WO2023119153A1 - Dispositif et procédé permettant de générer et maîtriser la formation de radicaux oh libres dans une cellule électrolytique contenant de l'eau et des composés ioniques - Google Patents

Dispositif et procédé permettant de générer et maîtriser la formation de radicaux oh libres dans une cellule électrolytique contenant de l'eau et des composés ioniques Download PDF

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WO2023119153A1
WO2023119153A1 PCT/IB2022/062537 IB2022062537W WO2023119153A1 WO 2023119153 A1 WO2023119153 A1 WO 2023119153A1 IB 2022062537 W IB2022062537 W IB 2022062537W WO 2023119153 A1 WO2023119153 A1 WO 2023119153A1
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liquid
electrode
electrodes
ions
cell
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Claudio Antolini
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Multim S.R.L.
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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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • 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
    • C25B15/04—Regulation of the inter-electrode distance
    • 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
    • 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

Definitions

  • the present invention relates to a device and a method which, by means of the passage of current in an electrolytic cell containing water and ionic compounds, is able to use the phenomenon of autoprotolysis of water, i.e. the spontaneous generation in water of oxonium ions H 3 O- and hydroxyl ions OH-, to obtain the transformation of the hydroxyls OH- into the free OH radical by maximizing the number of OH produced or even inhibiting the phenomenon of autoprotolysis.
  • the phenomenon of autoprotolysis of water i.e. the spontaneous generation in water of oxonium ions H 3 O- and hydroxyl ions OH-
  • the method object of the present invention is a consequence of the discovery that in electrolytic cells containing an aqueous-based liquid, there is a transport of electrical charges due to a natural and spontaneous behavior of water: a water molecule bumping into an electrode loses an electron and becomes a positive water molecule, which in subsequent collisions with adjacent water molecules can in turn steal an electron from the water molecule with which it collided; the repetition of these events causes the positive electric charge to “move” in the liquid by random collisions and in this path can get to touch the other electrode thereby closing the electric circuit in the liquid.
  • This phenomenon is a physical characteristic of the water molecule, it is always present and cannot be eliminated due to the fact that water molecules in a liquid have a natural kinetic movement due to thermal agitation, which causes them to collide with adjacent molecules about 10 20 times per second, so that all electrolytic cells with waterbased liquids, however they are made, are affected.
  • the traditional electrolysis theory states that the closing of the electrical circuit of an electrolytic cell, i.e. the passage of current, occurs because two complementary reactions take place simultaneously on the electrodes: a positive ion takes an electron and at the opposite pole a negative ion gives up an electron.
  • the continuous and simultaneous exchange of electrons of the ions on the electrodes results in electrical charges seen passing through the closed circuit outside the liquid, whereas in the liquid there is no passage of electrical charges but only the movement of ions towards the electrodes, i.e. the movement of a mass within a mass.
  • the electric field in the liquid between the electrodes cannot be relevant to the reduction of the circulating current because it is possible to create multiple combinations of cells in which the positioning of the electrodes and the voltage applied generate infinitesimal electric forces in the liquid between the electrodes, so that further distancing of the electrodes from each other does not affect the force field, while the reduction of the current is immediate and measurable.
  • the theory not only has scientific value, but also opens the way to the possibility of exploiting the propagation of electric charge in the liquid autonomously and independently of the ionic transport of the traditional theory.
  • AC electrolytic cells have always been marginal from an industrial and electrochemical point of view, exactly because no products are generated, or if they are, they are not separated from each other. Therefore, these AC electrolytic cells have not received any special attention, have not been developed except for simple niche devices such as conductometers, and have not been subjected to any theoretical investigation.
  • the aim of the present invention is therefore to define a device and a method applicable to electrolytic cells containing water and ionic compounds which allows to increase the number of charged water molecules in the immediate vicinity of the electrodes which can diffuse into the liquid and transform the OH- ions produced by autoprotolysis into OH, or to saturate the immediate vicinity of the electrodes with charged water molecules so as to inhibit autoprotolysis and trigger electrochemical reactions at the electrodes which traditionally cannot take place.
  • the method object of the present invention derives from the discovery that the fundamental component of the so-called leakage currents in the electrolytic cells containing a water-based liquid is actually a natural and spontaneous behavior of water, which results to be the indispensable trigger of the electrolytic reaction, and which allows its continuous functioning.
  • baffle S includes a “plug” T that can be opened on command in order to obtain a passage P (Fig.4) that allows to restore a path in the liquid between the two electrodes E1 and E2, it is noted that the phenomenon of voltage and current always reappears every time the plug T is opened.
  • V threshold defined as the minimum value of potential difference (p.d.) necessary to have the electrolysis (decomposition potential of the electrolytes).
  • the spontaneous voltage cannot generate an electric field around the electrodes suitable for moving an ionic mass in the liquid, and even more so cannot generate a significant electric field between the electrodes because of their distance.
