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WO2019118163A1 - Dispositifs et procédés d'élimination d'ions dissous dans l'eau à l'aide d'électrodes de résine composite - Google Patents

Dispositifs et procédés d'élimination d'ions dissous dans l'eau à l'aide d'électrodes de résine composite Download PDF

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Publication number
WO2019118163A1
WO2019118163A1 PCT/US2018/062472 US2018062472W WO2019118163A1 WO 2019118163 A1 WO2019118163 A1 WO 2019118163A1 US 2018062472 W US2018062472 W US 2018062472W WO 2019118163 A1 WO2019118163 A1 WO 2019118163A1
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WO
WIPO (PCT)
Prior art keywords
electrode
ions
ion
water
chamber
Prior art date
Application number
PCT/US2018/062472
Other languages
English (en)
Inventor
Chinmayee V. Subban
Ashok J. Gadgil
Robert Kostecki
Guoying Chen
Original Assignee
The Regents Of The University Of California
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
Priority claimed from US15/843,712 external-priority patent/US10662082B2/en
Application filed by The Regents Of The University Of California filed Critical The Regents Of The University Of California
Publication of WO2019118163A1 publication Critical patent/WO2019118163A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4613—Inversing polarity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • This invention relates generally to selectively removing dissolved ions from water.
  • TDS total dissolved solids
  • Methods to reduce ionic concentrations to more palatable levels include distillation, solar distillation, reverse osmosis, and ion exchange. In many cases these are not considered affordable, practical, or effective (e.g., owing to lack of adequate capital, land surface, solar insolation, or energy access). For years, membranes and ion exchange have been used to lower TDS from water and wastewater. These methods are not economical, practical or efficient for drinking water treatment, as they require high capital investment, substantive maintenance, large scale engineering, and energy inputs, and/or require use of toxic and corrosive chemicals.
  • Capacitive Deionization is a process that applies a direct current electrical bias across a pair of electrodes immersed in the aqueous electrolyte to separate positively charged cations and negatively charged anions via migration and physical adsorption at the electrodes. For instance, in saline waters the positively charged sodium migrates to the negative electrodes and the negatively charged chloride ion migrates to the positive electrode.
  • EWP Electronic Water Purifier
  • the Electronic Water Purifier is a new technology developed in the last 10 years that has low operating costs, low rejection wastewater volume, low capital expenditure, no chemical requirements, a small footprint and is now available in sizes ranging from under-the- LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472 sink water purifiers to large commercial units.
  • EWP uses a CDI process to remove dissolved ions from water and utilizes a semi-permeable, ion-specific membrane to increase salt capture efficiency of the electrodes.
  • the device consists of multiple layers including current collectors, conductive high surface area electrodes, and an ion-specific membrane.
  • An electrically non- conductive spacer material separates the plates from one another, while allowing a flow of water between the electrodes, parallel to the electrode surfaces.
  • these electrodes are alternately connected to the two sides of a DC power supply.
  • the device works on the principle of capacitive deionization to purify water, with the application of a low voltage DC potential to attract and discharge ions to the electrode surface.
  • the high-surface-area carbon electrode layers attract and hold ions on their surface removing them from the water stream flowing through the inter-electrode gaps. After some time interval of such operation, all the charged sites are filled, and the device must then be regenerated by discharging the ions from the electrode surfaces. This is accomplished by shorting the electrodes or reversing the polarity of the applied DC potential. Once a substantial number of the newly displaced ions are flushed in the waste stream, after a length of time, the unit begins to charge again by attracting ions from the feed solution under the influence of the reverse potential.
  • Treatment of low- TDS water sources has wide ranging applications and includes municipal, agricultural, and industrial sectors among others.
