GB2491355A - Metal and sodium hydr(oxide) composite powder for hydrogen generation - Google Patents
Metal and sodium hydr(oxide) composite powder for hydrogen generation Download PDFInfo
- Publication number
- GB2491355A GB2491355A GB1109036.2A GB201109036A GB2491355A GB 2491355 A GB2491355 A GB 2491355A GB 201109036 A GB201109036 A GB 201109036A GB 2491355 A GB2491355 A GB 2491355A
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- GB
- United Kingdom
- Prior art keywords
- composite material
- hydrogen
- water
- metal
- salt
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 70
- 239000001257 hydrogen Substances 0.000 title claims abstract description 70
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 title claims abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims description 5
- 239000011734 sodium Substances 0.000 title claims description 5
- 229910052708 sodium Inorganic materials 0.000 title claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- 239000004411 aluminium Substances 0.000 claims abstract description 32
- 239000000446 fuel Substances 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 6
- 239000004291 sulphur dioxide Substances 0.000 claims abstract description 6
- 235000010269 sulphur dioxide Nutrition 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001311 chemical methods and process Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000012255 powdered metal Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000005057 refrigeration Methods 0.000 claims 2
- 235000012054 meals Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 230000006641 stabilisation Effects 0.000 description 9
- 238000011105 stabilization Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000003388 sodium compounds Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000009718 spray deposition Methods 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010944 pre-mature reactiony Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019443 NaSi Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000008713 feedback mechanism Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012354 overpressurization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
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
-
- 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
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)
- Fuel Cell (AREA)
Abstract
A composite material is used for the generation of hydrogen gas from water in an exothermic reaction. The composite material is a powder form of a metal, such as aluminium, along with sodium oxide or sodium hydroxide. The composite material powder is exposed to an acidic gas, such as hydrogen chloride or sulphur dioxide. The acidic gas allows the alkali component of the composite material powder to be coated with a layer of salt, which salt is inert to aluminium and soluble in water. Once the composite material is exposed to water and the soluble layer of salt is dissolved, the exothermic reaction between the composite material and the water allows for the generation of low pressure hydrogen gas. A hydrogen generator adapted to use a composite material and water to generate hydrogen comprises a reaction chamber and preferably a thermal engine, a fuel cell and a cartridge system to contain the composite material.
Description
ENERGY POWDER MATERIAL FOR HYDROGEN GENERATION
Technical field of invention
The present invention relates to a composite material for use in Hydrogen generator units, for example to Hydrogen generator units suitable for use in Hydrogen fuelling systems for fuel cells and internal combustion engine standalone energy systems.
Moreover, the invention relates to methods of using the aforesaid composite material for generating Hydrogen gas and the manufacture of the composite material.
Background to the invention
Hydrogen is a well known energy vector which has many practical uses within the chemical and energy industrial sectors. These practical uses require Hydrogen to be generated from chemically rich compounds containing Hydrogen via one or more process steps, for example steam reformation of methane and other hydrocarbon fuels or via electrolysis of water. Hydrogen generated from aforesaid one or more process steps can be utilized to fuel numerous applications: (i) for vehicle propulsion; (ii) for fuel for micro energy system (battery replacements); and (iii) for emergency power supply systems.
In portable applications, one or more additional process steps are required after Hydrogen generation in respect of Hydrogen storage and transport. As the lightest know element) Hydrogen often requires extensive external equipment and energy input to achieve practical energy densities appropriate for use in transportation or portable systems market for Hydrogen units. Often bulky, high pressure tanks limit the application of Hydrogen in vehicle propulsion systems.
In an alternative approach for achieving high densities of Hydrogen storage, Hydrogen is often stored within a metal hydride wherein Hydrogen molecules are disassociated into individual hydrogen atoms that are able to absorb or dissolve into a metal phase. It is also often required to add heat to recover all of the stored hydrogen. In a yet further approach, Hydrogen is stored cryogenically as liquid Hydrogen, or at a high pressure in gaseous form, for example in vehicle applications.
Further liquid hydrogen needs to be maintained at temperatures not exceeding -253°C to prevent boiling.
