US20190309427A1

US20190309427A1 - Method for combined electrochemical modification of selected liquid stream characteristics

Info

Publication number: US20190309427A1
Application number: US15/946,158
Authority: US
Inventors: Patrick Ismail James
Original assignee: Blue Planet Strategies LLC
Current assignee: Blue Planet Strategies LLC
Priority date: 2018-04-05
Filing date: 2018-04-05
Publication date: 2019-10-10

Abstract

The current invention pertains to methods for chemical modification of constituents of liquid stream containing organic or inorganic constituents. The methods include steps of: providing at least one reactor device having one or more reaction chambers that include at least one first boundary substance and containing liquid streams; generating at least one second boundary substance from the at least one first boundary substance and the at least one organic or inorganic constituent of the at least one liquid stream; dissolving the at least one second boundary substance in at least one another liquid stream and generating a solution of greater dissolved second boundary substance concentration than the respective constituent initial occurrence in the at least one liquid stream; regenerating the at least one first boundary substance for subsequent generation of the at least one second boundary substance.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims benefits from, the Provisional U.S. Application No. 62/382,274, filed Apr. 6, 2017. Furthermore, the current application is related to and claims benefits from co-owned U.S. patent applications Ser. No. 14/737,827 entitled “METHOD FOR ELECTROCHEMICAL MODIFICATION OF LIQUID STREAM CHARACTERISTICS” (resulting in the U.S. Pat. No. 9,371,592); Ser. No. 13/926,291, entitled, “APPARATUS AND METHOD FOR ADVANCED ELECTROCHEMICAL MODIFICATION OF LIQUIDS” (resulting in the U.S. Pat. No. 9,605,353); Ser. No. 13/621,349, entitled “APPARATUS AND METHOD FOR ELECTROCHEMICAL MODIFICATION OF LIQUIDS” (resulting in the U.S. Pat. No. 9,011,669); Ser. No. 13/117,769, entitled “APPARATUS AND METHOD FOR ELECTROCHEMICAL MODIFICATION OF CONCENTRATIONS OF LIQUID STREAMS” (resulting in the U.S. Pat. No. 8,545,692); Ser. No. 13/251,646, entitled “APPARATUS FOR ELECTROCHEMICAL MODIFICATION OF LIQUID STREAMS” (resulting in the U.S. Pat. No. 8,409,408); Ser. No. 13/020,447 entitled “A METHOD FOR ELECTROCHEMICAL MODIFICATION OF LIQUID STREAMS” (resulting in the U.S. Pat. No. 8,262,892); and Ser. No. 11/623,658 entitled “APPARATUS AND METHOD FOR ELECTROCHEMICAL MODIFICATION OF LIQUID STREAMS” (resulting in the U.S. Pat. No. 7,967,967); all of which (the applications and the resulting patents) are incorporated herein by reference in respective entireties.

FIELD OF THE INVENTION

The invention relates to a method for improved electrochemical modification of concentrations of constituents of liquid streams which contain organic and/or inorganic impurities. More particularly, the current invention pertains to methods of application of combinations of electroregenerated and chemical electron sources or sinks and split compartment electrochemical cells with available electron sinks to drive targeted redox reactions to treat process liquid streams to directly control their chemistry and to separate and/or convert constituents (contaminants, solvent, or dissolved additives like oxygen) info useful byproducts via the treatment.

