedly in the mixing chamber 204. Thereby, the unreacted raw material gas Gp1 and the water vapor ST are stirred, and the reforming reaction is promoted.
Regarding the shock wave reflection in the mixing chamber 204, it is important that the inner surface of the mixing chamber 204 is spherical and the outer surface shape is irrelevant. Therefore, the mixing chamber 204 does not necessarily have a spherical shell shape. That is, the mixing chamber 204 may have a spherical shape whose inner surface is open in one direction. However, in the practical manufacture of the mixing chamber 204, it is advantageous to form a spherical shell that opens in one direction with heat-resistant stainless steel in the entire mixing chamber 204.

  As the reforming reaction proceeds in the mixing chamber 204, the pressure in the mixing chamber 204 increases, and the generated reformed gas Gc0 is discharged from the opening 205 together with the unreacted raw material gas Gp1 and the water vapor ST.

An outlet pipe 206 having the same diameter as the opening 205 is connected to the opening 205, and the reformed gas Gc0 and unreacted gas are led out from the outlet pipe 206 and introduced into the aqueous shift reactor 114 through the heat exchangers 115 and 116. Is done.
Here, since the discharge directions of the raw material gas introduction pipe 202 and the water vapor introduction pipe 200 are set to an acute inclination angle θ with respect to the direction of the opening 205, the momentum of the raw material gas Gp1 and the water vapor ST at the time of discharge is effective. Utilized, the reformed gas Gc0 and the unreacted gas from the outlet pipe 206 are smoothly led out.

  In the mixing chamber 204, a pressure gauge 602 and a thermometer 604 are provided, and the state of the reforming reaction in the mixing chamber 204 can be detected.

As shown in FIGS. 2A and 3A, the water vapor introduction pipe 200 is provided with a pressure gauge 212 and a thermometer 214, and the pressure and temperature of the water vapor ST in the water vapor introduction pipe 200 can be measured.
The source gas introduction pipe 202 is provided with a pressure gauge 216 and a thermometer 218, and the pressure and temperature of the source gas Gp1 in the source gas introduction pipe 202 can be measured.
The outlet pipe 206 is provided with a pressure gauge 208 and a thermometer 210, and the pressure and temperature of the reformed gas Gc0 in the outlet pipe 206 can be measured.

  In the hydrogen production apparatus of the present embodiment, the heaters 108 and 110 only generate the amount of heat that heats the raw material gas Gp0 and the steam ST to the temperatures at which the reforming reaction occurs, respectively. Compared to the case where the endothermic reaction of the reforming reaction in the reactor is compensated, the necessary minimum amount of heat is sufficient.

  Further, since the raw material gas Gp0 and the steam ST heated to the temperature at which the reforming reaction occurs are brought into contact, it is possible to cause the reforming reaction without using a catalyst, and for the introduction, replacement, regeneration, etc. of the catalyst. No cost is required. The equipment is downsized by saving the amount of heat from the heater and eliminating the need for catalyst storage.

  Furthermore, since the source gas Gp0 and the steam ST are separately heated and the reforming reaction is caused only by the mixing and contact, there is no possibility of unexpected hydrogen generation before the mixing and the safety is high.

  As shown in FIG. 4A, the hydrogen production apparatus is provided with a control unit 400. The control unit 400 includes pressure gauges 130, 132, 208, 212, 216, 602, thermometers 210, 214, 218, 604, liquid level. A total 126 and flow meters 138 and 140 are connected. The control unit 400 controls the heaters 108 and 110, the valves 134 and 136, the source gas introduction valve 220, the water vapor introduction valve 230, and the drain discharger 120 based on the measurement signals of these measuring instruments.

  A timer 402 is further connected to the control unit 400, and the valves 102, 127 and 128 can be controlled based on a schedule signal from the timer T.

  Regarding the control of the valves 127 and 128, for example, when the pressure of the waste gas tank 124 is measured by the measurement signal of the pressure gauge 132 and it is determined that the pressure is sufficiently high and sufficient waste gas is stored, the source gas Gp0 is changed. The waste gas WG is immediately used without being used as fuel for the boiler 106. At this time, the valve 127 is closed and only the valve 128 is opened.

When it is determined that sufficient waste gas is not stored in the waste gas tank 124, the raw material gas Gp0 is once used as fuel for the boiler 106, and then the waste gas WG is used when the waste gas WG is sufficiently stored. To resume. At this time, the valve 127 is further opened, and when the pressure of the pressure gauge 132 becomes sufficiently high, the valve 127 is closed and the valve 128 is opened.
When an abnormality of the device is detected based on signals from the pressure gauges 130, 132, 208, 212, 216, 602, thermometers 210, 214, 218, 604, liquid level gauge 126, and flow meters 138, 140, The control unit 400 issues an abnormal alarm signal.

  For example, the control unit 400 performs the processing of FIG. 4B, that is, preheating setting (step S4B01), reforming start / stop (step S4B02), waste gas usage setting (step S4B03), drain water usage setting (step S4B04), Quality reaction control (step S4B05) is sequentially executed.

Preheating is a method in which when the reforming reaction is not being performed, only the steam ST is supplied to the reforming reactor 112 to maintain a high temperature, thereby speeding up the start of the reaction when the reforming reaction is started.
As shown in FIG. 4C, in the preheating setting (step S4B01), first, whether or not preheating is required is input (step S4C01) by a manual switch (not shown). When preheating is required, the preheating flag F1 = 1 is set (step S4C02), and when preheating is not required, the preheating flag F1 = 0 is set (step S4C05).
When the flag F1 = 1, it is determined whether or not the reforming operation is being performed (the valve 136 is open and the raw material gas Gp1 is being supplied to the reforming reactor 112) (step S4C03). When the reforming operation is in progress, the preheating setting process is terminated as it is, and when it is not in operation, the valve 134 is set to an opening for preheating in order to execute preheating (step S4C04). The opening for preheating is smaller than the opening during the reforming reaction, and preheating is performed with the minimum necessary energy consumption.

As shown in FIG. 4D, the reforming start / stop (step S4B02) process first determines whether or not the reforming start flag F2 = 1 (step S4D01). That is, it is determined whether or not “start” has been set.
When F2 = 1, the process jumps to step S4D05, and when F2 = 0, the process proceeds to step S4D02.

  In step S4D02, the control unit 400 determines that the pressure of the pressure gauge 130 in the hydrogen tank 122 decreases and the hydrogen storage amount is insufficient, or determines the start of reforming by operating a manual switch. When the reforming is started, the process proceeds to step S4D03, and when it is not started, the process jumps to step S4D05.

In step S4D03, the flag F2 = 1 is set, and the process proceeds to step S4D04.
In step S4D04, the opening degree of the valves 134 and 136 and the number of the double pipes 203 in which the valves 220 and 230 are opened are initialized to the state at the start of reforming, and the heaters 108 and 110 are started.
Thereafter, the process proceeds to step S4D05.