  • the present invention provides for a system for removing dissolved ions from water, comprising: (a) at least one first electrode in contact with a first plurality of ion exchange resin (IER) particles, (b) at least one second electrode in contact with a second plurality of IER particles, (c) a voltage source, (d) a chamber containing or defined by the at least one first electrode and the at least one second electrode, (e) an inlet, (f) a first outlet, and (g) optionally a second outlet, wherein the at least one first electrode, the at least one second electrode, and the electricity source are in electrical communication with each other, and the chamber is in fluid communication with the inlet, the first outlet, and optionally the second outlet, and optionally the voltage source is configured so that the direction of a current to the at least one first electrode and the at least one second electrode can be switched.
  • IER ion exchange resin
  • the present invention also provides for a system for removing dissolved ions from water, comprising: (a) an inlet, (b) at least one first electrode in contact with a first plurality of ion exchange resin (IER) particles, (c) an electrically insulating, water-permeable separator, (d) at least one second electrode in contact with a second plurality of IER particles, (e) an outlet, and (f) a DC or AC voltage source, wherein (i) the insulating separator separates the at least one first electrode and the at least one second electrode, (ii) the at least one first electrode, the at least one second electrode, and the electricity source are in electrical communication with each other, and (iii) there is fluid communication in the following order: the inlet, the region between the at least one first and the at least one second electrodes including the insulating separator, and the outlet, and (iv) optionally the voltage source is configured so that the direction of a current to the at least one first electrode and the at least one second electrode
  • the first plurality of IER particles comprises cation exchange resin (CER).
  • the second plurality of IER particles comprises anion exchange resin (AER).
  • the IER particles are spherical having an average diameter that of about 5 nm to about 0.5 mm.
  • the electrodes comprise one or more metal meshes wherein the IER particles are packed into metal meshes.
  • the at least one first and at least one second electrode comprises two or more than two of each first and second electrode. In some embodiments, a plurality of first and second electrodes is provided.
  • a device or apparatus comprising the system has two steps: a desalinating step and a regenerating step.
  • ion-containing water LI WO 2019/118163 ⁇ 0 PCT/US2018/062472 flows into the system and the cations in the ion-containing water associate with the CER, and the anions in the ion-containing water associate with the AER.
  • Water flowing out of the outlet is relatively deionized water, and has fewer ions than the ion-containing water flowing into the inlet.
  • the AER and CER are capable of trapping charges (chemically) without any applied voltage.
  • the saturated CER and AER (or spent CER and AER) are regenerated by applying a voltage to the electrodes.
  • the IER particles are made electrically conducting, and do not need to be part of a“composite” electrode.
  • a voltage does not need to be applied for the desalinating step, and a voltage only needs to be applied for the regenerating step.
  • At least part or all of the IER particles of the first and/or second pluralities of IER particles are particles produced by the ball milling of IER beads. In some embodiments, at least part of all of the IER particles of the first and/or second pluralities of IER particles comprise a surface that is conducting. In some embodiments, the conducting surface is made by pyrolyzing the bead surface. In some embodiments, the surface of an IER bead has a conductive and ion-porous surface coating made from a second material.
  • the IER particles or IER beads have an average surface area of equal to or more than 0.1 m 2 /g, 1 m 2 /g, 10 m 2 /g, 1,000 m 2 /g, 2,500 m 2 /g, 5,000 m 2 /g, 7,500 m 2 /g, 10,000 m 2 /g, or 12,500 m 2 /g, or within any range of one thereof to equal to or less than 15,000 m 2 /g.
  • the at least one first electrode is the cathode, and at least part or all of the IER particles of the first plurality of IER particles are cation exchange resin (CER).
  • the at least one second electrode is the anode, and at least part or all of the IER particles of the second plurality of IER particles are anion exchange resin (AER).
  • the at least one first electrode and/or the at least one second electrode comprise a conductive matrix, wherein the IER particles are embedded on the surface of, held in place by, or both, by the conductive matrix.
  • the at least one first electrode and/or the at least one second electrode comprise one or a plurality of conductive matrices that support a plurality of layers of IER particles.
