EP3980370A1 - Composition à base de poudre de silicium pour la production d'hydrogène - Google Patents
Composition à base de poudre de silicium pour la production d'hydrogèneInfo
- Publication number
- EP3980370A1 EP3980370A1 EP20743247.7A EP20743247A EP3980370A1 EP 3980370 A1 EP3980370 A1 EP 3980370A1 EP 20743247 A EP20743247 A EP 20743247A EP 3980370 A1 EP3980370 A1 EP 3980370A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- kit
- silicon
- water
- hydrogen
- composition according
- 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.)
- Pending
Links
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
- C01B3/08—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
-
- 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
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- 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 the field of hydrogen production.
- a system combining a fuel cell and hydrogen storage can provide up to 2 to 3 times the specific energy of a Li-ion battery.
- the density of hydrogen is very low (0.09 g / l) and requires storage in compressed or liquid form for its transport (with the exception of industrial uses of hydrogen which use pipelines). Under 700 bars, a volume of 38 liters is needed to store 1 kg of hydrogen, i.e. 26 kg fh / m 3 . The cost of high pressure storage remains high and the safety instructions with regard to such pressures are restrictive.
- Aluminum has been extensively studied due to its low stability in the presence of water and a high hydrogen mass / metal mass ratio.
- the authors of the present invention have developed a technique for using micrometric silicon powders which, associated with appropriate additives and in the presence of water, allows hydrogen to be produced instantaneously, with yields which can be reduced. equal to or greater than 85%, relative to the theoretical amount (1.6 liters of normal hydrogen / g Si).
- micrometric silicon powders have particles whose size is generally less than or equal to 150 microns and in particular less than or equal to 10 microns, depending on the standardization of the sieves. These silicon particles are naturally covered with oxide, whose thickness can reach 1.6 nm depending on storage conditions, temperature and humidity being determining factors ("Oxidation of Silicon powder in humid air", Thesis June 2012, Anne Marthe Nymark).
- the purity of silicon powders covers a broad spectrum, from 95% to 99.999%, and the cost of silicon of course depends on its purity, as on its method of obtaining.
- US Pat. No. 9,751,759 describes a process which consists in mixing nanoscale silicon powders which have been exceeded, according to specific criteria, and an alkaline agent soluble in water which, in contact with the latter, releases heat.
- micrometric silicon powders thus brought to nanometric size, requires complex equipment, solvents, operations carried out in the absence of air, and a significant expenditure of energy, with a benefit in terms of kinetics. hydrogen production and yield that is not clearly established.
- US patent application number US 2015/0321911 proposes a composition comprising a silicon powder, an alkaline substance which is a weak acid of an alkali metal (and which is therefore not strictly speaking an alkaline substance, etc.) and a precipitating agent, these compounds being present in defined proportions.
- the precipitating agent is an oxide and / or a hydroxide of calcium.
- the international application published under the number WO2018 / 037819 relates to a formulation intended to improve animal health, comprising silicon and optionally a pH adjuster (sodium bicarbonate, citric acid).
- US patent application number US 2012/199789 relates to a composition based on silica gel and a group I metal (alkalis).
- the US patent application published under the number US 2015/0266729 discloses a composition comprising non-passivated silicon, a dispersing agent, a dispersant and a colloidal stabilizer.
- a dispersing agent is cited a carbohydrate (monosaccharide, disaccharide, oligosaccharide and polysaccharide and an alcoholic sugar).
- the dispersant may be sodium or potassium hydroxide.
- a colloidal stabilizer a carboxylated or sulfonated organic polymer is cited.
- the present invention proposes an implementation which differs from the state of the prior art in that it allows a simplification and a reduction in the cost of the preparation processes, through the elimination of the stages of reduction of the silicon powders. nanometric size and / or surface silicon oxide pickling, and avoiding having to carry out any treatment step whatsoever in the absence of oxygen.
- the present invention thus relates to the preparation of compressed preparations based on micrometric silicon powder carried out without any particular precaution towards with respect to ambient air, these powders being intended for the production of hydrogen by reaction with water.
- the invention relates to a composition in accordance with the following point 1:
- composition intended for the production of hydrogen by decomposition of water, this composition being distinguished in that it comprises at least one additive chosen from cellulose derivatives.
- cellulose additive is chosen from methylcellulose, carboxymethylcellulose and its salts, hydroxypropylcellulose and hydroxypropylmethylcellulose.
- the invention relates to a kit in accordance with the following point 10:
- At least one corrosion agent preferably in solid form and soluble in water.
- the invention relates to a process for producing hydrogen in accordance with the following point 18:
- the present invention proposes the implementation of compressed preparations of silicon powder whose particle size is between 0 (excluded) and 150 microns (included), and preferably predominantly between 0 (excluded) and 50 microns (included) for better reactivity in the presence of water.
- the silicon powder is combined on the one hand with a corrosion agent which is an alkaline hydroxide such as potash, soda or ammonia (because ammonia is not a alkali metal hydroxide), and secondly to an agent inhibiting the spontaneous corrosion reaction of silicon by the corrosion agent.
- the corrosion agent is preferably potash or sodium hydroxide, and is preferably supplied in solid, powder or granular form.
- the three components are mixed thoroughly before compression to form a compressed preparation (preparation mode A).
- preparation mode B the corrosion agent used in the form of compressed powder and / or in the form of granules is implemented separately from the compressed preparation of silicon powder
- the corresponding preparations were carried out using a silicon powder supplied by the company Alfa Aesar, sieved at 40 microns, and granulated potash, which can be lightly ground.
