WO2022172241A1 - System for recycling condensates and plant for generating hydrogen comprising the recycling system - Google Patents

System for recycling condensates and plant for generating hydrogen comprising the recycling system Download PDF

Info

Publication number
WO2022172241A1
WO2022172241A1 PCT/IB2022/051294 IB2022051294W WO2022172241A1 WO 2022172241 A1 WO2022172241 A1 WO 2022172241A1 IB 2022051294 W IB2022051294 W IB 2022051294W WO 2022172241 A1 WO2022172241 A1 WO 2022172241A1
Authority
WO
WIPO (PCT)
Prior art keywords
plant
electrolytic cell
hydrogen
control unit
condensates
Prior art date
Application number
PCT/IB2022/051294
Other languages
French (fr)
Inventor
Ledi ZUCCHIATTI
Original Assignee
Hydorghen S.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hydorghen S.R.L. filed Critical Hydorghen S.R.L.
Priority to EP22709801.9A priority Critical patent/EP4291693A1/en
Publication of WO2022172241A1 publication Critical patent/WO2022172241A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
    • C25B15/027—Temperature
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083—Separating products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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

Definitions

  • This invention relates to a plant for generating hydrogen from water.
  • Said plants comprise a control unit which controls the electricity supply to said plates.
  • the electricity supplied to the plates allows the breaking of the molecular links of the water causing separation of the hydrogen and oxygen atoms.
  • the two electrodes are separated by a diaphragm which has the purpose of keeping separate the gases produced, for reasons of efficiency and safety, but it is permeable for the hydroxide ions and the water molecules.
  • the process follows the Faraday law, according to which the quantity of gas produced is directly proportional to the quantity of current passing through the electrodes.
  • the oxidation reduction reaction occurs at the electrodes under the effect of a difference of potential which feeds the exchange of ions (positives) to the cathode, which is negative, and electrons (negative) to the positive anode.
  • Alkaline electrolysis currently constitutes the most commonly used technology but still has problems relative to a low efficiency.
  • the diaphragm does not completely prevent the recombination of the gases produced and the diffusion of oxygen in the cathode chamber may occur, with a reduction in efficiency.
  • the liquid electrolyte is unsuitable for operating at high pressures, making the configuration of the electrolytic cells bulky.
  • the electrolyte consisting of potassium hydroxide (at 10-40%) is highly corrosive.
  • the aim of the invention is to provide a plant for generating hydrogen and a method for generating hydrogen which overcome the above-mentioned drawbacks of the prior art.
  • the invention provides a plant for generating hydrogen from water (demineralised water).
  • the plant comprises an electrolytic cell.
  • the electrolytic cell is submerged in an alkaline bath, preferably including potassium hydroxide.
  • the cell comprises a first plate (first electrode), defining a cathode of the cell.
  • the cell comprises a second plate (second electrode), defining an anode of the cell.
  • the first and second plates are spaced from each other along a direction perpendicular to the first and second plates.
  • the plant comprises a water supply line, configured to feed water to the electrolytic cell.
  • the plant comprises a power supply unit, configured to supply electrical power to the plant.
  • the plant comprises a control unit, connected to the power supply unit.
  • the control unit is connected to said electrolytic cell to control an electric current transmitted by the power supply unit to the cell.
  • the plant comprises a system for collecting the gases produced.
  • the collecting system comprises a first tank.
  • the first tank is configured to collect the hydrogen coming from said cell.
  • the collecting system comprises a second tank.
  • the second tank is configured to collect the oxygen coming from said cell.
  • the first plate of each of said electrolytic cell is made from a special alloy including one or more of the following materials: iron, carbon, chrome, nickel, copper, manganese, silicon, phosphorous, thallium, tungsten, sulphur and palladium.
  • the special alloy is characterised by one or more of the following percentages:
  • the main advantage obtained from the above-mentioned composition consists of the best molecular dissociation of the water and the production of atomic hydrogen, since the action of the components of the alloy in those particular percentages has a particular and surprising catalytic effect.
  • the accelerated formation of gas results in a large advantage in terms of energy consumption.
  • the second plate is also made of the special alloy.
  • the electric current applied to the cell is applied with direct current.
  • the invention provides a system for recycling condensates, configured for recovering the condensates which are formed in the collecting system: the recycling system is configured for recirculating the condensates in the electrolytic cell.
  • the recovery system comprises a first cooler.
  • the first cooler is configured to cool the separated hydrogen.
  • the recovery system comprises a second cooler.
  • the second cooler is configured to cool the separated oxygen.
  • the first cooler comprises a respective first recovering element, configured to collect the condensate which is formed in response to the cooling.
  • the second cooler comprises a respective second recovering element, configured to collect the condensate which is formed in response to the cooling.
  • the condensate recovered in the first and/or second recovering elements is recirculated into the electrolytic cell.
  • the control unit is programmed to apply a pulsed electrical energy to the condensates recovered in the first and/or second elements.
  • the control unit is programmed to apply a low voltage current to the condensates recovered.
  • the low voltage current has an oscillation, preferably with a square wave.
  • the low voltage current has a variable frequency.
  • the control unit is programmed to generate a square wave with a frequency variation in a range of between 2 kHz and 25 kHz, preferably between 5 kHz and 20 kHz.
