US20030173229A1 - Process for producing hydrogen - Google Patents

Process for producing hydrogen Download PDF

Info

Publication number
US20030173229A1
US20030173229A1 US10/345,397 US34539703A US2003173229A1 US 20030173229 A1 US20030173229 A1 US 20030173229A1 US 34539703 A US34539703 A US 34539703A US 2003173229 A1 US2003173229 A1 US 2003173229A1
Authority
US
United States
Prior art keywords
particulates
alloy
catalyst metal
hydrogen
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/345,397
Inventor
Izuru Kanoya
Mitsuya Hosoe
Takanori Suzuki
Takeaki Isobe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honda Motor Co Ltd
Original Assignee
Honda Motor Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Honda Motor Co Ltd filed Critical Honda Motor Co Ltd
Assigned to HONDA GIKEN KOGYO KABUSHIKI KAISHA reassignment HONDA GIKEN KOGYO KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SUZUKI, TAKANORI, HOSOE, MITSUYA, ISOBE, TAKEAKI, KANOYA, IZURU
Publication of US20030173229A1 publication Critical patent/US20030173229A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a process for producing hydrogen, and particularly to a process for producing hydrogen by the reaction of an Mg alloy powder with water.
  • the conventional process has the following problems: NaBO 2 is produced by the reaction between NaBH 4 and water, and a strong alkali aqueous solution remains as a waste liquid, such that additional labor and high costs become necessary for disposal of the waste liquid.
  • a noble metal such as Pt, Pd and the like is used as a component of the catalyst, resulting in an increased hydrogen production cost.
  • the Mg alloy powder is a powder produced by hydrogenating an aggregate of Mg alloy particles each having an Mg particle and a plurality of catalyst metal particulates existing on a surface of the Mg particle and within the Mg particle, the catalyst metal particulates being at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates.
  • the Mg alloy powder having the above-described structure absorbs a relatively large amount of hydrogen with a hydrogenation-promoting function provided by the catalyst metal particulates in the hydrogenating treatment.
  • the catalyst metal particulates function to form cathode portions having a low hydrogenating voltage in the Mg particles to quickly convert Mg into hydroxide [Mg(OH) 2 ].
  • Mg(OH) 2 hydroxide
  • the hydrolysis of MgH 2 is promoted and hence, hydrogen can be produced quickly and in a large amount.
  • the waste liquid is an aqueous solution of Mg(OH) 2 and hence, is easily treated.
  • the above-described catalyst metal particulates are inexpensive, as compared with a noble metal catalyst, and hence a reduction in the hydrogen production cost can be achieved.
  • the Mg alloy powder is an aggregate of Mg alloy particles each having an Mg particle and a plurality of catalyst metal particulates existing on a surface of the Mg particle and within the Mg particle, the catalyst metal particles being at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates.
  • Hydrogen is produced by the reaction of a powder of pure Mg with water.
  • the period of hydrogen production is extremely short, and the amount of produced hydrogen is small.
  • the Mg alloy powder having the above-described structure continuously reacts with water by the above-described function of the catalyst metal particulates, and hence the period of hydrogen production can be extended to increase the amount of produced hydrogen.
  • FIG. 1 is a diagram illustrating an Mg alloy particle in accordance with embodiments of this invention.
  • FIG. 2 is a graph showing the relationship between the time and the temperature of an Mg alloy powder under H 2 absorbing
  • FIG. 3 is a graph showing the relationship between the time and the amount of hydrogen absorbed
  • FIG. 4 is a graph showing the relationship between the time and the amount of produced hydrogen.
  • FIG. 5 is a graph showing the relationship between the time and the amount of hydrogen produced.
  • the Mg alloy powder which is used is a powder made by hydrogenating an aggregate of Mg alloy particles 3 each comprising a Mg particle 1 and a plurality of catalyst metal particulates 2 existing on a surface of the Mg particle 1 and within the Mg particle 1 , as shown in FIG. 1.
  • the catalyst metal particulates 2 correspond to at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates.
  • the content G of the catalyst metal particulates 2 in the Mg alloy powder is set in a range of 0.1% by atom ⁇ G ⁇ 5.0% by atom. If the content G is lower than 0.1% by atom, no effect is provided by addition of the catalyst metal particulates 2 . On the other hand, if G>5.0% by atom, the amount of produced hydrogen is reduced and hence, a content higher than 5.0% by atom is not of practical use.
  • the content G of the catalyst particulates 2 is preferably in a range of 0.3% by atom ⁇ G ⁇ 1.0% by atom.
  • the Mg alloy powder is produced under application of a mechanical alloying, and hence an appropriate particle size D of the Mg particle 1 is in a range of 1 ⁇ m ⁇ D ⁇ 500 nm, and an appropriate particle size d of the catalyst metal particulates 2 is in a range of 10 nm ⁇ d ⁇ 500 2 nm.
