KR101394132B1 - High efficiency salinity gradient electric generating device - Google Patents

Abstract

The present invention relates to a concentration gradient generating device, which uses a closed circulation flow electrode having a solid phase medium introduced into a flow path of an anode electrode. The concentration gradient generating device is capable of: improving the membrane permeability of ion by increasing the ion concentration penetrated from salt water to fresh water; and improving the generation efficiency by increasing the charge movement caused due to the improved membrane permeability by means of a medium. The concentration gradient generating device comprises: a fluid oxidation electrode for moving electrode rinse solution containing a medium; a fluid reduction electrode which is spaced to face the fluid oxidation electrode and is to move the electrode rinse solution; and one or more pairs of concentration gradient flow paths which are arranged between the fluid oxidation electrode and the fluid reduction electrode, are arranged in the direction adjacent to the fluid oxidation electrode, have a fresh water flow path for flowing fresh water and a salt water flow path separated from the fresh water flow path by an anion exchange membrane to flow salt water and are classified by cation exchange membranes arranged on both ends thereof, wherein the electrode rinse solution of the fluid oxidation electrode and the fluid reduction electrode are circulated to be contained in a closed loop.

Description

[0001] The present invention relates to a high efficiency salinity gradient electric generating device,

The present invention relates to a high-efficiency salt-water power generation apparatus using the difference in ion concentration between seawater and fresh water, and more particularly, to an apparatus for increasing the ion permeability of ions by increasing the ion concentration of salt water to fresh water, To a dense difference power generation apparatus using a closed-loop flow electrode in which a solid medium is charged into both electrode flow path portions so as to increase power generation efficiency by increasing the power generation efficiency through a medium.

Due to the recent rise in fossil fuel prices and the accident at the Fukushima Nuclear Power Plant in Japan, it is required to abandon the existing production methods that relied solely on fossil fuels and nuclear power.

Hydroelectric power plant has a limitation in place to construct a power plant, and there is a huge problem of construction cost of a power plant. In addition, the electric power generation amount is insufficient, so that it is possible to supply electric power locally, but there is a limit to the stable electric power supply of the whole country.

There is a problem in that it is difficult to produce a constant intensity of power because wind power is not only limited in place but also changes in intensity with time. In addition, as with hydroelectric power generation, the amount of electricity generated is insufficient, and electricity can be supplied locally, but there is a limit to the stable supply of electricity throughout the country.

In addition, solar power generation requires a huge space for power generation, but also has a problem in that it generates only a small amount of electric power and a power generation efficiency varies greatly according to the weather, which is an auxiliary power supply source.

SUMMARY OF THE INVENTION It is an object of the present invention, which is devised to solve the above-described problems, to provide a method for supplying a medium to an electrode solution composed of a closed loop to fluidize a medium between an oxidizing electrode and a reducing electrode, And to provide a highly efficient dense power generation device using a medium capable of producing electrical energy with a potential difference obtained by increasing the gradient of the ion concentration between the fluid oxidation electrode and the fluidized-bed electrode.

According to an aspect of the present invention, there is provided a plasma display apparatus including: a flow oxidation electrode through which an electrode cleaning solution containing a medium moves; A fluidized-bed electrode disposed so as to face the flow-oxidized electrode so as to face away from the fluidized-oxidized electrode; And a brine flow channel disposed between the flow oxidation electrode and the fluidized-bed reduction electrode and disposed in a direction close to the fluidized oxidation electrode and through which fresh water flows, and a brine flow channel through which the brine flow separated from the fresh water flow channel and the anion exchange membrane flows, And the electrode cleaning solution in the flow oxidation electrode and the electrode cleaning solution in the flow reduction electrode are circulated so as to form a closed loop. Device.

In the two or more concentration-difference flow path pairs, the brine flow path and the fresh water flow path are characterized in that brine and fresh water are supplied in parallel, respectively. Alternatively, in the two or more concentration-difference flow path pairs, the brine flow path and the fresh water flow path are characterized in that brine and fresh water are supplied in series, respectively.