  • the plant comprises a temperature sensor, configured for capturing temperature signals, representing a temperature of the alkaline bath.
  • the temperature sensor is programmed to send the temperature signals to the control unit.
  • the control unit is programmed to vary the intensity and frequency of the low voltage current, on the basis of the temperature signals received.
  • the invention provides a method for generating hydrogen from water.
  • the method comprises a step of supplying water to an electrolytic cell.
  • the method comprises a step of supplying electricity to a first plate and a second plate of the electrolytic cell using a power supply unit.
  • the method comprises a step of controlling the electricity supply of the first and second plate using a control unit.
  • the method comprises a step of performing alkaline water electrolysis to separate hydrogen and oxygen.
  • the method comprises a step of collecting hydrogen and oxygen in a first tank and a second tank, respectively.
  • the method is performed with the first plate of said electrolytic cell made from a special alloy including at least the following materials: iron, carbon, chrome, nickel, copper and manganese.
  • the invention provides a method for making an electrolytic cell.
  • the method comprises a step of preparing a special alloy including one or more of the following materials: iron, carbon, chrome, nickel, copper, manganese, silicon, phosphorous, thallium, tungsten, sulphur and palladium.
  • the method comprises a step of melting the special alloy.
  • the method comprises a step of manufacturing a first plate and a second plate of the electrolytic cell using the special fused alloy.
  • the method comprises a recycling step.
  • a system for recycling the condensates recovers the condensates which are formed in the collecting system.
  • the collecting system recirculates the condensates in the electrolytic cell.
  • the method advantageously comprises a cooling step, in which the hydrogen and/or the oxygen are cooled in a first and/or a second cooler, respectively.
  • a first and/or a second collecting element collect the condensates formed in the first and/or in the second cooler, respectively.
  • the method comprises a charging step, in which the control unit applies to the condensates a pulsed electrical energy, preferably with a low voltage current with a variable frequency square wave oscillation.
  • the numeral 1 denotes a plant for generating hydrogen from water.
  • the water used is demineralised, that is to say, pure water.
  • the plant 1 comprises a demineralising unit, by which the water is demineralised before being processed.
  • the plant 1 comprises a supply line 10, configured for supplying water to the plant 1.
  • the supply line 10 may draw water from a tank 100 of demineralised water or from a continuous supply line.
  • the supply line 10 comprises a pump 101 , designed to provide a head to the water.
  • the plant 1 comprises an electrolytic cell 11.
  • the supply line 10 is connected to the electrolytic cell 11 for conveying inside the water.
  • the supply line 10 comprises a heater 102, configured to preheat the water before it is introduced into the electrolytic cell 11.
  • the electrolytic cell 11 is submerged in an alkaline bath, that is, submerged in an alkaline liquid electrolyte.
  • said alkaline liquid electrolyte is potassium hydroxide KOH.
  • the percentage of KOH may vary from 10% to 40%.
  • the electrolytic cell 11 comprises one or more pairs of plates 111. Hereinafter in this description, only one of the plates 111 will be described, observing that the same features can also be extended to the other pairs of plates 111.
  • Each pair of plates 111 comprises a first plate 111 A and a second plate 111 B.
  • Each pair of plates 111 comprises a diaphragm 111C, interposed between the first and the second plate 111 A, 111 B.
  • the purpose of the diaphragm 111C is to keep separate the gases produced by the plant 1 , for reasons of efficiency and safety, but it is permeable for the hydroxide ions and the water molecules.
  • Each of said first plate 111 A and second plate 111 B is connected to an electricity supply and constitute a cathode and an anode of the pair 111.
  • the plant 1 comprises a power supply unit 12, configured for supplying the electrolytic cell 11 (the pairs of plates 111) with an electrical power.
  • the water inside the electrolytic cell 111 undergoes the electrolysis process, according to which, according to the Faraday law, the quantity of gas produced is directly proportional to the quantity of current passing through the electrodes.
  • the energy with which the plates are supplied is in fact transmitted in the form of Gibbs free energy which breaks the atomic links in the molecule of water.
  • the plant 1 comprises a control unit 13.
  • the control unit 13 is connected to the power supply unit 12 to control the electrical power transmitted to the electrolytic cell 11.
  • the control unit 13 is configured to control the power supply unit 12 in such a way that the latter supplies the electrolytic cell 11 with a direct current, preferably 515 V.
  • the first plate 111 A and the second plate 111 B are made from a special alloy including one or more of the following materials: iron, carbon, chrome, nickel, copper, manganese, silicon, phosphorous, thallium, tungsten, sulphur and palladium.
  • both the first plate 111 A and the second plate 111 B are made with the same special alloy, precisely because the control could comprise a reversal of polarity.
  • the plant 1 comprises a first outlet line 14A.
  • the plant 1 comprises a second outlet line 14B.
  • the first outlet line 14A is configured to receive (that is to say, remove) the gaseous hydrogen obtained by the water electrolysis from the first plate 111 A.
  • the second outlet line 14B is configured to receive (that is to say, remove) the gaseous oxygen obtained by the water electrolysis from the second plate 111 B.
  • the plant 1 comprises a first tank 15A, configured for storing the gaseous hydrogen obtained before it is used.
  • the plant 1 comprises a second tank 15B, configured for storing the gaseous oxygen obtained before it is used.
  • Each of said first and second tanks 15A, 15B is configured to collect, on its bottom, any condensate which might be formed in the first or in the second tank 15A, 15B.
