WO2006108769A1 - Reaction gaz-phase solide - Google Patents

Reaction gaz-phase solide Download PDF

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Publication number
WO2006108769A1
WO2006108769A1 PCT/EP2006/061238 EP2006061238W WO2006108769A1 WO 2006108769 A1 WO2006108769 A1 WO 2006108769A1 EP 2006061238 W EP2006061238 W EP 2006061238W WO 2006108769 A1 WO2006108769 A1 WO 2006108769A1
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WO
WIPO (PCT)
Prior art keywords
reaction
reactor
hydrogen
metal oxide
energy
Prior art date
Application number
PCT/EP2006/061238
Other languages
German (de)
English (en)
Inventor
Martin Roeb
Christian Sattler
Peter-Michael Rietbrock
Ruth KÜSTER
Athanasios G. Konstandopoulos
Christos Agrafiotis
Lamark De Oliveira
Mark Schmitz
Original Assignee
Deutsches Zentrum für Luft- und Raumfahrt e. V.
Chemical Process Engineering Research Institute Center For Research And Technology-Hellas (Certh/Cperi)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102005017216A external-priority patent/DE102005017216A1/de
Application filed by Deutsches Zentrum für Luft- und Raumfahrt e. V., Chemical Process Engineering Research Institute Center For Research And Technology-Hellas (Certh/Cperi) filed Critical Deutsches Zentrum für Luft- und Raumfahrt e. V.
Priority to CA2608085A priority Critical patent/CA2608085C/fr
Priority to US11/918,359 priority patent/US20090028783A1/en
Publication of WO2006108769A1 publication Critical patent/WO2006108769A1/fr
Priority to US13/011,667 priority patent/US9492807B2/en
Priority to US15/286,066 priority patent/US20170021321A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/061—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 by reaction of metal oxides with water
    • C01B3/063—Cyclic methods
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/127—Sunlight; Visible light
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00038—Processes in parallel
    • 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 invention relates to a method and a reactor for the quasi-continuous performance of a chemical reaction on a surface of a fixed reaction partner in a gas-solid phase reaction. More particularly, the invention relates to a thermal process and a reactor for continuously producing hydrogen from water vapor on a surface of a metal oxide in a gas-solid phase reaction.
  • JP 03205302 A describes the production of high-purity hydrogen by means of activated magnetite as a reactive catalyst.
  • JP 2001270701 A is hydrogen is prepared by reacting metallic zinc, magnetite and water are reacted at 600 0 C.
  • Reaction chamber system can be performed in which no solid has to be separated and runs quasi-continuously at the lowest possible temperatures.
  • Another object is to provide a solar powered reactor in which a product (especially hydrogen) is continuously produced although at least two process stages (eg, cleavage and regeneration) are necessarily sequential.
  • the object of the present invention is in particular to provide a corresponding process for the production of hydrogen, which can be carried out in particular in at least one single reaction chamber.
  • This object of the invention is achieved in a first embodiment by a method for quasi-continuous Carrying out a chemical reaction consisting of at least two sequential reversible steps, characterized in that at least two reaction chambers are operated in parallel, in each of which at least one reaction partner is fixed locally, wherein cyclically alternating reaction conditions in the reaction chambers.
  • Sequential steps in the sense of the invention are successive reaction steps of a chemical reaction in which the reaction products can be isolated.
  • Reversible steps in the sense of the invention are reaction steps in which the chemical equilibrium can be adjusted so that either the forward or the backward reaction preferably proceeds preferentially.
  • a chemical reaction within the meaning of the invention is in principle any chemical reaction in which one of the reactants is fixed and in which the energy is supplied as heat energy, light energy, nuclear energy or in the form of other electromagnetic radiation.
  • the process according to the invention is preferably used in the following reaction types listed by way of example:
  • Me is a metal atom
  • X is a halogen or pseudohalogen
  • subscripts n, m, x or y are integer positive numbers.
  • the different sequential reaction steps can have a different reaction time, for optimum utilization of the reaction chambers it is advantageously possible to differentiate a) the energy input in the reaction chambers for adjusting the reaction rate, b) adapt the mass flow of the reactants, and / or c) number the reaction chambers are adjusted according to the reaction times in which the reactions proceed correspondingly time-delayed.
  • FIG. 1 shows, as in the case of two reaction steps, in which the second reaction step lasts twice as long as the first reaction step, with three reaction chambers a quasi-continuous process according to the invention can be operated.
  • reaction steps of the chemical reaction are carried out sequentially in the same reaction chambers. Separation or isolation of intermediates can thus be omitted.
  • radiation-heated reactors are used as reaction chambers.
  • thermal reactions can be carried out with light energy.
  • any electromagnetic radiation can be used.
  • photoreactions can advantageously also take place when carrying out the process.
  • thermal reactions can also take place according to the invention, in particular photoassisted.
  • Photo assisted according to the invention means that the reaction product is formed reinforced by a photoreaction.
  • the cyclically alternating reaction conditions are preferably set by a cyclic change in the temperature of the reaction chambers, for example by varying the heat output.
  • the required temperature in the reaction chambers is varied by a cyclical change of the heating power, thus enabling a quasi-continuous product flow.