In the case of contemporary fuel cell or Hydrogen internal combustion powered vehicles, Hydrogen is commonly stored at pressures of up to 7OMPA, for example within specially prepared composite Aluminium and Carbon fibre tanks. High pressure storage is required primarily to give comparable energy densities to that of existing hydrocarbon liquid or gaseous fuels.
It is known to employ metallic composite materials to generate Hydrogen through reaction with water. In a United States patent no. U53957483 issued on 18 May 1976 to M. Suzuki, it is disclosed how a Magnesium composition is utilized for producing Hydrogen. This document elucidates that the presence of one or more compounds selected from the group consisting of Sodium Chloride (NaCI), Potassium Chloride (KCI) and various similar metal salts leads to an increase in a quantity of Hydrogen gas generated. This type of solution allows for somewhat more convenient handling of the composite prior to use in a reaction to generate Hydrogen gas.
Similarly, in a United States patent no. US 6506360, there is described a system which utilizes a reaction of Aluminum with water in the presence of Sodium Hydroxide as a catalyst. The system uses a pressure and a temperature of the reaction to control a degree of immersion of a fuel cartridge in water and consequently to control a vigor and a duration of the reaction. The fuel cartridge exemplified has a volume of about I liter, contains about 500 ml of Magnesium composition, and is submersed in 10 liters of water for allowing for 2 hours of Hydrogen gas generation which is sufficient for cooking food on a burner plate. A control of the temperature of the water and a degree of immersion of the fuel cartridge in the water can become complicated if utilization in any type of portable solution is intended. The disclosed approach requires complex handling and is costly as temperatures and environments need to be controlled.
Additional United States patent nos. US 5143047, US 5494538, US 4600661, US4072514, US 4064226, US 3985865, and generation of Hydrogen gas in an uncontrolled manner in systems comprising mixtures of alkali or alkali earth metals and/or Aluminum and water or aqueous salt solutions. These processes all experience a common problem of highly reactive systems and solutions, as well as alkaline residues with high pH values and consequent difficulty associated with their disposal. In a Japanese patent no. JP 1061301 an Aluminium-ceramic composite has been proposed to initiate the water splitting reaction, the ceramic comprises calcined dolomite, namely Calcium/Magnesium oxide. Once contacted with water, these oxides cause a very substantial increase in the pH, which stimulates corrosion of Aluminium with accompanying release of Hydrogen. The system has all the disadvantages of the water splitting reaction using alkaline metals, namely very highly reactive materials alkalinity and difficult recyclability of generated reaction products. In a United States patent no. US 4072514, Magnesium and Aluminium are mechanically ground together to form a composite material which is then exposed to water to generate Hydrogen gas. In a French patent no. 2465683, a continuous removal of the passivation layer on Aluminum by mechanical means, in order to sustain an Aluminum-assisted water splitting reaction, has been disclosed.
The United States patent no. US 6440385, which refers to most of the patents and drawbacks outlined above, describes a method of automatic gas production by reaction of an alkaline solution reactant with a metal, wherein the method includes continuously feeding without interruption the reactant in conjunction with continuous cleaning of a surface of the metal, for producing Hydrogen for a given energy need.
The patent describes a process of generating Hydrogen gas from water at a pH close to neutral, in the pH range 4 to 9. Hydroxide with a high pH value due to the presence of alkali. It is mentioned how the Aluminum Hydroxide could be recyclable back to Aluminum metal through the well-known electrolysis process, but this is not always possible and is costly. There are still drawbacks with the approach as there is a need for close control of reaction environment to allow easy use.
In a published international PCT patent application no. WO 0174710, there is described a manner in which a Hydrogen generation system employs a wicking material to control a contact between a mixture of fuel contained in a fuel tank and a hydrolysing catalyst supply of Hydrogen. The system is portable but requires a complex feedback mechanism for automatically maintaining a constant pressure for Hydrogen-generating reactions.
In addition, Hydrogen and fuel cell systems have also been developed for use on electric vehicles for range extension purposes. Such systems provide a way of charging batteries during vehicle operation, thus extending the range of such vehicles. The storage of Hydrogen in such application therefore requires extensive ancillary equipment which increases vehicle weights in cases of vehicle applications.
