Regulation of process stream composition for improved electrolyzer performance
11492279 · 2022-11-08
Assignee
Inventors
- JOSHUA GRIFFIS (Ashburnham, MA, US)
- SIMON P. DUKES (Chelmsford, MA, US)
- Ll-Shiang Liang (Harvard, MA, US)
- Darren Dale (Chesterfield, GB)
- Michael Shaw (Derry, NH, US)
- Paul Beddoes (Shirehampton, GB)
- George Y. Gu (Andover, MA, US)
Cpc classification
C02F2209/005
CHEMISTRY; METALLURGY
B01D2311/25
PERFORMING OPERATIONS; TRANSPORTING
B01D2311/2665
PERFORMING OPERATIONS; TRANSPORTING
B01D2311/04
PERFORMING OPERATIONS; TRANSPORTING
C02F1/4674
CHEMISTRY; METALLURGY
B01D61/445
PERFORMING OPERATIONS; TRANSPORTING
C02F9/00
CHEMISTRY; METALLURGY
C02F1/46104
CHEMISTRY; METALLURGY
C02F2103/008
CHEMISTRY; METALLURGY
International classification
B01D61/02
PERFORMING OPERATIONS; TRANSPORTING
C02F1/469
CHEMISTRY; METALLURGY
Abstract
An electrochlorination system includes an electrolyzer fluidically connectable between a source of feed fluid and a product fluid outlet, and a sub-system configured to one of increase a pH of the feed fluid, or increase a ratio of monovalent to divalent ions in the feed fluid, upstream of the electrolyzer.
Claims
1. An electrochlorination system comprising: an electrolyzer fluidically connectable between a source of feed fluid and a product fluid outlet; and a sub-system configured to increase a pH of the feed fluid and increase a ratio of monovalent to divalent ions in the feed fluid, upstream of the electrolyzer.
2. The system of claim 1, wherein the sub-system comprises a nanofiltration unit having an inlet fluidly connectable to the source of feed fluid and configured to separate the feed fluid into a retentate and a permeate, the retentate having a higher ratio of divalent ions to monovalent ions than the permeate, and a permeate outlet configured to provide the permeate to an inlet of the electrolyzer.
3. The system of claim 2, wherein the nanofiltration unit is configured to produce the permeate with a monovalent ion concentration of from 2% to 10% lower than a monovalent ion concentration in the feed fluid.
4. The system of claim 2, wherein the nanofiltration unit is configured to produce the permeate with a divalent ion concentration of from 50% to 90% lower than a divalent ion concentration in the feed fluid.
5. The system of claim 1, wherein the sub-system comprises an electrodialysis unit having an inlet fluidly connectable to the source of feed fluid, one or more monovalent selective membranes, and a concentrate stream outlet in fluid communication with an inlet of the electrolyzer.
6. The system of claim 5, wherein the electrodialysis unit is configured to separate the feed fluid into a diluate stream and a concentrate stream and preferentially transport monovalent ions from the diluate stream to the concentrate stream.
7. The system of claim 6, wherein the electrodialysis unit is configured to increase a concentration of monovalent ions in the concentrate stream by from 3% to 400% relative to the feed liquid.
8. The system of claim 1, wherein the sub-system comprises a nanofiltration unit having an inlet fluidly connectable to the source of feed fluid and an outlet in fluid communication with an electrodialysis unit, the electrodialysis unit including one or more monovalent selective membranes and a concentrate stream outlet in fluid communication with an inlet of the electrolyzer.
9. The system of claim 8, further comprising an oxygen saturation unit in fluid communication between the electrodialysis unit and the electrolyzer and configured to add oxygen to the concentrate stream prior to the concentrate stream entering the inlet of the electrolyzer.
10. An electrochlorination system comprising: an electrolyzer fluidically connectable between a source of feed fluid and a product fluid outlet; and a sub-system configured to one of increase a pH of the feed fluid or increase a ratio of monovalent to divalent ions in the feed fluid, upstream of the electrolyzer, the sub-system comprising an electrodialysis unit having an inlet fluidly connectable to the source of feed fluid, one or more monovalent selective membranes, a diluate stream outlet in fluid communication with an inlet of a nanofiltration unit, a concentrate stream inlet in fluid communication with a permeate outlet of the nanofiltration unit, and a concentrate stream outlet in fluid communication with an inlet of the electrolyzer.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1) The accompanying drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures is represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. In the drawings:
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DETAILED DESCRIPTION
(29) Aspects and embodiments disclosed herein are not limited to the details of construction and the arrangement of components set forth in the following description or illustrated in the drawings. Aspects and embodiments disclosed herein are capable of being practiced or of being carried out in various ways. Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” “having,” “containing,” “involving,” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items.
