JP7152638B2 - A material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride, which is intended to improve the generation reaction of magnesium hydride, and a hydrogen manufacturing method using the hydrogen generating material containing magnesium hydride manufactured by the material manufacturing method - Google Patents

Description

The present invention uses a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride, which is intended to improve the generation reaction of magnesium hydride, and a hydrogen generating material containing magnesium hydride manufactured by the material manufacturing method. It relates to a method for producing hydrogen.

In recent years, hydrogen has been attracting attention as an energy source, and magnesium hydride is available as a method for storing the hydrogen.

Patent Document 1 discloses a method for producing magnesium hydride, specifically, a first procedure in which magnesium hydroxide is dehydrated by heating to form magnesium oxide, and a temperature of about 2000 (K). A second step of supplying magnesium oxide obtained in the first step into the plasma flame of a plasma torch having a and supplying methane and / or hydrogen, which is a gas as a reducing agent, to produce metallic magnesium; After generation, a method is disclosed in which a third procedure is performed to generate magnesium hydride from metallic magnesium using hydrogen as the gas supplied to the plasma flame.

In addition, in Patent Document 1, it is explained that when hydrogen is supplied in the second step, metallic magnesium becomes magnesium hydroxide due to a reversible reaction during cooling. is considered to be the second procedure as methane.

Japanese Unexamined Patent Application Publication No. 2011-32131

By the way, in Patent Document 1, since thermal plasma is used, the temperature of the plasma is as high as about 2000 (K), and the equipment needs to have high heat resistance, and the plasma temperature is set to 2000 (K). There is also the problem that energy loss is large because energy is used for both.

Therefore, we investigated the use of non-equilibrium plasma that allows plasma processing at relatively low temperatures to generate magnesium hydride. Although it has been found that it is possible to produce a hydrogen generating material containing, it is desired to further improve the production reaction of magnesium hydride.

The present invention has been made in view of such circumstances, and a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride, which is intended to improve the generation reaction of magnesium hydride, and a material manufacturing method thereof. An object of the present invention is to provide a method for producing hydrogen using a hydrogen generating material containing magnesium hydride produced.

In order to achieve the above objects, the present invention is grasped by the following configurations.
(1) A material manufacturing method of the present invention is a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride, and the material manufacturing method includes a depressurization step of maintaining a depressurization of a processing chamber for irradiating plasma on a raw material. , a supply step of heating the raw material and supplying it in a gaseous state into the plasma; and a recovery step of recovering the hydrogen generating material containing the magnesium hydride produced by the reaction between the raw material and the plasma. , the raw material is magnesium iodide, and the plasma is a plasma of a reactive gas containing hydrogen that forms a reducing atmosphere.

(2) In the configuration of (1) above, the depressurization step is performed by a pump connected to an exhaust pipe for discharging gas from the processing chamber, and the material manufacturing method extends from the processing chamber to the pump. reducing the volume of the gas exhausted from the processing chamber between, wherein the volume reducing step cools an exhaust pipe between the processing chamber and the pump to at least exhaust reducing the volume of the hydrogen iodide in the gas to liquid, solid, or a mixture of liquid and solid.

(3) In the configuration of (1) above, the depressurization step is performed by a pump connected to an exhaust pipe for discharging gas from the processing chamber, and the material manufacturing method extends from the processing chamber to the pump. a volume reduction step of reducing the volume of the gas discharged from the processing chamber, wherein the volume reduction step supplies ammonia gas into an exhaust pipe between the processing chamber and the pump; At least the hydrogen iodide in the discharged gas is converted to ammonium iodide and solidified to reduce the volume.

(4) A method for producing hydrogen according to the present invention is a method for producing hydrogen using a hydrogen generating material containing magnesium hydride produced by the method for producing a material having the configuration of (1) above, wherein the method for producing a material comprises: a solution obtaining step of exposing the gas discharged from the processing chamber in the decompression step to a solution to obtain a hydrogen iodide solution in which at least hydrogen iodide in the discharged gas is dissolved; a hydrogen generating step of adding the hydrogen generating material to a solution to generate hydrogen; and reacting an oxygen-containing magnesium compound produced as a by-product in the hydrogen generating step with the hydrogen iodide solution to produce magnesium iodide. a magnesium iodide-containing solution obtaining step of obtaining a magnesium iodide-containing solution containing; a hydrate obtaining step of obtaining magnesium iodide hydrate from the magnesium iodide-containing solution; and the magnesium iodide hydrate and and a dehydration step of reacting ammonium iodide to dehydrate magnesium iodide hydrate, wherein anhydrous magnesium iodide dehydrated in the dehydration step is used as the raw material.

(5) A method for producing hydrogen according to the present invention is a method for producing hydrogen using a hydrogen generating material containing magnesium hydride produced by the method for producing a material having the configuration of (2) above, wherein the method for producing a material comprises: A hydrogen iodide obtaining step of obtaining the hydrogen iodide in the form of a liquid, a solid, or a mixture of liquid and solid, wherein the method for producing hydrogen includes adding the hydrogen generating material to a solution to generate hydrogen. a generating step, and adding the hydrogen iodide to the solution after adding the hydrogen generating material to the solution, and reacting the oxygen-containing magnesium compound produced as a by-product in the hydrogen generating step with the hydrogen iodide; a magnesium iodide-containing solution obtaining step of obtaining a magnesium iodide-containing solution containing magnesium iodide; a hydrate obtaining step of obtaining magnesium iodide hydrate from the magnesium iodide-containing solution; and a dehydration step of reacting magnesium hydrate with ammonium iodide to dehydrate the magnesium iodide hydrate, wherein anhydrous magnesium iodide dehydrated in the dehydration step is used as the raw material.

(6) In the configuration of (4) or (5) above, the hydrogen production method includes an ammonium iodide obtaining step of obtaining ammonium iodide produced by reacting ammonia generated in the dehydration step with hydrogen iodide. wherein the ammonium iodide obtained in the ammonium iodide obtaining step is utilized in the dehydration step.

(7) A method for producing hydrogen according to the present invention is a method for producing hydrogen using a hydrogen generating material containing magnesium hydride produced by the method for producing a material having the configuration of (3) above, wherein the method for producing a material comprises: The method for producing hydrogen includes an ammonium iodide obtaining step of obtaining the ammonium iodide, wherein the method for producing hydrogen comprises: a hydrogen generating step of adding the hydrogen generating material to a solution to generate hydrogen; An oxygen-containing magnesium compound obtaining step of obtaining an oxygen-containing magnesium compound produced as a by-product in the hydrogen generation step from the solution after the addition of, and an anhydrous magnesium iodide by reacting the oxygen-containing magnesium compound and the ammonium iodide and a step of obtaining magnesium iodide, wherein the magnesium iodide obtained in the step of obtaining magnesium iodide is used as the raw material.

