Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
  • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
  • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
• • 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
• • 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
  • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
  • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
  • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M2008/1095—Fuel cells with polymeric electrolytes
• • 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
  • Y02E60/32—Hydrogen storage
• • 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
• • 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
  • Y02E60/50—Fuel cells

Definitions

• Solid compounds, self-sustaining hydrogen generators comprising borazane and / or polyaminoborane and at least one inorganic oxidant; hydrogen generation process.
• the main subject of the present invention is solid compounds which generate, by self-sustained combustion, hydrogen and a process for generating hydrogen based on the combustion of said compounds.
• the present invention is in the field of hydrogen production, a gas widely used as fuel or reducer in many industrial processes and devices. Its main object is new solid compounds, decomposable by generating hydrogen, according to a self-sustaining combustion reaction. It also relates to the use of these novel compounds to thereby generate hydrogen, more particularly in a hydrogen supply context of proton exchange membrane fuel cells.
• the Applicant has already proposed compounds of this type: decomposable solid compounds by generating hydrogen according to a self-sustaining combustion reaction, after initiation of combustion by a suitable heat source. It has more particularly described such compounds in the patent applications FR 2 823 203, FR 2 845 376, FR 2 845 377 and FR 2 857 358. These compounds comprise in their composition an inorganic hydride and an inorganic oxidant; the inorganic qualifier meaning without carbon.
• an alkaline borohydride such as NaBH 4 or UBH 4 or an alkaline earth borohydride, such as Mg (BH 4 ) 2 ;
• an inorganic oxidant such as ammonium perchlorate (NH4CIO4), strontium nitrate (Sr (NOs) 2 ), ammonium nitrate (NH 4 NO 3 ) and ammonium dinitramine (DNA ) (NH 4 N (NO 2 ) 2 ).
• an inorganic oxidant such as ammonium perchlorate (NH4CIO4), strontium nitrate (Sr (NOs) 2 ), ammonium nitrate (NH 4 NO 3 ) and ammonium dinitramine (DNA ) (NH 4 N (NO 2 ) 2 ).
• the Applicant has shown that the combustion of such compounds generates hydrogen with a mass yield of up to 12%.
• US Pat. No. 4,157,927 discloses pellets consisting of an amino borane such as borazane NH 3 BH 3 or an aminoborane derivative (for example example, of formula H 2 B (NH 3 ) 2 X (where X is a halogen)) and a compound or mixture, such as LiAIH 4 or
• US Patent Application 2008/0035252 discloses a pyrotechnic charge containing borazane arranged in a borazane-based container.
• the polyaminoborane polymer with -H 2 BNH 2 - units, corresponds more exactly to the formula H 3 N- (H 2 BNH 2 ) X -BH 3 with x> . 2 (and can not be equated with diammoniate diborane according to FR 2 834 710, ionic complex obtained by reaction of ammonia (gaseous) and borane (gaseous)).
• the Applicant proposes new solid compounds, capable of generating (by self-sustaining combustion) hydrogen at an interesting rate.
• Said new solid compounds are all the more interesting because they are weakly hygroscopic, insensitive to mechanical attack and in that their combustion generates no or very few reactive and / or toxic residues (see the examples below).
• the present invention therefore relates to solid compounds capable of generating hydrogen according to a self-sustaining combustion reaction (that is to say solid compounds, decomposable by generating hydrogen in a self-sustaining combustion reaction, after initiation of this reaction by a suitable heat source (such a heat source intervenes only to initiate combustion).
• This inorganic oxidizing charge provides the self-sustaining combustion oxidation-reduction reaction.
• said compounds comprise, in their composition:
• At least one (inorganic) oxidant chosen from ammonium nitrate (NH 4 NOB), alkaline nitrates (such as potassium nitrate: KNO3), alkaline earth nitrates (such as magnesium nitrate: Mg (NOa)) 2 ), metal nitrates (such as strontium nitrate: Sr (NOa) 2 ), metal oxides (such as ferric oxide: Fe 2 ⁇ 3 , vanadium oxide: Va 2 O 5 ), oxidants of the family of dinitramines (such as ammonium dinitramine (DNA): NH 4 N (NO 2 ) 2 ), and mixtures thereof.
