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WO2016046422A1 - Dispositif de mesure d'énergie produite par échange ionique - Google Patents

Dispositif de mesure d'énergie produite par échange ionique Download PDF

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Publication number
WO2016046422A1
WO2016046422A1 PCT/ES2014/070722 ES2014070722W WO2016046422A1 WO 2016046422 A1 WO2016046422 A1 WO 2016046422A1 ES 2014070722 W ES2014070722 W ES 2014070722W WO 2016046422 A1 WO2016046422 A1 WO 2016046422A1
Authority
WO
WIPO (PCT)
Prior art keywords
collectors
ion exchange
energy
measuring
collector
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/ES2014/070722
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English (en)
Spanish (es)
Inventor
Guillermo Ramón Iglesias Salto
Silvia Alejandra AHUALLI YAPUR
Ángel Vicente DELGADO MORA
María Luisa Jiménez Olivares
Fernando González Caballero
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidad de Granada
Original Assignee
Universidad de Granada
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universidad de Granada filed Critical Universidad de Granada
Priority to PCT/ES2014/070722 priority Critical patent/WO2016046422A1/fr
Publication of WO2016046422A1 publication Critical patent/WO2016046422A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof

Definitions

  • the sector of the technique where the present invention is framed is that of the cogeneration and generation systems associated with renewable energies (biomass, wind, water, oceanic, solar), in particular, that obtained from the blue energy that comes of the mixture of water with different salinity. More specifically, it is framed in the sector of energy measuring devices, in particular, energy generated by ion exchange. STATE OF THE TECHNIQUE
  • This osmotic pressure difference is of the order of 10 atm (unit of measurement of pressure expressed in atmospheres, atm) and therefore, the work that can be obtained by mixing 1 L of fresh water with a large amount of salt water is 2 kJ (Unit of measure of energy expressed in kilo Joule). So, taking into account the large amount of fresh water that reaches our coasts worldwide, the total energy extracted would be of the order of 2 TW (Power Unit expressed in Tera Watt) that coincides with the annual electricity demand. In order to extract this energy, current research focuses on the search for efficient methods. Among these methods, the techniques that are usually used in the opposite process stand out: desalination.
  • salt water is pumped into a pressure chamber and fresh water is forced to flow through a semipermeable membrane, thereby increasing the pressure inside the salt water chamber;
  • the pressure generated is used to obtain electrical energy by depressurization through a hydraulic turbine, for example.
  • the process can continue cyclically so that, if we replace seawater with fresh water inside the spacer, the external current now circulates in the opposite way, and energy can also be extracted in this part of the cycle.
  • This process can be repeated indefinitely when the ionic concentration in the cell is modified, for example when seawater is exchanged for river water.
  • the reciprocal of this CDP technique is deionization. Again the authors F. Liu and cois. (Environ. Sci. Technol., 2012, 5, 8642-8650) try to improve the power and reduce the ohmic losses to the maximum, which is a great task in every electrochemical technique.
  • the first object of the invention is an energy measuring device generated by ion exchange techniques between liquids, in particular saline exchange between liquids, in the presence of a catalyst element.
  • This device facilitates the experimental study of the techniques of energy extraction by ion exchange by offering a wide alternative in terms of its configuration for extended use in laboratories and test plants that will allow, among other things, to obtain experimental data in a standardized way so be able to make an accurate comparison between different laboratories that work or use the same measurement system.
  • a second object of the invention is the method of measuring energy generated by ion exchange using said device.
  • Figure 1 Scheme of the device for the measurement of energy generated by ion exchange showing two of collectors, e, located inside a container element, c, in a cavity, i, communicated with the outside through holes, f, and means, r, which allow to modify the distance, d, between the collectors.
  • Figure 2. Scheme of the device for the measurement of energy generated by ion exchange showing two collectors with parallel surfaces, e, located within a container element, c, in a cavity, i, communicated with the outside through holes, f , means, r, which allow modifying the distance, d, between the collectors, and elements, a, which limit said distance.
  • Figure 3. Diagram of the arrangement of the catalyst, k, on a disk-shaped manifold, e.
  • Figure 4. Scheme of the device for the measurement of energy generated by ion exchange in which the means that allow modifying the distance between the collectors, e, are part of them, c represents the container element, Figure 5.