Summary of the invention
The present invention seeks to provide an improved composite material for generation of Hydrogen gas on demand in accordance with claim 1. The added benefit of more reliable and user friendly composite material and final environmentally friendly disposal of any residue product after the Hydrogen gas generation are clear benefits of the invention.
According to a first aspect of the present invention, there is provided a composite material for Hydrogen gas generation from water in an exothermic reaction, wherein the composite material is a powder form of a metal and sodium oxide or sodium hydroxide, characterized in that the composite material powder is exposed to an acidic gas allowing the alkali component of the composite material powder to be coated with a layer of salt, which salt is inert to aluminium and soluble in water, and once the composite material is exposed to water and the soluble layer of salt is dissolved the exothermic reaction between the composite material and the water allows for the generation of low pressure hydrogen gas.
The benefit of the stabilization of the composite powder makes it much more user friendly and not so reactive with water moisture or water. Transportation and storage of the composite material can be costly as it needs to be done in a controlled environment where there is no risk of any water getting in contact with the composite powder material.
Optionally, the acidic gas is hydrogen chloride or sulphur dioxide and it is exposed transiently to the metal component of the alkali composite material creating a very fine, e.g. monolayer, layer of the salt on the composite powders particles. This prevents the premature reaction of the metal component with the alkali allowing for safer and more user friendly handling of the composite material.
Optionally, the metal in the composite material is Aluminium and the composite material is used in a Hydrogen generator where it is placed in a reaction chamber and exposed to water. Once the water has dissolved the stabilizing salt layer of the composite material the generation of low pressure hydrogen takes place in the reaction chamber. The invention is of advantage in that use and handling of the composite material is made much more convenient and safe.
Optionally, the Hydrogen generator unit is implemented so that the fuel cell is operable to generate clean water by way of a chemical reaction within the fuel cell, wherein said generator unit is adapted so that said water is recirculated for use in the extraction chemical process for generating low-pressure Hydrogen.
Optionally, the Hydrogen generator unit is implemented, such that the cartridge-based system is operable to receive replaceable cartridges for providing reactants for the extraction chemical process.
Optionally, the alkali residue material left after the Hydrogen has been generated is neutralized through the use of Carbon Dioxide (C02) to lower the pH of the residue from 9-12 to below 8.5 and preferably to 7.
According to a second aspect of the invention, there is provided a method of manufacturing a composite material, wherein that said method includes melting a metal and injecting the molten metal stream into an atomisation chamber. Injecting at least one inert gas at higher pressure to create metal droplets and control the environment in the chamber to avoid ignition. Then spraying the molten metal droplets onto a cooling plate where condensation and cooling takes place allowing for collection of the metal in powdered form post the cooling plate. The mixing of the powdered metal and the Sodium hydroxide then takes place to generate a well uniform and blended material. This mixture of blended material is then exposed to an acidic gas allowing a thin layer of a water soluble salt to form on the blended material and forming a stabilized composite material. The manufacturing approach of spray forming and the stabilization process allows for a very cost efficient and user friendly end product for future transportation and use by end users.
Description of the diagrams
Embodiments of the present invention will now be described, by way of example only, with reference to the following diagrams wherein: FIG. I is a flow diagram of the process when manufacturing a composite material; and FIG. 2 is an illustration of the use of a composite material in an operational cycle of a Hydrogen generator unit.
In the accompanying diagrams, an underlined number is employed to represent an item over which the underlined number is positioned or an item to which the underlined number is adjacent. A non-underlined number relates to an item identified by a line linking the non-underlined number to the item. When a number is non-underlined and accompanied by an associated arrow, the non-underlined number is used to identify a general item at which the arrow is pointing. An arrow in the drawings can also be used to indicate the positioning of some element within another part.