  • the electrodes are made of the same material, of the same size and immersed in the same liquid, therefore, even if we want to hypothesize the occurrence of unknown spontaneous chemical reactions between ions and electrodes, in order to have a current circulation in the external circuit it is necessary that on one electrode a chemical oxidation reaction takes place and at the same time on the other electrode a chemical reduction reaction takes place. Since they are absolutely identical electrodes, it is very unlikely that the same liquid with which they are both in contact can produce simultaneously opposite chemical reactions.
  • the electrodes are immersed in the liquid and are not connected to each other by an external electrical circuit.
  • the water molecule is polarized and the negative polarity zone, centered on the oxygen atom, is at least twice as large as the positive polarity zone.
  • a water molecule comes into contact with the electrode, it can then bump into the electrode surface with its negative polarity part (more frequently) or with its positive polarity part.
  • the molecule may transfer one or more electrons because the electrons more easily extractable from a water molecule are located in the outer, higher energy orbitals (HOMO orbitals), which in the case of water are located essentially on the oxygen atom and are the two non-bonding doublets thereof. If, on the other hand, the molecule hits the surface of the electrode with its positive polarity part, the transfer or capture of electrons is unlikely for the above reason.
  • HOMO orbitals higher energy orbitals
  • the ions present in the solution could hit the surface of the electrode and possibly transfer or capture electrons but their effect is negligible, both because the ions are present in a much smaller number than the water molecules and because the ions are surrounded by oriented water molecules and therefore to obtain a collision with the electrode an electric field is needed whose attraction force allows the ion to overcome the resistance of the barrier of water molecules between it and the electrode.
  • the water molecules that hit the surface of the electrode with the negative polarity part have transferred one or more electrons of their own electrons to the electrode and consequently have become “positive”, presumably modifying also their structure (for simplicity of exposure from here on it is assumed that a molecule transfers only one electron).
  • the propagation by collision in the immediate vicinity of the electrode is, however, influenced by the negative electric charge present on the electrode due to the electronic exchange that has just occurred. So, there is a high probability that a sequence of collisions brings an molecule against the electrode to take back the electron, and there is a low probability that an molecule can move away from the electrode's field of attraction.
  • the probability of leaving the electrode's area of influence increases significantly if there is an electric field disruptor in the immediate vicinity of the electrode, i.e. an ion that can allow more molecules to escape from the electrode's attraction field by altering the electric field. By the way, this is the reason why, as is experimentally known, pure water electrolysis cannot be obtained: molecules cannot escape the electrode and since they cannot reach the other electrode, they do not close the “circuit in the liquid”.
  • the continuous exchange of electrons between water molecules and electrode can generate at a time t an accumulation of N electrons on the electrode with charge , which are distributed on the surface of the electrode, while at the same time N molecules are formed in the liquid.
  • the overlapping of these processes over time leads each electrode to reach and oscillate around its own equilibrium condition, not necessarily equal to that of the other electrode, which depends on time, on the concentration of ionic compounds present in the immediate vicinity of the electrode and on the material, size and positioning of the electrode.
  • electrode E1 behaves as a "generator” of electrons and molecules while electrode E2 behaves as a "consumer” of electrons and molecules.
  • the flow of electrons between electrodes E1 and E2 occurs by means of an electric conductor while the positive charge moves in the liquid through the collisions between the molecules, therefore the speed of transfer of the negative charge is many orders of magnitude higher than that of the positive charge. It is therefore possible to consider the transfer of electrons in the electric circuit as immediate compared to the displacement of charges in the liquid.
  • the amount of the initial flow and the direction of flow of the charges in the circuit depend on the situation present on each electrode at the moment of closing the circuit. Therefore, each closing cycle will have the same operation, but the starting values may be different from time to time as well as the direction of flow of the electric charges.
  • the theory explained here proposes to integrate the current knowledge that the displacement of electrical charges within an aqueous solution, either of an electrolytic cell or galvanic cell or battery, is caused only by the movement of ions towards the anode and cathode due to the attraction of the electric field in the immediate vicinity of the electrode (migration), due to the effect of the concentration gradient as you move away from the electrode (diffusion) and to the convective movement and the simultaneous constant presence of leakage currents.
  • the explanation of the operation of the devices object of the present invention is based on the demonstration that the electrical conductivity of the liquid always has a component due to the presence of charges carried by water molecules that are generated by collision and that move in the liquid through collisions/interactions with other water molecules.
  • electrode E1 becomes the generator of molecules and the electrons given to electrode E1 are immediately transported to the positive pole of the battery, while electrode E2 becomes the consumer of molecules that neutralize the electrons present in the negative pole of the battery.
  • electrode E1 will continue to form molecules without the process slowing down and allowing an increasing flow of charges in the circuit connected to the battery.
  • the molecules carry the totality of electrical charges with the maximum intensity established by the system configuration (battery, electrode size and distance between them, ion concentration), and as the intensity of the current increases, the number of electrical charges that at a given instant t are on the surface of the electrode also increases.
  • These charges generate around the electrode an electric field, which in turn is gradually increasing, that extends into the liquid in the immediate vicinity of the electrode and influences the behavior of the ions present: the ions of the same sign are pushed away while, as soon as a certain value of the electric field is exceeded, the ions of the opposite sign present in the adjacent liquid undergo a force of attraction such that they can overcome the barrier of oriented water molecules surrounding them and hit the electrode, thus initiating the electrolysis process proper.
