JP4615240B2 - Gas purification device - Google Patents

Description

  The present invention relates to an apparatus for purifying a hydrogen mixed gas used as a fuel for a fuel cell or the like.

Development of fuel cells have been actively as a clean energy source that does not emit greenhouse gases such as toxic substances and CO _2, such as NOx and SOx, has already been put to practical use in some fields. As an important technology that supports this fuel cell technology, there is a technology for purifying hydrogen or the like as fuel for the fuel cell. As storage forms of hydrogen, compression storage by high-pressure cylinders, cooling storage by liquid hydrogenation, and storage by hydrogen storage materials are known. Among these forms, storage by hydrogen storage materials is used for distributed storage and transportation. This is advantageous. Hydrogen storage materials include materials with high hydrogen storage efficiency, that is, materials with a high hydrogen storage amount per unit weight or volume of the hydrogen storage material, materials that absorb / release hydrogen at low temperatures, and good durability. A material having is desired. Furthermore, a gas purifier capable of supplying high-purity hydrogen or the like that extends the life of the fuel cell is desired.

In compressed storage using a high-pressure cylinder or in cold storage where liquid hydrogenation is performed, moisture is mixed with air during the storage process or handling of hydrogen extraction, and when water is introduced into the fuel cell, it is poisoned. There was a general problem. For these, a material using a mixture of adsorbents of metal hydride and molecular sieves as a removal material is disclosed (Patent Document 1), but for removing impurities in the coexistence state of ammonia or water. An invention of an applicable purification apparatus is not disclosed. Regarding the storage of mixed gas containing hydrogen, a hydrogen storage method using lithium nitride represented by the following formula (1) has been reported (for example, see Non-Patent Document 2). Note that the reaction of the formula (1) is a reversible reaction.
Li ₃ N + 2H ₂ = Li ₂ NH + LiH + H ₂ = LiNH ₂ + 20 LiH (1)

Here, absorption of hydrogen by Li ₃ N started from about 100 ° C., and 9.3 mass% hydrogen absorption was confirmed at 255 ° C. for 30 minutes. In addition, the release characteristics of absorbed hydrogen are reported to pass through two steps: 6.3% by mass at a little less than 200 ° C and 3.0% by mass at 320 ° C or higher when heated slowly. . That is, the reaction of the following formula (2) corresponding to the right side portion of the above formula (1) starts to proceed at a little less than 200 ° C., and the reaction of the following formula (3) corresponding to the left side portion of the above formula (1) is about 320 It has been shown to begin to progress at ° C.
LiNH ₂ + ₂ LiH → Li ₂ NH + LiH + H ₂ ↑… (2)
Li ₂ NH + LiH → Li ₃ N + H ₂ ↑… (3)

However, the lithium nitride represented by the above formula (1) also has a problem that the hydrogen release rate is slow and a problem that the hydrogen release start temperature is high.
Further, NH ₃ generated by decomposition of LiNH ₂ in these reaction systems is included in the generated hydrogen, and when this NH ₃ is introduced into the fuel cell, there is a problem that the fuel cell is poisoned. .
JP 59-47599 R & D News Kansai 2002. 7, p38-40 Ping Chen et al, Interaction of hydrogen with metalnitrides and imides, NATURE Vol. 420, 21 NOVEMBER 2002, p302 ~ 304

  The present invention has been made in view of such circumstances, and provides a gas purifier capable of supplying high-purity hydrogen or the like that extends the life of a fuel cell and a hydrogen storage material.

Alkali metal hydride and / or alkaline earth in a flow path of hydrogen gas containing ammonia and / or water or a mixed gas composed of one or more selected from these and an inert gas of He, Ne, Ar, N ₂ a gas-body purification system installed a filter layer made of a metal hydride, hydrogen gas containing the ammonia and / or water is generated occluded or from which the storage material composed of a metal hydride and a metal amide A gas refining device (Claim 1) is provided, which is installed in a device that generates the hydrogen gas .