  • each of the particle sizes D and d is defined as a length of the largest portion of the Mg particle or the like in a microphotograph (a largest diameter).
  • the following aggregates were prepared: an aggregate of Mg particles having a purity of 99.9% and a particle size D 0 equal to or smaller than 180 ⁇ m; an aggregate of Ni particulates having a particle size d in a range of 10 nm ⁇ d ⁇ 100 nm; and an aggregate of Fe particulates having a purity of 99.9% and a particle size d in a range of 10 nm ⁇ d ⁇ 200 nm. These aggregates were weighed and mixed together to produce a mixed powder having an alloy composition represented by Mg 95 Ni 3.33 Fe 1.67 (each of the numerical values represents % by atom).
  • the mixed powder was placed in a pot (made under JIS SUS316) having a volume of 2,500 ml in a horizontal ball mill (made by Honda) along with 990 balls having a diameter of 10 mm (made under JIS SUS316), and was subjected to ball milling with the interior of the pot maintained in a hydrogen gas atmosphere of 2 MPa and under conditions of a pot rotational speed of 70 rpm and a milling time t of 15 minutes. In this case, an acceleration 3G three times the gravitational acceleration G p was generated in the pot. After completion of the ball milling, the produced Mg alloy powder was removed into the atmosphere. The Mg alloy powder was hydrogenated during the process of the ball milling, and hence was subjected to a dehydrogenating treatment by conducting an evacuation under conditions of 350° C. for one hour.
  • the Mg alloy powder was subjected to SEM and TEM observations, and as a result it found that the particle size was decreased by pulverization of the powder or increased by the agglomeration and aggregation and thus, the particle size D of the Mg particles 1 was in a range of 2 ⁇ m ⁇ D ⁇ 300 ⁇ m. The particle size of each of the Ni and Fe particulates 2 was not decreased. It was also found in the Mg alloy particles 3 constituting the Mg alloy powder that a plurality of the Ni and Fe particulates 2 in the form of black spots exist on the surface of the Mg particle I and within the Mg particle 1 .
  • the Mg alloy powder was placed in a vessel, and then the temperature of the Mg alloy powder was constantly maintained at 250° C. Thereafter, hydrogen was introduced into the vessel, and when the internal pressure in the vessel reached up to 1 MPa, the introduction of hydrogen was terminated, and the temperature of the Mg alloy powder was no longer maintained at 250° C. Thereafter, the temperature of the Mg alloy powder was measured to provide the results shown in FIG. 2. As shown in FIG. 2, it was found that the Mg alloy powder generated heat with the hydrogenation thereof, namely, the absorption of hydrogen thereinto and as a result, the temperature of the Mg alloy powder rose up to about 310° C. in about 40 seconds after termination of the introduction of hydrogen. Therefore, it is possible to cause the Mg alloy powder to absorb hydrogen under the application of a pressure (equal to or higher than 0.1 MPa), while maintaining the temperature of the Mg alloy powder at 310° C. or lower.
  • a pressure equal to or higher than 0.1 MPa
  • the Mg alloy powder was placed in a vessel. Then, the temperature of the Mg alloy powder was constantly maintained at 310° C., and hydrogen was introduced into the vessel while the internal pressure in the vessel was constantly maintained at 1 MPa. In this state, the amount of hydrogen absorbed by the Mg alloy powder was measured in terms of change in pressure in the vessel after every 20 seconds, thereby providing the results shown in FIG. 3. It was found from FIG. 3 that the amount of hydrogen absorbed by the Mg alloy powder reached about 6.4% by weight of the maximum amount of hydrogen absorbed after about 8 hours from the start of the hydrogenation.
  • a line b in FIG. 4 indicates a case where the same hydrogen producing process as that described above was carried out under the same conditions, except that a powder produced by subjecting a powder of pure Mg to a hydrogenating treatment was used. Comparison between the lines a and b reveals an operational effect of the catalyst metal particulates.
  • an aggregate of Mg alloy particles 3 each comprising an Mg particle 1 and a plurality of catalyst particulates 2 existing on a surface of the Mg particle 1 and within the Mg particle 1 is used.
  • the catalyst metal particulates 2 correspond to at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Co particulates, Zr particulates, Zr alloy particulates, Co alloy particulates, Cr particulates and Cr alloy particulates.
  • the required numerical values for the content G of the catalyst metal particulates 2 in the Mg alloy powder as well as the particle size D of the Mg particles 1 and the particle size d of the catalyst metal particulates 2 are the same as those in Embodiment I.
  • an aqueous solution of ions such as an aqueous solution of NaCl, an aqueous solution of CaCl 2 , an aqueous solution of MgCl 2 and the like may be used as the water in place of the distilled water.