  • the molecules therefore constitute the “starting engine” of all the electrolytic processes that take place in water-based ionic solutions, because if there was not the mechanism of molecular transport of water, the ions present around the electrodes would not be able, on their own, to bring to the electrode the amount of charge necessary to create the electric field itself.
  • the ions present around the electrodes would not be able, on their own, to bring to the electrode the amount of charge necessary to create the electric field itself.
  • in open circuit on the terminals of a battery there are only “few” electrical charges, several orders of magnitude less than when a current begins to flow, regardless of the value of the applied p.d. If an electrode immersed in the liquid is connected to the battery terminal, even the electrode will have few electrical charges that generate in the liquid an electric field absolutely insufficient to attract the number of ions necessary to start the electrolysis process.
  • the intensity of the current circulating in the external circuit is therefore given by:
  • a total A water + A ions where A ions is the contribution of the normal electrochemical reaction and
  • a water is the contribution of charges provided by the molecular transport of water.
  • the value of A total is maximum and is formed only by A water while with the continuation of the process the A total value drops, because the value of A water drops drastically and the value of A ions starts to increase.
  • the system finds its equilibrium point with the maximum A ions value and a minimum A water value.
  • the electrolytic process in order to maintain it, it is necessary that there are always useful ions in the significant range of the electric field, therefore the ions consumed by the electrolytic reaction must be replaced by others who must take their place.
  • the ions move in the liquid by diffusion pushed by the concentration gradient, i.e. there is the movement of a physical mass that must open a path in the middle of other masses, therefore the speed of the ion in the liquid is limited by the characteristics of the ion and the liquid. The speed at which the replacement ions go to a point where they can touch the electrode determines the maximum A ions of the cell.
  • the electric field moves away the negative ions and in doing so reduces the number of molecules that can be released into the liquid, so the A water is reduced.
  • the value of A water cannot be reduced to zero because if this were to happen, e.g. by isolating the electrodes from each other via baffle S in the cell, the electrolytic process would stop instantly.
  • a sequence of ions A, B, C, D, E are initially positioned in a line perpendicular to surface K and equidistant from each other, being separated by polarized water molecules M.
  • ion A which is subject to the force of the electrostatic field, gets into contact with the electrode in K moving with velocity where is the acceleration impressed by the electric field at the distance P from point K.
  • the replacement ion B moves towards P instead with velocity where is the acceleration impressed by the electric field at the distance Q>P from point K, therefore and consequently
  • ion A arrives in K and gives an electron e to the electrode, but ion B cannot reach the distance P but only the distance P'>P.
  • the threshold value V threshold When the threshold value V threshold is reached, there is started the current A ions that “consumes” the ions that hit the electrode and are replaced thanks to the concentration of the ions in the liquid that diffuse towards the electrode.
  • the p.d. is increased, more and more ions are attracted towards the electrode but the ions closer to the electrode are attracted faster and faster than those further away because the force of attraction of the electric field follows the reciprocal of the square of the distance. Consequently, the velocity at which ions are replaced near the electrode depends not only on the concentration of the ions and the physical displacement of the ion mass in the liquid, but also on the fact that the force of attraction of the electric field acts more near the electrode and marginally at the limits of the electric field.
  • the liquid thus acts as a “reservoir” of positive charges that fills up as the electrolysis continues. It should be noted that this “reservoir” is able to be constantly increased during cell operation because the positive electrode generates more molecules than the negative electrode can absorb, for statistical reasons.
  • the normal water molecule has a slightly positive zone in correspondence of the hydrogen atoms and a negative zone in correspondence of the oxygen atom, therefore in front of the positive electrode it spontaneously tends to dispose itself showing to the electrode its negative zone, i.e. that relative to oxygen.
  • This is exactly the most favorable zone to exchange the electron with the electrode and generate the molecule while in front of the negative electrode there is a molecule of water which is all positive and therefore it is not arranged according to a preferred direction.
  • the probability that a normal water molecule bumping into the positive electrode gives an electron to the electrode is therefore greater than the probability that an molecule bumping into the negative electrode takes an electron, therefore the generator electrode produces more charges than the consumer electrode is able to consume.
  • the water molecule will be called Antolin, or H 2 O + if in the formulae; the theory explaining the propagation of electric charge in the liquid by the water molecule will be called the Antolin theory, the electrolytic cell supplied by a direct voltage generator will be called a DC cell for the sake of brevity to distinguish it from the electrolytic cell supplied by an alternating voltage generator, which will be called an AC cell; the chemical transformation reaction which takes place on an electrode through which a current flows and which produces chemical equivalents of the electrolyte will simply be called electrolysis.
  • an electrolytic cell consisting of an insulating container filled with an aqueous ionic solution, e.g. 0.9% NaCl saline, in which are at least partially immersed on one side an electrode E1 and on the other side an electrode E2, the electrodes being substantially identical in material, shape and size and spaced so that their respective faces F1, F2 in contact with the liquid are spaced not more than 1 cm apart.