(8) In the configuration of (7) above, the hydrogen production method includes an ammonia gas obtaining step of obtaining ammonia gas generated in the magnesium iodide obtaining step, and the ammonia gas obtained in the ammonia gas obtaining step is used for the ammonia gas supplied into the exhaust pipe between the process chamber and the pump in the volume reduction step.

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride in which the production reaction of magnesium hydride is improved, and a hydrogen generating material containing magnesium hydride manufactured by the material manufacturing method. can provide a method for producing hydrogen using

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing for demonstrating the manufacturing apparatus used for the material manufacturing method which manufactures the hydrogen-producing material containing magnesium hydride of 1st Embodiment which concerns on this invention. FIG. 4 is a cross-sectional view for explaining a manufacturing apparatus used in a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride according to a second embodiment of the present invention. FIG. 3 is a cross-sectional view for explaining a manufacturing apparatus used in a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride according to a third embodiment of the present invention;

EMBODIMENT OF THE INVENTION Hereinafter, with reference to an accompanying drawing, the form (henceforth, embodiment) for implementing this invention is demonstrated in detail.
The same numbers are given to the same elements throughout the description of the embodiment.

(First embodiment)
FIG. 1 is a cross-sectional view for explaining a manufacturing apparatus 10 used in a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride according to a first embodiment of the present invention.

As shown in FIG. 1, the manufacturing apparatus 10 has an opening/closing door 11A that is opened and closed when accessing the inside, and includes a processing chamber 11 for irradiating the raw material with plasma, and a processing chamber 11 during the processing for irradiating the plasma. and an evacuation pump P (vacuum pump) as a decompression means for keeping the pressure of the pressure.
It should be noted that the pump P is preferably a dry pump in order to avoid mixing oil into the exhausted gas.

Specifically, the manufacturing apparatus 10 includes an exhaust pipe 12 for discharging gas from the processing chamber 11 , and the pump P is connected to the middle of the exhaust pipe 12 .
The exhaust pipe 12 on the downstream side (the side away from the processing chamber 11) of the pump P is inserted into the solution in the processing tank 13 storing the solution (aqueous solution 13A). The gas discharged from the processing chamber 11 is released into the solution in a bubbling state through the provided through-hole 12A so as to be exposed to the solution. is discharged to the outside of the processing tank 13 from a discharge port (not shown) provided in the .

The manufacturing apparatus 10 also includes a recovery unit 14 that recovers the hydrogen generating material containing magnesium hydride produced by the reaction between the raw material and the plasma.
In addition, the recovery part 14 is a member to which a hydrogen generating material containing magnesium hydride adheres, as will be described later.

In this embodiment, in order to increase the content of magnesium hydride in the hydrogen generating material, the temperature of the surface SF of the recovery unit 14 on which the hydrogen generating material is deposited is kept at a temperature of 400° C. or higher and 800° C. or lower. For this purpose, a stainless steel plate having a thickness of 10 mm or less is used for the collecting portion 14 .

The manufacturing apparatus 10 also includes a raw material supply unit 15 that heats the raw material and supplies it in a gaseous state into the plasma.
Specifically, the raw material supply unit 15 is arranged outside the upper side of the processing chamber 11, and includes a heating unit 15A that heats the stored raw material to a gaseous state, and a heating unit 15A that heats the raw material so as to maintain the gaseous state. and an upper lid 15AA provided on the upper portion of the heating section 15A and opened and closed when the raw material is introduced into the heating section 15A.

Although illustration is omitted, the heating unit 15A and the raw material supply path 15B have a heater structure (for example, an electric heating structure, etc.) capable of heating the raw material to a temperature at which it becomes gaseous.

Furthermore, the manufacturing apparatus 10 includes a gas supply unit 16 that supplies a reactive gas that is turned into plasma and reacts with the raw material, a microwave supply unit 17 that supplies microwaves for generating plasma, and introduces into the processing chamber 11 . a window 18 of dielectric (eg, quartz, ceramic, etc.) transparent to microwaves.

Specifically, the gas supply unit 16 includes a gas cylinder or gas tank storing a reactive gas (for example, hydrogen gas) and a gas pipe connecting between the processing chamber 11 and the gas pipe (not shown). and a flow controller (for example, a mass flow controller) that is provided above and controls the flow rate of the reactive gas supplied to the processing chamber 11 .

The microwave supply unit 17 also includes a microwave generation unit 17A and a waveguide unit 17B that guides the microwave generated by the microwave generation unit 17A to the window 18 .

The microwave generation unit 17A includes a microwave generator (for example, a magnetron) and a power supply device that supplies power for generating microwaves to the microwave generator. is supplied to the microwave generator, the microwave generator generates microwaves, the generated microwaves are guided to the window 18 by the waveguide 17B, and introduced into the processing chamber 11 through the window 18. be done.

The plasma generated in such a configuration is a microwave surface wave plasma, and since the microwave surface wave plasma has a high electron density, the microwave irradiated through the window 18 is reflected on the surface of the microwave surface wave plasma. Although it does not enter the inside of the microwave surface wave plasma, it propagates along the surface of the microwave surface wave plasma.

Microwave surface wave plasma has a low electron temperature (e.g., about 1 eV) compared to other plasmas (e.g., high-frequency plasma, DC discharge plasma, etc.), and has a high electron temperature (e.g., about 1 eV). For example, unlike plasma that consumes energy to achieve 10 eV or more), it has the advantage of less energy loss and can be generated in a large area of 0.5 m ² or more, for example.

Furthermore, the microwaves incident into the processing chamber 11 propagate through the window 18 but are absorbed as surface waves. In addition to having a high degree of freedom in configuration, microwave surface wave plasma is characterized by the fact that the temperature of ions and molecules in the plasma is significantly lower (almost normal temperature) than that of thermal plasma, and is used in prior art documents. A process at a much lower temperature than thermal plasma can be realized.

In this embodiment, a plurality of (specifically two) windows 18 are provided on the upper side of the processing chamber 11, and a plurality of (specifically two) microwave supply units corresponding to the respective windows 18 are provided. 17 is provided, it is not always necessary to provide a plurality of windows 18 and microwave supply units 17 .

