KR102328131B1 - Hydrogen production device using high concentration ionic solution - Google Patents

Abstract

Disclosed is a hydrogen production device that generates hydrogen and electricity by supplying a high concentration ion solution, water, an acid solution and a base solution to an electrolyte part of the hydrogen production device.

Description

Hydrogen production device using high concentration ionic solution {HYDROGEN PRODUCTION DEVICE USING HIGH CONCENTRATION IONIC SOLUTION}

The present invention relates to a hydrogen production device that generates hydrogen and electricity using a high-concentration ionic solution.

In general, hydrogen has recently attracted a lot of attention due to its various uses, including clean energy sources, and methods for efficiently producing such hydrogen are being studied in various ways and in depth not only in the country but also in the world.

Accordingly, the main method for producing hydrogen is to steam reforming fossil fuels such as methane gas, then purifying and using it. We are actively developing and applying a method using water electrolysis.

That is, as a method of obtaining hydrogen by electrolysis of water, an alkaline water electrolysis method using an aqueous alkali solution as an electrolyte is representative, but this method requires a purification process due to low hydrogen purity, a separation process for separating oxygen and hydrogen, It has many disadvantages such as the need for process control that must continuously replenish the electrolyte in the aqueous solution state, corrosion of electrodes and components by the aqueous electrolyte, deterioration of hydrogen production efficiency due to low current density, and excessive power consumption due to high voltage. have.

On the other hand, the treatment cost increases and a large amount of raw water is wasted due to a large amount of highly concentrated ion-concentrated water discharged from water treatment systems such as electrodialysis (ED), reverse osmosis (RO), and nanofiltration (NF) method, and reverse osmosis membrane or The need for reuse of ion-concentrated water is further highlighted as enormous costs are involved in water intake, drinking water, water purification, and other treatment as influent water of the nanofiltration membrane facility.

In addition, due to the nature of some industries, including many chemical industries, a significant amount of waste acid or waste base is generated, which is considered hazardous waste and requires additional treatment before being discharged into the environment. .

Accordingly, the present inventors alternately arranged a high-concentration ionic solution and a low-concentration aqueous solution while conducting research by grafting the treatment of the ion-concentrated water discharged after the water treatment and the hydrogen production, and alternating an anion exchange membrane or a cation exchange membrane between each batch. The present invention was completed by developing a novel hydrogen production device capable of generating hydrogen and electricity with a difference in concentration between the high-concentration ionic solution and the low-concentration aqueous solution.

In addition, the hydrogen production device does not require the application of an additional external voltage for operation, and unlike the conventional hydrogen production device that operates only when a voltage of 1.5V or more is applied, it can be operated even when a voltage of 0.4V or more is applied have. In addition, since the high concentration ionic solution discharged from the water treatment system is utilized as well as the spent acid and/or the waste base, and the ionic solution and the waste acid and/or the waste base are discharged in the form of water and salt, it can greatly contribute to the environment.

In this regard, Korean Patent Registration No. 10-1263177 discloses an electrolytic cell for a photoelectric-electrolytic integrated hydrogen production system.

The present invention has been devised to solve the above problems, and an embodiment of the present invention is a hydrogen production device that generates hydrogen and electricity by supplying an acid solution, a base solution, water and a high concentration ion solution to the electrolyte part of the hydrogen production device provides

In addition, another embodiment of the present invention provides a stack in which the hydrogen production device is connected in series or in parallel.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. There will be.

As a technical means for achieving the above-described technical problem, an aspect of the present invention is

cathode; anode; an electrolyte part interposed between the cathode and the anode; and a conducting wire connecting the cathode and the anode, wherein the electrolyte unit includes an acid solution moving unit, a base solution moving unit, and an ion concentration difference generating unit, and the ion concentration difference generating unit crosses a water moving unit and an ionic solution moving unit. A hydrogen production device is provided.

One side of the acid solution moving unit is disposed adjacent to one side of the cathode, one side of the base solution moving unit is disposed adjacent to one side of the anode, and the ion concentration difference generating unit is located on the other side of the acid solution moving unit. It includes an anion exchange membrane and a cation exchange membrane that are sequentially and repeatedly arranged in the direction of the other side of the base solution moving part, and a water moving part is disposed between the anion exchange membrane and the cation exchange membrane according to the direction, and ions between the cation exchange membrane and the anion exchange membrane The solution moving part may be alternately disposed, and the number of the anion exchange membrane and the cation exchange membrane may be the same.