Also, hydrogen gas containing ammonia and / or water or these and He, Ne, Ar, N ₂ A gas purification apparatus in which a filter layer made of an alkali metal hydride and / or an alkaline earth metal hydride is installed in a flow path of a mixed gas consisting of one or more selected from the inert gas of / Or hydrogen gas containing water is a hydrogen storage material precursor having a metal imide compound that changes into a hydrogen storage material containing metal hydride and metal amide simultaneously by reacting with hydrogen, the metal imide compound, Occluded in or generated from a storage material obtained by storing hydrogen in a material synthesized without undergoing a reaction between the metal hydride and the metal amide, and installed in an apparatus for generating the hydrogen gas. A gas purifier (claim 2) is provided.

Also, hydrogen gas containing ammonia and / or water or these and He, Ne, Ar, N ₂ A gas purification apparatus in which a filter layer made of an alkali metal hydride and / or an alkaline earth metal hydride is installed in a flow path of a mixed gas consisting of one or more selected from the inert gas of Metal imide compound produced by thermal decomposition of metal amide compound, which is a hydrogen storage material precursor that reversibly changes to hydrogen storage material that can release hydrogen by reacting with hydrogen. A gas refining device (Claim 3) is provided, which is stored in or generated from a storage material obtained by storing hydrogen in the device and is installed in a device for generating the hydrogen gas. .

Furthermore, B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Nb, Mg, K as a catalytic functional substance to the alkali metal hydride and / or alkaline earth metal hydride. One or more metals selected from Ir, Nd, La, Ca, V, Ti, Cr, Cu, Zn, A1, Si, Ru, Mo, W, Ta, Zr, Hf, Ag, A gas purifier (Claim 4) according to any one of claims 1 to 3, wherein a compound or an alloy thereof is added. Furthermore, the said alkali metal hydride and / or alkaline-earth metal hydride are lithium hydride, magnesium hydride, or calcium hydride, The gas refiner | purifier of Claims 1 thru | or 4 (claim) Item 5) is provided.

In addition, the filter layer is a gas purification device that is installed in a state where it can be replaced at a predetermined cycle (Claim 6), and the filter layer is mounted on a cylindrical column with 3 millimeters. A gas refining device (Claim 7) filled with the following granular lithium hydride, calcium hydride, magnesium hydride and the like. Furthermore, the filter layer is supported by immersing, mixing or adhering lithium hydride, calcium hydride , or magnesium hydride to one or more selected from molecular sieves, activated alumina, or sepiolite clay mineral. A gas purifier (claim 8) is provided.

Alkali metal hydride and / or alkaline earth metal hydrogen in the flow path of hydrogen gas containing ammonia and / or water, and a mixed gas composed of one or more of inert gases such as He, Ne, Ar, and N ₂ When a filter layer made of a fluoride, for example, lithium hydride is installed, moisture is removed by the reaction LiH + H ₂ O = LiOH + H ₂ , and the generated hydroxide is LiH + LiOH = Li ₂ by the reaction of O + H _2, it is thought to cause the hydrogen. Since this reaction proceeds at a high reaction rate with a very small amount of water, it has been found that this reaction is suitable for removing a small amount of water as an impurity. Further, He, Ne, Ar, N _{2 and the} like are inactive with lithium hydride and have an advantage of selectively removing moisture and not causing other impurity components. In this way, there is an effect of preventing moisture from flowing into the fuel cell and preventing poisoning of the fuel cell.

When ammonia as an impurity passes through the filter layer in the generation path, it reacts with lithium hydride attached to and supported on the filter to become lithium amide (LiNH ₂ ) and hydrogen. Here, the ammonia is removed to prevent inflow into the fuel cell and to prevent poisoning by the ammonia in the fuel cell. Since the reaction proceeds sufficiently even at a room temperature of about 20 ° C., it can be sufficiently accelerated by, for example, residual heat of a hydrogen generator connected to the present apparatus. The reacted lithium amide (LiNH ₂ ) remains in the filter layer in the form of replacing lithium hydrogen, and can be prevented from being discharged out of the filter. In the above examples, similar effects are recognized in other alkali metal hydrides or alkaline earth metal hydrides. For example, this effect can be realized with calcium hydride or magnesium hydride.