In addition, it is considered preferable that the density of the plasma is high in order to increase the reactivity between the raw material and the plasma of the reactive gas.
In addition, the reactive gas is a gas containing hydrogen, which is an atom constituting magnesium hydride (MgH ₂ ) generated by reaction with the raw material (for example, hydrogen gas, methane, hydrocarbon gas such as propane), Therefore, noble gases are not reactive gases.

However, since hydrocarbon gas forms a reducing atmosphere in the same way as hydrogen gas, it is possible to generate plasma that can perform a reducing reaction, but since gas containing carbon is included in exhaust gas, reactive gas is preferably hydrogen gas.

For this reason, in the present embodiment, the microwave supply unit 17 generates microwaves having a peak value of 2.0 kilowatts or more in the microwave power of the microwaves supplied into the processing chamber 11 through at least the window 18. is used.

In addition, even when the plasma was generated by microwaves with a microwave power of less than 2.0 kilowatts, the generation reaction of magnesium hydride was observed, but when it was 2.0 kilowatts or more, it was overwhelmingly A state was reached in which a hydrogen generating material with a high content of magnesium hydride was obtained.

Specifically, a pulse-type power supply with a maximum average power consumption of 1.5 kilowatts is used as the power supply, and a microwave generator (e.g., magnetron) of about 6.0 kilowatts is used momentarily. Power is supplied to generate microwaves having a pulsed microwave power with a maximum microwave power of the order of 6.0 kilowatts.
Note that the minimum microwave power is 0 kilowatts and the time period between maximum microwave powers is 30 microseconds.

In this way, even if there is a moment when the minimum value of the microwave power becomes 0 kilowatts, the microwave is supplied with enough microwave power to maintain the lighting before the plasma density reaches the density at which the plasma disappears. If so, it is possible to maintain the ignition of the plasma, and if the time period between microwave power maxima is short, it is possible to maintain the plasma density corresponding to the microwave power maxima. can.

Thus, it is possible to maintain high plasma density plasma ignition while reducing the average microwave power, which reduces the average power used to generate the microwaves. means to be

However, it is not essential to use a pulse-type power supply as the power supply, and for example, a DC power supply capable of setting a power supply setting of 2.0 kilowatts or more may be used.

In order to make the peak value of the microwave power of the microwave supplied into the processing chamber 11 through the window 18 to be 2.0 kilowatts or more as in the present embodiment, the return attenuation up to the window 18 is In anticipation, in the case of a DC type power supply, it is preferable to select one that can be set to 2.5 kilowatts or more.

From the point of view of increasing the plasma density, the microwave supply unit 17 includes at least a microwave with a microwave power peak value of 3.0 kilowatts or more supplied into the processing chamber 11 through the window 18 . It is preferable to use one that generates waves, and more preferably one that generates microwaves of 4.0 kilowatts or more.

On the other hand, depending on the design of the waveguide section 17B, if the peak value of the microwave power of the microwave introduced from the window 18 is increased too much, the inside of the waveguide section 17B Since there is a problem that discharge occurs in the microwave supply unit 17, the microwave power of the microwave to be generated has a peak value of 24 kilowatts or less, further, 15 kilowatts or less. is preferred.

In addition, the manufacturing apparatus 10 maintains the temperature of at least the portion of the surface SF facing the window 18 of the collection unit 14 disposed at the lower position facing the window 18 at a temperature of 450° C. or more and 800° C. or less. It has a temperature control unit 19 capable of controlling the temperature.

Specifically, the temperature control unit 19 includes a heater 19A provided on the side surface of the processing chamber 11 and a temperature control unit 19B provided on the bottom surface of the processing chamber 11 so as to be in contact with or close to the recovery unit 14. , is equipped with

The temperature control unit 19B is positioned below the recovery unit 14, and has a circulation path for circulating a temperature control medium (for example, water) kept at a predetermined temperature so as not to leak into the processing chamber 11. A temperature controller (not shown) provided in the middle of the circulation path (for example, a portion of the circulation path positioned outside the processing chamber 11) for controlling the temperature of the temperature control medium, and the temperature control medium in the circulation path. a pump (not shown) for circulating the

The heater 19A of the temperature control section 19 also has the function of maintaining the temperature of the raw material in the gaseous state in the processing chamber 11. Then, for example, by cooling, the temperature of at least the portion of the surface SF of the collecting section 14 facing the window 18 can be maintained at a temperature of 450° C. or higher and 800° C. or lower.

In addition, although not shown in the drawings, the manufacturing apparatus 10 uses nitrogen gas or rare gas (for example, nitrogen gas or rare gas) when the internal pressure of the processing chamber 11 is changed from the reduced pressure state to the atmospheric pressure in order to open and close the open/close door 11A. A purge gas supply unit connected to the processing chamber 11 is provided in order to supply a gas with low activity (hereinafter also referred to as a purge gas) such as He or Ar to the processing chamber 11 .

The configuration itself of the purge gas supply unit is the same as that of the gas supply unit 16. A gas pipe connecting the gas cylinder or gas tank storing the purge gas and the processing chamber 11, and a gas pipe provided on the gas pipe to and a flow controller (for example, a mass flow controller) for controlling the flow rate of the purge gas supplied to 11 .

Furthermore, when the plasma starts to be turned on, it is easier to turn on the plasma if the reactive gas contains a rare gas. It should be.

The configuration of the rare gas supply unit itself may be the same as that of the gas supply unit 16. A gas pipe connecting the gas cylinder or gas tank storing the rare gas and the processing chamber 11, and provided on the gas pipe, and a flow rate controller (for example, a mass flow controller) that controls the flow rate of the rare gas supplied to the processing chamber 11 .

Once the plasma is turned on, even if the supply of the rare gas is stopped, there is no problem in keeping the plasma on. Therefore, once the plasma is turned on, the supply of the rare gas to the processing chamber 11 is stopped. In this embodiment, the supply of the rare gas is stopped.

Next, a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride using the manufacturing apparatus 10 having the above configuration, and a hydrogen manufacturing method using the manufactured hydrogen generating material will be described.

(Material manufacturing method)
First, in the material manufacturing method, the pump P described above is driven to exhaust the gas in the processing chamber 11 and reduce the pressure in the processing chamber 11 .
The inside of the processing chamber 11 is kept at a predetermined pressure until the material manufacturing process is completed. In the embodiment, the decompression step is performed by a pump P connected to an exhaust pipe 12 that exhausts gas from the processing chamber 11 .

Then, after starting to supply hydrogen gas, which is a reactive gas containing hydrogen for forming a reducing atmosphere, in the processing chamber 11, the microwave generator 17A of the microwave supply unit 17 is driven, and microwaves are supplied from the window 18. A plasma (microwave surface wave hydrogen plasma in this example) is ignited by introducing the plasma.
As mentioned above, the rare gas is also supplied to the processing chamber 11 at the start of the lighting, but the supply of the rare gas is stopped when the plasma is turned on.

