OA20834A - Process for the cold production of dihydrogen from rock formations resulting in a residue giving bitumen and fertilizer - Google Patents

Abstract

The present invention is a process for producing gaseous dihydrogen (H2) in the cold, from rock formations which are clays and kaolins rich in aluminosilicates. The process according to the invention consists in releasing the hydrogen trapped in the interstices or meshes of the inorganic polymers. The process according to the invention is carried out in several stages in a suitable non-expandable reactor, in the presence of sodium, water and catalyst, without prior heating to gradually reach a high temperature. The rock formations are first crushed and then introduced into a reactor in the presence of sodium, water and catalyst. The reaction starts and releases gaseous dihydrogen (H2) which serves as fuel. After the formation of dihydrogen, a solid residue and a liquid residue are collected which are used to produce bitumen very suitable for tropical climates or very effective fertilizer or to make concrete completely waterproof.

Description

Representative :

O Title: Process for the cold production of dihydrogen from rock formations resulting in a residue giving bitumen and fertilizer.

Abbreviated:

The present invention is a process for the production of dihydrogen gas (H2) in the cold, from rock formations which are clays and kaolins rich in aluminosilicates. The process in accordance with the invention consists in releasing the hydrogen trapped in the interstices or meshes of the inorganic polymers.

The process according to the invention is carried out in several stages in a suitable indilatable reactor, in the presence of sodium, water and catalyst, without prior heating in order to gradually reach a high temperature.

The rock formations are first crushed and then introduced into a reactor in the presence of sodium, water and catalyst. The reaction starts and releases dihydrogen gas (H2) which serves as fuel.

Single Board

After the formation of dihydrogen, a solid residue and a liquid residue are collected which are used to produce bitumen very suitable for tropical climates or very effective fertilizers or to make concrete totally impermeable to water.

O.A.P.I. - B.P. 887, YAOUNDE (Cameroon) - Tel. (237) 222 20 57 00 - Website: http:/www.oapi.int - Email: oapi@oapi.int

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DESCRIPTION OF THE INVENTION

Process for the cold production of dihydrogen from rock formations resulting in a residue giving bitumen and fertilizer

The invention relates to a process for the industrial production of dihydrogen gas without prior heating and having as raw material, clay and kaolin which are rock formations very rich in aluminosilicates.

The process according to the invention gives, after production of dihydrogen, a heterogeneous residue consisting of solid or sludge and liquid that can be transformed into bitumen for road surfacing and fertilizer for agriculture.

Hydrogen is the chemical element with atomic number 1, symbol H. The hydrogen present on Earth is almost entirely made up of the ¹ H isotope also called protium; it contains about 0.01% deuterium ( ² H). Both of these isotopes are stable. A third isotope, tritium ( ^3H ) is unstable and is produced in nuclear explosions. Hydrogen is present in the universe, it is even the molecule which is the most common there. In the Earth's atmosphere, however, it only exists in very small quantities (about 0.5 ppm). On Earth, hydrogen is mainly found in a form combined with oxygen in water (H2O), with carbon (CH4, C2H6, etc.) but also directly in gaseous form.

Indeed, more and more clues show that substantial natural emanations of dihydrogen exist: the molecule could, therefore, acquire the status of primary energy source, like fossil fuels. Compared to the latter, dihydrogen (H2) offers the advantages, from an environmental point of view, of emitting only water (H2O) during its combustion, as well as a mass energy density 2 to 3 times higher than that of hydrocarbons. Natural dihydrogen, compared to synthetic dihydrogen, could constitute a "clean" geo-resource to be developed in the context of the energy transition and the search for carbon-free fuels.