  • an aqueous ionic solution e.g. 0.9% NaCl saline
  • E1 becomes a generator of Antolins which, propagating by collisions through the liquid, reach E2 where they are neutralized.
  • E1 creates the maximum electric field in its surroundings and thus begins to attract the negative ions which, however, as already mentioned, must move through the liquid and therefore have a limited speed.
  • the frequency ⁇ is greater than 1 kHz: in fact, for lower values the ions are able to hit the electrodes before the polarity reversal, triggering the electrolytic reaction that activates the A ion component. It can be verified that, all other variables being equal, when the frequency is reduced to values below 1 kHz, electrolysis is triggered, similar to that which would occur if the electrodes were connected to a battery.
  • the concentration of solute in the water is less than a Ptrigger value which differs according to the solutes.
  • P concentration of solute in the water
  • the number of ions present is such that the reversal of the electric field in the vicinity of the electrode is unable to remove all the ions and electrolysis will therefore be initiated. It can be verified, leaving the frequency and voltage fixed, that by reducing the concentration of that solute below the Ptrigger value, electrolysis stops while the passage of current remains.
  • the voltage V applied to the electrodes E1 and E2 is less than a V trigger value which depends on the distance between the electrodes and the frequency f. in fact, if the V trigger value is exceeded, an electric field is generated between the electrodes which exerts such a force on the ions in the immediate vicinity of the electrodes that they are attracted more quickly until they hit the electrode before the polarity is reversed, thus triggering an electrolytic reaction on that pole similar to that which would occur if the pole was connected to a battery. Leaving the concentration constant, it can be verified that by moving the electrodes apart or increasing the frequency to a value electrolysis stops while the current continues to flow.
  • the Antolin theory provides an explanation for the phenomenon whereby, once a voltage V ⁇ V trigger is set, as the frequency increases the value of the current A water decreases.
  • a faster variation of the polarity reduces the time available for the ions to approach the electrodes and therefore in the immediate vicinity of the electrodes there will be fewer ions and since the ions, as already written in paragraph 2, are the perturbing element of the electric field that allows the Antolins to escape the attraction of the electrode, it will happen that fewer Antolins can reach the opposite electrode and consequently the value of A water will be reduced.
  • the distance between oxygen and hydrogen is 0.96 ⁇ 10 -10 m and in a first approximation we can represent the molecule as a sphere of radius 0.96 ⁇ 10 -10 m.
  • This value is two orders of magnitude greater than the speed of light (3 ⁇ 10 8 m/s) and four orders of magnitude greater than the speed of the electron, and by this reasoning the greater the distance between the molecules, the greater the speed.
  • the speed v can be in the order of magnitude of the speed of light or at least greater than the speed of an electron can lead to a theory that explains why atoms and molecules interact with each other in what are called chemical reactions.
  • This behavior of the atoms defines chemical reactions as the result of a collision between atoms/molecules in which the nucleus of one atom has been able to approach within the zone where one or more of the other's electrons are normally present and, depending on the shape of the orbitals of each atom involved, this collision will be more or less likely.
  • all chemical reactions could be explained by statistical considerations only, on the basis of the shape and arrangement of the orbitals.
  • a total A water + A ions and that the component A ions is in turn formed by the sum of two different components A ions.transport and A ions.collision.
  • the A ions.transport component is given by the electrons that are released/acquired at an electrode when an ion moving “physically” in the liquid manages to hit the electrode, i.e. when the electric field in the vicinity of the electrode is sufficient to attract it despite the possible cloud of polarized molecules surrounding it (e.g. Na + , Ca ++ , Cl-).
  • the A ions.collision component is given by the electrons released/acquired at an electrode by ions that do not move in the liquid but acquire ion status by shifting their valence bond with hydrogen through collision with an adjacent molecule (e.g. H 3 O + , OH- and OH).
  • an adjacent molecule e.g. H 3 O + , OH- and OH.
  • a ions.transport needs to get physically close to the electrode and to do so must move through the liquid at a speed measurable in cm/sec driven by the concentration gradient of the substance in the liquid, whereas A ions.collision moves at an incomparably greater speed and throughout the liquid, regardless of concentration or electric field, because it moves by random collisions.
  • the A water component is similar to the A ions.collision component, but in this case the collision moves an electron from one molecule to another and the speed of movement in the liquid is maximum.
  • the mechanism of displacement of the positive electric charge carried by the Antolin which occurs using three simultaneous modes.
  • an Antolin can only give up its charge if it collides with a water molecule.
  • an Antolin can give up the charge in one of six possible directions (forward, backward, right, left, up or down); the forward direction is the one that allows the charge to reach the cathode placed in front of the anode, and the minimum number of collisions necessary to reach it is given by the number of water molecules that are arranged along the segment representing the minimum distance between the electrodes.
  • the probability of the event “forward” is equal to the probability of the event “backward”, the other four directions being irrelevant for the approach to the cathode, but since the anode at each instant generates other Antolins, it may occur that a previously created Antolin moving “backward” collides with an Antolin (or a positive ion) with the result that the electric charge does not move backwards because the collision does not move the electric charges.