BACKGROUND OF THE INVENTION

Contamination of liquid streams with various organic and inorganic pollutants is a serious global environmental problem affecting environment quality and represents significant threat to human health and safety. Substantial metal contamination of aquatic environments may arise from current or past commercial mining and metal extraction processes, surfaces modification and protection processes, or communal, and industrial waste sites resulting from a variety of active or defunct industrial fabrication and manufacturing activities. Similarly, significant organic water pollutants, like aliphatic, aromatic, or halogenated hydrocarbons and phenols are frequently associated with oil exploration, extraction and refining, chemicals production, manufacturing processes, or large-scale farming and food processing.
In addition to potential for significant environmental damage, polluted liquid streams represent dilute sources of desirable raw materials like heavy metals and metal oxides. For example, the Berkeley Mine Pit in Butte, Mont. alone at one time was estimated to represent an estimated 30 billion gallons of acid mine drainage which at that time contained ˜180 ppm of copper along with other metals and thus could yield up to 22,000 tons of pure copper by use of a small treatment facility.
An economically relevant group of prior art methods for concentration of heavy species from liquid solutions are based on chemical and physical separations applied separately or in concert as applicable. These processes are generally burdened by complexity, high cost, clear preference for extremely large facilities and high-volume operations. Solvent Extraction (SX) may be regarded as a dominant commercial scale treatment approach for metals concentration towards recovery. In general, several embodiments of this approach experience degraded performance when solution pH, solids or organics content, ionic strength, temperature are outside desired ranges. Many similar disadvantages burden alternative species concentration methods that may incorporate: filtration, ion exchange, distillation or evaporative methods, reverse osmosis, or combinations of listed processes.
Considerable market research conducted by many strategic metal mining and extraction industry consultants indicates that high grade ore reserves are becoming exhausted, leading world-wide to generally downward trending ore quality. For example, practitioners may need a way to use their existing recovery equipment and processes to recover metals from their often plentiful but presently unusable low-grade ore or tailings from legacy operations. Currently, mines can't economically process these ore sources into metals as the resultant process streams containing the target metal extracted from these ores are too weak and need strengthening (concentrating) to allow practical conventional target metal extraction. Thus, the economic considerations may be closely coupled with technology limitations providing for continuous motivation to improve all aspects of the extraction process as measured by cost (capital and operational) reduction metrics,
The extraction technologies enabled by several aspects of the current invention may be adapted to address at least some of the above considerations. In general, hydrometallurgical metal extraction methods frequently require acidity control and pH manipulation (such as lowering pH to refresh acid for processing streams, raising pH to improve processing and/or controllably (and selectively) drop out contaminants (metals) for elimination or recovery as valuable salts, or (potentially in conjunction with pH adjust via counter reaction)—manipulate target species redox states or concentrations to improve selected aspects of the target stream processing. Classic examples may incorporate but are not limited to conversions of Fe⁺³to Fe⁺², Fe⁺²to Fe⁺³, or Cu⁺¹to Cu⁺²and Cu⁺²to Cu⁺¹.
In particular, technologies for capture of mined metals (e.g. copper processing) from streams frequently include modification of mining streams (raffinate, wastewater, draindown, processing bleeds, Pregnant Leach Solution (PLS), and other streams') chemistry to improve mining productivity. The invention here affords a new ability to effect and control such modifications electrochemically to improve processing efficiency and/or operations.
Mining influenced waters like Acid Rock Drainage (ARD) (essentially a naturally occurring leach solution, typically considered wastewater) is often low pH (acidic) and frequently contains multiple metals in a high sulfate background. ARD could also be economically treated using electrochemical methods of the current invention while achieving new control and selectivity over solids generation during treatment.
Even more particularly, the new method could be employed to perform or mitigate a number of economically relevant treatments or needs traditionally accomplished by chemical additions. Nonexclusive examples include reduction of the presence of strongly interfering species for processing such as ferric (Fe⁺³) in hydrometallurgical copper processing streams. Similarly, one may separate and concentrate solubilized target stream copper species as conventionally performed by Solvent Extraction (SX) or Ion Exchange (IE). Similarly, one may lower acidity (raise pH) to enhance solvent extraction efficiency or avoid scale formation/fouling, and affect the selectivity/efficiency of other processes like solvent extraction or ion exchange.
Even further, various instantiations of the method for electrochemical stream characteristic modification may be utilized in embodiments concerning control of microbial (viral, bacterial, fungal/protozoal, and macromolecuiar including misfolded proteins and other malformed molecules, prions and fungal prions) infestations. Usage of acidic or alkaline conditions or inclusion of specific metal (such as silver or copper) for control, destruction, sterilization, and or inactivation of microbiological agents have been well understood by practitioners. In particular embodiments of the current inventions, electrochemically generated acidic or alkaline conditions and metal ions may be used to facilitate effectiveness of added or in-situ generated biocides and bio-suppressors in addition to being biocidal or bio-suppressive by itself.
Generally, electrochemical apparatus and methods in accordance to the current inventions utilize electricity as a convenient, easily-transportable, and efficiently-controllable “universal electrochemical agent” used in the desirable electrochemical reactions (in addition to conventional usage of electricity only as energy supply). Furthermore, in contrast to standard SX and IE concentrating processes requiring deliveries of significant amounts of chemicals, acids, alkalis, and/or salts to drive the targeted separation and concentration processes, various embodiments of the current inventions enable enhanced reduction of disposable byproducts (e.g. by in-situ recycling and regeneration of desirable components), and flexibility of process optimization achievable, for example, by active real time (continuous or batch-to-batch) controlling of concentrations, flows, efficiencies, and reaction rates of redox reactions in the targeted electrochemical cells.

SUMMARY OF THE INVENTION

A method in accordance with the current invention utilizes apparatus that includes at least one reaction chamber having at least one source acting as a sacrificial electroregenerated electron source or sink as appropriate utilized either separately or in conjunction with an electrolytic cell having at least one electrode compartment structured to contain a liquid electrolyte. The electroregenerated FBS electron source or sink may occur in solid, gaseous, or dissolved species forms. The at least one reaction chamber is structured to support redox reactions and to generate liquids and solids usable for creating and maintaining particular concentrations of selected targeted dissolved ions such as Hydrogen ions or ferric (Fe⁺³) conducive for applications such as the transformation or plating of targeted materials in internal or separate reactors.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other embodiments, features, and aspects of the present invention are considered in more detail in relation to the following description of embodiments shown in the accompanying drawings, in which;

FIG. 1. is a schematic cross-sectional side view of devices in accordance with prior art.

FIG. 2. is a graphic illustration of particular features in accordance with prior art.

FIG. 3. is a schematic illustration in accordance with one embodiment of the current invention.

FIG. 4. is a schematic illustration of one embodiment of the current invention,

FIG. 5. is a graphic illustration of process STEP 1 and STEP 2 in accordance with one embodiment of the current invention.

FIG. 6. is a graphic illustration of process STEP 3 and STEP 1 in accordance with one embodiment of the current invention.

FIG. 7. is a graphic illustration of particular features of STEP 1 in accordance with one embodiment of the current invention.

FIG. 8. is a another schematic illustration of one embodiment of the current invention.

FIG. 9. is a another schematic illustration of one embodiment of the current invention.

FIG. 10. is another schematic illustration of one embodiment of the current invention.

FIG. 11. is another schematic illustration of one embodiment of the current invention.

FIG. 12. is a schematic illustration of one embodiment of the current invention.

FIG. 13. is another schematic illustration of one embodiment of the current invention.

FIG. 14. is a graphic illustration of particular features in accordance with the current invention.

FIG. 15. is a schematic illustration of one embodiment of the current invention

FIG. 16. is another schematic illustration of one embodiment of the current invention.

FIG. 17. is another schematic illustration of one embodiment of the current invention,

FIG. 18. is another schematic illustration of one embodiment of the current invention.