Description of embodiments of the invention
Referring to FIG. 1, shows a flow diagram of the manufacture of a composite material 23 (shown as 23 in FIG. 2), also referred to as a fuel element in this description. The metal is preferably selected from the group of metals such as Aluminium, Calcium, Magnesium, Sodium, or Potassium. In one preferred embodiment the metal in the composite material 23 is Aluminium in a microstructure form. The manufacturing process to generate the powdered composite material is advantageously a form of Spray forming with gas atomisation and spray microstructure forming. There are certain considerations needed in the manufacturing process depending on what type of metal and state of such metal that is being used which would be apparent to the person skilled in the art due to residue and impurities in the different versions of the metal.
The Aluminium used for the manufacture of the composite material 23 can be of varied grade. The price per tonne of the aluminium varies with the most expensive being pure Aluminium, with a 30% drop in price for Aluminium cuttings, again a further drop in price by 30% for Aluminium turnings, and finally a cost of about 1/20 for Aluminium foil per tonne compared to the pure Aluminium.
As shown in FIG.1 the Aluminium in stage A) melted in e.g. a bottom pour induction unit with a temperature at ca. 50-150°C above the metal liquidus temperature. The molten metal stream is then in stage B) sprayed into a spray chamber where inert gas such as Ar or N2 is used to avoid destabilisation of the molten stream of metal. A first set of inert gas jets operate at 2-4 bar while a secondary set of gas jets at higher pressure ca 6-10 bar spray into the molten Aluminium stream to cause atomisation.
The particle size, droplet diameter and structure can be controlled by varied by altering the atomisation gas mass flow rate as well as the molten metal mass flow rate. In stage C) the molten metal droplets in the stream impact on an impact surface of a cooling plate that cools and condenses the particles which are collected as an Aluminium powder in a controlled, enclosed environment to avoid any ignition of the powder. The particle size will follow a normal bell curve and powder diameters up to ca 750-850 pm with a median diameter of about 180-200 pm.
The powdered Aluminium is then in stage D) placed in a mixing chamber where it is mixed in spray clouds of the powdered metal and precipitated Sodium hydroxide or Sodium oxide. The mixing takes place under controlled conditions allowing a blend of the composite material to be achieved. The Sodium hydroxide is present in the composite material blend of the powders to act as a catalyst when the blend comes into contact with water and the exothermic reaction of generating low pressure Hydrogen gas is initiated.
As this composite material 23, or fuel element 23 as also referred to, is highly reactive and hygroscopic it requires controlled environments and supervision during any handling and/or transportation. Therefore the composite material 23 is put through stabilization phase in stage E) where it is placed in a stabilization unit and exposed to an acidic gas, such as hydrogen chloride or sulphur dioxide. The exposure to the acidic gas is done transiently to the composite material. This creates a very fine, e.g. monolayer, layer of the salt on the composite powder particles. This prevents the premature reaction of the metal component with the alkali allowing for safer and more user friendly handling of the composite material, which is in a stabilized form. The resulting composite material has the benefit of being a robust fuel element, and can be handled in most traditional transport, shipping and commercial environments without the need to avoid the slightest contact with moisture or even high humidity environments. In addition it increases the storage life of the composite material, which can be of critical importance in applications where it is used to generate energy and power in remote locations e.g. off grid properties, forward operating military bases, or as emergency range extenders for vehicles.
In another embodiment the stabilization phase of the manufacturing process can be performed during the mixing phase, stage D), of the Aluminium and Sodium Hydroxide by exposing the mixing phase to e.g. the sulphur dioxide. This needs to be done in a controlled manner create a uniform coating throughout the composite material and generate a suitable layer of salt on the powdered composite material, which will allow for easy removal during the hydrogen generation process but still be sufficient to remove the hygroscopic properties of the mixture when in atmospheric or semi to fully open conditions with e.g. high air moisture percentage.
In a further embodiment the stabilization phase of the manufacturing process can be performed during the spray forming process where the metal component of the composite material is exposed to the acidic gas either just before, during or after the cooling step, stage C). This would allow for a more rapid manufacturing process as long as the process can remain safe and efficient.