Since the plasma is kept on until the material manufacturing process is completed, the start of plasma lighting is the start of the plasma generation step for maintaining the plasma generation state within the processing chamber 11 .

Then, when the plasma generation step is started, after adjusting the pressure in the processing chamber 11 to a predetermined reduced pressure state, the raw material supply unit 15 is driven to heat the raw material and supply it in the plasma in a gaseous state. to start.

For example, in order to generate high-density plasma with high reactivity, it is advantageous to have a low pressure in the processing chamber 11. Therefore, the pressure in the processing chamber 11 is reduced to 10% to adjust to a predetermined reduced pressure state. It is preferable to adjust the pressure to 1/1 atmosphere or less, more preferably to 1/100 atmosphere or less, and further preferably to 1/1000 atmosphere or less. The pressure is set to about 10 Pa, which is about 1/1 atmospheric pressure.
This adjustment is performed by adjusting the opening of a valve (not shown) provided on the exhaust pipe 12 on the upstream side of the pump P (on the processing chamber 11 side).

However, the reactivity also changes depending on the partial pressure of the reactive gas (hydrogen gas) present in the processing chamber 11. From the viewpoint of the partial pressure, the higher the pressure in the processing chamber 11, the more the inside of the processing chamber 11. Advantageously, the concentration of reactive gases present in the can be increased.

For this reason, it is preferable that the adjustment to the predetermined reduced pressure state is performed in the range of 10 KPa to 10 Pa.

Here, in the material manufacturing method of the present invention, the raw material is magnesium iodide (MgI ₂ ), and magnesium iodide decomposes at a temperature at which it becomes gaseous. ) and iodine (I ₂ ).

Among magnesium halides, for example, magnesium chloride (MgCl ₂ ) has a decomposition temperature higher than the temperature at which it becomes gaseous. will be supplied as is.

Therefore, in order to change to magnesium hydride (MgH ₂ ), it is considered that a reaction of decomposition into chlorine (Cl) and magnesium (Mg) by plasma is necessary, and magnesium and plasma generated by the decomposition are further It is believed that the reaction produces magnesium hydride.
When magnesium chloride is decomposed by plasma decomposition reaction, chlorine (Cl) changes into various states such as molecules, ions, and radicals.

However, when the raw material is magnesium iodide (MgI ₂ ), since the raw material decomposed into magnesium (Mg) and iodine (I ₂ ) is supplied to the processing chamber 11, the decomposition reaction as the pre-stage reaction is unnecessary, and the production reaction of magnesium hydride can be improved.

Then, when the supply step is started, the hydrogen generating material containing magnesium hydride produced by the reaction between magnesium iodide (MgI ₂ ) as a raw material and plasma begins to adhere to the surface SF of the recovery unit 14 at about the same timing. , a recovery step of recovering the hydrogen generating material will also be initiated.

Here, the hydrogen generating material adhering to the surface SF includes metal magnesium (Mg) and the like, but in order to obtain a hydrogen generating material with a large amount of hydrogen generation, materials other than magnesium hydride are included. A lower percentage is desirable.

Magnesium hydride begins to decompose into metallic magnesium and hydrogen when the temperature reaches approximately 100°C or higher under the condition of a pressure of approximately 10 Pa. Less than is considered desirable.

Certainly, when the temperature is maintained at a low temperature of less than 100° C., the adhesion amount per unit time tends to increase, and a hydrogen generating material with a high hydrogen generation rate tends to be obtained.

However, by keeping the surface SF at a low temperature, the adhering hydrogen-producing material could not be changed to a white state, which is the original color of magnesium hydride, and could not escape from a state containing metallic magnesium and the like. .

When the experiment was repeated, there was a time when the temperature of the surface SF reached a relatively high temperature. It was discovered that it was a product that foamed violently.
The amount of hydrogen generated was measured not only by the foaming state but also by a hydrogen detector tube.

Therefore, as a result of conducting an experiment in which the temperature of the surface SF was set to a high temperature, it was found that when the temperature of the surface SF was maintained at a temperature of 400°C or higher and 800°C or lower, the content of magnesium hydride, which was white and reacted violently with water, was reduced. It was found that a high hydrogen generating material can be obtained.

More preferably, at 450° C. or higher and 750° C. or lower, a whiter hydrogen generating material that reacts violently with water is obtained, and furthermore, at 450° C. or higher and 600° C. or lower, a whiter hydrogen generating material that reacts violently with water is obtained. We have found that materials are available.

Such a phenomenon cannot be understood when the equilibrium state is considered with the temperature at which magnesium hydride begins to decompose as described above. It is surmised that when plasma is generated, there is a large amount of highly reactive hydrogen, and the reaction to form magnesium hydride is progressing faster than the rate at which magnesium hydride is decomposed.

More precisely, in the process of disappearance of magnesium hydride, first, a reaction occurs to decompose into metallic magnesium and hydrogen, and then metallic magnesium becomes gaseous. The presence of a large amount of hydrogen with a high σ inhibits the process of decomposing into metallic magnesium and hydrogen at the beginning. I'm guessing not.

Moreover, when the pressure is about 10 Pa and the temperature rises to 400° C. or higher, it is thought that metallic magnesium begins to become a gaseous state. It is speculated that the change may result in a hydrogen generating material containing a large amount of magnesium hydride.

Therefore, in order to obtain a hydrogen generating material containing magnesium hydride at a high concentration, in the recovery step, the surface SF facing at least the window 18 of the recovery section 14 arranged in the processing chamber 11 is required as in the present embodiment. It is preferable to keep the temperature of the part of (1) at a temperature of 450° C. or higher and 800° C. or lower.

The gas discharged from the processing chamber 11 is released in a bubbling state into the solution (aqueous solution 13A) in the processing tank 13 through the exhaust pipe 12 and exposed to the solution.

In the processing chamber 11, hydrogen iodide (HI) is also generated by a reaction between iodine (I ₂ ) and the hydrogen gas plasma, along with a reaction that generates magnesium hydride (MgH ₂ ) by the hydrogen gas plasma, Since hydrogen iodide cannot adhere to the recovery unit 14 , it is discharged as a gas discharged from the processing chamber 11 .

Since hydrogen iodide (HI) is readily soluble in the solution (aqueous solution 13A), hydrogen iodide (HI) dissolves in the solution when exposed to the solution as described above. becomes a hydrogen iodide solution.