DETAILED DESCRIPTION OF THE INVENTION

The invention summarized above may be better understood by referring to the following description, which should be read in conjunction with the accompanying drawings. This description of an embodiment, set out below to enable one to build and use an implementation of the invention, is not intended to limit the invention, but to serve as a particular example thereof. Those skilled in the art should appreciate that they may readily use the conception and specific embodiments disclosed as a basis for modifying or designing other methods and systems for carrying out the same purposes of the present invention. Those skilled in the art should also realize that such equivalent assemblies do not depart from the spirit and scope of the invention in its broadest form.
It may be generally recognized that operation of reaction devices having reaction chambers (including electrochemical cells such as noted above in the SUMMARY OF THE INVENTION) is based on redox reactions and can employ embodiments which can occur in many forms. In general, the reaction devices (either of prior art or novel ones) may be classified in a class of chemical reactors (CR) and class of spilt compartment cells (SCC) (in their multitude of forms), which can provide examples of suitable apparatus to accomplish the current method disclosed herein. One example of the OR of prior art may be represented by the conventional conical cementation precipitation reactor developed several decades ago. Also, one such relevant SCC example typical of the class of Moving Bed Electrode (MBE) cells may be represented by the specific example from the subset of Spouted Bed Electrode (SBE) cells. The specific CR and SCC embodiments noted provide single, but nonexclusive examples of a relevant devices suitable for use in the appropriate process steps of the current method for illustrative purposes and it is understood that other specific CR and SCC forms and combinations could be employed to implement analogous treatment via the method disclosed herein.
A specific embodiment of the CR for cementation is schematically illustrated in the FIG. 1 providing an instantiation highlighting several significant features, and may include one or more electroregenerated sacrificial First Boundary Substance (FBS) 120 (here solid metals) contained in one or more reaction chambers 160 where the solution of liquid electrolyte 130 and solid electron sources 120 may or may not be agitated in a variety of ways after entering the reaction chambers 160 at 195 and open top of chambers 160 respectively, liquid electrolyte 130 flowing through reaction chambers 160 and exiting at 195 and solid reduction product Second Boundary Substance (SBS) 124 migrating 122 and accumulating for exit at 150 respectively. Various targeted reduction reactions can occur spontaneously at the solution/electroregenerated FBS interface; however unidirectional current may also be fed into the cell through connection of a cathode connection to the electron sources 120 and addition of corresponding anodes and an anode connection to further promote and control reactions of interest. The practitioners may note that other reaction chamber configurations (stacked, cylindrical, etc.) could readily also be employed and that units employing multiple and additional chambers may be of the same or different configurations and employ the same or different electroregenerated FBS electron sources 120 as chosen in any specific situation. Depending upon the state of control valves system 185 and 155 the cell may operate in a batch mode processing the fluid contained in the reservoir 197 or in a flow-through mode modifying liquid streams delivered by external pipelines 195 and driven by an external catholyte pumping station 140. Furthermore, such a CR unit can also be used for effecting a Second Boundary Substance (SBS) consumption reaction where the aim is to put ions from a selected SBS electron source 120 into the liquid electrolyte 130.
A particular SCC example of the MBE subset of SCC cell types is schematically illustrated in the FIG. 2 for a specific instantiation case and may include of one or more anodes 210 coupled to one or more high surface area cathodes 220, here in the form of a spouted moving particulates bed, separated by a distance. Catholyte flow 230 of liquid electrolyte catholyte 224, driven by an external catholyte pumping station 240, is directed through the high surface cathode 220 to achieve vigorous convection in the particulates bed to facilitate a high degree of electrode utilization. Unidirectional current is fed into the cell via anode current feed 250(+) and out via cathode current feeder device 290 and cathode current feed 250(−). The cell illustrated in the FIG. 2. is shown in a well-known double chamber planar configuration comprising cathode cell chamber 260 and anode cell, chamber 270 (generally containing electrolytes, catholyte 224 and anolyte 214 respectively) each pair of which is separated by a separator allowing ionic conduction (a porous or selective membrane for example) 280 which directs the bulk flows of electrolytes (catholyte 224 and anolyte 214) while maintaining intimate electrochemical contact between the separated cathode 220 and anode 210 via ionic conduction. Practitioners may note that other cell configurations (stacked, cylindrical, etc.) may also be employed and that cells employing multiple and/or additional chambers may be of similar or different configurations and employ similar or different cathodes 220, anodes 210, and separators 280 as may be chosen in specific embodiments. Depending upon the state of control valve system 285 the cell may operate in a batch mode processing the fluid contained in the reservoir 297, or in a flow-through mode modifying liquid streams delivered by external pipelines 295.
One feature of the current invention pertains to utilization of pH adjustment through redox chemistry rather than conventional chemical neutralization. Traditional chemical neutralization customarily uses conjugate acid-base chemistry (proton transfer) via the addition of compounds which drive acid (proton, H⁺) consumption or generate hydroxide (OH⁻) to raise target solution pH.
The current invention entails electrochemical pH adjustment (electron transfer) concurrent with metal removal by either spontaneous or electro-assisted SBS formation reaction and contains several significant attributes. One attribute of the current invention pertains to initial treatment where selected reducing agents (often metals) are used to drive redox reactions to effect target feed stream pH adjustment during FBS consumption reactions (STEP 1). In effect, chemical addition may be replaced by the addition of electrons—here provided by the oxidation of the electroregenerated sacrificial metal or similarly by a reductant such as a reducing gas to provide FBS interfaces which can spontaneously or electrolytically drive reduction of at least one species present in solution which the reductants contact (FBS consumption reaction). When considering, at least in the context of the current invention, cases of spontaneous sacrificial oxidation of a metal to drive Electrowinning of a second target metal, STEP 1 of the process is analogous to conventional cementation and FBS is represented by a solid consumed sacrificial reducing agent. Here the reduction reactions, generally driven in STEP 1, are collectively referred to as FBS consumption reaction at least to facilitate the general process description for its various potential instantiations. The method avoids much of the sludge generation resulting from, the prevalent neutralization approach of lime based treatments and avoids the “blinding” of potential sludge fractionating which results from gypsum precipitation due to the high sulfate levels common in many relevant target water sources. This can facilitate the separation of components after treatment. It also allows driving and tailoring other redox reactions which may be of interest such as targeted metal removal via cementive plating (spontaneous electroplating)r thereby enabling new options to control the process and extract savings or value. A second attribute of the current invention pertains to its linking and balancing with additional redox reactions performed distinctly from the STEP 1 reactions (STEP 2) bat in conjunction with them. In particular, targeted, reduced products from STEP 1 may be retrieved and used directly in STEP 2 in a distinct but linked and balanced process to provide reduction boundary substances to reduce target constituents of the feed stream via oxidative dissolution of the reduced product recovered from STEP 1 (here termed SBS consumption reaction). To achieve the integrated targeted linked and balanced process, the STEP 1 and STEP 2 redox processes are coupled through the generation of the STEP 1 reduction product (SBS) and its subsequent consumption in STEP 2 so that ultimately component mass flows and the charge passed to effect the target reduction reaction(s) of STEP 1 link to and must correspond to and occur in concert with (i.e. balance) the oxidation reaction(s) of STEP 2 to achieve the integrated method of the invention. This innovation combining these processes into a linked and balanced process can be used to effectively concentrate the target species removed from a portion of the feed stream in STEP 1 into a smaller portion of the feed stream or STEP 1 anolyte via STEP 2 treatment. A third attribute of the current invention pertains to pairing either or both STEP 1 and STEP 2 with one or more similarly linked and balanced electrolytic systems (STEP 3: Electroregeneration, ERG) to