Methods, devices and systems for efficiently producing and / or distributing ferrate

Abstract

This disclosure provides techniques for efficient generation of concentrated ferrate, and for effective storage, distribution and use of that concentrated ferrate. In one embodiment, an electrochemical cell uses a low-carbon steel anode and a galvanostat to transfer iron to a reaction medium at a constant rate, to sustainably produce super-concentrated ferrate of consistent concentration. The ferrate can then be frozen (e.g., to less than negative 28 degrees Celsius) to arrest ferrate decomposition, and the ferrate can be stored or distributed in this state. Specific embodiments provide for local or remote treatment methods and service bureau generation methods.

Description

METHODS, DEVICES AND SYSTEMS FOR EFFICIENTLY PRODUCING AND / OR DISTRIBUTING FERRATERELATED APPLICATIONS

[0001] This disclosure claims the benefit of US Provisional Patent Application No. 63 / 647159, filed on behalf of first-named inventor Vladimir Dozortsev on May 14, 2024, for "Techniques For Electrolytic Ferrate Reagent Generation," and US Provisional Patent Application No. 63 / 760058, filed on behalf of first-named inventor Vladimir Dozortsev on February 18, 2025, for "Methods And System For Ferrate Generation." Each aforementioned patent application is hereby incorporated by reference, as is US Patent No. 11,530,143.BACKGROUND

[0002] Ferrate is a potent oxidizer which is sometimes used for sanitization and certain industrial and agricultural applications; it is typically considered a "green" chemical because it has a short half-life and produces chemical reaction byproducts that are relatively safe and typically insoluble.

[0003] One suitable application of ferrate is to the treatment of water, both potable water and waste water; ferrate, for example, can be used to kill viruses and bacteria, to neutralize (oxidize) undesired organics, and to cause unwanted and / or dangerous metals or other materials to react chemically and become insoluble, enabling their separation from the water. Ferrate can also be used to remove other substances (e.g., hydrogen sulfide) to make water more palatable. These same or similar types of processes can be used to treat other fluids and substances, including without limitation industrial coolants. For example, ferrate can be used to perform periodic reconditioning of these fluids, to improve pipe conditions, and to otherwise process fluid for recycling or release. Ferrates can also be used in batteries, to enhance certain chemical reactions, in soil treatment, and a range of other applications. Once spent in a reaction, ferrate typically is converted to simple rust; if this conversion happens in a liquid, the rust simply and quickly settles out of solution.

[0004] However, as mentioned, ferrate typically has a very short half-life, i.e., it decomposes quickly, often in minutes. Techniques do exist for shipping ferrate in a d ried / crystal I ine form, and then mixing this form into solution, but ferrate decomposes so quickly that even this process is of limited utility; the end result is that ferrate typically cannot be inexpensively and reliably manufactured, transported to locationswhere it is to be used, stored for any period of time and then applied; consequently, ferrate is typically underutilized, despite the applications and associated needs referenced above.

[0005] What is needed are techniques for more-readily producing, storing and / or distributing ferrate. For example, an ability to easily produce ferrate in-situ or otherwise locally, in sufficient quantities, can potentially overcome the difficulties associated with transport and storage, and associated decomposition. In addition, and / or instead, if suitable techniques were developed which permitted effective production, storage, transportation and / or shipping of ferrate, in a manner that reduced the tendency of ferrate to decompose, such would greatly improve both the efficacy of this useful chemical as well as its range of applications.

[0006] The present invention addresses one or more of these needs and provides further related advantages.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] FIG. 1 is a block diagram showing some of the optional features used in various embodiments disclosed herein. As noted elsewhere herein, it is contemplated that these optional features can be mixed and matched in any permutation or combination, whether or not explicitly called out below as a highlighted individual embodiment.

[0008] FIG. 2A is an illustrative view which shows one embodiment of an electrolysis-based ferrate generation system.

[0009] FIG. 2B is a block diagram showing another embodiment of an electrolysis-based ferrate generation system.

[0010] FIG. 3A is a perspective view which illustrates electrode arrangement in one embodiment of an electrochemical cell, namely, in which an electrode slowly dissolves in solution, under the influence of current, transferring electrolyzed metal to that solution.

[0011] FIG. 3B is a plan view of another embodiment of an electrochemical cell in which an electrode slowly dissolves in solution, under the influence of current, thereby transferring electrolyzed metal to solution.

[0012] FIG. 3C is an illustrative, perspective view which shows electrode arrangement and chemical processes.

[0013] FIG. 3D is a magnified plan view of a portion of an electrochemical cell; FIG. 3D is used to illustrate various gaps and distances which characterize electrode juxtaposition and consequent cell performance.

[0014] FIG. 3E is a plan view of another embodiment of an electrochemical cell; four dashed-line circles correspond to the position of ultrasound transducers, which are used in this embodiment to depassivate one or more of the electrodes.

[0015] FIG. 3F is a view of the electrochemical cell of FIG. 3E, taken from the perspective of arrows F-F in FIG. 3E.

[0016] FIG. 3G is an end-view of another embodiment of an electrochemical cell; in this embodiment, a gravity-fed trap 392 is used to collect sludge, generally rust and salts which precipitate out of solution.

[0017] FIG. 3H is a view of the electrochemical cell of FIG. 3G, taken along arrows H-H in FIG. 3G.

[0018] FIG. 4A is a block diagram of an electrolysis system which relies on multiple electrochemical cells, 403a-403n, arranged in parallel.

[0019] FIG. 4B is a plan view of a specific multicell embodiment in which cells are mounted side-by- side.

[0020] FIG. 4G is a plan view of another multicell embodiment in which cells mounted side-by-side.

[0021] FIG. 4D is a block diagram of a multicell embodiment in which electrochemical cells 403a-403n are arranged in series.

[0022] FIG. 5A is a plot showing steel anode composition effect (in terms of presence of silicon in the electrode) on ferrate generation efficiency; a first data set, represented by curve / line 503, shows electrolysis efficiency as a function of silicon composition of the dissolving anode, while a second data set, represented by curve / line 502, represents electrode passivation; for example, in the depicted embodiment, silicon presence in a dissolving steel anode of greater than about 3% was found to strongly inhibit electrode passivation, and thereby enhance electrolysis efficiency.

[0023] FIG. 5B is a plot representing ferrate generation efficiency as a function of reagent concentration; in this case, the reagent is NaOH (sodium hydroxide).

[0024] FIG. 5C is a plot showing reagent temperature effect on ferrate generation efficiency; once again, a second data set, represented by curve / line 532, represents electrode passivation (e.g., in the depicted embodiment, reagent temperatures of greater than about 17 degrees Celsius (C) were found to strongly inhibit electrode passivation, and thereby enhance electrolysis efficiency).

[0025] FIG. 5D is a plot showing current density effect on ferrate generation efficiency; once again, a second data set, represented by curve / line 542, represents electrode passivation (e.g., in the depicted embodiment, current densities of greater than about 40 milliamps per square centimeter (mA / cm2) were found to promote passivation, and thereby detract from electrolysis efficiency).

[0026] FIG. 6 is a block diagram showing techniques for controlling electrolysis to consistently produce concentrated output of a target substance, e.g., using a galvanostat.

[0027] FIG. 7 is a block diagram showing service bureau provision of ferrate related services to one or more clients.

[0028] FIG. 8 is a block diagram associated with treatment of an aqueous matrix or other substance using concentrated ferrate, e.g., from a refrigerated (or frozen) supply 809.

[0029] FIG. 9 is a block diagram showing administration or dosing of concentrated ferrate from a frozen or refrigerated source (e.g., from a modular consumable 907 contained with a refrigeration unit).

[0030] The subject matter defined by the enumerated claims may be better understood by referring to the following detailed description, which should be read in conjunction with the accompanying drawings. This description of one or more particular embodiments, set out below to enable one to build and use various implementations of the technology set forth by the claims, is not intended to limit the enumerated claims, but to exemplify their application. Without limiting the foregoing, this disclosure provides several different examples of (1) a ferrate product and its associated media, (2) techniques for efficient generation of concentrated ferrate and (3) techniques for the enhanced preservation, distribution and use of concentrated ferrate. Other related techniques / benefits / applications will become clear from the description provided below. These various techniques can be embodied as software / firmware, in the form of a product (i.e., a ferrate containing substance), a computer, a device, a local service, a cloud service, a system, a localized or distributed network of multiple systems, anelectrolytic cell or system based on one or more such cells, a dosing or treatment system (or method), a consumable for one or more of the foregoing (e.g., a modular replacement anode having specific constituency), or in some other manner. While specific examples are presented, the principles described herein may also be applied to other systems, applications, methods and devices as well.DETAILED DESCRIPTIONI. INTRODUCTION.

[0031] This disclosure presents a number of different inventions which can be used together, in the alternative, or in any desired combination. The embodiments below are example implementations only. It is specifically contemplated that the individual components of the various embodiments described below can be mixed and matched in any desired permutation and / or combination, regardless of whether they are presented together in a single, dedicated FIG or integrated, focused discussion.

[0032] One embodiment provides a system and / or related techniques for efficiently producing ferrate. An electrolysis system uses a low-carbon steel anode in an electrochemical (e.g., electrolytic) cell. A potential difference having defined parameters is regulated between the anode and a cathode, and a current is created, in solution, which causes the anode to dissolve as iron is slowly electrolyzed into solution from the anode; the chemistry of the solution is chosen such that a reaction occurs in solution, to form ferrate, and such that the ferrate does not overly react with material in that solution. To these ends, the solution, sometimes called a "reaction media," "reagent" or "analyte" herein, is selected to be a relatively strong base, which helps to preserve the ferrate as it is generated (i.e., ferrate typically reacts with and / or decomposes rapidly in the presence of water and / or an acidic environment). Specific cell design and / or regulation parameters can be used such that the reaction media does not react with cell materials and such that the electrode(s) does(do) not passivate, thereby becoming increasingly less effective. Techniques such as appropriate control / regulation over (a) temperature, (b) pH, (c) voltage, (d) current, (e) current density, (f) flow rate and / or analyte residence time, (g) electrode health (i.e., the buildup and cleaning / removal of surfactants, and the replacement of degrading / degraded electrodes) are all optional techniques that can be applied to enhance this electrolysis, in any combination or permutation. This is to say, some or all of these techniques can be employed in combination to not only generate ferrate, but to repeatably, reliably, and on a cost-effective basis, facilitate the generation of super-concentrated ferrate in a predictable, sustainable manner; this ability, in turn, enhances the manufacturability and / or application of the ferrate, e.g., it renders it easier to produce the ferrate ondemand, under machine control, in-situ, and / or to distribute that ferrate all while avoiding or minimizing decomposition. In one optional embodiment, the reaction mixture is heated to a temperature that more efficiently produces ferrate in a highly-concentrated form, e.g., to thirty-eight-to-forty-five degrees Celsius. In another optional embodiment, the voltage is regulated in dependence on anode-cathode separation with a relatively constant current control, e.g., using a specific anode current density of between four milliamps per square centimeter and thirty-six milliamps per square centimeter (mA / cm2), once again, helping efficiently produce ferrate in a highly-concentrated form. In yet another optional embodiment, cell parameters, such as voltage, current, electrolyzed iron concentration, ferrate concentration, pH and / or other parameters are monitored, in order to automatically ascertain anode health or remaining lifetime. This is to say, as the low-carbon steel (or other iron source) slowly dissolves as part of the electrolysis, the anode-cathode separation widens, and the cathode becomes smaller and / or thinner, and optimal cell control parameters can consequently change; the monitoring of electronic and other parameters permits a system to automatically alert an operator when it is time for maintenance or to order a new electrode, and it permits the system to automatically switch "off" a particular electrochemical cell used for ferrate generation. Similarly, in yet another optional embodiment, one or more ultrasonic transducers can be used to clean one or more of the electrodes to help maintain optional ferrate production. In yet other optional embodiments, a system can be scaled and used for localized and / or on-demand ferrate production. Note that a single, dedicated anode / cathode arrangement is not required for any embodiment, e.g., in one embodiment, there can be multiple anodes and / or cathodes in a single cell or multiple cells, and in another embodiment, an anode and cathode can be made of the same or similar material and change rolls, e.g., with current polarity intermittently being reversed.

[0033] To provide some nonlimiting examples, a hypothetical factory seeking to treat and recycle a 50,000L (liter) tank of waste water can, each time this tank is full, dynamically switch 'on' a ferrate- generating electrolysis system to generate super-concentrated ferrate on-demand, with this ferrate then being added to the tank; the ferrate reacts immediately or near immediately, e.g., in minutes, depending on environmental factors. Generally speaking, dosage needed, and whether follow-on doses are needed, can vary depending on application; a particular bacteriological treatment process might call for dosage sufficient to provide 1 part-per-million (1 PPM) in fluid in the tank, whereas removal of a toxic metal such as soluble chromium, lead, arsenic, copper or other metals in the same tank might require 5PPM. Some applications might also involve incremental dosing, e.g., addition of ferrate to achieve a ferrate concentration of 1PPM in a tank, with testing 30 minutes later to determine when a particular result hasbeen achieved, and with repeated cycles as necessary (e.g., one hypothetical result might be "no more than 1.0 part-per-bill ion ( PPB) or either lead or chromium remaining in drinking water", or "no remaining detected bacteria," etc.). The ferrate is generally speaking more useful than alternative treatment chemicals (e.g., chlorine) for some applications, as ferrate reacts with a much greater range of undesired materials, it breaks down quickly, and its by-products are generally much safer for the environment and much less harmful to human health.