  • the system comprises a device or apparatus 1 comprising: (a) at least one first electrode 2 comprising a first surface 3 in contact with a first plurality of IER particles 4, (b) at least one second electrode 5 comprising a second surface 6 in contact with a second plurality of IER particles 7, (c) an voltage source 8 in electrical communication with the at least one electrode 2 via a first electrical contact 9, and with the at least one second electrode 5 via a second electrical contact 10, (d) a chamber 11 defined by the at least one first electrode 2 and the at least one second electrode 5, (e) an inlet 12, (f) a first outlet 13, (g) a second outlet 14, (h) optionally a means 15 for sealing the inlet 12, (i) optionally LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472 a means 16 for sealing the first outlet 13, and (j) optionally a means 17 for sealing the second outlet 14.
  • the first outlet 13 and the second outlet 14 are the same
  • the IER particle comprises a surface coated with carbon 22.
  • the first surface 3 and/or the second surface 5 are modified to increase the surface area of the first surface 3 and/or the second surface 5.
  • the system comprises a means to divert the flow from the first outlet to more than one direction.
  • the direction of electric field generated by the potential applied by the at least one first and/or at least one second electrodes is perpendicular to the direction of water flow.
  • the at least one first electrode 2 and/or the at least one second electrode 5 may be thin and flexible, and may be placed in a chamber made of a different robust, but passive material.
  • the at least one first electrode and/or the at least one second electrode comprise multiple layers of conductive matrix and each layer of matrix comprises a layer, such as a monolayer, of IER particles (see Figure 2). Each layer is separated from the next, or adjacent, layer with an ion-permeable electrically insulating layer, such as an insulating porous spacer, or a layer of aerogel. Multiples of such layers make up the electrode. Each layer is provided with a different voltage so that a voltage gradient is established within each electrode, thereby resulting in a deeper penetration of ions in the electrode, and a larger capture capacity for ions before the need for regeneration.
  • the present invention provides for a method for removing dissolved ions from ion- containing water comprising: (a) providing the system or apparatus for removing dissolved ions from ion-containing water of the present invention; (b) flowing ion-containing water into the chamber via the inlet, (c) optionally running a direct or alternating current through the water via the at least one first electrode and the at least one second electrode, (d) continuously flowing ion- containing water from the inlet into the chamber and out of the first outlet, wherein, in the chamber, one or more cations in the ion-containing water associate to a IER particle of the first plurality of IER particles and one or more anions in the ion-containing water to associate to a IER particle of the second plurality of IER particles, such that relatively deionized water flows out of the chamber via the first outlet, (e) optionally stopping the flow of the ion-containing water of step (d), (f) running a direct current through the water in a direction
  • IER particles and the anions dissociate from the IER particle of the second plurality of IER particles to form waste water in the chamber, (g) flowing the waste water out of the chamber via the second outlet, and (h) optionally repeating steps (d) to (g).
  • the present invention provides for a method for removing dissolved ions from ion- containing water comprising: (a) providing the system or apparatus for removing dissolved ions from ion-containing water of the present invention; (b) flowing ion-water containing water into the system via the inlet, such that cations in the ion-water containing water associate with the CER, anions in the ion-water containing water associate with the AER, and water flowing out of the outlet has fewer ions than the ion-containing water flowing into the inlet, (c) regenerating the CER and AER comprising (i) flowing water containing fewer ions into the system via the inlet, optionally at a reduced flow rate relative to step (b), (ii) optionally, closing the outlet, and (iii) applying a voltage to the CER and AER, such that the cations disassociate from the CER and the anions disassociate from the AER, (d) opening the outlet to let
  • the water containing fewer ions of step (c) (i) is water obtained from step (b).
  • the outlet in step (c)ii remains open.
  • the outlet in step (c)ii is closed.
  • the flow rate of flowing water in step (c)i remains substantially unchanged relative to the flow rate in step b.
  • the flow rate of flowing water in step (c)i is reduced relative to the flow rate in step b.
  • the ion removed is any cation having an atomic number equal to or larger than 3.
  • the cation is an element of Group 1 or 2, or any cation with a valence of +1 or +2.