The change in charge amount depending on the cation moving through the cation exchange membrane from the electrode cleaning solution is characterized in that the redox double ion contained in the electrode cleaning solution is electrically canceled by the oxidation / reduction reaction conversion by the solid phase medium. There is no special restriction on the redox double ion. The present invention does not intend to limit the kind of redox pair and satisfies the idea of the present invention that the effect of injecting a solid medium by using any kind of redox double ion is obtained.

A bipolar plate may be provided in the brine flow passage in consideration of the convenience of lamination.

Through the present invention, it is possible to increase the ion generation efficiency by increasing the ion concentration by the redox electrode having the closed circuit using the medium and the salt water flow path and the fresh water flow path alternately installed.

Therefore, not only is it generated by the difference in the concentration of salt water and fresh water, but also concentrated salt water is stored by enriching the salt water with extra energy in the daytime, and when the electric power consumption is peaked, It can be utilized as a power storage device capable of reducing the peak load.

In addition, the high-efficiency salt-difference power generation apparatus according to the present invention is advantageous in that it is eco-friendly and maintains the permanence of power generation as an all-weather power generation apparatus which is free from climate and time limitation.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic block diagram of a concentration difference generator using a closed-loop flow electrode into which a fluid medium according to a first embodiment of the present invention is charged; FIG.
FIG. 2 is a schematic configuration diagram of a concentration difference generator using a closed-loop flow electrode into which a fluid medium according to a second embodiment of the present invention is charged.
3 is a schematic configuration diagram of a concentration difference generation device using a closed-loop flow electrode into which a fluid medium according to a third embodiment of the present invention is charged.
4 is a schematic configuration diagram of a concentration-difference power generation apparatus using a closed-loop flow electrode into which a fluid medium according to a fourth embodiment of the present invention is charged.
5 is a graph of the experimental result according to Experimental Example 1 of the present invention.
6 is a graph of an experimental result according to Experimental Example 1 of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. In the drawings, the same reference numerals are used to designate the same or similar elements in the drawings, unless otherwise indicated by the same reference numerals, Detailed description of functions and configurations is omitted.

Generally, the term 'salt water' refers to a solution having a salt concentration of at least 35,000 mg / L, which is the salt concentration of seawater, and a salt solution having a salt concentration of about 1,000 to 10,000 mg / L , "Fresh water" refers to a solution having a salt concentration of 0 to 1,000 mg / L. This is a classification of water quality according to salt concentration at the US Geological Survey.

However, in the present invention, a solution containing salt to be supplied for power generation is referred to as saline solution, and a solution having a relatively low concentration compared to saline solution for generating electricity is called a fresh water, And the discharged solution is called a radix, so that the concentration of ions in the radionuclide is smaller than the brine and larger than the freshwater.

The term " flow electrode " means that an electrode solution containing a medium flows in a closed loop between the oxidation and reduction electrodes. Here, the medium is a carbon material, a non-metal material, a metal material, ≪ / RTI > The particle size is on the order of nanometer (nm) and micro (um) size.

1 is a schematic diagram of a concentration-difference power generation apparatus 100 using a closed-loop flow electrode into which a medium according to Embodiment 1 of the present invention is charged.

The concentration-differentiating power generator 100 includes a flow oxidation electrode 112 on which an electrode cleaning solution containing a medium moves, and an electrode cleaning solution disposed so as to face the flow oxidation electrode 112 so as to face each other, And a concentration difference flow path pair disposed between the fluid oxidation electrode (112) and the fluidized bed electrode (118).

The fluidized oxidizing electrode 112 and the fluidized reducing electrode 118 form a closed loop through which the electrode cleaning solution containing the medium passes. Therefore, a circulation device such as a pump for circulating the electrode cleaning solution containing the medium may be provided between the fluid oxidation electrode 112 and the fluidized-bed electrode 118.