  • the plant 1 comprises a recycling system 17, configured for recovering the condensates obtained downstream of the electrolytic cell 11 , in the water processing path.
  • the first and the second tank 15A, 15B are connected with the recycling system 17, for conveying the condensates therein.
  • the plant 1 comprises a first cooler 16A.
  • the plant comprises a second cooler 16B.
  • the first cooler 16A is configured to cool the hydrogen.
  • the second cooler 16B is configured to cool the oxygen. The cooling of the hydrogen makes it possible to obtain a particularly pure product.
  • the cooling operation is an operation which results in a significant generation of condensate, in any case greater than that collected in the previous storage.
  • the first cooler 16A comprises a first recovering element 161 A, which collects the condensates which are formed during the cooling of the hydrogen.
  • the second cooler 16B comprises a second recovering element 161 B, which collects the condensates which are formed during the cooling of the oxygen.
  • the first recovering element 161 A and/or the second recovering element 161 B are connected to the recycling system 17 for conveying the condensates therein.
  • the recycling system 17 is connected to the electrolytic cell 11 for conveying again inside it the recovered condensates.
  • the plant comprises a pulsed current applicator 18.
  • the pulsed current applicator 18 intercepts the recycling system 17, in such a way as to apply to the condensates a pulsed current, with a square wave, with variable frequency.
  • the pulsed current applicator is connected to the control unit 13, which is programmed to control the frequency of the square wave of the pulsed current.
  • the recycling system 17 comprises a manifold 171 , on which are conveyed the condensates formed in the first and second tanks 15A, 15B and into the first and second coolers 16A, 16B.
  • the recycling system 17 comprises a recirculation pump 172, configured for pumping the condensates up to the electrolytic cell 111.
  • the control unit 13 is programmed to send control signals 131 , identifying a frequency of the square wave.
  • the frequency is adjusted in a range of between 5 kHz and 20 kHz.
  • the generation of the wave and the sequence of the frequency variations, managed by the control unit 13 using dedicated software, are carried out through a process of suitable filtering of one or more harmonics generated by the primary wave.
  • the plant 1 comprises a temperature sensor 19, which is positioned at the cell 11 for capturing temperature signals 132, representing a temperature of the alkaline bath.
  • the temperature sensor 19 is programmed to send the temperature signals 132 to the control unit 13.
  • the control unit 13 varies the frequency of the square wave on the basis of the temperature signals 132 received.
  • control unit 13 is programmed to generate the control signals 131 in response to the temperature signals 132.
  • the electrolytic cell comprises 274 plates with a spacing (distance from each other) of 2.5 mm.
  • the length of the electrolytic cell 11 is 760 mm, whilst its extension is 200 mm x 200 mm each.
  • control unit 13 is programmed to vary the voltage intensity of the pulsed current applied to the condensates, in response to the concentration of the electrolytic solution KOH and/or the distance between the first plate 111 A and the second plate 111 B of each pair 111.
  • a plant 1 for generating hydrogen from water comprising: - an electrolytic cell 11 , submerged in an alkaline bath and including:
  • a second plate 111 B spaced from the first plate 111A along a direction perpendicular to the first and second plates 111 A, 111 B and forming an anode of the cell; - a water supply line 10, configured to feed water to the electrolytic cell 11 ;
  • a power supply unit 12 configured for supplying an electrical power to the cell 11 ;
  • a control unit 13 connected to the power supply unit 12 to control an electrical current transmitted from the power supply unit 12 to said cell 11 ;
  • a collecting system including a first tank 15A, configured to collect the hydrogen coming from said electrolytic cell 11 , and a second tank 15B, configured to collect the oxygen coming from said electrolytic cell 11 , characterised in that the first plate 111 A of said electrolytic cell 11 is made from a special alloy, including iron and carbon. A00. The plant according to paragraph A0, wherein the special alloy includes phosphorous.
  • A13 The plant 1 according to any one of paragraphs A0 to A12, comprising a system for recycling the condensates 161 A, 161B, configured to recover the condensates which are formed in the first and in the second tank 15A, 15B and to recirculate them in the electrolytic cell.
  • A14 The plant 1 according to paragraph A13, wherein the control unit 13 is programmed to apply a pulsed electrical energy to said condensates.
  • a method for generating hydrogen from water comprising the following steps:
  • first plate 111 A of said electrolytic cell 11 is made from a special alloy, including one or more of the following materials: iron, carbon, chrome, nickel, copper, silicon, sulphur, palladium, phosphorous, thallium, tungsten and manganese.
  • a method for making an electrolytic cell comprising the following steps: - preparing a special alloy including one or more of the following elements: iron, carbon, chrome, nickel, copper, silicon, sulphur, palladium, phosphorous, thallium, tungsten and manganese;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Described is a plant (1) for generating hydrogen from water, comprising: an electrolytic cell (11), submerged in an alkaline bath and configured to perform an alkaline water electrolysis, to separate the hydrogen from the oxygen; a water supply line (10), configured to feed water to the electrolytic cell (11); a power supply unit (12), configured to provide the plant (1) with electrical power; a control unit (13), connected to the power supply unit (12) to control an electrical current transmitted from the power supply unit (12) to said cell (11); a collecting system (161 A, 161 B), configured to collect the hydrogen and the oxygen coming from said electrolytic cell; a condensate recycling system (17) configured to recover the condensates which are formed in the collecting system (161 A, 161 B) and to recirculate them into the electrolytic cell (11).