Several phenomena indeed lead to a continuous generation of hydrogen in the earth's crust. The water/rock interaction, diagenesis, will release hydrogen from the water during oxidation phenomena, phenomena that are observed in different geological contexts. As soon as there is, for example, "ferrous" iron (Fe ²⁺ ) in contact with water (sea or rain), it oxidizes to ferric iron (Fe ³⁺ ) and releases hydrogen. The same reaction can also take place (2] with other metals such as magnesium; it is fast and effective at high temperatures around 300°C but also possible at lower temperatures. Minerals in rocks emitted by subterranean volcanoes Marine materials from mid-ocean ridges, especially olivine, oxidize on contact with water and release hydrogen.

The history of hydrogen production begins with Cavendish's experiments in 1766. The alchemist Paracelsus, who lived in the ^16th century, saw the gas; a century later, Robert Boyle managed to collect it, but did not distinguish it from ordinary air. In 1603, Théodore de Mayerne ignited it, and John Mayow, towards the end of the XVII ^E century, distinguished it from the air. Finally, at the beginning of the ^18th century, Nicolas Lémery also noted its flammability. It was not until 1766 that this gas was studied by Cavendish. In 1783, Antoine Lavoisier discovered that Cavendish's "flammable air", which he baptized hydrogen (from the Greek for "water-former"), reacted with oxygen to form water.

The discovery of “flammable air” as it was called is therefore ancient. Théodore de Mayerne and Paracelse obtained it by reaction between "oil of vitriol" (from sulfuric acid) diluted and poured over iron or zinc. In 1870, the gas produced for the needs of gas balloons did not use any other means. In the ^21st century, most of the dihydrogen required is produced from the methane present in natural gas, by heterogeneous catalysis.

In other compounds, the hydrogen is interstitial. The hydrogen molecule dissociates and the hydrogen atoms settle into the holes in the crystal lattice. Very often, there is no stoichiometry; it is more of a solution. The hydrogen trapped in the network can migrate there, react with the impurities present and degrade the properties of the material.

For example, palladium hydride is not quite considered a compound yet although it probably forms PdHz. The dihydrogen molecule shares an electron with palladium in a yet unknown way and hides in the gaps of the palladium crystal structure. Palladium absorbs up to 900 times its own volume of hydrogen at room temperature and is thus, perhaps the best way to transport hydrogen for vehicle power cells. Hydrogen is released as a function of temperature and pressure but not as a function of chemical composition.

The Kyoto Protocol, signed on December 11, 1997, aims to reduce greenhouse gas emissions. Dihydrogen therefore appears to be an energy carrier of the future. Dihydrogen (Hz) is widely used in industry, mainly for

[3] refining of heavy oils and production of ammonia (fertilizer). Its use is particularly planned in transport, via the fuel cell. Since 1970, conclusive tests have allowed the use of hydrogen in internal combustion engines, this is the case of Mazda's Hydrogen RE vehicles and the BMW Hydrogen 7, presented in 2006. Incidentally, some garages offer descaling with hydrogen to clean engines by running them with hydrogen produced by electrolysis.

Industrially or artificially, hydrogen (H2) is produced by a number of methods, all based essentially on chemical reactions:

- Methane reforming: this is a chemical reaction that consists of producing hydrogen from the methane present in natural gas or biomethane. There are two main methane reforming processes: steam reforming and dry reforming.

^ Steam methane reforming: steam reforming also called steam reforming, in English steam reforming of methane (steam methane reforming or SMR) consists in reacting it with steam in the presence of a catalyst. This transformation takes place at high temperature (840 to 950°C), under moderate pressure (20 to 30 bar) and according to a highly endothermic reaction: CH4 + H2O CO + 3 H? ; ΔΗ°29β = +206.2 kJ mol ^-1 (1)

The carbon monoxide produced in the reaction also reacts with water according to a weakly exothermic reaction: CO + H2O θ CO2 + H2; ΔΗ ^Ο 298 = -41.1 kJ mol ¹ (2)

