Electrolysis system and method for a high electrical energy transformation rate
11186915 · 2021-11-30
Inventors
Cpc classification
C25B9/17
CHEMISTRY; METALLURGY
International classification
C25B11/00
CHEMISTRY; METALLURGY
Abstract
The invention relates to an electrolysis system to conduct oxidation and reduction reactions, comprising one or more electrolytic cells, with each one of them being formed by at least a pair of electrodes and an electrolyte provided between said electrodes, wherein the assembly of said one or more electrolytic cells defines an electrolyzer; and an energy source that supplies an electrical signal to the electrolyzer; wherein said electrolytic cell is built in the form of a capacitor of cylindrical plates, wherein said cylindrical plates are defined by the electrodes of the electrolytic cell formed by tubes arranged in a substantially concentric way within each other, thus defining a central electrode, an outer electrode and a space between electrodes, wherein the central electrode corresponds to the anode of the capacitor, the outer electrode to the cathode of the capacitor and the electrolyte to the dielectric means of the capacitor; wherein the electrical signal received by the electrolytic cell or cells that form the electrolyzer correspond to a direct current pulse, wherein said pulse is configured for each electrolyzer's electrolytic cell to operate: In a charge transient regime of each cell during the current pulse; and In a discharge transient regime of each cell during the time between current pulses; wherein said charge and discharge transient regimes are defined by the construction of each electrolytic cell in the form of a cylindrical plates capacitor. In addition, the invention also relates to associated method and uses.
Claims
1. An electrolysis system to conduct oxidation and reduction reactions, comprising: an electrolyzer having two or more groups of electrolytic cells, each electrolytic cell being formed by at least a pair of electrodes and an electrolyte provided between the electrodes; an energy source being connected to and supplying an electrical signal to the electrolyzer, wherein the electrical signal corresponds to a direct current pulse including a plurality of current pulses, the direct current pulse being characterized by a frequency (f) and a period (T); and a control unit being connected to and controlling the energy source or one or more switches connected to and being positioned between the energy source and the electrolyzer, the controlling including providing a sequential supply of the electrical signal, distributing the electrical signal over a first group of the electrolytic cells for a first certain time in a plurality of certain times, the plurality of certain times forming a duration of the direct current pulse, once the first certain time ends, distributing the electrical signal over a second group of the electrolytic cells for a second certain time in the plurality of certain times, and generating a current pulse in the plurality of current pulses over each group of the electrolytic cells within the period (T) of the direct current pulse; wherein the electrolytic cells form a capacitor having cylindrical plates, wherein the cylindrical plates are defined by the electrodes of the electrolytic cells formed by tubes arranged in a substantially concentric way within each other to define a central electrode, an outer electrode and a space between electrodes, wherein the central electrode corresponds to an anode of the capacitor, the outer electrode to a cathode of the capacitor and the electrolyte to a dielectric means of the capacitor; wherein each electrolytic cell of the electrolyzer, during the direct current pulse, is configured to operate: under a charge transient regime during each current pulse in the plurality of current pulses; and under a discharge transient regime between adjacent current pulses in the plurality of current pulses; wherein the charge and discharge transient regimes are defined by a construction of each electrolytic cell; and wherein the direct current pulse comprises an amplitude, the duration and the frequency (f) determined such that each electrolytic cell of the electrolyzer is energized in its corresponding charge and discharge transient regimes.
2. The system according to claim 1, wherein the central electrode is a hollow cylindrical electrode that defines an inner space, wherein a reduction reaction takes place over the inner side of the outer electrode and an oxidation reaction takes place over an outer side of the central electrode, wherein the oxidation reaction takes place alternatively over the inner side of the central electrode; wherein the system further comprising one or more first extraction ducts for extraction of a product of the oxidation reaction, wherein each of the first extraction ducts is in communication with the inner space of the central electrode; and one or more second extraction ducts for extraction of a product of the reduction reaction, wherein each of the second ducts is in communication with the space between electrodes.
3. The system according to claim 2, wherein the central electrode comprises one or more openings in its surface that communicate the space between electrodes with the inner space of the central electrode, with the one or more openings allowing a free circulation of the electrolyte between the space between electrodes and the inner space of the central electrode, wherein the one or more openings of the central electrode are provided to allow the product of the oxidation reaction to circulate from the outer side of the central electrode to the inner space of the central electrode.