Furthermore, alkali metal hydride and / or alkaline earth metal hydride, B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Nb, Mg, K, One or more metals selected from Ir, Nd, La, Ca, V, Ti, Cr, Cu, Zn, A1, Si, Ru, Mo, W, Ta, Zr, Hf, Ag, or compounds thereof Alternatively, an alloy thereof is added, or alkali metal hydride and / or alkaline earth metal hydride is refined by predetermined mechanical pulverization, and when these metals, metal compounds, and alloys are added, alkali metal hydride and / or Ammonia absorption of the alkaline earth metal hydride can be further promoted to prevent poisoning of the fuel cell. Examples of these metal compounds include halides such as chlorinated compounds, oxides, nitrides, and other compounds. The supported amount of the catalyst functional substance is preferably 0.1% by mass or more and 20% by mass or less of the alkali metal hydride and / or alkaline earth metal hydride.

Lithium hydrogen or the like is desirably formed into a filter layer in the form of granular lithium hydride having a diameter of 3 millimeters or attached to a carrier. If the diameter is 3 millimeters or more, the contact area with the gas is not sufficient. The packing rate with respect to the column refers to a volume that occupies the column volume, including, for example, an excluded volume of a granular solid such as lithium hydrogen. If this is 60% or less, sufficient purification cannot be realized when the gas flow rate is large, but if the gas flow rate is small, a sufficient effect can be obtained even with a filling rate of less than this.

As the carrier for lithium hydride and the like, a halloysite clay mineral (attapulgite, sepiolite) is particularly preferable among molecular sieves, activated carbon, activated alumina, silica gel, clay minerals having a large surface area, and clay minerals. This is to promote the reaction with water and ammonia. These carriers themselves have water and ammonia adsorption performance, and can be used particularly preferably. At this time, lithium hydrogen or the like may be mixed with the granular lithium hydride as it is, but a method of supporting powdered lithium hydride on these carriers can also be suitably used. For example, it can be prepared by immersing lithium hydride or the like in an aqueous solution in a carrier and drying it.

Further, lithium amide or the like generated by removing ammonia may generate ammonia by a reaction of 2LiNH ₂ → Li ₂ NH + NH _{3 or} the like. In order to prevent these, it is desirable to keep the temperature of the filter layer at 70 ° C. or lower. In addition, when lithium hydride is converted to lithium amide, the reaction with ammonia is unlikely to occur. Therefore, it is desirable that this filter layer be converted to a material in which new lithium hydride is attached and supported as appropriate. For this purpose, the filter layer is installed in the flow path in a state where it can be replaced at a predetermined cycle. For example, it can be installed by forming the filter layer installation part by a rotating type such as a revolver or an attaching / detaching method for inserting and removing. Lithium oxide is a stable substance, and other gases will not be released if the filter layer is kept at 70 ° C or lower.

Even in a hydrogen storage material composed of a metal hydride and a metal amide, ammonia produced by decomposition of the metal amide or the like has a problem of poisoning the battery when introduced into the fuel cell as it is. Further, the metal amide produced from the hydrogen storage material precursor described below has not yet solved this problem. Therefore, the installation of the above filter layer is an extremely effective means for obtaining high purity hydrogen.