  • Scheme of the device for the measurement of energy generated by ion exchange showing two collectors with parallel surfaces, e, attached to threaded rods, t, located inside a container element, c, in a cavity, i, communicated with the outside through holes , f, elements, a, that limit the distance, d, between the collectors when tightening the thread h.
  • Figure 6 Cartesian diagram in which the axis of abscissa represents the potential, ⁇ , and the axis of ordinates the charge, ⁇ x, that occurs in the different states of ion exchange A, B, C and D.
  • liquids with a salt concentration of 20 mM (milli Molar) and 600 mM were used.
  • FIG. 7 Scheme of the equivalent circuit used to control the exchange of liquids in the device that shows a switch connected to two resistors R c , (load resistance) and (discharge resistance), a power supply VS.
  • the exchange device called VC, whose potentials both VC and VS, are measured by voltmeters connected in parallel and designated by V. The current flowing through the circuit is measured by the ammeter A.
  • Figure 8.- Scheme of the device for measurement of energy generated by ion exchange in a particular embodiment, showing two collectors with parallel surfaces, e, joined to two rods, t, located within a container element formed by a tubular element, c ', and two elements in the form of disk, x, that make up a cavity, i, communicated with the outside through holes, f, and means, a, which allow the distance, d, between the collectors to be modified, e.
  • Figure 11. Representation of the potential, Ve, current, le, and energy, n, obtained over time, ts.
  • the power, w is calculated as the slope of the energy representation, in which 16 exchange cycles have been performed, using two graphite collectors.
  • the present invention relates to a device for measuring energy generated by ion exchange of two or more liquids in the presence of a catalyst, hereinafter “device of the invention", comprising the following elements:
  • a container element that has an inner cavity interconnected with the outside through two or more holes that allow the entry and exit of liquids, so that ion exchange takes place in said cavity;
  • collectors Two or more elements on which the catalyst is deposited (hereinafter “collectors") manufactured or coated with a conductive material;
  • the device object of the invention comprises a container element ( Figure 1, c), impermeable and manufactured or coated with an inert material, preferably made of plastic material that confers electromagnetic insulation, more preferably in methacrylate.
  • This element has an inner cavity (i) and at least two holes (f) that allow the entry and exit of liquids so that the ion exchange takes place within said cavity.
  • inert refers to materials that do not chemically react with water.
  • the inner cavity (i) of the container element will have appropriate dimensions to be able to place inside the collectors (e), which allow the measurement of energy generated by the ion exchange, without both being in contact and allowing its displacement in order to modify the distance (d) between them.
  • said cavity will have a range of measures from 5 mm to 200 mm wide and a height between 10 mm to 400 mm. More preferably it will have a cylindrical shape with a radius of 20 mm to 40 mm and a height between 50 mm to 100 mm.
  • collector or collector element means a piece of conductive material or coated with conductive material in which the catalyst is deposited.
  • the collectors used will have different ionic strength.
  • the collecting elements included in the device object of the invention can be manufactured or covered by the same material or different materials.
  • the device object of the invention comprises two or more collecting elements (e) on which the catalyst is placed. These collecting elements are separated from each other, so that the liquids that are going to perform the ion exchange can circulate between them and be in contact with the catalyst.
  • the separation (d) between the collecting elements will be variable and may be fixed prior to the measurement of energy generated by the ionic exchange of liquids, through the means arranged for it.
  • the distances between the collectors will range between 0.5 mm and 10 mm. Preferably between 1 and 6 mm.
  • the device comprises an even number of collectors, even more preferably two collector elements.
  • the collectors have a flat surface and are arranged so that said surfaces (or the planes containing them) are parallel to each other. More preferably, the collectors will have a disk shape ( Figure 3, e).
  • the collecting elements are preferably manufactured or coated in a metallic material selected from the following list: platinum, gold, zinc, aluminum, copper, steel, stainless steel, brass, iron, graphite, bronze, more preferably made of graphite or platinum.
  • Effective confrontation surface means the part of the surface of a collector that projected in the direction that determines the minimum distance between the surfaces, on the opposite collector, coincides on it. This projection is maximum and equal to the area of the collector when both surfaces are equal and are completely facing each other.
