LT5983B - Method of hydrogen extraction from water using water interaction with the surfaces of metals or their alloys activated in plasma - Google Patents

Abstract

The present invention relates to hydrogen energy technologies and in particular to hydrogen production using nanocrystalline metals and their alloys interaction with water, resulting in the emission of hydrogen and formation of a metal hydroxide. According the method of invention nanopowders of metals and their alloys are placed in the water to obtain hydrogen and the surface of the metal to cover with hydroxide layer. The resulting hydroxide is placed in H2 or Ar + H2, or water-based (H2O vapor, Ar + H2O, H2 + H2O, etc.) plasma in vacuum (at a pressure of up to 1-5 Pa) and maintained from 1 to 180 minutes (depending on the degree of activation of the demand). As a result of processes occurs full decomposition of hydroxide, surface of metal or metal alloys becomes metallic and it is possible again to repeat the cycle of hydrogen production. Cycles of hydrogen extraction and hydroxide decomposition can be repeated at least 100 times. The best results are obtained using the powder of high efficiency surface area.

Description

The present invention relates to a process for the production of hydrogen from water, more particularly the recovery (recovery) of hydrogen from water by the interaction of water with activated plasma surfaces of metals and their alloys to form metal hydroxides and hydrogen during the interaction. The present invention provides a method for recovering the resulting hydroxide back to the metal and repeating the chemical reactions of hydrogen production.

TECHNICAL LEVEL

Currently, hydrogen is produced in the industry using a variety of technologies:

1. Hydrogen is obtained from natural gas, petroleum products and other hydrocarbons (reforming process);

2. Hydrogen is obtained as a by-product of chlorine-sodium production;

3. Hydrogen is obtained by water electrolysis:

3.1. Using energy from any renewable sources (wind, solar, water, etc.);

3.2. Using nuclear power (high temperature reactors). This is the technology most suitable for large-scale centralized hydrogen production;

4. Experimental methods for the production of hydrogen at the stage of intensive research:

4.1. Production of hydrogen by micro-organisms;

4.2. Production of hydrogen by decomposition of water in high-temperature plasma;

4.3. Photodialysis method.

All of the above technologies (except reforming processes and water electrolysis) are still at the fundamental research stage. Their energy efficiency is quite low. Therefore, it will take a long time before a hydrogen economy can be created that can compete with the conventional organic fuel based economy. Experts in the field believe that hydrogen will only become more prominent in energy and transport if there is a clear scarcity of fossil organic fuels at several times the current price. Therefore, except for very specific cases and various demonstration projects, these promising technologies are unlikely to proliferate in the next 20 years. This scenario can change dramatically only with the discovery of new, cheaper and significantly improved materials for the currently accepted concept of hydrogen energy: hydrogen production-hydrogen storage and transportation-fuel cells generating electricity from hydrogen, or an internal combustion engine that emits hydrogen heat that is directly converted into electricity or mechanical energy, or by offering a whole new, more advanced concept of hydrogen energy.

As mentioned above, natural gas, oil, coal are currently the main sources of hydrogen production in the reform process. The following three thermochemical methods are commonly used for the decomposition of hydrocarbons: catalytic reforming with water vapor, partial oxidation and autothermal reforming.

Steam reforming is the most efficient and well-absorbed technology with a high conversion rate. However, endothermic reforming reactions require additional energy. In partial oxidation reactions, heat is released, so little additional energy is needed to release hydrogen in this way. However, its efficiency is lower than the hydrocarbon reforming steam. Autothermal reforming seeks to combine both of these techniques so that the heat of partial oxidation is used to support the reforming steam reactions. This hydrogen release technology has been successfully tested in the decomposition of natural gas, methanol and light petroleum products. However, major challenges remain in adapting it to hydrogen production from hydrocarbon-rich and more difficult hydrocarbon resources - biofuels, refinery waste - fuel oil, petroleum waste - used oil, used tires, etc. The process of decomposition of hydrocarbons must be organized in such a way as to obtain as much of the heat needed for its maintenance as possible from the oxidation of the carbon and to retain the hydrogen in products which are more easily broken down and separated in the final stage.

The present invention relates to the production of hydrogen by reaction of water with metals which have a more negative redox potential with respect to water:

M + xH ₂ 0 -> MOx + XH ₂

M + 2xH ₂ 0 - + M (OH) ₂ x + xH ₂ where M is metal or metal alloys (source - Solid state hydrogen storage:

Materials and Chemistry, Gavin Valker, Voodhead publishing limited (2008), p. 317).

There are a number of works which demonstrate that these reactions are well suited for hydrogen production and are mainly based on aluminum, nanocrystalline aluminum and aluminum-gallium and other aluminum compounds (JA V Patent No. 4358291; Kravchenco OV, Semenenko KN, Bulychev BM and Kalmykov KB (2005), J. Alloys and Compounds, 404, pp. 637-642; Lluis Soler, Jorge Macanas, Maria Munoz, Juan Casado, Journal of Power Sources 169 (2007), pp. 144-149; Journal of Physics and Chemistry of Solids 71 (2010) pp. 12511258). Unfortunately, there is no cheap and technologically easy way to reduce the forming metal oxides or metal hydroxides back to the metals and repeat the hydrogen extraction reactions more than 100 times. The present invention provides a novel method of reducing metal oxides or hydroxides back to metals using plasma technology and repeating hydrogen production reactions for more than 100 cycles. The proposed method relates to a new hydrogen energy concept: nano-powder production - chemical reactions: water + nano-powder resulting in hydrogen and metal hydroxides - use of hydrogen in fuel cells or internal combustion engines - plasma hydride recovery in plasma - and at least 100 iterations . This method avoids the need to store and transport hydrogen. Instead of hydrogen, this technology stores activated metals. In automotive transport, this technology can be used as follows: The car has a tank that holds nano-powders of metals or their alloys. The other tank is filled with water. When hydrogen is needed, the powder and water are fed into the reaction zone, producing hydrogen and metal hydroxides. Metal hydroxides can be reduced to pure metals in the car or removed using plasma technology and re-introduced into the reaction zone with water, repeating the hydrogen production cycle.