Examples of hydrogen storage materials that can generate ammonia include the following. This is a case where the hydrogen storage material is composed of a metal hydride and a metal amide and generates hydrogen by these reactions. Furthermore, it is a hydrogen storage material precursor that reversibly changes to a hydrogen storage material that can release hydrogen by reacting with hydrogen, and stores hydrogen in a metal imide compound produced by thermal decomposition of a metal amide compound. It is an example of a hydrogen storage material. In this hydrogen storage material precursor, the metal imide compound has been found to contain one or more of Li ₂ NH, Na ₂ NH, MgNH, and CaNH, particularly those containing Li ₂ NH. ing. Moreover, it is preferable that the metal imide compound carries a predetermined catalytic function substance, and thus it has been found that the reaction rate of the chemical change with the hydrogen storage material can be increased. Such catalytic functional materials include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Nb, Mg, K, Ir, Nd, La, Ca, V, Ti, Cr One, two or more metals selected from Cu, Zn, A1, Si, Ru, Mo, W, Ta, Zr, Hf, Ag, a compound thereof, an alloy thereof, or a hydrogen storage alloy is preferably used. . It has been found that the amount of the catalyst functional material supported is preferably 0.1% by mass or more and 20% by mass or less of the metal imide compound.

  In the production of such a hydrogen storage material precursor, the metal amide compound is preferably composed mainly of lithium amide, and the metal imide compound preferably carries a predetermined catalytic function substance. It has been found that the loading amount of the catalytic functional material is as described above.

  In this way, hydrogen storage materials consisting of the obtained hydrogen storage precursor and hydrogen, or other hydrogen storage materials, including those that may generate ammonia, hydrogen compression storage or liquid hydrogenation with a general high-pressure cylinder In the cold storage, water is mixed in during the processing and handling, and the remaining water can be finally led to the fuel cell and poisoned. When the filter layer is incorporated in a gas purifier installed in a hydrogen generator applied to a stationary fuel cell hydrogen generator or a fuel cell vehicle hydrogen generator, the hydrogen generator and the gas purifier are integrated. As a result, the performance of the refiner is further improved.

  According to the gas purification apparatus of the present invention, ammonia and / or water that poisons the fuel cell can be removed from these gases that are preferably used in a fuel cell or the like with high efficiency to the PPM order. .

Hereinafter, an embodiment of the present invention will be described by taking as an example the case of lithium imide (Li ₂ NH) as a hydrogen storage material precursor that may generate ammonia.
As shown in the following formula (4), lithium imide as a hydrogen storage material precursor reacts with hydrogen to form a composite of lithium amide (LiNH ₂ ), which is a hydrogen storage material, and lithium hydride (LiH). Change to body. The lithium amide / lithium hydride composite thus obtained releases hydrogen (H ₂ ) by heating to a predetermined temperature, and changes to lithium imide. That is, the chemical reaction represented by the following formula (4) is a so-called reversible disproportionation reaction in which the reaction proceeds reversibly between different substances, and such a reaction cycle is repeated.
LiNH ₂ + LiH = Li ₂ NH + H ₂ … (4)

According to the above formula (4), lithium imide can be synthesized by a method in which lithium amide and lithium hydride are mixed and heated to a predetermined temperature. However, in the method of mixing solid materials, there is a limit to the fine composite of lithium amide and lithium hydride, and there is a problem that it takes a long time for pulverization and mixing. Therefore, the inventors have found a method for synthesizing lithium imide without undergoing a reaction between lithium amide and lithium hydride.

A specific method for producing such a lithium imide is a method of thermally decomposing lithium amide as represented by the following formula (5).
2LiNH ₂ → Li ₂ NH + NH ₃ … (5)

Lithium imide synthesized by such a method is excellent in composition and structure uniformity, so that lithium amide and lithium hydride are uniformly and finely compounded by reacting such lithium imide with hydrogen. A hydrogen storage material can be obtained.

The lithium imide synthesized as described above is preferably loaded with a catalytic functional substance that promotes hydrogen storage / release. As this catalytic functional material, B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Nb, Mg, K, Ir, Nd, La, Ca, V, Ti, Cr, Cu One, two or more metals selected from Zn, Al, Si, Ru, Mo, W, Ta, Zr, Hf, and Ag, a compound thereof, an alloy thereof, or a hydrogen storage alloy. Examples of these metal compounds include halides such as chlorinated compounds, oxides, nitrides, and other compounds.