Therefore, the gas discharged from the processing chamber 11 in the decompression step is exposed to the solution (aqueous solution 13A) by the processing tank 13 to obtain a hydrogen iodide solution in which at least hydrogen iodide (HI) in the discharged gas is dissolved. A solution acquisition step is performed to

The gas discharged from the processing chamber 11 also contains hydrogen gas, but since hydrogen gas hardly dissolves in the solution, it is discharged from the processing tank 13 in a gaseous state. Recover with hydrogen gas recovery equipment.

As described above, in the material manufacturing method of the present embodiment, the depressurization step of keeping the processing chamber 11 under reduced pressure and the supply of hydrogen gas, which is a reactive gas containing hydrogen to form a reducing atmosphere in the processing chamber 11, are started. After that, a plasma generation step of driving the microwave generation unit 17A of the microwave supply unit 17 to turn on the plasma to maintain the plasma generation state in the processing chamber 11, and heating the raw material (magnesium iodide) to gas , a recovery step of recovering the hydrogen generating material containing magnesium hydride produced by the reaction between the raw material (magnesium iodide) and the plasma, and a decompression step. and a solution obtaining step of exposing the gas to a solution (aqueous solution 13A) to obtain a hydrogen iodide solution in which at least hydrogen iodide (HI) in the discharged gas is dissolved.

In this material manufacturing method, power is used in the depressurization step, plasma generation step, supply step, etc. Currently, when power demand is low, solar power generation, wind power generation, etc. are stopped. Also, in other power generation, surplus power is generated at nighttime, etc., and it is sufficient to use the surplus power when such power demand is low.

On the other hand, when the demand for electric power is high, hydrogen is generated using the hydrogen generating material containing magnesium hydride manufactured by the above material manufacturing method, and the hydrogen is used to generate power (for example, hydrogen turbine power generation, fuel cells, etc.) power generation).

Therefore, next, a hydrogen generation method (hydrogen production method) using the hydrogen generation material containing magnesium hydride produced by the above material production method will be described.
In the following, in order not to waste the material, a hydrogen production method that can regenerate magnesium (Mg) contained in the hydrogen generating material as a raw material (magnesium iodide) used in the material production method will be described.

(Hydrogen production method)
First, in the hydrogen production method, a hydrogen generation step of putting a hydrogen generation material into a solution (aqueous solution) to generate hydrogen is performed.
Specifically, the hydrogen generation step is carried out using a hydrogen generator equipped with a closed tank storing a sufficient solution (aqueous solution) and a hydrogen generating material supply section for supplying the hydrogen generating material into the closed tank. More specifically, the hydrogen generating material supply unit supplies the closed tank with enough hydrogen generating material to generate the necessary hydrogen.

It should be noted that even if it is a closed tank, it is not impossible to discharge the generated hydrogen. A pressure control valve, a flow rate control device, etc. are provided, and the sealing of the closed tank means that the generated hydrogen and the stored solution (aqueous solution) do not leak freely.

Further, the closed tank is provided with a solution discharge mechanism for discharging the solution when replacing the solution (aqueous solution) in the closed tank and a solution supply mechanism for supplying a new solution.

Then, when the hydrogen generating material containing magnesium hydride is added to the solution (aqueous solution), as shown in Equation 1, magnesium hydride (MgH ₂ ) and the solution (H ₂ O) react to generate hydrogen (H ₂ ) occurs.
MgH ₂ + 2H ₂ O → Mg(OH) ₂ + 2H ₂ (1)

Although the reaction of Formula 1 is considered to be the main reaction, the reaction of Formula 2 may partially occur as the reaction between magnesium hydride (MgH ₂ ) and the solution (H ₂ O).
MgH ₂ + H ₂ O → MgO + 2H ₂ (2)

Also, even if the hydrogen generating material contains metallic magnesium, hydrogen is generated by the reactions of formulas 3 and 4.
Mg + 2H ₂ O → Mg(OH) ₂ + H ₂ (3)
Mg + H ₂ O → MgO + H ₂ (4)

Then, no matter which reaction of formulas 1 to 4 occurs, in the hydrogen generation step, magnesium hydroxide (Mg(OH) ₂ ) and oxygen-containing magnesium compounds (Mg(OH ) ₂ , MgO) are produced, and such oxygen-containing magnesium compounds (Mg(OH) ₂ , MgO) are almost insoluble in aqueous solutions. ) can be obtained by filtering.

On the other hand, when oxygen-containing magnesium compounds (Mg(OH) ₂ , MgO) produced as by-products in the hydrogen generation step are introduced into the hydrogen iodide solution, iodine Since it becomes a state of magnesium iodide, it is possible to obtain a magnesium iodide-containing solution containing magnesium iodide by putting it in a hydrogen iodide solution.
Mg(OH) ₂ + 2HI → MgI ₂ + 2H ₂ O (5)
MgO + 2HI → MgI ₂ + H ₂ O (6)

In the material manufacturing method described above, the gas discharged from the processing chamber 11 is exposed to the solution (aqueous solution 13A) in the depressurization step, and at least hydrogen iodide (HI) in the discharged gas is dissolved into iodine. It has a solution obtaining step of obtaining a hydrogen solution.

Therefore, in the hydrogen production method of the present embodiment, the hydrogen iodide solution obtained in the solution obtaining step is used to obtain oxygen-containing magnesium compounds (Mg(OH) ₂ , MgO ) and a hydrogen iodide solution to obtain a magnesium iodide-containing solution containing magnesium iodide. I am trying to

However, since the magnesium iodide thus regenerated exists in a solution, the hydrogen production method of the present embodiment performs the following two steps in order to obtain anhydrous magnesium iodide. and

Specifically, in the hydrogen production method of the present embodiment, as the first step for obtaining anhydrous magnesium iodide, a hydrate obtaining step of obtaining magnesium iodide hydrate from a magnesium iodide-containing solution is performed. is doing.

For example, when a magnesium iodide-containing solution is heated to about 50° C., a hydrate of magnesium iodide (MgI _{2.6H 2 O or MgI 2.8H 2 O ) is} precipitated. A hydrate obtaining step is performed in such a manner as to obtain a substance.

Since the magnesium iodide hydrate obtained in the hydrate obtaining step is also a hydrate, it still contains water. As a second step for this purpose, a dehydration step is performed in which magnesium iodide hydrate and ammonium iodide are reacted to dehydrate the magnesium iodide hydrate to obtain anhydrous magnesium iodide.

