WO2007126325A1 - Procédé de production d'hydrogène par électrolyse d'eau (variantes) et procédé de régulation d'un processus de production d'hydrogène par électrolyse d'eau - Google Patents

Procédé de production d'hydrogène par électrolyse d'eau (variantes) et procédé de régulation d'un processus de production d'hydrogène par électrolyse d'eau Download PDF

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Publication number
WO2007126325A1
WO2007126325A1 PCT/RU2006/000213 RU2006000213W WO2007126325A1 WO 2007126325 A1 WO2007126325 A1 WO 2007126325A1 RU 2006000213 W RU2006000213 W RU 2006000213W WO 2007126325 A1 WO2007126325 A1 WO 2007126325A1
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Prior art keywords
water
hydrogen
cathode
electrodes
producing hydrogen
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PCT/RU2006/000213
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English (en)
Russian (ru)
Inventor
Igor Nikolaevich Mogilevsky
Robert Rikhardovich Salem
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Priority to PCT/RU2006/000213 priority Critical patent/WO2007126325A1/fr
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    • 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
    • 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

  • the invention relates to electrochemistry, in particular, relates to a method of producing hydrogen by electrolysis from water.
  • the invention relates to a method for producing hydrogen based on the electrolysis of water, without the use of acid or alkaline electrolytes.
  • Hydrogen is one of the most important elements in the chemical industry. It is used in the production of ammonia, in the synthesis of hydrogen chloride, in hydrogenation processes to convert unsaturated hydrocarbons to saturated ones. Hydrogen plays a major role in improving the quality of petroleum products, in the processes of desulfurization, de-nitriding and demetallation. Hydrogen is used in the process of contact hydrogenation of carbon dioxide to utilize the latter as a cause of global warming. Recently, hydrogen has been considered as an alternative energy source, replacing existing fossil fuels and not polluting the environment.
  • the usual technology for producing hydrogen is in extracting it from fossil fuels, such as oil and natural gas, as well as in the interaction of water with metal, electrolysis of water, etc.
  • these methods are economically disadvantageous, since their implementation requires a large amount of heat or electric energy.
  • These technologies are also characterized by the formation of large quantities of undesirable by-products, for example, carbon dioxide.
  • carbon dioxide is a serious source of environmental pollution, causing a greenhouse effect on a global scale.
  • the separation of oxygen formed during electrolysis it is associated with technological difficulties, due to which the process of separation of water into elements becomes more complicated. In any case, by-products create difficulties in obtaining high-purity hydrogen with a high yield of product.
  • Water is the most widespread substance on the planet, therefore the technology that allows the decomposition of water to efficiently produce high-purity hydrogen is very important because it solves the problem of creating replacement energy sources and providing raw materials to the chemical industry ..
  • electrolysis is currently actively used using a variety of methods and methods to increase the efficiency of the process (increasing the temperature, changing the concentration and nature of the electrolyte, various methods of supplying the solution to the surface of the electrodes, using various physical disturbances in the form of high-frequency pulses, ultrasonic excitation, photo effects and etc.).
  • a known method of producing hydrogen by electrolysis of water in which the electrolyte is an aqueous solution of KOH (350-400 g / l).
  • the pressure in the electrolytic cells varies from atmospheric to 4 MPa.
  • the performance of the electrolytic cells in the known method is 4-500 cubic meters per hour, and the energy consumption to produce 1 cubic meter. hydrogen is equal to 5.1-5.6 kW / h.
  • the disadvantage of this method is the high power consumption.
  • when In this way there is an inevitable accumulation of salt environmental pollution with volatile compounds, which necessitates the use of recycling devices.
  • a method for producing hydrogen by catalytic decomposition of water is known, proposed and developed by Natioper Technology Laboruto (USA) and Argopati Labo Laboru (USA) (Nutropertomp. 1, p. 19). This method significantly reduces the specific energy consumption compared to the traditional method of producing hydrogen by electrolysis of water.
  • water vapor continuously enters a chemical reactor, where hydrogen is released from ionized water molecules on the surface of a proton-electron-conducting membrane at a temperature of about 900 0 C. Electrons and protons pass through the membrane and recombine on its opposite sides, and oxygen remains in the volume reaction chamber.
  • the membranes used in this process are made of cermet composites containing yttrium, waxed descent of barium, as well as nickel or palladium. It is noted that in the production of hydrogen by this technology is practically not required energy costs, and the heating of the reactor can be achieved by utilizing energy from extraneous sources.
  • the present invention is aimed at solving the technical problem of minimizing the energy consumption spent on the process of producing hydrogen from water, based on taking into account the emission properties of metals from the condition of minimizing the work function of the electron from the metal.
  • the technical result achieved in this case is to increase the efficiency of the process of producing hydrogen from water due to the optimal use of the internal energy of the chemical reaction of water decomposition by utilizing dissipative (scattered) energy due to a decrease in the difference in the entropy of water molecules in the near-electrode layer and in the solution volume
  • the specified technical result for the first claimed method is achieved by the fact that in the method for producing hydrogen by water electrolysis, which consists in immersing electrodes in water and passing direct current through the water between the electrodes, the cathode They are made of a material with a reduced electron work function and provide a voltage drop of at least 1, 23 V.
  • the specified technical result for the second claimed method is achieved by the fact that in the method of regulating the process of producing hydrogen by water electrolysis, which consists in immersing electrodes in water and passing direct current between the electrodes through water, the cathode is made of a material with a reduced electron work function and provides a voltage drop across the anode and cathode of at least 1, 23 V, and the regulation in the direction of increasing the hydrogen output is carried out by shifting the current-voltage characteristics of the cathode to the negative side y, and the anode - in a positive way.