- the implementation of the present invention does not require any particular treatment of silicon powders or alkali powders or granules: elimination steps of grinding the silicon powders, leading to reduce them to nanometric size, and / or of stripping the surface silicon oxide; no treatment in the absence of oxygen from the air.
- the alkali hydroxide in particular potash, it is not necessary to dehydrate it.
- Table 2 shows that the addition of 10% zinc oxide or 10% tin oxide to a compressed mixture of silicon and potash powders, which makes it possible to preserve preparation by simply placing it away from the air after its completion, makes possible its final use for the production of hydrogen with excellent yield.
- potash or sodium hydroxide leads to identical results, for various concentrations, ranging from 2 to 50% of the overall mass of the composition.
- oxides of aluminum in the gamma form
- lead or tin leads to similar results. However, for reasons of toxicity, it may appear preferable to avoid the use of lead.
- Another option is to separate the silicon powder and the corrosion agent, which eliminates any risk of reaction spontaneous, and makes it possible to simplify the method of preservation of preparations, which can be done in the open air.
- zinc oxide and quicklime provide improvements in the yield of hydrogen production of the order of 15 to 25%, but which remain very insufficient with regard to the industrial objectives of the process.
- the mixture of additives (ZnO + CaO) does not provide any particular improvement compared to the sole presence of ZnO or CaO, just as the mixture of additives (CMC + ZnO) does not improve the yield. in hydrogen.
- Quicklime acts as a thermal "booster" (stimulator).
- the inventors believe that it is probable that the action of CMC is largely due to its capacity to fix water, by forming a gel which stabilizes the emulsions, a property which will allow the corrosion reaction to continue despite the evolution of hydrogen and the consumption of water (reaction 1). More broadly, the polysaccharides, whether natural or semi-synthetic, fulfill the same function as that of the CMC used in the tests described above as examples of the present invention.
- hydrocolloids are hydrocolloids, many of which are used in the food industry.
- polysaccharides such as alginates, carrageenan and gum arabic
- cellulose derivatives methylcellulose, carboxymethylcellulose and its salts, hydroxypropylcellulose, hydroxypropylmethylcellulose, these compounds possibly being used alone or as a mixture.
- silicon powders in particular sieved at 40 microns, were placed in an oven at controlled temperature at 60 ° C., in an atmosphere saturated with water, for times which varied from 4:30 to 25 days. Under the same conditions as above, this silicon powder stored at 60 ° C. and 100% humidity is used to produce, with CMC powder, a first compressed preparation, stable in air.
- compositions forming the subject of the present invention are thus demonstrated, in which the silicon powder does not require a treatment for partial or total elimination of the passivation layer, even if this powder is strongly passivated. .
- the compositions based on silicon powders have been assembled in agglomerated form, which offers great convenience in handling, packaging, and final processing for the production of hydrogen by decomposition. some water.
- potash alone has been used in agglomerated form, for the same reasons of convenience.
- these compressed preparations may be found to be disintegrated when they are brought into contact with water for the production of hydrogen, which may in particular result from the characteristics of the mode of introduction of the compounds. reactants in the reactor or the choice of a finely metered feed by injection of powders.
Landscapes
- 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)
- Silicon Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1905976A FR3096981B1 (fr) | 2019-06-05 | 2019-06-05 | Composition à base de poudre de silicium pour la production d’hydrogène |
PCT/IB2020/055176 WO2020245720A1 (fr) | 2019-06-05 | 2020-06-01 | Composition à base de poudre de silicium pour la production d'hydrogène |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3980370A1 true EP3980370A1 (fr) | 2022-04-13 |
Family
ID=67957086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20743247.7A Pending EP3980370A1 (fr) | 2019-06-05 | 2020-06-01 | Composition à base de poudre de silicium pour la production d'hydrogène |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3980370A1 (fr) |
FR (1) | FR3096981B1 (fr) |
WO (1) | WO2020245720A1 (fr) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2658181B1 (fr) * | 1990-02-15 | 1992-06-19 | Federation Nationale Batiment | Fluide reactif regenerable de stockage d'energie, et installation de production et d'utilisation d'hydrogene mettant en óoeuvre un tel fluide. |
CN1906140B (zh) * | 2003-11-24 | 2011-02-23 | 迈克尔·莱芬费尔德 | 包含碱金属和碱金属合金的硅胶组合物 |
GB201217525D0 (en) * | 2012-10-01 | 2012-11-14 | Isis Innovation | Composition for hydrogen generation |
CN103508415B (zh) * | 2012-11-30 | 2015-05-20 | 太仓克莱普沙能源科技有限公司 | 用于产生氢气的硅粉体组合物、方法、反应器及装置 |
JP6916184B2 (ja) * | 2016-08-23 | 2021-08-11 | 株式会社Kit | 配合物の製造方法 |
GB2573493B (en) * | 2018-02-16 | 2021-04-07 | Water Lane 6 Sf Ltd | Hydrogen generation |
-
2019
- 2019-06-05 FR FR1905976A patent/FR3096981B1/fr active Active
-
2020
- 2020-06-01 WO PCT/IB2020/055176 patent/WO2020245720A1/fr unknown
- 2020-06-01 EP EP20743247.7A patent/EP3980370A1/fr active Pending
Also Published As
Publication number | Publication date |
---|---|
FR3096981B1 (fr) | 2023-02-24 |
FR3096981A1 (fr) | 2020-12-11 |
WO2020245720A1 (fr) | 2020-12-10 |
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