JP3719153B2 - Hydrogen gas production method and apparatus, and hydrogen gas production unit - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method and apparatus for producing hydrogen gas, and a hydrogen gas production unit including the same.
[0002]
[Prior art]
The following methods are mainly mentioned as an industrial manufacturing method of hydrogen gas.
[0003]
1) Water electrolysis method In this method, 15 to 20% caustic soda solution is electrolyzed using a nickel plating electrode to obtain by-product oxygen along with pure hydrogen.
[0004]
2) Gasification of coke This is a method for producing water gas using coke as a raw material. Normally, intermittent hydrogen generation furnaces have been known for a long period of time in which air is blown into red-hot coke and burned, and blows that raise the furnace temperature and steam that feeds steam to generate gas have been known for a long time. In addition, a continuous water gas generation furnace that introduces a mixture of oxygen and water vapor has appeared. Here, the water gas undergoes purification steps such as dust removal, water washing, and desulfurization, and carbon monoxide in the gas is converted to hydrogen using a water gas conversion reaction, and carbon dioxide produced at the same time is removed by adsorption. Except for a small amount of carbon monoxide, it is hydrogen without impurities.
[0005]
3) Full gasification of coal This is a method of gasification by sending oxygen and water vapor into fine coal or pulverized coal, and the main reaction is a reaction of hydrocarbon, oxygen and water vapor, so that hydrogen, carbon monoxide, or A gas mainly composed of methane is produced. Most recently developed methods such as winker gas generator, copper soot gas generator, and Otto-Rummel gas generator belong to this. The properties of the product gas, the purification method, and the modification method are almost the same as the method 2).
[0006]
4) Gasification when petroleum is gasified, natural gas, coke oven gas, petroleum refining waste gas, etc. is a liquid fuel, and gasification is called gasification. Are the same in that a gas having the same property is obtained by the reaction of hydrocarbon and oxygen or water vapor. Moreover, the above-mentioned complete gasification of coal can be said to be the same reaction using coal, which is a solid hydrocarbon, as a raw material. In contrast to normal pressure gas generators such as copper soot check gas generators and fauser-Montecatini gas generators, the development of pressurized gas generators such as texaco gas generators and shell gas generators has been remarkable recently. Catalytic catalytic cracking methods are widely used to transform gaseous hydrocarbons.
[0007]
5) Separation from coke gas This is a method in which gas from a coke gas generator is compressed and cooled to liquefy and remove all gas other than hydrogen to separate hydrogen. Remove sulfur compounds from the furnace gas in a conventional manner, compress to about 12 atmospheres, wash with water and caustic soda solution, remove carbon dioxide, water at -40 ° C, methane and other hydrocarbons at -60 ° C, monoxide Carbon is condensed and removed, and hydrogen is separated.
[0008]
6) Reaction between iron and water vapor This method is called the Methaschmitt method. That is, Ryotetsu ore (FeCO_Three) To Fe3O4, which is further converted into water gas (CO + H₂) Etc. to reduce to FeO,₂By reacting O, FeO is oxidized, and pure hydrogen is obtained accordingly.
[0009]
[Problems to be solved by the invention]
By the way, the hydrogen gas production method 1) has advantages in using water as a raw material, but has the following disadvantages. In other words, it requires pure water, requires a large number of electrolytic cells, is not sufficiently adaptable to excess or shortage of current, has many problems in aging due to carbonation of the electrolyte, floor area, initial cost, Economic disadvantage. Therefore, in recent years, waste gas such as heavy oil and natural gas has been used as a hydrogen source, and therefore, the method 2-5) has become the mainstream.
[0010]
On the other hand, in the methods 2 to 6), the facility becomes large, which causes an increase in initial cost and running cost. Further, in the hydrogen gas production process, carbon dioxide such as carbon monoxide and carbon dioxide is by-produced, and a process for removing this must be provided, so that the production efficiency of hydrogen gas is not increased.
[0011]
The present invention has been made in view of such circumstances, and an object thereof is to provide a hydrogen gas production method, an apparatus thereof, and a unit thereof capable of producing hydrogen gas at low cost and efficiency.