In an alternative embodiment of the invention the manufacturing of the composite material 23 is performed through the process of milling down, or even grinding down, the metal used in a closely monitored environment to avoid ignition. Further the smaller the particle size in question the more stringent the milling process environment would need to be. The advantage of this process is that it does not require any specialist machinery and can be performed using equipment that is readily available. This milling process would replace stages A), B) , and C) above in the spray forming process. The mixing stage D) of metal e.g. Aluminium and catalyst e.g. Sodium hydroxide or Sodium oxide, can either be performed before or after the stabilization stage E) depending on the process. Preferably the stabilization is performed last allowing for uniform coating of the composite material 23 ready for distribution without major drawbacks of needing to vigilantly be aware of any moisture content during transportation, storage or use prior to the generation of low pressure Hydrogen gas.
The composite material 23 is preferably manufactured from Aluminium, but can also be manufactured from other compounds such as Sodium, Calcium, Magnesium, or Potassium as already discussed. Without prejudice to the invention we believe that the following formulae details examples of the chemical processes when stabilisation of Aluminium and Sodium, which are then employed to generate Hydrogen and heat from an exothermic reaction with water: Aluminium is a very reactive metal however its apparent lack of activity is due to a very thin, but coherent oxide film covering the surface of the metal which prevents further oxidation or hydrolysis. When Aluminium reacts with acid or alkali, the first stage is dissolution of the oxide file to expose the reactive metal surface, which then undergoes further reactions as shown: A1203 + 6HCI -> 2A1C13 + 3H20 A1203 + 2NaOH -> 2NaAIO2 + H20 These two reactions expose the surface of the Aluminium to allow further reaction: 2A1 + 6HCI -> 2A1C13 + 3H2 2A1 + 2NaOH + 2H20 -> 2NaAlO2 + 3H2 -10 -Thus aqueous acid or aqueous sodium hydroxide will react with Aluminium metal to produce hydrogen despite the presence of the oxide film.
Sodium oxide and hydroxide are very hygroscopic and will absorb water vapour from the atmosphere so that a mixture comprising Aluminium metal and either of these two sodium compounds would be very unstable, and have a tendency to liberate hydrogen on storage due to absorption of adventitious water. Following exposure of the sodium compounds to an acidic gas the sodium compounds are coated with a salt which is itself inert to the Aluminium metal, thus increasing the stability of the composite material 23. However, Carbon dioxide could be used as an alternative, as sodium carbonate/bicarbonate would be formed on the surface of the sodium compound, particularly in the presence of trace amounts of water.
Na20 + C02 -> Na2CO3 Na2CO3 + H20 + C02 -> 2NaHCO3 As carbon dioxide is only slightly soluble in water and carbonic acid, H2C03, is only very weakly ionised, with a pKa value of about 6.4, the reaction to stabilise the composite material 23 would be slow. The alternative would be to use a more strongly acidic gas at very low concentration under inert conditions. Suitable gases include hydrogen chloride and sulphur dioxide: Na20 + 2HCI -> 2NACI + H20 NaOH + S02 -> NaHSO3 These two salts, sodium chloride and sodium bisulphite are easily soluble in water and when the mixture of the stabilised composite material 23 with Aluminium powder is immersed in water, the salt dissolves thus allowing immediate access of the Aluminium metal to the sodium hydroxide solution, thus allowing facile generation of hydrogen as seen above. -11 -
Referring to FIG. 2, an illustration of how the composite material 23 in its stabilized form can be utilized in a hydrogen generator unit 40 as shown. A cartridge unit I is attached to a base of a single cylinder displacer-type engine 2; optionally, the engine 2 is a Stirling-type engine of either beta or alpha configuration. Alpha and beta configurations or Stirling engines are elucidated in Wikipedia. The cartridge unit 1 contains the composite material 23 used as a source to generate Hydrogen gas when in contact with water, which water acts as a Hydrogen source during an associated reaction.
In the hydrogen generator unit 40 there is further a connection made between the cartridge unit I and the engine 2 via a heat exchanger 15, which heat exchanger 15 allows heat generated from an exothermic chemical reaction in the cartridge unit I to be transferred from the cartridge unit 1 directly to the base of the engine 2. This heat exchange acts to initiate an engine cycle, such as a Stirling Engine cycle, moving a displacement cylinder 4 and subsequently moving a piston 5 connected to a flywheel 6.