  • the different thermal control of the reactors allows, for example, the simultaneous reaction of the water splitting at a lower temperature and the regeneration at a higher temperature. The juxtaposition of these different batch processes thus ensures, for example, a quasi-continuous hydrogen production.
  • the process is carried out in several successive cycles quasi-continuous reproducible.
  • One cycle for example, takes a period of time in one area from 0.3 to 1.5 h, especially 0.3 to 1 h. Above all, this has economic advantages over a discontinuous process. However, depending on the reaction to be carried out, the cycles may also be considerably shorter or even longer.
  • the absorbed energy of the optical component is used to heat fluids.
  • These fluids can be, inter alia, reactants, auxiliaries or heat transfer media. With the preheating the fluids no longer need as much radiant power in the reactor space.
  • the optical component is a tube bundle, which is flowed through by the fluid.
  • the required temperature may preferably be generated by combustion of fossil energy and / or use of electrical energy, because common methods use these energy sources. Also advantageous is the generation of the required temperature by nuclear energy, since in nuclear reactions only about one third of the heat generated in the reactor can be used to generate electricity. The resulting (residual) heat can be used to generate the required temperature. On a large scale, no climate-damaging emissions of CO2 are produced here.
  • the energy input advantageously takes place by means of light energy and in particular by concentrated solar radiation, since this energy source is available in a particularly cost-effective manner and is suitable both for thermal and likewise for photoreactions.
  • the generation of the required temperature by means of light energy is advantageous because conventional power generation systems by burning fossil energy are not as resource efficient as the inventive method and light energy such as sunlight is available worldwide.
  • sunlight can radiate into the reaction chamber in order to generate the required temperature.
  • optical arrangements have particularly preferred forms such as solar tower systems, paraboloid concentrators, solar ovens, elliptical or spherical mirrors, or line focusing concentrators.
  • solar-thermochemical water splitting hydrogen can be produced as a possible energy carrier of the future without climate-damaging emission of carbon dioxide on an industrial scale.
  • the required radiation power is preferably achieved by a group of heliostats and the radiation power required for regeneration is achieved by another group of heliostats, the focus of the second group being switched to the individual reaction fields.
  • the heliostat data field is separated such that at least one group of heliostat covers the base load of necessary radiation power corresponding to the reaction step with the lowest energy requirement by "regular" the daily routine of the sun is tracked, and that at least one group of heliostats additional loads of necessary radiation power for reaction steps with higher energy requirements by the focus of this group is directed at certain intervals after each step of the reaction to another area of the radiation receiver.
  • two different reaction temperatures can be easily realized.
  • the reaction chambers can therefore preferably be variable relative to the optical arrangement in order to vary the heating power.
  • a change of the temperature with the same radiant power can take place uncomplicatedly.
  • optical components to reduce the Exposure.
  • optical components particularly suitable for this purpose are spatially displaceable or, with regard to their transparency, optical attenuators, diaphragms, deflecting mirrors or filters.
  • this can advantageously be achieved by varying the focus position as a result of a change in the orientation of mirrors or mirror fields, so-called heliostat fields. This is much easier to implement than the displacement of the usually very heavy reactor.
  • the temperatures used may also differ significantly.
  • the fixed reactant in both reaction chambers is advantageously selected from the group of metal hydrides, dyes, chemical compounds with redox properties, and complexing agents.
  • Chemical compounds with redox properties in the context of the invention are those compounds which can be reversibly oxidized and reduced.
  • these chemical compounds having redox properties are selected from the group of metal oxides, mixed metal oxides and / or doped metal oxides.
  • metal oxides have been found to be particularly advantageous since they are most versatile applicable and can be particularly easily fixed, for example, in contrast to metal hydrides.
  • Multivalent in the context of the invention is a metal oxide which has several oxidation states next to one another and in particular when the metal is present in an oxidation state greater than + 1, in particular greater than +2.
  • the metal oxides preferably comprise ferrites and / or zinc oxides and / or manganese oxides and / or ceric oxides and / or lanthanum oxides and / or other lanthanide oxides and / or oxides of the general formula Me x 2+ Zni- X 2+ Fe 2 O 4 , where Me x 2 + a bivalent metal ion selected from the group Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, Sr, Sn, Ba, Cd or Pb, and / or mixtures of these oxides or oxides of the general formula Me' ⁇ Me " i - x FeO, where Me 'and Me "are metal ions selected from the group consisting of Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, Sr, Sn, Ba, Cd, Pb or lanthanides, since these are particularly efficient at the hydrogen cleavage can be used, wherein x is a number in a range of 1 to 5,
  • the chemical compound having redox properties is used as a coating of a heat-resistant, particularly preferred ceramic support structure.
  • a Carrier structure the chemical compound with redox properties must be present only in a thin layer in the reaction chambers.
  • a support structure with a conical, hemispherical or paraboloidal shape, as this allows optimum utilization of scattered radiation from the radiation source in the reaction chamber.