[0012]
[Means for Solving the Problems]
  there,The method for producing hydrogen gas according to the present invention comprises a solid electrolyte provided with a first electrode and a second electrode.SaidBringing water vapor into contact with the first electrode; andSaidBy bringing the ion source material into contact with the second electrode and simultaneously applying a voltage between these electrodes,SaidConvert water vapor to hydrogenIn the hydrogen gas production method, an ion source material deposited on the first electrode is applied via the solid electrolyte by applying a potential opposite to that at the time of hydrogen gas production between the first and second electrodes. Regenerating the ion source material by transferring to the second electrodeIt is characterized by.
[0013]
Here, as the solid electrolyte, there is a sodium conductor. As another solid electrolyte, a lithium conductor is also conceivable, but a sodium conductor may be adopted in consideration of the realization of inexpensive hydrogen gas production. At this time, sodium carbonate, sodium bicarbonate or sodium hydroxide is used as the ion source material. Moreover, as a sodium ion conductor, β-alumina (Na₂O ・ 11Al₂O_Three) Or NASICON (Na_{1 + X}Zr₂P_3-XSi_XO₁₂, X is a real number, 0 <X <3).
[0014]
The first and second electrodes are porous, and are based on a commonly used conductive material, such as Pt, Au, Cr, Cu and Ni or their oxides.
[0015]
As a power source for applying the voltage, a general constant potential power source (potentiostat or the like) can be used, but a power source capable of charging and discharging is desirable. Moreover, what can respond | correspond by the operation which reverses an electric potential at the time of carbon dioxide gas discharge | release is still better.
[0016]
The voltage applied at the time of hydrogen gas manufacture is about -0.5-3V. Further, the voltage (discharge voltage) at the time of regeneration of the ion source material is about +0.5 to 3V. The application and discharge voltages are not limited to the above values.
[0017]
As described above, during the production of hydrogen gas, water vapor (H₂O) Hydrogen gas (H₂). At this time, when the water vapor contains carbon monoxide and carbon dioxide, these are separated and removed on the surface of the first electrode in the form of carbonate (sodium carbonate). These steps are performed at about 350 ° C.
[0018]
In addition, when the ion source material is regenerated, the ion source material deposited on the first electrode is applied to the second electrode by applying a reverse potential between the first and second electrodes. Simultaneously with the transfer to the electrode side, the separated carbonic acid component can be transferred out of the system. This regenerates the ion source material and avoids waste of chemical costs. At this time, it is possible to shift to a hydrogen gas production process by carrying out at about 650 to 850 ° C.
[0019]
When regenerating the ion source material, water vapor (H₂O) may be supplied (hydrogen gas production method according to claim 4). As a result, regeneration of the ion source material is promoted and hydrogen gas (H₂) Can also be generated.
[0020]
The solid electrolyte may have any shape, but considering the maintenance aspect such as confirmation of the filling amount of the ion source material and appropriate adjustment of the contact surface area of the electrode in accordance with the load of water vapor, it will be described later. It is good to form in a container shape like a gas production apparatus and a hydrogen gas production unit. In addition, for example, various conditions such as use conditions are appropriately taken into account, such as a circular shape, an elliptical shape, a multi-polygonal shape, and a streamline shape in consideration of gas flow resistance and the like.
[0021]
  That is, an apparatus for carrying out the hydrogen gas production method according to the present invention includes a pipe through which water vapor flows,thisA single or a plurality of solid electrolytes formed in a pipe and formed into a vessel shape;thisCovered on the outer surface of the solid electrolyteSaidA first electrode in contact with water vapor;The solid electrolyteA hydrogen gas generator comprising a second electrode that is covered on the cavity surface of the first electrode and is filled with an ion source material;SaidWhen the solid electrolyte is a sodium ion conductor, comprising a power source that is electrically connected to the first and second electrodes and is capable of switching the applied potential.SaidThe ion source material is a hydrogen gas production apparatus consisting of sodium carbonate, sodium hydrogen carbonate or sodium hydroxide,SaidThe power supply is used for hydrogen gas production.By connecting the negative electrode with the first electrode and the positive electrode with the second electrode,The first electrodeIt is characterized in that water vapor in contact with water is converted into hydrogen.