The hydrogen production device further includes an acid solution supply unit and a base solution supply unit for supplying an acid solution and a base solution to the acid solution moving unit and the base solution moving unit, respectively, and water and ions to the water moving unit and the ion solution moving unit It may further include a water supply unit and an ionic solution supply unit for supplying solutions, respectively, and each of the supply units supplies an acid solution, a base solution, water and an ionic solution to each of the moving units.

The hydrogen production device may generate an electromotive force of 0.4V or more.

At the cathode, H ⁺ contained in the acid solution may be reduced to generate hydrogen gas.

The hydrogen production device may further include a hydrogen collection unit for storing the generated hydrogen gas.

The anion exchange membrane and the cation exchange membrane may be at least two or more, respectively.

The ionic solution may be a solution containing cations and anions.

The ratio of the concentration of the ionic solution to the concentration of water may be 1:2 to 500.

At least one of the acid solution or the base solution may be a spent acid solution or a waste base solution.

The cathode and the anode may have a porous structure.

The porous structure may include micropores of 1 to 100 μm.

The cathode and anode may have water-repellent surfaces.

The hydrogen production device may further include a current collector plate on the other side of each of the cathode and anode.

The current collector plate may have a flow path through which gas flows.

The hydrogen production device is discharged from the first discharge unit discharging the solution discharged from the ion solution moving unit in the acid solution moving unit, the base solution moving unit and the ion concentration difference generating unit and the water moving unit in the ion concentration difference generating unit. It may be to further include a second discharge unit for discharging the solution.

Water may be discharged from the first discharge unit, and salt may be discharged from the second discharge unit.

In addition, another aspect of the present invention,

It provides a stack in which a plurality of the hydrogen production devices are connected in series or in parallel.

According to an embodiment of the present invention, since the hydrogen production device can generate hydrogen by using waste acid and/or waste base, water, and a high concentration ion solution to generate its own electric power with a difference in ion concentration, additional external voltage for operation It does not require the application of , and can be operated at a lower voltage than a conventional hydrogen production device. In addition, when a catalyst made of a carbon material is used, since a relatively low voltage is applied to the hydrogen production device, corrosion of the catalyst can be suppressed, which is very economical.

On the other hand, since the high concentration ionic solution discharged from the water treatment system as well as the spent acid and/or the waste base is utilized, and the ionic solution and the waste acid and/or the waste base are discharged in the form of water and salt, it can greatly contribute to the environment. In addition, since the waste acid and/or waste base, water and high concentration ion solution are supplied to the hydrogen production device, hydrogen generated can be collected and used as an eco-friendly energy source such as a hydrogen car, a hydrogen bus, and a hydrogen charging station, so it is very efficient am.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a schematic diagram showing a hydrogen production device including two each of an anion exchange membrane and a cation exchange membrane in an ion concentration difference generator according to an embodiment of the present invention.
2 is a schematic diagram showing a hydrogen production apparatus including three or more anion exchange membranes and cation exchange membranes, respectively, in the ion concentration difference generator according to an embodiment of the present invention.
3A is a schematic diagram showing the shape of a current collector plate according to an embodiment of the present invention.
3B is a schematic diagram showing the shape of a current collector plate according to another embodiment of the present invention.
4 is a schematic diagram showing a stack in which a plurality of hydrogen production devices are connected in series according to an embodiment of the present invention.
5 is a schematic diagram showing a stack in which a plurality of hydrogen production devices are connected in parallel according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail. However, the present invention may be embodied in various different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, the terminology used in the present invention is only used to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' any component means that other components may be further included, rather than excluding other components, unless otherwise stated.

The first aspect of the present application is

cathode; anode; an electrolyte part interposed between the cathode and the anode; and a conducting wire connecting the cathode and the anode, wherein the electrolyte unit includes an acid solution moving unit, a base solution moving unit, and an ion concentration difference generating unit, and the ion concentration difference generating unit crosses a water moving unit and an ionic solution moving unit. A hydrogen production device is provided.

Hereinafter, the hydrogen production apparatus 101 according to the first aspect of the present application will be described in detail with reference to FIGS. 1 and 2 .