Description

DESCRIPTION
SYSTEM FOR RECYCLING CONDENSATES AND PLANT FOR GENERATING HYDROGEN COMPRISING THE RECYCLING SYSTEM
Technical field This invention relates to a plant for generating hydrogen from water.
Background art
In the sector of plants for generating hydrogen, the use is known of plants which use the process of alkaline electrolysis of demineralised water. Said electrolysis processes comprise the use of electrolytic cells, embedded in an alkaline solution, which include a first plate (first electrode - cathode) and a second plate (second electrode - anode). The alkaline solution commonly used is potassium hydroxide KOH.
Said plants comprise a control unit which controls the electricity supply to said plates.
The electricity supplied to the plates allows the breaking of the molecular links of the water causing separation of the hydrogen and oxygen atoms. The two electrodes are separated by a diaphragm which has the purpose of keeping separate the gases produced, for reasons of efficiency and safety, but it is permeable for the hydroxide ions and the water molecules. The process follows the Faraday law, according to which the quantity of gas produced is directly proportional to the quantity of current passing through the electrodes.
The oxidation reduction reaction occurs at the electrodes under the effect of a difference of potential which feeds the exchange of ions (positives) to the cathode, which is negative, and electrons (negative) to the positive anode.
The atomic links in the water molecule are broken by the Gibbs free energy. Alkaline electrolysis currently constitutes the most commonly used technology but still has problems relative to a low efficiency. Moreover, the diaphragm does not completely prevent the recombination of the gases produced and the diffusion of oxygen in the cathode chamber may occur, with a reduction in efficiency. Moreover, the liquid electrolyte is unsuitable for operating at high pressures, making the configuration of the electrolytic cells bulky. The electrolyte, consisting of potassium hydroxide (at 10-40%) is highly corrosive.
Examples of plants for generating hydrogen are described in the following patent documents: EP2213769A1 , CN111364052A, JPH0885892A, US2013032472A1 and US2010163407A1.
Aim of the invention
The aim of the invention is to provide a plant for generating hydrogen and a method for generating hydrogen which overcome the above-mentioned drawbacks of the prior art.
Said aim is fully achieved by the plant and the method according to the invention as characterised in the appended claims.
According to an aspect of the invention, the invention provides a plant for generating hydrogen from water (demineralised water). The plant comprises an electrolytic cell. The electrolytic cell is submerged in an alkaline bath, preferably including potassium hydroxide. The cell comprises a first plate (first electrode), defining a cathode of the cell. The cell comprises a second plate (second electrode), defining an anode of the cell. The first and second plates are spaced from each other along a direction perpendicular to the first and second plates.
The plant comprises a water supply line, configured to feed water to the electrolytic cell. The plant comprises a power supply unit, configured to supply electrical power to the plant.
The plant comprises a control unit, connected to the power supply unit. The control unit is connected to said electrolytic cell to control an electric current transmitted by the power supply unit to the cell.
The plant comprises a system for collecting the gases produced. The collecting system comprises a first tank. The first tank is configured to collect the hydrogen coming from said cell. The collecting system comprises a second tank. The second tank is configured to collect the oxygen coming from said cell.
According to an aspect of the invention, the first plate of each of said electrolytic cell is made from a special alloy including one or more of the following materials: iron, carbon, chrome, nickel, copper, manganese, silicon, phosphorous, thallium, tungsten, sulphur and palladium.
It should be noted that phosphorous, thallium, tungsten and palladium, both individually and in combination with each other, make it possible to significantly increase the catalysing capacity of the electrolysis process, resulting in an increased efficiency of the hydrogen production system. These results have been checked by numerous experimental tests.
Said experimental tests have also shown that the manganese and copper, both individually and in combination, make it possible to significantly increase the conductive capacity of the first plate, increasing, overall, the efficiency of the process.
Lengthy and complex tests have also determine operational ranges in which significant advantages are obtained in terms of efficiency. In effect, according to an embodiment, the special alloy is characterised by one or more of the following percentages:
- percentage of iron between 68% and 69%;
- percentage of carbon between 0.10% and 0.14%;
- percentage of chrome between 17.5% and 17.9%;
- percentage of nickel between 9.7% and 9.9%;
- percentage of copper of between 0.2% and 0.35%;
- percentage of manganese between 1.5% and 3%;
- percentage of silicon between 0.5% and 1%;
- percentage of phosphorous between 0.02% and 0.06%; - percentage of thallium between 0.5% and 0.8%;
- percentage of sulphur between 0.01% and 0.04%;
- percentage of tungsten between 0.05% and 0.15%;
- percentage of palladium between 0.05% and 0.09%.
The main advantage obtained from the above-mentioned composition consists of the best molecular dissociation of the water and the production of atomic hydrogen, since the action of the components of the alloy in those particular percentages has a particular and surprising catalytic effect. The accelerated formation of gas results in a large advantage in terms of energy consumption.
Preferably, the second plate is also made of the special alloy.
According to a preferred embodiment, the electric current applied to the cell is applied with direct current.
According to an aspect of the invention, the invention provides a system for recycling condensates, configured for recovering the condensates which are formed in the collecting system: the recycling system is configured for recirculating the condensates in the electrolytic cell. According to an embodiment, the recovery system comprises a first cooler. The first cooler is configured to cool the separated hydrogen. According to an embodiment, the recovery system comprises a second cooler. The second cooler is configured to cool the separated oxygen. The first cooler comprises a respective first recovering element, configured to collect the condensate which is formed in response to the cooling.
The second cooler comprises a respective second recovering element, configured to collect the condensate which is formed in response to the cooling.
According to an embodiment, the condensate recovered in the first and/or second recovering elements is recirculated into the electrolytic cell. Advantageously, the control unit is programmed to apply a pulsed electrical energy to the condensates recovered in the first and/or second elements. Preferably, the control unit is programmed to apply a low voltage current to the condensates recovered. The low voltage current has an oscillation, preferably with a square wave. The low voltage current has a variable frequency. According to an aspect of the invention, the control unit is programmed to generate a square wave with a frequency variation in a range of between 2 kHz and 25 kHz, preferably between 5 kHz and 20 kHz.
With this particular electricity supply, which only occurs on the flow of the condensates, the following advantages are obtained:
- the energy transfer on the molecules of water increases, causing a resonance effect with the relative frequencies of the molecule;