Abstract

An Mg alloy powder is reacted with water to produce hydogen. The Mg alloy powder is produced by hydrogenating an aggregate of Mg alloy particles each having an Mg particle and a plurality of catalyst metal particulates existing on a surface of and within the Mg particle. The catalyst metal particulates are at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates. Thus, hydrogen can be produced quickly and in large amounts, and waste liquid is easily treated. Moreover, hydrogen production cost can be reduced using an inexpensive catalyst.

Description

    BACKGROUND OF THE INVENTION
  • 1. FIELD OF THE INVENTION [0001]
  • The present invention relates to a process for producing hydrogen, and particularly to a process for producing hydrogen by the reaction of an Mg alloy powder with water. [0002]
  • 2. DESCRIPTION OF THE RELATED ART [0003]
  • There is a conventional hydrogen producing process in which sodium borohydride (NaBH[0004] 4) and a catalyst are used, and water is added to them for reaction with NaBH4 (for example, see Japanese Patent Application Laid-open No.2001-199701).
  • However, the conventional process has the following problems: NaBO[0005] 2 is produced by the reaction between NaBH4 and water, and a strong alkali aqueous solution remains as a waste liquid, such that additional labor and high costs become necessary for disposal of the waste liquid. In addition, a noble metal such as Pt, Pd and the like is used as a component of the catalyst, resulting in an increased hydrogen production cost.
    • SUMMARY OF THE INVENTION
  • Accordingly, it is an object of the present invention to provide a hydrogen producing process, in which hydrogen can be produced quickly and in a large amount; the waste liquid can be easily treated; and the hydrogen production cost can be reduced by using an inexpensive catalyst. [0006]
  • To achieve the above object, according to the present invention, there is provided a process for producing hydrogen by the reaction of an Mg alloy powder with water, in which the Mg alloy powder is a powder produced by hydrogenating an aggregate of Mg alloy particles each having an Mg particle and a plurality of catalyst metal particulates existing on a surface of the Mg particle and within the Mg particle, the catalyst metal particulates being at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates. [0007]
  • The Mg alloy powder having the above-described structure absorbs a relatively large amount of hydrogen with a hydrogenation-promoting function provided by the catalyst metal particulates in the hydrogenating treatment. [0008]
  • On the other hand, the catalyst metal particulates function to form cathode portions having a low hydrogenating voltage in the Mg particles to quickly convert Mg into hydroxide [Mg(OH)[0009] 2]. Thus, the hydrolysis of MgH2 is promoted and hence, hydrogen can be produced quickly and in a large amount. Furthermore, the waste liquid is an aqueous solution of Mg(OH)2 and hence, is easily treated.
  • Moreover, the above-described catalyst metal particulates are inexpensive, as compared with a noble metal catalyst, and hence a reduction in the hydrogen production cost can be achieved. [0010]
  • According to the present invention, there is also provided a process for producing hydrogen by the reaction of an Mg alloy powder with water, in which the Mg alloy powder is an aggregate of Mg alloy particles each having an Mg particle and a plurality of catalyst metal particulates existing on a surface of the Mg particle and within the Mg particle, the catalyst metal particles being at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates. [0011]
  • Hydrogen is produced by the reaction of a powder of pure Mg with water. However, the period of hydrogen production is extremely short, and the amount of produced hydrogen is small. The Mg alloy powder having the above-described structure continuously reacts with water by the above-described function of the catalyst metal particulates, and hence the period of hydrogen production can be extended to increase the amount of produced hydrogen.[0012]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The above and other objects, features and advantages of the invention will become apparent from the following description of the preferred embodiment taken in conjunction with the accompanying drawings, in which: [0013]
  • FIG. 1 is a diagram illustrating an Mg alloy particle in accordance with embodiments of this invention; [0014]
  • FIG. 2 is a graph showing the relationship between the time and the temperature of an Mg alloy powder under H[0015] 2 absorbing;