[0034] Note that the in-situ processes referenced in this disclosure typically produce concentrated ferrate in concentrations exceeding may thousands PPM, e.g., 25,000 PPM or greater; the hypothetical factory seeking to treat a 50,000L tank to obtain a 1 PPM concentration of ferrate in the tank would need to generate only 2.0L of 25,000 PPM-concentrated ferrate (10L *25,000 PPM = 50,000L * 5 PPM). Note that the various embodiments described herein can be scaled to quickly produce ferrate in these, or indeed, any other desired quantities. Note also that while these specific examples suggest batched ferrate generation and / or treatment, it is also contemplated that implementations can be designed for continuous and / or throttled ferrate generation or treatment, e.g., variable-rate generation and / or consumption.

[0035] In one embodiment, a specific electrochemical cell design can use a cation exchange membrane positioned between an anode and a cathode. In addition, and / or instead, the electrochemical cell can be designed and / or structured to have various design parameters, such as gaps, sizes, heights and other dimensions, inlet / outlet positioning, materials and flow engineering, multiple electrodes, doubleduty electrodes, and so forth, to enhance or optimize ferrate production and / or concentration in the reaction product. Other system parameters, such as use a galvanostat (which automatically adjusts voltage to maintain a constant current flow as electrode mass changes and anode-cathode distances change), use of parallel electrochemical cells can also be used to enhance ferrate production. When these features are used in combination or permutation, the ability to produce ferrate in-situ, for localized consumption, becomes both feasible and cost effective, enabling the production of concentrated ferrate which can then be applied as needed.

[0036] Yet another embodiment provides methods and systems for producing ferrate for later usage, long term storage and / or remote shipping or application. In this regard, ferrate typically breaks down quickly, but the inventors have found that immediately chilling and / or freezing concentrated ferrate in a suitable medium slows and / or completely arrests degradation. Accordingly, one embodiment produces concentrated ferrate in predetermined volumes, where a chiller and / or freezer is used an in-line part ofthe production process. Generated ferrate can then be produced, in one nonlimiting example, much like a "tray of ice cubes;" a consumer stores frozen, super-concentrated ferrate in set volumes and, as treatment is needed, that consumer simply adds the required number of cubes to a target that is to be treated so as to achieve required dosing. These general techniques can optionally be implemented on an automated and / or service bureau basis, in which super-concentrated, frozen is selectively applied locally or shipped to customers for a fee. For example, 25000 PPM ferrate of the type produced by the techniques of this disclosure freezes solid at approximately minus twenty-eight degrees Celsius (C), at which point the degradation process is arrested virtually indefinitely. Produced serially or an arrayed group of predefined consumable volumes (e.g., 1.0 milliliter ("mL") to 2.0 liters each, as nonlimiting examples), the frozen ferrate can be ordered and shipped to consumers on demand, e.g., overnight, on dry ice or in another suitably-refrigerated / frozen manner, for application at the customer's discretion or by an automated dosing system. A small manufacturer, for example, needing to treat a 5000L tank of fluid with 1.0 PPM ferrate can be shipped a 200mL vial of frozen 25,000 PPM concentrated ferrate for immediate application / treatment on receipt or for later use. As should be appreciated, these techniques can be advantageously applied in situations where ferrate consumption is not sufficiently regular to justify the local presence of a ferrate generation system.

[0037] While some consumers of concentrated ferrate will have lower consumption needs, there will also exist consumers with much greater needs, for example, requiring many liters per day of concentrated ferrate for industrial applications, for large scale water treatment or for other applications. As noted earlier, the techniques introduced herein can be scaled, both in terms of electrochemical cell size and number (e.g., relying on use of numerous electrochemical cells), for localized, short term and / or commercial consumption.

[0038] Because ferrate decomposes very quickly, with a short half-life at room temperature (e.g., 20 degrees Celsius), and because ferrate treatments under normal conditions result in production of relatively safe byproducts (e.g., ferric oxide or "rust"), easily separated from solution, the techniques provided herein enable much more widespread use of ferrate and much more aggressive use of "green" treatment processes.

[0039] Note that there exist embodiment which do not use a steel anode, which do not use NaOH as a reaction medium, and which do not produce ferrate; alternate embodiments combine some or all of the techniques set forth above with techniques from US Patent No. 11,530,143 ("the '143 Patent"), which has been incorporated by reference; the '143 Patent relates to a tin electrolysis system. When combined withtechniques from this disclosure, an electrolysis system using an anion exchange membrane and a hydrochloric (HCL) acid solution, using the same or similar parameters to those discussed herein, is used to efficiently produce high-concentrations of stannous material. Extending this example further, an anode made out of food grade tin and using a similar cell design to that introduced below, but with an anion exchange membrane and, e.g., 20% HCL, can be used to produce super-concentrated stannous material in solution; when combined with the optional refrigeration / freezing techniques, it is believed that this process can similarly provide for stannous concentrations not thought possible with conventional techniques, one again, being amendable to service bureau models, e.g., as discussed herein in the case of ferrate.

[0040] These and other advantages will be apparent from the various systems and elements described below. It is again noted that suitable permutations and combinations of elements described below enable much more efficient production of concentrated ferrate than has previously been possible, enabling, as a practical matter, the localized production of ferrate for in situ application; additionally, the combination of concentrated ferrate production processes, with suitable production methods and controls over reaction media and ferrate storage, e.g., chilling and / or freezing the ferrate, also facilitate on-demand production on a batched basis for later use and / or for effective storage and shipment.

[0041] Prior to proceeding to this additional description, however, it would be helpful to first discuss several specific terms. Firstly, it should be understood that contemplated embodiments can include "hardware logic," "circuits" or "circuitry" (each meaning one or more electronic circuits). Generally speaking, and unless otherwise specified, these terms can include analog and / or digital circuitry, and can be, in nature, special purpose or general purpose. For example, as used herein, the term "circuitry" for performing a particular function can include one or more electronic circuits that are either "hard-wired" or are configurable circuits to perform the stated function (i.e., in some cases without assistance of instructional logic), and the term can include a microcontroller, microprocessor, FPGA or other form of processor which is general in design but which runs software or firmware (e.g., instructional logic) that causes or configures general circuitry (e.g., configures or directs a circuit processor) to perform the particular function. Note that as these statements imply, "circuits" and "circuitry" for one purpose are not necessarily mutually-exclusive to "circuits" or "circuitry" for another purpose, e.g., such terms indicate that one or more circuits are configured to perform a function, and one, two, or even all circuits can be shared with "circuitry" to perform another function (indeed, such is often the case where the "circuitry" includes a processor); this is to say, "circuitry to perform (function X)" and "circuitry to perform (function Y)" can encomoass exactlv the same circuitry or respective circuits, depending on implementation.Related to these points, the term "logic" can encompass hardware logic, instructional logic, or both, unless otherwise specified. Instructional logic can be code written or designed in a manner that has certain structure (architectural features) such that, when the code is ultimately executed, the code causes the one or more general purpose machines (e.g., a processor, computer or other machine) each to behave as a special purpose machine, having structure that performs, upon occurrence of defined events, described tasks with respect to processing operands, or else take specific actions or produce specific outputs. Generally speaking, circuits and / or processes described herein can, in some embodiments, be implemented as instructional logic (e.g., as instructions stored on non-transitory machine-readable media or other software logic), as hardware logic, or as any combination or permutation of these things, depending on embodiment or specific design. In connection with various embodiments herein, the term "device" is used to refer to an electronic product (e.g., based in, but not limited to, a chip, system, or board) with circuitry and possibly, but not necessarily, resident software or firmware; examples of a 'device' include, without limitation, a server, an end consumer product, a computer, a smart phone, an integrated circuit, a die, an electronic board, and / or other manifestations. "Non-transitory," to the extent used herein, refers to any tangible (i.e., physical structure) medium or mediums, irrespective of the type of technology used to express data on that medium and irrespective of the format of data storage; for example, in one case, a particular expression can be optically stored on physical media, and in another case, the particular expression can be magnetically stored on physical media. Thus, when applied to storage and / or computer-readable and / or machine-readable subject matter, the term "non-transitory" indicates that data and / or instructions can be stored on such a physical structure storage medium using optical, magnetic, electronic, resistive and / or other storage formats / technologies, i.e., where some type of physical device, including without limitation, random access memory, hard disk memory, optical memory, a floppy disk, a compact disk ("CD"), a solid state drive ("SSD"), server storage, volatile memory, and / or nonvolatile memory, i.e., a physical thing, is used as the storage medium. Each such medium and / or device can be in standalone form (e.g., a program disk or solid state device, or mass storage servicing an "app store") or embodied as part of a larger mechanism, for example, resident memory that is part of an electronic device such as a smart phone, computer, digital television, automobile, portable device, chip-card, dongle, server, printer, etc., or embodied as one or more such devices. "Instructions" can be implemented in different formats, depending on embodiment; for example, instructions can take form as metadata that when called is effective to invoke a certain action, as Java code or web scripting, as code written in a specific programming language (e.g., as C++ code), as a processor-specific instruction set, or in some other form. Depending on design, the instructions can also be executed by the same processor, different processors or processor cores, FPGAs or other configurable circuits, for example,being adapted for execution by a single computer in some cases, and in other cases, being adapted for execution on a distributed basis, e.g., using one or more servers, web clients, or application-specific devices, not necessarily all operating at the same time. "Module" as used herein refers to a structure (e.g., hardware, or software, or both) dedicated to a specific function; for example, a "first module" to perform a first specific function and a "second module" to perform a second specific function, when used in the context of instructions (e.g., computer code), refers to mutually-exclusive code sets. When used in the context of mechanical or electromechanical structures (e.g., an "encryption module," the term "module" refers to a dedicated set of components which might include hardware and / or software, depending on the purpose of that module). In all cases, the term "module" is used to refer to a specific structure for performing a function or operation that would be understood by one of ordinary skill in the art to which the subject matter pertains as a conventional structure used in the specific art, and not as a "generic placeholder" or "means" for "any structure whatsoever" (e.g., "a team of oxen") for performing a recited function (e.g., "encryption of a digital input"). The term "integrated circuit" (or "IC") typically refers to a structure having at least one die, packaged or otherwise, and, as implied, a single IC and / or die can also be a type of electronic "device." The term "low-carbon" (i.e., in the context of steel) refers to steel having an carbon constituency of less than one-third percent (0.0033); such steel typically has at least 50% iron constituency and it may have other materials presence, for example (but not by limitation), magnesium, metal, copper, lead or other metals or substances. "Passivation" or "passivate" when used in connection with an electrode or electrolytic reaction refers to a tendency of an electrode to become befouled with a layer of chemical scale, oxidation and / or other material, which reduces current flow or otherwise compromises electrolysis efficiency; when this happens, it is generally desired to "de-passivate" the affected electrode, to clean or remove this layer, or to otherwise renew it so as to return it to a higher state of efficiency. "Refrigerated" or "chilled" as used herein refers to any type of cooling, including by way of example but not limitation, freezing a liquid; unless otherwise specified, any type of refrigerator or chiller can be used, e.g., a liquid heat exchange system, an ice bath or similar immersion system, a concentric flow system, a Seebeck-effect chiller and / or, indeed, any type of cooling system. Conversely, "heated" or "heating" as used herein refers to any temperature elevation, for example, heating concentrated ferrate from a "frozen" temperature of minus twenty-eight degrees Celsius to a cold-but- liquid state at minus ten degrees Celsius; again, any type of suitable device can be used, including without limitation, and electric heater, a Seebeck-effect heater, a heat exchange system, etc. "Concentrated" and "super-concentrated" are generally used herein interchangeably and, in the context of ferrate or stannous material, refer to ferrate concentrations and / or stannous concentrations that are much higher than doses of diluted ferrate in a substance to be treated, i.e., generally in the realm of thousands PPM (parts-per-million). "Efficiency," when used in connection with electrolysis or reagent generation efficiency, refers to how easily and / or how completely metal from a dissolving electrode forms a desired end product material; for example, in the case of ferrate generation, it can be a function of ferrate concentration in the reaction product per unit of dissolved electrode material and / or per unit of applied electric power - as this statement implies, it can be a function of one of or both of (1) ratio of a desired product out per unit of input material (e.g., electrode material), and / or (2) quantity of desired product out per unit of energy used (e.g., applied electric power). "Reagent" as used in the expression "reagent generation efficiency" refers to ferrate (or stannous material in the case of tin electrolysis), but note that "reagent" is also sometimes used herein to refer to a substance provided to foster a chemical reaction, e.g., it is also sometimes used to refer to the reaction mixture (e.g., an acid in the case of stannous production and a base, e.g., NaOH, in the case of ferrate production).

[0042] The meaning of other terms used herein should be clear based on context. Note that, to the extent that any document is incorporated herein by reference, the definitions of this document should be understood to predominate over any inconsistent definitions provided by such incorporated-by-reference documents with respect to the subject matter discussed herein. It is again emphasized that it is expressly contemplated that the various elements discussed above or below, in any embodiment, can be used in any desired permutation or combination regardless of specifically illustrated together in a single common figure or example discussed below. Selection and / or omission of structures for any given design or application is within the level of ordinary skill in the art, and none of the elements / structures discussed below are to be deemed "essential" for any purpose or function.II. FERRATE GENERATION, DISTRIBUTION AND / OR USE SYSTEMS GENERALLY.

[0043] FIG. 1 shows various embodiments which can be used independently or together to provide ferrate generation, distribution and / or treatment; various components of one or more of these embodiments are generally designated by 101.