• NH 4 NOB ammonium nitrate
• alkaline nitrates such as potassium nitrate: KNO3
• alkaline earth nitrates such as magnesium nitrate: Mg (NOa)) 2
• metal nitrates such as strontium nitrate: Sr (
• said at least one inorganic oxidant (the nature of which is more particularly optimized with reference to the problem of the generation of harmful species), it is very advantageously chosen from;
• the aim is to minimize or avoid, during combustion, any formation of CO 2 , CO 2.
• the compounds of the invention are mainly constituted by constituent ingredients identified above, namely borazane and / or polyaminoborane, on the one hand, and said at least one inorganic oxidant, on the other hand; that is to say that said constituent ingredients are weighted majority.
• the compounds of the invention "only” consisting of said borazane and / or polyaminoborane and at least one inorganic oxidant are particularly preferred.
• Such additives may be commercial products.
• said borazane and / or said polyaminoborane and said at least one inorganic oxidant are very advantageously nearly 100% or even 100% by weight of the mass of the compound compounds.
• the solid compounds of the invention are compacted materials that have a given geometric shape.
• they are in the form of grains, pellets or blocks.
• Said grains, pellets or blocks have any shape, for example spherical, ovoid or cylindrical.
• the pellets may have a constant thickness or not and therefore any peripheral geometry, for example circular, elliptical, square or rectangular ...
• the grains generally have a mass of a few milligrams, the pellets a mass of a few tenths of grams to a few grams and the blocks a mass of a few tens of grams to a few hundred grams.
• the inventors have found that the compounds of the invention make it possible to reach a theoretical mass yield of hydrogen of 12%. Said yield can obviously advantageously be optimized according to the exact nature and the relative proportions of the constituents of said compounds.
• Such methods can be carried out dry or wet.
• a homogeneous mixture, granular or powdery, of the various constituents can it be, for example, agglomerated by compacting in a press pot, having the desired shape and size for the final compounds.
• the constituents in question can be put in solution and / or suspension in a liquid medium.
• the solution and / or suspension obtained is homogenized and placed in a mold of appropriate dimensions.
• the liquid is then removed, for example by evaporation; which leads, within said mold, to obtain a compact compound.
• the powder mixtures (comprising borazane and / or polyaminoborane, in powder form + at least one inorganic oxidant, in the pulverulent state), precursors of the compact compounds of the invention (starting material for the implementation of the methods by analogy mentioned above), constitute another object of the present invention.
• the mixtures in question are powdery solid compositions, precursors of the solid compounds of the invention, as described above.
• said powdery solid compositions contain borazane and / or polyaminoborane (in the form of powder) and at least one inorganic oxidant, advantageously of one of the types specified above (also in powder form). .
• the present invention also relates to a process for generating hydrogen, which comprises self-sustaining combustion of at least one solid compound.
• Said combustion process known per se, is typically carried out with at least one compound of the invention, as described above (compound whose composition contains borazane and / or polyaminoborane and at least one oxidant inorganic, advantageously of one of the types specified above).
• Said method generally comprises the following steps; firstly, a homogeneous, powdery or granular solid composition comprising said borazane and / or (advantageously or) said polyaminoborane and said at least one oxidizer;
• this composition is then agglomerated with appropriate means (according to a suitable method), for example those mentioned above, to form a compound in the form of a compact material; then
• the compact material (the compound) is placed in a combustion chamber which is purged under inert gas or under vacuum.
• a combustion chamber which is purged under inert gas or under vacuum.
• the combustion of the compact material (of the compound) is then initiated with the aid of a suitable heat source, which causes the self-sustaining combustion of the material with generation of hydrogen until the end of the combustion.