  • the specified technical result for the third claimed method is achieved by the fact that in the method for producing hydrogen by electrolysis of direct current water with low overvoltage, which consists in immersing electrodes in water and passing direct current through the water between the electrodes, a cathode is used from a material with a low electron work function.
  • the claimed methods differ from the known methods in that: - selection of the material of the electrodes is based on the emission properties of metals and is selected from the condition of minimizing the electron work function
  • the efficiency of the hydrogen production process tends to 1, i.e. the internal energy of the decomposition process is completely converted into free energy (useful work).
  • the method of producing hydrogen from water and aqueous solutions is universal, i.e. applicable without limitation to all types of hardware design of electrolyzers for chemical and energy, as well as transport engineering - energy costs for the electrolysis process are several times less compared to existing ones, and also allow the use of environmental waste
  • FIG. 1 shows the current-voltage characteristics of the cathode and anode, as well as the range of redox potentials of the thermodynamic stability of water.
  • a method for producing hydrogen by water electrolysis consists of immersing electrodes in water and passing direct current through the water between the electrodes, in which the cathode is made of a material with a reduced electron work function and provides a voltage drop of at least 1, 23 V at the anode and cathode. And the regulation in the direction of increasing the hydrogen output is carried out by shifting the current-voltage characteristics of the cathode to the side of negative potentials, and the anode to the side of positive ones.
  • the electrolysis process is due to the emission of electrons on a negatively charged electrode (cathode).
  • D (W, ⁇ ) exp (-2 ⁇ Sfc F ) is the coefficient transparency of the potential barrier (Gamow factor)
  • k F (3 ⁇ 2 p) m is the Fermi wave vector
  • n is the density of free electrons in the volume of the metal
  • ⁇ is the thickness of the potential barrier, which in the simplest case is equated to the effective length of the double electric layer. Since tunneling phenomena are not accompanied by thermal effects, the coefficient D can be considered, to a first approximation, constant.
  • FIG. 1 schematically depicts the current-voltage characteristics of the cathode and anode, as well as the interval of redox potentials of water stability
  • the left dash-dotted line ab (the left dash-dotted line ab and separates the steady state water from unstable associated with the release of hydrogen under the action of current.
  • the potential range is more positive than the direct cd corresponds to the decomposition of water with the release of oxygen.
  • the straight lines ab and cd are separated by 1, 23 V and limit the region of thermodynamic resistance of water to oxidation or reduction. Thus, within the region of potentials limited by the area of abcd, water does not decompose into elements.
  • the region of the act is characterized by a small deviation from equilibrium; the entire charge supplied from an external source is used to charge the double electric layer.
  • the double layer is formed by dipoles of water molecules, so that the orientation component of the total dipole polarization at the metal-water interface is degenerate, due to its full orientation already at the water-air interface. Therefore, the dipole polarization of water molecules is due only to deformation polarization (the displacement of electronic clouds of water molecules) under the influence of a metal field and an external (external) field. Small deviations of the metal potential from equilibrium (in Fig. 1 - the transition from the state at point k to point k ').
  • thermodynamic properties of water in the surface region close to the metal approach the properties of the solid phase.
  • the calculation of the difference in the entropy of solid and liquid water indicates a decrease in energy by about 2 kcal / mol, i.e. 10% of the energy required for the spontaneous process of decomposition of water.
  • FIG. Figure 1 allows you to determine the areas in which the process of electrolysis of water should be carried out in order to maximize hydrogen evolution, as well as select the optimal coating materials for the anode and cathode in terms of minimizing the electron work function.
  • the emission of electrons from a metal into its environment is determined not only by the properties of the metal itself (this is usually explained by the catalytic activity of the metal), but also by external factors that contribute to the intensification of the emission process electrons from the surface of the metal.
  • this method is the simplest - the method of applying an external electric field that promotes (or slows down) the emission of electrons. As a result, the external current flowing along the electrolyzer circuit increases or decreases.
  • the present application does not consider examples of specific performance of electrolyzers, since the essence of the method is not based on changing the design of these plants, but on optimizing the choice of voltages on the electrodes and the material of these electrodes.
  • the proposed method for increasing the efficiency of electrolysis of water differs from the known ones in that
  • cathode materials with a reduced electron work function allows you to fully use: a) the internal energy of the chemical reaction of water decomposition by utilizing dissipative (scattered) energy by reducing the difference in entropy (due to lower overvoltage potential) of water molecules in the near-electrode layer and in the solution volume, b) lowering the overvoltage of hydrogen evolution increases the efficiency of the process.
  • a decrease in the work function entails an acceleration of the process of hydrogen evolution, depending on the magnitude of the decrease in work function.
  • a process with a maximum stoichiometric output can occur at a very small overvoltage compared with the equilibrium decomposition potential of 1, 23V with a significantly higher output and significant acceleration.
  • the present invention is industrially applicable, as it can be implemented on known electrolytic plants.
  • the novelty of the method is to optimize the selection of voltages on the electrodes.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention relève du domaine de l'électrochimie et concerne en particulier un procédé de production d'hydrogène par électrolyse d'eau, lequel procédé consiste à plonger des électrodes dans l'eau et à faire passer du courant continu dans l'eau entre des électrodes dont la cathode ou l'électrode est composée d'un matériau présentant un travail d'extraction électronique réduit, la différence de tension entre l'anode et la cathode étant au moins égale à 1,23 V. Le procédé de régulation d'un processus de production d'hydrogène visant à accroître la production d'hydrogène consiste à déplacer les caractéristiques tension-courant de la cathode du côté négatif et les caractéristiques tension-courant de l'anode du côté positif.
PCT/RU2006/000213 2006-04-27 2006-04-27 Procédé de production d'hydrogène par électrolyse d'eau (variantes) et procédé de régulation d'un processus de production d'hydrogène par électrolyse d'eau Ceased WO2007126325A1 (fr)