[0044] One embodiment provides a ferrate-generating electrolysis system 103; as indicated by text at the right side of the FIG., this system can optionally be rooted in an electrochemical cell and associated reaction control which are geared to produce super-concentrated ferrate, e.g., a reaction product having a ferrate concentration of 25,000 parts-per-million (PPM) or potentially greater. One optional feature of such an electrolysis system is a galvanostat which maintains a constant current flow between electrodes (at least one anode and at least one cathode). The anode can optionally be made of low-carbon steelhaving a silicon constituency of between 3.5-8.0 percent; the cathode can optionally be formed of highgrade stainless steel (e.g., in embodiments which do not use alternating electrode polarity). "Low-carbon" steel is steel having a carbon percentage of less than about one-third percent, which renders this electrode relatively soft (malleable) and amenable to electrolysis, that is, relative to other forms of steel; as is known, this steel can also have trace elements of other metals (e.g., magnesium) although the predominant element present is iron (Fe). Note that as this discussion implies, as the anode electrolytically dissolves (i.e., slowly, under the influence of a current flow), the degrading electrode produces iron ions in solution, as well as free electrons, which migrate to the cathode. While the anode is therefore used as an iron source in this embodiment, in other embodiments, use of contemplated alternate chemistries can feature a dissolving cathode, or a cathode and anode that perform double-duty (e.g., based on alternating current polarity, applied according to a desired duty cycle). Whichever electrode serves as a source of iron, as the electrode dissolves, its mass slowly changes, resulting in a changing gap (distance) between electrodes. To ensure reliable production of ferrate in high concentrations, generally at a target concentration, the galvanostat changes electrode parameters so as to maintain a constant current - for example, as an electrode gap widens, the galvanostat gradually increases the potential difference between electrodes so as to compensate for a greater distance, and it thereby maintains a constant current flow between electrodes (and a constant, predictable rate of iron electrolysis). Note that there are two general embodiments contemplated; a first embodiment, which relies on continuously-flowing analyte, i.e., the liquid reagent is pumped or drawn into the electrochemical cell, and has an average dwell time in that cell, and simultaneously, reaction product having ferrate is drawn or pumped out of a different part of the cell; and / or a second embodiment, which relies on use of a "start / stop" pumping mode, i.e., fresh analyte is pumped or drawn into the cell where it is maintained for a scheduled time (e.g., "20 minutes," depending on embodiment), and where ferrate- rich reaction product is then pumped out at the end of that dwell time and the cell is renewed for a fresh ferrate generation cycle.

[0045] Irrespective, one optional implementation uses a multiple cathode approach, i.e., where an iron-source anode is dissolved evenly on one or more sides; for example, in some embodiments described below, an anode is configured as a plate having opposing flat surfaces, with a cathode juxtaposed opposite each surface; such a configuration produces electrolysis evenly, from both sides of the slowly-dissolving anode plate, resulting in more-even electrode wear and more efficient generation of ferrate. Note that while two cathodes can be used (as represented by text at the right-hand-side of the FIG.), generally speaking, such an embodiment can use an anode having any number of faces (e.g., any type of polyhedralconfiguration) or any number of anodes, with a cathode parallel to each anode face or surface at a relatively constant gap distance - for example, three, four, five, or indeed, any number of cathodes can be used with a common anode, or vice-versa, to facilitate efficient electrolysis. Note again that this configuration is not required, e.g., it is possible to use a single anode and single cathode only and / or a multi-electrolysis cell ("multicell") configuration. In still other contemplated embodiments, a circular or arcuate anode surface can be used, e.g., with a reciprocally-curved cathode surface, so as to provide for a relatively uniform electrode gap over matching anode and cathode surfaces; as a nonlimiting example, concentric anodic and cathodic rods / pipes can be used.

[0046] In some optional implementations, electrochemical cells can further benefit one or more control features which are tuned (given cell design and other system parameters) so as to efficiently produce ferrate; for example, as indicated by the right-hand side of FIG. 1, temperature regulation, pH regulation, current flow parameters (including voltage), specific reagent particulars, flow rate or flow mode, anode makeup, and many other factors can each be tailored to enhance the efficiency of ferrate generation. Some embodiments use several or all of these control features together to reliably produce super-concentrated ferrate on a predicable basis for storage, transportation and dosed application. This is to say, empirical data will be presented below relating to specific ranges of parameters which were specifically found to enhance ferrate generation and resulting ferrate concentrations. Without limiting these parameters / ranges, one embodiment uses a reaction temperature during electrolysis of approximately forty-two degrees Celsius; it was found that heating the reaction mixture, alone or in combination with other factors, to a range encompassing this temperature yielded suitable electrolysis efficiency while simultaneously reducing electrode passivation. Similarly, another embodiment uses a solution of eighteen-to-forty percent sodium hydroxide (NaOH) and / or control over pH (i.e., through optional mixing of a concentrated caustic with a dilution medium) to optimize electrolysis efficiency; generally speaking, it is often desired to use as little caustic and as weak a caustic solution as is feasible and, to this end, it was found that a basic solution corresponding to this range helps minimize electrode passivation while at the same time maximizing ferrate generation efficiency and maximizing half-life of generated ferrate. Note that, in one embodiment, a cell housing (e.g., a frame which holds the anode and cathode) is made of non-reactive material, such as a suitable polymer (polypropylene or another inert plastic material), molded so as to provide a liquid-tight reservoir, as appropriate, or produced from a three-dimensional (3D) printing process. A polymer can be selected which is capable of maintaining chemical resistance in alkalis up to 50% concentrations and ferrate concentrations above 50g / L (grams per liter), as well as elevated temperatures (e.g., 50C). Another embodiment uses an anode currentdensity regulated to a specific value chosen to lie between about 4 and 36 milliamps per square centimeter (mA / cm2), which similarly, was found to maximize ferrate generation efficiency while minimizing electrode passivation. Any of these control features can be used in combination or in combination with other features disclosed herein (e.g., silicon anode constituency of between 3 and 8 percent), each helping to render the electrolysis process still more efficient, and thereby enable the production of an improved, low-cost ferrate reaction product, having very high ferrate concentrations, conventionally thought not possible or practical, through electrolysis.

[0047] Note again that these techniques can be extended to stannous material generation, e.g., using some or all of the particulars of the embodiments introduced above, but with one or more food-grade tin electrodes, a HCL reaction medium, and an anion exchange membrane (e.g., in place of the cation exchange membrane used in some embodiments for ferrate generation).

[0048] FIG. 1 references still other optional features which can be used to provide for reliable, high- quality ferrate production. As again indicated textually in the FIG., one embodiment relies on a cation exchange membrane to help form concentrated ferrate; when interposed between the anode and the cathode, this membrane permits sodium to pass freely through the membrane while blocking the passage of ferrate oxyanions from the an anodic portion of the cell (anodic compartment) to a cathodic portion of the cell (cathodic compartmentO. As these statements imply, the electrochemical cell can be structured such that an anodic compartment defined by an anodic side of the membrane is in fluidic communication with an outlet, used to output a reaction product having super-concentrated ferrate. Other embodiments use one or more electrode maintenance / preservation functions, including but not limited to: the presentation of operator alerts that it is time to clean or replace the anode once it has worn to a certain extent, or to order a new anode as electrode end of life is approaching; automated ultrasound cleaning according to some predefined trigger or duty cycle; operator alerts that it is time to clean or replace a trap or otherwise remove collected precipitate / sediment; and / or the use of automated on-off functions when there is a system fault, as necessary to scale production, or otherwise for maintenance. As part of these functions, a preservation function can optionally be used to clean or renew the cell and / or to immerse the membrane and / or anode in a preservative, to keep the electrodes de-passivated and to preserve membrane permeability and longevity. In some embodiments, the same reagent as is used for electrolysis can also be used for this purpose (e.g., a 20% NaOH solution for ferrate and a 20% HCL solution for stannous material), with or without an optional flush cycle.

[0049] Some implementations can be structured for relatively large scale electrolysis production and, to this end, can utilize multiple electrochemical cells, either in parallel or in series. To this end, a control and sequencing function 105 can be used to automatically perform automated electrolysis cell production scaling control, including the switching, powering, and depowering of individual electrochemical cells and their pump(s) as needed. For example, in a hypothetical environment where the instantaneous need for concentrated metal in solution (e.g., ferrate) varies, a parallel configuration of electrolytic cells can feature multiple individual cells (and associated fluid flow) which are dynamically switched "on" or "off," so as to throttle production; in some implementations, each individual cell produces reaction product having a predetermined, consistent metal concentration (e.g., 25,000 PPM ferrate), with overall reaction product volume being the sum of the outputs of the individually-enabled cells. The sequencing and control function 105 can optionally employ automated functions relating to electrode servicing and operability, for example, automatically taking individual electrochemical cells offline as faults occur or an anode (or optional trap) require servicing. Conversely, a series arrangement of cells might be preferred for some implementations; these options will be discussed further below.

[0050] As denoted by reference numeral 107, one contemplated embodiment is simply as a reaction product having a specific chemical composition, e.g., super-concentrated metal suspended in a suitable longevity medium (e.g., a frozen 18-20% caustic in the case of iron and frozen 18-20% HCL in the case of stannous material). As will be apparent to those having ordinary skill in the art, some portion of the reaction medium is consumed by a chemical reaction which produces e.g., ferrate (i.e., [FeO4]2', is produced by iron which combines with oxygen from the hydroxide), with the result that the reaction medium analyte concentration drops slightly as the ferrate-rich (or stannous-rich) reaction product is formed; for example, if a 20% NaOH reaction medium is used to produce ferrate, a reaction product having super-concentrated ferrate might feature a 18-19% NaOH constituency. One novel form of the teachings herein is therefore a product featuring super-concentrated ferrate suspended in such a medium (e.g., 18- 19% NaOH), or super-concentrated stannous material in the pertinent medium (e.g., 18-19% HCL). Note that other reaction media can also be used, including without limitation, other sources of hydroxide and / or chloride.

[0051] Numeral 107 also references certain optional features related to electrolyzed metal production, storage and longevity. In this regard, one optional implementation of the teachings of this disclosure is in the service bureau-based production of electrolyzed metal product, e.g., ferrate for a disparate client base. To this end, an electrolysis system can be designed to generate super-concentrated ferrate in oredefined batch or volume sizes, for example, as an array of individual volumes of 50mL(milliliters), 250 L, O.SOL(liters), 1.0L, or some other desired size. Whether for service bureau distribution or direct consumption by a producer, ferrate longevity can further be enhanced by immediately refrigerating and / or freezing concentrated ferrate. In this regard, at room temperature, ferrate typically oxides rapidly, with a half-life of minutes to hours depending on conditions. It was earlier mentioned that, with some embodiments, ferrate generation can be enhanced at reaction temperatures of "around" forty- two degrees Celsius; some embodiments therefore feature immediate chilling, refrigeration and / or freezing of a reaction product having concentrated ferrate following extraction from the electromagnetic cell. For example, a reaction product can optionally be directly driven from the outlet of an electrochemical cell through an ice bath or other chiller, thereby enhancing longevity; alternatively, a ferrate mass production system can be designed to produce an array of super-concentrated ferrate "vials," and then to robotically transfer the entire array as a unit to a freezer. [Note that the term "freeze" in this context depends on the ferrate concentration and the makeup of the liquid holding that ferrate - 25,000 PPM ferrate in a 18% NaOH solution "freezes" at about minus 28 degrees Celsius; Note also that "freezing" is not required for all embodiments, e.g., generally speaking, the colder the liquid reaction product, the more half-life is extended - some embodiments can chill generated ferrate without actually freezing it.] By chilling super-concentrated ferrate in its medium, the half-life of the concentrated ferrate can be extended, almost indefinitely in the case of frozen reaction product. As therefore represented in FIG. 1, some implementations feature one or more of: in-line chilling or freezing; batched ferrate generation; bulk / arrayed generation; and / or robotic transfer to a freezer or other refrigeration system. For example, as referenced previously, one hypothetical ferrate generation system can produce "ice cubes" of ferrate, which are then transferred to customers (e.g., shipped with dry ice or in other frozen storage) as part of a service bureau distribution scheme or simply added to a treatment system as desired. Note once again that as part of process 107, such production can be scaled as needed, and that these techniques can also be extended to the production of stannous material, as referenced.

[0052] As denoted by numeral 109, still another independent embodiment of the techniques described herein is in the form of an automated dosing system, for example, a system or method which draws a selected volume from or otherwise administers part a batch of super-concentrated ferrate and applies the particular ferrate volume to a target, to obtain a desired effect. As one nonlimiting example of this, a system receiving a batch of concentrated ferrate (e.g., 50m L of frozen 25,000 PPM ferrate) can maintain this batch in a chilled (e.g., frozen or near-frozen) state, transferring "just enough" of this superconcentrated ferrate to achieve a desired effect. Elaborating, a system dosing a hypothetical 500L tank to 1 PPM ferrate concentration can selectively transfer approximately 2mL of the super-concentrated(25,000 PPM) ferrate to obtain the desired dosage. In still more specific implementations, users of a with dynamic refreezing capabilities can control the selective freezing / thawing of frozen ferrate, for purposes of intermittent use or application, thereby maximizing longevity of any unconsumed, re-frozen concentrated ferrate. Once again, these features are not required for all embodiments. As again textually-noted in FIG. 1, dosing and / or treatment systems are configured in some embodiments to perform dynamic, continuous treatment (for example, dynamically throttling a ratio of superconcentrated ferrate being added to a flowing target via an in-line feed). As with many of the other embodiments described herein, it is contemplated that a dosing management system as just introduced can be used as an embodiment independent of the other techniques introduced by this disclosure, e.g., regardless of whether the specific electrolytic cells and / or ferrate generation systems described herein are also used.

