Hydrogen production method and plant

Abstract

A method for producing hydrogen from an aqueous solution containing hydrochloric acid in dissociated form, in which at least one electrode is present, made of a metal alloy containing a plurality of metals having different standard reduction potentials, the method comprising the steps of reducing hydronium ions present in the aqueous solution to hydrogen as a result of electrons generated in the electrode flowing between the metal pair from the metal with the lower potential to the metal with the higher potential, and removing the resulting hydrogen from the aqueous solution.

Description

[Technical Field]

[0001] The present invention relates to a method for producing hydrogen. [Background technology]

[0002] Hydrogen is an important feedstock currently used in the chemical and refining industries, and there is growing interest in using it as a fuel due to its low environmental impact and high energy content.

[0003] Currently, the most common methods for large-scale hydrogen production involve using hydrocarbons or fossil fuels as starting materials.

[0004] The main hydrocarbon conversion process is steam reforming, which consists of the endothermic catalytic conversion of light hydrocarbons (e.g., methane) in the presence of steam.

[0005] Another method is partial oxidation, in which heavy hydrocarbons (eg, heavy oil residues from the petrochemical industry) are thermally treated in the presence of oxygen.

[0006] However, the use of hydrocarbons has a very negative impact on the environment, as it involves the emission of large amounts of CO2 into the atmosphere, increasing the Earth's heat budget and causing the greenhouse effect.

[0007] Many technologies are currently being researched to produce hydrogen without the co-production of CO2.

[0008] One of these is water electrolysis. However, this technology has many drawbacks, such as the limited amount of hydrogen produced and the high cost of using electricity. For these reasons, the water electrolysis process currently covers only a very small amount of hydrogen produced.

[0009] Hydrogen can also be obtained from water through biological production or by thermal pyrolysis, however even these techniques are inefficient for large scale hydrogen production.

[0010] Therefore, there is an urgent need to develop a method for producing large amounts of hydrogen that is more energy efficient, reduces CO2 emissions into the atmosphere, and is less expensive. Summary of the Invention

[0011] The present invention aims to provide a method for producing large amounts of hydrogen with reduced energy consumption and less impact on the environment.

[0012] This is achieved by the method according to claim 1.

[0013] According to the method of the present invention, hydrogen is produced from an aqueous solution containing hydrochloric acid in dissociated form, said aqueous solution containing hydronium ions (HO + ), wherein in the aqueous solution there is present at least one electrode made of a metal alloy containing multiple metals having different standard reduction potentials. Electrons generated at the at least one electrode between the metal pair flow from the metal at the lower potential to the metal at the higher potential, resulting in the formation of hydronium ions (HO) present in the aqueous solution. + ) to hydrogen gas (H2); removing the hydrogen gas thus obtained from the aqueous solution; Includes:

[0014] The aqueous solution is prepared by introducing hydrochloric acid into water, which dissociates to produce free hydronium ions (HO) according to the following equations: + ) and releases chloride ions (Cl - ) is formed. HCl + HO → HO + + Cl - (1)

[0015] Standard reduction potential (E 0 ) is a measure of the tendency of a chemical species to gain electrons, i.e., to be reduced. E 0The higher the value of standard reduction potential E, the higher the electron affinity of the chemical species and the easier it is to reduce. 0 is the potential E 0 = 0.00 V (volts) and is measured under standard conditions, i.e., a temperature of 298 K (25°C) and a pressure of 100 kPa (1 bar).

[0016] The potential difference between each pair of metals must be large enough to ensure that this flow of electrons moves from the metal at lower potential to the metal at higher potential, preferably said potential difference is equal to at least 0.20 volts, more preferably at least 0.50 volts.

[0017] In each pair of metals where the electron flow is generated, the metal that gives up the electrons acts as the anode and oxidizes, acting as a reducing agent according to the half-reaction. M → M n+ + ne - (2)

[0018] "n" is an integer, preferably 2 or 3.

[0019] The metal that accepts the electrons acts instead as an inert cathode. At the cathode, the HO present in the solution + The ions act as oxidizing agents and gain electrons according to the half-reactions. 2H + + 2e - → H2(3)

[0020] In particular, the following redox reaction takes place on said at least one electrode: H2O(l) → O2(g) + 2H2(g) (4)

[0021] This reaction produces hydrogen gas along with oxygen.

[0022] The metal alloy forming the at least one electrode preferably comprises magnesium (Mg) and at least one of the following metals: beryllium (Be), aluminum (Al), manganese (Mn), zinc (Zn), iron (Fe), copper (Cu), silicon (Si), and nickel (Ni).