  • the probability that the “backward” event causes the charge to recede changes in favor of the “forward” event.
  • the increased Antolin concentration progressively extends from the anode towards the cathode, making it statistically possible for the positive charge to reach the cathode.
  • the Antolin is attracted to the negative ions and participates in the cloud of water molecules that surrounds them; as mentioned earlier, the Antolin requires this to escape the attraction of the anode that created it but also to facilitate its movement in the liquid because its path to the cathode can be seen as a sequence of negative ions to be reached one after the other, crossing the short stretch of water molecules that separates them. In this way, it is more likely that on a short path the random dominance of a sequence of “forward” events can make it reach the next negative ion, and the presence of more Antolins remaining in the cloud surrounding the preceding ions contributes to the dominance of the “forward” event.
  • a total ⁇ A water is the case of an AC or DC cell with negligible electrolysis which we will call Passive Cell.
  • a total ⁇ A ions is the case of an AC or DC cell with electrolysis on both electrodes, which we will call Active Cell.
  • a total A water + A ions is the special case where an AC or DC cell performs electrolysis at the cathode counterbalanced by Antolin emission at the anode, which we will call Hybrid Cell.
  • the Hybrid Cell is feasible if the applied voltages do not exceed a threshold value which is a function of the ions dissolved in the liquid, it is a peculiarity that can only be explained by the theories presented here and will be demonstrated in one of the experiments illustrated below.
  • the autoprotolysis of water can be defined as a natural phenomenon whereby collisions between two water molecules give rise to the reaction
  • the number of dissociations occurring at a given time depends primarily on the number of water molecules present in the liquid: obviously the more water molecules present, the greater the number of generations and consequently the more ions produced
  • the lifetime of the ions depends on the probability which determines the quantity of ions present in the liquid at that instant.
  • the dissociation event is given by the reaction [1] and the presence of an Antolin in the liquid is not capable of altering this reaction, which therefore remains the only way of generating the oxonium and hydroxyl ions.
  • the collision between a water molecule and an Antolin does not generate dissociation but, as seen in the Antolin theory, can at most exchange the electron and reverse the condition; whereas the collision of two Antolins, which are two positive (and nonpolarized) molecules, is disfavored by the repulsive electric field and in any case even if the collision occurred it would not be able to generate OH- and H 3 O + .
  • an Antolin in the liquid leads to a decrease in the dissociation event in two different ways. Firstly, because it reduces the total number of water molecules, thereby decreasing the total number of dissociation events and consequently the total number of dissociated ion pairs. Secondly, because the collision of a water molecule with a “modified” water molecule such as the Antolin interrupts the average sequence of consecutive collisions between water molecules, making the reaction [1] less likely. This dual effect means that as the number of Antolins present in the liquid increases, the number of hydroxyl and oxonium ions gradually decreases.
  • Oxonium and hydroxyl ions have a lifetime in which they remain distinct in the liquid, the t ap time duration of which is equivalent to the time from [1] until the intermediate products become two water molecules again with [2],
  • the combined effect of the above processes means that the passage of current in an electrolytic cell generates Antolins, which in turn collide with the OH- produced by the autoprotolysis of water to generate the free OH radical. Given a sufficient number of Antolins. it is possible to transform all OH- into OH.
  • the liquid in the cell must be isolated from water molecules in the connecting pipes, feed or drains, and any separating bulkheads must be made of electrically non- conductive material. Since the electrical charge moves through the liquid by means of collisions between Antolins and adjacent water molecules, it is essential that the Antolin generated does not find a path which causes it to disperse anywhere along the pipes, preventing the achievement of significant concentration values.
  • the electrodes E1, E2 must have at least one face F1, F2 in contact with the liquid of equal area (with a tolerance of 5%) and must be positioned with these faces F1, F2 facing each other at a fixed distance D, which must be between 0.5 and
  • A be a point on the surface of an electrode from which a straight line is drawn perpendicular to its surface meeting the surface of the opposite electrode at B, the electrodes are said to be at a fixed distance if, when it is possible to draw the segment AB, it always has the same length. Based on experimental experience and calculations, it is considered that if the distance between anode and cathode is greater than 10 millimeters, the electrical efficiency of the cell is not acceptable.
  • electrodes E1, E2 which must have in contact with the liquid at least one flat face F1, F2 either linear or curved, which is necessary to ensure that the distribution of Antolins in the liquid is statistically calculable and thus that the behavior of the cell is predictable and constant.
  • electrodes E1, E2 may have a part, to the left of the dotted line in the examples shown, which is not in contact with the liquid.
  • the faces F1, F2 are to be understood as only the opposing faces of electrodes E1, E2 that are in contact with the liquid.
  • an Antolin must have another Antolin (or a positive ion) behind it, and therefore the anode surface must be able to generate enough Antolins at any one time that they do not disperse into too much liquid to permit advancement. This calculation also explains why the distance between the electrodes cannot be more than 10 millimeters, as indicated in point 2: referring to the previous example, if the distance increases to 9 mm, the positions to be reached are tripled and the average number of collisions available to advance a single position is reduced to 33, making the event of reaching the cathode statistically less likely.