[0053] Finally, as denoted by numeral 111, one embodiment features a method or service for: local or remote management of storage, and / or the administration / dosing of super-concentrated ferrate, and / or the management of their associated systems; service bureau production and / or distribution of super-concentrated ferrate; and / or service bureau supply of replacement consumable specially adapted for one or more embodiments described herein, e.g., including without limitation a low-carbon steel, 6% silicon electrode module fitted for client installation to replace worn electrodes. To cite a number of illustrative example, an entity operating an optional electrolysis-based ferrate generation system can distribute super-concentrated ferrate (e.g., shipped by overnight courier, on dry ice or in other frozen storage) to clients on an ad-hoc or calendared basis. In a variation, local ferrate generation and / or dosing systems can be remote controlled by a service, e.g., via a wide area network (a "WAN," e.g., the Internet); local sensors detect a need for treatment, and an in-situ dosing and / or ferrate generation system is electronically operated by the remote entity, which also monitors one of more of electrode health, depletion of other consumables, treatment conditions and so forth, as appropriate, each via remote communication. A subscriber-client, for example, can pay a service to install a localized dosing system, with periodic resupply of consumables and servicing provided by the service bureau. As further implied by the text of options listed in FIG. 1, a service bureau management system can perform tasks such as account management, order fulfillment and shipping (e.g., offerrate or consumables, such as replacement electrodes for in-situ generation), and in some embodiments, management of a subscription-based service, related to these things; once again, these techniques can also be extended to services relating to stannous material generation, storage, shipment and usage.

[0054] With a number of different embodiments and their associated components thus introduced, this disclosure will now proceed to a discussion of one or more detailed systems. As noted earlier, it is contemplated that these optional features can be mixed and matched in any permutation or combination, whether or not specifically illustrated in combination in a specific one of the FIGs. or specific combinations highlighted below - that is, the individual embodiments described herein are not limiting.III. ELECTROLYSIS SYSTEMS' AND CELL DESIGN.

[0055] FIG. 2A is an illustrative view which shows one embodiment of an electrolysis-based ferrate generation system 201. A container 203 receives a concentrated base / caustic from supply 205 which is mixed into solution, e.g., with distilled water, reverse-osmosis ("RO") water or any other source of appropriate water; as noted earlier, the based can optionally be sodium hydroxide, mixed to form a reaction medium having about twenty percent sodium hydroxide (about 5 molar). The depicted container 203 illustrates presence of a mechanical mixer, but this representation serves as a proxy for any mixing means, whether manual, pump driven, turbulence-driven or otherwise. Alternatively, 20% sodium hydroxide solution can be prepared by blending higher concentration sodium hydroxide solutions with appropriate water at corresponding ratios, e.g., in an automated manner. Reaction medium from the container 203 is then fed via a pump 207 to a heating module 209, which raises temperature of the reaction media to approximately forty-two degrees Celsius, and the media is then fed into the electrolytic cell 211, via an inlet (not called out by reference numeral). Note that many equivalent alternate implementations exist, e.g., including without limitation, embodiments where the cell is heated to thereby heat the reaction mixture, where the analyte is gravity fed or drawn through negative pressure, where the pump is downstream from the electrolytic cell 211, etc.

[0056] The electrolytic cell 211 provides a current and is otherwise managed so as to cause the transfer of metal iron from one or both of the electrodes into the solution, thereby creating a ferrate-rich reaction output or reaction product (e.g., ~18% NaOH having super-concentrated ferrate). This reaction product is then continuously or at stages drawn out of the electrolytic cell via an outlet (also not called- out by reference numeral in this FIG.). This reaction product, in turn, is sampled by an online monitor 213, i.e., a measurement device; depending on embodiment, this monitor can be a temperature sensor, a pH sensor, a voltammetry device which measures NaOH concentration or ferrate concentration, a chromatograph or mass-spectrometer, or some other time of sensing or measurement device. In the specific embodiment of FIG. 2A, the monitor is a mercury-based voltametric device, having a built-in, suitable consumables supply, which doses a drawn sample of reaction product with chemistries that causeiron from the ferrate to migrate to a working electrode and undergo red / ox reaction at the working electrode; such a voltammetry device is capable of measuring, e.g., metal concentrations at a PPM or PPB (parts-per-bill ion) level resolution. See, e.g., commonly-owned US Patent No. 11808728 for a description of a suitable voltammetry device. The reaction product more generally is then directly fed to a chiller, refrigerator or freezer 214, which suppresses ferrate decomposition, enabling the reaction product to be stored or shipped, as conceptually represented by storage icon 215. Naturally, many variations of these elements and their ordering will readily occur to those having skill in the art; for example, and not by limitation, the monitor 213 can be omitted, or feedback / testing can be performed via intermittent manual or other sampling of stored product 215, or a voltammetry device can be used to sample iron generation as it occurs within the electrolytic cell.

[0057] FIG. 2B shows a block diagram of an embodiment 251 of another electrolysis-based ferrate generation system. Once again, this system employs a dissolving iron-based electrode 253 under the auspices of an associated reaction control system 255; this control system operates a pump 257, to supply an electrolytic cell with reaction media at a controlled rate (e.g., flow rate) or set volume and a heater 259 to raise temperature of the reaction media te a level which facilitates efficient electrolysis and high ferrate concentration levels in the reaction product. Generally speaking, the longer the residence time of the reaction media in the presence of electrolysis, the greater the produced ferrate concentration; given some of the various cell parameters discussed in this disclosure, ferrate concentrations of 25,000 PPM or greater were observable with a residence time of approximately forty minutes in a "start / stop" mode electrolytic cell with fixed analyte residence time; naturally, these parameters are dependent on the other various parameters, such that some designs may be able to reduce this residency time, or different values of some of these parameters may be used at the expense of others. Note that, in alternate implementations, the depicted system can be operated in a continuous mode of operation, that is, where analyte is continuously pumped into the electrolytic cell in one location and where ferrate-rich reaction product is continuously pumped out of the cell from an outlet at a different location. In the particular embodiment seen in FIG. 2B, the reaction control system 255 also uses a galvanostat 261 to regulate current through so as produce electrolyzed metal at a consistent rate, and notwithstanding changing electrode dimensions as electrolysis is performed. Whether continuous mode or start-stop mode is used, the reaction control system controls the supply of the reaction media (e.g., 20% NaOH) and extraction of ferrate-rich reaction product, as indicated by reference line 265 for further, optional, treatment or processing. For example, the reaction product can then be refrigerated / frozen, per numeral 267. As indicated by numerals 268 and 269, individual batches of predefined volumes of the reaction product can optionally be separated and / orstored (e.g., as individual supply consumables or "ice cubes") or can be directly used for treatment or other applications. Per numeral 270, any of these processes can be automated and / or robotically controlled via suitable mechanisms / handlers, as suitable to the embodiment.

[0058] FIG. 2B also shows a number of further options, which are generally represented by numerals 271, 272, 273, 275, 277, 278 and 279. A fluid level or other sensor can be used to monitor the supply of base to automatically detect when the reaction media needs to be replaced, for example, refilled with additional reaction medium and / or caustic. Similarly, a temperature or other sensor can be used to identify reaction temperature, with the reaction control system 255 using feedback to the heater to increase or decrease reaction temperature, as appropriate. Similarly, a pH meter can be used to detect sub-optimal caustic levels, and thereby trigger different mixing ratios, fluid flow rates (e.g., pump speed), temperature, and so forth, from the reaction control system. A current / voltage monitor or other monitor of electrical parameters can be used to assess electrode health, for example, computing remaining anode / electrode life expectancy or serviceability from measured current and voltage and possible other factors (such as downstream ferrate concentration as measured by a voltammetry device). In turn, operator alerts and / or signals can be generated, for example, indicating that it is time to replace the anode, clean the electrolytic cell, order a new anode / electrode, and so forth. A level or similar sensor can be used with in vessel which collects reaction product, for example, to determine that a predetermined volume has been collected and that it is time to refrigerate or freeze the collected volume as a discrete, batch or to advance a robotic control mechanism. Again, many possibilities and variations will readily occur to those having ordinary skill in the art.

[0059] Two further optional features of the depicted embodiment are represented by numerals 281 and 283. In this regard, while many embodiments will use a sealed electrolytic cell, it can generally be expected that a ferrate-generating reaction involving caustic will generate gases as a byproduct, including hydrogen gas, oxygen gas, and noxious fumes from the sodium hydroxide - many cell designs will therefore feature some type of outgassing mechanism 281, for example, vent holes and an associated filter or ventilation system, in order to sequester, dilute and / or dispose of these fumes. A NaOH trap for example can be used to restrain larger molecules while permitting the venting of oxygen and / or hydrogen gas. Further, as conceptually indicated by a 'computer icon' 283, it is contemplated that any of these described functions can be computer-controlled, for example, with communications to / from one or more suitably- coded processors, which then control sequencing steps, systems' control and / or actions consistent with the embodiments just described. Any of these one or more processors can be local and / or remote, withcontrol in one example being provided by a laptop, server or other smart device or collection of devices, via a local-area network (LAN) or WAN.

[0060] FIG. 3A is a perspective view which illustrates electrode arrangement in one embodiment of an electrochemical cell 301. This embodiment features a centrally-disposed flat anode plate 303 with two cathodic plates 305a and 305b, one on either side of the anode plate. Once again, the anode plate can optionally be made of low-carbon steel with a 3-8% silicon content, and each cathode can optionally be made of high-grade stainless steel. FIG. 3A also shows a cell base plate 307, which is either part of an integrated (non-reactive) housing or is a removable bottom, e.g., to permit electrode servicing and / or cell cleaning. In this regard, during operation, a space between the various electrodes is filled with a reaction media or mixture, as graphically represented in the FIG. by the presence of liquid 309. The depicted cell in this embodiment comprises two anodic compartments and two cathode compartments, with an anodic compartment on either side of the anode plate 303, with each anodic compartment separated from an adjoining cathodic compartment by a cation exchange membrane 311a / 311b, and with a perforated cathode 305a / 305b attached to the membrane or in close proximity (see pan view provided in FIG. 3D). Each cell is equipped with an opening at the bottom to allow the supply of the analyte. The cation exchange membrane, generally speaking, is permeable to cations (such as sodium ions) but not anions (such as oxy anion FeO42'), such that electrolyzed metal (e.g., ferrate product) tends to remain in between the anode 303 and each membrane 311a / 311b. In this regard, if implemented in a continuous flow design, the depicted electrolytic cell can be designed so as to maximize fluid flow path, conceptually represented in this embodiment by flow arrows 313, which are shown in the FIG. adjacent the depicted electrolytic cell. Optional baffles 314 or other fluid flow structures, can be provided within the cell so as to increase this flow path and thereby maximize contact area of fluid with the anode as that fluid flows from a cell inlet to a cell outlet (these are represented for this embodiment by flow arrows 316 and 319, respectively). Reaction mixture entering the depicted cell flows or is pumped through apertures 315 at the bottom of the cell, and ferrate-rich reaction product is then pumped or drawn out of the cell near the lateral-top of the cell, i.e., as indicated by arrows 316 and 319. [Many of the apertures in the bottom of the cell are hidden from view, and are conceptually represented collectively by a dashed-line arrow 317.] Note once again that undesired gasses are vented, e.g., through a top plate of the cell (not illustrated in this FIG), as represented by flow arrows 320. As stated earlier, some embodiments can be designed for or feature continuously-flowing analyte, while other embodiments can use a stop / run mode of operation, e.g., analyte is pumped or drawn into the cell, the cell is run for a discrete period of time (e.g., 20-40 minutes),ferrate-rich analyte is then pumped or drawn out of the cell, and new analyte is then added for an ensuing production cycle.

[0061] FIG. 3B is a plan view of another embodiment of an electrochemical cell 331. This cell 331 differs slightly from the design shown in FIG. 3A, e.g., inlet apertures for the reaction mixture are seen as being in the cathodic compartments of the cell, as represented by dashed-line base plate apertures (e.g., 345); alternatively, a reaction media inlet can instead be provided at a lateral end of the cell, as conceptually represented by numeral 346. For a bottom-fed embodiment, fresh reaction media (20% NaOH) is fed through the depicted openings, as referenced by arrow 343; this media then flows into the anodic compartment from the adjoining cathodic compartment. The cathodes in this embodiment are optionally permeable or otherwise have apertures (e.g., 341), which permit passage of liquid from a regions outside of the cathode (e.g., 342a / 342b), in the manner indicated by flow arrows (e.g., 343), into the anodic compartments 344a / 344b, i.e., between the anode 303 and each cation exchange membrane 337a / 337b. The fluid levels in the cathodic compartments are, in practice, several millimeters (mm) above that in the anodic compartment, which allows the cell to maintain small positive pressure between compartments and help minimize ferrate penetration into cathodic compartments. FIG. 3B shows, among other things, a lateral casing or housing used in this embodiment to provide a liquid-tight cell body, as referenced by numeral 332. In this embodiment, the casing / housing can be a piece of molded, non- reactive plastic or other material which is compatible with highly-caustic reaction media. The container can be provided with grooves or slots to slidably-receive mating edges of the anode plate 333, each cathode 335a / 335b and each cation exchange membrane 337a / 337b. In addition, each plate 333 / 335a / 335b (and even the membrane) can optionally feature a specially-designed frame or edge gasket 338 in order to provide a liquid-tight interface with the grooves or slots of the housing 332 and / or to provide a protected frame region that is resistant to erosion (e.g., so as to facilitate each removal and modular replacement of the various electrodes). In the depicted design, reaction product is collected once again from one or more outlets near the vertical tops of the cell 331, e.g., from regions 347a / 347b.

[0062] As noted earlier, the same electrochemical cells as described herein can be applied to the low-cost, high-efficiency generation of stannous material, e.g., instead of ferrate; such a design advantageously uses an anion exchange membrane in place of each cation exchange membrane, one or more food grade tin electrodes as a metal source for the electrolysis function, and a suitable reaction media (e.g., HCL) to support stannous generation. In this regard, an anion exchange membrane permits exchange of chlorine while blocking the exchange of electrolyzed tin, one again, enabling the offloadingof high-concentrations of stannous material from the anodic compartment, e.g., using either a continuously run cell or a cell operated in start / stop mode.