regenerate the consumed feedstocks for either STEP 1 or STEP 2 via an integrated targeted electrolysis reaction from selected relevant species generated by STEP 1 or STEP 2. An example would be effecting linked and balanced Electrowinning (EW) in one or more such electrolytic systems to reduce and electroplate a metal(s) consumed in the initial FBS consumption reaction and pH adjustment treatment (STEP 1); thereby regenerating the metal reactant (STEP 3) for reuse in STEP 1 as the solid reducing surface to produce the second electron source feedstock SBS for consumption in reaction (STEP 2). The oxidized form of the metals added in STEP 1 can be transformed back into the metal in STEP 3 by reduction via the injection of electrons from an external source. Similarly, an analogous series of linked and balanced modifications could be driven by targeted electrolysis in one or more electrolytic systems in STEP 3 for regeneration of the oxidizer reactant consumed in STEP 2 as the electron sink. Typically an electrolytic cell apparatus of the appropriate form selected from a wide range of potential cell configurations may be used for STEP 3 with electrons supplied at a cathode or removed at the anode as appropriate via electricity generation and transmission through the cell. However, chemical facilitated reduction means could also be utilized. Proper selection and balancing of target reactions could even further simplify the process for special cases and achieve completion of the noted three (3) linked and balanced reaction steps in two coupled SCC units.
The new method of the current invention provides several significant benefits over conventional chemical based treatments. In addition to avoiding much of the problematic buildup of reaction residuals and possible sludge generation resulting from chemical consumption, it may utilize simple, low-cost, proven technologies in the three main process steps. This may allow cost-effective and rapid implementation. It may be noted that for the example case of iron metal as the primary FBS feedstock utilized to modulate pH in conjunction with the FBS consumption reaction, a given mass of iron contains essentially the same neutralizing power via redox chemistry in terms of moles of electrons as the equivalent mass of lime contains for standard acid/base chemistry in terms of hydroxide and its cost as a feedstock and efficiency for utilization are comparable to lime. Furthermore, the current method presented provides the possibility of neutralizer feedstock recycle/reuse. It also allows decoupling of key portions of the metal recovery and pH adjustment challenge so that overall neutralizer loads present in the feed stream can be moved around on the pH scale to tailor and improve the overall pH adjustment process targeted.
It is well understood that the operation of a CR unit may be based in multiple redox chemical reduction reactions generally resulting in reduction of potential species present in the feed stream being reacted. It may be noted that the specific species reduced and the relative rates and extent of the species reductions achieved may be controlled by the specific design and components of the apparatus, control of the fluid flows plus reactant and system chemistry. Traditional cementation may emphasize metal plating as the primary reaction with other reactions being considered parasitic and reducing the efficiency of the primary reaction. Various embodiments innovation may shift emphasis to other goals such as pH adjustment and, correspondingly, target other reactions as desirable. For example, SBS Formation Reactions [SBSFR-1] to [SBSFR-3] summarize the main STEP 1 reactions for CR cementive copper (SBS) recovery with iron [Fe(s)] (FBS) oxidation under acid conditions.
Fe(s)+2 Fe⁺³→3 Fe⁺² [SBSFR-1]
Fe(s)+Cu⁺²→Cu(s)+Fe⁺² [SBSFR-2]
Fe(s)+2 H⁺→H₂(g)+Fe⁺² [SBSFR-3]
Traditional cementation targets reaction [SBSFR-2] as the primary goal. As a result, practical application of cementation has been limited to cases where reactions [SBSFR-1] and [SBSFR-3] are minor or can be sufficiently suppressed. In the current invention, the reactions [SBSFR-1] and [SBSFR-3] may be facilitated as equally or more desirable goals. The reaction [SBSFR-1] capitalizes on the ferric hydrolysis equilibrium such that reducing the ferric (Fe⁺³) to ferrous (Fe⁺²) when in the appropriate pH regime effectively releases a hydroxide complexed with the ferric and achieves solution neutralization through the addition of electrons—a phenomenon common among transition metal elements. The reaction [SBSFR-3] capitalizes on the hydrogen evolution reaction and effectively directly eliminates protons through the addition of electrons. It thereby can adjust treated solution pH and also potentially provide an electroregenerated gaseous feedstock electron source that might be used as a reductant FBS in STEP 1. This may make methods in accordance with the current invention comparatively more suitable for application to sources with high oxidizer and acid contents—scenarios not practically and often not functionally amenable to traditional cementation. After the oxidizing power and acid content of the target source may be sufficiently lowered by the targeted electrochemical neutralization and FBS consumption reaction(s) (either by use of the electroregenerated reduction product iron or via additional reduction by direct electrolysis during further treatment in STEP 3), metal EW (reaction [SBSFR-2]) may also occur appreciably via rapid oxidative corrosion and dissolution of solid FBS.
It is presented that a CR unit may also be utilized to effect the method STEP 2 innovation SBS consumption reaction. It is well understood that the operation of a CR unit may be based in multiple redox chemical oxidation reactions generally resulting in oxidation of potential species present in the electroregenerated FBS incorporated for reaction with the feed stream being reacted. It may be also noted that the specific species oxidized and the relative rates and extent of the species oxidations achieved may be controlled by the specific design and components of the apparatus, control of the fluid flows plus reactant and system chemistry. Whereas traditional cementation emphasizes reductive processes like metal plating as the primary reaction, SBS consumption reaction (STEP 2) shifts the primary emphasis to oxidative processes like metal dissolution and in particular increasing the dissolved target species concentration over that dissolved in the original source solution. By utilizing recovered metal generated in method STEP 1 as the solid reducing surface feedstock SBS for process STEP 2, chemically driven SBS consumption reactions (SBSCR-x) capitalize on the potentially high oxidizing power and capacity of the feed stream to resolubilize and concentrate the metal(s) of interest in the treated feed stream (Analogous electrolysis driven STEP 2 is not so restricted as the effective oxidizing power and capacity is driven via external energy input and is thereby tailorable). For example, reactions [SBSCR-1] to [SBSCR-3] summarize SBS copper and residual FBS iron consumption reactions (STEP 2) by ferric (Fe⁺³) to ferrous (Fe⁺²) conversion under acid conditions such as might result from STEP 2 treatment of conventional cement copper which is typically 60-90% pure with considerable unreached iron [Fe(s)] as a key impurity.
2 Fe⁺³+Cu(s)→Cu⁺²+2 Fe⁺² [SBSCR-1]
2 Fe⁺³+Fe(s)→3 Fe⁺² [SBSCR-2]
Fe(s)+2 H⁺→H₂(g)+Fe⁺² [SBSCR-3]
Theoretically, pure copper could be generated by reaction [SBSCR-1] to achieve a STEP 2 treated product stream concentration of up to ˜57% of the feed stream ferric (Fe⁺³) concentration on a (g/L) basis. Thus for high oxidizing capacity streams of sufficient oxidative power such as those containing high levels of ferric (Fe⁺³), high concentrations of the target metal (in this example cupric) may be achieved by STEP 2 treatment and enable target metal recovery by a variety of conventional methods.
It is well-understood that the operation of a SCC cell may be based in redox chemical reactions with a non-exclusive illustrative example focusing on applications generally resulting in changes of pH values of the anolyte 214 from relatively high input (beginning value in the batch operation embodiments) value to relatively lower output value (ending value in the batch operation embodiments), while in opposition, the catholyte 224 may be reacted from respective states of relatively low pH into states of relatively high pH values. It may be noted that such acidity changes may be controlled by the specific design and components of the apparatus, control of the fluid flows and electrical discharge parameters. It may be additionally noted that, by arranging and controlling of transport (motions and reactions) of charged species (e.g. ions and electrons) through any simple or composite (multi-chamber) cell one can change oxidation states and/or pH of the electrolytes (and other compounds) in the pertinent chambers of the particular electrolytic cell. Thus, in the simple example in FIG. 2, one may note that the electrochemical redox process generally increase acidity (reduce pH) of the anolyte 214, while simultaneously increasing alkalinity (increasing pH) of the catholyte 224. For example, at the cathode 220 the pH might be raised by proton reduction and hydrogen formation (typical—water splitting at elevated pH or acid neutralization at low pH Eqs. (1)-(3)). Alternatively, oxygen reduction might be targeted to generate alkaline hydroxide or even a potential reactant like hydrogen peroxide (which can then be used as an oxidant or a reductant depending on the detailed chemistry created).