  • the water molecules must be between the F1, F2 faces or in the holes of electrodes E1, E2 of opposite polarity because the Antolin is created by collision between water molecule and electrode, and it is essential to maximize the surface area of the electrodes.
  • the molecules located between the Fl, F2 faces of the opposite polarity electrodes E1, E2 occupy a volume (indicated by the darker shading in a grid pattern) which will be called the working region (LAV), while the liquid not in the working region will be in a volume (indicated by the lighter shading in a dotted pattern) called the accumulation region (ACC). Note that this 50% condition is fulfilled even if all the liquid is included in the working region LAV, so the accumulation region ACC may not even be present.
  • the entire liquid of the accumulation region ACC must completely cover at least one electrode, i.e. the electrode must be immersed in the liquid, and must be in contact with air or a gaseous mixture over an air contact surface SCA having an area at least equal to the area of the wetted surface of contact between the electrode and the part of the liquid that is in the accumulation region ACC.
  • this “saturation” means that less and less Antolins will be created from the electrode face in contact with the accumulation region ACC with the result that the Antolin production phenomenon would stop.
  • the liquid present in the accumulation region ACC must be in contact with air or a gaseous mixture so that the Antolin can interact with the gaseous molecules present at the water surface, e.g. oxygen, and discharge the charge onto them: in this way, at least part of the Antolins produced in the accumulation region ACC can be cancelled out and the production of Antolins on the electrode face can continue.
  • this electrode will be called a solid electrode, as in Fig.7, or
  • - have holes which allow the liquid to pass through the electrode (for example a net or grid electrode which we will call a grid-like electrode), as in Fig.8.
  • These gridlike electrodes must all have holes of the same size, each hole cannot have a volume greater than the cube of the distance D between the electrodes as defined in point 2, the total area of the perforated surface of a face must be less than or equal to 50% of the area of the opposite face of a similar solid electrode, and they must be completely immersed in the liquid.
  • the perforated surface of the grid-like electrode ensures that an Antolin created by the anode can reach the accumulation region ACC without being obstructed by constrictions or bottlenecks, which would be the case with a solid electrode because then the passage of the Antolin to the accumulation region ACC could only occur by passing into the liquid present on the outside of the edges of the electrode surface (as in Fig. 7).
  • Antolin maximization which will be used to capture carbon dioxide in the air and put it into a stable compound.
  • the electrodes connected to the two poles of a power supply consist of a 50x 100x 1 millimeter zinc plate and a zinc grid of the same size as the plate with square holes of 1 mm side on 50% of the surface.
  • the plate is placed horizontally, and the grid is superimposed on the plate, spacing it 2 mm apart.
  • 12.5 ml of a 10% aqueous solution of CaCh are poured into the center of the device while waiting for the liquid to distribute spontaneously between the grid and the plate; the temperature of the solution is 20°C and the experiment is carried out at room temperature. In this way, the liquid in contact with the plate is not in contact with air while the liquid in contact with the grid is in contact with air.
  • the cell meets the conditions 1 to 6 of the method.
  • the DC power supply is switched off, it is verified that the white gelatinous foam remains stable and that it becomes a whitish powder when placed in an oven at 300 degrees.
  • Analysis of the solid compound shows that it is predominantly CaCO 3 and to a lesser extent ZnCO 3 . Since the liquid did not contain any carbon, which is instead present in the final product, this must necessarily have been taken from the air with which the liquid is in contact, and the most plausible form is CO 2 .
  • the presence of zinc carbonate is explained by the fact that the anode releases Zn ++ ions into the liquid which, although numerically smaller than the Ca ++ ions, also interact with CO 2 .
  • the anode can be impacted by H 2 O and Cl- and give rise to the following reactions: H 2 O H 2 O + + e forming the A water component [4]
  • the cathode can be impacted by H 2 O + , Ca ++ and Zn ++ and give rise to the following reactions:
  • the cell is a Hybrid Cell because the anode produces Antolins and releases zinc ions but does not react with chlorine because a barrier of Zn ++ ions and Antolins is formed in front of the anode, surrounding the Cl- ions and preventing them from touching the positive electrode and reacting ([5] does not occur).
  • Antolins reduces autoprotolysis, which in turn reduces the number of OH in the vicinity of the carbonic acid, and as a result fewer H + ions are generated which reduce the A ions current, which leads to a reduction in Antolin production which returns to the original value, allowing the sequence to be repeated.
  • the current varies cyclically in a sinusoidal pattern over a period of about 10 seconds between a maximum and a minimum.
  • Continuous treatment can be obtained by placing the plate on a support inclined at 45° and letting the liquid containing the CaCl 2 fall onto the grid via a dripper, so that by gravity the liquid drops from the bottom of the plate and falls into a collection vessel, from which it is pumped into the feed tank to which the dripper is connected.
  • the plate is spaced out from both the dripper and the collection vessel, so that both the incoming and outgoing droplets must pass through a section in the air, thus being electrically isolated and separated from any liquid, thus preventing the dispersion of Antolins.