4. The system according to claim 3, wherein the one or more openings are located in different zones of extraction of the central electrode, with the extraction zones being distributed along at least one portion of the central electrode, where each zone of extraction comprises at least one stopping device arranged over the outer side of the central electrode, wherein the at least one stopping device prevents a circulation of the product of the oxidation reaction over the outer side of the central electrode, conveying the product to the inner space of the central electrode through the one or more openings, wherein the at least one stopping devices extend in the space between electrodes, leaving a circulation space for the electrolyte near the inner side of the outer electrode, wherein the circulation space is provided for the free circulation of the product of the reduction reaction.
5. The system according to claim 1, wherein the amplitude of the direct current pulse is defined by a maximum or peak voltage of the energy source (V.sub.max), and an effective average voltage (V.sub.average), wherein the effective average voltage is defined as the optimum voltage that favors a production of each electrolytic cell, and wherein the duration of the direct current pulse is defined by a duration factor (D) of the direct current pulse, or working cycle, in relation to the period (T) of the direct current pulse, wherein the duration of the direct current pulse corresponds to a product between D and T, and wherein the duration factor D is defined by:
6. The system according to claim 5, wherein the frequency (f) or the period (T) of the direct current pulse is defined as:
7. The system according to claim 5, wherein the direct current pulse generates an effective average current flow circulating through each electrolytic cell, wherein the current flow is defined as:
8. The system according to claim 1, wherein the control unit operates the energy source in order to provide the direct current pulse received by the electrolytic cells of the electrolyzer.
9. The system according claim 1, wherein the control unit operates an activation and a deactivation of each switch in the one or more switches by controlling the duration and the frequency of the direct current pulse received by each of the electrolytic cells, wherein the control unit activates and deactivates the one or more switches to supply the electrical signal provided by the energy source sequentially, distributing the electrical signal over the first and second groups of the electrolytic cells, wherein each group of the electrolytic cells is formed by two or more of the electrolytic cells connected in series.
10. The system according to claim 1, wherein said two or more groups of the electrolytic cells are connected in parallel.
11. The system according to claim 1, wherein the central electrode is surrounded by a separation mesh.
12. The system according to claim 1, wherein the electrolytic cells are vertically arranged and operated at atmospheric pressure, wherein the electrodes making up the cells are formed by hollow vertical tubes.
13. An electrolysis method for conducting one or more oxidation reactions and reduction reactions, comprising: providing an electrolysis system, comprising: an electrolyzer having two or more electrolytic cells, with each electrolytic cell being formed by at least a pair of electrodes and an electrolyte provided between the electrodes; an energy source being connected to and supplying an electrical signal to the electrolyzer; and a control unit being connected to the energy source or to one or more switches connected and being positioned between the energy source and the electrolyzer; wherein the electrolytic cells form a capacitor having cylindrical plates, wherein the cylindrical plates are defined by the electrodes of the electrolytic cells formed by tubes arranged in a substantially concentric way within each other to define a central electrode, an outer electrode and a space between electrodes, wherein the central electrode corresponds to an anode of the capacitor, the outer electrode to a cathode of the capacitor and the electrolyte to a dielectric means of the capacitor; applying the electrical signal over the electrolytic cells, wherein the electrical signal corresponds to a direct current pulse including a plurality of current pulses, the direct current pulse being characterized by frequency (f) and a period (T); controlling the energy source or the one or more switches, the controlling including providing a sequential supply of the electrical signal, distributing the electrical signal over a first group of the electrolytic cells for a first certain time in a plurality of certain times, the plurality of certain times forming a duration of the direct current pulse, the plurality of certain times forming a duration of the direct current pulse, once the first certain time ends, distributing the electrical signal over a second group of the electrolytic cells for a second certain time in the plurality of certain times, generating a pulse of the current pulses in the plurality of current pulses over each group of the electrolytic cells within the period (T) of the direct current pulse; and configuring each electrolytic cell of the electrolyzer, during the direct current pulse, to operate: under a charge transient regime during each current pulse in the plurality of current pulses; and under a discharge transient regime between adjacent current pulses in the plurality of current pulses; wherein the charge and discharge transient regimes are defined by a construction of each electrolytic cell; and wherein the configuring includes determining an amplitude, the duration and the frequency (f) of the direct current pulse such that each electrolytic cell of the electrolyzer is energized in its corresponding charge and discharge transient regimes.