[0023] In a preferred embodiment, the metal alloy comprises mainly magnesium, and in a particularly preferred embodiment, the metal alloy comprises magnesium in an amount in the range of 85% to 95% by weight, preferably in the range of 90% to 91% by weight.

[0024] Magnesium has the lowest standard reduction potential among the metals, and therefore has the greatest tendency to transfer electrons. Therefore, when the metal alloy comes into contact with an aqueous solution, electrons are transferred from magnesium to each of the metals. As a result, magnesium always acts as the anode and oxidizes according to half-reaction (1), where n is the value "2."

[0025] Silicon is the metal with the highest standard reduction potential among the set of metals and therefore always acts as an inert cathode, allowing hydronium ions present in solution to gain electrons to form hydrogen gas according to half-reaction (2).

[0026] Metals with standard reduction potentials intermediate between magnesium (Mg) and silicon (Si) behave as inert cathodes or anodic oxidation according to half-reaction (1), depending on the metal with which the electron exchange takes place. When half-reaction (1) includes metals such as Be, Mn, Zn, Fe, Cu, and Ni, n takes the value "2," and when it includes metals such as Al instead, n takes the value "3."

[0027] In a preferred embodiment of the present invention, the metal alloy has a composition, in weight percent, of Mg: 90.81%, Al: 5.83%, Zn: 2.85%, Mn: 0.45%, Si: 0.046%, Cu: 0.0036%, Be: 0.0012%, Fe: 0.0010%, and Ni: 0.00050%.

[0028] According to another embodiment of the present invention, the metal alloy has a composition, in weight percent, of Mg: 90.65%, Al: 5.92%, Zn: 2.92%, Mn: 0.46%, Si: 0.043%, Cu: 0.0036%, Be: 0.0012%, Fe: 0.0010%, Ni: 0.00050%.

[0029] According to a particularly advantageous embodiment of the invention, the at least one electrode is coated on its outer surface with a coating layer comprising at least one metal fluoride, in particular magnesium fluoride, aluminum fluoride and / or zinc fluoride.

[0030] Preferably, the at least one electrode is externally coated with a coating layer containing one or more of the metal fluorides mixed with a methacrylic resin, more preferably the methacrylic resin contains 50% to 70% by weight of PFTE, 15% to 25% by weight of 1,2-propanediol monomethacrylate (CAS 27813-02-1), and 15% to 25% by weight of hydroxyethyl methacrylate (CAS 868-77-9).

[0031] According to a preferred embodiment of the present invention, the methacrylic resin comprises 60% by weight of PFTE, 20% by weight of 1,2-propanediol monomethacrylate (CAS 27813-02-1), and 20% by weight of hydroxyethyl methacrylate (CAS 868-77-9).

[0032] Preferably, this coating layer of said at least one electrode has a thickness of 0.5 mm to 3.0 mm, more preferably 1.0 mm to 2.0 mm.

[0033] According to a further preferred embodiment of the invention, said at least one electrode comprises at one end a graphite element not covered by said coating layer on the outer surface of the electrode.

[0034] Advantageously, the interior of said at least one electrode is also provided with a metal element, for example an iron or carbon steel rod, which is in contact with said graphite element of the electrode.

[0035] According to yet another embodiment of the present invention, the outer covering layer of the at least one electrode is wrapped with a perforated tape or a PTFE mesh, preferably the tape or PTFE mesh applied onto the covering layer has a thickness of a few microns, for example 1 μm to 3 μm.

[0036] According to another embodiment of the present invention, the outer covering layer of the at least one electrode is wrapped with a semi-permeable fabric tape that is permeable to aqueous solutions in the direction towards the electrode and impermeable to aqueous solutions in the opposite direction, and the fabric is also permeable to hydrogen.

[0037] The aqueous solution is prepared by introducing hydrochloric acid into water to form a mixture. Preferably, the mixture contains hydrochloric acid in an amount ranging from 5% to 10%, preferably from 6% to 7%. The percentage values ​​are by volume.

[0038] Due to the presence of hydrochloric acid in the aqueous solution, the process of the present invention is carried out in an acidic environment, the pH at which the process is carried out is preferably in the range of 2 to 4, more preferably in the range of 2 to 3.4.

[0039] The process is preferably carried out at a temperature in the range of 20°C to 70°C, preferably in the range of 55°C to 60°C.

[0040] The process is preferably carried out at sub-atmospheric pressure, for example at a pressure of 0.3 bar to 0.5 bar (absolute).