  • the DC cell with a negative pole on the grid-like electrode can be used to extract CO 2 from the air and simultaneously store it in a stable compound.
  • the hydrogen gas produced could be collected and used separately.
  • a similar result could also be achieved with an AC cell with a power frequency >1kHz, but this produces less calcium carbonate for the same power consumption.
  • the Hybrid Cell is the only way to achieve significant production of Antolins, which in turn generate OH, and at the same time neutralize the hydrogen ions that are produced by the calcium carbonate formation reactions.
  • the particular composition of the cell in particular the use of a metal anode that dissolves in the liquid without interacting with the ions present, allows for the significant generation of both the A water component and the A ions component: the production of OH added to the electrolysis on the cathode makes it possible to create an absolutely innovative system capable of producing constant results that are always reproducible and otherwise unattainable.
  • zinc is the most advantageous in terms of both cost and availability.
  • Zn ++ ion that dissolves and does not bind to CO 2 accumulates in the liquid circulating in a closed circuit and can be recovered periodically with a separate device to reform a new anode.
  • ZnCh can also be dissolved in water to limit anode consumption.
  • the electrical power required to power a large-scale process could be obtained by using wind or hydroelectric power plants at night and photovoltaic panels during the day.
  • the DC cell with a positive pole on the grid and a negative pole on the plate only operates at voltages V2 at least three times as high as V 3, generating electrolysis but no carbonate production.
  • the Antolins are created by the grid-like electrode on both faces of the anode and, as we have just discussed, the components A ions .transport and A ions .
  • the free OH radical is very useful in the treatment of bacteria-polluted liquids because it is known to attack bacterial cells and lead them to death.
  • the use of an AC- powered Passive Cell with frequency >lkHz with stainless steel electrodes is extremely advantageous in this field because, a fundamental aspect, it does not alter the original liquid as the electrodes do not interact measurably with the substances dissolved in the water, and the production of OH occurs directly in the liquid with the lowest possible cost of electrical energy since the total electric current that circulates in the cell is formed by the A water component only, which is the only one that can generate OH.
  • the Active Cell produces different reactions on the two poles, and it is obvious that if you put a compound into the water that obtains OH on one pole, on the other pole you will have a different reaction and therefore great attention must be paid to the study of additional compounds and the materials with which the electrodes of each pole are made.
  • anomalous substances resulting from illicit spills in the sewers may be present in the water to be treated, which could participate in the electrolytic reactions of the Active Cell, perhaps creating compounds more dangerous to human or animal life than the original ones.
  • Hybrid Cells are also unsuitable for the treatment of water intended for human or animal use, because even if you can limit electrolysis to the cathode alone, you can never be completely certain that no undesired reactions will occur.
  • the electrodes consist of a 200x200x 1 millimeter stainless steel plate and a stainless steel grid of the same size as the plate and with square holes of 1 mm side on 50% of the surface.
  • the plate is arranged horizontally, and the grid is superimposed on the plate, spacing it 2 mm apart.
  • 120 ml of a water sample collected from a purification plant is poured, before the water is poured into the final treatment tank with chlorination, and one waits for the liquid to distribute spontaneously between the grid and the plate.
  • a voltage value is applied to the AC cell such that it provides 6 Amperes of current without generating electrolysis: the cell now meets the conditions 1 to 6 of the method.
  • the voltage value may vary depending on the sample taken, since the composition of the water taken varies throughout the year, but it is generally of the order of 3 Volts. Leaving the generator switched on for 3 seconds results in a 99% reduction in the value of Escherichia coli at the end of the treatment.
  • the OH radical can act in all the volume of the liquid, and therefore on all cells anywhere in the liquid of the electrolytic cell, because: a) OH can be produced anywhere in the liquid; b) OH are able to move around in the liquid, during their lifetime, by collision with an Antolin.
  • a) OH can be produced anywhere in the liquid
  • b) OH are able to move around in the liquid, during their lifetime, by collision with an Antolin.
  • the economic cost of the electrical consumption of the purification treatment depends solely on the voltage value that must be applied to the electrodes to obtain the OH. only value, but it is advisable, in order to build a truly functional device in a civil purification plant, to seek a compromise between the maximum approach of the electrodes and the amount of water that can be treated in the unit of time.
  • a plate is arranged horizontally and a circular plastic gasket 15 mm in diameter and 1.1 mm thick is placed in the center of the plate;
  • the OH. stop current value is exceeded and a soft noise of continuous bursts begins to be heard while the plates increase in temperature by one degree;
  • the anode can be hit by H 2 O, H 2 O + and Cl- and give rise to: H 2 O ⁇ H 2 O + + e- (Antolin formation) [4]
  • the cathode can be hit by H 2 O + , H 2 O ++ , H + and Na + and give rise to:
  • the reaction [13] can be explained by the large number of Antolins present in the immediate vicinity of the electrode: in fact, it cannot be ruled out that an Antolin will in any case collide with the positive electrode, because if the Antolins present in large numbers in the vicinity of the electrode never touched the positive electrode, it would mean that the electrode would be physically isolated from the liquid and would have no pressure on its surface, which cannot be the case. So the collision of an Antolin with the positive electrode must occur, and then it can happen that this collision causes the oxygen atom of the Antolin to lose the second of its outer orbital electrons, thus making it an Antolin plus.