[0022]
  For example, the hydrogen gas production apparatus is configured by dropping a plurality of vessel-shaped hydrogen gas generators having the first and second electrodes in a pipe through which water vapor flows. At this time,SaidIn the pipe, an obstacle means for bypassing the gas flow passing through the lower end of the hydrogen gas generator may be arranged.SaidThe obstacle means is means for efficiently bringing gas into contact with the solid electrolyte,SaidThere is a bypass plate for bypassing the gas flow passing through the gap between the lower end of the solid electrolyte and the inner wall surface of the pipe.SaidIn the hydrogen gas production apparatus, the number of hydrogen gas generators installed is determined by the amount of steam load.
[0023]
  SaidIn hydrogen gas production equipment,The power supply connects the positive electrode with the first electrode and the negative electrode with the second electrode.,SaidThe ion source material deposited on the first electrode through the solid electrolyte,SaidIt is made to transfer to the 2nd electrode side.ThisSimultaneously with the release of the occluded carbon dioxide, the ion supply source is regenerated, so that waste of chemical costs is avoided.
[0024]
  Also,In the hydrogen gas generator, a pipe for supplying water vapor to the ion source material on the second electrode side and a pipe for discharging the hydrogen gas generated during the regeneration of the ion source material may be provided.
[0025]
  Furthermore, the hydrogen gas production unit provided with the hydrogen gas production apparatus according to the present invention is a hydrogen gas production unit comprising at least two hydrogen gas production apparatuses to which water vapor is supplied at regular intervals,SaidThe hydrogen gas production apparatus has a pipe through which water vapor flows,thisA single or a plurality of solid electrolytes formed in a pipe and formed into a vessel shape;thisCovered on the outer surface of the solid electrolyteSaidA first electrode that is in contact with the DC power source while being in contact with water vapor;The solid electrolyteWhen the solid electrolyte is a sodium ion conductor, comprising a hydrogen gas generator comprising a second electrode that is covered with an ion source material and that is filled with an ion source material and is connected to a DC power source,SaidThe ion source material consists of sodium carbonate, sodium hydrogen carbonate or sodium hydroxide and is supplied with water vaporOneHydrogen gas production equipmentBy connecting the negative electrode of the DC power supply with the first electrode and connecting the positive electrode of the DC power supply with the second electrode,SaidConverting water vapor in contact with the first electrode into hydrogen, water vapor is not suppliedThe otherHydrogen gas production equipmentBy connecting the negative electrode of the DC power supply with the second electrode and connecting the positive electrode of the DC power supply with the first electrode,,SaidThe ion source material deposited on the first electrode, through the solid electrolyte,SaidBy moving to the second electrode side,SaidThe ion source material is regenerated.
[0026]
Here, the hydrogen gas production apparatuses are connected in parallel through valve means. For example, when hydrogen gas production apparatuses are connected in parallel, one hydrogen gas production apparatus performs hydrogen gas production according to the present invention, and the other hydrogen gas production apparatus separates and fixes carbon dioxide during hydrogen gas production. By taking out gas alternately, continuous hydrogen gas production and carbon dioxide gas removal are possible. At this time, the DC power source can convert the connection phase, and is preferably shared equipment for each hydrogen gas production apparatus. Further, when three are arranged in parallel, for example, the timing of switching can be set as appropriate according to the number and the like, such as shifting the timing of fixing and discharging by 1/2 each. However, when three or more hydrogen gas production units are installed, it is necessary to appropriately provide a plurality of power sources according to the switching timing or the like.
[0027]
As described above, in the hydrogen gas production method and the apparatus thereof according to the present invention, an ideal secondary battery is configured, so that it is possible to store electricity as long as water vapor is supplied from the outside of the system. The redox reaction that occurs at both ends of the electrolyte of the vessel is a reversible reaction, and by causing a discharge phenomenon, the ion source material is regenerated, so that the consumption of chemical costs can be minimized. Moreover, since the electric energy can be taken out by this discharge, the running cost can be kept low. Furthermore, since the electrolyte is solid, there is no risk of liquid leakage, and the apparatus can be miniaturized. As a result, not only can the initial cost be reduced, but also the effective reaction capacity can be adjusted according to the amount of water vapor gas load, so that applications from small to large facilities are expanded. Further, even when carbon monoxide or carbon dioxide is contained in the gas to be treated, these can be captured as carbonates during the production of hydrogen gas, so there is no need to provide a step for removing carbon dioxide.