[0063] FIG. 3C is an illustrative, perspective view of showing electrode arrangement 301 and showing chemical processes which occur in some embodiments. More particularly, FIG. 3C shows a "stripped down" embodiment so as to better illustrate detail (i.e., regarding the production of ferrate as a product of electrolysis). The left side of FIG. 3B shows an anode, 353, while the cathode 355 is seen on the right side. The anode, for example, can be the anode plate 303 from FIG. 3A and the cathode can be either cathodic plate 305a or cathodic plate 305b from FIG. 3A. FIG. 3C also shows the presence of a cation exchange membrane 361, which similarly can be item 311a or 311b from FIG. 3A. This FIG. also shows the presence of a sodium hydroxide vapor trap 357a / 357b, which is configured to retain sodium and larger molecules (hydroxide) and to release / vent oxygen and hydrogen gas, as conceptually represented by respective flow arrows 359a / 359b. During cell operation, a current flows through solution between the anode 353 and the cathode 355; dissociated hydroxide penetrates through the cation exchange membrane 361 and reacts with iron from the anode. In general, the process of electrochemical generation of ferrate with separated cathode and anodic spaces can be represented by the following electrode processes:Reaction at anode: Fe + 8OH -> FeO42-+ 4H2O + 6e" (1);Reaction at cathode: 6H2O + 6e -> 3H2( / ) + 6OH' (2); andOverall reaction: Fe + 2OH + 2H2O -> 3H2+ FeO42' (3).

[0064] Note that the "up arrow" in the equations above represent the formation of volatile media (i.e., gas).

[0065] While this embodiment features anodic dissolution of iron to form ferrate (e.g., reaction (1)), other embodiments are also contemplated, including as mentioned, and without limitation, dual electrode dissolution and / or toggling polarity between anode and cathode (e.g., such that each electrode operates alternately as anode / cathode according to a defined duty cycle, such as 50 / 50); in this latter case, each one of multiple electrodes can be made of the same consumable material, e.g., low-carbon steel having an optional silicon constituency of between 3 and 8 percent. Whichever embodiment is used, there can also be parallel (parasitic) anodic reactions, the main one being oxidation of the hydroxyl ion with oxygen (4).Parasitic reaction: 40H - 4e ^ O2( ) + 2H2O (4)

[0066] The presence of the cation exchange membrane 361 helps concentrate generated ferrate within a relatively small space, e.g., the anodic compartment represented by bracket 360 in the FIG. In turn, the outlet of the depicted electrochemical cell is in fluidic communication with this space, i.e., so as to extract the reaction product having the soluble concentrated ferrate.

[0067] It is generally desired to produce concentrated ferrate on a consistent basis at the highest sustainable concentration level possible, e.g., at a specific target level, which in some embodiments is 25,000 PPM or higher. Achieving this goal on a consistent, sustainable basis is facilitated by precise control of the cell electoral parameters, and these parameters in turn can depend on some or all of the distances dl-d6 which are illustrated in FIG. 3D.

[0068] FIG. 3D is a plan view of a magnified plan view of a portion of an electrochemical cell 361. This magnified portion corresponds to the embodiment of FIG. 3B; it should be understood, however, that this discussion is more generally pertinent to any of the electrolysis embodiments discussed herein. The FIG. shows a cell housing 332, as well as the anodic plate 333, the cathodic plates 335a / 335b and the cation exchange membranes 337a / 337b from FIG. 3B; the FIG. also shows an expanded view 363 at its lower right-hand side, to illustrate the optional use of a porous cathode material in one embodiment. Dimensional markings dl-d6, as noted, illustrate six different cell parameters, defined as follows: dl: distance from anodic plate surface to cathode plate surface; d2 distance from cathodic plate surface to cation exchange membrane; d3 distance from cell side wall to cathodic plate outer surface; d4 one-half anodic plate thickness; d5 distance from anodic plate surface to cation exchange membrane; and d6 distance from anode centerline to cathode inner surface.

[0069] The cell length and height dimensions (i.e., longitudinal cross-sectional area) may vary depending on the required productivity. One contemplated embodiment, designed for small to mid-scale commercial use, features cell parameters as follows:- ratio of the length and height of the anode - 4.0-1.0;- dl - 4 -20 mm (millimeters);- d2 - 0.5 - 4.0 mm;- ratio of anode / cathode surface area - 1.0-2.5;- electrolyte residence time in cell - 15-45 min;- anode surface area to anolyte volume ratio - 3.0 - 0.5; and- cathode area to catholyte volume ratio - 1.0 - 0.2.

[0070] Generally speaking, a galvanostat is used in some embodiments to automatically adjust applied voltage so as to maintain a constant current, i.e., as distance d4 decreases due to anode erosion / electrolysis, and as distance dl increases; this control configuration facilitates relatively constant ferrate production parameters, e.g., the same electrolytic cell with the same reaction media temperature and composition and effective analyte flow rate and / or residence time should produce a target ferrate volume on a highly-rel iable, repeatable / sustainable basis. As alluded to earlier, some embodiments can use an alternating anode / cathode duty cycle, e.g., the cation exchange membrane is not used and electrodes 333 and 335a / 335b are made to have the same general design and constituency. In such a case, an electrode polarity alternation cycle of between 1 - 10 minutes can be used; this duty cycle is typically 50 / 50 but this is not a requirement for any embodiment, and other duty cycles can be used (e.g., 33.3 / 66.7), and / or the respective electrodes can have different thicknesses. Also, distances / parameters d3, d5 and d6 can be selected depending on design, cathode permeability, desired analyte flow, and other factors; the selection of suitable values of these parameters is within the skill level of those having ordinary skill in the art given the specifics of the particular implementation.

[0071] Some embodiments, as noted, use one or more ultrasound transducers, mounted within or adjacent the electrolysis cell, to provide for automated, intermittent electrode cleaning / de-passivation, and to thereby facilitate reliable, efficient production of ferrate, with relatively constant electrochemical cell operating parameters. In general, ultrasound cleaning can be performed with a duty cycle of every minute (e.g., for ten seconds) to every few minutes (e.g., for a on cycle ranging from seconds to minutes). FIGS. 3E-3F are used to discuss such a configuration.

[0072] FIG. 3E is a plan view of an electrolytic cell 381 in which four dashed-line circles 385 denote the position of ultrasound transducers; these transducers are mounted beneath the depicted electrolyticcell and are generally circular in area of impact, arranged in this embodiment so as to span the substantial footprint of the cell's house and thereby de-passivate each of the depicted electrodes. In FIG. 3F, the side view of this same electrolytic cell 383 illustrates each of the four ultrasound transducers, in profile, as well as their mounting against a base-plate or bottom 389 of the cell's housing.

[0073] Other embodiments feature a built-in trap to collect sediment and other precipitate; such a configuration is shown in FIGS. 3G and 3H, which respectively show side and plan views. More particularly, the side view 391 of FIG. 3G features a central anode 392 and reciprocal cathodes 393a and 393b; the FIG. also illustrates an upper and lower seals or plates 395a / 395b, respectively, used to encase the cell. In this design, a removable, gravity fed trap 397 is mounted to the bottom plate 395b. The trap in this embodiment has two, vertically-distinct portions, including a canted gravity chute 394, and a terminal portion or cup 396 to collect accumulated sediment; a sensor 398 can also optionally be used, to provide for automated detection of a state where the trap is full. In operation, apertures 394 in the base plate serve to pass precipitate, which gravitationally settles into the terminal portion 396. FIG. 3H illustrates a portion of this same cell design, but in plan view (designated by numeral 399), to better illustrate the positioning of apertures 394; note that these apertures are illustrated as optionally lying partially or entirely within the anodic compartment, i.e., as this is where most of the precipitate will be expected.

[0074] FIGS. 4A-4D are used to illustrate a number of multicell arrangements, and their associated control.

[0075] More particularly, FIG. 4A is a block diagram of an electrolysis system which relies on multiple electrochemical cells, 403a-403n, arranged in parallel. An electronic control system 405 exercises individualized control over both power and fluid flow functions (e.g., pump control) via respective signaling resources 407a-407n. These signaling resources can be via dedicated line paths, e.g., an analog control scheme, or a time-multiplexed bus, for example, using a digital addressing scheme or communication of a LAN. In this regard, it was earlier-mentioned that one embodiment provides for a scalable generation system where a volume of dynamically-produced concentrated ferrate can be scaled to meet demand; in such an implementation, in response to demand increases, the control system 405 adds (i.e., switches 'on') additional cells to increase production of, e.g., each producing 25,000 PPM concentrated ferrate; conversely, as demand decreases, or as maintenance conditions dictate for a given electrolytic sell, the control system 405 takes cells offline. As each individual cell is taken offline, that cell can be depowered to stop electrolytic current flow, and the cell can be emptied after completion of a current ferrate generation cycle (if in start / stop mode). Cells can also be subjected to an optional,automated cleaning cycle (e.g., ultrasonic cleaning, as pertinent to the cell configuration) and refilled with a preservative (e.g., fresh caustic, so as to preserve both electrodes and a cation exchange membrane, if present). Some embodiments will also support a cycle where the cell can be emptied or rinsed with a non-caustic solution, for example, to facilitate modular replacement of an electrode or electrodes or a cation exchange membrane, emptying of a trap, or for purposes of other types of maintenance, or a periodic cell renewal cycle, each as appropriate. Note that the electronic control system can feature analog electronics, an application-specific digital implementation, and / or a digital implementation, such as one or more suitably-coded processors; additionally, any of the depicted system elements can be local or remote. For example, as mentioned, one contemplated embodiment features a control system which is at least partially or fully distributed over a LAN or WAN, such as the Internet, or control over cells which are in distributed locations. These examples are nonlimiting. As denoted by reference numeral 411, in this embodiment, each measurement cell outputs a volume of reaction product having concentrated ferrate in a caustic solution; although not specifically indicated in this FIG., as before, the control system and / or each electrolytic cell can feature galvanostatic control and control over each individual cell's parameters, such that the pertinent cell consistently and sustainably produces a reaction product having a consistent ferrate concentration (e.g., 25,000 PPM ferrate or some other target concentration). The electronic control system 405 advantageously monitors each individual cell 403a-403n and the respective reaction product so as to ensure consistent adherence to a target volume or target production rate, per numeral 413, and monitors respective sensor inputs to detect faults in the individual cells or elsewhere in the system, per numeral 415. The electronic control system 405 also, per numeral 417, optionally receives inputs from dosing or treatment control systems, so as to responsively scale ferrate production volume and so as to generate textual or audiovisual alerts for a human operator, per numeral 419. In some embodiments, these alerts can be displayed via a computer monitor, via a light, or other user interface, while in others, they can be formatted electronically and transmitted to a human user, for example, via short message system (SMS) text, email, or some other manner.

[0076] FIG. 4B is a plan view of another multicell embodiment 421. As seen in this FIG., a number of electrochemical cells 422a-n are also mounted in parallel; each cell has its own fluidic chamber defined, for example, by two ends 423a / 423b and two sidewalls 423c / 423d, as called out by numeric references in the case of a first cell 422a. Each cell has its own, dedicated cathode pair, e.g., 424a / 424b, mounted on opposite sides of a central, anode plate 425. Ellipses 426 denote that there can be any number of these cells, e.g., from 2 to any desired number (e.g., n=20). In the illustrated embodiment, electrolyte / reaction media is pumped into each cell via an inlet (e.g., 427), mounted near the vertical baseof the cell, with ferrate-rich reaction product being pumped out of the cell at a corresponding cell outlet 429, following a suitable average or discrete cycle dwell time. In the depicted embodiment, as with the example provided in connection with FIG. 4A, any individual cell as desired can be taken off-line independently of the other cells; for example, if it is desired to replace the central anode plate of cell 422a, the electronic control system (not shown in this FIG.) can optionally drain all fluid from cell 422a, rinse the cell, again drain the cell to permit servicing / electrode replacement by a human operator, and thereafter, when replacement is complete, initiate one or more cycles to prepare the cell once again for ensuing operation, all while cells 422-422n continue to operate to generate concentrated ferrate. As denoted by aggregation icon 430, the reaction output of each cell 429 can optionally be mixed together or used for arrayed ferrate consumable generation.

[0077] FIG. 4C shows yet another parallel cell embodiment 431, this time with adjacent cells (e.g., 433a / 433b, 433b / 433c, 433c / 433d) sharing an electrode, e.g., 437b in the case of calls 433a / 433b; the shared electrode is depicted in the case of this FIG. using the same hashing as used to represent an anode, as was the case with others of the FIGs., but it should be understood that the shared electrode representation 437b in this FIG. is a proxy for either a shared anode or a shared cathode, depending on design. In this exemplary configuration each electrolysis cell (e.g., 433a) once again has one electrode of a first type (e.g., 435 serving as a first one of anode or cathode) and two electrodes of a second type (e.g., 437a / 437b serving as the second one of anode or cathode). Each electrolysis cell in this example, e.g., cell 433a, therefore defines two fluidic compartments 436, one on either side of electrode 435. Once again, in this example, the cells are constructed such that a reaction mixture, e.g., a caustic analyte 441, is pumped into an inlet of the cell via one cell end, e.g., as indicated by arrows 441, and such that ferrate- rich analyte is removed from the cell via an outlet at the other cell end, e.g., as indicated by arrows 443. Note that this embodiment differs slightly from the embodiment of FIG. 4D, in that there is a common housing 438 provided for all of the cells, e.g., with electrode plates such as electrode 435 being vertically slid into grooves (not shown) defined by the housing, and removed in the opposite manner.