  • reaction [13.1] Since [13] takes place in the immediate vicinity of the electrodes where there is little presence of water molecules, reaction [13.1] has a great advantage over [13.2], The four hydrogen ions produced by [13.1] will be transformed by [15] into H2 hydrogen atoms upon polarity reversal. Reaction [5] does not take place because already normally the Cl- ions would be surrounded by a cloud of polarized water molecules that would make its path to the anode difficult, but since the ion is in an area where more Antolins (positive) than normal water molecules are present, the Cl- ion is surrounded by a “persistent” cloud of Antolins and its path to the cathode is further impeded.
  • reaction [14] With reaction [14], the Antolins plus that were generated by [13] but not utilized by reaction [13.2] at the previous polarity reversal of the electrode become Antolins again.
  • reaction [16] normally the Na + ions would be surrounded by a cloud of polarized water molecules that would make their path to the cathode difficult but, since the ion is in an area where more Antolins (positive) than normal water molecules are present the Na + ion is not surrounded by a cloud and its path to the cathode is not impeded. The Na + ion is then in competition at the cathode with the Antolin or Antolin plus which have faster displacements so that [16] occurs, but only episodically.
  • the water thus produced temporarily reduces the concentration of Antolins and brings the liquid back to a condition in which the sequence can be repeated cyclically.
  • the heat in Joules that can be measured on the plates is also greater than the sum of the Joules expended to power the cell and the heat in Joules produced by the combustion of gaseous hydrogen and oxygen in [17], and it is therefore justified that [13.1] produces heat because, due to its episodic nature, the heat produced by [16.1] cannot be considered effective.
  • This apparatus can be used as a heating element as an alternative to a resistor, for example in a domestic water heater, because it is capable of achieving energy savings of at least 50%.

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Abstract

L'invention concerne un dispositif et un procédé qui utilisent la propagation de charges électriques au moyen de collisions cinétiques entre une molécule d'eau et une molécule d'eau positive dans une solution aqueuse contenant des composés ioniques placée à l'intérieur d'une cellule électrolytique. Le procédé décrit comment transformer les ions hydroxyle produits par autoprotolyse de l'eau en radicaux OH libres, afin d'effectuer des traitements de désinfection bactérienne ou un traitement de liquides pollués par des hydrocarbures ou pour le stockage de dioxyde de carbone gazeux, et également comment inhiber l'autoprotolyse à proximité des électrodes afin d'obtenir des réactions chimiques autres que celles traditionnellement connues.
PCT/IB2022/062537 2021-12-23 2022-12-20 Dispositif et procédé permettant de générer et maîtriser la formation de radicaux oh libres dans une cellule électrolytique contenant de l'eau et des composés ioniques WO2023119153A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632497A (en) * 1962-09-20 1972-01-04 Pullman Inc Electrochemical cell
EP2277833A2 (fr) * 2001-02-15 2011-01-26 The Procter and Gamble Company Cellule électrolytique haute efficacité pour générer des oxydants dans des solutions
US20140272640A1 (en) * 2013-03-15 2014-09-18 Mcalister Technologies, Llc Multifunctional electrochemical devices
WO2018044153A1 (fr) * 2016-08-29 2018-03-08 W&F Technologies B.V. Système électrochimique de récupération de constituants à partir d'un flux de déchets et son procédé
EP3887574A1 (fr) * 2018-11-29 2021-10-06 Multim S.r.l. Procédés et dispositifs d'utilisation de la propagation de charges électriques par impacts entre des molécules d'eau dans une cellule d'électrolyse contenant de l'eau et des composés ioniques
WO2021224722A1 (fr) * 2020-05-05 2021-11-11 Sabic Global Technologies B.V. Réacteur photo-électro-chimique unifié pour la production d'hydrogène solaire

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632497A (en) * 1962-09-20 1972-01-04 Pullman Inc Electrochemical cell
EP2277833A2 (fr) * 2001-02-15 2011-01-26 The Procter and Gamble Company Cellule électrolytique haute efficacité pour générer des oxydants dans des solutions
US20140272640A1 (en) * 2013-03-15 2014-09-18 Mcalister Technologies, Llc Multifunctional electrochemical devices
WO2018044153A1 (fr) * 2016-08-29 2018-03-08 W&F Technologies B.V. Système électrochimique de récupération de constituants à partir d'un flux de déchets et son procédé
EP3887574A1 (fr) * 2018-11-29 2021-10-06 Multim S.r.l. Procédés et dispositifs d'utilisation de la propagation de charges électriques par impacts entre des molécules d'eau dans une cellule d'électrolyse contenant de l'eau et des composés ioniques
WO2021224722A1 (fr) * 2020-05-05 2021-11-11 Sabic Global Technologies B.V. Réacteur photo-électro-chimique unifié pour la production d'hydrogène solaire

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