[0041] The hydrogen thus obtained is of low molecular weight and therefore spontaneously releases from the solution.

[0042] The oxygen generated during the process, due to its high molecular weight, tends to remain in the aqueous solution instead and combine with the chlorine present in the aqueous solution to form hypochlorous acid (HClO).

[0043] According to a preferred embodiment of the invention, in order to avoid the accumulation of hypochlorous acid in the aqueous solution, the latter is advantageously regenerated by a recirculation step of the aqueous solution and a degassing step, which are adapted to remove the oxygen produced together with the hydrogen during the reduction step described above with reference to half-reaction (3). The degassing step includes a filtration step in which oxygen is removed.

[0044] In particular, the filtration step is preferably carried out using porous baffle membrane filters filled with MnO, during which both oxygen (O) and chlorine (Cl) are released separately, and the chlorine is then recovered by reintroducing it into the aqueous solution, preferably by bubbling.

[0045] Preferably, the degassing step is carried out under vacuum.

[0046] Since the reaction forming the basis of the process according to the invention is exothermic, said recycling step also comprises a step of cooling the aqueous solution, preferably adjusted so as to maintain the reaction temperature within the aforementioned range.

[0047] Another aspect of the invention relates to a plant for producing hydrogen according to the method described above. This plant is at least one buffer reservoir for storing an aqueous solution containing hydrochloric acid in dissociated form; at least one reactor for producing hydrogen containing at least one electrode made of a metal alloy including a plurality of metals having different standard reduction potentials; at least one supply line for supplying the aqueous solution from the at least one buffer tank to the at least one reactor; at least one recirculation line for recirculating an aqueous solution from the at least one reactor to the at least one buffer tank; at least one device for regenerating the aqueous solution, the at least one device being arranged along said at least one recirculation line; means for removing hydrogen gas from said at least one reactor; Includes:

[0048] Preferably, the regeneration device comprises a filtration device, e.g., at least one porous baffle membrane filter, preferably filled with MnO, adapted to separate oxygen (O) formed during hydrogen production (degassing) in the at least one reactor. Preferably, the filtration device operates under vacuum.

[0049] Preferably, the plant according to the invention also comprises at least one cooling device along said recirculation line, which cooling device comprises at least one heat exchanger adapted to cool the aqueous solution effluent from said at least one reactor and maintain the reaction temperature in the range of 20°C to 70°C.

[0050] According to a particularly advantageous embodiment, said cooling device is arranged upstream of the regenerator.

[0051] In some embodiments, the plant comprises two reactors arranged in parallel, each having a supply line and a recycle line for the aqueous solution, a regenerator for the aqueous solution circulating in the recycle line, and a means for removing hydrogen.

[0052] Another subject of the present invention relates to an electrode made of a metal alloy for use in the above-mentioned hydrogen production method. With regard to the composition of the metal alloy from which the electrode is made, as well as the actual structure of the electrode and its coating layer, reference can be made to the description provided in connection with the process.

[0053] The subject of the present invention is also the hydronium ion (HO + ) and chloride ions (Cl- ) for use in the above hydrogen production method.

[0054] A further object of the present invention is a method for coating the outer surface of said at least one electrode.

[0055] The method comprises: - immersing said at least one electrode in a bath of hydrofluoric acid and water, whereby the metal comprising the outer surface of the electrode reacts with the hydrofluoric acid to form a fluorinated patina of metal fluoride salt; - a first step of drying said fluorinated patina of metal fluoride salts; - applying a methacrylic resin gel onto the fluorinated patina, the methacrylic resin being of the type described in connection with the method; a second step of drying the mixture thus obtained, comprising the metal fluoride and the methacrylic resin, in order to obtain an outer coating layer of the electrode; Includes:

[0056] Preferably, said second drying step has a duration of 10 to 16 hours, more preferably 12 hours.

[0057] According to a preferred embodiment of the present invention, the method for coating an electrode further comprises, at the end of the second drying step, wrapping the electrode with perforated tape or PTFE mesh, preferably having a thickness of a few microns, for example 1 μm to 3 μm.

[0058] According to another embodiment of the invention, the process of wrapping the electrodes is carried out using a semi-permeable fabric tape that is permeable to aqueous solutions towards the electrodes and impermeable to aqueous solutions in the opposite direction, the fabric also being permeable to hydrogen.

