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

The present invention relates to a process for the production of hydrogen from water, more particularly to the recovery of hydrogen from water by the interaction of water with activated plasma surfaces of metals and their alloys, whereby metal hydroxides and hydrogen are formed during the interaction. The present invention provides a method for regenerating the resulting hydroxide back into the metal and to repeat the chemical reactions of hydrogen production.

TECHNICAL LEVEL

At present, hydrogen is produced in industry by a variety of technologies:

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

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

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 hydrogen production in the intensive research stage:

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 traditional organic fuel based economy. Experts in the field believe that hydrogen will only become more prominent in energy and transport if a clear shortage of fossil organic fuels begins and costs 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 hydrogen energy concept: hydrogen production — hydrogen storage and transportation — fuel cells that generate electricity from hydrogen, or an internal combustion engine that, when burning hydrogen, produces 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 removal technology has been successfully tested in the decomposition of natural gas, methanol and light petroleum products. However, important challenges remain in adapting it to hydrogen production from hydrocarbon-rich and less hydrocarbon resources - biofuels, refinery waste - fuel oil, refined 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 at 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 + xH₂0 -> MOx + XH₂

M + 2xH₂0 - + M (OH)₂x + xH₂ 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 that aluminum, nanocrystalline aluminum, and aluminum-gallium and other aluminum compounds are mainly used in these reactions (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). 144-149; Vatanabe of Masao, Journal of Physics and Chemistry of Solids 71 ​​(2010) p. 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 regeneration 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 container is filled with water. When hydrogen is required, 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 by 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 novel hydrogen mining technology 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 hydroxy metal decomposition, 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. In the process of the present invention, the hydrogen recovery 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. In the production of hydrogen, metal shavings, metal powders and nanomaterials can be used. The best hydrogen yields (hydrogen production and reaction kinetics) will be obtained using nano-powders with the highest effective surface area.

DESCRIPTION OF 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 presents the experimental XRD result demonstrating that water + Mg-based nano-powders form Mg (OH)₂, and when hydroxide-containing powder is introduced into plasma, hydroxide is decomposed in 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 in H₂ or Ar + H₂ or water-based {H₂0 vapor, Ar + H₂0; H₂+ H₂0 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. We dip the resulting activated nanomaterials into water. A chemical reaction occurs in which the metal surface is oxidized or hydroxides are formed and hydrogen is released during the reaction:

M + xH₂0 - »MOx + xH₂

M + 2xH₂0 M (OH)₂x + xH₂MeO_x

3. We remove the powder from the water and dry it. The resulting material with a passive hydroxide surface is placed in H2 or Ar + hh or water-based (H2O vapor, Ar + H₂0; H₂+ H₂0 etc.) in vacuo (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 keep 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 substances in water, the powder is drained and placed again in the plasma conditions described in point 3;

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

7th 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 the PDF-2 database from the International Center for Diffraction Data (ICDD). The analysis shows that the starting nanomaterial (Mg_BM_4h) is composed of pure Mg and MgO, as the ball milling was carried out in an air environment. The NanoMg2 _2 sample was maintained in water until the hydrogen evolution was practically non-existent. We observe clearly formed Mg (OH)₂ peak at 38 °, 51 °, 58.5 ° which disappear after plasma exposure - sample nanoMg2_3.

DEFINITION OF INVENTION