[0028]
In particular, in the hydrogen gas production unit equipped with the hydrogen gas production device according to the present invention, a plurality of hydrogen gas production devices according to the present invention are provided, and hydrogen gas production and ion source material regeneration are performed alternately. Low-cost and continuous production of hydrogen gas becomes possible.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0030]
FIG. 1 is a diagram for explaining the outline of a method for producing hydrogen gas according to the present invention. FIG. 1 (a) shows an outline of the principle of the present invention, and FIG. 1 (b) shows a reaction that occurs on the surface of each electrode during hydrogen gas generation.
[0031]
The hydrogen gas production apparatus according to the present invention is configured by including a hydrogen gas generator 11 in a pipe 10 through which a gas to be treated flows.
[0032]
As shown in FIG. 1A, the hydrogen gas generator 11 includes a solid electrolyte 11, two electrodes 22a and 22b installed on the solid electrolyte 11, and a power source (direct current) 24 connected to the electrodes 22a and 22b. Consists of.
[0033]
The solid electrolyte 21 uses a sodium ion conductor on the surface of the electrode 22a. Sodium conductors include β-alumina (Na₂O ・ 11Al₂O_Three) Or NASICON (Na_{1 + X}Zr₂P_3-XSi_XO₁₂, X is a real number, 0 <X <3).
[0034]
Sodium ion source materials include sodium hydroxide (NaOH) and sodium carbonate (Na₂CO_Three) Or sodium bicarbonate (NaHCO 3)_Three)
[0035]
The solid electrolyte 21 may have any shape, and may be formed in a container shape, for example, as shown in FIG. At this time, for example, sodium hydroxide (NaOH) is supplied as the ion source material 23 to the side of the electrode 22b covered on the cavity surface of the electrolyte, and the electrode 22a covered on the outer surface of the electrolyte is supplied to the electrode 22a. Steam is supplied.
[0036]
As the electrodes 22a and 22b, porous electrodes based on known conductive materials (Pt, Au, Cr, Cu and Ni, or oxides thereof) are used, and are deposited on the solid electrolyte 21 by vapor deposition. Provided. In addition to vapor deposition, it may be formed by thermal spraying, dip coating, or the like.
[0037]
The principle of hydrogen gas production in the present invention will be described with reference to FIGS. Here, sodium hydroxide is used as the ion source material, and water vapor gas (H₂The case of O) will be described.
[0038]
Generation of hydrogen gas in the hydrogen gas generator 11 is performed by applying a voltage (direct current) between both electrodes 22a and 22b of the generator 11. Specifically, the positive electrode of the DC power source 24 is used as the electrode 22b, and the negative electrode of the power source is used. Is connected to the electrode 22a (FIG. 1A). At this time, reaction (1) occurs on the electrode 22b, and reaction (2) occurs on the electrode 22a (FIG. 1B). Furthermore, reaction (3) occurs on the same polarity 22a, and reaction (4) also occurs (FIG. 1 (b)).
[0039]
That is, when a voltage is applied from the DC power supply 24, the surface of the electrode 22b has sodium ions (Na⁺) And electrons (e^-) And are released.
[0040]
2NaOH → 2Na⁺+ 2H2O + 1 / 2O₂+ 2e^-  ... (1)
And the liberated sodium ion (Na⁺) Migrates through the solid electrolyte 21 after passing through the electrode 22b and reaches the electrode 22a. On the other hand, Na₂CO_ThreeElectrons released from (e^-) Reaches the electrode 22 a via the DC power supply 24. The following reaction occurs on the surface of the electrode 22a.
[0041]
2Na⁺+ H₂O + 2e^-  → Na₂O + H₂  ... (2)
When the water vapor introduced into the system comes into contact with the electrode 22a, the following reaction occurs.
[0042]
2H₂O + 2e^-  → 2OH^-  + H₂  ... (3)
Further, Na produced in the reaction (2)₂A part of O further reacts with water vapor in the gas phase to generate NaOH.
[0043]
Na₂O + H₂O → 2NaOH (4)
In addition, the hydrogen gas generator 11 includes carbon monoxide (CO) and carbon dioxide (CO₂), Hydrogen gas is generated while capturing these carbon dioxide gases. That is, when carbon dioxide (carbon monoxide, carbon dioxide) is contained in the water vapor, the hydrogen gas generator 11 separates and fixes this in the form of sodium carbonate.
[0044]
For example, when carbon monoxide (CO) stays in the pipe 10, the following reaction occurs on the electrode 22a.