  • the cation is, for example, one or more of Li + , Na , K , Be , Mg , or Ca .
  • the ion removed is any anion having an atomic number equal to or larger than 5.
  • the anion is an element of Group 16 or 17, or any anion with a valence of -1 or -2.
  • the anion is, for example, F , CT, Br , N0 3 , S0 4 2 , or Se 2 .
  • the present invention further provides a method of selectively removing at least a portion of dissolved ions from water containing a first concentration of ions to be removed.
  • the method comprises (a) providing a system for selectively removing at least a portion of the dissolved ions to be removed from an ion-containing water, the system comprising at least one first electrode in contact with a first plurality of selective ion exchange resin (IER) particles, at least one second electrode in contact with a second plurality of IER particles, a direct or alternating current voltage source, a chamber defined by, or containing, the at least one first electrode and the at least one second electrode, an inlet, and a first outlet, wherein the at least one first electrode, the at least one second electrode, and the direct current voltage source are in electrical LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472 communication with each other and the chamber is in fluid communication with the inlet and the first outlet, wherein the direct current voltage source is configured so that the direction of a current to the at least
  • the method further comprises, in step (b), passing a direct current through the water in the chamber containing the first concentration of ions to be removed via the at least one first electrode and the at least one second electrode.
  • the at least one first electrode is negatively charged and the at least one second electrode is positively charged.
  • the current is applied at an absolute magnitude of voltage from about 0 to about 5 volts across the at least one first and at least one second electrodes. In some embodiments, the current in absolute magnitude is from about 10 ⁇ A/cm 2 to about 10 mA/cm 2 .
  • the method further comprises repeating steps (c) and (d) one or more times.
  • the device further comprises a second outlet in fluid communication with the chamber, the inlet and the first outlet.
  • the waste water is flowed out of the second outlet.
  • the method further comprises reducing, increasing or stopping the flow of water of step (b) during step (c).
  • the current in step (c) is applied at a voltage from about 0.1 to about 5 volts.
  • the current in step (c) is from about 10 ⁇ A/cm 2 to about 10 mA/cm 2 .
  • the current is applied for a time sufficient to dissociate from about 20% to about 95% of the ions associated with the selective IER. In some embodiments, the time is from about 1 second to about 2 hours. In some embodiments the time is from about 30 seconds to about 30 minutes.
  • the device provided within the method comprises a plurality of first and second electrodes, such as two, at least two, or at least two or more of each first and second electrode. LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472
  • the ions to be selectively removed are anions and/or cations comprising one or more elements from any one or more of Periodic Table Groups 1 to 17.
  • at least one of the anions or cations comprise an element of Group 1 or 2.
  • at least one of the anions or cations comprise one or more elements from any one or more of Groups 3-14.
  • At least one of the anions or cations comprise one or more elements selected from the group consisting of sodium, potassium, lithium, calcium, fluorine, chlorine, bromine, antimony, arsenic, bismuth, boron, cadmium, chromium, copper, gallium germanium, gold, indium, iridium, iron, lead, manganese, mercury, nickel, nitrogen, phosphorous, platinum, radium, rhodium, ruthenium, selenium, silver, sulfur, thallium, tin, uranium, and zinc.
  • the anions to be selectively removed are one or more of arsenate, fluoride, bromate, chloride, chromate, cyanide, nitrate, perchlorate, phosphate, selenate, or sulfate.
  • the cations to be selectively removed are one or more of lithium, sodium, potassium, or calcium.
  • the first plurality of selective ion exchange resin particles and the second plurality of selective ion exchange resin particles are each independently selected from the group consisting of strongly acidic resins bearing sulfonic acid groups, strongly basic resins bearing quaternary amino groups, weakly acidic resins with carboxylic acid groups, weakly basic resins bearing primary, secondary, and/or tertiary amino groups, chelating resins bearing iminodiacetic acid groups, ion selective resins, gel-type resins and macroporous resins.
  • the first plurality of selective ion exchange resin particles and the second plurality of selective ion exchange resin particles are different.