As a method for supporting a catalytic functional substance on lithium imide, a method in which a catalytic functional substance is added to the synthesis atmosphere of lithium imide, or the synthesized lithium imide is exposed to a reagent atmosphere (liquid or vapor) of the catalytic functional substance. Examples thereof include a method of adsorbing a catalytic functional substance on the surface, a method of adding catalyst fine powder to the synthesized lithium imide and mixing them. The supported amount of such a catalyst functional substance is preferably 0.1% by mass or more and 20% by mass or less of lithium imide. The effect is not exhibited when the supported amount of the catalytic functional material is 0.1% by mass or less, and when it exceeds 20% by mass, the reaction between the reactants such as lithium imide is inhibited, and the hydrogen release rate per mass Will be diminished.

A hydrogen storage material obtained by storing hydrogen in lithium imide is converted into a metal amide and a metal hydride. In this exemplified hydrogen storage material, the metal amide generates ammonia as a side reaction, and when the ammonia from the hydrogen storage material is introduced into the fuel cell as it is, the fuel cell is poisoned, and Reduce lifespan. In addition, moisture stored in the storage material or generated from the storage material may be introduced into the fuel cell and poisoned. Furthermore, occlusion and release ability of the occlusion material may be reduced by occlusion of moisture in the occlusion material. Therefore, the gas purifier according to the present invention is installed at the end portion or the like in the hydrogen flow path in the hydrogen storage device. Specifically, a column having a diameter of 0.6 cm and a length of 300 cm was installed, and a filter layer was formed therein. In the filter layer, lithium hydride was prepared to a particle size of 30 mesh diameter, mixed with molecular sieves and supported. The column forming the filter layer was kept at room temperature, 20 ° C. This is to suppress the reversible reaction. Also, when lithium hydride becomes lithium imide, reaction with ammonia is unlikely to occur, so this filter layer is a revolver rotating column that is automatically replaced after 180 minutes on a new lithium hydride attached and supported as appropriate. Was installed. Even if the lithium hydride is replaced with calcium hydride or magnesium hydride, good results can be obtained.

Next, the embodiment of the present invention will be described more specifically.
Lithium amide (purity 95%), lithium hydride (purity 95%), titanium trichloride (TiC1 ₃ ), chromium trichloride (CrC1 ₃ ) (all of these are made by Sigma-Aldrich) It was. Here, titanium trichloride and chromium trichloride are catalytic functional substances. Molecular sieves are manufactured by Wako Pure Chemical Industries, activated alumina is manufactured by Sumitomo Chemical, sepiolite is Turkish sepiolite, and Taiheiyo Cement. The column is made of stainless steel GL Sciences.

Production of precursors that serve as storage materials for generators;
Lithium imide was produced by heat-treating the starting lithium amide at 450 ° C. in vacuum. The lithium imide was pulverized using a planetary ball mill (Fritsch, P-5 type) to prepare a sample of Example 1. In this grinding process, 1 g of lithium imide powder and a predetermined amount of high-chromium steel balls were placed in a high-chromium steel mill container (volume: 250 m1), the inside of the mill container was evacuated, and then argon gas was introduced into the mill container. (Grade: α2) 1. It introduced so that it might become OMPa, and it carried out for 15 minutes at 250 rpm under room temperature 20 degreeC. The sample of Example 2 has a composition in which lithium imide and titanium trichloride are blended at a mass ratio of 100: 5, and Example 3 has a mass ratio of lithium imide, titanium trichloride, and chromium trichloride of 100. : 4: 1 composition. The samples of Examples 2 and 3 were also prepared by pulverization and mixing treatment using a planetary ball mill apparatus as in Example 1. The sample after the pulverization and mixing treatment is taken out in a glove box with an argon gas (Ar; purity 99.995%) atmosphere in order to minimize the effects of oxidation and moisture adsorption. It was transferred to a reaction vessel for hydrogen release experiments in the atmosphere. The production conditions for Examples 1 to 3 are shown in Table 1.