[0059] The present invention has the advantages of providing a method for producing large amounts of hydrogen, which consumes little energy because hydrogen can be obtained substantially without external input of thermal energy and electrical energy, has little impact on the environment because no CO2 is emitted into the atmosphere, and is inexpensive because hydrochloric acid is a substance that is widely available commercially.

[0060] The advantages of the present invention will become more clearly apparent from the following detailed description of preferred embodiments, given as non-limiting examples. [Brief explanation of the drawings]

[0061] [Figure 1] FIG. 1 shows a diagram of a plant for producing hydrogen according to a preferred embodiment of the method according to the invention. [Figure 2] FIG. 2 is a detailed view of the electrodes of the plant diagram of FIG. DETAILED DESCRIPTION OF THE INVENTION

[0062] 1 shows a plant 100 for the continuous production of hydrogen. It essentially comprises a buffer tank 1 for storing an aqueous solution 20, two reactors 2 and 3 for producing hydrogen that are identical to each other and arranged in parallel, lines 21, 22 and 21, 23, respectively, for feeding the aqueous solutions from the buffer tank 1 to the reactors 2 and 3, and means 4 and 5, for example conventional discharge pipes, for removing the hydrogen gas produced in said reactors 2 and 3.

[0063] Reactors 2 and 3 each contain a cartridge, designated by the numerals 6 and 7, respectively, each cartridge equipped with a plurality of electrodes made of a metal alloy of metals having different standard reduction potentials.

[0064] The metal alloy contains magnesium and at least one metal selected from the group consisting of beryllium (Be), aluminum (Al), manganese (Mn), zinc (Zn), iron (Fe), copper (Cu), silicon (Si), and nickel (Ni), preferably in an amount of 85 to 95% by weight, more preferably 90 to 91% by weight.

[0065] The electrodes are obtained from the metals present in granular form by a process in which the metals present in granular form are mixed and heated until completely melted, the molten mass thus obtained is cast into a dedicated mold in which it cools and solidifies, and finally the electrode according to the invention is removed from the mold.

[0066] According to a preferred embodiment of the present invention, prior to casting the molten mass, a metal element, such as an iron or carbon steel rod, is placed in the mold. Preferably, the metal element is placed inside the mold so that one end of the metal element is not in contact with the molten mass. When the molten mass cools and the electrode is removed from the mold, the end of the metal element is located outside the electrode and protrudes from it.

[0067] A preferred embodiment of the electrode according to the present invention is shown in FIG.

[0068] 2 shows a schematic representation of an electrode 200 comprising a substantially cylindrical body 201 made of the metal alloy. The cylindrical body 201 has a metal rod 202 housed therein. The metal rod 202 has one end 203 protruding from the cylindrical body 201. The end 203 has a graphite element 204 fixed thereto. Preferably, the graphite element is screwed onto the end of the metal rod 202, and a plastic washer 205 is disposed between the graphite element 204 and the cylindrical body 201. In this way, contact is formed between the graphite element 203 and the metal rod 202.

[0069] The cylindrical body 201 in turn has an outer coating layer generally designated 206. The outer coating layer 206 comprises a layer 207 of at least one metal fluoride (in particular magnesium fluoride, aluminum fluoride and / or zinc fluoride) mixed with a methacrylic resin 208, preferably 60% by weight PFTE, 20% by weight 1,2-propanediol monomethacrylate (CAS 27813-02-1) and 20% by weight hydroxyethyl methacrylate (CAS 868-77-9).

[0070] The outer coating layer 206, consisting of at least one metal fluoride and methacrylic resin, is in turn advantageously coated by wrapping with a perforated tape or PTFE mesh 209 having a thickness of a few microns, for example 1 μm to 3 μm.

[0071] In the example of FIG. 1, the electrodes and cartridges 6 and 7 are each placed inside reactors 2 and 3 in an elevated position relative to the bottom.

[0072] Each of the reactors 2 and 3 is in fluid communication with the buffer tank 1 by respective lines 26, 28 and 27, 28 for recirculating the aqueous solution, which passes through a series of devices for treating said aqueous solution. In particular, each of the reactors 2 and 3 is in fluid communication with a cooling device 8, 9, consisting of at least one heat exchanger (not shown), via the aforementioned recirculation line. From the cooling devices 8 and 9, the aqueous solution flows into a filtration device 10, which includes a porous baffle membrane filter. The porous baffle membrane filter is preferably filled with MnO (not shown) and is capable of separating (degassing) the oxygen (O) produced during hydrogen production in the reactors 2 and 3.