Conditions

2H⁺+2e⁻→H₂(g) (1) ACID
H⁺+H₂O+2e⁻→H₂(g)+OH⁻ (2) Neutral/Alkaline
O₂+2H₂O+4e⁻→4OH⁻ (3) Neutral/Alkaline
The devices and methods of several embodiments of the current invention may be understood using the above concepts of electrochemically controlling of the acidity of pertinent electrolytes and the oxidation states of selected constituents for treatment of preexisting liquid media and/or ad hoc prepared solutions using electricity. More particularly, in some embodiments one or more SBS formation chemical reactors or one or more SCC electrochemical cells may be used in combinations to distinctly yet essentially simultaneously act as a combined reactor for linked and balanced realization of desired chemical reactions to control certain electrolyte parameters such as: pH values and the generation of particular oxidation states and/or concentrations of the constituents (e.g. plating or dissolution of desired metals, adjusting the oxidation states and populations of soluble species, or precipitation of desired low solubility salts such as metal hydroxide, metal sulfide, or metal halide based compounds or combinations thereof as specific non-exclusive examples).
Non-exclusive examples that consider specific chemistries targeted during treatment using the described method follow where, for clarity and not to express limits on the process the discussion is here restricted to situations where the FBS is here taken to be A=a metal(s) added in STEP 1 and recycled by Electroregeneration in STEP 3, and in STEP 2 the SBS is here taken to be B=the product metal(s) generated from STEP 1 and used in STEP 2, and the process steps are briefly discussed for the specific examples. The noted examples focus on examples treating and raising the pH of acidic streams. However, the amphoteric nature of various potential constituents such as transition element metals means this approach could potentially also toe applied to alkaline waters and be used to adjust the pH downwards towards neutral pH.
One exemplary and non-exclusive application concerning methods of electrochemical treatment of acidic mining waters incorporating concentrations of aluminum ions and various oxidation states of iron (Fe) ions is given schematically in FIG. 3 and showing the integrated linked and balanced use of a combination of CRs and SCCs. The illustrated example includes raising the pH of an incoming representative raw target ARD stream (acidic, pH˜1 and containing a combinations of metals including ferric ion (Fe⁺³) and aluminum (Al⁺³)) in a controlled and staged fashion to enable enhanced and selective metal recovery via either or combinations of electrowinning or hydroxide driven sequential precipitation of the target metals. It also notes the potential concurrent acid generation in the anolyte of SCCs employed as a potentially useful byproduct of the targeted reduction reactions in the treated solution. At each SCC electrode single or multiple reactions can be targeted to be driven either essentially sequentially or simultaneously within one or more of the electrochemical cells or cell chambers within a given cell (and similarly by analogy at the FBS and SBS interfaces in the one or more CR units). For example, initial pH adjustment of the catholyte by ferric (Fe⁺³) reduction to iron (Fe(s)) is shown in FIG. 4: by integrated linked and balanced copper SBS formation reaction 410 with concurrent cupric ion concentrating by SBS consumption reaction 420 as an initial combined and complementary precursor reaction to the catholyte proton elimination and iron electrogeneration at a electrolytic cell 430 cathode (with concurrent anolyte acid generation) is noted as a specific embodiment of the disclosed method. This innovation for linking and balancing such reactions offers new options for effecting and controlling the desired target reactions in a combined and integrated process (method).
FIG. 3 illustrates the application and utility of the disclosed method for the specific exemplary embodiments, not exclusive of other applications, of treatment of metal impacted waters by electrochemical tailoring the oxidation state of selected contaminants and also the overall solution pH with the creation of a raised cupric ion concentration (strengthened) output facilitating recovery of valuable copper initially contained in the target stream to be treated at levels hampering practical conventional recovery. The initial step 360 of FIG. 3 includes introduction of raw target stream (here acidic mining water) into a first Chemical Reactor (CR-1) arranged here for ferric reduction in combination with proton reduction and copper plating via FBS iron consumption reaction while raising the feed solution pH to ≤3.5. An example demonstrating this process is illustrated 510 in FIG. 5. The targeted solid (plated copper) is introduced 520 into the SBS consumption reactor 350 (FIG. 3 CR-2) along with liquid target stream (Leachant: here a portion of the Raw Target Stream in FIG. 3) arranged to redissolve the targeted solid (plated copper) in a smaller volume of solution to create a liquid product strengthened copper stream 530 (FIG. 3 SCS-1) containing higher dissolved target SBS metal (copper) concentrations than present in the untreated raw target stream and amenable to recovery by various conventional means. 310 of FIG. 3 includes introduction of the liquid product from 360 into the cathode chamber of electrochemical cell SCC-1 arranged here for catholyte ferrous reduction to iron metal in conjunction with catholyte proton reduction while raising the feed solution pH to ≤4.0. This serves to regenerate the 360 FIG. 3 CR-1 feedstock metal FBS (here iron) by electrowinning and allow its subsequent recovery/recycle while further neutralizing the solution (mainly eliminating its buffering capacity). An example demonstrating this process; FBS iron plating 630 (STEP 3) and plated product FBS consumption 610 (STEP 1) is illustrated in FIG. 6. Further FIG. 7 illustrates how the pellet iron product demonstrated is favorable to very finely divided and non-uniformly sized iron as the FBS by producing much less product contamination yet provides comparable neutralization rates. The separated chamber nature general to SCCs—split compartment cells, (as recited above pertinent to the general class