  In step S4D05, the pressure of the pressure gauge 130 in the hydrogen tank 122 increases, and the control unit 400 determines that the hydrogen storage amount is sufficient, or determines that reforming is stopped by operating a manual switch. When the reforming is stopped, the process proceeds to step S4D06. When the reforming is not stopped, the reforming start / stop process is terminated as it is.

  In step S4D06, the flag F2 = 0 and a flag F3 = F4 = 0, which will be described later, are initialized, and the reforming start / stop process ends.

As shown in FIG. 4E, in the processing of the waste gas use setting (step S4B03), it is first determined whether or not the waste gas use flag F3 = 1 (step S4E01). That is, it is determined whether or not “use” is set.
When F3 = 1, the process proceeds to step S4E05, and when F3 = 0, the process proceeds to step S4E02.

In step S4E02, the control unit 400 determines whether the pressure of the pressure gauge 132 of the waste gas tank 124 has increased and the waste gas storage amount has become sufficient. When the storage amount is sufficient, the process proceeds to step S4E03, and when the storage amount is insufficient, the waste gas use setting process is terminated.
In step S4E03, the flag F3 = 1 is set, and the process proceeds to step S4E04.
In step S4E04, the valve 127 is closed and the valve 128 is opened to supply the waste gas WG to the boiler.

In step S4E05, the control unit 400 determines whether or not the pressure of the pressure gauge 132 of the waste gas tank 124 has decreased and the waste gas storage amount has become insufficient. When the storage amount is insufficient, the process proceeds to step S4E06, and when the storage amount is not insufficient, the waste gas use setting process is terminated.
In step S4E06, the flag F3 = 0 is set, and the process proceeds to step S4E07.
In step S4E07, the valve 127 is opened and the valve 128 is closed to stop the supply of the waste gas WG.

As shown in FIG. 4F, the drain water use setting (step S4B04) process first determines whether or not the drain water use flag F4 = 1 (step S4F01). That is, it is determined whether or not “use” is set.
When F4 = 1, the process proceeds to step S4F05, and when F4 = 0, the process proceeds to step S4F02.

In step S4F02, the control unit 400 determines whether or not the water level of the liquid level gauge 126 of the steam separator 118 has increased and the drain water WD has accumulated sufficiently. When the drain water storage amount is sufficient, the process proceeds to step S4F03, and when the storage amount is insufficient, the drain water use setting process is terminated.
In step S4F03, the flag F4 = 1 is set, and the process proceeds to step S4F04.
In step S4F04, the supply of drain water WD to the boiler is started.

In step S4F05, the control unit 400 determines whether or not the water level of the liquid level gauge 126 of the steam separator 118 has decreased and the drain water storage amount has become insufficient. When the storage amount is insufficient, the process proceeds to step S4F06, and when the storage amount is not insufficient, the drain water use setting process is terminated.
In step S4F06, the flag F4 = 0 is set, and the process proceeds to step S4F07.
In step S4F07, the supply of drain water WD is stopped.

As shown in FIG. 4G, in the reforming reaction control (step S4B05), first, it is determined whether or not the pressure (pressure gauge 602) in the mixing chamber 204 is lower than a predetermined threshold value Pt1 (step S4G01). The threshold value Pt1 is the minimum pressure when a normal reforming reaction is occurring, and when the pressure is lower than that, a normal reforming reaction is not occurring.
When the pressure is lower than the threshold value Pt1, the process proceeds to step S4G02. When the pressure is not lower, the process proceeds to step S4G09.

In step S4G02, it is determined whether or not the opening degrees of the valves 134 and 136 are maximum. That is, it is determined whether or not the reforming reaction can be promoted by operating the valves 134 and 136. When the opening is maximum, the process proceeds to step S4G04, and when not, the process proceeds to step S4G03.
In step S4G03, the opening degree of the valves 134 and 136 is increased by a predetermined amount, and the process proceeds to step S4G05.
On the other hand, in step S4G04, the flag MAX = 1 indicating that the opening degree of the valves 134, 136 is maximum is set, and the process proceeds to step S4G05.
The flag MAX is a flag indicating that the necessary adjustment cannot be performed with the valves 134 and 136, and is also used as a flag for the minimum opening of the valves 134 and 136.

In step S4G05, it is determined whether or not the valves 220 and 230 are open in all the double pipes 203.
That is, it is determined whether or not the reforming reaction can be promoted by operating the valves 220 and 230. When the raw material gas Gp1 and the water vapor ST are supplied from all the double pipes 203, the reforming reaction control by the number of the double pipes 203 is impossible, so the process proceeds to step S4G07.
When all the double tubes 203 are not used, the process proceeds to step S4G06, one double tube 203 to be used is added, and the process proceeds to step S4G17.
In step S4G17, an initialization process for flag MAX = 0 is performed, and the reforming reaction control process ends.

In step 4G07, it is determined whether or not the flag MAX = 1. That is, when the valves 134 and 136 are at the maximum opening and the number of the double pipes 203 is the maximum, further reforming reaction cannot be promoted, and sufficient reforming reaction has not occurred. Therefore, the process proceeds to step S4G16.
In step S4G16, an abnormal alarm signal is issued, and the process proceeds to step S4G17.

In step S4G09, it is determined whether or not the pressure (pressure gauge 602) in the mixing chamber 204 is higher than a predetermined threshold value Pt2. The threshold value Pt2 is an abnormally high pressure in the mixing chamber 204.
When the pressure is higher than the threshold value Pt2, the process proceeds to step S4G10, and when not higher, the process proceeds to step S4G17.

In step S4G10, it is determined whether or not the openings of the valves 134 and 136 are minimum. That is, it is determined whether or not the reforming reaction can be suppressed by operating the valves 134 and 136. When the opening is minimum, the process proceeds to step S4G12, and when not, the process proceeds to step S4G11.
In step S4G11, the opening degree of the valves 134 and 136 is decreased by a predetermined amount, and the process proceeds to step S4G13.
On the other hand, in step S4G12, the flag MAX = 1 indicating that the opening degree of the valves 134, 136 is minimum, and the process proceeds to step S4G13.

In step S4G13, it is determined whether or not the number of the double pipes 203 in which the valves 220 and 230 are opened is the minimum (for example, one).
That is, it is determined whether or not the reforming reaction can be suppressed by operating the valves 220 and 230. When the raw material gas Gp1 and the steam ST are supplied from the minimum number (for example, one) of the double pipes 203, the reforming reaction control by the number of the double pipes 203 is impossible, so step S4G15 Proceed to
When the number of the double pipes 203 is not the minimum, the process proceeds to step S4G14, one double pipe 203 to be used is decreased, and the process proceeds to step S4G17.