  • the collectors In order to achieve a better performance of the device of the invention, the collectors must be positioned so that the effective facing surface is as large as possible. Thus, in a preferred embodiment, the collectors are completely facing each other. In an even more preferred embodiment, two disk-shaped collectors are used and are arranged completely facing each other.
  • the effective facing surface is 314.1 7 mm 2 .
  • the device also comprises means (r) that allow the distance (d) between the collectors to be modified, with the "distance between two collectors” being understood as the minimum of the distances, d (x, y), between a point, x, of a collector, ei, and a point, and, from another collector, e ⁇ . That is to say:
  • the means (r) must allow the distances between the collectors to range between 0.5 mm and 1.0 mm. Preferably between 1 and 6 mm. More preferably, the means must allow the collectors to be placed 1, 2, 3, 4, 5 and 6 mm away.
  • said means can be part of the collector itself, forming a single element (Fig. 4).
  • the means for modifying the distance between the collectors comprises a rod (t) that is fixed to the collector and which has a threaded part; a plurality of elements (a) of known thickness, preferably washers, which limit the distance between the manifolds and nuts or threads (h) that fix the assembly, arranged in such a way that the elements (a) function as a regulating stop of the distance limiting the movement of the collectors.
  • the means for modifying the distance comprise one or more elements, hereinafter "stops" located inside the inner cavity that limit the minimum distance between the collectors and a plurality of elements of known thickness, preferably washers, which, located between the collector and the stop, allow to increase the distance between the collectors in a precise and controlled way.
  • stops located inside the inner cavity that limit the minimum distance between the collectors and a plurality of elements of known thickness, preferably washers, which, located between the collector and the stop, allow to increase the distance between the collectors in a precise and controlled way.
  • the stems will be tubes fixed to the collectors through which a cable connecting the collectors to the measuring device is located. Catalyst arrangement
  • the catalyst To measure the energy generated by the ion exchange in the presence of the catalyst, said catalyst must be in simultaneous contact with the collectors and with the liquids that perform the ion exchange. To achieve this, it is fixed to the collectors.
  • the way to fix the catalyst to the collector can be done in multiple ways.
  • the catalyst (k) is arranged on the collector elements in the form of particles, preferably smaller than 10 micrometers, which are fixed to the collector with any mechanical fastening system that allows the liquid to contact With the particles.
  • An example of a mechanical system is a permeable membrane.
  • sheets of a conductive material preferably of graphite, will be used on which the catalyst material is fixed.
  • the sheet is fixed to the collector with any mechanical fastening system.
  • the device object of the invention also comprises means that allow each collector to be connected to a device or apparatus that allows measuring the energy generated by the ion exchange, such as a supercondenser being a direct current source or, in general, any device capable of measuring electrical variables such as energy, voltage or current.
  • a supercondenser being a direct current source or, in general, any device capable of measuring electrical variables such as energy, voltage or current.
  • these means are copper wires or other conductive material arranged so that the interior of the container element remains tight.
  • the collector and the rod that allows to fix its position are the same piece, it will be sufficient to connect the measuring device to the end of the rod that is outside the container element.
  • the device of the invention is connected, through the holes (f) arranged for this purpose, to two containers containing liquids with different ionic strength.
  • the collectors connect to a device that allows measuring the energy generated by the ion exchange.
  • a device that allows measuring a potential difference will be used.
  • the procedure for measuring the energy generated by the ion exchange comprises the following steps:
  • the inner cavity (i) is filled with a liquid with a certain ionic strength.
  • the device of the invention is connected again to the measuring device.
  • the voltage between the collectors and the load accumulated in them changes spontaneously to ⁇ 0 and to CD , respectively (State C).
  • the measuring device is switched off again leaving the circuit open.
  • the liquid is exchanged in the cavity (i) by introducing the original liquid.
  • the load does not change but the voltage changes to ⁇ 2 (State D).
  • the device of the invention is reconnected to the measuring device.
  • the voltage and load return to the initial values, ⁇ 0 and ⁇ ⁇ , respectively (State A).
  • the net work extracted per unit area of collector can be calculated by calculating the area delimited by the four points ( Figure 6, curves A - BCDA).
  • the energy generated at a time t can be calculated as:
  • Step 1 The collectors are charged to a certain potential (typically in the range of a few hundred milli Volts) through a resistor (Re). This corresponds to the passage from state D to state A in the procedure described and shown in Figure 6.
  • Step 2 The circuit is opened and the liquid contained in the device of the invention is exchanged for another liquid with greater ionic strength. As the load remains constant, there is an increase in potential due to the decrease in capacity of the Electrical Double Layer (DCE). This corresponds to the passage from state A to state B.
  • DCE Electrical Double Layer
  • Step 4 The circuit is opened again and the liquid contained in the device is replaced again with the one with the lowest ionic strength. This returns to the initial state D. In all steps, the current and potential variables of both the collectors and the external load source are measured. Representing the potential values
  • the device of the invention comprises the following elements:
  • the container element is formed by three pieces made of methacrylate, the first, hereinafter “center element (c '), is a cylindrical element, with an outside diameter of 50mm and 20 mm in height, which has been milled in its two flat faces, to give rise to two cylindrical cavities of 8mm depth and a diameter of 20mm, later, these two cavities are finished communicating by practicing a new circular milling concentric to the previous ones that leaves a hole of 19mm in diameter. With this milling it is possible to have an element (w), hereinafter “stop” that limits the minimum distance (do) of the collectors.
  • stop limits the minimum distance (do) of the collectors.
  • the container element is completed with two identical disc-shaped pieces (x), hereinafter “covers”, with a diameter of 50 mm and 5 mm thick that are placed on both sides of the central element.
  • Each of the covers has, in its central part, a circular hole with a diameter of 5 mm.
  • the central element (c ') is made two holes (f) 5mm in diameter on its surface, which allow the entry and exit of liquid.
  • a sleeve is connected to each hole so that once all the elements of the device are connected, a liquid with different ionic strength will enter through each of these holes, in particular fresh water and salt water, so that the ion exchange takes place in The inside of the cavity.
  • the inner cavity (i) is sealed by the covers (x), fixed with screws to the central element (c ').
  • a rubber washer (g) with a thickness greater than the distance between the collector and the lid is placed, so that it is compressed by screwing the covers preventing the leakage of liquid.
  • the device comprises two collector elements (e) with a disk shape of 20mm in diameter and 5mm thick to which a rod (t) of 50mm in length and 5mm radius is attached forming a single piece. Although they can be made of any conductive material, the collectors used in the tests shown below have been manufactured in graphite.
  • each collector is inserted into a rubber washer and then through the circular hole of the lid so that when the caps are screwed to the central element, the surfaces of the collectors on which the collector is deposited are facing and parallel.
  • the effective confrontation surface is 314.17 mm2.
  • washers (a) of 0.5 mm thick and an inner diameter of 19 mm (1 mm smaller than the collector element) are placed in the center of the container, between the disk of the collector element and about the catalyst. Adding washers Separations between the collectors of 0.5, 1 .5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 and 6 mm are achieved.
  • the catalyst is placed on the collector using graphite sheets, on which the material to be tested is deposited and fixed to the collector when its surface is pressed on the stop (w) or on the washers used to increase the distance between the collectors.
  • This arrangement of the washers solves the problems of adhesion of the catalyst on the collector.
  • the device is completed with cables that connect the collectors to an external potential source.
  • State D With the inner cavity of the device filled with salt water, the collectors are connected to the battery at an initial potential of 500 mV reaching state A;
  • Step B to C The battery is reconnected with the inner cavity filled with fresh water (potential of the cavity is greater than battery potential) through a discharge resistance until the potential of the cavity equals the battery;
  • Step from State D to State A The battery is reconnected with the inner cavity filled with salt water, starting the cycle again.
  • the net work extracted per unit area of collector can be calculated by calculating the area delimited by the four points ( Figure 6, curves A - BCDA)
  • the two lower graphs in Figure 9 show an example of experimental data on the potential and intensity as a function of time obtained with this procedure.
  • the distance between the collectors in the container is 2.5 mm and the discharge resistance is 20 ohms.
  • Table 1 summarizes the data obtained by varying the distance between collectors with a separation of 1 mm between tests.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