  • the at least one first and the at least one second electrodes comprise a conductive substrate.
  • the conductive substrate is one or more of a conductive metal, a conductive metal alloy, a conductive semi-metal, or a conductive polymer.
  • the conductive metal is stainless steel.
  • the conductive semi-metal is carbon.
  • the conductive polymer is a nylon composite plate, mesh or film.
  • the ion-containing water contains ions in an amount from about 1 ppm to about 10,000 ppm.
  • the first concentration of ions to be removed is from about 1 ppm to about 10,000 ppm.
  • the second concentration of ions is from about 0.01 ppm to about 4,000 ppm.
  • the ion-containing water contains dissolved ions comprising at least a first species of ion and a second species of ion, and selective removal of the first species of ion in the presence of the second species of ion occurs with a selectivity for the first species of ion from about 5 to about 200 fold.
  • the first species of ion is nitrate and LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472 the second species of ion is sulfate. In this embodiment, nitrate is selectively removed in the presence of sulfate.
  • the method further comprises the step (e) of collecting the waste water for recovery of the dissociated ions.
  • the ion-containing water is provided from an agricultural, municipal, industrial, food and beverage, mining, construction, brackish groundwater aquifers, or other waste source.
  • FIG. 1 A is a schematic of a CDI apparatus. Brackish water flows between two electrodes held at a constant voltage difference. The ions in the influx are drawn to and held at oppositely charged electrode surfaces. The layer of charge inside the electrode and the layer of oppositely charged ions outside the electrode constitute the "electric double layer.” Once the electrode surface area is saturated with ions, the flow is stopped and voltage reversed, so the ions re-enter the solution. This highly concentrated solution is passed to a waste stream, and the process repeats.
  • Figure 1B is a schematic illustration of an exemplary embodiment of the apparatus of the present disclosure.
  • FIG. 2 is a schematic illustration of an exemplary embodiment of the apparatus of the present disclosure wherein the electrodes comprise multiple layers of electrodes and each layer comprises a layer, such as a monolayer, of IER particles.
  • Figure 3 is a graph demonstrating that desalination occurs in an embodiment of the device of the present disclosure without an applied voltage, followed by regeneration with an applied voltage.
  • Figure 4 is a graph demonstrating feasibility of system operation in an embodiment of the present disclosure under a range of applied voltages.
  • Figure 5 is a graph demonstrating robustness of the electrodes in an embodiment of the present disclosure under continuous operation.
  • Figures 6A and 6B are graphs demonstrating (A) feasibility of approach using specialty resin, and (B) targeted ion removal from a mixed ion solution.
  • the system comprises the building of a series of hybrid CDEion (cation and anion) exchange composite electrodes for ion transport, capture and removal.
  • the ion exchange process can be controlled and accelerated via voltage polarization.
  • IERs may be impregnated or coated with a conductive medium, such as carbon black (i.e., soot), and these modified particles are used to form anode and cathode (using anion type and cation type resins) of the presently disclosed device.
  • an electric field is used to draw ions to these electrodes.
  • ions are drawn to the electrodes by diffuse transport. LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472
  • the ions Once the ions reach the IER, they are captured with ion exchange occurring in the resin. As the electric field is relaxed or reversed, the IER is electrochemically regenerated without need for toxic and corrosive chemicals.
  • the conducting medium could be impregnated into the IER either (a) during the synthesis or final physical processing of the IER itself, or (b) by reprocessing commercially available resins.
  • Path A would require re-engineering the synthesis process.
  • Path B requires developing a method of coating the resin particles with a layer of conductive coating that is both thin and/or porous enough to allow ions to reach the IER and thick enough to provide a continuous and low resistance path of electronic conductivity within the composite electrode.
  • One method of coating commercially available IER with thin layers of carbon would involve using a methane flame to generate soot. To achieve a uniform 3D coating a fluidized bed may be used. Coated beads could be attached to a wire mesh to facilitate conductivity and electrode integrity. The derived conductive layers may then be subject to further processing to control surface and chemical properties of the electrodes.