In step 4G15, it is determined whether or not the flag MAX = 1. That is, when the valves 134 and 136 are at the minimum opening and the number of the double pipes 203 is the minimum, further reforming reaction cannot be promoted, and an abnormally active reforming reaction occurs. Therefore, the process proceeds to step S4G16.
In step S4G16, an abnormality alarm signal is issued, and the process proceeds to step S4G17.

  4B to 4G, the reforming reaction can be optimized, and the economy and operability are improved.

  Next, a second embodiment of the hydrogen production apparatus according to the present invention will be described with reference to the drawings. In the figure, the same or corresponding parts as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted.

  As shown in FIG. 6, the reforming reactor 112 of the present embodiment has a second mixing chamber 612 connected between the opening 205 of the mixing chamber 204 and the outlet pipe 206 similar to that of the first embodiment, and the opening. 205 is provided with a damper 600. Similar to the mixing chamber 204, the second mixing chamber 612 has a spherical shell shape and has an opening 207 in the same direction as the mixing chamber 204. The lead-out tube 206 is connected to the opening 207.

  In the second mixing chamber 612, the unreacted source gas Gp1 and water vapor ST discharged from the mixing chamber 204 are subjected to a reforming reaction. As in the mixing chamber 204, the second mixing chamber 612 is also agitated by the shock wave accompanying the reforming reaction to promote the reforming reaction. As a result, the hydrogen concentration of the reformed gas Gc0 discharged from the outlet pipe 206 is increased. Is increased.

  The damper 600 adjusts the discharge amount of the reformed gas Gc0 and the unreacted gas from the mixing chamber 204, and the reformer discharged from the outlet pipe 206 according to the balance of the reforming reaction rates in the mixing chambers 204 and 612. The hydrogen concentration of the gas Gc0, that is, the reforming rate is maximized.

  In the second mixing chamber 612, a pressure gauge 606 and a thermometer 608 are provided, and the status of the reforming reaction in the second mixing chamber 612 can be detected.

  In addition to the effect of the first embodiment, the second embodiment can obtain an effect that the reforming rate can be further improved.

  As shown in FIG. 7A, the control unit 400 in the second embodiment acquires measurement signals from the pressure gauge 606 and the thermometer 608 and performs reforming reaction control by the damper 600 in addition to the same control as in the first embodiment. .

  The control unit 400 performs preheat setting (step S4B01), reforming start / stop (step S4B02), waste gas use setting (step S4B03), and drain water use setting (step S4B04) shown in FIG. 4B of the first embodiment. At the same time, the following reforming reaction control (referred to as step S7B05) is executed.

As shown in FIG. 7B, in the reforming reaction control (step S7B05), first, as in step S4G01, it is determined whether or not the pressure (pressure gauge 602) in the mixing chamber 204 is lower than a predetermined threshold value Pt1. To do.
When the pressure is lower than the threshold value Pt1, the process proceeds to step S7G02. When the pressure is not lower, the process proceeds to step S7G11.

In step S7G02, it is determined whether or not the opening of damper 600 is minimum. That is, it is determined whether or not the reforming reaction can be promoted by operating the damper 600. When the opening is minimum, the process proceeds to step S7G04, and when not, the process proceeds to step S7G03.
In step S7G03, the opening degree of the damper 600 is decreased by a predetermined amount, and the process proceeds to step S7G05.
On the other hand, in step S7G04, a flag M1 = 1 indicating that the opening degree of the damper 600 is minimum is set, and the process proceeds to step S7G05.
The flag M <b> 1 is a flag indicating that the damper 600 cannot perform the necessary adjustment, and is also used as a minimum opening flag of the damper 600.

In step S7G05, as in step S4G02, it is determined whether or not the opening degree of the valves 134, 136 is maximum. When the opening is maximum, the process proceeds to step S7G07, and when not, the process proceeds to step S7G06.
In step S7G06, the opening degree of the valves 134 and 136 is increased by a predetermined amount, and the process proceeds to step S7G08.
On the other hand, in step S7G07, the flag M2 = 1 indicating that the opening degree of the valves 134, 136 is maximum, and the process proceeds to step S7G08.
The flag M2 is a flag indicating that the necessary adjustment cannot be performed with the valves 134 and 136, and is also used as a flag for the minimum opening of the valves 134 and 136.

In step S7G08, as in step S4G05, it is determined whether or not the valves 220 and 230 are open in all the double pipes 203. When the source gas Gp1 and the water vapor ST are supplied from all the double pipes 203, the process proceeds to step S7G10, and when all the double pipes 203 are not used, the process proceeds to step S7G09.
In step S7G09, the number of double tubes 203 to be used is increased by 1, and the process proceeds to step S7G22.
In step S7G22, an initialization process of flag M1 = M2 = 0 is performed, and the reforming reaction control process ends.

In step S7G10, it is determined whether or not flag M1 = M2 = 1. That is, when the damper 600 has the minimum opening, the valves 134 and 136 have the maximum opening, and the number of the double pipes 203 is the maximum, the further reforming reaction cannot be promoted, and Since sufficient reforming reaction has not occurred, the process proceeds to step S7G21.
In step S7G21, an abnormality alarm signal is issued, and the process proceeds to step S7G22.

  In step S7G11, as in step S4G09, it is determined whether the pressure in the mixing chamber 204 (pressure gauge 602) is higher than a predetermined threshold value Pt2. When the pressure is higher than the threshold value Pt2, the process proceeds to step S7G12, and when not higher, the process proceeds to step S7G22.

In step S7G12, it is determined whether or not the opening of damper 600 is the maximum. That is, it is determined whether or not the reforming reaction can be suppressed by operating the damper 600. When the opening is maximum, the process proceeds to step S7G14, and when not, the process proceeds to step S7G13.
In step S7G13, the opening degree of the damper 600 is increased by a predetermined amount, and the process proceeds to step S7G15.
On the other hand, in step S7G14, a flag M1 = 1 indicating that the opening degree of the damper 600 is maximum is set, and the process proceeds to step S7G15.

In step S7G15, as in step S4G10, it is determined whether or not the openings of the valves 134 and 136 are minimum. When the opening is minimum, the process proceeds to step S7G17, and when not, the process proceeds to step S7G16.
In step S7G16, the opening degree of the valves 134 and 136 is decreased by a predetermined amount, and the process proceeds to step S7G18.
On the other hand, in step S7G17, the flag M2 = 1 indicating that the opening degree of the valves 134, 136 is minimum, and the process proceeds to step S7G18.

  In step S7G18, as in step S4G13, it is determined whether or not the number of double tubes 203 in which the valves 220 and 230 are opened is the smallest. When it is the minimum, the process proceeds to step S7G20. If not, the process proceeds to step S7G19, one double tube 203 to be used is decreased, and the process proceeds to step S7G22.