[0073] Each of the recirculation lines 26, 28, 27, 28 is connected to the interior of the reactors 2, 3 via a special outlet pipe 12, 13 that extends substantially to the bottom of said reactors. In particular, the openings of said outlet pipes 12, 13 are located below the cartridges 6, 7, between the bottom of the reactors 2, 3 and the base of the cartridges themselves.

[0074] The plant also has one or more lines for the internal recirculation of the aqueous solution present in the buffer tank 1. If required, these lines can be connected via respective connecting ducts to lines for feeding the reactor with the aqueous solution. In the example shown in Figure 1, there are two internal recirculation lines 24 and 25 connected to the feed lines 22 and 23 via respective connecting ducts 24b and 25b.

[0075] The plant also comprises a section 14 upstream of the buffer tank 1, in which the aqueous solution 10 is prepared by mixing an acid solution 40 of hydrochloric acid with main water 41. This section 14 essentially comprises a tank 15 for storing the acid solution 40, a device 16 for filtering the main water, and a line 42 for supplying the filtered water.

[0076] The flow of main water 41 is controlled by valve V1 upstream of filtration device 16 and check valve V2 downstream of it. Instead, solution 40 is pumped by pneumatic pump P1 connected to tank 15. Pneumatic pump P1 is activated when buffer tank 1 is filled, opening pneumatic valve V3. Solution 40 then passes through check valve V4 and mixes with filtered main water 42 to form the aforementioned aqueous solution 20.

[0077] The aqueous solution 20 preferably contains hydrochloric acid in an amount of 3% to 20% by volume, 5% to 10% by volume, and preferably 6% to 7% by volume.

[0078] In use, the plant 100 operates as follows.

[0079] The buffer tank 1 is filled with an aqueous solution 20. The aqueous solution is then fed into reactors 2 and 3 until it reaches liquid levels L1 and L2, respectively.

[0080] More specifically, and with reference to the example shown in Figure 1, the aqueous solution leaving buffer tank 1 via line 21 is pumped by pump P2, conveyed through flow meter 17 which controls the filling of reactors 2 and 3, and then split into two portions, each of which is fed to reactors 2 and 3 via lines 22 and 23, passing through respective pneumatic valves V6 and V7.

[0081] Once the reactor is filled, the aqueous solution remains in the reactor for a predetermined time (preferably in the range of a few minutes) and reacts in the presence of the electrodes to produce oxygen and hydrogen gas according to reaction (4): HO(l) → O(g) + 2H(g). The reaction temperature is preferably between 55°C and 60°C, and the pressure is between 2.5 bar and 3 bar.

[0082] The hydrogen gas thus obtained is low in molecular weight and is released from the solution and accumulated in the collection chambers in the reactors 2 and 3. The collection chambers are located between the liquid levels L1 and L2 and the lids of the respective reactors. The hydrogen accumulated in the collection chambers is removed from the reactors 2 and 3 through the respective discharge pipes 4 and 5 and stored in a suitable vessel (not shown).

[0083] Instead, the aqueous solutions are withdrawn through respective outlet pipes 12, 13 and recirculated in recirculation lines 26, 27. The withdrawal of the aqueous solutions is controlled by pneumatic valves V5 and V6, the opening of which is controlled by the liquid levels L1 and L2 in reactors 2, 3.

[0084] The openings of the outlet pipes 12, 13 below the cartridges 6, 7 are positioned so that the hydrogen gas produced at the electrodes is not drawn into the recirculation lines 26, 27 along with the aqueous solution.

[0085] The aqueous solution removed from the reactors via recirculation lines 26, 27 is first subjected to a cooling step in the heat exchangers of cooling devices 8, 9 by indirect heat exchange with a cooling water stream (not shown). The aqueous solution circulating in recirculation lines 26, 27 is cooled so as to maintain a constant temperature (preferably 55°C to 60°C) inside reactors 2, 3.

[0086] The thus cooled aqueous solution is then subjected to a degassing step in order to remove oxygen from the aqueous solution. This degassing step preferably involves a filtration step carried out under vacuum inside a filtration device 10, whereby oxygen is separated from the aqueous solution and removed via a dedicated outlet pipe 32. The term under vacuum means a pressure slightly below 1 bar, for example between 0.5 bar and 0.8 bar.

[0087] In addition to oxygen, chlorine (Cl) is also released separately during the filtration process carried out inside the apparatus 10, preferably using a porous baffled membrane filter filled with MnO (not shown). The chlorine is then recovered by reintroducing it into the aqueous solution, preferably by bubbling.