La présente invention concerne un dispositif de mesure de l'énergie générée par des techniques d'échange ionique entre liquides, en particulier d'échange salin entre liquides, en présence d'un élément catalyseur.
PCT/ES2014/070722 2014-09-25 2014-09-25 Dispositif de mesure d'énergie produite par échange ionique Ceased WO2016046422A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/ES2014/070722 WO2016046422A1 (fr) 2014-09-25 2014-09-25 Dispositif de mesure d'énergie produite par échange ionique

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PCT/ES2014/070722 WO2016046422A1 (fr) 2014-09-25 2014-09-25 Dispositif de mesure d'énergie produite par échange ionique

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11895671B2 (en) 2016-06-30 2024-02-06 Nec Corporation Method and apparatus for signal configuration in a wireless communication system

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010104387A1 (fr) * 2009-03-12 2010-09-16 Redstack B.V. Dispositif et procédé de production d'énergie électrique mettant en œuvre des solutions de concentrations ioniques différentes
WO2012061429A2 (fr) * 2010-11-02 2012-05-10 Fabio La Mantia Piles pour extraction d'énergie efficace d'une différence de salinité

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010104387A1 (fr) * 2009-03-12 2010-09-16 Redstack B.V. Dispositif et procédé de production d'énergie électrique mettant en œuvre des solutions de concentrations ioniques différentes
WO2012061429A2 (fr) * 2010-11-02 2012-05-10 Fabio La Mantia Piles pour extraction d'énergie efficace d'une différence de salinité

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FERNANDEZ M.M. ET AL.: "Multi-ionic effects on energy production based on double layer expansión by salinity exhange.", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 446, 14 August 2014 (2014-08-14), NEW YORK, NY, US, pages 335 - 344, ISSN: 0021-9797 *
IGLESIAS G.R ET AL.: "Materials selection for optimum energy production by double layer expansion methods.", JOURNAL OF POWER SOURCES ELSEVIER SA, CH, vol. 261, pages 371 - 377, XP028652874, ISSN: 0378-7753, DOI: doi:10.1016/j.jpowsour.2013.12.125 *
JIMÉNEZ M L ET AL.: "Predictions of the maximum energy extracted from salinity exchange inside porous electrodes.", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 402, 12 April 2013 (2013-04-12), NEW YORK, NY, US, pages 340 - 349, XP028564174, ISSN: 0021-9797, DOI: doi:10.1016/j.jcis.2013.03.068 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11895671B2 (en) 2016-06-30 2024-02-06 Nec Corporation Method and apparatus for signal configuration in a wireless communication system

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