This steam reforming process consists of two reactions: the first is the reaction of methane with water which produces a gas rich in CO and H2, also containing CO2 from reaction (2). It takes place around 800 to 900°C under a pressure of 25 bar, the catalyst is nickel. The second, called shift conversion, occurs at lower temperature, it is the reaction of water gas (between water and CO) which provides H? additional and CO2. For this, one or two reactors can be used depending on the desired conversion efficiency (HTS or LTS): the first is brought to around 400°C (HTS: high temperature shift), with iron-chromium as a catalyst, the second at at a lower temperature (200°C) (LTS: low temperature shift), the catalyst is copper-iron. Downstream of these two reactors, there is generally a decarbonation unit to remove the CO2 formed by the shift conversion (1).

* Dry methane reforming: dry methane reforming is a process that uses CH ₄ and CO2: CH ₄ + CO2 θ 2CO + 2 H ₂ ; ΔΗ° ₂ 98 = +247 kJ mol ¹ (3)

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This reaction is highly endothermic, the temperature range in which it is thermodynamically favorable is above 640°C. This reaction has three major advantages: at equilibrium, the H2/CO ratio is equal to unity. This ratio is highly sought after for the Fischer-Tropsch process and other industrial applications. Then, this reaction consumes carbon dioxide which is a constituent of biogas and a greenhouse gas. Finally, this reaction is one of the most important reactions for converting biogas into hydrogen or syngas.

The steam reforming of hydrocarbons and methane in particular, which constitutes the main constituent of natural gas, biogas and most of biomethane, is a method widely used to produce hydrogen.

Decomposition of water: it can be done with cold water, hot water and boiling water or even steam:

* Decomposition of cold water: cold water is decomposed by aluminum amalgam, i.e. an alloy of aluminum and mercury which is made by rubbing aluminum foil with mercuric chloride wet: 2AI + 6 H2O =$ 2 AI(0H)3 + 3 Hz * Decomposition of hot water: hot water is decomposed by the zinc-copper couple according to the following reaction: Zn + 2 H2O => Zn(OH) ? + Hz * Decomposition of boiling water: boiling water is slowly decomposed by magnesium; Mg + 2 HzO => Mg(OH)z + Hz * Decomposition of water vapour: water vapor is decomposed by action on heated magnesium, zinc or iron. The reaction of iron on water vapor is reversible, depending on the experimental conditions. The reaction equations are as follows:

Mg + H2O => MgO + H2; Zn + H2O => ZnO + Hz and Fe + H2O <=> Fe3Û4 + 4Ha.

* Decomposition of water by potassium: hydrogen is obtained by decomposing water by potassium: this metal, very easily oxidized, seizes oxygen by releasing Hz. The products obtained are potash and hydrogen: 2HzO + 2K 2KOH + Hz

- Action of an acid on a metal: hydrogen is prepared in the laboratory by the action of acids on metals: dilute sulfuric acid containing one volume of concentrated acid for five volumes of water, or dilute hydrochloric acid containing one part concentrated acid to four parts water, is added to the granulated zinc. Zinc sulfate or zinc chloride are formed, hydrogen is released. This metal, under the influence of acid, decomposes water, passes to the state

[5] of zinc oxide which combines with the acid, and the hydrogen becomes free. The reaction equations are: Zn(s) + hbSO^aq) H2(g) + ZnS04(aq) and Zn + 2HC1 —> ZnCh + Hz

- Electrolysis: today, the purest grade of hydrogen commercially available is produced by electrolysis of water. Pure hydrogen is best prepared by electrolysis with nickel electrodes and a hot saturated solution of barium hydroxide. The gas is passed through hot platinum gauze which oxidizes any residual oxygen in the gases, and is then dried by passing over potassium hydroxide pellets and redistilled phosphorus pentoxide powder.

However, even if the environmental impact of this process is lower, its production cost is much higher.

- Production of hydrogen from biomass: it is done by methanation or by thermolysis of poorly fermentable waste or biomass.