  • FIG. 3 is a graph showing the relationship between the time and the amount of hydrogen absorbed; [0016]
  • FIG.[0017] 4 is a graph showing the relationship between the time and the amount of produced hydrogen; and
  • FIG. 5 is a graph showing the relationship between the time and the amount of hydrogen produced.[0018]
    • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • (Embodiment I) To produce hydrogen, a process for producing hydrogen by the reaction of an Mg alloy power with water is employed. The Mg alloy powder which is used is a powder made by hydrogenating an aggregate of [0019] Mg alloy particles 3 each comprising a Mg particle 1 and a plurality of catalyst metal particulates 2 existing on a surface of the Mg particle 1 and within the Mg particle 1, as shown in FIG. 1. The catalyst metal particulates 2 correspond to at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates.
  • The content G of the [0020] catalyst metal particulates 2 in the Mg alloy powder is set in a range of 0.1% by atom≦G≦5.0% by atom. If the content G is lower than 0.1% by atom, no effect is provided by addition of the catalyst metal particulates 2. On the other hand, if G>5.0% by atom, the amount of produced hydrogen is reduced and hence, a content higher than 5.0% by atom is not of practical use. The content G of the catalyst particulates 2 is preferably in a range of 0.3% by atom≦G≦1.0% by atom. The Mg alloy powder is produced under application of a mechanical alloying, and hence an appropriate particle size D of the Mg particle 1 is in a range of 1 μm≦D≦500 nm, and an appropriate particle size d of the catalyst metal particulates 2 is in a range of 10 nm≦d≦500 2nm. In this case, each of the particle sizes D and d is defined as a length of the largest portion of the Mg particle or the like in a microphotograph (a largest diameter).
  • Specific examples will be described below. [0021]
  • (A) Production of Mg Alloy Powder [0022]
  • The following aggregates were prepared: an aggregate of Mg particles having a purity of 99.9% and a particle size D[0023] 0 equal to or smaller than 180 μm; an aggregate of Ni particulates having a particle size d in a range of 10 nm≦d≦100 nm; and an aggregate of Fe particulates having a purity of 99.9% and a particle size d in a range of 10 nm≦d≦200 nm. These aggregates were weighed and mixed together to produce a mixed powder having an alloy composition represented by Mg95Ni3.33Fe1.67 (each of the numerical values represents % by atom).
  • The mixed powder was placed in a pot (made under JIS SUS316) having a volume of 2,500 ml in a horizontal ball mill (made by Honda) along with 990 balls having a diameter of 10 mm (made under JIS SUS316), and was subjected to ball milling with the interior of the pot maintained in a hydrogen gas atmosphere of 2 MPa and under conditions of a pot rotational speed of 70 rpm and a milling time t of 15 minutes. In this case, an acceleration 3G three times the gravitational acceleration G[0024] p was generated in the pot. After completion of the ball milling, the produced Mg alloy powder was removed into the atmosphere. The Mg alloy powder was hydrogenated during the process of the ball milling, and hence was subjected to a dehydrogenating treatment by conducting an evacuation under conditions of 350° C. for one hour.
  • The Mg alloy powder was subjected to SEM and TEM observations, and as a result it found that the particle size was decreased by pulverization of the powder or increased by the agglomeration and aggregation and thus, the particle size D of the [0025] Mg particles 1 was in a range of 2 μm≦D≦300 μm. The particle size of each of the Ni and Fe particulates 2 was not decreased. It was also found in the Mg alloy particles 3 constituting the Mg alloy powder that a plurality of the Ni and Fe particulates 2 in the form of black spots exist on the surface of the Mg particle I and within the Mg particle 1.
  • (B) Hydrogenation of Mg Alloy Powder and Change in Temperature of the Powder [0026]
  • The Mg alloy powder was placed in a vessel, and then the temperature of the Mg alloy powder was constantly maintained at 250° C. Thereafter, hydrogen was introduced into the vessel, and when the internal pressure in the vessel reached up to 1 MPa, the introduction of hydrogen was terminated, and the temperature of the Mg alloy powder was no longer maintained at 250° C. Thereafter, the temperature of the Mg alloy powder was measured to provide the results shown in FIG. 2. As shown in FIG. 2, it was found that the Mg alloy powder generated heat with the hydrogenation thereof, namely, the absorption of hydrogen thereinto and as a result, the temperature of the Mg alloy powder rose up to about 310° C. in about 40 seconds after termination of the introduction of hydrogen. Therefore, it is possible to cause the Mg alloy powder to absorb hydrogen under the application of a pressure (equal to or higher than 0.1 MPa), while maintaining the temperature of the Mg alloy powder at 310° C. or lower. [0027]