  • Another method uses plasma to pyrolyze the surface layer of the existing organic resin particles.
  • the process would be tuned to create a thin layer of carbon without overheating and destroying the resin or its unique properties.
  • a metal catalyst such as Cu or Ni, may be deposited on the resin prior to pyrolysis to promote growth of carbon nanotubes and other high surface area carbon structures, increasing the ion removal capacity and also conductive properties.
  • each layer comprising a conducting fine wire mesh layered with a monolayer of IER beads/particles, separated from the next layer with a non-permeable insulating layer, which can be an insulating porous spacer (or a thin layer of aerogel).
  • a non-permeable insulating layer which can be an insulating porous spacer (or a thin layer of aerogel).
  • Multiple layers make up the electrode.
  • Each wire mesh is given a different voltage so a voltage gradient within the electrode is established, allowing deeper penetration of ions in the electrode, and a larger capture capacity for ions before the need for regeneration.
  • microfluidic channels can be used to aid the separation of concentrated ion solution from free-ion solution.
  • a silica aerogel can be used as an insulator between the electrodes. The aerogel can fully occupy the space between the electrodes and suppress diffusive remixing of the separated ions.
  • a thin layer of silica aerogel coats the electrodes, leaving a small gap that forms a microfluidic channel between the electrodes. This avoids the high pressure gradient needed to push the water through the gel, LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472 while still suppressing remixing of ions.
  • the thin layer of gel acts as a porous insulator only, allowing the ions to pass through to the electrode perpendicular to the direction of water flow (which would not be through the aerogel).
  • the present invention further provides a method of selectively removing at least a portion of dissolved ions from water containing a first concentration of ions to be removed.
  • the method comprises: (a) providing a system for selectively removing at least a portion of the dissolved ions to be removed from an ion-containing water, the system comprising at least one first electrode in contact with a first plurality of selective ion exchange resin (IER) particles, at least one second electrode in contact with a second plurality of IER particles, a direct current voltage source, a chamber defined by or containing the at least one first electrode and the at least one second electrode, an inlet, and a first outlet, wherein the at least one first electrode, the at least one second electrode, and the direct current voltage source are in electrical communication with each other and the chamber is in fluid communication with the inlet and the first outlet, wherein the direct current voltage source is configured so that the direction of a current to the at least one first electrode and the at least one second electrode can be switched; and wherein the first and second pluralit
  • the method further comprises, in step (b), passing a direct current through the water in the chamber containing the first concentration of ions to be removed via the at least one first electrode and the at least one second electrode.
  • a direct current may increase efficiency of ion association with resin.
  • the at least one first electrode is negatively charged and the at least one second electrode is positively charged.
  • the at least one first electrode is positively charged and the at least one second electrode is negatively charged.
  • no current is applied, and no charge LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472 exists.
  • the current is applied at a voltage in absolute magnitude from about 0 to about 5 volts. In some embodiments, the current is in absolute magnitude from about 10 ⁇ A/cm 2 to about 10 mA/cm 2 .
  • the at least one first and at least one second electrodes comprise a conductive substrate.
  • the conductive substrate can be, for example, one or more of a conductive metal, a conductive metal alloy, a conductive semi-metal, or a conductive polymer.
  • a non-limiting example of a conductive metal is stainless steel.
  • a non limiting example of a conductive semi-metal is carbon.
  • Carbon may be utilized in many forms (e.g., graphite, powder, embedded in polymer, etc.), and may be of various surface areas, porosities, particle sizes, and chemical and physical properties.
  • a non-limiting example of a conductive polymer is a nylon composite, which may be in multiple forms. Non-limiting examples include plate, mesh or film forms.
  • the device provided within the method comprises a plurality of first and second electrodes, such as two, at least two, or at least two or more of each first and second electrode.
  • first and second electrodes such as two, at least two, or at least two or more of each first and second electrode.