• a suitable heat source which causes the self-sustaining combustion of the material with generation of hydrogen until the end of the combustion.
• Suitable heat sources allowing the initiation of combustion by "Joule" effect are well known to those skilled in the art, in particular electrical initiators.
• the use of a nickel-chromium ignition filament, placed in contact or coated with the compound to be initiated, which is imposed a sufficient voltage and current intensity (therefore sufficient power), is perfectly suitable. It is possible, for example, for a given voltage, to increase the intensity of the current until the initiation of combustion.
• the above process generally comprises the preparation and combustion of several compounds.
• the hot gases generated by the self-sustaining combustion (of the compact material) of the at least one compound of the invention circulate through at least one additional charge containing borazane and / or or polyaminoborane, or only borazane and / or polyaminoborane.
• the thermal energy provided by said hot gases leads to the decomposition of said at least one additional charge which thus contributes to the production of hydrogen.
• a heat exchange is implemented between said hot gases and said at least one additional charge for the decomposition of said at least one additional charge.
• the process of the invention - a process for generating hydrogen comprising the combustion of the solid compounds described above - is advantageously used to supply hydrogen to a fuel cell.
• proton exchange membrane fuel Such a battery, familiar to those skilled in the art, comprises at least one electrochemical cell and a pyrotechnic hydrogen generator. In the context of the process of the invention, said generator has its operation based on the combustion of solid compounds of the invention.
• the method of the invention can quite be analyzed in terms of use of the compounds of the invention.
• the differential scanning calorimetry (“DSC”) analysis of the obtained aminoborane polymer shows a decomposition of said polymer between 373 K and 503 K (pic onset at 409 K).
• the polymer of the aminoborane of the invention had its mass increased by a factor of 1.2; rate much lower than that of NaBH 4 which sees its mass increased by a factor of 5.
• Sensitivity tests were carried out on powder beds of compound A of the present example. The results obtained are compared with those obtained with powder beds of a compound B of the prior art, comprising a mixture of 60% of NaBH 4 and 40% of Sr (NO 3 ) 2 (% by weight).
• Compound A of the invention is less sensitive to the impact sensitivity (***) and sensitivity to friction (****) tests than the compound B of the prior art.
• Sensitivity to impact The test carried out corresponds to that described in standard NF T 70-500, itself similar to UN test 3a) ii) resulting from "Recommendations on the Transport of Dangerous Goods" - Manual of Tests and Criteria, Fourth Revised Edition, ST / SG / AC.10 / ll / Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 ".
• the energy resulting in 50% (method of treatment of Bruceton results) of positive results of an explosive substance subjected to shocks of a sheep is determined.
• the material to be tested is confined in a steel device consisting of two rollers and a guide ring.
• the load is placed in a gas generator equipped with a pressure regulating valve, which makes it possible to maintain the pressure at a level sufficient to ensure the most complete combustion possible.
• a gas generator equipped with a pressure regulating valve, which makes it possible to maintain the pressure at a level sufficient to ensure the most complete combustion possible.
• This type of generator is described in particular in patent application EP 1 496 332.
• the generator delivers combustion gases to a tank provided with gas analysis means. In order not to generate other parasitic combustion species, ignition of the charge in the gas generator is achieved by means of a hot wire, welded across a sealed penetration.

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• 2008
  • 2008-04-16 FR FR0852540A patent/FR2930245B1/fr not_active Expired - Fee Related
• 2009
  • 2009-04-16 US US12/934,885 patent/US8562768B2/en not_active Expired - Fee Related
  • 2009-04-16 JP JP2011504515A patent/JP5473165B2/ja not_active Expired - Fee Related
  • 2009-04-16 KR KR1020107023070A patent/KR101620424B1/ko not_active IP Right Cessation
  • 2009-04-16 WO PCT/FR2009/050705 patent/WO2009138629A1/fr active Application Filing
  • 2009-04-16 EP EP09745948A patent/EP2265545A1/fr not_active Withdrawn

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