(30) This disclosure describes various embodiments of systems including electrochlorination cells and electrochlorination devices, however, this disclosure is not limited to systems including electrochlorination cells or devices and the aspects and embodiments disclosed herein are applicable to systems including electrolytic and electrochemical cells used for any one of multiple purposes.
(31) Current commercially electrochlorination cells are typically based on one of two electrode arrangements, concentric tubes (CTE) and parallel plates (PPE).
(32) Aspects and embodiments disclosed herein are generally directed to systems including electrochemical devices to generate disinfectants such as sodium hypochlorite. The terms “electrochemical device” and “electrochemical cell” and grammatical variations thereof are to be understood to encompass “electrochlorination devices” and “electrochlorination cells” and grammatical variations thereof. Aspects and embodiments of electrochemical cells disclosed herein are described as including one or more electrodes.
(33) Embodiments of electrochemical cells included in systems disclosed herein may include metal electrodes, for example, one or more anodes, one or more cathodes, and/or one or more bipolar electrodes. The term “metal electrodes” or grammatical variation thereof as used herein is to be understood to encompass electrodes formed from, comprising, or consisting of one or more metals, for example, titanium, aluminum, or nickel although the term “metal electrode” does not exclude electrodes including of consisting of other metals or alloys. In some embodiments, a “metal electrode” may include multiple layers of different metals. Metal electrodes utilized in any one or more of the embodiments disclosed herein may include a core of a high-conductivity metal, for example, copper or aluminum, coated with a metal or metal oxide having a high resistance to chemical attack by electrolyte solutions, for example, a layer of titanium, platinum, a mixed metal oxide (MMO), magnetite, ferrite, cobalt spinel, tantalum, palladium, iridium, silver, gold, or other coating materials. “Metal electrodes” may be coated with an oxidation resistant coating, for example, but not limited to, platinum, a mixed metal oxide (MMO), magnetite, ferrite, cobalt spinel, tantalum, palladium, iridium, silver, gold, or other coating materials. Mixed metal oxides utilized in embodiments disclosed herein may include an oxide or oxides of one or more of ruthenium, rhodium, tantalum (optionally alloyed with antimony and/or manganese), titanium, iridium, zinc, tin, antimony, a titanium-nickel alloy, a titanium-copper alloy, a titanium-iron alloy, a titanium-cobalt alloy, or other appropriate metals or alloys. Anodes utilized in embodiments disclosed herein may be coated with platinum and/or an oxide or oxides of one or more of iridium, ruthenium, tin, rhodium, or tantalum (optionally alloyed with antimony and/or manganese). Cathodes utilized in embodiments disclosed herein may be coated with platinum and/or an oxide or oxides of one or more of iridium, ruthenium, and titanium. Electrodes utilized in embodiments disclosed herein may include a base of one or more of titanium, tantalum, zirconium, niobium, tungsten, and/or silicon. Electrodes for any of the electrochemical cells in any of the systems disclosed herein can be formed as or from plates, sheets, foils, extrusions, and/or sinters.
(34) Some aspects and embodiments of electrochemical cells included in systems disclosed herein are described as including rigid electrodes. As the term is used herein, a “rigid” object is one that maintains its shape in the absence of an applied force at a normal operating temperature and/or at an elevated temperature. A “rigid electrode,” as the term is used herein, is considered to have sufficient mechanical stiffness such that it maintains its shape and separation between adjacent electrodes or electrode windings in the various embodiments of electrochemical cells and devices disclosed herein without the need for spacers. For example, a flexible film including a metal coating is not to be considered a “rigid electrode” as the term is used herein.
(35) The term “tube” as used herein includes cylindrical conduits, however, does not exclude conduits having other cross-sectional geometries, for example, conduits having square, rectangular, oval, or obround geometries or cross-sectional geometries shaped as any regular or irregular polygon.
(36) The terms “concentric tubes” or “concentric spirals” as used herein includes tubes or interleaved spirals sharing a common central axis but does not exclude tubes or interleaved spirals surrounding a common axis that is not necessarily central to each of the concentric tubes or interleaved spirals in a set of concentric tubes or interleaved spirals.
(37) In some embodiments, a line passing from a central axis of an electrochlorination cell toward a periphery of the electrochlorination cell in a plane defined normal to the central axis passes through multiple electrode plates. The multiple electrode plates may include multiple anodes and/or multiple cathodes and/or multiple bipolar electrodes. The central axis may be parallel to an average direction of flow of fluid through the electrochemical cell.