  • (C) Hydrogenation of Mg Alloy Powder [0028]
  • The Mg alloy powder was placed in a vessel. Then, the temperature of the Mg alloy powder was constantly maintained at 310° C., and hydrogen was introduced into the vessel while the internal pressure in the vessel was constantly maintained at 1 MPa. In this state, the amount of hydrogen absorbed by the Mg alloy powder was measured in terms of change in pressure in the vessel after every 20 seconds, thereby providing the results shown in FIG. 3. It was found from FIG. 3 that the amount of hydrogen absorbed by the Mg alloy powder reached about 6.4% by weight of the maximum amount of hydrogen absorbed after about 8 hours from the start of the hydrogenation. [0029]
  • (D) Releasing of Hydrogen from the Mg Alloy Powder [0030]
  • 0.1 gram of the Mg alloy powder resulting from the hydrogenating treatment was placed in a vessel kept at 85° C., and 5 cc of distilled water having a temperature of 85° C. was then poured into the vessel, to thereby generate a reaction represented by a reaction formula, MgH[0031] 2+2H2O→Mg(OH)2+2H2. The amount of hydrogen produced was measured to provide results shown by a line a in FIG. 4. In this case, the theoretical value of the amount of hydrogen produced is 152 cc, but an amount of hydrogen corresponding to 90% or more of the theoretical value was produced five minutes after the start of the reaction. Such rapid production of hydrogen is attributable to the presence of the Fe and Ni particulates which were the catalyst metal particulates. A line b in FIG. 4 indicates a case where the same hydrogen producing process as that described above was carried out under the same conditions, except that a powder produced by subjecting a powder of pure Mg to a hydrogenating treatment was used. Comparison between the lines a and b reveals an operational effect of the catalyst metal particulates.
  • (Embodiment II) To produce hydrogen by the reaction of an Mg alloy power with water, an aggregate of [0032] Mg alloy particles 3 each comprising an Mg particle 1 and a plurality of catalyst particulates 2 existing on a surface of the Mg particle 1 and within the Mg particle 1 is used. The catalyst metal particulates 2 correspond to at least one selected from Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Co particulates, Zr particulates, Zr alloy particulates, Co alloy particulates, Cr particulates and Cr alloy particulates.
  • In this case, the required numerical values for the content G of the [0033] catalyst metal particulates 2 in the Mg alloy powder as well as the particle size D of the Mg particles 1 and the particle size d of the catalyst metal particulates 2 are the same as those in Embodiment I.
  • For example, 104 mg of the Mg alloy powder in Embodiment I (Mg[0034] 95Ni3.33Fe1.67) but not subjected to a hydrogenating treatment was placed in a vessel kept at 85° C. Then, 5 cc of distilled water having a temperature of 85° C. was poured into the vessel, to thereby generate a reaction represented by a reaction formula, Mg+2H2O→Mg(OH)2+H2, and the amount of hydrogen produced was measured to provide results shown by a line a1, in FIG. 5. It was found from the line a1, in FIG. 5 that the production of hydrogen was continued, leading to an increase in amount of hydrogen produced. A line b1 in FIG. 5 corresponds to a case where the same hydrogen producing process as that described above was carried out under the same conditions, except that 80 mg of a pure Mg powder was used. The hydrogen production using the pure Mg powder was continued for about 1 minute after the start of the reaction, but thereafter the reaction advanced little, and hence the amount of hydrogen produced was small. It is clear from these results that an effect of promoting the production of hydrogen is provided by the catalyst metal particulates.
  • In each of Embodiments I and II, an aqueous solution of ions such as an aqueous solution of NaCl, an aqueous solution of CaCl[0035] 2, an aqueous solution of MgCl2 and the like may be used as the water in place of the distilled water.
  • Although embodiments of this invention have been described in detail, it will be understood that this invention is not limited to the above-described embodiments, and various modifications in construction may be made without departing from the spirit and scope of the invention in the following claims. [0036]