Specifically, magnesium iodide hydrate (MgI 2.6H ₂ O or MgI _{2.8H 2} O) is a hydrate at about 550° C., which is the decomposition temperature of ammonium iodide, in an atmosphere of pressure ₁ atm. Dehydration occurs when reacted with several moles of ammonium iodide (NH ₄ I).

Since magnesium iodide decomposes at 700° C. in an atmosphere with a pressure of 1 atm, the temperature when reacting with ammonium iodide is 550° C. or higher and lower than 700° C., more preferably 600° C. or higher and 650° C. or lower. is preferred.

For example, in the case of magnesium iodide octahydrate, a dehydration reaction as shown in Formula 7 below occurs.
_{MgI2.8H2O + 8NH4I}
→ MgI ₂ + 8NH ₃ + 8HI + 8H ₂ O (7)

Magnesium iodide that has been dehydrated in the dehydration step in this way to become anhydrous magnesium iodide is again used as magnesium iodide as a raw material used in the material manufacturing method in the present embodiment.

The dehydration step includes a reaction chamber containing a mixture of magnesium iodide hydrate and ammonium iodide, a reaction chamber for heating the mixed material, and gases (NH ₃ , HI, H ₂ O) generated by the reaction. Ammonia (NH ₃ ) and hydrogen iodide (HI) quickly react to solid ammonium iodide (NH ₄ I).

For this reason, in the present embodiment, a dust collector for obtaining ammonium iodide is provided in the gas discharge mechanism of the dehydrator, and the hydrogen production method uses iodide produced by the reaction between ammonia generated in the dehydration step and hydrogen iodide. It includes an ammonium iodide obtaining step of obtaining ammonium iodide, wherein the ammonium iodide obtained in the ammonium iodide obtaining step is utilized in the dehydration step.

(Second embodiment)
FIG. 2 is a cross-sectional view for explaining a manufacturing apparatus 10 used in a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride according to a second embodiment of the present invention.

As can be seen from FIG. 2, most of the configuration of the manufacturing apparatus 10 of the present embodiment is the same as that of the first embodiment. Description of the same points as in the first embodiment may be omitted.
That is, this embodiment is the same as the first embodiment unless otherwise specified.

As shown in FIG. 2, the manufacturing apparatus 10 of the present embodiment includes a cooler 20 for cooling a part of the exhaust pipe 12 on the upstream side (processing chamber 11 side) of the pump P of the exhaust pipe 12, and and a collection container 21 connected to a portion where the branch pipe of the exhaust pipe 12 branched in the cooler 20 exits the cooler 20 .

As described above, the gas discharged from the processing chamber 11 contains hydrogen iodide (HI), which liquefies at a relatively high temperature.
Hydrogen iodide (HI), for example, has a boiling point of about −35° C. in an atmosphere with a pressure of 1 atm. It can be sufficiently liquefied by cooling.

Then, when the exhaust pipe 12 is cooled to a temperature between the melting point and the boiling point of hydrogen iodide, the hydrogen iodide (HI) in the discharged gas is liquefied, and the exhaust pipe 12 located vertically below branches. The liquefied hydrogen iodide flows toward the tube and is recovered in the recovery container 21 .

The recovery container 21 has a connection pipe for connecting to the branch pipe of the exhaust pipe 12, and the connection pipe has a check mechanism 21A for preventing backflow of hydrogen iodide (HI). is provided.

Although not shown in the drawings, an opening/closing valve is provided on the upstream side (exhaust pipe 12 side) of the check mechanism 21A, and the recovery container 21 contains a There are also pipes for taking out the

As described above, when the gaseous hydrogen iodide (HI) is liquefied, its volume is greatly reduced. Since the load is greatly reduced, the capacity of the pump P itself can be made small, and the power required for the pump P can be reduced.

In the above description, the case where the hydrogen iodide (HI) is liquefied by the cooler 20 has been described, but the same effect can be obtained by cooling the exhaust pipe 12 below the melting point and solidifying it. In this case, a dust collector for collecting solid hydrogen iodide and a closed collection container for containing the hydrogen iodide collected by the dust collector may be provided.

(Material manufacturing method)
As described above, in the manufacturing apparatus 10 of the present embodiment, the volume of the gas is reduced until it reaches the pump P. Therefore, the material manufacturing method using the manufacturing apparatus 10 of the present embodiment includes the process chamber 11 to the pump P includes a volume reduction step for reducing the volume of the gas discharged from the processing chamber 11 .

In the volume reduction step, as described above, the exhaust pipe 12 between the processing chamber 11 and the pump P is cooled, and at least hydrogen iodide (HI) in the exhausted gas is converted into a liquid. , a solid, or a mixture of liquid and solid to reduce its volume.

In addition, by recovering hydrogen iodide (HI) in the recovery container 21, the material manufacturing method of the present embodiment acquires hydrogen iodide (HI) in the form of liquid, solid, or a mixture of liquid and solid. and a hydrogen iodide obtaining step.

Although the illustration is omitted in case the hydrogen iodide in the gas is not completely recovered in the recovery container 21, the structure of the processing tank 13 described in the first embodiment is also provided in this embodiment. ing.

(Hydrogen production method)
On the other hand, the hydrogen production method of this embodiment is basically the same as that of the first embodiment, except for the magnesium iodide-containing solution obtaining step.

That is, in the first embodiment, oxygen-containing magnesium compounds (Mg(OH) ₂ , MgO) generated as by-products in the hydrogen generation step in the hydrogen iodide solution obtained in the solution obtaining step for obtaining the hydrogen iodide solution was introduced to obtain the magnesium iodide-containing solution, but this embodiment is different.

Specifically, in the present embodiment, after the hydrogen generating material is added to the solution in the hydrogen generating step, the post-input solution (the waste liquid discharged from the closed tank by the solution discharge mechanism described above) is added to the material manufacturing method. The hydrogen iodide (HI) obtained in the hydrogen iodide obtaining step is introduced (dissolved), and oxygen-containing magnesium compounds (Mg(OH) ₂ , MgO) and iodide produced as by-products in the hydrogen generation step A magnesium iodide-containing solution obtaining step of reacting hydrogen to obtain a magnesium iodide-containing solution containing magnesium iodide (MgI ₂ ).

Even in this case, since a magnesium iodide-containing solution is obtained, if the hydrate obtaining step and the dehydration step described in the first embodiment are further performed, anhydrous magnesium iodide can be obtained, and the dehydration step Anhydrous magnesium iodide dehydrated in can be used as a raw material used in the material manufacturing method.

(Third Embodiment)
FIG. 3 is a cross-sectional view for explaining a manufacturing apparatus 10 used in a material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride according to a third embodiment of the present invention.