In one embodiment of the present application, the hydrogen production device 101 includes a cathode 110 , an anode 120 , an electrolyte unit 200 , and a conducting wire 300 similarly to a general fuel cell.

However, the hydrogen production device 101 of the present application is an acid solution supply unit 500, a water supply unit 530, and an ionic solution for respectively supplying an acid solution, water, an ionic solution and a base solution to the electrolyte unit 200, respectively. It may further include a supply unit 550 and a base solution supply unit 600 .

In one embodiment of the present application, the electrolyte unit 200 in the hydrogen production device 101 includes an acid solution moving unit 260, a base solution moving unit 290 and an ion concentration difference generating unit 220, and , the ion concentration difference generating unit 220 may be one in which the water moving unit 270 and the ionic solution moving unit 280 are cross-arranged.

One side of the acid solution moving unit 260 is disposed adjacent to one side of the cathode 110 , and one side of the base solution moving unit 290 is disposed adjacent to one side of the anode 120 . The ion concentration difference generating unit 220 is an anion exchange membrane 240 and cations arranged sequentially and repeatedly from the other side of the acid solution moving unit 260 to the other side of the base solution moving unit 290 . It includes an exchange membrane 250, a water moving part is disposed between the anion exchange membrane 240 and the cation exchange membrane 250 according to the direction, and an ion solution moving part between the anion exchange membrane 240 and the cation exchange membrane 250 ( 280) are alternately arranged, and the number of the anion exchange membrane 240 and the cation exchange membrane 250 may be the same.

The hydrogen production device 101 further includes an acid solution supply unit 500 and a base solution supply unit 600 for supplying an acid solution and a base solution to the acid solution moving unit 260 and the base solution moving unit 290, respectively. and a water supply unit 530 and an ion solution supply unit 550 for supplying water and an ionic solution to the water moving unit 270 and the ionic solution moving unit 280, respectively, wherein each of the supply units is the moving unit An acid solution, a base solution, water and an ionic solution may be supplied to each.

In one embodiment of the present application, by supplying an acid solution, a base solution, water and an ionic solution to the electrolyte unit 200, hydroxide ions react with the catalyst in the anode 120 to form electrons, water and oxygen as shown in Formula 1 below. may be generated.

<Formula 1>

4OH ^- → 4e ^- + 2H ₂ O + O ₂ (g)

In this case, the oxidation reaction may have a potential value of 0.4 V at room temperature.

The electrons generated in Chemical Formula 1 may be transferred to the cathode 110 through the conductive wire 300 .

In addition, at this time, since the anode 120 is in contact with the base solution moving unit 290 of the adjacent ion concentration difference generating unit 220 , hydroxide ions contained in the base solution supplied to the base solution moving unit 290 . This may be transferred to the anode 120 .

Meanwhile, in one embodiment of the present application, the anode 120 may further include an oxygen collecting unit (not shown) for collecting oxygen gas generated by oxidation ^{of OH − contained in the base solution.}

In one embodiment of the present application, electrons generated in the anode 120 move to the cathode 110 through the conducting wire 300, and hydrogen ions react with electrons in the cathode 110 to obtain the following Chemical Formula 2 Similarly, hydrogen gas may be generated through a reduction reaction.

<Formula 2>

4H ⁺ + 4e ^- → 2H ₂ (g)

In this case, the reduction reaction may have a reduction potential value of 0 V at room temperature.

In one embodiment of the present application, the cathode 110 may further include a hydrogen collecting unit 400 for collecting hydrogen gas generated by reduction ^{of H + contained in the acid solution.}

In one embodiment of the present application, the hydrogen production device 101 may generate an electromotive force due to a difference in concentration of ions. Specifically, the electromotive force may be generated by a difference in ion concentration between the ion solution supplied from the ion solution supply unit 550 of the ion concentration difference generator 220 and the water supplied from the water supply unit 530 . For example, when the ionic solution is sodium chloride (NaCl) and the water is diluted water, the membrane open circuit electromotive force may be generated as shown in Equation 1 below,