(38) In embodiments of electrochemical cells included in systems disclosed herein including multiple anode or cathode tube electrodes, the multiple anode tube electrodes may be referred to collectively as the anode or the anode tube, and the multiple cathode tube electrodes may be referred to collectively as the cathode or the cathode tube. In embodiments of electrochemical cells included in systems including multiple anode and/or multiple cathode tube electrodes, the multiple anode tube electrodes and/or multiple cathode tube electrodes may be collectively referred to herein as an anode-cathode pair.
(39) In some aspects and embodiments of electrochemical cells included in systems disclosed herein including concentric tube electrodes, for example, one or more anodes and/or cathodes as disclosed herein, the electrodes are configured and arranged to direct fluid through one or more gaps between the electrodes in a direction parallel to a central axis of the electrochemical cell. In some aspects and embodiments of electrochemical cells including concentric tube electrodes, for example, one or more anodes and/or cathodes as disclosed herein, the electrodes are configured and arranged to direct all fluid introduced into the electrochemical cell through the one or more gaps between the electrodes in a direction parallel to a central axis of the electrochemical cell.
(40) Electrochlorination cells are used in marine, offshore, municipal, industrial and commercial applications. The design parameters of electrochlorination cells including a plurality of concentric electrode tubes, for example, inter-electrode spacing, thickness of electrodes and coating density, electrode areas, methods of electrical connections, etc., can be selected for different implementations. Aspects and embodiments disclosed herein are not limited to the number of electrodes, the space between electrodes, the electrode material or spacer material, number of passes within the electrochlorination cells or electrode coating material.
(41) PCT application PCT/US2016/018210 is incorporated herein by reference in entirety for all purposes.
(42) Aspects and embodiments disclosed herein include systems and processes for the regulation of the composition of an electrolyzer feed stream. Through the use of these techniques, it is possible to decrease the rate of precipitate formation and increase the concentration of hypochlorite produced by an electrolyzer.
(43) Configurations of concentric tubular electrolyzer (CTE) cells for improving system performance have been discussed in US 62/633,790 which is incorporated herein by reference in its entirety for all purposes. Electrolyzer systems including various arrangements of electrochemical cells (e.g., CTE systems including multiple CTE cells) are disclosed in PCT Application PCT/US2019/019072 which is incorporated herein by reference in its entirety for all purposes. In addition to the cell arrangement, however, CTE system performance strongly depends on its feed stream composition.
(44) CTE systems are intended to operate with a seawater feed stream over a wide range of compositions, for example, as illustrated in Tables 1 and 2 below. The concentration of different dissolved solids in seawater may vary depending on location, however, one example of seawater may include the following components:
(45) TABLE-US-00001 TABLE 1 Typical seawater components and concentrations Common name Symbol mg/l (ppm) Chloride Cl 19,350 Sodium Na 10,750 Sulfate SO.sub.4 2,700 Magnesium Mg 1,290 Calcium Ca 410 Potassium K 380 Bicarbonate HCO.sub.3 140 Bromide Br 65 Strontium Sr 13 Aluminum Al 1.9 Silicon Si 1.1 Fluoride F .8 Nitrate NO.sub.3 .8 Boron B .4 Barium Ba .2 Iron Fe .1 Manganese Mn .1 Copper Cu .1 Lithium Li .1 Phosphorous P .06 Iodide I .04 Silver Ag .02 Arsenic As <.01 Nitrite NO.sub.2 <.01 Zinc Zn <.01 Total: 35,000 (excluding H & O)
(46) The different ionic components of seawater from different locations are indicated in Table 2 below:
(47) TABLE-US-00002 TABLE 2 Major Ion Composition of Seawater (mg/L) Typical Eastern Arabian Gulf Red Sea at Ion Seawater Mediterranean at Kuwait Jeddah Chloride 18,980 21,200 23,000 22,219 (Cl.sup.−) Sodium 10,556 11,800 15,850 14,255 (Na.sup.+) Sulfate 2,649 2,950 3,200 3,078 (SO.sub.4.sup.2−) Magnesium 1,262 1,403 1,765 742 (Mg.sup.2+) Calcium 400 423 500 225 (Ca.sup.2+) Potassium 380 463 460 210 (K.sup.+) Bicarbonate 140 — 142 146 (HCO.sub.3.sup.−) Strontium 13 — — — (Sr.sup.2+) Bromide 65 155 80 72 (Br.sup.−) Borate 26 72 — — (BO.sub.3.sup.3−) Fluoride 1 — — — (F.sup.−) Silicate 1 — 1.5 — (SiO.sub.3.sup.2−) Iodide <1 2 — — (I.sup.−) Others — — — — Total Dissolved 34,483 38,600 45,000 41,000 Solids (TDS)
(48) The overall electrochemical reaction conditions for the generation of NaOCl from seawater in a CTE system are listed in the Background section of this disclosure in equation sets A1 and A2.