[0078] FIG. 4D shows still another multicell embodiment 451, this time with multiple electrolysis cells 453a-453n arranged in series; as once again denoted by ellipses 455, any number of cells can be arranged in this manner, as desired. Each individual cell is optionally modular, for example, having its own housing 457a-457n and dedicated anode, such as depicted central electrodes 461a-461n. The cells can optionally be mounted together, for example, via a common frame or mounting 459, with an outlet of one cell connected to the inlet of the next (e.g., fluid from the outlet represented by arrow 463n ultimately passes to the inlet 465a of cell 453a). Note that it is not required for any embodiment that each cell has discreteinlets and outlets, e.g., it is possible simply to have electrode plates or concentric electrodes mounted in series, effectively acting as one or more segmented electrode pairs. As with previous examples, an electronic control system (not shown) can detect faults in an individual cell and responsively depower electrodes without substantially impacting overall performance of the system. Unlike previous examples, however, because fluid passes sequentially from cell to cell, taking one or more individual cells offline can correspondingly affect ferrate concentration in the reaction product as a whole; this can be remedied, if desired, by correspondingly changing other system parameters, for example, average analyte dwell time in the cell.

[0079] As should be appreciated, a parallel cell approach might be desired for some implementations, e.g., a consistent concentration of ferrate in produced reaction media is generally more amendable to mass production, to storage of concentrated ferrate for later dosing, or for distribution and / or sale of ferrate (and / or stannous material) on a commercial basis.IV. HIGH CONCENTRATION ELECTROLYZED METAL GENERATION / CELL EFFICIENCY CONSIDERATIONS.

[0080] FIGS. 5A-5D are used to discuss some electrochemical cell parameters which provide synergistic electrolyzed generation in some embodiments. Naturally, as individual system parameters are varied, for example, specific cell dimensions, the optimal choice of parameters discussed below can be expected to vary. The discussion below is intended to exemplify to those having skill in the art some parameters that can be adjusted to enhance production, e.g., to provide the highest possible sustainable electrolyzed metal yield for a given implementation.

[0081] FIG. 5A is a plot 501 representing steel anode composition effect (in terms of presence of silicon in the electrode) on ferrate generation efficiency. Generally speaking, the higher the value on the vertical axis, the more efficient the resultant ferrate generation and, as seen from curve 503, an electrode composition of between about 3% to 7% silicon helps foster best results. FIG. 5A also shows a second curve 502, representing electrode passivation, e.g., generally for insufficient levels of silicon, the electrodes (e.g., the anode) passivate quickly, i.e., after a small number of cycles, but starting about 2% silicon constituency levels, the passivation effects following a cell cycle fall off quickly and are negligible at silicon ranges of 5-7%.

[0082] What this FIG. suggests is that anode material composition can play a role in electrolytic efficiency (e.g., anode current efficiency and production stability) and that, in order to maintain de-passivated anode status and high ferrate generation efficiency, the anode material should contain a certain amount of silicon. The presented data suggests three specific ranges of electrode composition, which are represented conceptually by brackets 504, 505 and 507 in the FIG.: Bracket 504 denotes a range corresponding to no significant de-passivation and electrolysis efficiency of at least 60%, which suggests that in one embodiment, electrode composition (anode composition) should be between about 3.5% and 7.9% silicon. A second bracket 505 denotes a more preferred range, i.e., where electrolysis efficiency is at least 80%, suggesting that another embodiment should feature electrodes having between about 4.2% and 7% silicon content; finally, a third bracket 507 corresponds to a silicon range of between about 5.2% and 6.5% silicon, and suggests that an embodiment having this composition has potential to produce greater ferrate concentrations than electrolysis systems lacking this structure. Exemplary cell operating conditions associated with the data appearing in this diagram are:Anode current density - 25mA / cm2;NaOH temperature - 35C;NaOH concentration - 20%; andResidence time in cell - 40 min.

[0083] Note that while silicon constituency is the specific example of the presented data, it is expected that use of similar materials might provide similar effects, e.g., germanium. Those of ordinary skill in the art are capable of testing and evaluating the performance of these and similar materials to identify the optimum constituency for a given implementation or application.

[0084] FIG. 5B provides another plot 521, this time relating to ferrate generation efficiency as a function of reagent concentration; in this case, the reagent is NaOH (sodium hydroxide) and ferrate generation efficiency is graphed against various concentrations (mass percentage) of sodium hydroxide in the reaction media.

[0085] As seen, increase in hydroxide concentration (e.g., increase in pH) generally increases ferrate generation efficiency and stability of the reaction product. However, high caustic concentration can also increase process operation expenses and present health risks to system operators. Electrolyte concentration effect (mass %) on the ferrate generation efficiency is seen to increase reagent efficiency above about 80% for test cell conditions for hydroxide concentrations above about 13%, increasing toapproximately 85 percent for hydroxide concentrations above about 20%. Exemplary cell operating conditions associated with the data appearing in this diagram are:Anode current density - 25mA / cm2;NaOH temperature - 35C;Anode Si (%) - 5%; andResidence time - 40 min.

[0086] As seen from FIG. 5B, for the test parameters considered, the lowest ferrate generation efficiency observed in a 10% NaOH reaction media, likely due to parasitic oxygen evolution (reaction (4), noted earlier). In NaOH concentrations of about 20, 30 and 40% generation efficiencies varied between 84-87%. This data suggests three preferred ranges of NaOH composition as enhancing resultant ferrate generation efficiency and ferrate concentration in the end-product: a first range, identified by bracket 525, where ferrate generation efficiency was observed above about 80% (13%+ NaOH composition by mass); a second, more preferred range 526 corresponds to relatively invariant, but still high levels of ferrate in generation efficiency, with minimum NaOH concentration (i.e., NaOH concentration of between about 20-30%); and a third range of about 20% NaOH, + / - 10% of this concentration about the point of optimal efficiency (i.e., 18-22% NaOH), marked by bracket 527.

[0087] FIG. 5C shows yet another plot 531, this time representing the effects of temperature variation on reagent generation efficiency for a given cell design. This FIG. once again shows two curves / lines, including a first curve 532 / line, representing electrode passivation, and a second curve / line 533, corresponding to ferrate generation. Curve / line 532 indicates that reagent temperatures of greater than about 17 degrees Celsius (C) were found to inhibit electrode passivation, and thereby enhance electrolysis efficiency, while curve / line 533 indicates that temperatures of between about 17 degrees Celsius and 55 degrees Celsius generally produced the best results. Exemplary cell operating conditions associated with the data appearing in this diagram are:Anode current density - 25mA / cm2;NaOH concentration - 20%;Anode Si(%) - 6.0%; andResidence time 40 min.

[0088] The depicted data once again suggests three ranges associated with different embodiments; represented by a first bracket 534, a range of between about 17 degrees Celsius and 55 degrees Celsius was found to enhance the ferrate generation process generally and ferrate concentrations in the finished product, by providing for reagent generation efficiency of 60% or greater. A second range, demarked by bracket 535, suggests that at least 80% efficiency is obtained in other embodiments by limiting reaction temperature to the range of about 20 degrees Celsius through 48 degrees Celsius. Finally, optimal results, that is, maximum efficiency, was found for a temperature of about 42 degrees Celsius, + / -10%, suggesting that a third range (537) of between about 38 degrees Celsius to 46 degrees Celsius might be preferred for some embodiments.

[0089] Finally, FIG. 5D plots reagent generation efficiency (curve / line 543) as a function of anode current density (represented by the horizontal axis of the FIG.). In this regard, Faraday's second law implies that increases in the current load on the electrolytic cell will intensify the process of the electrolysis and increase the system productivity. However, this approach has its limitations: increasing the anode current density above a certain level causes an increase in the voltage on the cell and, in turn, increased risk of electrode passivation as well as increased parasitic reaction of oxygen (see, e.g., reaction equation (4), noted earlier). High voltage or current levels may also cause cation exchange membrane damage, leading to an increase of the temperature of the electrolyte and unwanted ferrate decomposition. Obviously, the energy consumption of the system also increases significantly with higher current densities. Therefore, current density at the anode is another cell parameter which can be selected in some embodiments in a manner calculated to enhance ferrate production and associated concentration levels in the end product while minimizing cost, minimizing electrode passivation and / or promoting cell longevity.

[0090] In general, the cell operating conditions associated with FIG. 5D are:NaOH temperature - 20C;NaOH concentration - 20%;Anode Si(%) concentration - 6%; andAnolyte residence time - 40 min.

[0091] As seen in the FIG. from curve / line 542 (representing electrode passivation), passivation was observed for current densities of greater than about 45mA / cm2. Also, curve / line 543 shows that ferrate efficiency begins decreasing with anodic current density above about 15mA / cm2, presumably due to a parasitic reaction (e.g., per reaction (4), referenced above); the decrease is slight at first and becomes more exaggerated above current densities of about 40mA / cm2. The highest ferrate efficiency (96%) was observed with a current density of about 15mA / cm2.

[0092] This data, taken together, once again suggests three exemplary ranges which can be used in different embodiments: e.g., a first range, noted by bracket 544, where reagent generation efficiency is above about 60% and there is no observed passivation (i.e., using an anode current density of between about 3mA / cm2and 42mA / cm2); a second range, marked by bracket 545, where reagent generation efficiency is above about 80% (i.e., an anode current density of between about 4.5mA / cm2and 36mA / cm2); and a third range, marked by bracket 546, where reagent generation efficiency is within about 10% of its peak value (i.e., an anode current density of between about 5mA / cm2and 23mA / cm2).

[0093] It is lastly noted in connection with these plots that ferrate concentration in the end product generally increases with dwell time of the reaction mixture in electrolysis conditions (i.e., both with average dwell time for continuous-flow cells and for discrete dwell times used for start / stop generation processes). However, due to ferrate decomposition as the result of its reaction with water, it is desired at some point to extract concentrated ferrate and to refrigerate and / or freeze that ferrate so as to retard / arrest that decomposition. Note that this decomposition is generally believed to correspond to reaction (5), represented below:2[FeO4]2+ 5H2O ^2[Fe(OH)3] + 3H2O + 4OH' + 1.5 O2(^) (5).

[0094] The inventors have generally found that a 40 minute average or discrete cycle dwell time provides a good tradeoff for maximizing ferrate concentrations in the end product and batch production rates, while minimizing decomposition; however, this result might vary for other cell parameter choices, including without limitation, cell dimensions, current density, electrode sizes, and so forth. Selection of a suitable dwell time / average electrolysis time for a specific implementation is within the level of skill of an ordinary systems designer, given cell design and application needs. It is again noted that while some of the test embodiments described above use a start and stop mode (i.e., where electrolyte is pumped into a cell, electrolysis is run, and the entire electrolyte volume is pumped out following a desired dwell time), embodiments are also specifically contemplated which use continuous flow reaction media.V. PRODUCTION CONSIDERATIONS AND SERVICE BUREAU USE CASES.

[0095] FIG. 6 is a block diagram showing techniques associated with controlling and maintaining an degrading electrode and / or cell in a ferrate production system. As with some of the other embodiments described herein, an electronic control system adjusts electrical and system parameters to generate a reaction product having a sustainable target concentration of ferrate, per numeral 603. This electronic control system can once again optionally use a galvanostat for this purpose, e.g., to maintain a relatively consistent current flow through the electrolytic cell, notwithstanding changing electrode distances (e.g., per numeral 609). The target concentration can be selected to be a predetermined value, e.g., 25,000 PPM ferrate in the reaction product, as denoted by numeral 605. In one embodiment, referenced by numeral 607, a voltammetry device can measure ferrate in intermittently-drawn samples of the reaction product (e.g., using suitable built-in voltammetry chemistries associated with this measurement), and thereby provide feedback to the electronic control system, which can be programmed to adjust system parameters using this feedback so as to maintain a consistent concentration of ferrate in produced batches, i.e., at the target concentration (605). The electronic control system also advantageously monitors current draw and voltage and input from various sensors, per numeral 611, in order to balance these parameters and monitor electrode health (e.g., per numeral 613). In this latter regard, the electronic control system can perform some or all of the functions indicated at the right-hand side of FIG. 6, including without limitation: (1) computing current electrode gap (i.e., distance dl, illustrated in FIG. 3D) and / or calculating, based on monitored electrode mass loss, a remaining electrode expected life (see, e.g., numerals 615-616); (2) identifying a maintenance event based on one or more conditions being met, e.g., exceeding a maximum permitted electrode gap or identifying that a minimum anode thickness is not met, per condition 619); (3) identifying that voltage exceeds a maximum allowable value, per numeral 621; (4) identifying a system fault, for example, that instantaneous cell current has dropped below a minimum or exceeds a maximum, per numeral 621; or (5) some other complex condition, per numeral 625. As represented by block 627, for example, system software can be programmed to detect an event corresponding to a complex Boolean condition such as identifying a state where (by way of illustration) {condi<xo+ cond2>Xi}, and to take consequent actions, i.e., as referenced by block 631. For example, in one embodiment, the electronic control system uses ultrasonic cleaning to intermittently de-passivate the anode and / or cathode(s), per numeral 633. These conditions / actions / events can also take the form of a calendared event (e.g., "every hour"), they represent a predefined duty cycle (e.g., every ten minutes for 30 seconds) and they can also be dynamically-evaluated event (e.g., monitoring of current and voltage suggests electrode passivation of more than a threshold metric). Many different events will be identifiedby those having ordinary skill in the art as some type of event which should provoke some type of reactive system measure. As alluded to earlier and, as represented by blocks 635 and 637, the system can also perform functions (in a single or multi-electrolytic cell environment) of turning electrolysis and / or individual cells "on" or "off," shunting cells, and / or scaling production, as needed, to meet demand or responsive to faults; or initiating a cell preservation cycle, in which a cell is emptied, cleaned, and / or filled with a preservative either for purposes of maintenance or for periods of non-use. Per numeral 639, an electronic control system in some embodiments can generate operator alerts to indicate, for example, that it is time to replace an electrode or perform other servicing, such as cell and / or electrode cleaning, emptying of accumulated sediment, and so forth; these alerts can be signaled to an operator via a user interface (Ul), either on the system itself, or on a smart device or computer, or via a text (SMS) or email message. As will be further discussed below, an additional function performed by the electronic control system in some embodiments is automated electrode reordering, e.g., via a WAN such as the Internet, per numeral 641. For example, the electronic control system can be configured in such a way, through suitable programming, that if it is detected that an anode has less than 20% service life left, the electronic control system automatically places an order with a supplier via a WAN for electrode replacement. Naturally, many variations of these different options will occur to those having skill in the art.