Claims (16)

What is claimed is:
1. A process for producing hydrogen, comprising reacting an Mg alloy powder with water, wherein said Mg alloy powder is a powder produced by hydrogenating an aggregate of Mg alloy particles each comprising an Mg particle and a plurality of catalyst metal particulates existing on a surface of said Mg particle and within said Mg particle, said catalyst metal particulates being at least one selected from the group consisting of Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates.
2. A process for producing hydrogen, comprising reacting an Mg alloy powder with water, wherein said Mg alloy powder is an aggregate of Mg alloy particles each comprising an Mg particle and a plurality of catalyst metal particulates existing on a surface of said Mg particle and within said Mg particle, said catalyst metal particulates being at least one selected from the group consisting of Ni particulates, Ni alloy particulates, Fe particulates, Fe alloy particulates, V particulates, V alloy particulates, Mn particulates, Mn alloy particulates, Ti particulates, Ti alloy particulates, Cu particulates, Cu alloy particulates, Ag particulates, Ag alloy particulates, Ca particulates, Ca alloy particulates, Zn particulates, Zn alloy particulates, Zr particulates, Zr alloy particulates, Co particulates, Co alloy particulates, Cr particulates and Cr alloy particulates.
3. The process for producing hydrogen of claim 1, wherein the content G of said catalyst metal particulates is in a range of 0.1% by atom≦G≦5.0% by atom.
4. The process for producing hydrogen of claim 2, wherein the content G of said catalyst metal particulates is in a range of 0.1% by atom≦G≦5.0% by atom.
5. The process for producing hydrogen of claim 1, wherein the content G of said catalyst metal particulates is in a range of 0.3% by atom≦G≦1.0% by atom.
6. The process for producing hydrogen of claim 2, wherein the content G of said catalyst metal particulates is in a range of 0.3% by atom≦G≦1.0% by atom.
7. The process for producing hydrogen of claim 3, wherein the content G of said catalyst metal particulates is in a range of 0.3% by atom≦G≦1.0% by atom.
8. The process for producing hydrogen of claim 4, wherein the content G of said catalyst metal particulates is in a range of 0.3% by atom≦G≦1.0% by atom.
9. The process for producing hydrogen of claim 1 wherein the particle size D of said Mg particles is in a range of 1 μm≦D≦500 μm, and the particle size d of said catalyst metal particulates is in a range of 10 nm≦d≦500 nm.
10. The process for producing hydrogen of claim 2 wherein the particle size D of said Mg particles is in a range of 1 μm≦D≦500 μm, and the particle size d of said catalyst metal particulates is in a range of 10 nm≦d≦500 nm.
11. The process for producing hydrogen of claim 3 wherein the particle size D of said Mg particles is in a range of 1 μm≦D≦500 μm, and the particle size d of said catalyst metal particulates is in a range of 10 nm≦d≦500 nm.
12. The process for producing hydrogen of claim 4 wherein the particle size D of said Mg particles is in a range of 1 μm≦D≦500 μm, and the particle size d of said catalyst metal particulates is in a range of 10 nm≦d≦500 nm.
13. The process for producing hydrogen of claim 5 wherein the particle size D of said Mg particles is in a range of 1 μm≦D≦500 μm, and the particle size d of said catalyst metal particulates is in a range of 10 nm≦d≦500 nm.
14. The process for producing hydrogen of claim 6 wherein the particle size D of said Mg particles is in a range of 1 μm≦D≦500 μm, and the particle size d of said catalyst metal particulates is in a range of 10 nm≦d≦500 nm.
15. The process for producing hydrogen of claim 7 wherein the particle size D of said Mg particles is in a range of 1 μm≦D≦500 μm, and the particle size d of said catalyst metal particulates is in a range of 10 nm≦d≦500 nm.
16. The process for producing hydrogen of claim 8 wherein the particle size D of said Mg particles is in a range of 1 μm≦D≦500 μm, and the particle size d of said catalyst metal particulates is in a range of 10 nm≦d≦500 nm.
US10/345,397 2002-01-18 2003-01-16 Process for producing hydrogen Abandoned US20030173229A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-10688 2002-01-18
JP2002010688A JP4187970B2 (en) 2002-01-18 2002-01-18 Hydrogen generation method