Hydrogen gas generated by the reaction in the cartridge unit I is allowed to enter into a diaphragm of a pump 7 via a separate pipe connection 16 from an outlet of the cartridge unit 1. A rotational motion of the flywheel 6 moves the diaphragm pump 7 to create a partial vacuum which extracts any Hydrogen gas from the cartridge 1.
Hydrogen then enters a chamber of the diaphragm pump 7 until continued movement of the flywheel 6 moves the diaphragm to close an inlet valve of the diaphragm pump 7. As the diaphragm continues to move, it compresses the Hydrogen gas and then releases the compressed Hydrogen gas through the outlet valve to the input a fuel cell 8. The capacity of the diaphragm pump 7 is chosen to incorporate a factor of safety to avoid over pressurization of the fuel cell 8 and is of sufficient capacity to safely pressurize Hydrogen generated from the cartridge unit 1.
The heat therefore applied to a base of the Stirling engine 2 acts to compresses the Hydrogen released from the cartridge unit 1 to a pressure greater than atmospheric pressure. The compressed Hydrogen gas is matched to a required input of an external energy conversion device, for example a high temperature proton exchanged membrane (REM) fuel cell 8 (or other suitable fuel cell operating at a -12 -temperature in excess of 6000). To facilitate a steady stream of Hydrogen gas, the input of the external energy conversion device optionally incorporates a small buffer tank to hold an amount of Hydrogen gas to ensure a constant supply for operation of the device. The flywheel 6, or in the case of a beta type Stirling engine the gear arrangement, facilitates the movement of the piston back to its starting position to facilitate a start of a second cycle of operation. The cooling element of the Stirling cycle in this example is aided by utilizing a heat exchanger 9 which uses external cooling water required in the normal operation of a PEM fuel cell 8 (or in the case of an internal combustion engine energy conversion technology the input to the engine cooling facility) to cool the gas around the displacement cylinder 4. This cooling element 9 completes the cycle which is repeated until either all the Hydrogen is released or a stop single is generated by the energy conversion device (fuel cell or internal combustion engine). For example, a Stirling engine setup (with a displacer or beta type Stirling engine or other suitable heat engine cycle), provides a small light Is weight apparatus for further compression and controlled injection into either a direct injection internal combustion engine or saturated Hydrogen suitable for use within a fuel cell energy system. The injection of Hydrogen gas into an internal combustion engine cleans up the emissions from the engine by more than 25% compared to conventional ICEs; considerable output soot reduction and NOX reduction is potentially feasible to achieve by employing the present invention.
FIG. 2 also illustrates a water collection unit 10 which extracts water generated by the fuel cell 8 and recycles this into a separate water storage tank 11. Prior to starting the reaction, it is necessary to remove air in the cartridge unit 1 to avoid explosive mixtures of Hydrogen and air arising. This is achieved by using either a separate pump or incorporating a back pressure of the cooling water pump 12 of the fuel cell 8. The pumping of the water to the fuel cell 8 is designed to create a back pressure in the cartridge unit 1. The effect of back pressure is to create a partial vacuum. The difference in pressure between the cartridge unit I and water storage tank 11 allows water to be feed into the cartridge unit 1 without the pumping once valve 13 needing to be opened. The water entering the cartridge unit 1 initially dissolves the stabilizing salt layer around the composite material 23 before the Hydrogen gas generation process is initiated.
-13 -After a plurality of cycles of operation (optionally determined to release a maximum amount of Hydrogen from the cartridge unit 1), the cartridge unit I is rejected/ejected.
Continued operation is achieved either by loading a new cartridge unit 1 into position for the Hydrogen reaction to take place through, for example, a spring loaded mechanism 14.
The utilization of the cartridge unit 1 setup allows for a very compact and user friendly solution for numerous applications such as portable units, vehicle Hydrogen generation units, or even for stationary units which need a safe and easy disposal of the residual waste from the Hydrogen reaction in the cartridges. The residue in the cartridges is often of alkaline nature with a pH value in the range of 8 to 14, but most often with a pH value in a range of 9 to 12. This waste product is today a major drawback for Hydrogen generator systems using metallic powder systems.