In step S7G20, it is determined whether or not flag M1 = M2 = 1. That is, when the damper 600 has the maximum opening, the valves 134 and 136 have the minimum opening, and the number of the double pipes 203 is the minimum, the further reforming reaction cannot be suppressed, and Since an abnormally active reforming reaction has occurred, the process proceeds to step S7G21.
In step S7G21, an abnormality alarm signal is issued, and the process proceeds to step S7G22.

  By the process of FIG. 7B, in addition to the effect of Example 1, the effect that the reforming reaction can be further optimized is obtained.

  Next, a third embodiment of the hydrogen production apparatus according to the present invention will be described with reference to the drawings. In the figure, the same or corresponding parts as those in the first and second embodiments are designated by the same reference numerals, and the description thereof is omitted.

  As shown in FIGS. 8A and 8B, the raw material gas heater 112 according to the third embodiment includes a heated gas pipe 908 that is heated by introduction of the heated gas GH, and the heated gas pipe 908 is provided around the heated gas pipe 908. A water vapor introduction pipe 200 and a raw material gas introduction pipe 202 are provided coaxially. The steam introduction pipe 200 and the raw material gas introduction pipe 202 have the same diameter and face each other with the mixing chamber 204 interposed therebetween.

The heated gas pipe 908 passes through the centers of the water vapor introduction pipe 200 and the raw material gas introduction pipe 202, and heats the water vapor ST in the water vapor introduction pipe 200 and the raw material gas Gp1 in the raw material gas introduction pipe 202, respectively. That is, the portion where the heated gas pipe 908 penetrates the water vapor introduction pipe 200 functions as the water vapor heater 110, and the portion where the heated gas pipe 908 penetrates the raw material gas introduction pipe 202 functions as the raw material gas heater 108.
Thus, by adopting a configuration in which the heaters 108 and 110 are incorporated in the reforming reactor 112, the apparatus can be further reduced in size as compared with the first to third embodiments. Further, since the distance from the heaters 108 and 110 to the reforming reactor 112 is the shortest, heat radiation is minimized and the thermal efficiency is high.

  The mixing chamber 204 is formed in an annular shape extending in the axial direction around the heated gas pipe 908, and the outer diameter thereof is equal to that of the water vapor introducing pipe 200 and the raw material gas introducing pipe 202. The mixing chamber 204 has an outer shape formed of a metal mesh member 902 or the like, and is filled with incombustible particles such as ceramic balls 900 that are incombustible particles. The mixing chamber 204 functions as a holding member that holds the ceramic balls 900, and allows the raw material gas Gp1 and the water vapor ST to pass therethrough.

  The water vapor ST and the raw material gas Gp1 are introduced from the side into the mixing chamber 204, mixed while flowing around the ceramic ball 900, and come into contact with each other. As a result, a reforming reaction occurs and a reformed gas Gc0 is generated.

An annular lead-out chamber 904 is formed around the steam inlet pipe 200 and the source gas inlet pipe 202 so as to surround the mixing chamber 204 and extend in the axial direction. The outer periphery of the mixing chamber 204 is exposed in the lead-out chamber 904, and the reformed gas Gc0 generated in the mixing chamber 204 has a small specific gravity, so that the lead-out chamber 904 is radially upward from the mixing chamber 204. Is released inside.
The lead-out chamber 904 is eccentric upward with respect to the heating gas pipe 908, the water vapor introduction pipe 200, and the raw material gas introduction pipe 202, and the lower end portions thereof are located at the lower end portions of the water vapor introduction pipe 200 and the raw material gas introduction pipe 202. .
The inner surface of the lead-out chamber 904 has a cross-sectional shape in which the distance from the outer surface of the mixing chamber 204 increases from the lower end portion upward, has a large space in the upper portion, and the reformed gas Gc0 generated in the mixing chamber 204. Is guided upward.

  The upper end portion of the outlet chamber 904 is connected to a horizontal chamber outlet tube 906, and the second mixing chamber 612 is connected to the chamber outlet tube 906.

A hollow portion 910 that opens upward is provided in the upper portion of the mixing chamber 204, and the hollow portion 910 is not filled with the ceramic balls 900. By providing the hollow portion 910, the reformed gas Gc0 is smoothly discharged to the outlet chamber 904, and the residence time in the mixing chamber 204 is shortened. Thereby, the reforming reaction in the mixing chamber 204 is promoted, and the reforming rate is increased.
When the reforming reaction, which is an endothermic reaction, proceeds rapidly in the mixing chamber 204, the temperature of the unreacted raw material gas Gp0 and the water vapor ST may be lowered, but by smoothly discharging the reformed gas Gc0, A reduction in the reforming rate can be prevented.

  In the lead-out chamber 904, annular flow control valves 912 and 914 are slidably fitted on the outer circumferences of the water vapor introduction pipe 200 and the source gas introduction pipe 202. Drive shafts 916 and 918 are connected to the flow rate control valves 912 and 914, respectively, and can slide in the axial direction of the water vapor introduction pipe 200 and the raw material gas introduction pipe 202 by a drive source (not shown). The flow rate control valves 912 and 914 can cover the periphery of the mixing chamber 204 partially or entirely, and can adjust the discharge amount of the reformed gas Gc0 and the unreacted gas from the mixing chamber 204 to the outlet chamber 904. The drive source drives the drive shafts 916 and 918 so that the flow rate adjusting valves 912 and 914 are symmetrical with respect to the center in the axial direction of the mixing chamber 204, and the reformed gas Gc0 is output from the mixing chamber 204 to the axis of the outlet chamber 904. It is discharged to the center in the direction, and then smoothly discharged to the outlet pipe 206 through the center of the second mixing chamber 612.

  By providing the flow rate control valves 912 and 914, the hydrogen concentration of the reformed gas Gc0 discharged from the outlet pipe 206 according to the balance of the reforming reaction rates in the mixing chambers 204 and 612, as in the second embodiment, That is, the reforming rate is maximized.

  The water vapor introduction pipe 200 is provided with a pressure gauge 212 and a thermometer 214, the raw material gas introduction pipe 202 is provided with a pressure gauge 216 and a thermometer 218, respectively, and the second mixing chamber 612 is provided with a pressure gauge 606 and a thermometer 608. Is provided. Accordingly, the steam ST supplied to the mixing chamber 204, the pressure and temperature of the raw material gas Gp1, and the state of the reforming reaction in the second mixing chamber 612 can be detected.

  In the third embodiment, the raw material gas Gp1 and the water vapor ST are mixed in the mixing chamber 204 filled with the nonflammable particles 900. Therefore, in addition to the effects of the second embodiment, the water vapor and the raw material gas are caused by the flow around the nonflammable particles. The contact frequency is increased, and the modification rate is improved. Thereby, the reforming reactor can be further downsized.

  As illustrated in FIG. 9A, the control unit 400 according to the third embodiment controls the flow rate control valves 912 and 914 instead of the control of the damper 600 according to the second embodiment.