In the first embodiment of the present invention, the concentration difference flow path pair has one, and a fresh water flow path 114 is provided on the left side and a salt water flow path 116 is provided on the right side. Fresh water is supplied to the fresh water channel 114 and the nose passing through the fresh water channel 114 is discharged to the outside. The brine is supplied to the brine flow path 116, and the brine flowing past the brine flow path 116 is discharged to the outside.

Cation exchange membranes 106 and 110 are disposed at both ends of the concentration difference flow path pair and an anion exchange membrane 108 is provided between the salt water flow path 114 and the fresh water flow path 116.

Accordingly, the flow oxidation electrode 112 has a limited space through which the electrode cleaning solution containing the medium flows into the cathode current collector 102 and the cation exchange membrane 106, and the flow reduction electrode 118 is connected to the cation exchange membrane 110 ) And the negative electrode current collector 104 through which the electrode cleaning solution containing the medium flows.

Spacers may be provided in the inside of the fresh water channel 114, the salt water channel 116, the flow oxidation electrode 112, and the fluidized-bed electrode 118 to prevent the gap from fluctuating. In addition, an adsorbing active material 120 having a high ion adsorptivity may be contained in the fresh water channel 114. As the adsorbent active material 120, there can be used activated carbon (ANC), carbon nanotube (CNT), carbon nano powder (CNP), or metal powder capable of catalytic function, having nanoparticles having a specific surface area.

The electrode cleaning solution contains the same cation as the salt water flowing in the salt water flow path 116, and is represented by sodium ion (Na ⁺ ) in the embodiment of the present invention. In addition, the adsorption active material 120 having good ion adsorptivity may be contained in the flow reduction electrode flow paths 112 and 118. As the adsorbent active material 120, there can be used activated carbon (ANC), carbon nanotube (CNT), carbon nano powder (CNP), or metal powder capable of catalytic function, having nanoparticles having a specific surface area. In addition, a metal having catalytic activity or a metal oxide can be carried on the surface of the carbon particles to accelerate the redox reaction more rapidly and / or improve the electron storage / transportation function. In the electrode cleaning solution, the surplus amount or insufficient amount of electrons due to the entry and exit of sodium ions is compensated by the switching between the redox couple, and the positive electrode current collector 102 and the So that a current flows between the anode current collectors 104.

      An example of electron generation by the electrode material redox proceeds in an equilibrium reaction as shown in Scheme 1, and the reaction proceeds on the electrode surface. However, when the solid particles are present in the electrode solution as in the present invention, since the redox reaction illustrated in the reaction formula 1 proceeds on these surfaces, the surface area necessary for the reaction progression is infinitely widened compared to the conventional electrode.

The electrons generated during the reaction are adsorbed on the surface of the solid particles for a predetermined period of time. When they contact the particles in the vicinity of the solution according to the solution flow, they reach the equilibrium concentration, and electrons are transferred to the electrodes 102, 202, 302 and 402. 206, 306, and 406 because the reaction of Equation 1, which is dependent on the Na ⁺ ion concentration change, is accelerated because the redox material does not need to be directly diffused to the electrode surface in order to proceed with Reaction 1, The Na ⁺ permeation rate is further improved, and accordingly, the electron generation and extinction rate are further accelerated and the power generation efficiency can be improved.

[Reaction Scheme 1]

Fe ²⁺ ↔ Fe ³⁺ + e ^-

An example of such an electrode solution is a solution containing a carbonaceous material, a noble metal and a non-metallic solid phase medium in a mixed solution of NaCl and / or ferrocyanide (Fe (CN) ₆ ) alone or at the same time capable of causing redox couple Can be used. In addition, the salt is a chlorine ion (Cl ^-) by anion include.

The concentration difference generation device 100 according to the first embodiment of the present invention is configured as described above. Hereinafter, the operation principle of the concentration difference generation device 100 will be described.

The theoretical amount of energy that can be obtained by the salinity difference is described by Veerman (J. Veerman et al., Reverse electrodialysis: Performance of a stack with 50 cells on the mixing of sea and river water, J. Membr. Sci. -144) are shown in Table 1.