Exposing the alkali residue material left in the cartridge unit I to Carbon Dioxide, which in this instance is used to lower the pH of the residue, is a way of reducing the pH to about 7, which makes it user friendly to handle. This is illustrated by the equations without prejudice to the invention we believe: 2NaOH + C02 -> Na2CO3 H20 + C02 -> H2C03 Na2CO3 + C02 -> 2NaHCO3 The cartridge system can be designed to supply the unit 1 with a right amount of composite material for implementing improved handling of the composite material 23.
It allows for safe disposal or return of the cartridge for safe disposal or treatment by e.g. acids or other pH lowering methods like the Carbon Dioxide mentioned above.
Beneficially, the cartridge 1 is capable of being cleaned and refilled, therefore rendering recycling possible.
-14 -Further, the applications of the Hydrogen generator unit 40 and the engine 2 encompass from in an order of 1W to 500W output systems for portable electronic devices, to in an order of 500W to 10kW output for bigger systems. Further, the cartridge unit 1 loaded with 1 kg (the typical size of a single cartridge) of fuel element/composite material 23, e.g. NaSi (s) as seen below, is capable of producing 1500 litres of hydrogen or 134g of hydrogen.
2NaSi (s) + 5H20 (I) -* Na2Si2O5 (aq.) + 5H2 + Heat (-175 kJ/mol).
Therefore 10kg (10 nominal cartridges) of the composite material 23 therefore will generate 1.34kg of hydrogen, equating to 45kWhr of power. Converted to electricity through the fuel cell 8 this hydrogen (assuming an industry standard Fuel Cell operating at an energy efficiency of 50%) is capable of producing 22.SkWhr of electricity. The element/composite therefore would be comparable to an industry standard 24kWhr Lithium Ion battery pack. Such a pack when used to power an electric vehicle would give a range of lOOmiles and therefore is highly desired by within the motor industry. Simple manual cartridge replacement loaded into a magazine arrangement feed from a separate on board water supply would therefore provide an additional 100 miles of range. Most electric vehicles in the market today has a range below 100 miles, hence requires recharging over night or part charging of battery pack at charging stations, which today are few and far apart. A real advantage of the system is that a 24kWhr (e.g. Nissan Leaf) battery pack normally makes up a substantial amount of the total car costs and has to be replaced every five years. The use of the described hydrogen system according to the invention would substantially reduce the cost of a vehicle utilizing battery packs.
Modifications to embodiments of the invention described in the foregoing are possible without departing from the scope of the invention as defined by the accompanying claims. Expressions such as "including", "comprising", "incorporating", "consisting of", "have", "is" used to describe and claim the present invention are intended to be construed in a non-exclusive manner, namely allowing for items, components or elements not explicitly described also to be present. Reference to the singular is also to be construed to relate to the plural. Numerals included within parentheses in the -15 -accompanying claims are intended to assist understanding of the claims and should not be construed in any way to limit subject matter claimed by these claims.
Claims (8)
- -16 -CLAIMS1. A composite material for Hydrogen gas generation from water in an exothermic reaction, wherein the composite material is a powder form of a metal and sodium oxide or sodium hydroxide, characterized in that the composite material powder is exposed to an acidic gas allowing the alkali component of the composite material powder to be coated with a layer of salt, which salt is inert to aluminium and soluble in water, and once the composite material is exposed to water and the soluble layer of salt is dissolved the exothermic reaction between the composite material and the water allows for the generation of low pressure hydrogen gas.
- 2. A composite material as claimed in claim 1, wherein the acidic gas is hydrogen chloride or sulphur dioxide and it is exposed transiently to the metal component of the alkali composite material creating a very fine layer of the salt on the composite material particles.
- 3. A composite material as claimed in claim 1 and 2, wherein the metal of the composite material is at least one of: Aluminium, Calcium, Magnesium, Sodium, Potassium.