<Equation 1>

In Equation 1, E _OCV is the electromotive force (OCV), N is the number of ion solution moving parts 280, R is a gas constant (gas constant), T is a temperature (temperature), Z is the ion valence (valence of the ions), F is the Faraday constant, γ _High is the activity coefficient (-) of the respective ion in solution at a known concentration as determined from the CRC handbook), γ _Low is the activity coefficient of cations or anions of diluted water, γ _NaOH,Na+ is the activity coefficient ^{of Na +} of sodium hydroxide (NaOH) _{, γ HCl,Cl -} is the activity coefficient ^{of Cl -} of hydrochloric acid (HCl) _{, C High} is the concentration of ionic solution (NaCl), C _Low is the concentration of diluted water, and α _CEM,Na+ is the concentration of Na ⁺ ions. It is the perm-selectivity of the membrane (with α =1 representing a perfect charge-selective membrane), and α _AEM,Cl- is Cl ^- ion in the anion exchange membrane (AEM). It is transmembrane selectivity.

In one embodiment of the present application, the hydrogen production device 101 is operated when the applied voltage is 0.4V or more, and may be capable of producing hydrogen together with electricity production. On the other hand, the hydrogen production device may not require the application of an additional external voltage for operation, and the electromotive force generated by the ion concentration difference between the ion solution moving unit 280 and the water moving unit 270 is may be driven by This may be a difference in electromotive force generated according to the difference in ion concentration, and the greater the difference in ion concentration between the ion solution moving part 280 and the water moving part 270 is, the better the performance of the hydrogen production device may be. . For example, when the ion concentration difference between the ion solution moving unit 280 and the water moving unit 270 is 10 times, the electromotive force generated per one ion solution moving unit 280 of the ion concentration difference generating unit 220 . is 0.1V, so at least five ion solution moving units 280 may be required to operate the hydrogen ion device. In addition, when the ion concentration difference between the ion solution moving unit 280 and the water moving unit 270 is 100 times, the electromotive force generated per one ion solution moving unit 280 of the ion concentration difference generating unit 220 is It is 0.2V, so at least three ion solution moving parts 280 may be required to operate the hydrogen ion device. In addition, the ionic solution used to measure the ion concentration difference may be NaCl 1M, and the water may be 0.01M real river water.

In one embodiment of the present application, when the electromotive force is generated above 0.4V, the cathode 110 may produce hydrogen and the anode 120 may produce oxygen.

In one embodiment of the present application, the ionic solution may be a solution containing a cation and an anion. Specifically, the ion solution is a wastewater by microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) or reverse osmosis (RO) using a general water treatment method using a membrane, etc. It may be ion-concentrated water discharged after water treatment, and water treatment using an electric water treatment method such as electrodialysis (ED), electrodeionization (EDI), capacitive deionization (CDI), etc. It may be ion-concentrated water released after washing, and if it is a solution released from water treatment, it may be used without limitation.

In one embodiment of the present application, the concentration of the ionic solution may be generally 500 mg/L or more. Specifically, the concentration refers to total dissolved solids (TDS), which is the total amount of solid substances dissolved in water, and refers to the total amount of cations and anions in water. On the other hand, the ion solution may preferably be ion-concentrated water released after water treatment, and the concentration of the ion-concentrated water may be 50,000 mg/L or more, and more preferably, the concentration of the ion-concentrated water is 50,000 to 300,000 mg/L It may be L.

In one embodiment of the present application, the water may be seawater, brackish water or fresh water.

The ratio of the concentration of the ionic solution to the concentration of water may be 1:2 to 500. Specifically, the concentration of the water is about 10,000 to 50,000 mg/L (35,000 mg/L for standard seawater) in sea water, and about 1,000 to 10,000 mg/L in brackish water, fresh water When it is fresh water, it may be about 1,000 mg/L or less.

In one embodiment of the present application, at least one of the acid solution and the base solution may be a spent acid solution or a spent base solution. The spent acid solution or the waste base solution may be a conventional waste acid solution or a waste base solution that can be industrially released. In addition, industrially, it is common for only one of the waste acid solution and the waste base solution to be discharged. In the case of an industry that discharges a waste acid solution, the base solution may be separately purchased and supplied. In the opposite case, the acid solution is purchased separately. may be supplied. However, in the case of an industry that discharges both the spent acid solution and the spent base solution, it may be to supply both the discharged waste acid solution and the waste base solution.

In one embodiment of the present application, the concentration of the acid solution and the base solution may be the same.