  The control unit 400 of the third embodiment replaces the steps S7G02, S7G03, S0704, S0712, S7G13, and S7G14 related to the damper 600 adjustment in the reforming reaction control (FIG. 7B) of the second embodiment. Steps S9G02, S9G03, S0904, S9G12, S9G13, and S9G14 related to adjustment are executed. Other processes are the same as those in the second embodiment.

As shown in FIG. 9B, in the reforming reaction control (step S9B05), first, as in step S7G01, it is determined whether or not the pressure (pressure gauge 602) in the mixing chamber 204 is lower than a predetermined threshold value Pt1. To do.
When the pressure is lower than the threshold value Pt1, the process proceeds to step S9G02. When the pressure is not lower, the process proceeds to step S9G11.

In step S9G02, it is determined whether or not the opening amounts of the flow rate control valves 912 and 914 are minimum. That is, it is determined whether or not the reforming reaction can be promoted by operating the flow rate control valves 912 and 914. When the opening is minimum, the process proceeds to step S9G04, and when not, the process proceeds to step S9G03.
In step S9G03, the opening degree of the flow control valves 912 and 914 is decreased by a predetermined amount, and the process proceeds to step S9G05.
On the other hand, in step S9G04, the flag M1 = 1 indicating that the opening degree of the flow rate adjusting valves 912, 914 is minimum, and the process proceeds to step S9G05.
The flag M1 is a flag indicating that the necessary adjustment cannot be performed by the flow rate control valves 912 and 914, and is also used as a maximum opening degree flag of the flow rate control valves 912 and 914.

  In step S9G11, as in step S7G11, it is determined whether or not the pressure (pressure gauge 602) in the mixing chamber 204 is higher than a predetermined threshold value Pt2. When the pressure is higher than the threshold value Pt2, the process proceeds to step S9G12, and when not higher, the process proceeds to step S9G22.

In step S9G12, it is determined whether or not the opening amounts of the flow rate control valves 912 and 914 are maximum. That is, it is determined whether or not the reforming reaction can be suppressed by operating the flow rate control valves 912 and 914. When the opening is maximum, the process proceeds to step S9G14, and when not, the process proceeds to step S9G13.
In step S9G13, the opening degree of the flow rate adjusting valves 912 and 914 is increased by a predetermined amount, and the process proceeds to step S9G15.
On the other hand, in step S9G14, the flag M1 = 1 indicating that the opening degree of the flow rate control valves 912, 914 is the maximum, and the process proceeds to step S9G15.

  Other processes in the reforming reaction control, that is, steps S9G05 to S9G10 and S9G15 to S9G22 are the same as steps S7G05 to S7G10 and S7G15 to S7G22.

  The process of FIG. 9B can optimize the reforming reaction in a small apparatus.

  Next, a fourth embodiment of the hydrogen production apparatus according to the present invention will be described with reference to the drawings. In the figure, the same or corresponding parts as in the first, second, and third embodiments are denoted by the same reference numerals, and the description thereof is omitted.

  As shown in FIG. 10, in the reforming reactor 112 in Example 4, the raw material gas introduction pipe 202 is inserted into the steam introduction pipe 200, and the downstream portion of the steam introduction pipe 200 is used as the outlet pipe 206 as it is. . That is, the water vapor introducing pipe 200 and the outlet pipe 206 are formed as an integral pipe. The vicinity of the tip of the source gas introduction pipe 202 in this pipe is configured as a mixing chamber 204.

  A raw material gas introduction valve 220 and a water vapor introduction valve 230 are provided at the tip of the raw material gas introduction pipe 202.

  The source gas introduction valve 220 includes a drive shaft 220 </ b> C inserted into the source gas introduction pipe 202, a spherical valve body 220 </ b> A provided at the tip of the drive shaft 220 </ b> C, and a tip portion of the source gas introduction pipe 202 in the distal direction. And a tapered valve seat 220B that expands. The source gas introduction valve 220 can control the amount of introduction of the source gas Gp1 into the reforming reactor 112. The valve body 220A can move forward and backward with respect to the valve seat 220E by the drive shaft 220C, and can adjust the introduction amount of the source gas Gp1.

The water vapor introduction valve 230 includes a valve body 230A formed at the periphery of the leading end of the source gas introduction pipe 202,
A valve seat 230B formed integrally in an annular shape so as to face the valve body 230A is provided on the inner surface of the water vapor introduction pipe 200. The raw material gas introduction pipe 202 is movable in the axial direction with respect to the water vapor introduction pipe 200, and the valve body 230A can move forward and backward with respect to the valve seat 230B to adjust the amount of water vapor introduced.
The water vapor introduction valve 230 is configured by a leading end portion of the raw material gas introduction pipe 202 and a valve seat 230B that is integrally formed on the inner surface of the water vapor introduction pipe 200 so as to face the valve body 230A. And the outlet pipe 206 are integrally formed, and the valve seat 220B of the source gas introduction valve 220 is formed in the source gas introduction pipe 202, so that the reforming reactor 112 can be manufactured at a very low cost.

The outer periphery of the front end portion of the raw material gas introduction pipe 202 has a tapered surface that extends smoothly toward the front end, and when the water vapor introduction valve 230 is open, the water vapor ST is smoothly introduced.
The downstream side of the valve seat 230 </ b> B in the steam introduction pipe 200 is a tapered surface that spreads smoothly, and the source gas Gp <b> 1 and the steam ST are smoothly introduced into the mixing chamber 204.

  In the fourth embodiment, a part of the water vapor introduction pipe 200 is used for the mixing chamber 204, the raw material gas introduction pipe 202 itself is used as the water vapor introduction valve 220, and only one valve body 220A is provided. The reforming reactor 112 can be configured with a minimum number of parts, and an extremely small and inexpensive apparatus can be provided. ,

  As shown in FIG. 11A, the control unit 400 according to the fourth embodiment controls each of the valves 220 and 230 in place of the control of the plurality of valves 220 and 230 according to the first embodiment. The supply amount of ST is mainly performed by the valves 220 and 230. Therefore, the valves 134 and 136 can be small and inexpensive, which perform simple operations only for opening and closing. In this respect as well, the entire apparatus can be reduced in size and cost.

  The control unit 400 executes the processing of the waste gas use setting (step S4B03) and the drain water use setting (step S4B04) similar to those in the first embodiment, and the following preheating setting (referred to as step S11B01) and reforming start. Stop (referred to as step S11B02) and reforming reaction control (referred to as step S11B05).

As shown in FIG. 11B, in the preheating setting (step S11B01), first, whether or not preheating is required is input (step S11C01) by a manual switch (not shown). When preheating is necessary, the preheating flag F1 is set to 1 (step S11C02), and when preheating is not necessary, the preheating flag F1 is set to 0 (step S11C05).
When the flag F1 = 1, it is determined whether or not the reforming operation is being performed (the valve 220 is open and the raw material gas Gp1 is being introduced into the reforming reactor 112) (step S11C03). When the reforming operation is in progress, the preheating setting process is finished as it is, and when it is not in operation, the valve 230 is set to an opening for preheating in order to execute the preheating (step S11C04). The opening for preheating is smaller than the opening during the reforming reaction, and preheating is performed with the minimum necessary energy consumption.