- the outflow of gas from the electrodes is facilitated and increased, avoiding processes of re-association of the gases inside the cell.
According to an embodiment, the plant comprises a temperature sensor, configured for capturing temperature signals, representing a temperature of the alkaline bath. The temperature sensor is programmed to send the temperature signals to the control unit. The control unit is programmed to vary the intensity and frequency of the low voltage current, on the basis of the temperature signals received.
According to an aspect of the invention, the invention provides a method for generating hydrogen from water.
The method comprises a step of supplying water to an electrolytic cell. The method comprises a step of supplying electricity to a first plate and a second plate of the electrolytic cell using a power supply unit.
The method comprises a step of controlling the electricity supply of the first and second plate using a control unit.
The method comprises a step of performing alkaline water electrolysis to separate hydrogen and oxygen.
The method comprises a step of collecting hydrogen and oxygen in a first tank and a second tank, respectively.
Preferably, the method is performed with the first plate of said electrolytic cell made from a special alloy including at least the following materials: iron, carbon, chrome, nickel, copper and manganese.
According to an aspect of the invention, the invention provides a method for making an electrolytic cell.
The method comprises a step of preparing a special alloy including one or more of the following materials: iron, carbon, chrome, nickel, copper, manganese, silicon, phosphorous, thallium, tungsten, sulphur and palladium.
The method comprises a step of melting the special alloy. The method comprises a step of manufacturing a first plate and a second plate of the electrolytic cell using the special fused alloy.
According to an aspect of the invention, the method comprises a recycling step. In the recycling step, a system for recycling the condensates recovers the condensates which are formed in the collecting system. During the recycling step, the collecting system recirculates the condensates in the electrolytic cell.
The method advantageously comprises a cooling step, in which the hydrogen and/or the oxygen are cooled in a first and/or a second cooler, respectively. In the cooling step, a first and/or a second collecting element collect the condensates formed in the first and/or in the second cooler, respectively.
According to an aspect of the invention, the method comprises a charging step, in which the control unit applies to the condensates a pulsed electrical energy, preferably with a low voltage current with a variable frequency square wave oscillation.
Brief description of the drawings
These and other features of the invention will become more apparent from the following detailed description of a preferred, non-limiting example embodiment of it illustrated in the accompanying drawing of a plant for generating hydrogen from water. Detailed description of preferred embodiments of the invention
With reference to the accompanying drawing, the numeral 1 denotes a plant for generating hydrogen from water. Preferably, the water used is demineralised, that is to say, pure water. In other cases, the plant 1 comprises a demineralising unit, by which the water is demineralised before being processed.
The plant 1 comprises a supply line 10, configured for supplying water to the plant 1. The supply line 10 may draw water from a tank 100 of demineralised water or from a continuous supply line. The supply line 10 comprises a pump 101 , designed to provide a head to the water.
The plant 1 comprises an electrolytic cell 11. The supply line 10 is connected to the electrolytic cell 11 for conveying inside the water. According to an embodiment, the supply line 10 comprises a heater 102, configured to preheat the water before it is introduced into the electrolytic cell 11.
The electrolytic cell 11 is submerged in an alkaline bath, that is, submerged in an alkaline liquid electrolyte. Preferably, said alkaline liquid electrolyte is potassium hydroxide KOH. The percentage of KOH may vary from 10% to 40%. The electrolytic cell 11 comprises one or more pairs of plates 111. Hereinafter in this description, only one of the plates 111 will be described, observing that the same features can also be extended to the other pairs of plates 111.
Each pair of plates 111 comprises a first plate 111 A and a second plate 111 B. Each pair of plates 111 comprises a diaphragm 111C, interposed between the first and the second plate 111 A, 111 B.
The purpose of the diaphragm 111C is to keep separate the gases produced by the plant 1 , for reasons of efficiency and safety, but it is permeable for the hydroxide ions and the water molecules.
Each of said first plate 111 A and second plate 111 B is connected to an electricity supply and constitute a cathode and an anode of the pair 111. The plant 1 comprises a power supply unit 12, configured for supplying the electrolytic cell 11 (the pairs of plates 111) with an electrical power. The water inside the electrolytic cell 111 undergoes the electrolysis process, according to which, according to the Faraday law, the quantity of gas produced is directly proportional to the quantity of current passing through the electrodes.
On each of said first and second plates 111 A, 111 B (which constitute a pair of electrodes) the oxidation reduction reaction occurs under the effect of a difference of potential which feeds the exchange of ions (positives) to the cathode, which is negative, and electrons (negative) to the positive anode.
The energy with which the plates are supplied is in fact transmitted in the form of Gibbs free energy which breaks the atomic links in the molecule of water.
The plant 1 comprises a control unit 13. The control unit 13 is connected to the power supply unit 12 to control the electrical power transmitted to the electrolytic cell 11. In particular, the control unit 13 is configured to control the power supply unit 12 in such a way that the latter supplies the electrolytic cell 11 with a direct current, preferably 515 V.
According to an embodiment, the first plate 111 A and the second plate 111 B are made from a special alloy including one or more of the following materials: iron, carbon, chrome, nickel, copper, manganese, silicon, phosphorous, thallium, tungsten, sulphur and palladium.
Preferably, both the first plate 111 A and the second plate 111 B are made with the same special alloy, precisely because the control could comprise a reversal of polarity.
According to an embodiment, the plant 1 comprises a first outlet line 14A. The plant 1 comprises a second outlet line 14B. The first outlet line 14A is configured to receive (that is to say, remove) the gaseous hydrogen obtained by the water electrolysis from the first plate 111 A.
The second outlet line 14B is configured to receive (that is to say, remove) the gaseous oxygen obtained by the water electrolysis from the second plate 111 B.
According to an embodiment, the plant 1 comprises a first tank 15A, configured for storing the gaseous hydrogen obtained before it is used. The plant 1 comprises a second tank 15B, configured for storing the gaseous oxygen obtained before it is used. Each of said first and second tanks 15A, 15B is configured to collect, on its bottom, any condensate which might be formed in the first or in the second tank 15A, 15B.
The plant 1 comprises a recycling system 17, configured for recovering the condensates obtained downstream of the electrolytic cell 11 , in the water processing path.
The first and the second tank 15A, 15B are connected with the recycling system 17, for conveying the condensates therein.