Anaerobic digestion or biomethanation is a biological process of degradation of organic matter in the absence of oxygen; the biomass is transformed by anaerobic microorganisms by hydrolysis, acidogenesis and acetogenesis into methane precursor products and a solid residue called digestate. Methane precursors give methane according to the following reactions: CO2 + 4H2 CHU + 2H2O and CH3COOH -> CH ₄ + CO2. The methane obtained is then converted into hydrogen by catalytic reforming.

Thermolysis consists of a succession of treatments carried out, first of all, in the absence of oxygen between temperatures of 300 to 600°C, then, in the presence of water vapor and oxygen at high temperature ranging from 900 to 1300°C. Lignocellulosic biomass captures solar energy to produce a set of molecules, (cellulose, hemicellulose and lignin), of composition equivalent to C6H9O4 which is then transformed into hydrogen according to the following reaction: C6H9O4 ⁺ 2H2O —> 6CO + 6, 5H2.

None of the hydrogen production processes described uses rock formations as raw material and does not take place at room temperature. In addition, the industrial production of hydrogen is made from another source of energy at the cost of a significant energy and environmental cost. And even if the existence of natural emanations of hydrogen is now proven, its economic interest remains to be demonstrated. It therefore appears the need for humanity to seek more suitable ways for the production of hydrogen.

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The aim of the present invention is to develop a process for the production of ecological, simple and less expensive dihydrogen from easily accessible natural products.

This goal is achieved by the process of cold dihydrogen (Hz) production, from rock formations which are clays and kaolins rich in aluminosilicates and made up of inorganic or mineral polymers. These are therefore polymers whose skeleton does not contain carbon atoms and containing decarbonated hydrogen. The dihydrogen production process in accordance with the invention consists in releasing the hydrogen trapped in the interstices or meshes of the inorganic polymers and makes it possible to obtain pure dihydrogen of high density.

The process according to the invention is carried out in several stages in a suitable indilatable reactor, in the presence of sodium, water and catalyst, without prior heating to gradually reach a high temperature.

The rock formations that are clays and kaolins, rich in aluminosilicates are first ground to give a fine powder which is then introduced into a rigid and sealed reactor that can withstand high pressures. After addition of sodium, water and catalyst, the reaction starts and releases hydrogen gas (Hz). The dihydrogen thus obtained is stored and conditioned to serve as fuel.

The dihydrogen production process according to the invention gives rise to two types of residue: a solid and a liquid.

- the solid residue serves as a binder very suitable for the tropical climate; it is mixed with gravel, fatty latex and cement, all sprinkled with the liquid residue to make the waterproof, solid and damping bitumen of the tracks, which can last at least fifty years;

- and the liquid residue, doped with nitrate, potassium, phosphorus, chlorine and sulphur, gives a fertilizer or manure for agriculture which leads to ultra-rapid plant growth, capable of tripling the yield per hectare. But on its own, this liquid residue is mixed into the concrete to make it completely waterproof.

The process for producing dihydrogen (Hz) according to the invention has many advantages which are as follows:

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- its implementation is less expensive and does not entail the installation of gigantic and sophisticated installations;

- the raw material for its implementation is easily accessible and available;

- it is ecological because it does not lead to the formation of carbon dioxide (CO2);

- it produces solid and liquid residues with very useful uses in the field of building and public works.

The other characteristics of the invention will appear more clearly on reading the following description which relates to a non-limiting example of embodiment defined by plate 1, comprising figure 1.

Figure 1 is a diagram which illustrates the process according to the invention and the exploitation of the by-products.

The invention is a process for the production of ecological, simple and less expensive dihydrogen from rock formations which are clays and kaolins rich in aluminosilicates and made up of inorganic or mineral polymers. These are therefore polymers whose skeleton does not contain carbon atoms and containing decarbonated hydrogen.

The dihydrogen production process according to the invention starts cold, without external heating, to gradually reach a high temperature. It consists in releasing the hydrogen trapped in the interstices or meshes of the inorganic polymers to give pure and high-density dihydrogen.