[0045]
2Na⁺+ CO + 2H₂O + 2e^-  → Na₂CO_Three  + 2H₂
In addition, carbon dioxide (CO₂) Is retained, the following reaction occurs on the electrode 22a.
[0046]
2Na⁺+ CO₂+ H₂O + 2e^-  → Na₂CO_Three  + H₂
By the way, the hydrogen gas generator 11 can also regenerate the ion source material at a predetermined temperature (about 650 to 850 ° C.).
[0047]
The regeneration of the ion source material is performed by connecting a power source connected to the electrodes 22a and 22b in a phase opposite to that when carbon dioxide is fixed. That is, the positive electrode of the DC power supply 24 is connected to the electrode 22a, and the negative electrode of the power supply 24 is connected to the electrode 22b. Alternatively, the ion source material may be regenerated by connecting and discharging an external load between the electrodes 22a and 22b. At this time, a reaction reverse to that at the time of hydrogen gas generation proceeds, reaction (1) occurs on the electrode 22a side, and reactions (2), (3), and (4) occur on the electrode 22b, and NaOH is regenerated.
[0048]
During regeneration of the ion source material, water vapor (H₂O) may be supplied (FIG. 1A). While regeneration of the ion source material is promoted, hydrogen gas (H₂This is because the generation of) is also possible.
[0049]
Next, an embodiment of the method for producing hydrogen gas according to the present invention will be described.
(Embodiment 1)
FIG. 3 is a schematic configuration diagram of an embodiment of a hydrogen gas production apparatus according to the present invention. (A) is a top view of this apparatus, (b) is AA sectional drawing of this apparatus. Note that this embodiment is not limited to this.
[0050]
The hydrogen gas production apparatus includes a hydrogen gas generator 41 in a pipe 40 through which a gas to be treated flows. Although not shown in the figure, the function of causing a charging phenomenon to apply a voltage to the hydrogen gas generator 41, the transition of sodium hydroxide already exposed on the surface of the electrode 22a to the electrode 22b, and the electrode 22a A power source (direct current) having a function of causing a discharge phenomenon to take out carbon dioxide gas fixed on the surface is provided.
[0051]
The hydrogen gas generator 41 has a container shape as described above (FIG. 1B), and is formed so as to have a circular cross section as shown in FIG. 4A. In the pipe 40, a plurality of hangings are supported. The hydrogen gas generator 41 is detachable, and an arbitrary number of hydrogen gas generators 41 are installed in the pipe 40 in accordance with the load amount of the gas to be processed. The hydrogen gas generator 41 is appropriately supplemented with an ion supply source material (for example, sodium hydroxide). In the pipe 40, obstacle means for bypassing the gas flow passing through the lower end of the hydrogen gas generator 41 is installed. According to this configuration, since the contact efficiency between the hydrogen gas generator 41 and the gas to be processed is increased, carbon monoxide and carbon dioxide in the gas phase are efficiently separated and removed. As the obstacle means, a bypass plate 42 is installed in FIG. The height of the plate 42 is adjusted as appropriate.
[0052]
Although not shown, in the hydrogen gas generator 41, a pipe for supplying water vapor to the ion source material on the second electrode side, and a pipe for discharging the hydrogen gas generated during the ion source material regeneration May be provided. This is because, as described above, by introducing water vapor from the outside of the system during the regeneration of the ion supply source material, the regeneration of the material is promoted and the generation of hydrogen gas is also executed.
[0053]
FIG. 4 is a characteristic diagram showing the change over time of the gas components discharged from the hydrogen gas production apparatus according to the present invention.
[0054]
The hydrogen gas production apparatus shown in FIG. 3 was adopted as the hydrogen gas production apparatus related to the experiment. The hydrogen gas generator 41 employs NASICON as a solid electrolyte, sodium hydroxide as an ion source material, and platinum (Pt) as an electrode. The filling rate of the hydrogen gas generator in the hydrogen gas production apparatus was 80%. In addition, water vapor (H₂O) supply flow rate is 1.0m^Three/ H, the operating temperature was about 350 ° C. The applied voltage at the time of hydrogen gas production is −3 V, and the applied voltage at the time of ion source material regeneration is +3 V. As is apparent from FIG. 4, since almost 100% of the introduced water vapor is converted into hydrogen gas in about 20 minutes, it is shown that the hydrogen gas production apparatus can convert water vapor into hydrogen gas. It was.