According to an embodiment, the plant 1 comprises a first cooler 16A. The plant comprises a second cooler 16B. The first cooler 16A is configured to cool the hydrogen. The second cooler 16B is configured to cool the oxygen. The cooling of the hydrogen makes it possible to obtain a particularly pure product.
The cooling operation is an operation which results in a significant generation of condensate, in any case greater than that collected in the previous storage. For this reason, the first cooler 16A comprises a first recovering element 161 A, which collects the condensates which are formed during the cooling of the hydrogen.
The second cooler 16B comprises a second recovering element 161 B, which collects the condensates which are formed during the cooling of the oxygen.
The first recovering element 161 A and/or the second recovering element 161 B are connected to the recycling system 17 for conveying the condensates therein.
The recycling system 17 is connected to the electrolytic cell 11 for conveying again inside it the recovered condensates. According to an embodiment, the plant comprises a pulsed current applicator 18. The pulsed current applicator 18 intercepts the recycling system 17, in such a way as to apply to the condensates a pulsed current, with a square wave, with variable frequency.
In particular, the pulsed current applicator is connected to the control unit 13, which is programmed to control the frequency of the square wave of the pulsed current.
The recycling system 17 comprises a manifold 171 , on which are conveyed the condensates formed in the first and second tanks 15A, 15B and into the first and second coolers 16A, 16B.
Moreover, the recycling system 17 comprises a recirculation pump 172, configured for pumping the condensates up to the electrolytic cell 111.
The control unit 13 is programmed to send control signals 131 , identifying a frequency of the square wave. The frequency is adjusted in a range of between 5 kHz and 20 kHz.
The generation of the wave and the sequence of the frequency variations, managed by the control unit 13 using dedicated software, are carried out through a process of suitable filtering of one or more harmonics generated by the primary wave.
The plant 1 comprises a temperature sensor 19, which is positioned at the cell 11 for capturing temperature signals 132, representing a temperature of the alkaline bath.
The temperature sensor 19 is programmed to send the temperature signals 132 to the control unit 13.
The control unit 13 varies the frequency of the square wave on the basis of the temperature signals 132 received.
In other words, the control unit 13 is programmed to generate the control signals 131 in response to the temperature signals 132.
According to an embodiment, of the system, the electrolytic cell comprises 274 plates with a spacing (distance from each other) of 2.5 mm.
The length of the electrolytic cell 11 is 760 mm, whilst its extension is 200 mm x 200 mm each.
According to an aspect of the invention, the control unit 13 is programmed to vary the voltage intensity of the pulsed current applied to the condensates, in response to the concentration of the electrolytic solution KOH and/or the distance between the first plate 111 A and the second plate 111 B of each pair 111.
The paragraphs listed below, labelled with alphanumeric references, are non-limiting example modes of describing this invention.
AO. A plant 1 for generating hydrogen from water, comprising: - an electrolytic cell 11 , submerged in an alkaline bath and including:
- a first plate 111 A, defining a cathode of the cell 11 ;
- a second plate 111 B, spaced from the first plate 111A along a direction perpendicular to the first and second plates 111 A, 111 B and forming an anode of the cell; - a water supply line 10, configured to feed water to the electrolytic cell 11 ;
- a power supply unit 12, configured for supplying an electrical power to the cell 11 ;
- a control unit 13, connected to the power supply unit 12 to control an electrical current transmitted from the power supply unit 12 to said cell 11 ; - a collecting system, including a first tank 15A, configured to collect the hydrogen coming from said electrolytic cell 11 , and a second tank 15B, configured to collect the oxygen coming from said electrolytic cell 11 , characterised in that the first plate 111 A of said electrolytic cell 11 is made from a special alloy, including iron and carbon. A00. The plant according to paragraph A0, wherein the special alloy includes phosphorous.
A01. The plant according to paragraph A0 or A00, wherein the special alloy includes thallium.
A02. The plant according to paragraph A0, A00 or A01 , wherein the special alloy includes tungsten.
A03. The plant according to any one of paragraphs A0 to A02, wherein the special alloy includes palladium.
A04. The plant according to any one of paragraphs AO to A03, wherein the special alloy includes manganese.
A05. The plant according to any one of paragraphs from AO to A04, wherein the special alloy includes copper.
A06. The plant according to any one of paragraphs AO to A05, wherein the special alloy includes chrome.
A07. The plant according to any one of paragraphs AO to A06, wherein the special alloy includes nickel.
A08. The plant according to any one of paragraphs AO to A07, wherein the special alloy includes silicon.
A09. The plant according to any of the paragraphs from AO to A08, wherein the special alloy includes sulphur.
A10. The plant 1 according to any of the paragraphs from AO to A09, wherein the special alloy is characterised by one or more of the following percentages:
- percentage of copper of between 0.2% and 0.35%;
- percentage of manganese between 1.5% and 3%;
- percentage of silicon between 0.5% and 1%;
- percentage of phosphorous between 0.02% and 0.06%;
- percentage of thallium between 0.5% and 0.8%;
- percentage of sulphur between 0.01% and 0.04%;
- percentage of tungsten between 0.05% and 0.15%;
- percentage of palladium between 0.05% and 0.09%.
A11. The plant 1 according to any one of paragraphs A0 to A10, wherein the second plate 111 B is also made of the special alloy.
A12. The plant 1 according to any one of paragraphs A0 to A11 , wherein the electric current applied to the cell is applied in direct current.
A13. The plant 1 according to any one of paragraphs A0 to A12, comprising a system for recycling the condensates 161 A, 161B, configured to recover the condensates which are formed in the first and in the second tank 15A, 15B and to recirculate them in the electrolytic cell. A14. The plant 1 according to paragraph A13, wherein the control unit 13 is programmed to apply a pulsed electrical energy to said condensates.
BO. A method for generating hydrogen from water, the method comprising the following steps:
- feeding water to an electrolytic cell 11 ;
- supplying electricity to a first plate 111 A and a second plate 111 B of the electrolytic cell 11 through a power supply unit 12;
- controlling the electricity supply of the first and second plates 111 A, 111 B through a control unit 13;
- performing alkaline water electrolysis to separate hydrogen and oxygen;
- collecting hydrogen and oxygen in a first tank 15A and a second tank 15B, respectively, characterised in that the first plate 111 A of said electrolytic cell 11 is made from a special alloy, including one or more of the following materials: iron, carbon, chrome, nickel, copper, silicon, sulphur, palladium, phosphorous, thallium, tungsten and manganese.
BOO. A method for making an electrolytic cell, comprising the following steps: - preparing a special alloy including one or more of the following elements: iron, carbon, chrome, nickel, copper, silicon, sulphur, palladium, phosphorous, thallium, tungsten and manganese;
- melting the special alloy;
- manufacturing a first plate 111 A and a second plate 111 B of the electrolytic cell 11 using the molten special alloy.