(49) The major reaction product at the anode of a CTE system generating NaOCl from seawater is Cl.sub.2. Anode current and the concentration of NaCl in solution regulate the rate at which Cl.sub.2 is produced, which in turn determines the amount of NaOCl formed in solution. The amount of NaOCl formed relative to the volumetric flow rate of the system dictates the overall product strength.
(50) The major reaction products at the cathode of a CTE system generating NaOCl from seawater are H.sub.2 and OH.sup.−. Current, and therefore cathode current density, regulates the rate at which they are produced, and those production rates impact pH within the system.
(51) Although the bulk pH of seawater is generally 7.5-8.4, the kinetics of the above reactions, along with other factors, drive pH within the system.
(52) Above its solubility, H.sub.2 will outgas as it is produced in a CTE cell, displacing fluid volume and blinding the cathode. Decreasing the local fluid volume while maintaining the same OH.sup.− production rate will increase local pH at the cathode.
(53) Local OH.sup.− concentration at the cathode of a CTE cell is also a function of velocity, since turbulence, and therefore mixing, are a function of velocity. Decreasing the flow rate will therefore also increase the local cathode pH.
(54) At a pH threshold of 8, seawater is supersaturated with CaCO.sub.3. At a pH threshold of 10.7-11, Mg(OH).sub.2 begins to form. Both of these species will impair the performance of a CTE cell.
(55) Varying the concentrations of Mg.sup.2+ and Ca.sup.2+ in solution will also impact both the rate and amount of precipitate formation.
(56) Variations in the TDS of the process stream will affect its conductivity, and thus the overall power consumption of an electrolyzer, since cell voltage and conductivity are inversely related.
(57) A current Evoqua state of art CTE cell is shown in
(58) At a flow velocity of 2-3 m/s, a system as illustrated in
(59) For these feed conditions, NaOCl output concentrations between about 2,000 ppm and about 3,000 ppm are achievable. Again, this product strength is theoretically limited by the rate of precipitate formation and by the amount of NaCl in solution. To improve the performance of an electrochlorination system, one may, for example: Mitigate precipitation (via pH regulation or Mg.sup.2+/Ca.sup.2+ removal); and/or Increase the concentration of NaCl in the feed stream
Regulation of Process Stream Composition
(60) Techniques exist to compensate for divalent hardness and/or enhance monovalent salt concentrations. For systems as described above, however, many processes are impractical. Examples of both suitable and unsuitable processes are listed below.
(61) Unsuitable:
(62) Anti-scalant dosing: Reagent cost for the mass to be treated is prohibitive Chelation: Reagent cost for the mass to be treated is prohibitive Distillation: Energy costs to treat the required volumes are prohibitive Electrodeionization (EDI): Requires a low hardness feed, outside of the process range Ion exchange: Requires manned operation; cost and hazardous nature of regenerative chemicals is prohibitive Lime softening/Clark's process: Requires manned operation; mass for treatment and sludge disposal costs are prohibitive Magnetic water treatment (AMT): Unproven process, with little supporting data.
Suitable: Acid dosing: Acid injection can reduce pH, which may mitigate scale formation Capacitive Deionization (CAPDI): Can reduce divalent and enhance monovalent ion concentrations; relatively low energy (cyclical adsorption/desorption) Nanofiltration/Reverse osmosis: Can reduce divalent ion concentrations, with a concurrent reduction in monovalent ion concentrations; relatively low energy Electrodialysis (ED): Can selectively transport monovalent ions and/or generate acid
Non-Limiting Embodiments
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(64) In this configuration, monovalent ion concentrations may be reduced by roughly 2-10%, while divalent ion concentrations may be reduced by roughly 50-90%.
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(68) In the system of
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(70) A controller used for monitoring and controlling operation of the various elements of embodiments of the systems disclosed herein may include a computerized control system. Various aspects of the controller may be implemented as specialized software executing in a general-purpose computer system 1000 such as that shown in
(71) The output devices 1010 may also comprise valves, pumps, or switches which may be utilized to introduce product water (e.g. brackish water or seawater) from the feed source into an electrochlorination system as disclosed herein or a point of use and/or to control the speed of pumps. One or more sensors 1014 may also provide input to the computer system 1000. These sensors may include, for example, pressure sensors, chemical concentration sensors, temperature sensors, fluid flow rate sensors, or sensors for any other parameters of interest to an operator of an electrochlorination system. These sensors may be located in any portion of the system where they would be useful, for example, upstream of point of use and/or an electrochlorination system or in fluid communication with a feed source. In addition, computer system 1000 may contain one or more interfaces (not shown) that connect computer system 1000 to a communication network in addition or as an alternative to the interconnection mechanism 1006.