V _R (m 3) V _S (m 3) V _R / V _S G (J) ∞ One ∞ ∞ 10 One 10 6.1 2 One 2 2.8 One One One 1.76 1.26 0.74 1.72 1.87 One 2 0.5 2.06 One 10 0.1 2.43 One ∞ 0 2.55

In Table 1, Gibbs free energy (G) is a value obtained at a difference of 298 K between seawater (salt concentration: 30 kg NaCl / m ³ ) and fresh water (salt concentration: 0 kg NaCl / m ³ ) _R is the river volume and V _s is the sea water volume. According to the present invention, energy that can be obtained by such a difference in salinity can be obtained as electric energy.

A fresh water channel 114 and a salt water channel 116 which are sequentially disposed between a fluid oxidation electrode 112 which is an anode electrode containing a medium and a fluidized-bed electrode 118 which is a cathode electrode, The migration of ions as shown in Fig. 1 is induced. That is, cations such as Na ⁺ migrate through the cation exchange membranes 106 and 110, and anions such as Cl ^- move through the anion exchange membrane 108. Therefore, the positive ions of the flow oxidation electrode 112 move to the fresh water flow path 114, and the positive ions of the salt water flow path 116 move to the flow reduction electrode 118. Further, the anion of the salt water flow path 116 is moved to the fresh water flow path 114. As a result, in the seawater where the salt concentration is high, the ions move toward the right cathodic electrode while the ions move to the low-salt freshwater portion. On the contrary, . When the ion current flows from right to left, an oxidation reaction occurs in the flow oxidation electrode 112, and electrons are obtained from the electrolyte. In the flow reduction electrode 118, a reduction reaction occurs, . At this time, the electrons flow along the external conductor in the direction from the node to the cathode so that the current is generated.

An electrode cleaning solution containing a medium for circulating the fluidizing oxidizing electrode 112 and the fluidizing reducing electrode 118 is supplied to the positive electrode collector 102 and the negative electrode collector 104, Side reaction and fouling, as well as promoting oxidation and reduction of redox materials and electron transfer.

Accordingly, in the present invention, the concentration of ions per unit volume can be increased by arranging the pair of concentration-dependent flow paths of the fluidized oxidizing electrode 112 and the fluidized reducing electrode 118 containing such a medium to increase the potential of the ions , Resulting in an increase in ion current. That is, when an ion current is generated, it means the charge movement, which means that the current increases.

In other words, when brine and fresh water are introduced, the cation and anions of the salt water permeate into the fresh water part through the ion exchange membrane, resulting in a concentration gradient. At this time, the negative ions are attracted toward the anode electrode and the positive ions are attracted toward the cathode electrode, thereby forming an ion current, whereby the electrons are moved through the redox reaction at both electrode portions That is, an electron current. Particularly, when the adsorbing active material 120 is injected into the fresh water channel 114 to fluidize it, the permeation rate of cations and anions passing through the ion exchange membrane is further increased, so that the ion concentration is increased in both electrode portions, You can make it happen quickly.

2 is a schematic diagram of a concentration difference generator 200 using a closed-loop flow electrode containing a medium according to Embodiment 2 of the present invention. The concentration-difference generation device 200 has the same structure as the concentration-difference generation device 100 of the first embodiment, but there is a difference in that two concentration-difference flow path pairs are arranged.

Therefore, the concentration-difference power generation device 200 includes a flow oxidation electrode 216 to which an electrode cleaning solution containing a medium moves, and an electrode cleaning solution 216 disposed so as to face the flow oxidation electrode 216, And a pair of concentration difference flow paths disposed between the fluid oxidation electrode 216 and the fluidized-bed return electrode 226. The flow-

Therefore, the cation exchange membranes 206, 210, 214 and the anion exchange membranes 208, 212 are alternately arranged between the cathode current collector 202 and the anode current collector 204, An oxidation electrode 216, a fresh water channel 218, a salt water channel 220, a fresh water channel 222, a salt water channel 224 and a fluidized-bed electrode 226 are sequentially arranged. Further, the fresh water channels 218 and 222 may contain adsorbing active materials 228 and 230 having good ion adsorptivity.