In one embodiment of the present application, the cathode 110 and the anode 120 may include an electrode or a metal catalyst that can be used as the cathode 110 and the anode 120 catalyst, for example, the cathode ( 110) and the anode 120 electrode is silver (Ag), silver alloy, platinum, iridium, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy or platinum-M alloy (M is Ir, Ga , Ti, V, Cr, Mn, Fe, Co, Ni, one or more transition metals selected from the group consisting of Cu and Zn) may include one or more catalysts selected from, for example, silver (Ag ), silver alloy, platinum, iridium, ruthenium, osmium, platinum-iridium alloy, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, platinum-cobalt alloy, and platinum-nickel. can In addition, as the metal catalyst of the cathode 110 and the anode 120 electrode, as supported on a carrier, a catalyst supporting a metal using carbon such as acetylene black, graphite, alumina, silica, zirconia, titania, etc. as a carrier is used. Can be used. When a noble metal supported on a carrier is used as a catalyst, a commercially available one may be used, or it may be prepared and used by supporting the noble metal on a carrier. Preferably, a metal catalyst made of carbon may be used.

In one embodiment of the present application, since the hydrogen production device 101 can be operated when a voltage of 0.4V or more is applied, when using a metal catalyst made of carbon, compared to a conventional hydrogen production device that needs to be applied more than 1.5V Thus, since a low voltage is applied to the hydrogen production device, it may be possible to suppress corrosion of the catalyst.

In one embodiment of the present application, the sizes of the cathode 110 and the anode 120 are not limited, and may preferably be the same as the sizes of the anion exchange membrane 240 and the cation exchange membrane 250 . Meanwhile, the cathode 110 and the anode 120 may be characterized in that they have a porous structure. Specifically, the cathode 110 and the anode 120 may include micropores of 1 to 100 μm. The size of the micropores may be preferably 2 to 75 μm, and more preferably 10 to 50 μm. In addition, the cathode 110 and the anode 120 may be characterized in that the surface is water-repellent treatment. That is, the cathode 110 and the anode 120 may have a water repellent property by treating the surface with a material having a water repellent function in the same way as coating. On the other hand, since the coating is only an example, it is not limited thereto, and if it is a conventional technique for performing water repellency treatment on the electrode surface, it can be used without limitation, and the material having the water repellency function is preferably polytetrafluoroethylene ( It may include a hydrophobic material such as poly(tetrafluoroethylene)) or polyethylene. A description thereof is briefly shown in FIGS. 3A and 3B . That is, referring to FIGS. 3A and 3B , an acid solution or a base solution flows adjacent to the cathode 110 or the anode 120, respectively. Accordingly, only hydrogen gas generated in the acid solution or oxygen gas generated in the base solution passes through the cathode 110 or anode 120, and liquid water or salt may not permeate. This may be an effect achieved because the cathode 110 and the anode 120 have a porous structure with micropores, and the surface is water-repellent treated as described above. On the other hand, the cathode 110 and the anode 120 may have outer surfaces in contact with the current collector plate 800 , respectively, and the current collector plate 800 is hydrogen that has passed through the cathode 110 and the anode 120 . It may form a flow path through which gas or oxygen gas can flow. At this time, the shape of the flow path minimizes contact with the porous electrode catalyst to increase the reaction sites between the electrode catalyst and the acid solution or base solution, and there is no significant limitation as long as the resistance to the flow of the permeated gas is minimized. can That is, the shape of the flow path may be, for example, a concave-convex shape as shown in FIG. 3A , or a zigzag shape as shown in FIG. 3B . In this regard, in FIGS. 3A and 3B, the distance between the electrode and the current collector plate 800 is expressed somewhat wider to help understanding, but in an actual embodiment, the gap between the electrode and the current collector plate 800 may be narrow. In an embodiment, they may be disposed adjacent to each other. On the other hand, the material of the current collector plate 800 is not particularly limited, and the outer surface is cut off from the outside of the device to prevent the permeated gas from being discharged to the outside of the hydrogen production device 101 . Also, preferably, the size of the current collector plate 800 may be the same as that of the cathode 110 and the anode 120 .