[0055]
In this experiment, the voltage applied during hydrogen gas production is −3 V, and the voltage applied during ion source material regeneration is +3 V. However, the applied voltage is not limited to these values, and is set appropriately. Shall.
[0056]
The operating temperature may be set at an arbitrary temperature according to various conditions such as the ion source material to be used. For example, by utilizing the exhaust heat from the fuel cell equipment installed at the subsequent stage, the hydrogen gas You may make it ensure by heating manufacturing apparatus itself.
[0057]
As described above, the hydrogen gas generator in the hydrogen gas production apparatus according to the present invention forms an ideal secondary battery, and therefore can store electricity as long as water vapor is supplied from outside the system. The redox reaction that takes place at both ends of the electrolyte of the generator is a reversible reaction, and by causing a discharge phenomenon, the ion source material is regenerated, so that the chemical cost consumption can be minimized. . Moreover, since the electric energy can be taken out by this discharge, the running cost can be kept low. Furthermore, since the electrolyte is solid, there is no risk of liquid leakage, and the apparatus can be miniaturized. As a result, not only can the initial cost be reduced, but also the effective reaction capacity can be adjusted according to the amount of water vapor gas load, so that applications from small to large facilities are expanded. Moreover, even if carbon monoxide and carbon dioxide are contained in the gas to be treated, these can be captured as carbonates during the production of hydrogen gas, so there is no need to provide a step for removing carbon dioxide.
(Embodiment 2)
FIG. 2 is also an example of an embodiment of the method for producing hydrogen gas according to the present invention, and is an example of a unit in which the method for producing hydrogen gas is introduced. Here, (a) is an outline of one embodiment of the hydrogen gas production unit, and (b) is an example of the operation time schedule of the unit. Note that this embodiment is not limited to this.
[0058]
The hydrogen gas production unit includes a plurality of hydrogen gas production apparatuses 30 and valve means (V0 to V3) according to the present invention, and a DC power supply 31, and is controlled by a control means (not shown) storing a time schedule. .
[0059]
In the hydrogen gas production unit, two hydrogen gas production apparatuses according to the present invention (30a, 30b) are arranged in parallel, and hydrogen gas production and ion source material regeneration are performed alternately. In FIG. 2A, hydrogen gas production apparatuses 30a and 30b are arranged in parallel via valve means V0 (hereinafter referred to as V0) in the upstream path and valve means V3 (hereinafter referred to as V3) in the downstream path. . Further, the valve means V1 (hereinafter referred to as V1) is installed in the downstream path of the hydrogen gas production apparatus 30a, and the valve means V2 (hereinafter referred to as V2) is installed in the downstream path of the hydrogen gas production apparatus 30b. Is connected to a gas discharge path 321 to the gas storage tank 32. A carbon monoxide and carbon dioxide concentration meter 33 is attached downstream of the hydrogen gas production apparatuses 30a and 30b (on the downstream side of V3 in FIG. 2), and carbon dioxide in the hydrogen gas production apparatuses 30a and 30b. The concentration is monitored.
[0060]
The DC power supply 31 is a shared facility of the hydrogen gas production device 30a and the hydrogen gas production device 30b, and enables switching of the connection phase. That is, the DC power supply 31 connects the positive electrode of the power supply 31 to the gas side electrode (hereinafter, positive electrode) of the hydrogen gas production apparatuses 30a and 30b and supplies the negative electrode of the power supply 31 to the ions of the apparatuses 30a and 30b during the hydrogen gas production. It connects with a source material side electrode (henceforth, negative electrode) (henceforth, charge connection). Further, at the time of ion source material regeneration, the positive electrode of the power supply 31 is connected to the negative electrode of the hydrogen gas production apparatuses 30a and 30b, and the negative electrode of the power supply 31 is connected to the positive electrode of the apparatus 30a and 30b (hereinafter referred to as discharge connection).
[0061]
The hydrogen gas production unit is not limited to providing two hydrogen gas production apparatuses 30a and 30b. For example, when three hydrogen gas production apparatuses 30 are installed in parallel, the timing of switching can be appropriately set according to the number of installations, such as shifting the timing of fixing and releasing by 1/2 each. However, when three or more hydrogen gas production apparatuses are installed, it is necessary to appropriately provide a plurality of power sources 31 according to the switching timing or the like.