  • the ions to be selectively removed are anions and/or cations comprising one or more elements from any one or more of Periodic Table Groups 1 to 17.
  • anion is meant an ionic species bearing a negative charge.
  • cation is meant an ionic species bearing a positive charge.
  • at least one of the anions or cations comprise an element of Group 1 or 2.
  • the cation may be the ion produced by loss of one or more valence electrons of the corresponding element.
  • Non-limiting examples include lithium (as Li +1 ), sodium (as Na +1 ), or calcium (as Ca +2 ) and the like.
  • such anions and cations will be present from dissolution of a salt in the water.
  • a non-limiting example is the presence of sodium chloride, which, dissolved in water, provides sodium ions (cation) and chloride ions (anion).
  • at least one of the anions or cations comprise one or more elements from any one or more of Groups 3-14.
  • At least one of the anions or cations comprise one or more elements selected from the group consisting of sodium, potassium, lithium, calcium, fluorine, chlorine, bromine, antimony, arsenic, bismuth, boron, cadmium, chromium, copper, gallium, germanium, gold, indium, iridium, iron, lead, manganese, mercury, nickel, nitrogen, phosphorous, platinum, radium, rhodium, ruthenium, selenium, silver, sulfur, thallium, tin, uranium, and zinc.
  • elements selected from the group consisting of sodium, potassium, lithium, calcium, fluorine, chlorine, bromine, antimony, arsenic, bismuth, boron, cadmium, chromium, copper, gallium, germanium, gold, indium, iridium, iron, lead, manganese, mercury, nickel, nitrogen, phosphorous, platinum, radium, rhodium, ruthenium, selenium,
  • the LI WO 2019/118163 ⁇ 0 PCT/US2018/062472 anion to be selectively removed is one or more of arsenate, fluoride, bromate, chloride, chromate, cyanide, nitrate, perchlorate, phosphate, selenate, or sulfate.
  • the ion to be removed is a cation.
  • the cation to be selectively removed is one or more of lithium, sodium, potassium, or calcium. It will be recognized that the ions referred to may be present in various combinations simultaneously or individually, and may be present in various amounts.
  • the presently disclosed method is useful in removing, individually or multiply, various ions which may be present in varied concentrations.
  • the ion-containing water may contain an initial concentration of one or more ions to be removed in an amount from about 1 ppm to about 10,000 ppm.
  • the water subjected to the selective ion removal of the present disclosed method has, after step (b), a second concentration of ions. This second concentration is generally less than the first concentration, and for example, may be from about 0.01 ppm to about 4,000 ppm.
  • the first and second concentrations of ions present may be determined by techniques know to those skilled in the art.
  • the present method may be standard quantitative analytical techniques, or, conveniently, conductivity may be used as a surrogate measure of ion content of the influent and effluent waters provided according to the present method.
  • multiple ion species may be present, and the present method contemplates preferentially removing one or more of these species. Therefore, the method provides selective or even specific removal of ions.
  • the selectivity for removal of a first species of ion in the presence of a second species of ion is from about 5 to about 200 fold.
  • nitrate is selectively removed in the presence of sulfate.
  • the first plurality of selective ion exchange resin particles and the second plurality of selective ion exchange resin particles are each independently selected from the group consisting of strongly acidic resins bearing sulfonic acid groups, strongly basic resins bearing quaternary amino groups, weakly acidic resins with carboxylic acid groups, weakly basic resins bearing primary, secondary, and/or tertiary amino groups, chelating resins bearing iminodiacetic acid groups, ion selective resins, gel-type resins and macroporous resins.
  • the first plurality of selective ion exchange resin particles and the second plurality of selective ion exchange resin particles are different. Such resins are known to those skilled in the art and are commercially available. Resins may be used in the present devices as obtained, or may be subject to further processing steps according to the specific application intended.
  • the resins of the present method will become saturated with the associated ions and present a diminished capacity to further remove ions from the water.