14. The method according to claim 13, wherein the configuring further comprises defining the amplitude for the direct current pulse by a maximum or peak voltage of the energy source (V.sub.max), and an effective average voltage (V.sub.average), wherein the effective average voltage is defined as the optimum voltage that favors a production of each electrolytic cell; and defining the duration of the direct current pulse by a duration factor (D) of the direct current pulse, or working cycle, in relation to the period (T) of the direct current pulse, wherein the duration of the direct current pulse corresponds to a product between D and T, and wherein the duration factor D is defined by:
15. The method according to claim 14, wherein the configuring further comprises defining the frequency (f) or the period (T) of the direct current pulse as:
16. The method according to claim 14, wherein the configuring further comprises applying an average effective current flow circulating through each electrolytic cell defined by:
17. The method according to claim 13, wherein the controlling further comprises providing the direct current pulse received by each of the electrolytic cells of the electrolyzer.
18. The method according to claim 13, wherein the controlling further comprises operating an activation and a deactivation of the one or more switches arranged between the energy source and the electrolyzer by controlling the duration and frequency of the direct current pulse, activating and deactivating the one or more switches supplying the electrical signal provided by the energy source sequentially, and distributing the electrical signal over the first and second groups of the electrolytic cells, wherein each group is formed by two or more electrolytic cells connected in series and wherein the certain time corresponds to the duration of the direct current pulse.
19. The method according to claim 13, further comprising extracting a product of the one or more oxidation reactions through one or more first ducts, wherein each of the one or more first ducts is in communication with an inner space of the central electrode; and extracting a product of the one or more reduction reactions through one or more second ducts, wherein each of the one or more second ducts is in communication with the inner space of the central electrode.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) As part of the present application the following figures are shown, which are representative of the invention and teach a preferred embodiment thereof; therefore, they should not be construed as limiting the definition of the matter claimed by the present application.
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
(10)
(11)
(12)
(13) Additionally,
(14) As an example, if the electrolyzer 12′ comprises a first set of electrolytic cells 14.1 formed by 50 cells connected in series, with each cell requiring a peak voltage of 2.5 v, a direct current source of 125v will be required to supply these 50 cells, distributing said 125 v in an equivalent form over each one of the 50 cells. This configuration can be supplemented with additional groups of electrolytic cells 14.2 connected in parallel to the first group, with each group having a switch in communication with the control unit for the pulsed distribution of direct current provided by the energy source. The number of groups of cells connected in parallel will be defined preferably according to the duration factor of the current pulse.
(15)
(16) According to an embodiment, the central electrode 21 comprises openings in its surface allowing electrolytes entering the inner space 23 of the central electrode and the circulation of ions, and also allowing the oxidation reaction to occur both in the outer side 21′ of the central electrode 21 and in the inner side 21″ thereof. Additionally, and alternatively, the central electrode 21 can be surrounded by a separation mesh 24 with a physical barrier of separation provided that separate the oxidation zone (central electrode 21) from the reduction zone (outer electrode 22), thus facilitating the separation of gases generated in the electrolytic cell. Under this arrangement, the central electrode 21 comprises separation means (not shown) that keep distance between the separation mesh 24 and the outer side 21′ of the central electrode 21, allowing the generation of the oxidation product over the surface of said outer side 21′. Additionally, this distance allows the gas generated on the outer side 21′ of the central electrode 21 to circulate to its extraction point, whether by going into the inner space 23 of the central electrode 21 through the openings or circulating over the outer side 21′ of the electrode into the extraction point without being transferred to the generation zone of the reduction product.
(17) In regard as openings, according to alternative embodiments, they may be formed by circular holes 25′ and/or continuous grooves 25″. The openings distribute along at least one part of the central electrode 21, preferably an upper part thereof, distributed in the extraction zones 27 provided to communicate the space between electrodes with the inner space of the central electrode 21.
(18) The constructive aspects of the electrodes according to the preferred embodiment allow taking advantage of the capacitive and resonant characteristics of the electrolytic cell, preventing the saturation of the walls of the electrodes with the gases generated by maximizing the cell's resonant aspects, including the effect of overdamping and taking advantage of the diffusion and transfer of ions from one electrode to other in the standby cycle given by the intervals in the current supply of pulsing wave making use of the cell's capacitive aspects.
(19)
(20)
(21)
(22)
(23) Finally,
Working Example
(24) In order to exemplify the implementation of the solution proposed by the present invention, the production of hydrogen and oxygen through water electrolysis is considered, using the system and methods of the present invention.