- 4. A Hydrogen generator unit for generating low-pressure Hydrogen from water, characterized in that the generator unit includes at least one reaction chamber which is adapted to employ an extracting chemical process to generate low-pressure Hydrogen from an exothermic reaction between a composite material and water, wherein the composite material has a water soluble salt layer which needs to dissolve prior to the exothermic hydrogen gas generating reaction is initiated.
- 5. A Hydrogen generator unit as in claim 4, wherein a thermal engine is adapted to be used as a part of a refrigeration cycle to generate cooling and electricity for providing associated refrigeration.
- 6. A Hydrogen generator unit as claimed in claim 4, wherein a fuel cell is operable to generate clean water by way of a chemical reaction within the fuel cell, -17 -wherein said generator unit is adapted so that said water is recirculated for use in the extraction chemical process for generating low-pressure Hydrogen.
- 7. A Hydrogen generator unit as claimed in claim 4, wherein a cartridge-based system, which contains the composite material, is operable to receive replaceable cartridges for providing reactants for the extraction chemical process.
- 8. A method of manufacturing a composite material, wherein that said method includes the steps of: melting a metal and injecting the molten metal stream into an atomisation chamber; injecting at least one inert gas at higher pressure to create metal droplets and control the environment in the chamber to avoid ignition; spraying the molten metal droplets onto a cooling plate where condensation and cooling takes place; collecting the meal in powdered form post the cooling plate; mixing the powdered metal with Sodium hydroxide to generate a blended material; and exposing the blended material to an acidic gas allowing a thin layer of a water soluble salt to form on the blended material and forming a stabilized composite material.
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Cited By (3)
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GB2510805A (en) * | 2012-12-04 | 2014-08-20 | Inova Power Ltd | Composite material for hydrogen generation |
RU2544652C2 (en) * | 2013-07-30 | 2015-03-20 | Степан Георгиевич Тигунцев | Hydrogen generation method |
US10886548B2 (en) | 2014-05-07 | 2021-01-05 | L3 Open Water Power, Inc. | Hydrogen management in electrochemical systems |
Families Citing this family (1)
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CN109795985A (en) * | 2017-11-16 | 2019-05-24 | 银隆新能源股份有限公司 | Circulating renewable energy hydrolytic hydrogen production system and method based on aluminium energy storage |
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GB1070127A (en) * | 1964-10-26 | 1967-05-24 | Diamond Alkali Co | Improvements in or relating to free-flowing alkaline compositions |
DE2447227A1 (en) * | 1974-08-06 | 1976-02-19 | Lonza Ag | Safer siphons-/drains-deblocking compsn. - contains coated particulate strong base, opt. together with dispersed aluminium powder |
FR2552773A1 (en) * | 1983-09-29 | 1985-04-05 | Solvay | Sodium hydroxide particles for unblocking pipes |
EP1749796A1 (en) * | 2005-07-25 | 2007-02-07 | Air Products and Chemicals, Inc. | Method for generating hydrogen gas |
US20080251753A1 (en) * | 2004-08-30 | 2008-10-16 | Taiichi Sugita | Hydrogen Generating Composition |
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GB1070127A (en) * | 1964-10-26 | 1967-05-24 | Diamond Alkali Co | Improvements in or relating to free-flowing alkaline compositions |
DE2447227A1 (en) * | 1974-08-06 | 1976-02-19 | Lonza Ag | Safer siphons-/drains-deblocking compsn. - contains coated particulate strong base, opt. together with dispersed aluminium powder |
FR2552773A1 (en) * | 1983-09-29 | 1985-04-05 | Solvay | Sodium hydroxide particles for unblocking pipes |
US20080251753A1 (en) * | 2004-08-30 | 2008-10-16 | Taiichi Sugita | Hydrogen Generating Composition |
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GB2510805A (en) * | 2012-12-04 | 2014-08-20 | Inova Power Ltd | Composite material for hydrogen generation |
RU2544652C2 (en) * | 2013-07-30 | 2015-03-20 | Степан Георгиевич Тигунцев | Hydrogen generation method |
US10886548B2 (en) | 2014-05-07 | 2021-01-05 | L3 Open Water Power, Inc. | Hydrogen management in electrochemical systems |
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