[0096] FIG. 7 is a block diagram associated with service bureau provision or remote provision / control of ferrate generation services to one or more clients; again, some or all of these described techniques can also be applied to stannous generation, as appropriate. A system, generally represented by reference numeral 701, features one or more computers 703 which manage functions such as account management and authentication, per numeral 711, and one or more of: electrode and consumables replacement for clients, per numeral 713; ferrate shipments / supply to clients, per numeral 715; and / or remote management of ferrate generation and / or treatment systems, per numeral 717.

[0097] Firstly, as discussed above, electrolysis systems of the type discussed above can be used in situ to produce ferrate for various entities, per numeral 727 - as represented by numeral 713, the service bureau functions of FIG. 7 can optionally include the manufacture and sale of replacement parts for such systems, including without limitation, consumables and parts which are specially adapted for use in ferrate generation systems of the novel type introduced by this disclosure. For example, a service bureau can provide specially adapted modular electrodes, cell housing, reaction media, and other parts, all as textually signified by block 713. A specially adapted electrode, for example, can feature a modular anode (e.g., a framed plate or complete electrode assembly, e.g., with multiple electrodes) having specific thickness, dimensions and constituency, such as without limitation, a low-carbon steel plate with 6%silicon constituency corresponding generally to the discussion earlier. Such a product is specially adapted for use in the novel ferrate generation systems as discussed earlier. Similarly, other embodiments of the techniques described herein can include, without limitation, the supply electrochemical cells specially adapted to receive electrodes as discussed above, or fitted for engagement with ultrasound transducers, or with a trap for sediment collection and disposal. Embodiments specifically contemplated by this disclosure include any such specially-adapted parts or consumables, regardless of whether or not these things are bundled with a complete ferrate generation electrolysis system.

[0098] Secondly, per numeral 715, another embodiment features the production and distribution of super-concentrated ferrate in reaction media, in a batch consumable size, for service bureau shipping and / or distribution. For example, an entity can produce specific consumable volume sizes (e.g., 50mL, 250m L, IL and so forth) which can be frozen and then shipped as part of an order fulfilment process, e.g., as further referenced by block 719. In this latter regard, it should be recalled that refrigeration and / or freezing of super-concentrated ferrate has been found to indefinitely extend its half-life; 25000 PPM super-concentrated ferrate in 18% NaOH freezes at approximately negative 28 degrees Celsius so, related to this, a service bureau can produce and / or store super-concentrated in sub-minus-28-C storage 721 and maintains the ferrate below this temperature through refrigerated expedited shipment and delivery to a customer (e.g., dry ice, with a temperature of approximately minus 78.5 degrees Celsius, is well-adapted to this purpose).

[0099] Thirdly, per numeral 717, service bureau functions can also include remote management of ferrate generation and / or dosing systems; for example, a service bureau can lease fully automated systems to its customers, with the service bureau remotely managing control of these systems, i.e., electronically, over a WAN, including automatically and remotely monitoring their performance and their need for maintenance and consumables replacement. As should be clear, a hypothetical client that treats waste water might possess a system configuration which accumulates water to be treated, with the service bureau remotely managing in-situ dynamic monitoring for a treatment event (e.g., a full tank with presence of a target substance), and then automatically and / or responsively activating localized dynamic ferrate generation and / or dosing systems. Some implementations can use a recursive process, e.g., with treatment / dosing processes being repeated until dynamic monitoring indicates that the target substances have been reduced to below threshold levels. The ferrate generation systems referenced by this example can advantageously feature a WAN-based communication system (e.g., a digital modem of some sort or wireless transceiver,) which reports information relating to electrode health and system status to theservice bureau, and which receives network-level control signals from the service bureau, all as represented conceptually by dashed-line automated control block 725.

[0100] FIG. 7 also shows two other optional systems' demarcations, represented by a computer icon 705 and database icon 707; each of these is depicted as optionally separated from service bureau system 703, for example, by a lightning icon 708a to signify wireless or remote transmission, and by a network separation line 708b, denoting that elements 703, 705 and 707 can each optionally reside in fully separate networks associated with different entities, if desired. It should further be noted, in this regard, that icons 703, 705 and 707 proxy / signify any digital device, instructional logic or hardware logic, or any combination of these things, and further, that each of these elements can include one or more distributed or co-located processor-based systems. In this regard, database icon 707 represents the maintenance and storage of client account, authentication, and systems configuration information, with associated functions of billing and payment processes 712.

[0101] Numeral 723 denotes that individual clients can themselves perform ferrate dosing in some configurations, for example, adding ferrate once received from a service bureau provider to treat a substance as necessary; if the client does not have suitable cold storage capabilities, a received ferrate batch can be stored in a refrigerator to slow decomposition and added to a target manually, as-needed. Further, per numeral 709, it is possible for the client to have an automated treatment system, with supplied ferrate either being received on a service bureau basis, as described, or locally generated (e.g., in-situ, as denoted by reference numeral 727).

[0102] FIG. 8 is a block diagram associated with an automated treatment or dosing system 801. The system is hypothetically used to treat liquid which has been accumulated in a tank 803, though it can be applied to other treatment or usage targets as well. In this example, the tank is depicted as accompanied by a mechanical stirrer 805, which mixes the target with ferrate to promote a homogeneous mixture. The dosing system includes a refrigerated supply 807, which is optionally configured to receive and attach to modular consumables 810, for example, to a vial 809 having a predetermined size and shape, and an interface for modular connection to extract super-concentrated ferrate. In one embodiment, the refrigerated supply is configured so as to maintain the concentrated ferrate in a liquid state, for example, slight above freezing (i.e., slightly about minus 28 degrees C), such that the ferrate has a long half-life, yet is sufficiently-fluid that sub-volumes of the ferrate supply can be individually withdrawn from the vial 809 and injected into the tank 803; for example, a hypothetical embodiment might draw only 5 mL of superconcentrated ferrate from vial 809, leaving the remainder of container contents in the refrigerated supply.One optional embodiment, denoted by numeral 812, features dynamic temperature cycling, for example, permitting the system to maintain super-concentrated ferrate in a frozen stated and then, when dosing is needed, to raise the ferrate temperature to adopt a cold, liquid state (i.e., for extraction of a sub-volume, if appropriate) and, subsequently, re-freezing unused ferrate, to thereby inhibit decomposition. Per numeral 811, the ferrate can be supplied either by a local ferrate generation system (e.g., whether or not electrolysis-based) or it can be provided on a service bureau basis, for example, it can be received as a frozen consumable, as just discussed.

[0103] As represented by numerals 813, 815 and 817, in one embodiment, the automated dosing system operates continuously, for example, mixing dynamically-selected amounts of concentrated ferrate with an inline feed for the liquid to be treated (813), with the mixture then being added to the tank 803. A suitably-coded computer or other digital system 821 can identify flow rate of the liquid and required dosing, and then controls pump 818 such that concentrated ferrate is added at the appropriate rate / ratio to achieve desired tank dosing. Other embodiments, however, can feature intermittent, batched dosing and treatment, with the computer or digital system 821 interacting with a sensor in the tank 803 to identify liquid level or volume, and then controlling pump 818 and stirrer 805 so as to inject and mix the required amount of concentrated ferrate into the tank contents. As represented by numerals 827 and 829, the computer or other digital system 821 performs dose calculation and dosage control, and is configured to control on-demand ferrate generation and / or siphoning, and ferrate consumable reordering, as appropriate; as with other embodiments discussed herein, some or all of these functions can be dictated by software, which is conceptually represented in the FIG. by a "floppy disk icon" 823 (note again that, as stated earlier, instructional logic can reside on any physical storage media, whether or not a "floppy disk").

[0104] FIG. 9 is a block diagram associated with one embodiment 901 of a system for administering concentrated ferrate from a frozen or refrigerated source (e.g., from a modular consumable 907). The method generally begins with occurrence of a dosing trigger 903; by way of nonlimiting example, this trigger can be in the form of a signal supplied from an online monitor 904, e.g., indicating that a target substance (e.g., an unwanted metal, pathogen, organic or other substance) has been detected in a specific media (e.g., potable or waste water). The dosing system identifies the amount or concentration of the target substance present, per numeral 905 and - based on programmed criteria - it identifies a tank dosing concentration needed to neutralize the target substance and / or reduce its concentration to below threshold levels.

[0105] A few examples might be helpful here - it might be that one hypothetical application calls for ferrate to be added to waste water to neutralize some pathogen (e.g., a bacteria) having 'level X.1In this case, the software can be coded so as to apply ferrate dosing according to a desired algorithm 909. For example, the system might have been preprogrammed with information regarding ferrate concentration (e.g., 25,000 PPM), a reaction to dose bacteria levels of "0.5 X" with 1 PPM ferrate, and also to identify a volume associated with the tank (e.g., 500L). In this case, a designer's selected algorithm might identify a target tank dosing level of 2 PPM ferrate (e.g., given that measured bacteria levels are 'double' 'level X'); to administer dosing, such a hypothetical algorithm might be designed to take tank volume (500L), to multiply this by the desired dosing level (2 PPM), and to divide the result by the ferrate concentration (25,000 PPM), i.e., e.g., arrive at a decision that a sub-volume of 0.04L of the super-concentrated ferrate should be automatically injected into the 500L tank in order to achieve required dosing, followed by an immediate mixing cycle. Other designers might choose to implement a different treatment algorithm, e.g., instead of pre-calculating dosing, a different designer's algorithm might be configured to inject a predetermined amount of super-concentrated ferrate (e.g., 0.04L of 25,000 PPM ferrate into a 500L tank), perform stirring, wait ten minutes, and then re-sample the liquid of interest, with dosing being reapplied as many times as needed, e.g., on an indefinite or limited-cycles basis, until testing shows no presence of the pathogen. As these hypothetical examples indicate, there are many possible dosing algorithms which can be selected, with a suitable choice being dependent on implementation, the treatment application and the needs / choice of a designer. As a hypothetical illustration of application-level variance and / or designer choice variance, a potable water supplier might choose to overdose potable water to sterilize that water, whereas a waste water supplier might choose an incremental dosing strategy to reduce pathogen presence simply to tolerable levels. Again, the choice of dosing strategy is a task for the system designer and will vary depending on application; whichever dosing strategy / algorithm 909 is implemented, a system or method corresponding to FIG. 9 applies that algorithm to identify the desired dosing and it controls systems automatically in response to the dosing trigger, to inject concentrated ferrate into / apply to the target of interest.

[0106] To perform these tasks, the concentrated ferrate is first placed into a state where it can be administered on an automated and / or variable basis. For example, refrigerated supply 807 (from FIG. 8), if it has variable heating / cooling control and selective unfreezing / refreezing capabilities, can be controlled, per numeral 911, to raise the temperature of frozen concentrated ferrate to a level where, it is still chilled, but can readily be administered as a liquid on an automated basis. To perform this task, the dosing system initiates a heating cycle 913 in order to raise ferrate temperature sufficiently, and it thenoperates a pump or other dosing system 915 in order to inject ferrate into the fluid of interest. This step is then followed by a wait cycle 917, optionally accompanied by a robotic mixing cycle 919. Per numeral 921, the method then proceeds to identify whether dosing is complete, for example, by optionally controlling and / or interacting with an online monitor to remeasure the liquid of interest, per numeral 923, with ensuing dosing cycles initiated as-needed, as represented by icon 925. Depending on the amount of consumable ferrate needed or used, the system / method can optionally be provisioned to compute remaining consumable life (e.g., remaining concentrated ferrate), to reorder more ferrate, or to generate an error message, all as represented by numeral 927. The dosing system can be configured to refreeze unused ferrate if refreezing is supported, as indicated by numeral 929. Finally, as represented by elements 931, 933 and 935, the dosing system can optionally include any number of digital control systems, for example, a local control system 931 and / or a network control service 935 configured to communicate with a dosing system or local control system via a wired or wireless network connection 933. Any of these systems can be implemented as dedicated circuitry, instructional logic, or one or more processors, whether or not co-situated. Note also that the use of a liquid dose of concentrated ferrate is not required for all embodiments, e.g., an alternate dosing manager can administer variable numbers of frozen "ice cubes" as part of an automated dosing scheme, as referenced earlier.VI. CLOSING THOUGHTS.