(25) In the process of water alkaline electrolysis to generate H.sub.2 and O.sub.2, processes of oxidation and reduction take place as follows:
2H.sub.2O.fwdarw.O.sub.2+4H.sup.++4e oxidation (anode)
4H.sup.++4e.fwdarw.2H.sub.2 Reduction (cathode)
2H.sub.2O.fwdarw.2H.sub.2+O.sub.2 Overall reaction
(26) The electrolysis of a mole of water produces one mole of hydrogen gas and half mole of oxygen gas in the normal diatomic forms thereof. A detailed analysis of the process shows the use of the thermodynamic potentials and the first law of thermodynamics. It is assumed that this process is carried out at 298° K and at one atmosphere of pressure, and that the relevant values are taken from the following table of thermodynamic properties (table 1):
(27) TABLE-US-00001 TABLE 1 Amount H.sub.2O H 0.5O.sub.2 Change Enthalpy −285.83 kJ 0 0 H = 285.83 kJ Entropy 69.91 J/K 130.68 J/K 0.5 × TS = 48.7 kJ 205.14 J/K
(28) The process must provide energy for the dissociation plus the energy to expand the produced gases. Both are included in the enthalpy change of the above table. At a temperature of 298° K and one atmosphere of pressure the system operation is as follows:
W=PΔV=(101.3×103 Pa)(1.5 mol)(22.4×10.sup.−3 m.sup.3/mol)(298 K/273 K)=3715 J
(29) As the enthalpy H=U+PV, the change of internal energy Y is therefore:
ΔU=ΔH−PΔV=258.83 kJ−3.72 kJ=282.1 kJ
(30) This change in the internal energy must be accompanied by the expansion of the gases produced, so the change in enthalpy represents the energy necessary to carry out the electrolysis. Nevertheless, it is not necessary that the energy source inserts this energy in total, as electrical power, since the entropy increases in the dissociation process; the TΔS amount can be provided by the environment at temperature T. Then, the amount of energy to be supplied by the energy source is in fact the change in Gibbs' free energy, which is expressed as follows:
ΔG=ΔH−TΔS=285.83 kJ−48.7 kJ=237.1 kJ
(31) As the result of the electrolysis process there is an increase of the entropy, the environment “helps” the process by providing a TΔS amount. The usefulness of Gibbs' free energy consists in indicating the amount of other energy forms that must be supplied in order to execute the process.
(32) For practical purposes of calculating the mass obtained in an electrolysis process, and considering the unified Faraday's law and a distribution of constant current, the equation can be presented as:
(33)
(34) For hydrogen, the electro-chemical equivalent is:
(35)
(36) Using the known values of the Chemical Equivalent of H.sub.2 and Faraday's Constant, and considering the generation of 1 g of H.sub.2 in one second, the following is obtained:
I=95724.9 A
(37) With this information it is possible to calculate the optimum voltage matching the input energy of the cell with the output energy. In this case, once the current necessary has been obtained to produce one unit of mass of the reaction product using the chemical equivalent to said product for that purposes, it is possible to determine the electrical energy required at the cell entry for the time of 1 second, for the production of one gram H.sub.2 through the following equation:
Entry energy=∫.sub.t=0.sup.t=1[s](I*V.sub.optimal)dt
(38) Then, and considering the output energy as the thermal product of the reaction, this case considering that the energy contained in 1 gram of H.sub.2 is 120011 J (Low Heat Value) and considering a 100% electrical efficiency, the following result is obtained:
V.sub.optimal=1.24[v]
(39) Here it is important to note that the electrolysis process for the generation of hydrogen is widely known; thus, it is not an object of the present invention to restate the thermodynamics balances and equations associated with said process. Without prejudice to that and as shown by the present example of application, the optimum application to favor reactions in the production of hydrogen through electrolysis is about 1.24 volts, so that to obtain the maximum efficiency of energy transformation.