  • At least one of the mobile reactants is advantageously selected from the group consisting of water, alcohols, carbon dioxide, hydrogen sulfide, nitrogen oxides,
  • Hydrocarbons, halogen or pseudohalides, ammonia and sulfur oxides are particularly advantageous because it is readily available and, especially in the gas phase, an easy-to-handle reactant.
  • the object underlying the invention is therefore achieved by a process for the production of hydrogen from water vapor on a surface of at least one chemical compound with redox properties, wherein in the first step, water vapor thermally cleaves by the addition of oxygen to the excited chemical compound with redox properties and releasing hydrogen and, in a second step, at a higher temperature than the first step, regenerating the chemical compound having redox properties and releasing bound oxygen.
  • the invention can thus relate to a method of thermally splitting water vapor in a multi-stage process by using concentrated radiation and consequently of generating solar hydrogen.
  • water vapor can be thermally split by concentrated sunlight, thereby generating hydrogen.
  • direct thermal splitting of water which takes place only at a few thousand degrees Celsius, is preferably produced here in a two stage cycle process at temperatures in a range from 800 0 C to 1200 0 C hydrogen from water vapor.
  • a metal oxide system which can split off oxygen from water molecules and reversibly integrate it into its crystal structure is circulated.
  • the hot steam flowing past the metal oxide is split by bonding the oxygen to the excited metal oxide grid at temperatures preferably in a range of 500 to 1000 ° C., in particular 550 to 850 ° C., and liberates hydrogen.
  • the oxygen previously introduced into the grid is released again and the metal oxide is regenerated or reduced again to the more energetic state.
  • These temperatures are preferably for ferrites or mixed iron oxides.
  • the reaction temperature can advantageously be in the range from 600 ° C. to 800 ° C. and the regeneration temperature in the range from 900 to 1200 ° C. All in all, water is split into its elements with the help of the metal oxide.
  • the metal oxides used are advantageously mixed oxides, particularly preferably zinc-doped ferrites.
  • An important innovation of the process is the advantageous combination of a ceramic carrier and absorber structure, which can be heated to high temperatures with concentrated solar radiation, with a redox system capable of reversibly splitting water, for example.
  • a redox system capable of reversibly splitting water, for example.
  • porous honeycomb structures which function as radiation absorbers, with ferrites coated.
  • the ceramic structure coated with metal oxide advantageously forms the core in a receiver reactor.
  • a concentrating solar system preferably a solar tower
  • the structure is brought by the incident concentrated solar radiation to the necessary temperature.
  • the reactions take place on the surface of the coated ceramic.
  • the reactor is preferably integrated into a small system for checking and optimizing the operating behavior during water splitting or regeneration.
  • This system preferably includes valves and mass flow controllers for supplying the required gases, a water vapor dosing system, pressure and temperature measuring systems, product gas treatment, as well as data acquisition and control.
  • the analysis of the concentrations of hydrogen produced or of released oxygen is preferably carried out by a mass spectrometer. For efficient use of the reactor, it is preferably required that continued operation to produce the product hydrogen may occur. Since two reactions are to be carried out with different conditions, a cyclic change of the reaction conditions or gases as well as the required energy (temperature) must take place.
  • the lower temperature range is easier to handle in terms of materials and processes, and considerably reduces the costs of the process.
  • the object underlying the invention is therefore preferably achieved by a process for the quasi-continuous production of hydrogen from water vapor on a surface of a metal oxide and subsequent regeneration of the surface.
  • the hydrogen synthesis by water splitting and in another reactor the regeneration of the metal oxide take place.
  • the regenerated reaction chamber can then absorb new reactants again.
  • hydrogen can be produced continuously and simply thermally compared to the prior art.
  • the object underlying the invention is achieved in a further embodiment by a thermal process for producing hydrogen from water vapor on a surface of a metal oxide in a gas-solid phase reaction, wherein in a reaction chamber in the first step, water vapor by the addition of oxygen to the excited metal oxide is thermally split, hydrogen is released and regenerated in a second step at a temperature higher than the first step, the metal oxide and bound oxygen is released, so that the metal oxide is available for further reactions.
  • the invention thus relates to a method of thermally splitting water vapor in a multi-stage process by using concentrated radiation and consequently to produce solar hydrogen.
  • the object underlying the invention is achieved by a photoreactor for carrying out the method according to the invention, characterized in that it has two reaction chambers.
  • the object underlying the invention is achieved by a radiation-heated reactor for carrying out the method according to the invention, characterized in that it has at least two reaction chambers.
  • This is preferably a reactor for the thermal production of hydrogen from water vapor on a surface in a gas-solid phase reaction with at least one connected tube, which allows a gas flow of educt gases into a reaction chamber and product gases out and a heat source, wherein metal oxide in a reaction chamber is provided as a reactant (or reactant).
  • the metal oxide is coated on a heat-resistant ceramic support structure.
  • This fixation has the advantage that the metal oxide is always available and can be optimally exposed in the reactor of the heat source. Fixing the metal oxide on the support structure does not require laborious recovery of the metal oxide via separation processes.