of applicable electrochemical cells (SCC-X, where X=1-4) as illustrated in FIG. 3) such as the specific SBS version described in FIG. 2 and noted here for illustration, may limit significantly bulk electrolyte mixing. This may minimize parasitic counter reaction losses (i.e. neutralization of anode generated protons by cathode proton consumption and by reacting with cathode generated hydroxide or similarly anode oxidation of cathode generated catholyte ferrous (Fe⁺²) and anode regeneration of ferric (Fe⁺³). Removal of ferric (Fe⁺³) in FIG. 3 step 360 reduces the possibility of ferric oxyhydroxides like ferric hydroxide (Fe(OH)₃) precipitation initiating at pH ˜3, thus clearing the way for subsequent metal salts (such as oxyhydroxides or others) precipitation in step 320 by creation of appropriate conditions to limit their solubility. Step 320 of precipitation and extraction of other metal oxyhydroxides like Al(OH)₃may be achieved by controlling the pH (for this embodiment to about pH˜5) in a reactor using product catholyte from cell SCC-1. Subsequently, in Step 330 separate precipitation of low solubility salts such as oxyhydroxides of any remaining Fe(OH)₂and most other remaining transition metals (copper, cobalt, nickel, and zinc for example) may be conducted in a reactor characterized by relatively reduced acidity (e.g. having substantially neutral pH˜8) through use of product catholyte from cell SCC-2. Following step 340 may include separation of additional low alkaline solubility salts such as metal oxihydroxides from more strongly alkaline solutions (e.g. pH ˜11) produced using product catholyte from cell SCC-3 and outputting of the resulting alkaline liquid products to SCC-4 to generate high pH catholyte for other uses such as neutralizer in 360, 320, 330, or 340 and/or reusing all or part of it as constituents of electrolyte feedstocks for cells SCC-X where X=1 to 4. A non-exclusive reuse example for the neutralized or acidic products may be to chemically leach additional metals out of predisposed materials (natural or man-made deposits of low grade ores or similar). The disclosed method can be used in different embodiments beyond the illustrative exemplary application and embodiment (FIG. 4, Example 1: A=Fe/B=Cu) to alternative chemistries and operation modes conceived for treatment of other species potentially occurring in targeted mining influenced waters (MIW) and industrial waters. As already noted above, in contrast to conventional chemical pH adjustment which uses proton transfer via conjugate acid-base chemistry, the process of present invention utilizes electrochemical pH adjustment via electron transfer. The present invention also uses electroregenerated FBS (A) and SBS (B) as electron shuttles (i.e. sacrificial metal substrates as a solid electron shuttle as highlighted in this exemplary embodiment for example) to create associated spontaneous reaction boundaries to separate and control targeted reduction reactions in novel ways. The process is applicable to a variety of industrial processing and wastewaters including but not limited to those such as acidic high sulfate, high nitrate, high chloride sources, or alkaline streams such as cyanide based leaching streams found in hydrometallurgical processing. The overall treatment approach can be extended in a variety of ways to fine tune the process through tailoring of the relative competitions of the salient component reactions within the system and analogous to reactions [SBSFR-1 to SBSFR-3, SBSCR-1 to SBSCR-3, and (1) to (3)] for the exemplary embodiment. Such extension can be achieved through selection of particular combinations of process operating conditions and electroregenerated FBS denoted as (A) and SBS denoted as (B) acting as chemical, agent electron sources in various forms like metallic substrates (solid electron shuttles) or appropriate analogous electroregenerated oxidizing agents acting as electron sinks to improve process efficacy or to achieve specific goals. As a result, a multitude of potential separations/recoveries may be structured as separate embodiments or in combinations.
Solid Electron Shuttle Alternative Embodiments: A variety of FBS and SBS components acting as electron sources and occurring as solid electron shuttles (reducing agents) and their combinations may be applicable depending on the target stream chemistry and desired treatment products. For example, in 410 of FIG. 4 (STEP 1), for the FBS=A, zinc (Zn) metal could be substituted for iron (Fe) metal to adjust parameters such as the relative extent of pH modification vs. ferric (Fe⁺³) reduction (FIG. 8). Such substitution would, of course, also impact 430 (STEP 3)—the FBS Electroregeneration, here metal electrowinning, electron shuttle recycle step and might be used to potentially adjust and facilitate the relative electrowinning cell operation rate (current density), pH modification, and plating efficiency in desirable ways. Such substitution with a stronger reducing agent than iron (Fe) may be applicable for application to target streams with different buffering capacities and different relative major metal constituent concentrations than found in representative hydrometallurgical copper production and wastewater streams. More examples using alternative STEP 1 FBS components (A) and STEP 1 EW targets/STEP 2 SBS components (B) embodiments may be identified from consideration of the electrochemical potentials for the appropriate associated metals and solution species. It should be noted that as agents (A) and (B) are both acting as reducing agents in this example, similar examples can be used subject to the conditions imposed when considering particular A/B pairs to accomplish the targeted reactions. Generally metal substrates with electrochemical potentials more negative than the STEP 1 primary target reduction reaction can work spontaneously for both the FBS and SBS and usually STEP 2 SBS is restricted to solid metal(s) to facilitate STEP 1 product harvesting. The primary feed stream oxidization driver considered in FIGS. 3-7 is the reduction of ferric (Fe⁺³) to ferrous (Fe⁺²) in acidic aqueous solution [E°=+0.77 V (NHE—Normal Hydrogen Electrode)]. Possible STEP 1=A/STEP 2=B single metal combinations for the ferric reduction scenario include (but are not limited to):