Fresh water is supplied to the two fresh water channels 218 and 222, respectively, and the nose passing through the fresh water channels 218 and 222 is discharged. Salt water is supplied to the two salt water channels 220 and 224, respectively, and the nodules passing through the salt water channels 220 and 224 are respectively discharged. That is, the fresh water channels 218 and 222 and the salt water channels 220 and 224 are arranged in parallel.

Therefore, since the slope of the ion concentration becomes larger than that of the apparatus 100 for generating electricity in the first embodiment, it is possible to produce a larger electric energy.

3 is a schematic diagram of a concentration difference generator 300 using a closed-loop flow electrode containing a medium according to Embodiment 3 of the present invention. The concentration difference generator 300 has the same structure as the concentration difference generator 200 of the second embodiment but differs in the connection method of the fresh water channels 318 and 322 and the salt water channels 320 and 324.

Therefore, the concentration-difference power generation device 300 includes a flow oxidation electrode 316 through which the electrode cleaning solution containing the medium moves, and an electrode cleaning solution 315 disposed so as to face the flow oxidation electrode 316 and facing the electrode, And a pair of concentration difference flow paths disposed between the flow oxidation electrode 316 and the fluidized-bed return electrode 326. The flow-

Therefore, the cation exchange membranes 306, 310, and 314 and the anion exchange membranes 308 and 312 are alternately disposed between the cathode current collector 302 and the anode current collector 304, An oxidation electrode 316, a fresh water channel 318, a salt water channel 320, a fresh water channel 322, a salt water channel 324, and a fluidized-bed electrode 326 are sequentially arranged. Further, the fresh water channels 318 and 322 may contain adsorbing active materials 328 and 330 having good ion adsorptivity.

Fresh water is supplied to the fresh water channel 318 and the fresh water having passed through the fresh water channel 318 is supplied to the fresh water channel 322 and the nose having passed through the fresh water channel 322 is discharged to the outside. The salt water is supplied to the salt water channel 320. The salt water that has passed through the salt water channel 320 is again supplied to the salt water channel 324 and the water having passed through the salt water channel 324 is discharged to the outside. , The fresh water channels 318 and 322 and the salt water channels 320 and 324 are arranged in series.

Therefore, it is possible to produce a larger electric energy because the slope of the ion concentration becomes larger than that of the concentration-difference power generation device 100 of the embodiment 1, and the cation and anion contained in the unit volume per unit volume through the series connection can be maximally exchanged Can pass. In more detail, since the surface area of the ion exchange membrane in contact with the actual fluid is constant, it is possible to increase the electric production efficiency by increasing the contact time between the fluid and the membrane surface.

4 is a schematic diagram of a concentration-difference power generation apparatus 400 using a closed-loop flow electrode containing a medium according to Embodiment 4 of the present invention. The concentration difference generation apparatus 400 has the same structure as the concentration difference generation apparatus 200 of Embodiment 2 except that bipolar plates 436 and 438 are installed in the fresh water flow paths 418 and 422.

Therefore, the concentration-difference power generation device 400 includes a flow oxidation electrode 416 through which the electrode cleaning solution containing the medium moves, and an electrode cleaning solution 415 disposed so as to face the flow oxidation electrode 416, And a pair of concentration difference flow paths disposed between the fluidized oxidizing electrode 416 and the fluidized-bed return electrode 426. The flow-

Therefore, the cation exchange membranes 406, 410, and 414 and the anion exchange membranes 408 and 412 are alternately disposed between the cathode current collector 402 and the anode current collector 404, An oxidizing electrode 416, a fresh water passage 418, a salt water passage 420, a fresh water passage 422, a salt water passage 424, and a fluidized reducing electrode 426 are sequentially arranged.