[0088] The substantially oxygen-free aqueous solution is then recycled to the buffer tank 1 via the recirculation line 28 .

[0089] The aqueous solution 20 is continuously reintroduced from the buffer tank 1 into the reactors 2 and 3 via feed lines 21, 22, 23, 24 so as to maintain constant liquid levels L1 and L2. The aqueous solution 20 is kept in constant motion by being recirculated through internal recirculation lines 24 and 25. To enable the recirculation, the aqueous solution is pumped by respective pumps P3 and P4.

[0090] During operations involving inspection or maintenance of reactors 2 and 3, reactors 2 and 3 are emptied via respective flow paths 29 and 30, and the aqueous solution is sent as stream 31 to a waste collection tank (not shown). During these operations, the electrodes can be regenerated, if necessary. In particular, the outer coating layer 206 of the electrodes can be restored by immersing the electrodes in an aqueous solution of hydrofluoric acid for a suitable time (e.g., 10 to 20 minutes, preferably 15 minutes).

[0091] If desired, during operation of the plant, a portion of the aqueous solution circulating in the internal recycle lines 24, 25 can be fed to the reactors 2, 3 via respective ducts 24b, 25b connecting the recycle lines 24, 25 to the respective feed lines 22, 23.

[0092] The equipment used in the plant is advantageously realized in a sealed manner, preferably made of steel, and in addition to the filtering device 10, the buffer tank 1 also operates under vacuum. In this case, the pressure in the buffer tank 1 is 0.03 bar to 0.08 bar. This prevents the oxygen present in the aqueous solution from coming into contact with the outside air. [Example]

[0093] In the following, an example of the method according to the invention will be described.

[0094] Two identical cylindrical reactors with a height of 120 cm and a diameter of 30 cm were used.

[0095] Into each reactor was introduced a cartridge containing 32 electrodes, also cylindrical, 40 cm high and 4 cm in diameter, made of a metal alloy consisting of 90.81% Mg, 5.83% Al, 2.85% Zn, 0.45% Mn, 0.046% Si, 0.0036% Cu, 0.0012% Be, 0.0010% Fe, and 0.00050% Ni.

[0096] The cartridge was positioned at a height of approximately 20 cm from the bottom of the reactor.

[0097] Each reactor was then filled with a solution containing water and hydrochloric acid to a total volume of 25 liters.

[0098] Said solution was prepared by introducing 2.36 liters of 38% hydrochloric acid solution into a quantity of main water corresponding to the aforementioned volume of 25 liters.

[0099] Therefore, the composition of the solution in the reactor was 26.464 liters of water and 0.896 liters of hydrochloric acid.

[0100] In other words, the mixture contained 96.72% by volume of primary water and 3.28% by volume of hydrochloric acid.

[0101] The solution residence time was approximately 15 minutes, and the 3 / h of hydrogen gas could be produced. In this hydrogen production method, an energy consumption of less than 1.5 kWh was advantageously achieved.

[0102] According to a further embodiment, the method of the present invention also comprises providing hydrofluoric acid (HF) in an aqueous solution (20) containing hydrochloric acid in dissociated form. Preferably, such hydrofluoric acid (HF) is added in an amount of 50 ml to 70 ml, most preferably 60 ml, per 10,000 ml of said aqueous solution.

[0103] In this regard, aqueous solutions for use in the methods of the present invention may also contain hydronium ions (HO + ) and chloride ions (Cl - In addition to the above amount of hydrofluoric acid (HF), the aqueous solution contains the above amount of hydrofluoric acid (HF). In such an aqueous solution, the hydrofluoric acid undergoes ionic dissociation.

[0104] Particularly satisfying results are obtained by illuminating the electrodes with visible coherent light, especially LED light, which increases the production of hydrogen gas (H2) by up to 20%.

Claims

1. A method for producing hydrogen starting from an aqueous solution (20) containing hydrochloric acid in dissociated form, comprising: The aqueous solution contains hydronium ions (H ３ O ＋ ) in which at least one electrode made of a metal alloy containing a plurality of metals having different standard reduction potentials is present; Electrons generated at the at least one electrode flow from the metal with the lower potential to the metal with the higher potential between the metal pair, resulting in the formation of hydronium ions (H ３ O ＋ ) into hydrogen gas (H ２ ) and removing the resulting hydrogen gas from the aqueous solution; Including, The outer surface of the at least one electrode is coated with a coating layer containing at least one metal fluoride. method.