A=Rh, Re, Cu, Bi, As, Sb, Bi, Ir, Te, W, Pb, Zn, Ni, V, Co, Tl, In, Se, Cd, Fe, Cr, Ga, Zn, Ti, Mn, Pd, Ag, Au, Pt
B=Rh, Re, Cu, Bi, As, Sb, Bi, Ir, Te, W, Pb, Sn, Ni, V, Co, Tl, In, Se, Cd, Fe, Cr, Ga, Zn, Ti, Mn, Pd, Ag, Au, Pt

Where the electrochemical potential for FBS (A) is less than for SBS (B) and the electrochemical potential of a major or primary oxidant in the untreated source (for this illustrative discussion the reduction of ferric (Fe⁺³) to ferrous (Fe⁺²) in acidic aqueous solution) is greater than the electrochemical potential of SBS (B) so as to spontaneously drive the target SBS formation (reduction of B) and SBS consumption (oxidation of B) reactions respectively, and it is understood that, at least for the purposes of the current class of embodiments, the denoted substances A and B means real metal materials dominant in these elements and not the completely pare element. That is for example, A drives the reduction of ferric to ferrous and then drives the reduction/plating of B via SBS formation reaction and then solution containing sufficient ferric drives SBS consumption reaction of B to create the strengthened solution of dissolved B. When the reaction is driven in a SCC electrolysis cell, the noted restrictions on the relative electrochemical potentials for A and B are removed as the target reactions may be driven by the input of electrical potential energy from an external source and a range of well-established appropriate electrode materials can be used to support the target reactions.
Some Additional and/or Alternative Embodiments: In other embodiments, additional methods of extending the treatment process application might also be employed. Alloys or mixtures of metals or non-metallic solids could be employed in such embodiments as solid electroregenerated FBS and SBS electron sources to effectively generate more nuanced reaction control as could analogous electroregenerated FBS components ranging in forms such as gaseous, liquid, or dissolved species acting as electron sources (reducing agents) or conversely alternative electron sinks (oxidizing agents) to drive corresponding reduction (or conversely oxidation) reactions of interest. Possible STEP 1 consumed FBS=A single gas, liquid, or dissolved species combinations and formed SBS=B metal examples for the ferric reduction scenario include (but are not limited to):