THE SUBSTANCE OF THE INVENTION

It is an object of the present invention to provide a new technology for the production of hydrogen by reacting metals and their alloys with water to form metal hydroxides and hydrogen. The present invention provides for the use of plasma technology for hydroxide decomposition of metals, which allows hydroxide decomposition and, on the surface of metals and their alloys, the hydroxides decompose to metals and OH groups that are absorbed from the surface. Once formed, the activated metal surface can again be successfully used for hydrogen production purposes. In the process of the present invention, hydrogen extraction can be carried out at least 100 times in the following reactions: Reaction: Metals + Water - Hydrogen and Hydroxides; hydroxide decomposition; reaction: metals + water - + hydrogen and hydroxides are obtained. Metal shavings, metal powders and nanomaterials can be used in hydrogen production. The best hydrogen yields (hydrogen production and reaction kinetics) will be obtained using nano-powders with the highest effective surface area.

DESCRIPTION OF THE DRAWING FIGURES

The invention will now be described with reference to the accompanying drawings, in which:

FIG. 1 is a schematic diagram of the process of the present invention;

FIG. 2 is a hydroxide decomposition chamber;

FIG. Figure 3 shows an experimental XRD result demonstrating that water + Mg-based nano-powders form Mg (OH) ₂ , and that hydroxide-decomposition occurs when plasma is added to the plasma.

DESCRIPTION OF THE INVENTION

The concept algorithm of the invention is presented in FIG. 1. Detailed description of the process:

1. We take at least any metals and their alloys (eg Mg, Mg-Ni, Mg-AI, Ti, etc.) in the form of chips or powders or nano-powders and place them on H ₂ or Ar + H ₂ or water based (H ₂ 0 vapors) , Ar + H ₂ 0; H ₂ + H ₂ 0, etc.) in vacuo (pressure up to 1-5 Pa) and maintained for 1 min. up to 180 minutes (depending on the degree of activation required);

2. Immerse the resulting activated nanomaterials in water. A chemical reaction occurs whereby the metal surface is oxidized or hydroxides are formed and hydrogen is released during the reaction:

M + xH ₂ 0 - »MOx + xH ₂

M + 2xH ₂ 0 M (OH) ₂ x + xH ₂ MeO _x

3. Remove the powder from the water and drain. The resulting material with a passive hydroxidised surface is placed in H2 or Ar + hh or water-based (H2O vapor, Ar + H ₂ 0; H ₂ + H ₂ 0, etc.) plasma under vacuum (pressure up to 1-5 Pa) and maintained for 1 min. . up to 180 min (depending on the degree of activation required). An experimental scheme is shown in FIG. 2;

4. We remove the resulting material from plasma to air or store it in an inert environment and immerse it in water. The reaction described in point 1 is repeated and hydrogen is released. We keep the powder in the water for as long as it is active (hydrogen evolution in the form of bubbles is observed);

5. After complete passivation of the surface of the materials in the water, the powder is drained and resuspended in the plasma conditions described in point 3;

6. After the plasma activation, the powder is refilled with water and the reaction of hydrogen evolution is monitored;

7. The process can be repeated at least 100 times. The best results are obtained with the highest amount of hydrogen released and reaction kinetics - using nanomaterials. Confirmation of hydroxide reduction is given in FIG. 3, where X-ray diffraction experiments using a Bruker D8 Discover diffractometer at 28 between 20 ° and 70 ° using Cu cathode Ka radiation and a step of 0.01 ° are shown. Peak identification was performed using a PDF-2 database from the International Center for Diffraction Data (ICDD). The analysis shows that the starting nanomaterial (Mg_BM_4h) is made up of pure Mg and MgO, because ball milling was carried out in an air environment. The NanoMg2 _2 sample was kept in water until the hydrogen evolution was practically non-existent. We observe clearly formed Mg (OH) ₂ peaks at 38 °, 51 °, 58.5 °, which disappear after plasma exposure - sample nanoMg2_3.

DEFINITION OF INVENTION

Claims (2)

DEFINITION OF INVENTION A process for the production of hydrogen from water by the interaction of water with plasma-activated metal or metal alloy surfaces, comprising: (a) depositing plasma-activated metal or metal alloy filings or powder or nanomaterial into water and forming hydrogen and metal or hydroxides of their alloys; (b) After the chemical reaction (hydrogen evolution) has finished, the metal or alloy shavings or powders or nano-powders are removed from the water, drained and placed in a H ₂ or Ar + H ₂ or water-based plasma under vacuum (1-5 Pa) and from 1 min up to 180 minutes (depending on the degree of activation required); (c) during plasma processes, the surface of metals or their alloys is intensively bombarded with ions emitted from the plasma, decomposes the hydroxides into metals and OH groups, which are subsequently resorbed from the metal surface; (d) reactivating the activated metals or their alloys in water and repeating the hydrogen production cycle according to steps a to c at least 100 times. 2. A process for the production of hydrogen from water according to claim 1, characterized in that in step (a) Mg, Mg-Ni, Mg-Al or Ti shavings or powders or nano-powders are used.