2. 10. The method of claim 1, wherein the metal alloy comprises magnesium and at least one metal selected from the group consisting of beryllium (Be), aluminum (Al), manganese (Mn), zinc (Zn), iron (Fe), copper (Cu), silicon (Si), and nickel (Ni).

3. The method of claim 2 wherein the metal alloy comprises primarily magnesium.

4. The method of claim 3, wherein the metal alloy comprises magnesium in an amount ranging from 85% to 95% by weight.

5. The metal alloy of the at least one electrode is A) Mg: 90.81%, Al: 5.83%, Zn: 2.85%, Mn: 0.45%, Si: 0046%, Cu: 0.0036%, Be: 0.0012%, Fe: 0.0010%, Ni: 0.00050% or b) Mg: 90.65%, Al: 5.92%, Zn: 2.92%, Mn: 0.46%, Si: 0043%, Cu: 0.0036%, Be: 0.0012%, Fe: 0.0010%, Ni: 0.00050% 5. The method of any one of claims 2 to 4, comprising:

6. 6. The method of claim 1, wherein the coating layer comprises the at least one metal fluoride mixed with a methacrylic resin.

7. 7. The method of claim 6, wherein the methacrylic resin comprises 50% to 70% by weight of PFTE, 15% to 25% by weight of 1,2-propanediol monomethacrylate (CAS 27813-02-1), and 15% to 25% by weight of hydroxyethyl methacrylate (CAS 868-77-9).

8. 8. The method of claim 7, wherein the methacrylic resin comprises 60% by weight of PFTE, 20% by weight of 1,2-propanediol monomethacrylate (CAS 27813-02-1), and 20% by weight of hydroxyethyl methacrylate (CAS 868-77-9).

9. The method according to any one of claims 1 to 8, wherein the coating layer of the at least one electrode has a thickness of 0.5 mm to 3.0 mm.

10. 10. The method according to claim 1, wherein the at least one electrode has a graphite element at one of its ends, and the coating layer on the outer surface of the at least one electrode does not cover the graphite element.

11. The method of claim 10 , wherein a metal element is provided within the at least one electrode, the metal element being in contact with the graphite element.

12. 12. The method according to claim 1, wherein the covering layer on the outer surface is wrapped with a perforated tape or a PTFE mesh, or a semi-permeable cloth tape that is permeable to the aqueous solution towards the electrode and impermeable to the aqueous solution in the opposite direction.

13. 13. The method according to any one of claims 1 to 12, wherein the aqueous solution comprises hydrochloric acid at a concentration of 5% to 10%.

14. 14. The method of any one of claims 1 to 13, wherein the pH of the aqueous solution is in the range of 2 to 4.

15. 15. The method of any one of claims 1 to 14, wherein the reduction reaction of hydronium ions to hydrogen gas is carried out at a temperature of 20°C to 70°C.

16. 16. The method of any one of claims 1 to 15, wherein the reduction of hydronium ions to hydrogen gas is carried out at a pressure below atmospheric pressure.

17. 17. The method of any one of claims 1 to 16, wherein the aqueous solution is regenerated by a step of recycling the aqueous solution and a step of degassing, the step of degassing comprising a step of filtering in which oxygen is removed from the aqueous solution.

18. The filtration step is carried out using a porous baffle membrane filter, and oxygen (O ２ ) and chlorine (Cl ２ 18. The method of claim 17, wherein both the active ingredient and the active ingredient are released separately.

19. 20. The method of claim 18, wherein the released chlorine is recovered and reintroduced into the aqueous solution.

20. 20. The method of any one of claims 17 to 19, wherein the recycling step comprises cooling the aqueous solution adjusted to maintain a substantially constant reaction temperature.

21. 21. The method of any one of claims 1 to 20, further comprising providing hydrofluoric acid (HF) in the aqueous solution (20) containing hydrochloric acid in dissociated form.

22. 22. The method of claim 21, wherein the hydrofluoric acid (HF) is added in an amount of 50 ml to 70 ml per 10,000 ml of the aqueous solution.

23. 23. The method of any one of claims 1 to 22, comprising illuminating the electrode(s) with visible coherent light.

24. 24. The method of claim 23, comprising illuminating the electrode(s) with LED light.