Bipolar plates 436 and 438 are installed in the fresh water flow paths 418 and 422 and cationic adsorption active materials 428 and 430 are disposed on the left side of the bipolar plates 436 and 438 in the fresh water flow paths 418 and 422, Anion adsorption active materials 443 and 434 are disposed. Therefore, cations and anions that have passed through each ion-exchange membrane are separated and stored. This is to recover the ion-adsorbing active material added to the fresh water part more quickly by removing the ion adsorbed on the ion-adsorbing active material placed in the fresh water part by reversing the direction.

Fresh water is supplied to the two fresh water passages 418 and 422, respectively, and the nodules passing through the fresh water passages 418 and 422 are respectively discharged. Salt water is supplied to the two salt water channels 420 and 424, respectively, and the nodules passing through the salt water channels 420 and 424 are respectively discharged. That is, the fresh water channels 418 and 422 and the salt water channels 420 and 424 are arranged in parallel.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It can be understood that

[Experimental Example]

This is an experimental example in which an electrode solution containing the solid-phase medium of the present invention is used as a flow electrode to conduct an experiment of salinity concentration difference generation.

[Experimental Example 1]

The experimental apparatus is configured as shown in Fig. However, a multi-layered cell was constructed by adding 5 sheets of cation and anion separator C-A and one sheet of cation separator on the rightmost outermost side.

The supply rate of the electrode solution (K ₃ Fe (CN) ₆ , 50 mM, aqueous solution of 3 wt% NaCl) was 5 ml / min, and fresh water and brine were supplied at 30 ml / min. At this time, the brine was prepared by adding 3.0 wt% of NaCl to distilled water.

As a result of the experiment, the maximum power of 1.6 mW was obtained as shown in Fig.

[Experimental Example 2]

Except that CNP (carbon nano particle, diameter: 5-20 nm) was added to the electrode solution.

As a result, the maximum power of 3.2 mW was obtained as shown in FIG.

As shown in Experimental Example 1 and Experimental Example 2, it can be confirmed that the maximum power obtainable by adding the medium to the electrode cleaning solution is about twice the difference. That is, by adding a medium serving as a catalyst capable of transferring electrons to the electrode cleaning solution, the redox reaction is promoted by increasing the permeation rate of positive and negative ions passing through the ion exchange membrane, It is possible to explain the effect of the present invention that the larger electric energy can be produced in fresh water conditions.

100, 200, 300, 400:
102, 202, 302, 402:
104, 204, 304, 404:
106, 110, 206, 210, 214, 306, 310,
108, 208, 212, 308, 312, 408, 412:
112, 216, 316, 416:
114, 218, 222, 318, 322, 418, 422:
116, 220, 244, 320, 324, 420, 424:
118, 226, 326, 426:
228, 230, 328, 330: adsorbing active material
428,430: Cation-adsorbing active material 432,434: Anion-adsorbing active material

Claims (5)

A flow oxidation electrode through which the electrode cleaning solution containing the medium moves;
A fluidized-bed electrode disposed so as to face the flow-oxidized electrode so as to face away from the fluidized-oxidized electrode; And
A fresh water passage arranged between the fluidized oxidizing electrode and the fluidized-bed electrode and arranged in the direction close to the fluidized oxidizing electrode, and a brine flow channel through which the fresh water channel and the anion exchange membrane are separated, At least one pair of concentration-difference channels separated by a cation exchange membrane,
The electrode cleaning solution of the fluidized oxidation electrode and the fluidized-bed electrode is circulated to form a closed loop,
Wherein the adsorption active material is contained in the fresh water channel.
The apparatus as claimed in claim 1, wherein in the at least two concentration-difference flow path pairs, the brine flow paths and the fresh water flow paths are supplied with brine and fresh water in parallel, respectively.
The concentration difference generation apparatus according to claim 1, wherein in the two or more concentration difference flow path pairs, each of the salt water flow path and the fresh water flow path is supplied with the salt water and the fresh water in series.
The method of claim 1, wherein the change in the amount of charge according to the cation moving through the cation exchange membrane from the electrode cleaning solution is electrically canceled by the redox couple conversion of the electrode cleaning solution. Concentration difference generator using electrodes.
The apparatus as claimed in claim 1, wherein a bipolar plate is provided in the brine flow channel.

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