  • the resin may be recharged by dissociating the previously associated ions. In the present method, this is accomplished through application of a voltage across the electrodes. Without wishing to be LI ( WO 2019/118163 ⁇ 0 PCT/US2018/062472 bound by theory, it is believed that application of this current may both promote dissociation of ions by charge repulsion as well as by local generation of acidic and basic species which displace the ions occupying the resin.
  • the current is applied at an absolute magnitude voltage of from about 0.1 to about 5 volts. In some embodiments, the current applied is at an absolute magnitude of from about 10 DA/cm 2 to about 10 mA/cm 2 . In some embodiments, the current is applied for a time sufficient to dissociate from about 20% to about 95% of the associated ions. In some embodiments, the time required is from about 1 second to about 2 hours. In some embodiments, the time required is from about 30 seconds to about 30 minutes.
  • the method further comprises repeating steps (c) and (d) one or more times.
  • steps (c) and (d) one or more times.
  • the device provided further comprises a second outlet in fluid communication with the chamber, the inlet and the first outlet.
  • the waste water is flowed out of the second outlet.
  • the flow of water of step (b) during step is reduced, increased, stopped or diverted during step (c).
  • the ion-containing water is provided from an agricultural, municipal, industrial, food and beverage, mining, construction, brackish groundwater aquifers, or other waste source.
  • the method further comprises the step (e) of collecting the waste water for recovery of the dissociated ions. Such collection may be useful, for example, to reclaim valuable metallic species from various mining or industrial processes.
  • Valuable metallic species may include, by non-limiting example, silver, gold, platinum, rhodium, ruthenium, indium, and the like.
  • the presently disclosed invention is useful for creating new affordable water sources by desalination of low salinity sources such as brackish ground and surface waters, and for water reuse and recycling (such as from municipal and industrial wastewater reclamation) by removing trace contaminants from polluted streams.
  • Another application is for the removal of toxic, naturally occurring ionic contaminants, such as arsenic, boron, and fluoride, from ground water supplies.
  • the technology can be operated under varying applied voltages during the regeneration step. In certain cases using a minimal applied voltage even during the desalination step may be favorable for enhancing the ion diffusion rates.
  • the ability to operate the system under varying applied voltages allows for optimizing the energy consumption of the system.
  • the applied voltage has a clear effect on the ion removal capacity of the system as shown in Figure 4. The higher the applied voltage, the higher the salt removal capacity. However, beyond a certain voltage, undesirable secondary reactions at the electrode surface are a concern.
  • nitrate and sulfate ions co-exist in the environment. While consuming nitrate contaminated water is harmful to human health, sulfates are not a concern. Being able to target and remove nitrates over sulfates from a water source has clear applications.
  • nitrate-specific resins which selectively capture nitrates over sulfates, however they require regular regeneration using corrosive chemicals.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

La présente invention concerne un dispositif comprenant ou configuré pour comprendre des électrodes en résine composite. L'invention concerne en outre des procédés d'utilisation du dispositif pour éliminer sélectivement des ions dissous de l'eau.
PCT/US2018/062472 2017-12-15 2018-11-26 Dispositifs et procédés d'élimination d'ions dissous dans l'eau à l'aide d'électrodes de résine composite WO2019118163A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15/843,712 2017-12-15
US15/843,712 US10662082B2 (en) 2014-10-03 2017-12-15 Devices and methods for removing dissolved ions from water using composite resin electrodes

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5804057A (en) * 1996-06-07 1998-09-08 Faraday Technology, Inc. Method of removing metal salts from solution by electrolysis an electrode closely associated with an ion exchange resin
US20170247268A1 (en) * 2014-10-03 2017-08-31 Chinmayee V. Subban Devices and methods for removing dissolved ions from water using composite resin electrodes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5804057A (en) * 1996-06-07 1998-09-08 Faraday Technology, Inc. Method of removing metal salts from solution by electrolysis an electrode closely associated with an ion exchange resin
US20170247268A1 (en) * 2014-10-03 2017-08-31 Chinmayee V. Subban Devices and methods for removing dissolved ions from water using composite resin electrodes

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