25. A plant for producing hydrogen according to the method of claims 1 to 24, comprising: at least one buffer tank (1) for storing an aqueous solution (20) containing hydrochloric acid in dissociated form; At least one reactor (2, 3) for producing hydrogen, the reactor (2, 3) containing therein at least one electrode made of a metal alloy containing a plurality of metals having different standard reduction potentials; at least one supply line (22, 23) for supplying the aqueous solution from the at least one buffer tank (1) to the at least one reactor (2, 3); at least one recirculation line (26, 28; 27, 28) for recirculating the aqueous solution from the at least one reactor (2, 3) to the at least one buffer tank (1); at least one device (10) for regenerating said aqueous solution, arranged along said at least one recirculation line (26, 28; 27, 28); means (4, 5) for removing hydrogen gas from said at least one reactor; Plants including.

26. The at least one regenerator (10) extracts oxygen (O ２ 26. The plant of claim 25, further comprising a filtration device comprising at least one porous baffle membrane filter capable of separating the condensate.

27. 27. The plant of claim 26, wherein the filtration device operates under vacuum.

28. 28. Plant according to any one of claims 25 to 27, comprising at least one cooling device (8, 9) along said at least one recirculation line (26, 28; 27, 28).

29. An electrode used in the method for producing hydrogen according to any one of claims 1 to 24, An electrode made of a metal alloy containing magnesium and at least one metal selected from the group consisting of beryllium (Be), aluminum (Al), manganese (Mn), zinc (Zn), iron (Fe), copper (Cu), silicon (Si), and nickel (Ni).

30. 30. The electrode of claim 29, wherein the metal alloy comprises magnesium in an amount ranging from 85% to 95% by weight.

31. The metal alloy is A) Mg: 90.81%, Al: 5.83%, Zn: 2.85%, Mn: 0.45%, Si: 0046%, Cu: 0.0036%, Be: 0.0012%, Fe: 0.0010%, Ni: 0.00050% or b) Mg: 90.65%, Al: 5.92%, Zn: 2.92%, Mn: 0.46%, Si: 0043%, Cu: 0.0036%, Be: 0.0012%, Fe: 0.0010%, Ni: 0.00050% 31. The electrode of claim 30, comprising:

32. 32. The electrode of any one of claims 29 to 31, wherein the coating layer comprises the at least one metal fluoride mixed with a methacrylic resin.

33. 33. The electrode of claim 32, wherein the methacrylic resin comprises 50% to 70% by weight of PFTE, 15% to 25% by weight of 1,2-propanediol monomethacrylate (CAS 27813-02-1), and 15% to 25% by weight of hydroxyethyl methacrylate (CAS 868-77-9).

34. 34. The electrode of claim 33, wherein the methacrylic resin comprises 60% by weight of PFTE, 20% by weight of 1,2-propanediol monomethacrylate (CAS 27813-02-1), and 20% by weight of hydroxyethyl methacrylate (CAS 868-77-9).

35. 35. The electrode of any one of claims 29 to 34, wherein the coating layer of the electrode has a thickness of 0.5 mm to 3.0 mm.

36. 36. The electrode of claim 29, wherein the at least one electrode has a graphite element at one of its ends, and the coating layer on the outer surface of the at least one electrode does not cover the graphite element.

37. 37. The electrode of claim 36, wherein a metal element is provided within the electrode, the metal element contacting the graphite element.

38. 38. The electrode of any one of claims 29 to 37, wherein the covering layer on the outer surface is wrapped with perforated tape or PTFE mesh, or semi-permeable cloth tape that is permeable to aqueous solutions towards the electrode and impermeable to the aqueous solutions in the opposite direction.

39. 1. A method for coating an electrode made of a metal alloy containing a plurality of metals having different standard reduction potentials, comprising: The electrode is used in a method for producing hydrogen according to any one of claims 1 to 24, - immersing said electrode in a bath of hydrofluoric acid and water, in which the metal comprising the outer surface of said electrode reacts with said hydrofluoric acid to form a fluorinated patina of metal fluoride salt; a first drying step for drying said fluorinated patina of metal fluoride salts; - applying a methacrylic resin gel onto said fluorinated patina; a second drying step of drying the resulting mixture containing the metal fluoride and the methacrylic resin; A method for coating an electrode, comprising:

40. 40. The method of coating an electrode according to claim 39, wherein the methacrylic resin comprises 50% to 70% by weight of PFTE, 15% to 25% by weight of 1,2-propanediol monomethacrylate (CAS 27813-02-1), and 15% to 25% by weight of hydroxyethyl methacrylate (CAS 868-77-9).

41. 41. A method of coating an electrode according to claim 39 or claim 40, wherein at the end of the second drying step, the electrode is wrapped in perforated tape or PTFE mesh, or in semi-permeable cloth tape that is permeable to the aqueous solution towards the electrode and impermeable to the aqueous solution in the opposite direction.

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