[0062]
The hydrogen gas production unit performs hydrogen gas production alternately on the basis of a time schedule (FIG. 2B) having a hydrogen gas production process and an ion source material regeneration process, so that continuous hydrogen gas production and ion supply are performed. Source material regeneration is possible. Here, the flow rate of the water vapor is adjusted so that the residence time of the gas supplied to the hydrogen gas production apparatus 30 is constant. Moreover, the switching time of hydrogen gas production is arbitrarily set according to the steam load.
[0063]
2B, when the hydrogen gas production apparatus 30a finishes the hydrogen gas production process, the hydrogen gas production apparatus 30b proceeds to the ion supply source material regeneration process, and the hydrogen gas production apparatus 30b proceeds to the hydrogen gas production process. At this time, the water vapor supply path is set on the hydrogen gas production apparatus 30b side by V0, and the concentrated hydrogen gas discharge path from the hydrogen gas production apparatus 30b is set on the out-of-system transfer side by V2 and V3.
[0064]
In the hydrogen gas production apparatus 30a that has shifted to the ion supply source material regeneration step, the connection of the power source 31 is switched to the discharge connection. At this time, V1 is set on the path 321 side, and the carbon dioxide liberated and the generated oxygen and water vapor are sucked by a blower or the like due to the discharge, and out of the system (for example, the gas storage tank 32 in FIG. 2). Be transported. A part of the water vapor is supplied to the hydrogen gas production apparatuses 30a and 30b via the path 322, and again used for hydrogen gas production and ion source material regeneration.
[0065]
On the other hand, in the hydrogen gas production apparatus 30b that has shifted to the hydrogen gas production process, the connection of the power source 31 is switched to the charge connection. The description of hydrogen gas production here will be left to the principle in FIG. The hydrogen gas concentrated by the hydrogen gas production apparatus 30b is sucked by a blower or the like and transferred out of the system. And if a hydrogen gas manufacturing process is digested, the hydrogen gas manufacturing apparatus 30b will transfer to an ion supply source material reproduction | regeneration process, and the hydrogen gas manufacturing apparatus 30a will transfer to a hydrogen gas manufacturing process.
[0066]
Thus, the hydrogen gas production unit arranges a plurality of hydrogen gas production apparatuses according to the present invention in parallel and alternately performs hydrogen gas production and removal of the ion source material. Concentration hydrogen gas can be produced inexpensively and continuously.
[0067]
【The invention's effect】
As is clear from the above description, the present invention has the following effects.
[0068]
According to the method and apparatus for producing hydrogen gas according to the present invention, it is possible to store electricity as long as water vapor is supplied from outside the system in order to form an ideal secondary battery, and the electrolyte of the hydrogen gas generator. The oxidation-reduction reaction that occurs at both electrodes is a reversible reaction, and by causing a discharge phenomenon, the ion source material is regenerated, so that the consumption of chemical costs can be minimized. Moreover, since the electric energy can be taken out by this discharge, the running cost can be kept low. Furthermore, since the electrolyte is solid, there is no risk of liquid leakage, and the apparatus can be miniaturized. As a result, not only can the initial cost be reduced, but also the effective reaction capacity can be adjusted according to the amount of water vapor gas load, so that applications from small to large facilities are expanded. Further, even when carbon monoxide or carbon dioxide is contained in the gas to be treated, since these can be captured as carbonates during the production of hydrogen gas, there is no need to provide a process for removing the carbon dioxide gas. In addition, carbon dioxide emissions outside the system can be suppressed, greatly contributing to global warming countermeasures.
[0069]
In particular, according to the hydrogen gas production unit equipped with the hydrogen gas production apparatus according to the present invention, a plurality of hydrogen gas production apparatuses according to the present invention are provided, and hydrogen gas production and ion source material regeneration are performed alternately. This makes it possible to produce hydrogen gas continuously at a low cost.
[0070]
Thus, according to the hydrogen generation method and apparatus and unit thereof according to the present invention, it is possible to produce hydrogen gas at low cost and efficiently.
[Brief description of the drawings]
FIG. 1 is a schematic explanatory diagram of a method for producing hydrogen gas according to the present invention, wherein (a) outlines the principle of the present invention, and (b) shows a reaction that occurs on the surface of each electrode when hydrogen gas is generated.
FIG. 2 shows an example of a hydrogen gas generation unit. (A) is an outline of one embodiment of the hydrogen gas production unit, and (b) is an example of an operation time schedule of the unit.
3A and 3B are schematic configuration diagrams showing an example of a hydrogen gas production apparatus according to the present invention, in which FIG. 3A is a plan view of the apparatus, and FIG. 3B is a cross-sectional view taken along line AA of the apparatus.
FIG. 4 shows a change with time of gas components discharged from the present invention.
[Explanation of symbols]
10 ... Piping
11 ... Hydrogen gas generator
21 ... Solid electrolyte
22a, 22b ... electrodes
23 ... Ion source material
24, 31 ... DC power supply
30a, 30b ... Hydrogen gas production equipment
33 ... Carbon monoxide, carbon dioxide concentration meter

Claims (6)

By contacting the steam with the first electrode of a solid electrolyte provided with a first electrode and a second electrode, and at the same time contacting the ion source material to the second electrode, a voltage is applied between the electrodes , a hydrogen gas production process for converting the vapor into hydrogen,
By applying a reverse potential between the first and second electrodes during the production of hydrogen gas, the ion source material deposited on the first electrode is transferred to the second electrode via the solid electrolyte. A method for producing hydrogen gas , wherein the ion source material is regenerated by transferring . In the hydrogen gas manufacturing method of Claim 1,
The method for producing hydrogen gas , wherein when the solid electrolyte is a sodium conductor, the ion source material is made of sodium carbonate, sodium hydrogen carbonate or sodium hydroxide . The method for producing hydrogen gas according to claim 1 or 2,
Wherein during regeneration of the ion source material, producing hydrogen gas wherein the <br/> supplying water vapor (H ₂ O) to the second electrode side. Piping through which water vapor flows;
Within the pipe is s installation, a solid electrolyte formed on the vessel shape, a first electrode of the solid electrolyte is Kutsugae設the outer surface of the contact is the water vapor, is Kutsugae設the cavity surface of the solid electrolyte ion A hydrogen gas generator consisting of a second electrode filled with a source material;
The conductive with the first and second electrodes, comprising a power supply and freely switch between applied potential and,
If the solid electrolyte is a sodium ion conductor, the ion source material is sodium carbonate, the sodium bicarbonate or sodium hydroxide, a hydrogen gas production apparatus,
The power source is configured to convert water vapor in contact with the first electrode into hydrogen by conducting a negative electrode with the first electrode and a positive electrode with the second electrode during hydrogen gas production. Hydrogen gas production equipment. The hydrogen gas production apparatus according to claim 4 , wherein
Wherein the power source, by conduction with the second electrode a negative electrode causes conduct positive electrode and the first electrode, the said ion source material is deposited on the first electrode, through the solid electrolyte, the second An apparatus for producing hydrogen gas, wherein the ion source material is regenerated by shifting to the electrode side. A hydrogen gas production unit comprising at least two hydrogen gas production apparatuses to which water vapor is supplied at regular intervals,
The hydrogen gas production apparatus is
Piping through which water vapor flows;
Within the pipe is s installation, a solid electrolyte formed on the vessel shape, a first electrode that conducts a DC power supply together with the water vapor is Kutsugae設the outer surface of the solid electrolyte is in contact, the cavity of the solid electrolyte ion source material is Kutsugae設the surface is filled consists of a second electrode for conducting said DC power source, comprising a hydrogen gas generator,
If the solid electrolyte is a sodium ion conductor, the ion source material becomes sodium carbonate, from sodium bicarbonate or sodium hydroxide,
One of the hydrogen gas production apparatus steam is supplied, by the positive electrode of the DC power supply causes conduct negative electrode of the DC power supply and the first electrode is electrically connected to the second electrode, in contact with the first electrode Converting water vapor to hydrogen,
The other of the hydrogen gas production apparatus steam is not supplied, by conducting the positive electrode of the DC power supply and the first electrode causes a negative electrode of the DC power source is electrically connected to the second electrode, said deposited on the first electrode the ion source material, via the solid electrolyte, by shifting to the second electrode side, the hydrogen gas production unit, characterized in that for reproducing the ion source material.

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