The process according to the invention is carried out in several stages in a suitable indilatable reactor, in the presence of sodium, water and catalyst, without prior heating. The steps can be summarized as follows:

Grinding: clay and kaolin, rich in aluminosilicates, are first ground to obtain a fine powder;

- preparation of the reactor: the mixture of clay powder and kaolin previously obtained is introduced into a rigid and sealed reactor capable of withstanding high pressures;

- Triggering of the reaction: to the powder contained in the reactor, sodium, water and a catalyst are added. Immediately the reaction starts and releases gaseous dihydrogen (H2) and the temperature of the reactor increases gradually to reach a high value;

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Storage and packaging: the dihydrogen released is stored and packaged to serve as fuel.

After release of dihydrogen, inorganic polymers; the clay and the kaolin having served as raw material lead to the formation of two types of residue or waste: a solid residue and a liquid residue due to the presence of water. These residues are formatted to be used as bitumen and as fertilizers or fertilisers. Thus :

- the solid residue serves as a binder very suitable for the tropical climate. It is mixed with gravel, fatty latex and cement, the whole soaked in the liquid residue, to give a waterproof, waterproof, solid and shock-absorbing bitumen which is used for coating or bitumenizing ίο tracks and able to resist bad weather for at least fifty years;

- the liquid residue, doped with nitrate, potassium, phosphorus, chlorine and sulphur, constitutes a very effective fertilizer for agriculture. This fertilizer thus obtained leads to ultra-rapid plant growth, capable of tripling the yield per hectare. But this liquid residue, is added alone to the concrete to make it completely impermeable to water.

Claims (9)

1- Industrial process for the production of dihydrogen gas (H?) characterized in that said process consists in reacting cold, fine powder of clay and kaolin very rich in aluminosilicates with sodium and water in the presence a catalyst to obtain gaseous dihydrogen (H2) and a residue that can give bitumen and fertilizer, 2- Industrial process for the production of dihydrogen gas (H2) from inorganic polymers according to claim 1, characterized in that the principle of said process consists in releasing the hydrogen trapped in the interstices or meshes of the inorganic polymers and makes it possible to obtain pure dihydrogen, 3- Industrial process for the production of gaseous dihydrogen (Hz) from inorganic polymers according to claims 1 and 2, characterized in that the release of dihydrogen during said process leads to the formation of a heterogeneous residue consisting of sludge and of liquid. 4- Industrial process for the production of hydrogen gas (H2) from inorganic polymers according to claims 1 and 3, characterized in that the solid residue or sludge is used as a binder very suitable for the tropical climate. 5- Industrial process for the production of gaseous dihydrogen (H ₂ ) from inorganic polymers according to claims 1, 3 and 4, characterized in that the solid residue, mixed with gravel, fatty latex and cement, all soaked of the liquid residue, gives a very waterproof, solid and damping bitumen which is used for surfacing the tracks. 6- -Procédé industrial production of hydrogen gas (Hz) from inorganic polymers according to claims 1, 4 and 5, characterized in that the bitumen produced with the solid and liquid residues can last at least fifty years. 7- Industrial process for the production of gaseous dihydrogen (Hz) from inorganic polymers according to claims 1 and 3, characterized in that the liquid residue, doped [ίο] of nitrate, potassium, phosphorus, chlorine and sulphur, gives a fertilizer or manure for agriculture. 8- Industrial process for the production of dihydrogen gas (H2) from polymers 5 inorganic materials according to claims 1 and 3, characterized in that the liquid residue is mixed with the concrete to make it totally impermeable to water. θ- Industrial process for the production of gaseous dihydrogen (H2) from inorganic polymers according to claims 1, 3 and 7, characterized in that the fertilizer thus 10 achieved results in ultra-rapid plant growth, capable of tripling the yield per hectare