Occlusion of hydrogen into the occlusion material of the generator;
After evacuating the inside of the reaction vessel, the inside of the reaction vessel was set to a hydrogen atmosphere of 3 MPa, and this reaction vessel was held at 180 ° C. for 8 hours, whereby hydrogen storage treatment of Examples 1 to 3, that is, lithium amide and lithium hydride Conversion to a hydrogen storage material consisting of Thereafter, the inside of the reaction vessel was evacuated.

Separately from the hydrogen storage material described above, a hydrogen mixed gas containing 10 vol% hydrogen, 1 vol% ammonia, 1 vol% moisture, and 88 vol% Ar was adjusted in a cylinder at a filling pressure of 2 atm to obtain a hydrogen generator. (Example 4)
In addition, a hydrogen generator in which Ar was replaced with He, Ne, and N ₂ having the same volume in the above apparatus was installed. (Examples 5 to 7)

Installation of filter layers and manufacture of refiners;
The filter was formed in a column having a diameter of 6 mm and a length of 300 cm as follows. 12 ml of lithium hydride prepared to a particle size of 30 mesh was mixed with 5 ml of molecular sieves of 30 mesh and supported. Since the column on which the filter was formed was kept at about 20 ° C. at room temperature, it was not necessary to perform a control by energization. The reversible reaction was suppressed. Further, in order to maintain the water removal performance, when lithium hydride becomes lithium imide, reaction with ammonia is difficult to occur. Therefore, this filter layer is appropriately attached to a material to which new lithium hydride is attached and supported for 180 minutes. A rotating column of revolver to be replaced automatically later was installed.

The gas purifying apparatus according to the present invention is installed in the hydrogen generator (Examples 1 to 7), and hydrogen gas containing ammonia and / or water, and inert to He, Ne, Ar, and N ₂ A mixed gas composed of one or more kinds of gases was supplied, and the performance experiment was conducted. A purifier was installed at the discharge port portion which is the end of the path of each hydrogen generator.

In addition, as a comparative example, in the hydrogen generator corresponding to Examples 1 to 7, those without the purifier of the present invention are set as Comparative Examples 1 to 7, and the amount of hydrogen, the amount of ammonia, and the amount of water are the same as in Examples. It was measured.

Measurement of hydrogen release, residual ammonia and residual moisture;
Samples of hydrogen storage materials prepared from Examples 1 to 3 were sealed, respectively, and the evacuated reaction vessel was heated in an electric furnace from room temperature to 250 ° C. at a heating rate of 5 ° C./minute, and then at 250 ° C. for 90 minutes. Retained. During holding at 250 ° C., the gas pressure was adjusted using a buffer container so that the gas pressure released from the reaction container was 20 kPa or less. The gas released at each temperature and 250 ° C is stored in a gas collection cylinder, the collected gas is cooled to 20 ° C, and the pressure of the released gas is measured with a pressure gauge. Detector, column: Molecular Sieve 5A) was introduced, and the amount of hydrogen was measured. The amount of hydrogen released was determined by dividing the amount of hydrogen thus measured by the mass of the sample before heating. The residual ammonia amount was measured by FIA (flow injection analysis) method. The residual water content was measured with a Karl Fischer trace moisture meter.

Table 2 shows the measured ammonia content in the generated hydrogen generated in Examples 1 to 7 and Comparative Examples 1 to 7. Regarding the water content, the detection limit of the Karl Fischer method was about 5 ppm, and in (Examples 1 to 7, Comparative Examples 1 to 3), it was below the detection limit (5 ppm). In Comparative Examples 4 to 7, it was 5000 ppm.
In both examples, it was found that the amount of ammonia and the amount of water were remarkably reduced to the PPM order with respect to those corresponding to the comparative examples.