As shown in FIG. 11C, in the reforming start / stop (step S11B02) process, it is first determined whether or not the reforming start flag F2 = 1 (step S11D01).
When F2 = 1, the process jumps to step S11D05, and when F2 = 0, the process proceeds to step S11D02.

  In step S11D02, the control unit 400 determines that the pressure of the pressure gauge 130 in the hydrogen tank 122 decreases and the hydrogen storage amount is insufficient, or determines the start of reforming by operating a manual switch. When the reforming is started, the process proceeds to step S11D03. When the reforming is not started, the process jumps to step S11D05.

In step S11D03, the flag F2 = 1 is set, and the process proceeds to step S11D04.
In step S11D04, the valves 134 and 136 and the valves 220 and 230 are initialized to the opening at the start of reforming, and the heaters 108 and 110 are started.
Thereafter, the process proceeds to step S11D05.

  In step S11D05, the control unit 400 determines that the pressure of the pressure gauge 130 in the hydrogen tank 122 is increased and the hydrogen storage amount is sufficient, or determines that the reforming is stopped by operating a manual switch. When the reforming is stopped, the process proceeds to step S11D06. When the reforming is not stopped, the reforming start / stop process is terminated as it is.

  In step S11D06, the flag F2 = 0 is set and the flag F3 = F4 = 0 is set, and the reforming start / stop processing is ended.

  As shown in FIG. 11D, in the reforming reaction control (step S11B05), first, it is determined whether or not the pressure (pressure gauge 602) in the mixing chamber 204 is lower than a predetermined threshold value Pt1 (step S11G01). When the pressure is lower than the threshold value Pt1, the process proceeds to step S11G02. When the pressure is not lower, the process proceeds to step S11G04.

In step S11G02, it is determined whether the opening degree of the valves 220 and 230 is the maximum. That is, it is determined whether or not the reforming reaction can be promoted by operating the valves 220 and 230. When the opening degree is maximum, the process jumps to step S11G07 to issue an abnormality alarm signal. If not, the process proceeds to step S11G03.
In step S11G03, the opening degree of the valves 220 and 230 is increased by a predetermined amount, and the reforming reaction control process is terminated.

In step S11G04, it is determined whether or not the pressure in the mixing chamber 204 (pressure gauge 602) is higher than a predetermined threshold value Pt2. When the pressure is higher than the threshold value Pt2, the process proceeds to step S11G05, and when not higher, the reforming reaction control process is terminated.

In step S11G05, it is determined whether or not the opening degree of the valves 220 and 230 is the minimum. When the opening is the minimum, the process jumps to step S11G07 and issues an abnormal alarm signal. When it is not the minimum, the process proceeds to step S11G06.
In step S11G06, the opening degree of the valves 220 and 230 is decreased by a predetermined amount, and the reforming reaction control process is terminated.

The reforming reaction control in FIG. 11D can optimize the reforming reaction with a very simple process. Therefore, high-speed processing by an inexpensive CPU is possible.
In the present embodiment, the raw material gas introduction pipe 202 is arranged inside the water vapor introduction pipe 200, but the water vapor introduction pipe 200 can also be arranged inside the raw material gas introduction pipe 202. In this case, the steam introduction valve 230 functions as a source gas introduction valve, and the source gas introduction valve 220 functions as a steam introduction valve.

Next, a fifth embodiment of the hydrogen production apparatus according to the present invention will be described with reference to the drawings. In the figure, the same or corresponding parts as those in the fourth embodiment are designated by the same reference numerals, and the description thereof is omitted.
In the fifth embodiment, an expansion wall 240 that adjusts the volume of the mixing chamber 204 is added to the configuration of the fourth embodiment.

As shown in FIG. 12, the reforming reactor 112 in the fifth embodiment is similar to the fourth embodiment in the steam introduction pipe 200, the source gas introduction pipe 202, the mixing chamber 204, the outlet pipe 206, the source gas introduction valve 220, the steam. An introduction valve 230 is provided, and an expansion wall 240 is provided downstream of the mixing chamber 204.
The expansion wall 240 includes a piston 240 </ b> A facing the mixing chamber 204 and a piston rod 240 </ b> B extending from the piston 240 </ b> A toward the outlet pipe 206, and the piston 240 </ b> A is axially driven by the piston rod 240 </ b> B. Advance and retreat. In FIG. 12, the piston 240A in the forward state is indicated by a solid line, and the piston 240A in the reverse state is indicated by an imaginary line. The volume of the mixing chamber 204 is increased or decreased by the advance / retreat of the piston 240A, and the reforming reaction in the mixing chamber 204 is further promoted or suppressed.
As a result, the optimum reforming conditions can be set both by adjusting the introduction amount of the raw material gas Gp1 and the water vapor ST by the valves 220 and 230 and by adjusting the volume of the mixing chamber 204.

The contact surface of the valve body 220A with the valve seat 220B is a spherical surface as in the fourth embodiment, but the surface facing the mixing chamber 204 is a concave curved surface having a small diameter smoothly in the downstream direction, and the source gas Gp1 and The steam ST is smoothly guided to the mixing chamber 204.
The outer peripheral surface of the piston 240 </ b> A is a tapered surface that expands in the downstream direction, and the reformed gas Gc <b> 0 generated in the mixing chamber 204 is smoothly guided to the outlet pipe 206.

  As illustrated in FIG. 13A, the control unit 400 according to the fifth embodiment controls the expansion wall 240 in addition to the control according to the fourth embodiment.

As shown in FIG. 13B, in the reforming reaction control (referred to as step S13B05), as in step S4G01, first, is the pressure in the mixing chamber 204 (pressure gauge 602) lower than a predetermined threshold value Pt1? It is determined whether or not (step S13G01).
When the pressure is lower than the threshold value Pt1, the process proceeds to step S13G02. When the pressure is not lower, the process proceeds to step S13G08.

In step S13G02, it is determined whether the volume of the mixing chamber 204 is minimum. That is, it is determined whether or not the reforming reaction can be promoted by operating the extension wall 240. When the capacity is minimum, the process proceeds to step S13G04. When the capacity is not minimum, the process proceeds to step S13G03.
In step S13G03, the expansion wall 240 is advanced to reduce the volume of the mixing chamber 204, and the process proceeds to step S13G05.
On the other hand, in step S13G04, the flag MAX = 1 indicating that the volume of the mixing chamber 204 is minimum is set, and the process proceeds to step S13G05.
The flag MAX is a flag indicating that the necessary adjustment cannot be performed by operating the expansion wall 240, and is also used as a flag with the maximum volume of the mixing chamber 204.