  • the heat required for the reactions can also be supplied from the support structure.
  • the ceramic support structure consists of a porous honeycomb structure, because porous ceramic honeycomb structures have been found to be particularly resistant to heat. Pores in the sense of this invention are the spaces provided by the honeycomb structure. This does not exclude that the material per se advantageously itself has a porosity in a range of 10 to 60%. The porosity is given by the weight ratio of the actual weight to the weight assuming the theoretical maximum density.
  • the ceramic support structure is conical, hemispherical or paraboloid-shaped in order to capture the radiation optimally on the metal oxide.
  • edge radiation can also be captured better.
  • the reaction chamber is advantageously equipped with a transparent window, since in this way the light source can be arranged outside the actual reactor.
  • reaction chamber run between the reaction chamber and energy source tubes that attenuate the flow of energy, as this allows a better control of the reaction is possible.
  • the tubes contain a fluid, as a result, the heat exchange can be adjusted individually.
  • the reactor is advantageously provided with a multi-way valve to allow the supply of the gaseous reactants.
  • the multi-way valve is designed so that the gaseous products can be removed separately.
  • the reactor is advantageously constructed modularly from at least two reaction chambers, since this makes it possible to implement the above-described quasi-continuous process particularly easily.
  • both reaction chambers are alternately supplied with steam or inert gas, in particular nitrogen, wherein the circuit is effected so that a time constant hydrogen production takes place.
  • the energy source used is a concentrating solar thermal system such as a solar tower system, a paraboloid concentrator, a solar furnace, an elliptical or spherical mirror or a line-focusing concentrator.
  • the required radiation power is achieved by a group of heliostats and the radiation power required for regeneration is achieved by another group of heliostats, the focus of the second group being switched to the individual reaction fields.
  • the inventive method of solar-thermochemical water splitting based on metal oxide for continuous hydrogen production can be carried out continuously with the aid of the design of a suitable receiver reactor described here.
  • Fig. 1 is a schematic representation of the timing of various reactions in different reaction chambers in the quasi-continuous process according to the invention.
  • 2 is a perspective schematic representation (vertical horizontal section) of the continuous reactor according to the invention.
  • Fig. 4 is an illustration of the heat-resistant four-way valve in the reactor.
  • FIG. 2 shows the receiver reactor, with the concentrated solar radiation falling from the right side onto the aperture with quartz windows (FIG. 1).
  • the power of the incident light can be adjusted by a shutter.
  • the receiver reactor is based on the already described compound of the metal oxide redox system with a carrier and absorber structure consisting of a ceramic monolith with a honeycomb structure (2).
  • the monolith is coated with the metal oxide and installed in a cylindrical housing (3).
  • the honeycomb structure enables the generation of high temperatures with low re-radiation losses in a directly absorbing receiver.
  • the reactor consists of a modular two-component system of permanently installed honeycomb absorbers. Two adjacent but separate reaction chambers form a minimal array of modules for the continuous production of hydrogen.
  • the square aperture (1) allows the formation of large and flexible receiver areas by juxtaposing individual modules.
  • a double tube is provided for preheating the supplied gases nitrogen and water vapor by recovering the heat of the product gas (4).
  • the operation of the Konti reactor is based on the simultaneous use of both modules. While in one of the reaction chambers water is split, the regeneration takes place in the other. After completion of the reactions, changing the gas supply, the regenerated module is switched to splitting and vice versa.
  • a prerequisite for this continuous operation and the production of hydrogen is the separate supply of nitrogen gas, which is used as a carrier gas or purge gas, as well as water vapor (6).
  • separate lines for the products of the cleavage on the one hand and for the oxygen-containing purge gas regeneration on the other hand necessary (7). This is made possible by four-way valves (5 or 5a), which are each switched after completion of a reaction step.
  • One of these valves (5) has to withstand high temperatures up to 600 ° C.
  • Fig. 4 shows the positions of this valve.
  • the two steps of the process are carried out in the same reactor at different temperature levels with different heat requirements.
  • the regeneration is endothermic and advantageously proceeds in a temperature range of 1100 to 1200 0 C.
  • the water vapor cleavage is slightly exothermic and takes place at 800 0 C. Therefore, some of the modules (regeneration) require a higher solar flux density than the second part for water splitting, which requires little energy to compensate for heat losses. Thus, a cyclic change in irradiance is required when the cycle is switched from regeneration to cleavage or vice versa.
  • For a change of the mirror focus between two identical focal points is provided by a suitable adjustment of the concentrating mirror of the solar system.
  • the periodic change in the irradiance is achieved by time-varying optical components, for example optical gratings as attenuators, deflecting mirrors or semitransparent mirrors. Such a component is movable and located in front of one of the two apertures. When changing the supplied gas whose position can be switched accordingly. Equally possible, but technically more complex is a temporal change in the receiver position between locations of different irradiation intensity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