(72) The storage system 1012, shown in greater detail in
(73) The computer system may include specially-programmed, special-purpose hardware, for example, an application-specific integrated circuit (ASIC). Aspects and embodiments disclosed herein may be implemented in software, hardware or firmware, or any combination thereof. Further, such methods, acts, systems, system elements and components thereof may be implemented as part of the computer system described above or as an independent component.
(74) Although computer system 1000 is shown by way of example as one type of computer system upon which various aspects and embodiments disclosed herein may be practiced, it should be appreciated that aspects and embodiments disclosed herein are not limited to being implemented on the computer system as shown in
(75) Computer system 1000 may be a general-purpose computer system that is programmable using a high-level computer programming language. Computer system 1700 may be also implemented using specially programmed, special purpose hardware. In computer system 1000, processor 1002 is typically a commercially available processor such as the well-known Pentium™ or Core™ class processors available from the Intel Corporation. Many other processors are available, including programmable logic controllers. Such a processor usually executes an operating system which may be, for example, the Windows 7, Windows 8, or Windows 10 operating system available from the Microsoft Corporation, the MAC OS System X available from Apple Computer, the Solaris Operating System available from Sun Microsystems, or UNIX available from various sources. Many other operating systems may be used.
(76) The processor and operating system together define a computer platform for which application programs in high-level programming languages are written. It should be understood that the invention is not limited to a particular computer system platform, processor, operating system, or network. Also, it should be apparent to those skilled in the art that aspects and embodiments disclosed herein are not limited to a specific programming language or computer system. Further, it should be appreciated that other appropriate programming languages and other appropriate computer systems could also be used.
(77) One or more portions of the computer system may be distributed across one or more computer systems (not shown) coupled to a communications network. These computer systems also may be general-purpose computer systems. For example, various aspects of the invention may be distributed among one or more computer systems configured to provide a service (e.g., servers) to one or more client computers, or to perform an overall task as part of a distributed system. For example, various aspects and embodiments disclosed herein may be performed on a client-server system that includes components distributed among one or more server systems that perform various functions according to various aspects and embodiments disclosed herein. These components may be executable, intermediate (e.g., IL) or interpreted (e.g., Java) code which communicate over a communication network (e.g., the Internet) using a communication protocol (e.g., TCP/IP). In some embodiments one or more components of the computer system 200 may communicate with one or more other components over a wireless network, including, for example, a cellular telephone network.
(78) It should be appreciated that the aspects and embodiments disclosed herein are not limited to executing on any particular system or group of systems. Also, it should be appreciated that the aspects and embodiments disclosed herein are not limited to any particular distributed architecture, network, or communication protocol. Various aspects and embodiments disclosed herein are may be programmed using an object-oriented programming language, such as SmallTalk, Java, C++, Ada, or C #(C-Sharp). Other object-oriented programming languages may also be used. Alternatively, functional, scripting, and/or logical programming languages may be used, for example ladder logic. Various aspects and embodiments disclosed herein are may be implemented in a non-programmed environment (e.g., documents created in HTML, XML or other format that, when viewed in a window of a browser program, render aspects of a graphical-user interface (GUI) or perform other functions). Various aspects and embodiments disclosed herein may be implemented as programmed or non-programmed elements, or any combination thereof.
EXAMPLE
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(80) In this setup, a 3.5% Instant Ocean® synthetic seawater solution (
(81) Per the background discussion, it is believed that venting H.sub.2 would prevent cathodic blinding, thus maintaining the local pH near the bulk value and mitigating Mg(OH).sub.2 scale. As confirmation, the bulk pH was measured to be between 8.6 and 8.8, and no observable precipitation was formed.
(82) After sustained operation, the NaOCl product strength was measured via iodometric titration. Product strengths between about 750 and 6,200 ppm (
(83) It is anticipated that, through the regulation of feed stream composition, the aspects and embodiments disclosed herein would be able to achieve similar or greater performance
(84) The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term “plurality” refers to two or more items or components. The terms “comprising,” “including,” “carrying,” “having,” “containing,” and “involving,” whether in the written description or the claims and the like, are open-ended terms, i.e., to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of” and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as “first,” “second,” “third,” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.
(85) Having thus described several aspects of at least one embodiment, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Any feature described in any embodiment may be included in or substituted for any feature of any other embodiment. Such alterations, modifications, and improvements are intended to be part of this disclosure, and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only.