Claims

1. A plant (1 ) for generating hydrogen from water, comprising:
- an electrolytic cell (11), submerged in an alkaline bath and configured to perform alkaline water electrolysis, to separate the hydrogen from the oxygen;
- a water supply line (10), configured to feed water to the electrolytic cell
(11 );
- a power supply unit (12), configured to provide the plant (1) with electrical power;
- a control unit (13), connected to the power supply unit (12) to control an electrical current transmitted from the power supply unit (12) to said cell (11 );
- a collecting system (161 A, 161 B), including a first tank (15A), configured to collect the hydrogen coming from said electrolytic cell (11), and a second tank (15B), configured to collect the oxygen coming from said electrolytic cell (11), characterised in that it comprises a condensate recycling system (17) configured to recover the condensates formed in the collecting system (161 A, 161 B) and to recirculate them into the electrolytic cell (11 ).
2. The plant (1) according to claim 1 , wherein the recycling system comprises a first cooler (16A), configured to cool the separated hydrogen, and a second cooler (16B), configured to cool the separated oxygen.
3. The plant according to claim 2, wherein each of said first and second coolers (16A, 16B) comprise a respective first and second recovering element (161 A, 161 B), configured to collect the condensate.
4. The plant (1) according to claim 3, wherein the condensate recovered in the first and second recovering elements (161 A, 161 B) is recirculated into the electrolytic cell (11).
5. The plant (1) according to claim 4, wherein the control unit (13) is programmed to apply a pulsed electrical energy to the condensates recovered in the first and second recovering elements (161 A, 161 B).
6. The plant (1) according to claim 5, wherein the control unit (13) is programmed to apply to the condensates recovered a low voltage current with variable frequency square wave oscillation.
7. The plant (1) according to claim 6, wherein the control unit (13) is programmed to generate a square wave with a frequency variation in a range between 5 Hz and 20 Hz.
8. The plant (1) according to claim 6 or 7, comprising a temperature sensor (19), configured to capture temperature signals (132), representing a temperature of the alkaline bath and to send the temperature signals (132) to the control unit (13), wherein the control unit (13) is programmed to vary the intensity and frequency of the low voltage current based on the temperature signals (132) received.
9. A method for generating hydrogen from water, the method comprising the following steps:
- feeding water to an electrolytic cell (11 );
- supplying electric power to the electrolytic cell through a power supply unit (12);
- controlling the electric power supply of the electrolytic cell (11) through a control unit (13);
- performing alkaline water electrolysis to separate hydrogen and oxygen;
- collecting the hydrogen and the oxygen in a collecting system including a first tank (15A) and a second tank (15B), characterised in that it comprises a step of recycling, in which a condensate collecting system (161 A, 161 B) recovers the condensates formed in the collecting system and the recirculates them in the electrolytic cell (11).
10. The method according to claim 9, comprising a step of cooling, in which the hydrogen and the oxygen are cooled in a first and a second cooler (16A, 16B), respectively, and in which, in the step of cooling, a first and a second recovering element (161 A, 161 B) collect the condensates downstream of the first and second coolers (16A, 16B).
11. The method according to claim 9 or 10, comprising a step of charging, in which the control unit (13) applies to the condensates a pulsed electrical energy, with a low voltage current with variable frequency square wave oscillation.
PCT/IB2022/051294 2021-02-15 2022-02-14 System for recycling condensates and plant for generating hydrogen comprising the recycling system WO2022172241A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22709801.9A EP4291693A1 (en) 2021-02-15 2022-02-14 System for recycling condensates and plant for generating hydrogen comprising the recycling system