In step S13G08, it is determined whether the pressure (pressure gauge 602) in the mixing chamber 204 is higher than a predetermined threshold value Pt2. The threshold value Pt2 is an abnormally high pressure in the mixing chamber 204.
When the pressure is higher than the threshold value Pt2, the process proceeds to step S13G09, and when not higher, the process proceeds to step S13G16.

In step S13G09, it is determined whether or not the volume of the mixing chamber 204 is maximum. That is, it is determined whether or not the reforming reaction can be suppressed by operating the extension wall 240. When the volume is maximum, the process proceeds to step S13G11. When the volume is not maximum, the process proceeds to step S13G10.
In step S13G10, the expansion wall 240 is retracted to increase the volume of the mixing chamber 204, and the process proceeds to step S13G12.
On the other hand, in step S13G11, the flag MAX = 1 indicating that the volume of the mixing chamber 204 was maximum is set, and the process proceeds to step S13G12.

  By the process of FIG. 13B, the reforming reaction can be optimized, and the economy and operability are also improved.

Next, a sixth embodiment of the hydrogen production apparatus according to the present invention will be described with reference to the drawings. In the figure, the same or corresponding parts as those in the fifth embodiment are designated by the same reference numerals, and the description thereof is omitted.
The sixth embodiment employs another aspect of the expansion wall 240 in the fifth embodiment. The expansion wall 240 includes a cylinder 240D that slides in the axial direction while being in contact with the inner surface of the outlet pipe 206, and an annular plate 240E that is formed at the rear end of the cylinder 240D. The annular plate 240E faces the mixing chamber 204, and advances and retreats by the axial sliding of the cylinder 240D to change the volume of the mixing chamber 204. The annular plate 240E is provided with a through hole 240F in the center, and the reformed gas Gc0 generated in the mixing chamber 204 is led out from the outlet pipe 206 through the through hole 240F.

  In the sixth embodiment, the same control unit 400 as in the fifth embodiment is provided, and the same control is performed, and the same effects as in the fifth embodiment are obtained.

In the above embodiment, the configuration in which the catalyst is not necessary has been described. However, in the hydrogen production apparatus of Embodiment 3, it is possible to employ a ceramic ball 900 that has a catalytic action in part or all, for example, As a catalyst for steam reforming, a nickel-coated ceramic ball may be employed. Thereby, the reforming rate can be improved and the mixing chamber 204 can be cleaned.
Further, in the hydrogen production apparatus of Examples 1 and 2, ceramic balls having a catalytic action are attached to the inner surface of the mixing chamber 204 to improve the heat insulating property of the mixing chamber 204, improve the reforming rate, and clean the mixing chamber 204. You can plan.
In the first and second embodiments, the inner surface of the mixing chamber 204 is coated with nickel which is a main component of the catalytic action for steam reforming, which is effective for improving the reforming rate and cleaning the inside of the mixing chamber 204.

100 Propane gas tank 102, 127, 128, 134, 136 Valve 104 Desulfurization device 106 Boiler 108 Raw material gas heater 110 Steam heater 112 Reforming reactor 114 Aqueous shift reactor 115, 116, 117 Heat exchanger 118 Steam-water separator 119 PSA Device 120 Drain discharger 122 Hydrogen gas tank 124 Waste gas tank 126 Liquid level gauge 138, 140 Flow meter 142 Carbon filter 200 Water vapor introduction pipe 202 Raw material gas introduction pipe 203 Double pipe 204 Mixing chamber 205 Opening 206 Outlet pipe 207 Opening 130, 132, 208, 212, 216, 602, 606 Pressure gauge 210, 214, 218, 604, 608 Thermometer 220 Raw material gas introduction valve 220A Valve body 220B Valve seat 220C Drive shaft 230 Water vapor introduction valve 2 0A Valve body 230B Valve seat 230C, 230D Flow path wall 240 Expansion wall 240A Piston 240B Piston rod 240C Tapered surface 240D Drive cylinder 240E Annular plate 240F Through-hole 300 Introduction path 302, 306, 310, 314, 318, 322, 326 Collision surface 304, 308, 312, 316, 320, 324 Flow path 328 Derivation path 400 Control unit 402 Timer 600 Damper 612 Second mixing chamber 800 Throttle valve 900 Ceramic ball (non-combustible particles)
902 Holding member 904 Leading chamber 906 Chamber leading tube 908 Heating gas tube 910 Cavity 912, 914 Flow rate control valve 916, 918 Drive shaft Gh Hydrogen gas Gp0, Gp1 Raw gas Gp1 Raw gas Gc0, Gc1 Reforming gas GH Heating gas P11 P12, P21, P22, P3, P4, P5 Process ST Water vapor W water WD Drain water WG Waste gas

Claims (26)