Procédé et réacteur permettant l'exécution en quasi-continu d'une réaction chimique sur la surface d'un réactif fixé lors d'une réaction gaz-phase solide. La présente invention concerne en particulier un procédé thermique et un réacteur pour la production en continu d'hydrogène à partir de vapeur d'eau sur la surface d'un oxyde métallique lors d'une réaction gaz-phase solide.
PCT/EP2006/061238 2005-04-14 2006-03-31 Reaction gaz-phase solide WO2006108769A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA2608085A CA2608085C (fr) 2005-04-14 2006-03-31 Reaction en phase gaz-solide
US11/918,359 US20090028783A1 (en) 2005-04-14 2006-03-31 Gas/solid phase reaction
US13/011,667 US9492807B2 (en) 2005-04-14 2011-01-21 Gas/solid phase reaction
US15/286,066 US20170021321A1 (en) 2005-04-14 2016-10-05 Gas-solid reactor

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102005017216A DE102005017216A1 (de) 2005-04-14 2005-04-14 Thermische Wasserstoffherstellung in einer Gas-Festphasenreaktion
DE102005017216.4 2005-04-14
EP05106614.0 2005-07-19
EP05106614.0A EP1712517B1 (fr) 2005-04-14 2005-07-19 Réaction entre un gaz et une phase solide