[0107] From the foregoing, it should be apparent that this disclosure provides methods, systems, devices, and products associated with the production and / or use of super-concentrated ferrate. Without limitation, this disclosure has presented a novel electrolysis cell and related ferrate generation system capable of producing extremely high ferrate concentrations, all on a repeatable and automated basis. In addition, the use of chillers and / or sequencing which build suitable cooling control into the process enables the significant extension of ferrate half-life, making it far easier to store, distribute and administer this highly-useful substance. As just noted, one hypothetical entity might choose simply to make "ice cubes" of concentrated ferrate, each of consistent volume and potency, for desired, later, on-demand dosing; the entity for example adds as many prefabricated "ice cubes" to a tank as needed to obtain desired dosing, e.g., adding one 50mL cube for every 1.0 PPM dosing desired for a 1250L tank. Finally, service bureau and / or automated dosing systems, as described, make it possible for an entity to rely on external ferrate generation, supply and / or control as desired, eliminating the need, for example, for a client to itself support the handling of, or administration of, caustic, or related systems' operation.

[0108] As noted earlier, it is specifically contemplated that any of the foregoing elements may be mixed and matched regardless of whether or not used called out in a dedicated example highlighted discussed above or single FIG. For example, one embodiment provides a dosing system having features as described above, regardless of whether electrolysis-based ferrate generation is employed. Similarly, another embodiment is a generated ferrate product having specifics as just described, regardless of whether an electrolysis cell or ferrate dosing system is employed. Still other embodiments feature application of some or all of the elements described above to stannous material generation, storage, shipment and / or application. Many variations of the techniques and elements described above, and their combination, will occur to those having skill in the art, whether or not specifically called out above, which nevertheless are within the spirit and scope of this disclosure.

[0109] Without limiting the foregoing, this disclosure contemplates subject matter represented by or similar to the content of the following clauses, on a nonlimiting basis:

[0110] Techniques which rely on a galvanostat to maintain a constant current density and / or ferrate production rate as electrode gaps change as a function of dissolving electrode matter;

[0111] Techniques which administer ferrate from a concentrated source to achieve desired dosing levels in a volume of liquid in a tank or vessel, with or without associated freezing and re-freezing control to preserve the lifetime of unused ferrate;

[0112] Techniques which control the temperature of concentrated ferrate in a source of consumable ferrate to selectively freeze and unfreeze remaining ferrate and / or so as to administer doses of concentrated ferrate and to maximize ferrate longevity, e.g., by freezing unused portions of the concentrated ferrate;

[0113] Techniques for generation of discrete consumable ferrate supply volumes, with integrated refrigeration and / or cooling / freezing control, for use with service bureau distribution or otherwise;

[0114] Techniques for ferrate production with a multiple-cathode system or concentric cathode system or a system where electrodes serve alternately as anode and cathode;

[0115] Techniques for ferrate production with specific electrolytic cell parameters, including one or more of specific anode composition, one or more cation -exchange membranes, galvanostat usage, ultrasound-transducer-based electrode de-passivation, reaction heatcontrol, voltammetry feedback based on generated ferrate, pH and / or reagent administration control and / or fluid flow control or cell residence time control as a function of detected pH;

[0116] Techniques for ferrate production which utilize one or more parameters of any of the described electrochemical cells, in any combination or permutation;

[0117] A cell housing, anode plate and / or other electrode having predefined chemical composition and / or module connection / replacement adaptation, for use in a ferrate electrolysis system;

[0118] Techniques for dynamic ferrate generation based on monitoring of a fluidic system;

[0119] An electrolysis cell with a preservation mode and associated buffer cycles when not in use for ferrate generation (e.g., with a caustic reagent);

[0120] Techniques for ferrate production with multiple electrochemical cells and individual cell management;

[0121] Techniques for ferrate production which use a low-carbon steel anode having a specific silicon composition to minimize passivation;

[0122] Techniques for remote ferrate electrolysis and treatment administration over a local- or wide-area network;

[0123] A modular product of super-concentrated ferrate having specific properties, for example, 25,000+ PPM ferrate in a sodium-hydroxide media of 18-22% sodium hydroxide by mass, and frozen to a temperature of below minus 28 degrees Celsius;

[0124] Techniques for ferrate electrochemical cell design with sludge sequestration; and / or

[0125] Techniques for tin electrolysis using some or all of the techniques referenced above including, without limitation, use of an anion exchange membrane and a hydrochloric (HCL) acid media (i.e., in place of the cation exchange membrane and NaOH media used for ferrate).

[0126] As mentioned, this listing is nonlimiting, and it is contemplated that any of the elements / particulars of the systems described herein can be mixed and matched in any desired order,permutation or combination. Advantages of such order, permutation or combination will be apparent to those having ordinary skill in the art.

[0127] It should therefore be appreciated that by providing techniques which address the need for cost-effective ferrate generation, distribution and usage, the present disclosure significantly enhances treatment techniques and applications which can take advantage of this "green" treatment chemical.

[0128] The foregoing description and in the accompanying drawings, specific terminology and drawing symbols have been set forth to provide a thorough understanding of the disclosed embodiments. In some instances, the terminology and symbols may imply specific details that are not required to practice those embodiments. The terms "exemplary" and "embodiment" are used to express an example, not a preference or requirement.

[0129] Various modifications and changes may be made to the embodiments presented herein without departing from the broader spirit and scope of the disclosure. Features or aspects of any of the embodiments may be applied, at least where practicable, in combination with any other of the embodiments or in place of counterpart features or aspects thereof. Accordingly, the features of the various embodiments are not intended to be exclusive relative to one another, and the specification and drawings are to be regarded in an illustrative rather than a restrictive sense.

Claims

CLAIMSWe claim:

1. (Original) An apparatus comprising: an electrochemical cell comprising: an anode comprising iron; a cathode; an inlet to receive a reaction medium, the reaction medium comprising a hydroxide; an outlet to output a reaction product, the reaction product comprising ferrate; a source of power electrically coupled to the anode and the cathode, to cause transfer of electrolyzed iron from the anode to the reaction medium; a galvanostat to control supply of power from the source of power so as to provide for a constant current flow between the anode and the cathode, notwithstanding a changing electrode gap between the anode and cathode as electrolyzed iron is transferred from the anode to the reaction medium; and a pump to control of at least one of supply of the reaction medium to the electrochemical cell or removal of the reaction product from the electrochemical cell.

2. (Original) The apparatus of claim 1 wherein the anode comprises low carbon steel and a silicon content of the low carbon steel of between 4.2 percent and 7.0 percent.

3. (Original) The apparatus of claim 1 wherein the hydroxide comprises sodium hydroxide and wherein the reaction medium comprises a solution having a concentration of at least eighteen percent sodium hydroxide.

4. (Original) The apparatus of claim 1 further comprising a temperature sensor and a heater, wherein the heater is in thermal communication with at least one of the electrochemical cell or the reaction medium so as to heat the reaction medium to a temperature of between thirty-seven and forty-six degrees Celsius.

5. (Original) The apparatus of claim 1 further comprising a cation exchange membrane in between the anode and the cathode, to define a first region on a first side of the cation exchange membrane, between the cation exchange membrane and the anode, and a second region on a second side of the cationexchange membrane, opposite the first side, the cation exchange membrane to inhibit the passage of iron from the first region to the second region.

6. (Original) The apparatus of claim 1 wherein the cathode is a first cathode and wherein the electrochemical cell comprises a second cathode, wherein the anode is positioned in between the first cathode and the second cathode, so as to define a first reaction chamber between the first cathode and the anode and a second reaction chamber between the second cathode and the anode, and wherein the outlet is in fluidic communication with each of the first reaction chamber and the second reaction chamber so as to receive the reaction product comprising the ferrate from both of the first reaction chamber and the second reaction chamber.

7. (Original) The apparatus of claim 1 wherein the electrochemical cell is configured such that, and the galvanostat is configured to control the electrochemical cell such that, the reaction product contains a ferrate concentration of at least 25000 parts-per-million (PPM).

8. (Original) The apparatus of claim 1 further comprising a chiller to receive the reaction product from the outlet and to chill the reaction product to have a temperature of no greater than zero degrees Celsius.

9. (Original) The apparatus of claim 8 wherein the apparatus further comprises a control system and the chiller comprises a freezer, wherein the control system is to identify when a predetermined volume of the reaction medium has been collected, and wherein the control system is operatively coupled to the freezer and the freezer is responsive to the control system so as to freeze the predetermined volume at a temperature of no greater than minus twenty-eight degrees Celsius.

10. (Original) The apparatus of claim 9 wherein the apparatus further comprises a dosing control system, the dosing control system operable to identify an event, wherein the freezer is operatively coupled to the dosing control system so as to, in response to the identified event, heat the predetermined volume so as to cause the predetermined volume to assume a liquid state, wherein the dosing control system is further operable to cause the transfer of a selective amount of the predetermined volume to a treatment vessel, and wherein the freezer is operable to re-freeze a remainder of the predetermined volume following the transfer of the selective amount to the treatment vessel.

11. (Original) The apparatus of claim 1 further comprising at least one ultrasound transducer and a control system to control the ultrasound transducer to selectively direct ultrasound to the anode, and thereby de-passivate the anode, according to a predetermined duty cycle.

12. (Original) The apparatus of claim 1 further comprising at least one processor and instructions stored on at least one physical storage medium, wherein the instructions, when executed, are to cause the at least one processor to: identify one or more electrical parameters associated with generation of the ferrate by the electrochemical cell; identify, from the one or more electrical parameters, a condition of the anode; and generate a textual message adapted for display to a human user, wherein the textual message relates to at least one of a current state of the anode or an anode remaining life expectancy.

13. (Original) The apparatus of claim 1 wherein the apparatus further comprises a membrane in between the anode and the cathode and wherein the apparatus further comprises a control system configured to selective place the apparatus in an inactive state, the control system being further configured to selectively, in association with the inactive state: selectively disable the constant current flow; and fill the electrochemical cell with a preservative, so as to immerse the membrane.

14. (Original) The apparatus of claim 1 wherein: the electrochemical cell is a first electrochemical cell; the apparatus further comprises a second electrochemical cell comprising: an anode comprising iron; a cathode; an inlet to receive the reaction medium, the reaction medium comprising a hydroxide; an outlet to output the reaction product; the source of power is a first source; at least one of the first source or a second source of power is electrically coupled to the anode of the second electrochemical cell and the cathode of the second electrochemical cell, to cause transfer of electrolyzed iron from the anode of the second electrochemical cell to the reaction medium;the galvanostat is to control the at least one of the first source of power or the second source of power so as to provide for a constant current flow between the anode of the second electrochemical cell and the cathode of the second electrochemical cell, notwithstanding a changing electrode gap, between the anode of the second electrochemical cell and the cathode of the second electrochemical cell, as electrolyzed iron is transferred from the anode of the second electrochemical cell to the reaction medium; the first electrochemical cell and the second electrochemical cell are configured in parallel relative to flow of the reaction medium and the reaction product; and the apparatus further comprises a control system to selectively disable production of the reaction product by at least one of the first electrochemical cell or the second electrochemical cell.

15. (Original) The apparatus of claim 14 wherein the first electrochemical cell and the second electrochemical cell share at least one of a common anode or a common cathode, and wherein each of the first electrochemical cell and the second electrochemical cell comprise each of an anode and a cathode that is not shared between the first electrochemical cell and the second electrochemical cell.

16. (Original) The apparatus of claim 1 wherein: the electrochemical cell is a first electrochemical cell; the apparatus further comprises a second electrochemical cell comprising: an anode comprising iron; a cathode; an inlet to receive the reaction medium, the reaction medium comprising a hydroxide; an outlet to output the reaction product; the source of power is a first source; at least one of the first source or a second source of power is electrically coupled to the anode of the second electrochemical cell and the cathode of the second electrochemical cell so as to transfer electrolyzed iron from the anode of the second electrochemical cell to the reaction medium; the galvanostat is to control the at least one of the first source of power or the second source of power so as to provide for a constant current flow between the anode of the second electrochemical cell and the cathode of the second electrochemical cell, notwithstanding a changing electrode gap, between the anode of the second electrochemical cell and thecathode of the second electrochemical cell, as electrolyzed iron is transferred from the anode of the second electrochemical cell to the reaction medium; the first electrochemical cell and the second electrochemical cell are configured in series, with the inlet of the second electrochemical cell configured to receive an input of fluid that has passed through the outlet of the first electrochemical cell; and the apparatus further comprises a control system to selectively depower a first one of the first electrochemical cell or the second electrochemical cell while a second one of the first electrochemical cell or the second electrochemical cell continues to cause transfer electrolyzed iron to the reaction medium.

17. (Original) The apparatus of claim 1 wherein the apparatus further comprises: a voltammetry device configured to measure a ferrate concentration; and a control system to receive an indication of measured ferrate concentration from the voltammetry device and to take an automated action comprising at least one of: adjustment of a parameter used by the galvanostat to control the supply of the power; adjustment of the current flow; generation of a textual message to be transmitted to a human user; adjustment of a temperature of at least one of the electrochemical cell or the reaction medium; adjustment of a speed of the pump; adjustment of a concentration of the hydroxide in the reaction medium; or initiation of an automated electrode cleaning cycle.

18. (Original) The apparatus of claim 1 wherein: the electrochemical cell further comprises a removable trap, the removable trap in fluidic communication with the anode and configured to gravitationally collect sediment from the reaction product; and the apparatus further comprises a sensor and a control system, the sensor to detect when sediment collected within the trap corresponds to a predetermined condition, the control system configured to notify a human user, via at least one of a user interface or a text message, that the removable trap is to receive maintenance.

19. (Original) The apparatus of claim 1 wherein the galvanostat is configured to control supply of power from the source of power so as to provide for an anode current density of between four milliamps per square centimeter and thirty-six milliamps per square centimeter.

20. (Original) The apparatus of claim 1 further comprising a plurality of vessels to receive the ferrate, at least one sensor to detect when each of the of vessels contains a predetermined quantity of at least one of the reaction product or the ferrate, and a robotic transfer mechanism to transfer, once each of the vessels contains the predetermined quantity, the plurality of reaction vessels to a freezer.

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