    Further, in the above refiner, instead of the molecular sieves, the active alumina of the same mesh and the sepiolite clay mineral of the same mesh were used. As a result, in the active alumina carrier, the residual ammonia amount was 50 ppm, It was found that the amount of residual ammonia was about 1 ppm or less. (Example 8)

Furthermore, in the above purifier, when titanium trichloride powder was mixed with lithium hydride in an amount equivalent to 3% of the weight of lithium hydride, this was packed in a column, and the amount of residual ammonia and the amount of water were measured. Each could be kept below the detection limit. (Example 9)

   The purifier of the present invention is suitable for purifying occluded / generated hydrogen of a hydrogen generator used in a fuel cell that generates power using hydrogen and oxygen as fuel.

1 is a schematic overall view of a gas purification device and a hydrogen storage generator according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Hydrogen storage generator 11; Hydrogen storage material 2; Gas refiner
21; Filter section
211; Molecular sieves 212; Lithium hydride granules
22; scattering prevention member
23; Revolver 3; Gas outlet 4; Gas inlet

Claims (8)

Alkali metal hydride and / or alkaline earth in a flow path of hydrogen gas containing ammonia and / or water or a mixed gas composed of one or more selected from these and an inert gas of He, Ne, Ar, N ₂ A gas purification device provided with a filter layer made of metal hydride,
The hydrogen gas containing ammonia and / or water,
Occluded in or generated from a storage material composed of metal hydride and metal amide,
Pneumatic fluid purifier you characterized in that it is installed in the device for generating the hydrogen gas. Alkali metal hydride and / or alkaline earth in a flow path of hydrogen gas containing ammonia and / or water or a mixed gas composed of one or more selected from these and an inert gas of He, Ne, Ar, N ₂ A gas purification device provided with a filter layer made of metal hydride,
The hydrogen gas containing ammonia and / or water,
A hydrogen storage material precursor having a metal imide compound that changes into a hydrogen storage material that simultaneously contains a metal hydride and a metal amide by reacting with hydrogen, wherein the metal imide compound includes the metal hydride, the metal amide, Occluded in or generated from a storage material obtained by storing hydrogen in the synthesized without undergoing the reaction of
Pneumatic fluid purifier you characterized in that it is installed in the device for generating the hydrogen gas. Alkali metal hydride and / or alkaline earth in a flow path of hydrogen gas containing ammonia and / or water or a mixed gas composed of one or more selected from these and an inert gas of He, Ne, Ar, N ₂ A gas purification device provided with a filter layer made of metal hydride,
Hydrogen gas including the ammonia and / or water,
A hydrogen storage material precursor that reversibly changes to a hydrogen storage material capable of releasing hydrogen by reacting with hydrogen, and a storage material obtained by storing hydrogen in a metal imide compound produced by thermal decomposition of a metal amide compound Occluded or generated in the future,
Pneumatic fluid purifier you characterized in that it is installed in the device for generating the hydrogen gas. In the alkali metal hydride and / or alkaline earth metal hydride, B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Nb, Mg, K, Ir , Nd, La, Ca, V, Ti, Cr, Cu, Zn, A1, Si, Ru, Mo, W, Ta, Zr, Hf, Ag, one or more metals, compounds thereof or 4. The gas purifier according to claim 1, wherein the alloy is added. The gas purifier according to any one of claims 1 to 4, wherein the alkali metal hydride and / or alkaline earth metal hydride is lithium hydride, magnesium hydride or calcium hydride. The gas purifier according to any one of claims 1 to 3 , wherein the filter layer is installed in a state where it can be replaced at a predetermined cycle. The gas purification apparatus according to any one of claims 1 to 3 , wherein the filter layer is a cylindrical column packed with granular lithium hydride, calcium hydride, magnesium hydride or the like of 3 mm or less. The filter layer is supported by immersing, mixing or adhering lithium hydride, calcium hydride , or magnesium hydride to one or more selected from molecular sieves, activated alumina, or sepiolite clay mineral. The gas purifier according to any one of claims 1 to 3, wherein

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