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IT202100003392 2021-02-15
IT102021000003365 2021-02-15
IT102021000003392 2021-02-15
IT202100003365 2021-02-15

Publications (1)

Publication Number Publication Date
WO2022172241A1 true WO2022172241A1 (en) 2022-08-18

Family

ID=82837533

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2022/051294 WO2022172241A1 (en) 2021-02-15 2022-02-14 System for recycling condensates and plant for generating hydrogen comprising the recycling system

Country Status (2)

Country Link
EP (1) EP4291693A1 (en)
WO (1) WO2022172241A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0885892A (en) * 1994-09-20 1996-04-02 Shinko Pantec Co Ltd Oxygen and hydrogen generator
US20100163407A1 (en) * 2008-12-26 2010-07-01 Wilson David M Electrolysis type electrolyzer for production of hydrogen and oxygen for the enhancement of ignition in a hydrocarbon fuel and/or gas combustion device
US20130032472A1 (en) * 2010-04-09 2013-02-07 Hoeller Stefan Apparatus for the electrical production of hydrogen
CN111364052A (en) * 2020-04-03 2020-07-03 中国华能集团清洁能源技术研究院有限公司 Wide-power water electrolysis hydrogen production system and method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0885892A (en) * 1994-09-20 1996-04-02 Shinko Pantec Co Ltd Oxygen and hydrogen generator
US20100163407A1 (en) * 2008-12-26 2010-07-01 Wilson David M Electrolysis type electrolyzer for production of hydrogen and oxygen for the enhancement of ignition in a hydrocarbon fuel and/or gas combustion device
US20130032472A1 (en) * 2010-04-09 2013-02-07 Hoeller Stefan Apparatus for the electrical production of hydrogen
CN111364052A (en) * 2020-04-03 2020-07-03 中国华能集团清洁能源技术研究院有限公司 Wide-power water electrolysis hydrogen production system and method

Also Published As

Publication number Publication date
EP4291693A1 (en) 2023-12-20

Similar Documents

Publication Publication Date Title
US4457816A (en) Electrolysis method for decomposing water into hydrogen gas and oxygen gas
Mazloomi et al. Influencing factors of water electrolysis electrical efficiency
US7615138B2 (en) Electrolysis apparatus with pulsed, dual voltage, multi-composition electrode assembly
JP2009513829A (en) Electrolysis
JP7066245B2 (en) Processes and equipment for hydrogen production
US4369102A (en) Electrolysis apparatus for decomposing water into hydrogen gas and oxygen gas
CN105518184A (en) Hydrogen system and method of operation
CN113403630A (en) Hydrogen producing device by catalytic electrolysis
CN113913849A (en) Hydrogen production method based on water electrolysis of proton exchange membrane
US20220274061A1 (en) Carbon dioxide treatment apparatus, carbon dioxide treatment method, and method of producing carbon compound
US8043485B2 (en) Multi-pulse protocol for use with a dual voltage electrolysis apparatus
Nuttall Conceptual design of large scale water electrolysis plant using solid polymer electrolyte technology
US8157980B2 (en) Multi-cell dual voltage electrolysis apparatus and method of using same
WO2022172241A1 (en) System for recycling condensates and plant for generating hydrogen comprising the recycling system
JP2020149838A (en) Nitrogen gas generation method and device for filtering high-pressure fuel cell exhaust gas
KR101147491B1 (en) Electrolysis apparatus
CN1370732A (en) Hydrogen producing method and system from solid carbon and water
JP2004337843A (en) Method and apparatus for concentrating hydrogen isotope water
US20220282384A1 (en) Electrochemical reaction device, method of reducing carbon dioxide, and method of producing carbon compounds
US20220282387A1 (en) Electrochemical reaction device, method for reducing carbon dioxide, and method for producing carbon compound
US1980873A (en) Electrolyzer and electric accumulator
AU646884B2 (en) Alkali metal hydroxide generation system and the method therefor
KR102001213B1 (en) Fuel cell system having hydrogen generating and carbon dioxide removing apparatus using carbon dioxide
CN216864346U (en) Double-side water supply PEM electrolytic tank hydrogen production system
CN219280053U (en) Multipole type electrolytic device for producing hydrogen peroxide and hydrogen by electrolyzing ammonium bisulfate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22709801

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2022709801

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022709801

Country of ref document: EP

Effective date: 20230915