In one embodiment of the present application, the interval between the cation exchange membrane 250 and the anion exchange membrane 240 adjacent in the ion concentration difference generating unit 220 may be 100 μm to 300 μm, preferably 150 μm to 200 μm may be When the gap is less than 100 μm, the discharge of acid solution, water and base solution may not be smooth because the gap is very narrow and a lot of pressure loss occurs, and when it exceeds 300 μm, the cation exchange membrane 250 and the anion exchange membrane ( 240) is too wide and the distance that generated ions move to both ion exchange membranes increases, so the resistance for movement of ions may increase.

In one embodiment of the present application, the acid solution may be a solution containing hydrogen ions, and the base solution may be a solution containing hydroxide ions. That is, the acid solution is a solution having a hydrogen ion index (pH) of less than 7, preferably a strong acid solution, and more preferably hydrochloric acid (HCl). In addition, the base solution is a solution having a hydrogen ion index (pH) of 7 or more, preferably a strong base solution, and more preferably sodium hydroxide (NaOH).

In one embodiment of the present application, the hydrogen production device 101 is used in the solution moving unit 280 in the acid solution moving unit 260, the base solution moving unit 290 and the ion concentration difference generating unit 220. It may further include a first discharge unit 650 for discharging the discharged solution and a second discharge unit 700 for discharging the solution discharged from the water moving unit 270 in the ion concentration difference generating unit 220 . have.

In one embodiment of the present application, water may be discharged from the first discharge unit 650 , and salt may be discharged from the second discharge unit 700 . Specifically, in the acid solution supplied to the acid solution moving unit 270 , hydrogen ions are moved to the cathode 110 , and anions are moved through an anion exchange membrane so that only water is discharged when discharged. For the same reason, the base solution moves In the base solution supplied to the unit 290 , cations may be moved through the cation exchange membrane, and hydroxide ions may be moved to the anode 120 so that only water is discharged when discharged. In addition, water is supplied to the water moving unit 270 in the ion concentration difference generating unit 220 through the water supply unit 530, and the acid solution moving unit 270 or the ionic solution moving in contact through an anion exchange membrane on one side. In part 280, anions are transferred through the anion exchange membrane, and cations are transferred through the cation exchange membrane in the base solution moving part 290 or the ion solution moving part 280 in contact with the cation exchange membrane on the other side. It may be that only water is discharged when it is generated and discharged. Therefore, the solution discharged from the ion solution moving unit 280 in the acid solution moving unit 260, the base solution moving unit 290 and the ion concentration difference generating unit 220 may be water, which is the first discharge unit. It may be discharged to the same place through (650). On the other hand, water is supplied to the water moving unit 270 in the ion concentration difference generating unit 220 through the water supply unit 550, but the acid solution moving unit 270 or the ion solution in contact with the anion exchange membrane on one side. Anions are transferred from the moving unit 280, and cations are transferred from the base solution moving unit 290 or the ionic solution moving unit 280 in contact with the cation exchange membrane on the other side, and the anions and cations form a salt, so they are discharged. The solution to be used may be a salt, and the salt may be discharged to the same place through the second discharge unit 700 . On the other hand, the hydrogen production device 101 may further include a salt storage unit for storing the formed salt. That is, the salt storage unit may be the second discharge unit 700 .

In one embodiment of the present application, preferably, the acid solution contains hydrochloric acid (HCl), the base solution contains sodium hydroxide (NaOH), and the ionic solution is sodium chloride (sodium chloride, NaCl) may be included. Therefore, the chloride ions of the hydrochloric acid move to the water transfer unit 270 in contact with the acid solution transfer unit 260 through the anion exchange membrane 240 , and the sodium ions of the sodium hydroxide are transferred to the cation exchange membrane 250 . moves to the water moving unit 270 in contact with the base solution moving unit 290 through It may react with one sodium ion and a chloride ion to form sodium chloride (NaCl). Since the formed sodium chloride is formed of sodium ions and chloride ions transferred through the cation exchange membrane and the anion exchange membrane, it may be high-purity sodium chloride containing almost no impurities.

In one embodiment of the present application, in each of the acid solution supply unit 500, the water supply unit 530, the ionic solution supply unit 550 and the base solution supply unit 600, the acid solution moving unit 270, the water moving unit ( 270), the ion solution moving unit 280, and the pipe connected to the base solution moving unit 290 may be provided with a pump and a valve. By installing the pump and valve, the flow rate or flow rate of the supplied acid solution, water, ionic solution, and base solution may be appropriately adjusted to smoothly operate the hydrogen production device 101 .