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PCT/RU2006/000213 WO2007126325A1 (fr) 2006-04-27 2006-04-27 Procédé de production d'hydrogène par électrolyse d'eau (variantes) et procédé de régulation d'un processus de production d'hydrogène par électrolyse d'eau

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PCT/RU2006/000213 WO2007126325A1 (fr) 2006-04-27 2006-04-27 Procédé de production d'hydrogène par électrolyse d'eau (variantes) et procédé de régulation d'un processus de production d'hydrogène par électrolyse d'eau

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD20070144A (ro) * 2007-05-21 2009-01-31 Институт Энергетики Академии Наук Молдовы Procedeu de obţinere a fluxului ionilor de hidrogen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5782483A (en) * 1980-11-11 1982-05-22 Asahi Chem Ind Co Ltd Electrode for production of hydrogen and its production

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5782483A (en) * 1980-11-11 1982-05-22 Asahi Chem Ind Co Ltd Electrode for production of hydrogen and its production

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BILLITER Z.: "Promyshlenny elektroliz vodnykh rastvorov", MOSCOW, GOSUDARSTVENNOE NAUCHNO-TEKHNICHESKOE IZDATELSTVO KHIMICHESKOI LITERATURY, 1959, pages 19 - 22 *
YAKIMENKO L.M. ET AL., ELEKTROLIZ VODY. MOSCOW, KHIMIYA, 1970, pages 31, 36 - 39, 42 - 43, 202 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD20070144A (ro) * 2007-05-21 2009-01-31 Институт Энергетики Академии Наук Молдовы Procedeu de obţinere a fluxului ionilor de hidrogen

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