Publications (1)

Publication Number Publication Date
US20030173229A1 true US20030173229A1 (en) 2003-09-18

Family

ID=27648362

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/345,397 Abandoned US20030173229A1 (en) 2002-01-18 2003-01-16 Process for producing hydrogen

Country Status (2)

Country Link
US (1) US20030173229A1 (en)
JP (1) JP4187970B2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060210470A1 (en) * 2005-03-18 2006-09-21 Purdue Research Foundation System and method for generating hydrogen
EP1758815A1 (en) * 2004-04-09 2007-03-07 The University of British Columbia Compositions and methods for generating hydrogen from water
FR2892111A1 (en) * 2005-10-19 2007-04-20 Commissariat Energie Atomique Material for generating hydrogen gas by hydrolyzing tetrahydroborate powder of alkaline/alkaline-earth metals
EP2474501A1 (en) * 2011-01-07 2012-07-11 Jacques Julien Jean Dufour Energy production device and associated processes
CN115301239A (en) * 2022-07-21 2022-11-08 华北电力大学 Bimetal composite catalyst for hydrogen production by hydrolysis and preparation method thereof

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4036445B2 (en) * 2002-11-14 2008-01-23 本田技研工業株式会社 Supercritical water production method
US7393440B2 (en) 2005-05-09 2008-07-01 National Research Council Of Canada Hydrogen generation system
JP4083786B2 (en) * 2006-07-20 2008-04-30 友宏 秋山 Magnesium-based hydride manufacturing method and magnesium-based hydride manufacturing apparatus
US7998454B2 (en) 2007-05-10 2011-08-16 Bio Coke Lab. Co. Ltd. Method of producing magnesium-based hydrides and apparatus for producing magnesium-based hydrides
JP5405009B2 (en) 2007-09-06 2014-02-05 ホシザキ電機株式会社 Internal temperature controller for cooling storage
JP6447996B2 (en) * 2015-02-06 2019-01-09 国立研究開発法人物質・材料研究機構 Catalyst containing Ni-based intermetallic compound, method for producing the same, and method for producing hydrogen using the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5964965A (en) * 1995-02-02 1999-10-12 Hydro-Quebec Nanocrystalline Mg or Be-BASED materials and use thereof for the transportation and storage of hydrogen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5964965A (en) * 1995-02-02 1999-10-12 Hydro-Quebec Nanocrystalline Mg or Be-BASED materials and use thereof for the transportation and storage of hydrogen