In one embodiment of the present application, the hydrogen production device 101 collects electrical energy generated during operation by connecting an energy storage device (not shown) such as a capacitor, a capacitor, a secondary battery or a flow battery to the conducting wire 300 . may be doing Accordingly, the collected electrical energy may be used as a power source for other industries. That is, the hydrogen production device 101 supplies an acid solution and a base solution so that electrons generated from the anode 120 are transferred to the cathode 110 through the conducting wire 300 , at this time the conducting wire 300 . It may be to recycle the electrical energy generated by connecting a capacitor or a capacitor to the

The second aspect of the present application is

A plurality of hydrogen production devices 101 of the first side are connected in series or in parallel, and provide a stack.

Although detailed descriptions of parts overlapping with the first aspect of the present application have been omitted, the contents described with respect to the first aspect of the present application may be equally applied even if the description thereof is omitted from the second aspect.

Hereinafter, the stack according to the second aspect of the present application will be described in detail with reference to FIGS. 4 and 5 . 4 is a schematic diagram illustrating a stack in which the hydrogen production apparatus 101 is connected in series, and FIG. 5 is a schematic diagram illustrating a stack in which the hydrogen production apparatus 101 is connected in parallel.

In one embodiment of the present application, the hydrogen production apparatus 101 according to FIG. 4 may be connected in series to constitute a stack. At this time, the connection between the hydrogen production apparatus 101 may be connected by a wire 300, in this case, in the hydrogen production apparatus 101 according to the first aspect of the present application, the cathode 110 and the anode 120 The conductive wire 300 for connecting may be connected between neighboring hydrogen production devices 101 rather than a structure connected within a single hydrogen production device 101 . That is, in FIGS. 1 and 2 showing the schematic diagram of the hydrogen production device 101 of the first aspect of the present application, all configurations are the same as the respective configurations of the hydrogen production device 101 shown in FIG. 4, but only the conducting wire 400 is adjacent It is connected to the hydrogen production device 101 , and the hydrogen production device 101 at both ends of the stack connected in series may also be connected by the conducting wire 300 .

In one embodiment of the present application, when the hydrogen production device 101 is connected in series to form a stack, hydrogen ions react with electrons in the cathode 110 to generate hydrogen gas through a reduction reaction, and the anode ( In 120), hydroxide ions react with the catalyst to generate electrons, water, and oxygen, and the generated electrons may be transferred to the cathode 110 of the neighboring hydrogen production device 101 through the conducting wire 300. . Each of the hydrogen production devices 101 connected in series in the same manner as above may be operated, in which case electrons generated from the anode 120 of the hydrogen production device 101 located at one end are hydrogen production devices located at the other end. It may be transferred to the cathode 110 of 101 so that the stack operates as a whole.

In one embodiment of the present application, when the hydrogen production device 101 is connected in series to form a stack, electric energy generated from each hydrogen production device 101 is collected and used as a power source for other industries. In particular, although the current of the entire stack is constant, the power may be increased because the voltage is increased. For example, in the case of a stack in which 10 hydrogen production devices 101 are connected in series, assuming that a potential difference of 0.4 V occurs in each hydrogen production device 101, a potential difference of 4 V may occur in the entire stack. there may be

In one embodiment of the present application, the hydrogen production apparatus 101 according to FIG. 4 may be connected in parallel to constitute a stack. At this time, the connection between the hydrogen production apparatus 101 may be connected by a wire 300, in this case, in the hydrogen production apparatus 101 according to the first aspect of the present application, the cathode 110 and the anode 120 The conductive wire 300 for connecting may be connected between all the hydrogen production devices 101 rather than a structure connected within a single hydrogen production device 101 .

In one embodiment of the present application, when the hydrogen production device 101 is connected in parallel to form a stack, hydrogen ions react with electrons in the cathode 110 to generate hydrogen gas through a reduction reaction, and the anode At 120, hydroxide ions react with the catalyst to generate electrons, water, and oxygen, and the generated electrons may be transferred to the cathode 110 of all hydrogen production devices 101 through the conductive wire 300 . Each of the hydrogen production devices 101 connected in parallel in the same manner as above may be operated.

In one embodiment of the present application, when the hydrogen production device 101 is connected in parallel to form a stack, electric energy generated from each hydrogen production device 101 is collected and used as a power source for other industries. In particular, although the voltage of the entire stack is constant, the power may be increased because the current increases.