Publications (1)

Publication Number Publication Date
WO2006108769A1 true WO2006108769A1 (fr) 2006-10-19

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PCT/EP2006/061238 WO2006108769A1 (fr) 2005-04-14 2006-03-31 Reaction gaz-phase solide

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CA (1) CA2608085C (fr)
WO (1) WO2006108769A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009141549A1 (fr) * 2008-05-20 2009-11-26 Commissariat A L'energie Atomique Systeme de production autonome d'hydrogene pour un systeme embarque

Citations (3)

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Publication number Priority date Publication date Assignee Title
FR926020A (fr) * 1942-02-27 1947-09-19 Standard Oil Dev Co Production d'hydrogène
DE2649164A1 (de) * 1975-11-04 1977-05-12 Comp Generale Electricite Verfahren zur erzeugung von wasserstoff aus wasser
US6291686B1 (en) * 1997-10-01 2001-09-18 Imperial Chemical Industries Plc Exothermic process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR926020A (fr) * 1942-02-27 1947-09-19 Standard Oil Dev Co Production d'hydrogène
DE2649164A1 (de) * 1975-11-04 1977-05-12 Comp Generale Electricite Verfahren zur erzeugung von wasserstoff aus wasser
US6291686B1 (en) * 1997-10-01 2001-09-18 Imperial Chemical Industries Plc Exothermic process

Non-Patent Citations (3)

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Title
AGRAFIOTIS ET AL: "Solar water splitting for hydrogen production with monolithic reactors", SOLAR ENERGY, PERGAMON PRESS. OXFORD, GB, vol. 79, no. 4, October 2005 (2005-10-01), pages 409 - 421, XP005082271, ISSN: 0038-092X *
KODAMA T ET AL: "Thermochemical hydrogen production by a redox system of ZrO2-supported Co(II)-ferrite", SOLAR ENERGY, PERGAMON PRESS. OXFORD, GB, vol. 78, no. 5, May 2005 (2005-05-01), pages 623 - 631, XP004852079, ISSN: 0038-092X *
TAMAURA Y ET AL: "Oxygen-releasing step of ZnFe2O4/(ZnO+Fe3O4)-system in air using concentrated solar energy for solar hydrogen production", SOLAR ENERGY, PERGAMON PRESS. OXFORD, GB, vol. 78, no. 5, May 2005 (2005-05-01), pages 616 - 622, XP004852078, ISSN: 0038-092X *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009141549A1 (fr) * 2008-05-20 2009-11-26 Commissariat A L'energie Atomique Systeme de production autonome d'hydrogene pour un systeme embarque
FR2931471A1 (fr) * 2008-05-20 2009-11-27 Commissariat Energie Atomique Systeme de production autonome d'hydrogene pour un systeme embarque
CN102036910A (zh) * 2008-05-20 2011-04-27 原子能与替代能源委员会 机动系统用自主制氢系统
CN102036910B (zh) * 2008-05-20 2013-12-18 原子能与替代能源委员会 机动系统用自主制氢系统

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CA2608085A1 (fr) 2006-10-19
CA2608085C (fr) 2015-02-03

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