(40) The optimum voltage can be also obtained by applying the standard potentials of reduction corresponding to the potentials measured in each electrode to favor the reduction and oxidation processes under standard conditions. Using the standard potentials of reduction, it can be defined that the oxidation reactions in the anode (2H.sub.2OO.sub.2+4H.sup.++4e) has a reduction potential of 1.229 V, while the reduction reaction in the cathode (4H.sup.++4e.fwdarw.2H.sub.2) has a potential of 0 V, with this valued being defined as the reduction potential in reference. Then, it is possible to calculate the potential of the cell (E.sub.cellº) as follows:
E.sub.cellº=E.sub.cathodeº−E.sub.anodeº
(41) Wherein E.sub.cathodeº and E.sub.anodeº correspond to the potential standards of the cathode and anode for this reaction, respectively. Then, for the electrolytic cell in question the potential of the cell would be −1.229 V, this being the necessary potential to carry out the non-spontaneous reaction of hydrogen and oxygen production through water electrolysis.
(42) With this optimum voltage of the electrolysis process and with the cell design consideration, operating parameters of the current power supply can be obtained such as pulse duration time, frequency and amplitude thereof, thus optimizing the application of current by minimizing the voltage required to operate the electrolytic cell in a resonant and capacitive fashion. In fact, by using this value and the above-defined equations the duration factor of the current pulse is:
(43)
Then, and considering the design parameters, wherein the cell charge voltage in t=DT is V.sub.cell(DT)=2 [v] and the cell voltage in t=T is V.sub.cell(T)=1.8 [v], with those parameters being defined according to the constructive aspects of the cell, the frequency parameter (period) of the pulse wave is:
(44)
Therefore, the duration of the pulse wave is:
(45)
(46) Then, the current flowing through the cell under these design parameters is configured as:
(47)
(48) Obtaining the current values for several values of V.sub.max.
(49) Considering a power supply with V.sub.max=2.52 v is it possible to determine that the pulse duration factor is D≈0.24 for the optimum voltage desired. Then, considering the equation for the period and frequency and a high-capacitance electrolytic cell according to design parameters, as for example with a capacitance of 1.1 F and with a resistance resulting in a duty cycle of 0.18 ohm, it is possible to obtain that the pulse wave frequency supplying power to the system is about 50 Hz (a period of 0.02 seconds).
(50) With this information it is possible to calculate the current circulating through the cell, which in this case is about 7.19 A. Then, using the ohm law it is possible to evidence that applying an optimum voltage to an electrolytic cell under the constructive parameters of a high-capacitance capacitor and under the operating parameters of the present invention in transient regimes, results in an apparent resistance of the system of 0.17 ohm, which is an advantageous situation compared with the standard electrolytic cells. In fact, below comparative values are presented between a standard cell operated in a standard way with direct current (table 2) and a cell according to the present invention and operated according to the solution stated (table 3), both of them under the same parameters of amplitude and current flow.
(51) TABLE-US-00002 TABLE 2 Energy Effective Effective Consumption Effective Production H.sub.2 energy Efficiency consumed resistance voltage per kilo of H.sub.2 current [A] H.sub.2 [gr/hr] [Wh] [%] [Wh] [ohm] [V] [kWh/kg] 7.19 0.27 9.02 60.0% 15.0 0.2906 2.09 55.6
(52) TABLE-US-00003 TABLE 3 Effective Effective Energy Consumption Effective voltage resistance H.sub.2 production H.sub.2 energy consumed per kilo of H.sub.2 current [A] [V] [ohm] [gr/hr] [Wh] [Wh] [kWh/kg] 7.19 1.27 0.177 0.27 9.02 9.1 33.3
(53) In view of the above, it is possible to prove that for the same level of H.sub.2 production—considering the electrolysis system of the invention compared with a conventional system—reducing the energy consumption of the cell about 40% is possible, which translates into a substantial reduction of the disadvantages of implementing the alkaline electrolysis process at industrial scale. The big differences resulting between the implementation of a conventional solution and the solution of the present invention are given by the constructive considerations of the cell as capacitor, considering the capacitive and inductive aspects, along with the resistive ones in order to operate the cell under charge and discharge transient regimes. This approach results in current peaks over the electrolytic cell at the beginning of each charge period, which reflects in an apparent or reduce effective resistance, in this case about 0.17 ohm. Taking advantage of said current peak through supplying pulse wave and operation under transient regimes translates into increased efficiency, which exceeds the operation of a conventional cell and making the industrial solutions for the production of hydrogen and oxygen in an alkaline way competitive.
(54) At this point it should be highlighted that the preceding example of application can be extrapolated to other electrolysis processes, being relevant to calculate the optimal voltage of this process and consider the transient regimes of the electrolytic cell both in charge as in discharge, where the capacitive, inductive and resonant aspects of said cell should be stressed.