101: hydrogen production device
110: cathode
120: anode
200: electrolyte unit
220: ion concentration difference generating unit
240: anion exchange membrane
250: cation exchange membrane
260: acid solution moving unit
270: water moving unit
280: ion solution moving part
290: base solution moving part
300: lead wire
400: hydrogen collection unit
500: acid solution supply unit
530: water supply
550: ion solution supply unit
600: base solution supply unit
650: first discharge unit
700: second discharge unit
800: current collector plate

Claims (18)

cathode; anode; an electrolyte part interposed between the cathode and the anode; and a conductor connecting the cathode and the anode.
The electrolyte unit includes an acid solution moving unit, a base solution moving unit and an ion concentration difference generating unit,
One side of the acid solution moving part is disposed adjacent to one side of the cathode,
One side of the base solution moving part is disposed adjacent to one side of the anode,
The ion concentration difference generator includes an anion exchange membrane and a cation exchange membrane that are sequentially and repeatedly arranged from the other side of the acid solution moving part to the other side of the base solution moving part, and between the anion exchange membrane and the cation exchange membrane according to the direction A fresh water moving part is disposed in the ion solution moving part is arranged alternately between the cation exchange membrane and the anion exchange membrane according to the direction,
The number of the anion exchange membrane and the cation exchange membrane is the same hydrogen production device.
delete The method of claim 1 .
The hydrogen production device further includes an acid solution supply unit and a base solution supply unit for supplying an acid solution and a base solution to the acid solution moving unit and the base solution moving unit, respectively,
Further comprising a fresh water supply unit and an ion solution supply unit for respectively supplying fresh water and ionic solution to the fresh water moving unit and the ionic solution moving unit,
Each of the supply units is a hydrogen production device for supplying an acid solution, a base solution, fresh water and an ionic solution to each of the moving parts.
4. The method of claim 3,
The hydrogen production device is a hydrogen production device that generates an electromotive force of 0.4V or more.
4. The method of claim 3, wherein
^{H +} contained in the acid solution is reduced at the cathode to generate hydrogen gas.
◈Claim 6 was abandoned when paying the registration fee.◈ 6. The method of claim 5.
The hydrogen production device further comprises a hydrogen collection unit for storing the generated hydrogen gas.
According to claim 1,
The anion exchange membrane and the cation exchange membrane are at least two or more, respectively.
◈Claim 8 was abandoned when paying the registration fee.◈ The method of claim 1 .
The ionic solution is a hydrogen production device that is a solution containing cations and anions.
According to claim 1,
The hydrogen production device that the ratio of the total dissolved solids (TDS) of the fresh water to the total dissolved solids (TDS) of the ionic solution is 1:2 to 500.
◈Claim 10 was abandoned when paying the registration fee.◈ The method of claim 1 .
At least one of the acid solution or the base solution is a waste acid solution or a waste base solution.
The method of claim 1 .
The cathode and the anode are hydrogen production device of a porous structure.
◈Claim 12 was abandoned when paying the registration fee.◈ 12. The method of claim 11.
The porous structure is a hydrogen production device comprising micropores of 1 to 100 μm.
◈Claim 13 was abandoned when paying the registration fee.◈ According to claim 1,
The cathode and anode is a hydrogen production device that the surface is water-repellent treatment.
◈Claim 14 was abandoned at the time of payment of the registration fee.◈ The method of claim 1 .
The hydrogen production device further comprises a current collector plate on the other side of each of the cathode and the anode hydrogen production device.
◈Claim 15 was abandoned when paying the registration fee.◈ 15. The method of claim 14.
The current collector plate is a hydrogen production device having a flow path through which the gas flows.
According to claim 1,
The hydrogen production device is discharged from the first discharge unit discharging the solution discharged from the ion solution moving unit in the acid solution moving unit, the base solution moving unit and the ion concentration difference generating unit and the fresh water moving unit in the ion concentration difference generating unit. Hydrogen production apparatus further comprising a second discharge unit for discharging the solution to be.
17. The method of claim 16,
Hydrogen production apparatus that water is discharged from the first discharge unit, and salt is discharged from the second discharge unit.
A stack in which a plurality of the hydrogen production devices of claim 1 are connected in series or in parallel.

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