EP1899264A2 - Hydrogen generation catalysys and system for hydrogen generation - Google Patents

Hydrogen generation catalysys and system for hydrogen generation

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Publication number
EP1899264A2
EP1899264A2 EP06773824A EP06773824A EP1899264A2 EP 1899264 A2 EP1899264 A2 EP 1899264A2 EP 06773824 A EP06773824 A EP 06773824A EP 06773824 A EP06773824 A EP 06773824A EP 1899264 A2 EP1899264 A2 EP 1899264A2
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EP
European Patent Office
Prior art keywords
catalyst
metal
hydrogen generation
ruthenium
cobalt
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.)
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Application number
EP06773824A
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German (de)
French (fr)
Inventor
Qinglin Zhang
Ying Wu
Gregory M. Smith
Michael Binder
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Millennium Cell Inc
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Millennium Cell Inc
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Filing date
Publication date
Priority claimed from US11/167,607 external-priority patent/US20060292067A1/en
Priority claimed from US11/167,608 external-priority patent/US20060293173A1/en
Application filed by Millennium Cell Inc filed Critical Millennium Cell Inc
Publication of EP1899264A2 publication Critical patent/EP1899264A2/en
Withdrawn legal-status Critical Current

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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 catalysts and systems for the catalytic generation of hydrogen from, for example, aqueous chemical hydride solutions.
  • Chemical hydrides are known hydrogen storage materials characterized by relatively high gravimetric hydrogen storage density. Chemical hydrides, such as alkali metal hydrides and metal borohydrides, can generate hydrogen through a hydrolysis reaction with water. For these chemical hydrides, the gravimetric hydrogen densities range from about 4 to about 9% by weight.
  • Sodium borohydride (NaBH 4 ) is of particular interest because it can be dissolved in alkaline water solutions with virtually no reaction until it contacts a catalyst. In this case, the stabilized alkaline solution of sodium borohydride is referred to as "fuel” or "fuel solution.”
  • catalysts for hydrogen generation systems are needed that ensure fast dynamic system control and high fuel conversion over the lifetime of the system.
  • Durable catalysts that tolerate hot caustic solutions and that deliver high performance under catalyst reactor conditions, such as temperatures above 100 0 C and pressures exceeding 50 psig (pounds-force per square inch gauge), also are needed, as well as systems and methods for generating hydrogen gas employing such durable catalysts.
  • the present invention provides supported catalysts that promote the hydrolysis of fuel solutions to produce hydrogen.
  • the supported catalysts can be supported metallic catalysts comprising a support substrate carrying a mixture of at least a first transition metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, titanium, tin, cadmium, nickel, and iridium, and at least a second component selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, nickel, and iridium.
  • the catalyst according to the invention is bimetallic, although additional catalyst components, including but not limited to, a third transition metal may optionally be included.
  • the invention also provides a hydrogen generation supported catalyst, comprising a mixture of at least first and second metals, wherein each of the first and second metals is different and is independently selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, titanium, tin, cadmium, and iridium.
  • the invention further provides a hydrogen generation supported catalyst, comprising a support substrate; and a metallic mixture on the support, wherein the mixture comprises a first metal in an amount of about 0.05 to about 20% by weight, and a second metal in an amount of about 0.01 to about 25% by weight of the supported catalyst, hi a preferred embodiment, the invention provides a ruthenium/cobalt hydrogen generation catalyst, comprising a support; and ruthenium in an amount of about 0.1 to about 2% by weight, and cobalt in an amount of about 1 to about 5% by weight, based on the total weight of the supported catalyst.
  • the supported catalyst has a BET surface area greater than typically seen for common metallic wires, sheets, or fibers, for example, and preferably in the range of about 5 to 20 mVg.
  • the invention provides a system and method of generating hydrogen gas, comprising providing an aqueous fuel solution containing a material selected from the group consisting of boranes, polyhedral boranes, borohydride salts, and polyhedral borane salts; and contacting the aqueous fuel solution with a hydrogen generation catalyst comprising a support, a first metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, and iridium, the first metal being present in an amount of about 0.05 to about 20% by weight of the hydrogen generation catalyst; and a second metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, titanium, tin, cadmium, and iridium to produce hydrogen gas, the second metal being present in an amount of about 0.01 to about 25% by weight of the hydrogen generation catalyst.
  • a hydrogen generation catalyst comprising
  • Figure 1 illustrates the relation between fuel conversion and fuel space velocity for five samples of a ruthenium/cobalt catalyst according to the present invention.
  • Figure 2 illustrates the relation between reactor temperature and time at two reactor pressures using a ruthenium/cobalt catalyst according to the present invention. DESCRIPTION OF THE INVENTION
  • the present invention provides durable, highly active supported catalysts and systems for hydrogen generation from, for example, the hydrolysis of boron hydride compounds.
  • the systems of the present invention can serve to enhance the hydrolysis reactions of boron hydride compounds to produce hydrogen gas.
  • the hydrolysis reaction shown in equation (1) below is characteristic of borohydride compounds:
  • the high purity hydrogen produced by the above hydrolysis reaction is suitable for a variety of end use applications, including, but not limited to, use in proton exchange membrane (PEM) fuel cells, as the gas stream is warm and humidified due to the exothermic nature of the reaction.
  • PEM fuel cells require a humid hydrogen gas stream to prevent dehydration of the membrane and resultant loss of electrical efficiency.
  • the preferred supported catalysts of the present invention are highly active, durable and can be used repeatedly without significant loss of catalytic activity.
  • the supported catalysts of the present invention can comprise various mixtures of metals selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, nickel, and iridium.
  • the supported catalysts of the present invention contain bimetallic metal mixtures comprising a first component and a second component.
  • the first component is a transition metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, titanium, tin, cadmium, nickel, and iridium and is present in an amount of from about 0.05 to about 20% by weight, preferably from about 1 to about 10% by weight, and most preferably from about 1 to about 5% by weight.
  • the second component in this embodiment is a metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, nickel, and iridium and is present in an amount of from about 0.01 to about 25% by weight, preferably from about 0.1 to about 2% by weight.
  • cobalt-ruthenium, cobalt-zinc, cobalt-manganese, and cobalt- molybdenum are particularly preferred.
  • the cobalt is present in an amount ranging from about 0.05 wt-% to about 20 wt-%, preferably from about 1 wt-% to about 10 wt- %, and most preferably from about 1 to 5 wt-%
  • the second component is present in an amount ranging from about 0.01 wt-% to 25 wt-%, preferably from about 0.1 wt-% and 2 wt-%. All weight percentages herein are expressed as a percent of the total weight of the supported catalyst, i.e., the support and the metallic mixture, which may be deposited on or impregnated in the support.
  • the most reactive metals for initiating the hydrolysis of boron hydrides are the relatively expensive Group VIII metals, such as platinum, rhodium, and ruthenium, and thus catalysts comprising such metals can be a major contributor to the cost of a hydrogen generating system.
  • Group VIII metals such as platinum, rhodium, and ruthenium
  • catalysts comprising such metals can be a major contributor to the cost of a hydrogen generating system.
  • Table 1 shows that a higher loading of a less reactive metal (e.g., 3 wt-% cobalt) provides a similar hydrogen generation rate as compared to a lower loading of a more reactive metal (e.g., 0.5 wt-% ruthenium).
  • Table 1 further demonstrates that appropriate combinations of less reactive metals, which are often a tenth or a hundredth of the price of platinum, rhodium, and ruthenium, can offer effective hydrogen generation rates. Accordingly, catalyst components and loadings can be selected to meet the operating demands and cost constraints of particular hydrogen generation systems, given the teachings herein.
  • the above weight percentages are calculated based on the total weight of the individual component with respect to the total weight of all catalyst components including the support material.
  • the term "hydrogen generation catalyst” as used herein means the metal mixture together with the support substrate or carrier on which the mixture is deposited, impregnated, or otherwise carried.
  • the catalytically active species may include the metals in ineir re ⁇ uced elemental state or in high oxidation states as found in compounds such as metal oxides or metal borides.
  • Analytical techniques such as inductively coupled plasma-mass spectrometry (ICP-MS) and energy dispersive X-ray analysis (EDX) are useful as they permit measurement of the elements without regard to oxidation state.
  • the support or carrier may be any substrate that allows deposition of metals on its surface, or impregnation of metals, and which will not readily break apart or erode from the rapid formation of hydrogen gas on the surface and in internal pores.
  • the use of a support is preferred as it allows easy separation of the catalyst from the reaction media.
  • the rate of hydrogen generation can be controlled by regulating the contact with the catalyst, as disclosed in U.S. Patent No. 6,534,033 entitled "System for Hydrogen Generation,” the entire disclosure of which is hereby incorporated herein.
  • the carrier is preferably chemically inert in caustic solutions at pressures up to 200 psig or more and temperatures up to 200 °C or more.
  • Suitable carriers include (1) activated carbon, coke, or charcoal; (2) ceramics and refractory inorganic oxides such as titanium dioxide, zirconium oxide, cerium oxides, used individually or as mixtures thereof; (3) metal foams, sintered metals and metal fibers or composite materials of nickel and titanium; and (4) perovskites with the general formula ABO 3 , where A is a metallic atom with a valence of +2 and B is a metallic atom with a valence of +4.
  • the supported catalysts of the present invention may be formed by any suitable deposition method, including, for example, deposition on and/or impregnation of active elements, or mixtures of active elements, on a support. This deposition may be followed by a further surface treatment, including reduction with a reducing agent (hydrogen for example, although other reducing agents including sodium borohydride can be used), calcination, or oxidation with an oxidizing agent (such as, but not limited to, air and oxygen). Suitable methods are disclosed in, for example, U.S. Patent No. 6,534,033.
  • an impregnated support is prepared by mixing 50 g of 50:50 nickel powde ⁇ nickel fiber composite pads, cut into 0.25" x 0.25" chips, with about 30 mL of an aqueous solution containing 6.31g CoCl 2 *6H 2 O and 1.431 g RuCl 3 »H 2 O, heating the mixture to about 70 0 C and evaporating the water until completely dry.
  • the resulting supported catalyst is then heated in a tube furnace at about 240°C under a 20 mL/min hydrogen (4% in nitrogen) flow for about 3 hours at atmospheric pressure.
  • the final catalyst has a nominal loading of about 1.2% Ru by weight and about 3% Co by weight (assuming final total catalyst weight equals the Ni-pad plus the Ru metal plus the Co metal).
  • Various other methods for depositing or impregnating a transition metal mixture on a carrier may be employed as known in the art or determined by one skilled in the art given the teachings herein.
  • the supported catalysts of the invention also may be employed in the form of pellets, monoliths, chips, or other physical forms suitable for use in a fixed-bed, trickle-bed, or other reactor, such as the one described in co-pending U.S. Patent Application Serial No. 10/741,032, entitled “Catalytic Reactor for Hydrogen Generator Systems,” the entire disclosure of which is hereby incorporated herein.
  • the catalyst For highly efficient hydrogen generation from the hydrolysis of boron hydrides, it is preferred that the catalyst have a high surface area as a means to increase the number of potentially available and reactive catalytic sites.
  • the term "high surface area" as used in this application refers to a BET surface area of about 5 to about 100 m 2 /g, preferably between about 7 to about 25 m 2 /g, and most preferably of about 10 m 2 /g of the supported catalyst.
  • the supported catalyst is preferably porous with an average pore radius between 5 and 50 A, more preferably between 15 and 35 A, and most preferably between about 20 and 30 A.
  • a total pore volume is preferably about 5 to about 100 mL/g, more preferably about 30 to about 70 mL/g.
  • boron hydride or "boron hydrides” as used herein include boranes, polyhedral boranes, and anions of borohydrides or polyhedral boranes, such as those provided in co-pending U.S. Patent Application Serial No. 10/741,199, entitled “Fuel Blends for Hydrogen Generators,” filed December 19, 2003, the entire disclosure of which is hereby incorporated herein.
  • Suitable boron hydrides include, without intended limitation, the group of borohydride salts M(BH 4 ) n , triborohydride salts M(B 3 Hs) n , decahydrodecaborate salts M 2 (B 10 H 1O ) n , tridecahydrodecaborate salts M(BioH 13 ) n , dodecahydrododecaborate salts M 2 (B 12 H 12 ) n , and octadecahydroicosaborate salts M 2 (B 2 oH 18 ) n , among others, where M is a cation selected from the group consisting of alkali metal cations, alkaline earth metal cations, aluminum cation, zinc cation, and ammonium cation, and n is equal to the charge of the cation.
  • M is preferably sodium, potassium, lithium, or calcium.
  • a catalyst comprising 0.6 wt-% ruthenium and 2 wt-% cobalt supported on a nickel metallic mat containing pressed nickel fibers and sintered nickel particles in a 40:60 ratio was used to evaluate durability and hydrogen generation activity.
  • Fresh catalysts were subject to fuel treatments conducted under atmospheric pressure and using a 20 wt-% sodium borohydride and 3 wt-% NaOH fuel solution at about 70 °C, as a way to simulate multi-cycle usage of the catalyst.
  • 200 mL of fuel solution was added to a reactor immersed in a water bath preheated to about 30 0 C, and the reactor system thoroughly purged with hydrogen.
  • Catalyst was then added to the reactor and stirred with a magnetic stirrer for 0.5 hours. Rate of hydrogen generation and reaction temperature were measured.
  • Activity of the catalyst was evaluated based on initial rate of hydrogen generation at 30°C under the controlled conditions. Catalyst durability can be evaluated by comparison of activities obtained after the catalyst was subjected to different fuel treatment cycles.
  • the hydrogen generation activity of the catalyst was evaluated with a packed bed tubular reactor (0.842" internal diameter x 7" long) under various fuel flow conditions, hi operation, a fuel pump fed the fuel (20 wt-% sodium borohydride and 3 wt-% NaOH aqueous solution) from a storage tank to a reactor packed with a catalyst according to the present invention.
  • the fuel flow rate was monitored by using a scale and a timer.
  • the fuel solution generated hydrogen gas and sodium metaborate as shown in equation (1) above.
  • the hydrogen and metaborate solution were separated in a gas-liquid separator, and the humidified hydrogen then cooled down to room temperature after passage through a heat exchanger and a drier.
  • the steady-state hydrogen evolution rate was monitored with a mass flow meter.
  • Table 4 The operating conditions for the reactor tests are summarized in Table 4 below.
  • Figure 1 illustrates the relation between the fuel conversion and the fuel throughput (or space velocity) for five samples A, B, C, D and E of a ruthenium/cobalt catalyst according to the present invention.
  • the reactor was started at ambient conditions at a constant liquid fuel space velocity and operated continuously at 55 or 80 psig for about 6 to 8 hours before reactor shutdown. Following shutdown, the reactor was flushed with water to remove residual fuel inside the reactor. Fuel conversions of at least 90% were achieved over a wide range of fuel flow rates.
  • a high reactor throughput greater than 680 standard liters of hydrogen per minute (SLPM H 2 ) per liter reactor volume was achieved with fuel conversions greater than 92%.
  • Figure 2 illustrates the relation between reactor temperature and time at different pressures for a catalytic reactor containing a ruthenium/cobalt catalyst according to the present invention.
  • Fast reactor start up dynamics are preferred in the design of a hydrogen storage system.
  • reactor startup profiles were measured at a constant fuel flow rate of 20g/min at 55 and 80 psig pressure, as higher pressures lead to a faster reactor startup.
  • ruthenium/cobalt supported catalysts according to the present invention demonstrate rapid startup profiles.

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Abstract

Supported catalysts are provided to promote hydrogen generation from the hydrolysis of boron hydrides. The supported catalyst is a supported metallic mixture comprising a first transition metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, titanium, tin, cadmium, and indium, in an amount of from about 0.1 to about 20% by weight, and a second metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, titanium, tin, cadmium, boron, and iridium, in an amount of from about 0.05 to about 25% by weight of the supported catalyst.

Description

HYDROGEN GENERATION CATALYSTS AND SYSTEMS FOR HYDROGEN GENERATION
FIELD OF THE INVENTION
[0001] The present invention relates to catalysts and systems for the catalytic generation of hydrogen from, for example, aqueous chemical hydride solutions.
BACKGROUND OF THE INVENTION
[0002] Chemical hydrides are known hydrogen storage materials characterized by relatively high gravimetric hydrogen storage density. Chemical hydrides, such as alkali metal hydrides and metal borohydrides, can generate hydrogen through a hydrolysis reaction with water. For these chemical hydrides, the gravimetric hydrogen densities range from about 4 to about 9% by weight. Sodium borohydride (NaBH4) is of particular interest because it can be dissolved in alkaline water solutions with virtually no reaction until it contacts a catalyst. In this case, the stabilized alkaline solution of sodium borohydride is referred to as "fuel" or "fuel solution."
[0003] Various hydrogen generation systems have been developed for the production of hydrogen gas by the metal catalyzed hydrolysis of aqueous sodium borohydride fuel solutions. One current technology for hydrogen generation from stabilized sodium borohydride solutions involves feeding the fuel solution at ambient temperature to a catalyst bed packed with a catalyst to promote hydrogen generation.
[0004] Activity, durability and cost of the catalyst are the major barriers for meeting commercial specifications. Improvements in catalyst activity would enable higher reactor throughput, therefore reducing the required total volume of catalyst bed, and consequently the static liquid hold-up volume of the hydrogen generation system. A durable catalyst must ensure that such high throughput is maintained over a relatively long period of time, thus eliminating the need to over-design the amount of catalyst used in order to compensate for the reduced activity of the aged catalyst bed. Ultimately, improvements in catalyst activity are needed to achieve overall reduced system volume and higher system hydrogen storage densities.
[0005] hi addition, catalysts for hydrogen generation systems are needed that ensure fast dynamic system control and high fuel conversion over the lifetime of the system. Durable catalysts that tolerate hot caustic solutions and that deliver high performance under catalyst reactor conditions, such as temperatures above 100 0C and pressures exceeding 50 psig (pounds-force per square inch gauge), also are needed, as well as systems and methods for generating hydrogen gas employing such durable catalysts.
BRIEF SUMMARY OF THE INVENTION
[0006] The present invention provides supported catalysts that promote the hydrolysis of fuel solutions to produce hydrogen. The supported catalysts can be supported metallic catalysts comprising a support substrate carrying a mixture of at least a first transition metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, titanium, tin, cadmium, nickel, and iridium, and at least a second component selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, nickel, and iridium. Thus, in one embodiment the catalyst according to the invention is bimetallic, although additional catalyst components, including but not limited to, a third transition metal may optionally be included.
[0007] The invention also provides a hydrogen generation supported catalyst, comprising a mixture of at least first and second metals, wherein each of the first and second metals is different and is independently selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, titanium, tin, cadmium, and iridium.
[0008] The invention further provides a hydrogen generation supported catalyst, comprising a support substrate; and a metallic mixture on the support, wherein the mixture comprises a first metal in an amount of about 0.05 to about 20% by weight, and a second metal in an amount of about 0.01 to about 25% by weight of the supported catalyst, hi a preferred embodiment, the invention provides a ruthenium/cobalt hydrogen generation catalyst, comprising a support; and ruthenium in an amount of about 0.1 to about 2% by weight, and cobalt in an amount of about 1 to about 5% by weight, based on the total weight of the supported catalyst. In particularly preferred embodiments the supported catalyst has a BET surface area greater than typically seen for common metallic wires, sheets, or fibers, for example, and preferably in the range of about 5 to 20 mVg.
[0009] In another embodiment the invention provides a system and method of generating hydrogen gas, comprising providing an aqueous fuel solution containing a material selected from the group consisting of boranes, polyhedral boranes, borohydride salts, and polyhedral borane salts; and contacting the aqueous fuel solution with a hydrogen generation catalyst comprising a support, a first metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, and iridium, the first metal being present in an amount of about 0.05 to about 20% by weight of the hydrogen generation catalyst; and a second metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, titanium, tin, cadmium, and iridium to produce hydrogen gas, the second metal being present in an amount of about 0.01 to about 25% by weight of the hydrogen generation catalyst.
[0010] The accompanying drawings together with the detailed description herein illustrate these and other embodiments and serve to explain the principles of the invention. Other features and advantages of the present invention will also become apparent from the following description of the invention which refers to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Figure 1 illustrates the relation between fuel conversion and fuel space velocity for five samples of a ruthenium/cobalt catalyst according to the present invention; and
[0012] Figure 2 illustrates the relation between reactor temperature and time at two reactor pressures using a ruthenium/cobalt catalyst according to the present invention. DESCRIPTION OF THE INVENTION
[0013] The present invention provides durable, highly active supported catalysts and systems for hydrogen generation from, for example, the hydrolysis of boron hydride compounds. The systems of the present invention can serve to enhance the hydrolysis reactions of boron hydride compounds to produce hydrogen gas. The hydrolysis reaction shown in equation (1) below is characteristic of borohydride compounds:
MBH4 + 2 H2O -» MBO2 + 4 H2 + heat Equation 1
[0014] The high purity hydrogen produced by the above hydrolysis reaction is suitable for a variety of end use applications, including, but not limited to, use in proton exchange membrane (PEM) fuel cells, as the gas stream is warm and humidified due to the exothermic nature of the reaction. In particular, PEM fuel cells require a humid hydrogen gas stream to prevent dehydration of the membrane and resultant loss of electrical efficiency.
[0015] The preferred supported catalysts of the present invention are highly active, durable and can be used repeatedly without significant loss of catalytic activity. The supported catalysts of the present invention can comprise various mixtures of metals selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, nickel, and iridium. Preferably, the supported catalysts of the present invention contain bimetallic metal mixtures comprising a first component and a second component. In an exemplary embodiment, the first component is a transition metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, titanium, tin, cadmium, nickel, and iridium and is present in an amount of from about 0.05 to about 20% by weight, preferably from about 1 to about 10% by weight, and most preferably from about 1 to about 5% by weight. The second component in this embodiment is a metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, nickel, and iridium and is present in an amount of from about 0.01 to about 25% by weight, preferably from about 0.1 to about 2% by weight.
[0016] Mixtures of cobalt-ruthenium, cobalt-zinc, cobalt-manganese, and cobalt- molybdenum are particularly preferred. Most preferably, the cobalt is present in an amount ranging from about 0.05 wt-% to about 20 wt-%, preferably from about 1 wt-% to about 10 wt- %, and most preferably from about 1 to 5 wt-%, and the second component is present in an amount ranging from about 0.01 wt-% to 25 wt-%, preferably from about 0.1 wt-% and 2 wt-%. All weight percentages herein are expressed as a percent of the total weight of the supported catalyst, i.e., the support and the metallic mixture, which may be deposited on or impregnated in the support.
[0017] Typically, the most reactive metals for initiating the hydrolysis of boron hydrides are the relatively expensive Group VIII metals, such as platinum, rhodium, and ruthenium, and thus catalysts comprising such metals can be a major contributor to the cost of a hydrogen generating system. As shown in Table 1 below, a higher loading of a less reactive metal (e.g., 3 wt-% cobalt) provides a similar hydrogen generation rate as compared to a lower loading of a more reactive metal (e.g., 0.5 wt-% ruthenium). Table 1 further demonstrates that appropriate combinations of less reactive metals, which are often a tenth or a hundredth of the price of platinum, rhodium, and ruthenium, can offer effective hydrogen generation rates. Accordingly, catalyst components and loadings can be selected to meet the operating demands and cost constraints of particular hydrogen generation systems, given the teachings herein.
[0018] The above weight percentages are calculated based on the total weight of the individual component with respect to the total weight of all catalyst components including the support material. The term "hydrogen generation catalyst" as used herein means the metal mixture together with the support substrate or carrier on which the mixture is deposited, impregnated, or otherwise carried. The catalytically active species may include the metals in ineir reαuced elemental state or in high oxidation states as found in compounds such as metal oxides or metal borides. Analytical techniques such as inductively coupled plasma-mass spectrometry (ICP-MS) and energy dispersive X-ray analysis (EDX) are useful as they permit measurement of the elements without regard to oxidation state.
[0019] The support or carrier may be any substrate that allows deposition of metals on its surface, or impregnation of metals, and which will not readily break apart or erode from the rapid formation of hydrogen gas on the surface and in internal pores. The use of a support is preferred as it allows easy separation of the catalyst from the reaction media. In addition, when a support or carrier is employed, the rate of hydrogen generation can be controlled by regulating the contact with the catalyst, as disclosed in U.S. Patent No. 6,534,033 entitled "System for Hydrogen Generation," the entire disclosure of which is hereby incorporated herein.
[0020] The carrier is preferably chemically inert in caustic solutions at pressures up to 200 psig or more and temperatures up to 200 °C or more. Suitable carriers include (1) activated carbon, coke, or charcoal; (2) ceramics and refractory inorganic oxides such as titanium dioxide, zirconium oxide, cerium oxides, used individually or as mixtures thereof; (3) metal foams, sintered metals and metal fibers or composite materials of nickel and titanium; and (4) perovskites with the general formula ABO3, where A is a metallic atom with a valence of +2 and B is a metallic atom with a valence of +4.
[0021] The supported catalysts of the present invention may be formed by any suitable deposition method, including, for example, deposition on and/or impregnation of active elements, or mixtures of active elements, on a support. This deposition may be followed by a further surface treatment, including reduction with a reducing agent (hydrogen for example, although other reducing agents including sodium borohydride can be used), calcination, or oxidation with an oxidizing agent (such as, but not limited to, air and oxygen). Suitable methods are disclosed in, for example, U.S. Patent No. 6,534,033. In an exemplary embodiment, an impregnated support is prepared by mixing 50 g of 50:50 nickel powdeπnickel fiber composite pads, cut into 0.25" x 0.25" chips, with about 30 mL of an aqueous solution containing 6.31g CoCl2*6H2O and 1.431 g RuCl3»H2O, heating the mixture to about 70 0C and evaporating the water until completely dry. The resulting supported catalyst is then heated in a tube furnace at about 240°C under a 20 mL/min hydrogen (4% in nitrogen) flow for about 3 hours at atmospheric pressure. The final catalyst has a nominal loading of about 1.2% Ru by weight and about 3% Co by weight (assuming final total catalyst weight equals the Ni-pad plus the Ru metal plus the Co metal). Various other methods for depositing or impregnating a transition metal mixture on a carrier may be employed as known in the art or determined by one skilled in the art given the teachings herein.
[0022] The supported catalysts of the invention also may be employed in the form of pellets, monoliths, chips, or other physical forms suitable for use in a fixed-bed, trickle-bed, or other reactor, such as the one described in co-pending U.S. Patent Application Serial No. 10/741,032, entitled "Catalytic Reactor for Hydrogen Generator Systems," the entire disclosure of which is hereby incorporated herein.
[0023] For highly efficient hydrogen generation from the hydrolysis of boron hydrides, it is preferred that the catalyst have a high surface area as a means to increase the number of potentially available and reactive catalytic sites. The term "high surface area" as used in this application refers to a BET surface area of about 5 to about 100 m2/g, preferably between about 7 to about 25 m2/g, and most preferably of about 10 m2/g of the supported catalyst. The supported catalyst is preferably porous with an average pore radius between 5 and 50 A, more preferably between 15 and 35 A, and most preferably between about 20 and 30 A. A total pore volume is preferably about 5 to about 100 mL/g, more preferably about 30 to about 70 mL/g.
[0024] The terms "boron hydride" or "boron hydrides" as used herein include boranes, polyhedral boranes, and anions of borohydrides or polyhedral boranes, such as those provided in co-pending U.S. Patent Application Serial No. 10/741,199, entitled "Fuel Blends for Hydrogen Generators," filed December 19, 2003, the entire disclosure of which is hereby incorporated herein. Suitable boron hydrides include, without intended limitation, the group of borohydride salts M(BH4)n, triborohydride salts M(B3Hs)n, decahydrodecaborate salts M2(B10H1O)n, tridecahydrodecaborate salts M(BioH13)n, dodecahydrododecaborate salts M2(B12H12)n, and octadecahydroicosaborate salts M2(B2oH18)n, among others, where M is a cation selected from the group consisting of alkali metal cations, alkaline earth metal cations, aluminum cation, zinc cation, and ammonium cation, and n is equal to the charge of the cation. For the above-mentioned boron hydrides, M is preferably sodium, potassium, lithium, or calcium.
[0025] The following example further describes and demonstrates features of the present invention. The example is given solely for illustration purposes and is not to be construed as a limitation of the present invention.
Example
[0026] A catalyst comprising 0.6 wt-% ruthenium and 2 wt-% cobalt supported on a nickel metallic mat containing pressed nickel fibers and sintered nickel particles in a 40:60 ratio was used to evaluate durability and hydrogen generation activity.
[0027] Bulk and surface chemical composition were measured by ICP-MS and EDX to determine any catalyst degradation during use. Resulting data are summarized in Tables 2 and 3 below.
[0028] Fresh catalysts were subject to fuel treatments conducted under atmospheric pressure and using a 20 wt-% sodium borohydride and 3 wt-% NaOH fuel solution at about 70 °C, as a way to simulate multi-cycle usage of the catalyst. For each test, 200 mL of fuel solution was added to a reactor immersed in a water bath preheated to about 30 0C, and the reactor system thoroughly purged with hydrogen. Catalyst was then added to the reactor and stirred with a magnetic stirrer for 0.5 hours. Rate of hydrogen generation and reaction temperature were measured. Activity of the catalyst was evaluated based on initial rate of hydrogen generation at 30°C under the controlled conditions. Catalyst durability can be evaluated by comparison of activities obtained after the catalyst was subjected to different fuel treatment cycles.
[0029] The ICP-MS analysis revealed that bulk composition is close to nominal loading of 0.6 wt-% Ru and 2 wt-% Co. No significant changes in bulk composition were noted before and after fuel treatments. Initially, minor ruthenium metal leaching from the surface is observed, but the surface concentrations remain relatively stable after 2 and 35 fuel treatments.
[0030] The hydrogen generation activity of the catalyst was evaluated with a packed bed tubular reactor (0.842" internal diameter x 7" long) under various fuel flow conditions, hi operation, a fuel pump fed the fuel (20 wt-% sodium borohydride and 3 wt-% NaOH aqueous solution) from a storage tank to a reactor packed with a catalyst according to the present invention. The fuel flow rate was monitored by using a scale and a timer. Upon contacting the catalyst bed, the fuel solution generated hydrogen gas and sodium metaborate as shown in equation (1) above. The hydrogen and metaborate solution were separated in a gas-liquid separator, and the humidified hydrogen then cooled down to room temperature after passage through a heat exchanger and a drier. The steady-state hydrogen evolution rate was monitored with a mass flow meter. The operating conditions for the reactor tests are summarized in Table 4 below.
[0031] Figure 1 illustrates the relation between the fuel conversion and the fuel throughput (or space velocity) for five samples A, B, C, D and E of a ruthenium/cobalt catalyst according to the present invention. The reactor was started at ambient conditions at a constant liquid fuel space velocity and operated continuously at 55 or 80 psig for about 6 to 8 hours before reactor shutdown. Following shutdown, the reactor was flushed with water to remove residual fuel inside the reactor. Fuel conversions of at least 90% were achieved over a wide range of fuel flow rates. A high reactor throughput greater than 680 standard liters of hydrogen per minute (SLPM H2) per liter reactor volume was achieved with fuel conversions greater than 92%.
[0032] Figure 2 illustrates the relation between reactor temperature and time at different pressures for a catalytic reactor containing a ruthenium/cobalt catalyst according to the present invention. Fast reactor start up dynamics are preferred in the design of a hydrogen storage system. According to another embodiment of the present invention, reactor startup profiles were measured at a constant fuel flow rate of 20g/min at 55 and 80 psig pressure, as higher pressures lead to a faster reactor startup. As shown in Figure 2, ruthenium/cobalt supported catalysts according to the present invention demonstrate rapid startup profiles.
[0033] Although the invention has been described in detail in connection with the exemplary embodiments, it should be understood that the invention is not limited to the above disclosed embodiments. Rather, the invention can be modified to incorporate any number of variations, alterations, substitutions, or equivalent arrangements not heretofore described, but which are commensurate with the spirit and scope of the invention. Accordingly, the invention is not limited by the foregoing description, but is only limited by the scope of the appended claims and equivalents thereof.

Claims

CLAIMS[0034] What is claimed as new and desired to be protected by Letters Patent of the United States is:
1. A supported catalyst for the generation of hydrogen, comprising: a mixture of at least first and second metals, wherein each of the first and second metals is different and is independently selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, titanium, tin, cadmium, nickel, boron, and iridium; and wherein the supported catalyst has a BET surface area of about 5 to about 100 m2/g.
2. The hydrogen generation catalyst of claim 1, wherein the first metal is present in an amount of about 0.05 to about 20% by weight of the supported catalyst.
3. The hydrogen generation catalyst of claim 1 , wherein the first metal is present in an amount of about 1 to about 10% by weight of the supported catalyst.
4. The hydrogen generation catalyst of claim 1, wherein the first metal is present in an amount of about 1 to about 5% by weight of the supported catalyst.
5. The hydrogen generation catalyst of claim 1 , wherein the second metal is present in an amount of about 0.01 to about 25% by weight of the supported catalyst.
6 . The hydrogen generation catalyst of claim 1, wherein the second metal is present in an amount of about 0.1 to about 2% by weight of the supported catalyst.
7. The hydrogen generation catalyst of claim 1 , wherein the first metal is cobalt.
8. The hydrogen generation catalyst of claim 7, wherein the second metal is selected from the group consisting of ruthenium, manganese, molybdenum, and zinc.
9. The hydrogen generation catalyst of claim 1, further comprising a support containing a material selected from the group consisting of activated carbon, coke, and charcoal.
10. The hydrogen generation catalyst of claim 1, further comprising a support containing at least one refractory inorganic oxide.
11. The hydrogen generation catalyst of claim 1 , further comprising a support that contains a metal in the form of a foam, sintered particle, fiber, monolith, or a mixture thereof.
12. The hydrogen generation catalyst of claim 1, further comprising a support in the form of a perovskite of the formula ABO3, wherein A is a metallic atom with a valence of +2 and B is a metallic atom with a valence of +4.
13. The hydrogen generation catalyst of claim 1, wherein the catalyst has a BET surface area of about 5 to about 25 m2/g.
14. The hydrogen generation catalyst of claim 1, wherein the catalyst has a BET surface area of about 10 m2/g .
15. The hydrogen generation catalyst of claim 1, wherein the supported catalyst has pores and an average pore radius of about 5 to about 50 Angstroms.
16. The hydrogen generation catalyst of claim 1 , wherein the supported catalyst has pores having a volume of about 5 to 100 mL/g.
17. A supported catalyst for hydrogen generation , comprising: a support substrate; and a metallic mixture on the support, wherein the mixture comprises a first metal in an amount of about 0.05 to about 20% by weight, and a second metal in an amount of about 0.01 to about 25% by weight of the supported catalyst.
18. The supported catalyst of claim 17, wherein the first metal is selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, titanium, tin, cadmium, and indium.
19. The supported catalyst of claim 17, wherein the second metal is selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, iron, boron, titanium, tin, cadmium, and iridium.
20. The supported catalyst of claim 17, wherein the first metal is cobalt.
21. The supported catalyst of claim 17, wherein the first metal is present in an amount of about 1 to about 10% by weight.
22. The supported catalyst of claim 17, wherein the first metal is present in an amount of about 1 to about 5% by weight.
23. The supported catalyst of claim 17, wherein the second metal is ruthenium.
24. The supported catalyst of claim 17, wherein the second metal is present in an amount of about 0.05 to about 2% by weight.
25. The supported catalyst of claim 17, wherein the first metal is cobalt and the second metal is ruthenium.
26. The supported catalyst of claim 17, wherein the support comprises activated carbon, coke, or charcoal.
27. The supported catalyst of claim 17, wherein the support comprises a refractory inorganic oxide.
28. The supported catalyst of claim 17, wherein the support comprises a metal in the form of a foam, sintered particle or metal, fibers, monolith, or a mixture thereof.
29. The supported catalyst of claim 17, wherein the catalyst has a BET surface area of about 5 to about 50 m2/g.
30. The supported catalyst of claim 17, wherein the catalyst has pores having an average pore radius of about 5 to about 50 Angstroms.
31. A ruthenium/cobalt hydrogen generation catalyst, comprising: a support; and ruthenium in an amount of about 0.05 to about 2% by weight, and cobalt in an amount of about 1 to about 5% by weight.
32. The ruthenium/cobalt hydrogen generation catalyst of claim 31 , wherein the support comprises a nickel mat.
33. The ruthenium/cobalt hydrogen generation catalyst of claim 31 , wherein the support comprises granular carbon.
34. The ruthenium/cobalt hydrogen generation catalyst of claim 31 , wherein the catalyst has a BET surface area of about 5 to about 50 mVg.
35. The ruthenium/cobalt hydrogen generation catalyst of claim 34, wherein the
BET surface area is about 7 to about 15 m2/g.
36. The ruthenium/cobalt hydrogen generation catalyst of claim 34, wherein the
BET surface area is about 10 m2/g.
37. The ruthenium/cobalt hydrogen generation catalyst of claim 31, wherein the catalyst has pores having an average pore radius of about 5 to about 50 Angstroms.
38. A method of generating hydrogen gas, comprising: providing an aqueous fuel solution comprising a material selected from the group consisting of boranes, polyhedral boranes, borohydride salts, and polyhedral borane salts; and contacting the aqueous fuel solution with a hydrogen generation catalyst comprising a support, a first metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, titanium, tin, cadmium, and iridium, the first metal being present in an amount of about 0.05 to about 20% by weight of the hydrogen generation catalyst; and a second metal selected from the group consisting of cobalt, ruthenium, zinc, molybdenum, manganese, titanium, tin, cadmium, boron, and iridium to produce hydrogen gas, the second metal being present in an amount of about 0.01 to about 25% by weight of the hydrogen generation catalyst.
39. The method of claim 38, wherein the first metal is cobalt and the second metal is ruthenium.
40. The method of claim 38, wherein the first metal is present in an amount of about 1 to about 10% by weight.
41. The method of claim 38, wherein the first metal is present in an amount of about 1 to about 5% by weight.
42. The method of claim 38, wherein the second metal is present in an amount of about 0.1 to about 2% by weight.
43. The method of claim 38, wherein conversion of the aqueous fuel solution with the hydrogen generation catalyst is conducted with a conversion rate of at least 80%.
44. The method of claim 38, wherein the second metal is present in an amount of about 0.1 to about 2% by weight of the supported catalyst.
45. The method of claim 38, wherein the first metal is cobalt.
46. The method of claim 45, wherein the second metal is selected from the group consisting of ruthenium, manganese, molybdenum, and zinc.
47. The method of claim 38, wherein the support contains a material selected from the group consisting of activated carbon, coke, and charcoal.
48. The method of claim 38, wherein the support contains at least one refractory inorganic oxide.
49. The method of claim 38, wherein the support contains a metal in the form of a foam, sintered particle, fiber, monolith, or a mixture thereof.
50. The method of claim 38, wherein the support is in the form of a perovskite of the formula ABO3, wherein A is a metallic atom with a valence of +2 and B is a metallic atom with a valence of +4.
51. The method of claim 38, wherein the catalyst has a BET surface area of about 5 to about 25 m2/g.
52. The method of claim 38, wherein the catalyst has a BET surface area of about 10 m2/g .
53. The method of claim 38, wherein the supported catalyst has pores and an average pore radius of about 5 to about 50 Angstroms.
54. The method of claim 38, wherein the supported catalyst has pores having a volume of about 5 to 100 mL/g.
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