A hydrogen production method in which a raw material gas and steam undergo a reforming reaction,
The source gas and steam are heated separately to a temperature at which the reforming reaction occurs,
A method for producing hydrogen, wherein the heated source gas and steam are mixed and brought into contact with each other to cause a steam reforming reaction. A hydrogen production device for reforming reaction of raw material gas and steam,
A boiler that generates water vapor;
A steam heater that heats the steam to a temperature at which a reforming reaction occurs;
A raw material gas heater for heating the raw material gas to a temperature at which a reforming reaction occurs;
A reforming reactor in which the steam heated by the steam heater and the source gas heated by the source gas heater are mixed and brought into contact;
With
A hydrogen production apparatus for causing a steam reforming reaction in the reforming reactor. The reforming reactor is
A steam introduction pipe into which the heated steam is introduced;
A source gas introduction pipe into which the heated source gas is introduced;
A mixing chamber in which the water vapor introduced from the water vapor introduction pipe and the raw material gas introduced from the raw material gas introduction pipe are mixed and brought into contact with each other;
An outlet pipe for leading the reformed gas in the mixing chamber;
The hydrogen production apparatus according to claim 2, comprising: The mixing chamber has a spherical shape with an inner surface opened in one direction, and discharge directions of the raw material gas introduction pipe and the water vapor introduction pipe are set at an acute inclination angle with respect to the direction of the opening. The hydrogen production apparatus as described. The hydrogen production apparatus according to claim 3, wherein one of the source gas introduction pipe and the water vapor introduction pipe is configured as a double pipe inserted into the other. The hydrogen production apparatus according to claim 3, wherein a second mixing chamber is provided between the mixing chamber and the outlet pipe, and a damper for adjusting a flow rate is provided at an opening of the mixing chamber. The hydrogen production apparatus according to claim 6, further comprising: a pressure detector that detects a pressure in the mixing chamber; and a control unit that controls the opening degree of the damper based on the pressure detected by the pressure detector. The reforming reactor is
A steam introduction pipe into which the heated steam is introduced;
A source gas introduction pipe into which the heated source gas is introduced;
A mixing chamber in which the water vapor introduced from the water vapor introduction pipe and the raw material gas introduced from the raw material gas introduction pipe are mixed and brought into contact with each other;
An outlet pipe for leading the reformed gas in the mixing chamber;
An outlet chamber provided around the mixing chamber and communicating with the mixing chamber;
With
The steam introduction pipe and the source gas introduction pipe are connected to the mixing chamber such that the introduction direction of the steam and the introduction direction of the source gas introduction are substantially opposed to each other,
The lead-out chamber is formed along a plane substantially orthogonal to the direction of introduction of the water vapor and the direction of introduction of the raw material gas,
The mixing chamber is filled with incombustible particles, and the water vapor and the raw material gas are mixed in the mixing chamber while flowing around the periphery of the incombustible particles to generate a reformed gas. The hydrogen production apparatus according to claim 2, wherein the hydrogen production apparatus flows radially from the mixing chamber and is fed to the outlet chamber. The hydrogen production apparatus according to claim 8, wherein the mixing chamber is provided with a hollow portion not filled with ceramic balls in contact with the lead-out chamber. A second mixing chamber is provided between the lead-out chamber and the lead-out pipe, and further includes an annular flow control valve slidably fitted to the outer periphery of the water vapor introduction pipe and the source gas introduction pipe in the lead-out chamber. The hydrogen production apparatus according to claim 8. The hydrogen production apparatus according to claim 8, further comprising: a pressure detector that detects a pressure in the mixing chamber; and a control unit that controls an opening of the flow rate control valve based on the pressure detected by the pressure detector. . The reforming reactor is
A steam introduction pipe into which the heated steam is introduced;
A water vapor introduction valve for adjusting the amount of water vapor introduced;
A source gas introduction pipe into which the heated source gas is introduced;
A raw material gas introduction valve for adjusting the amount of raw material gas introduced;
A mixing chamber in which the water vapor introduced from the water vapor introduction pipe and the raw material gas introduced from the raw material gas introduction pipe are mixed and brought into contact with each other;
An outlet pipe for leading the reformed gas in the mixing chamber;
With
One of the water vapor introduction pipe and the raw material gas introduction pipe is inserted into the other,
The mixing chamber is formed in the vicinity of the tip portion of the inner introduction pipe inside the outer introduction pipe,
The hydrogen production apparatus according to claim 2, wherein a tip portion of the inner introduction pipe constitutes a part of a water vapor introduction valve and a raw material gas introduction valve. The hydrogen production apparatus according to claim 12, further comprising an expansion wall that adjusts the volume of the mixing chamber. The pressure detector for detecting the pressure in the mixing chamber, and the controller for driving the expansion wall based on the pressure detected by the pressure detector and thereby adjusting the volume of the mixing chamber. 13. The hydrogen production apparatus according to 13. A steam introduction pipe into which steam heated to a temperature at which a reforming reaction occurs is introduced;
A source gas introduction pipe into which a source gas heated to a temperature at which a reforming reaction occurs is introduced;
A mixing chamber in which the water vapor introduced from the water vapor introduction pipe and the raw material gas introduced from the raw material gas introduction pipe are mixed and brought into contact with each other;
An outlet pipe for leading the reformed gas in the mixing chamber;
A reforming reactor. The mixing chamber has a spherical shape with an inner surface opened in one direction, and the discharge direction of the source gas introduction pipe and the water vapor introduction pipe is set to an acute angle with respect to the direction of the opening. The reforming reactor described. The reforming reactor according to claim 15, wherein one of the source gas introduction pipe and the water vapor introduction pipe is configured as a double pipe inserted into the other. The reforming reactor according to claim 15, wherein a second mixing chamber is provided between the mixing chamber and the outlet pipe, and a damper for adjusting a flow rate is provided at an opening of the mixing chamber. 19. The reforming reactor according to claim 18, wherein the pressure detector detects the pressure in the mixing chamber, and the opening degree of the damper is controlled based on the pressure detected by the pressure detector. A steam introduction pipe into which steam heated to a temperature at which a reforming reaction occurs is introduced;
A source gas introduction pipe into which a source gas heated to a temperature at which a reforming reaction occurs is introduced;
A mixing chamber in which the water vapor introduced from the water vapor introduction pipe and the raw material gas introduced from the raw material gas introduction pipe are mixed and brought into contact with each other;
An outlet pipe for leading the reformed gas in the mixing chamber;
An outlet chamber provided around the mixing chamber and communicating with the mixing chamber;
With
The steam introduction pipe and the source gas introduction pipe are connected to the mixing chamber such that the introduction direction of the steam and the introduction direction of the source gas introduction are substantially opposed to each other,
The lead-out chamber is formed along a plane substantially orthogonal to the direction of introduction of the water vapor and the direction of introduction of the raw material gas,
The mixing chamber is filled with incombustible particles, and the water vapor and the raw material gas are mixed in the mixing chamber while flowing around the periphery of the incombustible particles to generate a reformed gas. Outflowing radially from the mixing chamber and fed to the outlet chamber,
The outlet pipe is set so as to be able to derive a derived amount of reformed gas corresponding to the amount of steam introduced from the steam inlet pipe and the amount of source gas introduced from the source gas inlet pipe. A reforming reactor. 21. The reforming reactor according to claim 20, wherein the mixing chamber is provided with a hollow portion not filled with nonflammable particles in contact with the lead-out chamber. 21. The reforming reactor according to claim 20, further comprising an annular flow control valve slidably fitted on the outer circumference of the water vapor introduction pipe and the raw material gas introduction pipe in the lead-out chamber. 21. A reforming reactor according to claim 20, wherein the pressure detector for detecting the pressure in the mixing chamber and the opening degree of the damper are controlled based on the pressure detected by the pressure detector. A steam introduction pipe into which steam heated to a temperature at which a reforming reaction occurs is introduced;
A water vapor introduction valve for adjusting the amount of water vapor introduced;
A source gas introduction pipe into which a source gas heated to a temperature at which a reforming reaction occurs is introduced;
A raw material gas introduction valve for adjusting the amount of raw material gas introduced;
A mixing chamber in which the water vapor introduced from the water vapor introduction pipe and the raw material gas introduced from the raw material gas introduction pipe are mixed and brought into contact with each other;
An outlet pipe for leading the reformed gas in the mixing chamber;
With
One of the water vapor introduction pipe and the raw material gas introduction pipe is inserted into the other,
The mixing chamber is formed in the vicinity of the tip portion of the inner introduction pipe inside the outer introduction pipe,
A reforming reactor in which a tip portion of the inner introduction pipe constitutes a part of a water vapor introduction valve and a raw material gas introduction valve. The reforming reactor according to claim 24, further comprising an expansion wall for adjusting the volume of the mixing chamber. The pressure detector for detecting the pressure in the mixing chamber, and the reforming reactor according to claim 24, wherein the expansion wall is driven based on the pressure detected by the pressure detector, thereby adjusting the volume of the mixing chamber. .

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