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1758815A1 (en) * 2004-04-09 2007-03-07 The University of British Columbia Compositions and methods for generating hydrogen from water
EP1758815A4 (en) * 2004-04-09 2008-12-24 Univ British Columbia Compositions and methods for generating hydrogen from water
US20060210470A1 (en) * 2005-03-18 2006-09-21 Purdue Research Foundation System and method for generating hydrogen
WO2006102332A1 (en) * 2005-03-18 2006-09-28 Purdue Research Foundation Method for generating hydrogen
FR2892111A1 (en) * 2005-10-19 2007-04-20 Commissariat Energie Atomique Material for generating hydrogen gas by hydrolyzing tetrahydroborate powder of alkaline/alkaline-earth metals
EP2474501A1 (en) * 2011-01-07 2012-07-11 Jacques Julien Jean Dufour Energy production device and associated processes
FR2970244A1 (en) * 2011-01-07 2012-07-13 Conservatoire Nat Arts DEVICE FOR GENERATING ENERGY AND ASSOCIATED METHODS
CN115301239A (en) * 2022-07-21 2022-11-08 华北电力大学 Bimetal composite catalyst for hydrogen production by hydrolysis and preparation method thereof

Also Published As

Publication number Publication date
JP4187970B2 (en) 2008-11-26
JP2003212501A (en) 2003-07-30

Similar Documents

Publication Publication Date Title
Singh et al. On the synthesis of the Mg2Ni alloy by mechanical alloying
CN1223423C (en) Nahocomposites with activated interfaces prepared by mechanical grinding of magnesium hydrides and use for storing hydrogen
US6387152B1 (en) Process for manufacturing nanocrystalline metal hydrides
US20030173229A1 (en) Process for producing hydrogen
US11912580B2 (en) Nano magnesium hydride and in-situ preparation method thereof
CN102634714A (en) Copper-added magnesium-aluminum hydrogen storage alloy and preparation method thereof
CN100431945C (en) Method for preparing magnesium based hydrogen storage material
Hsueh et al. Regeneration of spent-NaBH4 back to NaBH4 by using high-energy ball milling
JP2008156148A (en) Method for generating hydrogen
CN107324279A (en) It is a kind of to improve the method that silicon alkaline process prepares hydrogen
Lv et al. Improved hydrogen storage properties of TiFe alloy by doping (Zr+ 2V) additive and using mechanical deformation
CN101891151A (en) Magnesium-aluminum based hydride composite material for hydrolytic hydrogen production
Sazelee et al. Enhanced dehydrogenation performance of NaAlH4 by the addition of spherical SrTiO3
AU2003246975B2 (en) Reactive milling process for the manufacture of a hydrogen storage alloy
JP5491041B2 (en) Destabilized catalyzed borohydride for reversible hydrogen storage
JP2009132553A (en) Method for producing hydrogen storage material and hydrogen generation method
US4289744A (en) Material and method to dissociate water
JP2004196634A (en) Hydride powder used for hydrogen storing/discharging system
JP2003221201A (en) Hydrogen generating device
Qiu et al. Hydrogen generation from the hydrolysis of LaMg12H27 ball-milled with LiH
CN107585738B (en) Mg-Mg2Si composite hydrolysis hydrogen production material, preparation method thereof and method for hydrolysis hydrogen production
JP2004204309A (en) Hydrogen storage material, and production method therefor
JP2006007064A (en) Hydrogen storage material and manufacturing method thereof
JP2005095869A (en) Hydrogen storing material and its production method
CN114105090B (en) Mg-based composite hydrogen storage material for in-situ catalysis of high-entropy alloy and preparation method thereof

Legal Events

Date Code Title Description
AS Assignment

Owner name: HONDA GIKEN KOGYO KABUSHIKI KAISHA, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KANOYA, IZURU;HOSOE, MITSUYA;SUZUKI, TAKANORI;AND OTHERS;REEL/FRAME:014089/0987;SIGNING DATES FROM 20030325 TO 20030326

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION