WO2009127828A2 - Production d’hydrogène - Google Patents

Production d’hydrogène Download PDF

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Publication number
WO2009127828A2
WO2009127828A2 PCT/GB2009/000980 GB2009000980W WO2009127828A2 WO 2009127828 A2 WO2009127828 A2 WO 2009127828A2 GB 2009000980 W GB2009000980 W GB 2009000980W WO 2009127828 A2 WO2009127828 A2 WO 2009127828A2
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WO
WIPO (PCT)
Prior art keywords
acid
reactor
metal particles
hydrogen
permeable vessel
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.)
Ceased
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PCT/GB2009/000980
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English (en)
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WO2009127828A3 (fr
Inventor
Jonathan Woodward
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H2RENEW Ltd
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H2RENEW Ltd
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Publication of WO2009127828A2 publication Critical patent/WO2009127828A2/fr
Publication of WO2009127828A3 publication Critical patent/WO2009127828A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/08—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of inorganic compounds with 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • 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

  • Hydrogen use as a renewable fuel for transportation and fuel cells has the potential to solve several major challenges facing the world today: dependence on fossil fuels, poor air quality resulting from their burning, and greenhouse gas emissions.
  • To realize the full benefits of a hydrogen economy hydrogen must be produced cleanly, efficiently and affordably from regionally available, renewable resources.
  • the dominant hydrogen production technology is reforming of natural gas due to cost advantages over electrolysis and other renewable technologies.
  • renewable technologies attract tremendous interest with companies that use readily available and renewable sources of energy such as solar, biogas and biomass to produce hydrogen in large quantities.
  • Using hydrogen for energy applications requires a more efficient, lower cost production process, with low or no CO 2 emissions.
  • Getty et al. (U.S. Patent 6,395,252) discloses hydrogen production by reaction of metallic iron with an organic acid to generate a metal oxide and hydrogen, in which the organic acid is consumed in regenerating the metal.
  • a method for production of hydrogen comprising: providing one or more permeable vessel, the permeable vessel containing a plurality of entrapped metal particles; causing an acid to permeate the permeable vessel, wherein the entrapped metal particles react with the acid to generate hydrogen, and wherein the metal particles are exposed to a reducing atmosphere.
  • the method may also include collecting the hydrogen.
  • hydrogen gas is generated by reaction between an acid and the metal entrapped in the permeable vessel, in which the resulting metal oxide is constantly exposed to a reducing atmosphere provided by the hydrogen generated inside the permeable vessel, and is thereby reduced back to the metal. Hydrogen diffuses out of the permeable vessel and can be collected, and the metal is regenerated and is reusable.
  • the present invention thus provides a method for the sustainable production of hydrogen by the reaction of acid with metal particles entrapped inside a permeable vessel.
  • the approach exploits the fact that hydrogen is produced within the permeable vessel, and the entrapped metal oxides will be under a reducing atmosphere, causing the oxidised metal product inside the permeable vessel to be reduced back to the metallic state.
  • the present approach provides a method whereby hydrogen is generated without significant consumption of metal.
  • electrons become reattached to the metal ion to regenerate the metal and a dynamic equilibrium is established where the rate at which the metal ions are formed approximately equals the rate at which they are reduced back to the metallic state.
  • metallic iron in water or acid will lose electrons and go into solution as Fe 2+ ions, and the electrons will reduce protons formed by the dissociation of the acid to generate molecular hydrogen. Under reducing conditions however, some electrons are transferred back to the metal ion to regenerate metallic iron.
  • the steps of providing one or more permeable vessel containing a plurality of entrapped metal particles, and causing an acid to permeate the permeable vessel are either performed continuously or performed as a batch process.
  • inventive approach is amenable to a continuous process, permitting the continuous permeating of the permeable vessel with an acid, such as by flowing the acid over the permeable vessel, and collecting (or using) the hydrogen continuously from the vessel.
  • the method may comprise a batch process in which an acid is made to contact the permeable vessel containing the entrapped metal particles and the required quantity of hydrogen generated therefrom.
  • the steps of providing one or more permeable vessels containing a plurality of entrapped metal particles, and causing an acid to permeate the permeable vessel are carried out in anaerobic conditions. For example, using acid that has first been deaerated, using a vacuum to remove dissolved gas in the liquid, helps ensure that little or no oxygen comes into contact with the surface of the metal within the permeable vessel.
  • the steps of providing one or more permeable vessel containing a plurality of entrapped metal particles, and causing an acid to permeate the permeable vessel are carried out in a temperature-controlled environment.
  • the temperature may be controlled by a means for maintaining a fixed temperature such as a jacket surrounding the permeable vessel through which water is circulated at a given temperature.
  • the temperature is about 80°C.
  • the permeating of the permeable vessel with acid may be carried out at in a temperature-controlled environment, wherein the temperature is 40, 50, 60, 70 or 80°C.
  • the steps of providing one or more permeable vessel containing a plurality of entrapped metal particles, and causing an acid to permeate the permeable vessel are carried out in an environment of approximately neutral pH.
  • the permeable vessel is a gel bead or a slab.
  • the permeable vessel is made of one or more of: an alginate, a gelatin, a gum, a polysaccharide, a heteropolysaccharide and a resin.
  • the permeable vessel may be made of sodium alginate, guar gum, gum arabic, carrageehan, pectin, tragacanth gum, xanthan gum, or deacylated chitin (chitosan).
  • the entrapped metal particles are one or more of: silver, palladium, platinum, copper, nickel, lead, antimony, iron, zinc, aluminium, magnesium, gallium, calcium and sodium silver, palladium, platinum, copper, nickel, lead, antimony, iron, zinc, aluminium, magnesium, gallium, calcium, sodium, mixtures thereof and metal alloys.
  • alloys of metal may be suitable for the present inventive approach wherein at least one metal in the alloy is capable of acting as described above.
  • the entrapped metal particles are iron.
  • the entrapped metal particles are of a mesh size of between 2500 and 4.
  • the entrapped metal particles are of a mesh size of between 2500 and 100.
  • the entrapped metal particles may be, for example, microparticles or nanoparticles.
  • the acid is one of or a mixture of: gluconic acid, ascorbic acid, oxalic acid, citric acid, succinic acid, acetic acid, formic acid, a carboxylic acid and a precursor thereof.
  • the acid is gluconic acid. In yet another embodiment, the acid is degassed to permeating the permeable vessel.
  • the acid may be deaerated using a vacuum that removes the dissolved gas in the liquid by decompression, to help ensure that little or no oxygen comes into contact with the surface of the metal within the permeable vessel.
  • the permeable vessel is, for example, a gel bead, and the metal is, for example, iron, and the acid, is for example, a weak organic acid, such as gluconic acid.
  • aluminium powder may be entrapped within the permeable vessel, either alone or in combination with iron particles or another appropriate metal such as gallium.
  • the entrapped metal particle is an alloy or a mixture of suitable metals.
  • Gluconic acid is a renewable organic acid formed by fermentation of sugar (glucose) and is oxidised in the process forming 2-keto-D-gluconic acid.
  • a plurality of the permeable vessels containing entrapped metal particles is provided.
  • the method further comprises the step of separating the metal particles from the permeable vessel for subsequent reuse for hydrogen production.
  • a permeable vessel containing entrapped metal particles for hydrogen gas production comprising one or more of: propylene glycol alginate, sodium alginate, bone gelatin, guar gum, gum arabic, carrageehan, pectin, tragacanth gum, xanthan gum, deacylated chitin (chitosan), cellulose and combinations thereof; and a plurality of entrapped metal particles contained in the permeable vessel.
  • the permeable vessel may contain more than a single number of entrapped metal particles, as befitting the use thereof.
  • Such a permeable vessel may be made inexpensively, used, recovered easily and reused, or dried for ease of transportation to the site of hydrogen gas production.
  • the permeable vessel may comprise gel beads that can be dehydrated and rehydrated for their transportation and storage.
  • the gel beads could be used to store hydrogen, which has been generated by the reaction of an organic acid with metal (e.g. iron) micro/nanoparticles entrapped within them, perhaps following a dehydration step.
  • the permeable vessel is a gel bead having a diameter of between 0.2 mm and 5.0 mm.
  • the gel bead may be made of a gel forming polymer which forms a gel upon contact with a gelling inducer and is compatible with the metal particle to be encapsulated.
  • the gel forming polymer can be an ionotropic gel forming polymer such as a polysaccharide.
  • Suitable polysaccharides include those typically extracted from vegetable matter and include sodium alginate, guar gum, gum arabic, carrageehan, pectin, tragacanth gum, xanthan gum, and deacylated chitin (chitosan).
  • Exemplary gel beads may be manufactured out of propylene glycol alginate and bone gelatine and may have a diameter ranging from 200 microns to 5 mm.
  • Exemplary gel beads may contain iron powder particles (10-40 microns) or nanoparticles of iron (20-40 nm).
  • the gel beads may be manufactured by forcing a stream of gel through a nozzle which can be vibrated at a given frequency by ultrasound to control the dimensions of the gel beads, or for example, as described in the examples below.
  • inventive approach contemplates providing a plurality of the permeable vessels containing a plurality of entrapped metal particles inside a reactor.
  • system for production of hydrogen gas comprising: at least one reactor containing one or more of a permeable vessel containing a plurality of entrapped metal particles; the reactor having at least a first outlet for discharging generated hydrogen.
  • the reactor is configured for a continuous process, and further comprises a first inlet for flowing an acid into the reactor and a second outlet for egress of the acid.
  • system further comprises a pump in connection with the first inlet for pumping the acid into the reactor.
  • the reactor is a batch process reactor and is configured for an acid to be added to the reactor to cause hydrogen production.
  • the reactor further comprises an outer container in connection with the reactor, the outer container being enabled to flow a liquid (e.g. water) around the reactor for temperature control.
  • a liquid e.g. water
  • the inventive system may amount to the one or more permeable vessels containing the entrapped metal particles being housed in a reactor, and the reactor being housed in an outer container, the outer container being configured to permit the flow of water through it to provide temperature control of the reaction, and the reactor being, for example, a columnar container, such as a glass column, containing a plurality of the permeable vessel containing the entrapped metal particles.
  • the glass column may be thermo-jacketed for temperature control.
  • the reactor may be enabled for an acid to be flowed through it.
  • the entrapped metal particles will be under a hydrogen atmosphere since hydrogen is produced within the permeable vessels, ensuring reducing conditions around the metal particles.
  • Hydrogen diffuses rapidly into the fluid phase of the reactor (the fluid phase being the acid surrounding the permeable vessels), bubbles out of the reactor and is collected or used.
  • the acid for example, may be a dilute solution of a weak organic acid such as gluconic acid, and may be continuously passed through the reactor, while the hydrogen generated is collected from some point of egress out of the reactor, or used.
  • the buoyancy of hydrogen means it can pass out of the reactor quickly, such as by a point of egress at the top of the reactor, and be easily separated from the solution for subsequent storage, if desired.
  • the inventive approach provides for the continuous production of hydrogen gas in which the metal components are not consumed, because some of the hydrogen generated within the reducing environment of the entrapped metal particles results in the electrochemical reduction of the ionic metal products.
  • the metal is regenerated to be reusable or renewable.
  • the permeable vessel e.g. gel beads
  • a reducing environment produced by (for example) gluconic acid and the evolved hydrogen, slows down this oxidation process and results in yields of hydrogen from the metal and the acid. Stoichiometric (or even greater than stoichiometric) yields are possible.
  • the permeable vessel provides a form of enclosed environment which facilitates the reduction of the metal oxide.
  • the metal particles may be iron powder, for example, and upon passage through the reactor of an acid, such as for example a dilute solution of weak acids, such as gluconic and ethanoic acids, hydrogen is generated.
  • the (preferential) gel beads also offer a means of entrapping the metal particles, which can easily be recovered (after their use for extracting hydrogen from organic acids) by simple techniques such as sieving/filtration. At that stage, any oxidised metal particles not reduced during the regenerative process can be reduced back to their metal state, for re-use.
  • nanoparticles of metal e.g. iron
  • their entrapment within the permeable vessel e.g. gel bead
  • Metal nanoparticles by virtue of their extreme small size (hence large reactive surface area) and nature show an extreme susceptibility to oxidation and it is known that exposure to atmospheric air/oxygen can cause spontaneous combustion. Containing the metal particles within the permeable vessel (e.g. gel bead) prevents or greatly reduces the risk of this occurring.
  • permeable vessel e.g. gel bead
  • the reactor may be made of any dimensions to suit, and may be made of glass or any appropriate material that does not react with an organic acid.
  • the pH in the reactor may be neutral.
  • the temperature of the acid may be between 20 C and 80 C.
  • the acid may first be deaerated prior to being introduced into the reactor.
  • the hydrogen that evolves from the reactor may then either be stored or used immediately in a fuel cell application.
  • the amount of hydrogen generated may be made to depend upon the dimensions of the reactor, such as the dimensions of the cylindrical column.
  • a kit comprising a plurality of the permeable vessel described above, packaged.
  • the kit may a plurality of gel beads as described herein.
  • beads may be packaged in plastics (polythene) bags in air, in nitrogen or in carbon dioxide or under vacuum, at a minimum humidity. Such packaging prevents deterioration during storage.
  • Figure 1 - shows a diagram of a reactor system of the present invention.
  • Figure 2 - shows an exemplary gel bead producing apparatus in accordance with present invention.
  • Figure 3 - shows a photograph of exemplary 2 mm diameter gel beads containing iron particles.
  • Figure 4 - shows a photograph depicting the appearance of exemplary hydrated and dehydrated gel beads of the present invention.
  • Figure 5 - shows a graph of an exemplary hydrogen production in accordance with the present invention.
  • the electrochemical series for various metals shows the ability of certain metals to displace hydrogen from acid solutions.
  • the standard electrode potential (E 0 ) of a metal/metal ion combination is the emf measured when the metal/metal ion electrode is coupled to a hydrogen electrode under standard conditions.
  • Metals towards the top of the series are good reducing agents, donating electrons more easily to become positively charged metal ions, in which state they may for example form an oxide.
  • the reducing ability of a metal increases the higher up the series it is.
  • Metal ions at the bottom of the series are good electron acceptors, and are thus, good oxidising agents.
  • the oxidising ability of the metal ions increases the lower down the series they are.
  • the more negative the E° value the more the position of equilibrium lies to the left, or the more readily the metal loses electrons.
  • the more negative the value the stronger the reducing capability.
  • the more positive the E° value the more the position of equilibrium lies to the right, or, the less readily the metal loses electrons, and the more readily its ions accept electrons.
  • the metal iron (Fe) in water or a weak acid solution iron will lose electrons and go into solution as Fe ions.
  • the electrons will reduce protons formed by the dissociation of the acid, generating molecular hydrogen.
  • some electrons can remain attached to the metal, the metal is regenerated.
  • a dynamic equilibrium is established where the rate at which ions are formed is equal to the rate at which they are removed by reduction to the metallic state.
  • the redox potential (E) (in volts) measures the tendency of a substance to donate or accept electrons.
  • Example 1 Hydrogen production system Figure 1 shows an exemplary system (100) comprising reactor (101 ), suitable for hydrogen gas generation, surrounded by water jacket (102).
  • Reactor (101) contains propylene glycol bone gelatine gel beads (103) which enclose entrapped iron particles manufactured, as described below.
  • the volume of beads in the reactor will depend on the working volume of the reactor as will be understood by those skilled in the art.
  • the beads are held in place by two sintered discs (104) positioned at either end of reactor (101) providing a barrier plug for keeping the beads (103) in place in the reactor, but also optionally providing temperature insulation, and filtration of liquids.
  • fluid inlet means (105) for the introduction of acid
  • fluid outlet means (106) for egress of acid.
  • Water is circulated at a given temperature through jacket (102) surrounding reactor (101) via water inlet means (107) and water outlet means (108).
  • Gluconic acid is pumped into one end of the reactor (105) at a flow rate of 0.5 cm 3 min "1 and out of distal end of the reactor (106) using a peristaltic pump. This flow rate can be varied to provide optimal hydrogen production.
  • the concentration of gluconic acid can also be determined enzymatically.
  • Hydrogen gas exits the reactor from gas outlet (109) and is collected in a measuring vessel (by water displacement) from which the rate and amount of hydrogen gas production can be measured. The purity of the hydrogen is checked by GC/MS.
  • Reactor (101) can be built to any specifications depending on the hydrogen production requirement.
  • FIG 2 shows an exemplary bead producing apparatus (200) of the present invention.
  • Propylene glycol alginate, de-ionised bone gelatine, iron particles, glutaraldehyde, and mineral oil are all obtained commercially.
  • a suspension containing propylene glycol alginate (2%) bone gelatine (14.5%), and iron particles (10 microns or less) in water at 40 0 C is stirred in magnetic stirrer receptacle (201) until everything except the iron particles dissolves.
  • the viscous suspension is transferred to feed reservoir (202) and kept at 40 0 C, having air or nitrogen circulated via inlet (203).
  • Beads are formed by using 20 lb/in 2 of gas pressure (nitrogen) via pressure gauge (204) to force the viscous suspension along flexible tubing (205) and through a nozzle (206) (0.25-0.78 mm diameter) as discrete droplets which fall into magnetic stirrer bath (207) containing 500 cm 3 of mineral oil on the surface of 200 cm 3 of cold water, stirred by magnetic stirrer (208). Temperature control is via circulating fluids means (209). Flow of the viscous suspension via flexible tubing (205) is also controlled by sonic vibration transducer (210) and vibration frequency control (21 1). The volume of gel beads produced is dependent on the volume of the suspension.
  • the diameter of the beads ranges between 0.5 to 3.0 mm depending on the frequency at which the nozzle is vibrated which must also be tuned the velocity and fluid properties of the gel suspension.
  • the beads are removed from the oil/water interface and stored for 20 h at 23 0 C in
  • high intensity ultrasonic liquid processors may be used that atomize the liquid into micro-droplets whose median drop size can be 100 microns. The latter would be suitable for entrapment of nanoparticles of iron (20-40 nm).
  • Exemplary gel beads are shown in Figure 3.
  • Figure 4 shows an example of hydrated (Fig. 4a) and dehydrated gel beads (Fig. 4b).
  • the beads are made from materials such as carrageenan, alginates and gelatines which can be dehydrated for storage and transportation with subsequent rehydration. They may be packed into a tubular column made out of glass, although other corrosion resistant materials such as nickel alloys can be substituted for glass. Specific numbers of the beads can be made for the production of specific amounts of hydrogen for specific applications.
  • a working reactor may contain gel beads the diameter of which could range from 100 microns to 1 mm formed by high intensity ultrasonic liquid processors.
  • Exemplary gel beads with entrapped iron powder may have a particle size of 20 nm, 40 nm or 10-40 microns.
  • the gel beads contain aluminium powder.
  • the gel beads are placed into the reactor shown in Figure 1 until full and then the reactor is closed by means of the sintered discs. Water is then circulated around the reactor at a temperature of between 20 and 8O 0 C, and a 0.5M solution of gluconic acid solution is pumped into the reactor using a peristaltic pump at a flow rate of 0.5 cm 3 min "1 .
  • the gluconic acid solution may optionally be degassed. Prior to flowing the gluconic acid through the reactor, it may be deaerated using a vacuum that removes the dissolved gas in the liquid by decompression. This also helps to ensure that little or no oxygen comes into contact with the surface of the iron within the bead. However, because hydrogen diffuses at a faster rate than any other gas which helps to ensure the anaerobic conditions within the reactor.
  • oxidised iron is reduced in situ by the reducing atmosphere and the reducing potential of gluconic acid.
  • the gluconic acid solution permeates the gel beads and contacts the iron particles. Hydrogen gas is generated within the beads and diffuses out into the solution. The hydrogen gas exits the top of the reactor because of its buoyancy and is collected and stored or even used immediately in a fuel cell application. The solution leaving the bottom of the reactor may be stored for further processing or even returned to the reactor continuously until all the gluconic acid has been oxidised by the process.
  • the graph shown in Figure 5 illustrates a hydrogen production with respect to time, in which 3.5 g of entrapped iron inside the beads of the present invention are contacted with acid using a reactor configuration as exemplified in Figure 1 , by flowing 0.5 M gluconic acid at a pH of 1.86 and at a working temperature of 75°C over gel beads containing the entrapped iron. From the graph it can be seen that hydrogen production increases with time for a constant quantity of iron, without consumption of the iron metal.
  • the reaction may, for example, take place in a warmed environment of temperature of up to 80 0 C, at ambient pressure, and at neutral pH.
  • a solution of 1 M gluconic acid solution at pH 7.0 is pumped through the reactor at a flow rate of 1.0 cm 3 min ⁇ ', where the temperature of the water jacket is 4O 0 C.
  • the optimum rate of hydrogen production and the amount of hydrogen produced can be determined by water displacement and may be measured as a function of one or more of the following: 1. bead diameter; 2. size of iron particles; 3. temperature; 4. acid concentration;
  • An exemplary pH is that of the gluconic acid diluted with fresh water supplied to the laboratory, giving a pH of approximately 7.0.
  • a working reactor volume of a 2 cm diameter and 20 cm length glass cylinder (similar to that exemplified in Fig. 1) is 62.84 cm 3 .
  • Gel beads of diameter 2 mm (0.2 cm) with a volume of 0.0042 cm 3 per bead can fill 53% of the cylinder volume - the number of beads in the reactor will be approximately 7,930.
  • These beads will contain 2.51 g of iron powder particles, or 316.5 ⁇ g per bead.
  • a deaerated gluconic acid solution in water at a concentration of 0.5M and pH 7.0 is pumped through the reactor containing the beads at a flow rate of 0.5 cm 3 min ⁇ ' .
  • the thermojacket maintains the reactor and its contents at a constant temperature of 50 0 C.
  • Hydrogen is produced and collected in a measuring cylinder by water displacement. This allows the rate and amount of hydrogen production to be calculated, as follows: one mole of iron will generate 1 mol of hydrogen gas or 22.4 litres. Since the 0.5 M gluconic acid solution is the source of protons for the reduction by iron, approximately 0.13 litres of hydrogen (approximately 4 standard cubic feet (scf)) is generated by this reactor used in batch mode. IkW h is provided by 25-27 scf hydrogen.
  • a working reactor volume of 100 cm diameter and 1000 cm length cylinder is 7.855 x 10 6 cm 3 .
  • the number of beads filling this volume is 991 x 10 6 , containing 105 kg iron (1873.4 moles).
  • Approximately 1.9 x 10 3 moles of hydrogen gas is produced (in batch mode), or 42.6 x 10 3 litres of gas, or 1.28 x 10 6 scf of hydrogen (equivalent to 51 ,200 kW h)
  • the working reactor may be designed in order to produce a given volume of hydrogen gas for a given application and power requirement.
  • liquid media may be also introduced into the reactor, including, but not restricted to water, and sea water.
  • the produced hydrogen may for example, be stored for later use in cylinders under pressure or as a hydride, or for example, may be immediately used to provide electricity by a fuel cell, where the size of the reactor used will depend on the power output of the fuel cell.
  • Exemplary uses of the produced hydrogen include but are not limited to fuel cell applications for electricity (power) generation in transport, domestic and industrial heating systems.
  • a further exemplary use of the produced hydrogen is for combustion engines where hydrogen is burnt to provide engine power in lieu of gas or petrol, in automobiles and planes and trains and boats, space crafts, as public transport systems worldwide move toward hydrogen-powered engines as an alternative to petrol engines.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L’invention concerne un procédé de production d’hydrogène, qui comprend les étapes consistant à : i) fournir une ou plusieurs cuves perméables, la cuve perméable contenant une pluralité de particules métalliques piégées; ii) entraîner la perméation d’un acide dans la cuve perméable, les particules métalliques piégées réagissant avec l’acide pour générer de l’hydrogène, et les particules métalliques étant exposées à une atmosphère réductrice.
PCT/GB2009/000980 2008-04-15 2009-04-15 Production d’hydrogène Ceased WO2009127828A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0806810.8 2008-04-15
GB0806810A GB2459267A (en) 2008-04-15 2008-04-15 A method for producing hydrogen

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WO2009127828A2 true WO2009127828A2 (fr) 2009-10-22
WO2009127828A3 WO2009127828A3 (fr) 2009-12-10

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US20130167761A1 (en) * 2010-09-08 2013-07-04 Cor Brevis D.O.O. Fuel and combustible mixture used as a substitute for fossil fuels in thermoelectric power plants, industrial and central heating furnaces

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WO2021112778A1 (fr) * 2019-12-04 2021-06-10 Chitlig Enerji Uretim Ve Pazarlama A.S Méthode d'obtention de gaz hydrogène à partir de matériaux contenant de la chitine

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395252B1 (en) * 2000-09-29 2002-05-28 Ut-Battelle, Llc Method for the continuous production of hydrogen
US6645651B2 (en) * 2001-06-01 2003-11-11 Robert G. Hockaday Fuel generator with diffusion ampoules for fuel cells
JP2005243617A (ja) * 2004-01-28 2005-09-08 Kawaken Fine Chem Co Ltd 水素供給方法、その装置および携帯機器搭載用燃料電池
WO2006077256A1 (fr) * 2005-01-24 2006-07-27 Cinvention Ag Materiaux composites contenant du metal
US20060266159A1 (en) * 2005-05-25 2006-11-30 Hopkins P D Method and device for pure hydrogen generation from acidic solution
US8057939B2 (en) * 2005-12-06 2011-11-15 Honeywell International Inc. Electrical power generator
US20070217972A1 (en) * 2006-01-27 2007-09-20 Greenberg Daniel N Apparatus for production of hydrogen
US20100209338A1 (en) * 2007-09-05 2010-08-19 Takeshi Miki Hydrogen-generating material composition, hydrogen-generating material formed body, and method for producing hydrogen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102139859A (zh) * 2010-02-01 2011-08-03 无锡爱尼达新能源科技有限公司 一种自调式氢气发生器
US20130167761A1 (en) * 2010-09-08 2013-07-04 Cor Brevis D.O.O. Fuel and combustible mixture used as a substitute for fossil fuels in thermoelectric power plants, industrial and central heating furnaces

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