As can be seen from FIG. 3, most of the configuration of the manufacturing apparatus 10 of the present embodiment is the same as that of the first embodiment. Description of the same points as in the first embodiment may be omitted.
That is, this embodiment is the same as the first embodiment unless otherwise specified.

As shown in FIG. 3, the manufacturing apparatus 10 of the present embodiment is connected to an exhaust pipe 12 on the upstream side (processing chamber 11 side) of a pump P provided in the middle of the exhaust pipe 12, and ammonia gas (NH ₃ ), and a dust collector 23 provided on the exhaust pipe 12 between the ammonia gas supply unit 22 and the pump P.
Note that the dust collector 23 may be provided on the exhaust pipe 12 on the downstream side of the pump P (the side away from the processing chamber 11).

The ammonia gas supply unit 22 has substantially the same configuration as the gas supply unit 16, and includes a gas pipe connecting between an ammonia storage unit (not shown) storing ammonia and the exhaust pipe 12, and provided on the gas pipe, and a flow controller (for example, a mass flow controller) (not shown) that controls the flow rate of the ammonia gas supplied to the exhaust pipe 12 .

Then, as described above, ammonia (NH ₃ ) and hydrogen iodide (HI) are dissolved in ammonium iodide at a low temperature (approximately 550° C. or lower, which is the decomposition temperature of ammonium iodide (NH ₄ I)). becomes solid.

As described above, the gas discharged from the processing chamber 11 contains hydrogen iodide (HI), and the temperature inside the exhaust pipe 12 is close to room temperature. When ammonia gas (NH ₃ ) is supplied from the gas supply unit 22 to the exhaust pipe 12, hydrogen iodide reacts with ammonia to produce solid ammonium iodide, and the produced ammonium iodide collects dust. Acquired by being collected by the device 23 .

Although the illustration is omitted in case there is unreacted ammonia or hydrogen iodide, the structure of the processing tank 13 described in the first embodiment is also provided in this embodiment.

Even in this case, the gaseous hydrogen iodide (HI) is taken into the solid ammonium iodide, so the volume is greatly reduced, and the same as described in the second embodiment. You get the effect.

(Material manufacturing method)
As described above, the manufacturing apparatus 10 of the present embodiment also reduces the volume of the gas up to the pump P, as in the second embodiment. The material manufacturing method described above also includes a volume reduction step for reducing the volume of the gas discharged from the processing chamber 11 before reaching the pump P from the processing chamber 11 .

However, in this embodiment, the volume reduction step is performed by supplying ammonia gas into the exhaust pipe 12 between the processing chamber 11 and the pump P, and at least removing hydrogen iodide (HI) in the exhausted gas. Ammonium iodide (NH ₄ I) is solidified to reduce the volume.

In addition, since ammonium iodide (NH ₄ I) is recovered by the dust collector 23, the material manufacturing method of the present embodiment includes an ammonium iodide acquisition step of acquiring ammonium iodide.

(Hydrogen production method)
On the other hand, in the hydrogen production method of the present embodiment, the hydrogen generation step is the same as that of the first embodiment, but the subsequent steps are different. Hereinafter, the steps after the hydrogen generation step will be described.

As described in the first embodiment, in the hydrogen generation step, oxygen-containing magnesium compounds (Mg(OH) ₂ , MgO) such as magnesium hydroxide (Mg(OH) ₂ ) and magnesium oxide (MgO) are produced as by-products. However, such oxygen-containing magnesium compounds (Mg(OH) ₂ , MgO) are almost insoluble in aqueous solutions. can be obtained by

Then, the oxygen-containing magnesium compound (Mg(OH)2, MgO), which is a by-product thus obtained, is dried, for example, in a drying room to obtain a moisture-free oxygen-containing magnesium compound. conduct.

That is, in the hydrogen production method of the present embodiment, after the hydrogen generation step, after the hydrogen generation material is added to the solution, the post-input solution (waste liquid discharged from the closed tank by the solution discharge mechanism) is used as a secondary in the hydrogen generation step. An oxygen-containing magnesium compound obtaining step is performed in which an oxygen-containing magnesium compound (Mg(OH) ₂ , MgO) produced as a product is obtained in a dried state.

Then, by reacting the dried oxygen-containing magnesium compound (Mg(OH) ₂ , MgO) with ammonium iodide (NH ₄ I), anhydrous magnesium iodide (MgI ₂ ) can be obtained.

Specifically, magnesium hydroxide (Mg(OH)2) among oxygen-containing magnesium compounds (Mg(OH) ₂ , MgO) at a temperature equal to or higher than the decomposition temperature of ammonium iodide ( _NH4I ) is ammonium iodide. (NH ₄ I) to produce magnesium iodide (MgI ₂ ) as shown in Equation 8, and at the same temperature magnesium oxide (MgO) reacts with ammonium iodide (NH ₄ I) , magnesium iodide is produced as shown in Eq.
Mg(OH) ₂ + _2NH4I
→ MgI ₂ + 2NH ₃ + 2H ₂ O (8)
MgO + 2NH ₄ I → MgI ₂ + 2NH ₃ + H ₂ O (9)

Thus, in the hydrogen production method of the present embodiment, after the oxygen-containing magnesium compound obtaining step, the oxygen-containing magnesium compound (Mg(OH) ₂ , MgO) obtained in the oxygen-containing magnesium compound obtaining step and the material described above A magnesium iodide obtaining step is performed in which the ammonium iodide (NH ₄ I) obtained in the ammonium iodide obtaining step of the manufacturing method is reacted to obtain anhydrous magnesium iodide (MgI ₂ ).

Incidentally, the magnesium iodide acquisition step can be performed using a magnesium iodide production apparatus having the same configuration as that of the dehydration step described above.
That is, a production chamber containing a mixed material of oxygen-containing magnesium compound (Mg(OH) ₂ , MgO) and ammonium iodide (NH ₄ I), heating the mixed material, and a gas ( and a gas discharge mechanism for discharging NH ₃ , H ₂ O (water vapor)).

Anhydrous magnesium iodide (MgI ₂ ) obtained in the magnesium iodide obtaining step can be used as a raw material used in the material manufacturing method, as in the previous embodiments.

By the way, as can be seen from Equations 8 and 9, the gas discharged from the generation chamber of the magnesium iodide generator contains ammonia gas (NH ₃ ). A dry filter (e.g., molecular sieve) is provided in the gas discharge mechanism of the magnesium generator, and an ammonia storage unit for storing ammonia as an ammonia gas acquisition means for acquiring gas (i.e., ammonia gas) that has passed through the dry filter. I'm trying to set up.
Note that the ammonia storage unit is filled with ammonia gas via a pressure booster.

Therefore, the hydrogen production method of the present embodiment includes an ammonia gas acquisition step of acquiring ammonia gas (NH ₃ ) generated in the magnesium iodide acquisition step, and the ammonia storage unit stores the above-described ammonia gas. A gas pipe connecting between an ammonia storage unit (not shown) storing ammonia of the gas supply unit 22 and the exhaust pipe 12 is connected.

Therefore, in the present embodiment, the ammonia gas (NH ₃ ) obtained in the ammonia gas obtaining step is placed in the exhaust pipe 12 between the processing chamber 11 and the pump P in the volume reduction step of the material manufacturing method described above. It is used for the ammonia gas supplied inside.

As described above, the present invention has been described based on specific embodiments, but the present invention is not limited to the above specific embodiments, and the present invention may be modified or improved as appropriate. is included in the technical scope of the claims, which is clear to those skilled in the art from the description of the claims.

10 Manufacturing apparatus 11 Processing chamber 11A Open/close door 12 Exhaust pipe 12A Through hole 13 Processing tank 13A Aqueous solution 14 Recovery unit 15 Raw material supply unit 15A Heating unit 15AA Upper lid 15B Raw material supply path 16 Gas supply unit 17 Microwave supply unit 17A Microwave generation unit 17B waveguide portion 18 window 19 temperature control portion 19A heater 19B temperature control portion 20 cooler 21 collection container 21A check mechanism 22 ammonia gas supply portion 23 dust collector P pump SF surface

Claims (8)

A material manufacturing method for manufacturing a hydrogen generating material containing magnesium hydride,
The material manufacturing method includes:
a depressurization step of keeping the processing chamber for irradiating the raw material with plasma at a depressurized pressure;
a supplying step of heating the raw material and supplying it in a gaseous state into the plasma;
a recovering step of recovering the hydrogen generating material containing the magnesium hydride produced by the reaction of the raw material and the plasma;
The raw material is magnesium iodide,
A material manufacturing method, wherein the plasma is a plasma of a reactive gas containing hydrogen that forms a reducing atmosphere. The decompression step is performed by a pump connected to an exhaust pipe for discharging gas from the processing chamber,
The material manufacturing method includes a volume reduction step of reducing the volume of the gas discharged from the processing chamber from the processing chamber to the pump,
The volume reduction step cools an exhaust line between the process chamber and the pump to remove hydrogen iodide in at least the exhausted gas in a liquid, solid, or mixture of liquid and solid states. 2. The method of manufacturing a material according to claim 1, wherein the step of reducing the volume by The decompression step is performed by a pump connected to an exhaust pipe for discharging gas from the processing chamber,
The material manufacturing method includes a volume reduction step of reducing the volume of the gas discharged from the processing chamber from the processing chamber to the pump,
The volume reduction step includes supplying ammonia gas into an exhaust pipe between the processing chamber and the pump, and solidifying at least hydrogen iodide in the discharged gas into ammonium iodide to reduce the volume. 2. The method of manufacturing a material according to claim 1, wherein the step of causing A hydrogen production method using a hydrogen generating material containing magnesium hydride produced by the material production method according to claim 1,
The material manufacturing method includes a solution acquisition step of exposing the gas discharged from the processing chamber in the decompression step to a solution to obtain a hydrogen iodide solution in which at least hydrogen iodide in the discharged gas is dissolved. ,
The hydrogen production method is
a hydrogen generating step of introducing the hydrogen generating material into a solution to generate hydrogen;
a magnesium iodide-containing solution obtaining step of obtaining a magnesium iodide-containing solution containing magnesium iodide by reacting an oxygen-containing magnesium compound produced as a by-product in the hydrogen generating step with the hydrogen iodide solution;
a hydrate obtaining step of obtaining magnesium iodide hydrate from the magnesium iodide-containing solution;
a dehydration step of reacting the magnesium iodide hydrate and ammonium iodide to dehydrate the magnesium iodide hydrate;
A method for producing hydrogen, wherein anhydrous magnesium iodide dehydrated in the dehydration step is used as the raw material. A hydrogen production method using a hydrogen generating material containing magnesium hydride produced by the material production method according to claim 2,
The material manufacturing method includes a hydrogen iodide obtaining step of obtaining the hydrogen iodide in the form of a liquid, a solid, or a mixture of liquid and solid,
The hydrogen production method is
a hydrogen generating step of introducing the hydrogen generating material into a solution to generate hydrogen;
The hydrogen iodide is added to the solution after adding the hydrogen generating material to the solution, and the oxygen-containing magnesium compound produced as a by-product in the hydrogen generation step and the hydrogen iodide are reacted to form iodide. a magnesium iodide-containing solution obtaining step of obtaining a magnesium iodide-containing solution containing magnesium;
a hydrate obtaining step of obtaining magnesium iodide hydrate from the magnesium iodide-containing solution;
a dehydration step of reacting the magnesium iodide hydrate and ammonium iodide to dehydrate the magnesium iodide hydrate;
A method for producing hydrogen, wherein anhydrous magnesium iodide dehydrated in the dehydration step is used as the raw material. The hydrogen production method includes an ammonium iodide obtaining step of obtaining ammonium iodide produced by reacting ammonia generated in the dehydration step with hydrogen iodide,
6. The hydrogen production method according to claim 4, wherein the ammonium iodide obtained in said ammonium iodide obtaining step is used in said dehydration step. A hydrogen production method using a hydrogen generating material containing magnesium hydride produced by the material production method according to claim 3,
The material manufacturing method includes an ammonium iodide obtaining step of obtaining the ammonium iodide,
The hydrogen production method is
a hydrogen generating step of introducing the hydrogen generating material into a solution to generate hydrogen;
an oxygen-containing magnesium compound obtaining step of obtaining an oxygen-containing magnesium compound generated as a by-product in the hydrogen generating step from the solution after the hydrogen generating material is added to the solution;
a magnesium iodide obtaining step of reacting the oxygen-containing magnesium compound with the ammonium iodide to obtain anhydrous magnesium iodide;
A hydrogen production method, wherein the magnesium iodide obtained in the magnesium iodide obtaining step is used as the raw material. The hydrogen production method includes an ammonia gas obtaining step of obtaining ammonia gas generated in the magnesium iodide obtaining step,
3. The ammonia gas obtained in the ammonia gas obtaining step is used in the volume reduction step as the ammonia gas supplied into an exhaust pipe from the processing chamber to the pump. 8. The method for producing hydrogen according to 7.

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