A=H₂, SO₂, NO, NO₂, N₂O, N₂O₂ ⁻², CO, ClO₂, H₂S, H₂O, H₂O₁, HO₂ ⁻, NH₃,
- N₂O₄, NH₄OH, CH₂, C₂H₈, MeOH, EtOH, Propanol, HCOOH, and other hydrocarbons, V⁺², V⁺³, U⁺⁴, UO₂ ⁺, Tc⁺², Ru⁺², Bi⁺, H₂SO₃, S₂O₃ ⁻², S₂O₈ ⁻², HNO₂, MnO₂, Cu₂O, RuO₄ ⁻², ClO₃ ⁻, ClO₂ ⁻, PbO, In⁺, In⁺², Sn⁺²,
- Fe⁺², Cu⁺, Co⁺², OH⁻, Br⁻, I⁻, IO⁻, SO₃ ⁻²
B=Rh, Re, Cu, Bi, As, Sb, Bi, Ir, Te, W, Pb, Sn, Ni, V, Co, Tl, In, Se, Cd, Fe, Cr, Ga, Zn, Ti, Mn, Pd, Ag, Au, Pt

Where the electrochemical potential for FBS (A) is leas than for SBS (B) and the electrochemical potential of a major or primary oxidant in the untreated source (for this illustrative discussion the reduction of ferric (Fe⁺³) to ferrous (Fe⁺²) in acidic aqueous solution) is greater than the electrochemical potential of SBS (B) so as to spontaneously drive the target SBS formation (reduction of B) and SBS consumption (oxidation of B) reactions respectively, and it is understood that, at least for the purposes of the current class of embodiments, the denoted substances A and B means real materials dominant in these components and not the completely pure component. That is for example, A drives the reduction of ferric to ferrous and then drives the reduction/plating of B via the SBS formation reaction and then solution containing sufficient ferric drives SBS consumption reaction via oxidation of B to create the strengthened solution of dissolved B. When the reaction is driven in a SCC electrolysis cell, the noted restrictions on the relative electrochemical potentials for A and B are removed as the target reactions may be driven by the input of electrical potential energy from an external source and a range of well-established appropriate electrode materials can be used to support the target reactions.
Also, the target stream chemistry may be adjusted via additives to refine the process. For example, inclusion of chloride or a complexing agent or a catalyst or supplementary redox reagent or other additive(s) in STEP 2 [SBS consumption reaction] could be used to modify the SBS reducing agent interface reactivity and adjust, for example, the effective treatment relative target proton/metal reduction rates. One could also electrolytically augment the reactivity of a solid SBS with an imposed electrical signal in a redox cell configuration to further tailor the targeted competing reactions. Similar additive inclusion may be also utilized to tailor and facilitate relevant STEP 1 and STEP 3 FBS and SBS reactions and as additionally may electrical augmentation be applied to relevant STEP 1 reactions.
The extent of how much more negative the effective electrochemical potential for the (STEP 1) FBS target reducing agent A must be than the electrochemical potential for the SBS product target B may require consideration of secondary oxidizers present in the target stream of interest or potential addition of modifiers to adjust the FBS reducing agent and SBS product reactivity. Also, adjustment of a target species' electrochemical potential to account for the species' concentration and chemical activities as noted in the Nernst equation may need to be considered for specific scenarios. Additionally practical considerations such as product solubility, substrate cost, toxicity, passivation/surface kinetics, ability for plating/electro-regeneration and other characteristics may wish to be considered for particular substrate and target solution combinations.
Several cases targeting spontaneous realization of the STEP 1 and STEP 2 reactions via illustrative examples of target A/B metal pairings including, but not limited to, the following noted six (6) (of many possible) embodiments have been presented below (FIGS. 8-13). Similar extensions to cases where metal SBS oxidation is dominated by reactions other than reduction of ferric (Fe⁺³) to ferrous (Fe⁺²) or is electrolytically driven can also be considered and appropriate embodiments of this invention identified in a similar manner. One alternative embodiment of a processing method in accordance with the above processing scheme has been illustrated in FIG. 8—Example 2: A=Zn/B=Cu. The method utilizes three main steps which are briefly summarized. STEP 1 (SBS formation reaction) 810 uses sacrificial sine corrosion as a solid FBS reducing agent interface to adjust the target water chemistry in desirable ways. Here emphasis is on adjusting the pH and oxidative power of the target stream with solid copper (SBS) recovery as a secondary byproduct. At the reducing solid FBS surface (here zinc) ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²). This lowers the oxidative power of the stream being treated and can raise the solution pH via release hydroxide completed during iron ion hydrolysis. Also, direct proton consumption and hydrogen evolution from reaction of the FBS reducing agent with protons/acid in the solution can also occur and raise the solution pH. When the oxidative power of the target solution has been sufficiently lowered, metals, such as copper, present in target feed stream being treated can be electrowon as the SBS at the FBS reducing agent solid surface via cementive plating and then they can be readily separated using common solid/liquid separation techniques for use as the consumed SBS reducing agent in the STEP 2 reactions. More specific examples may pertain to embodiments with other, either more positive electrochemical potentials or more noble metals or less positive electrochemical potentials or less noble metals in target feed solutions, although, the practitioners may note that the above process may depend upon the specific reactivity of metal/solution constituent combinations. For example, chloride might attack one metal much more than another and considerably adjust the effective reactivity or relative redox potentials of the two metals as compared to their relative electrochemical potential values under standard conditions associated with the common redox table values often quoted.
STEP 2 (SBS consumption reaction) 820 employs the 810 STEP 1 captured copper product (SBS) as a sacrificial reducing solid surface and corrodes it with highly oxidizing feed stream. This solution may represent untreated target stream solution as shown in FIG. 8 or potentially electroregenerated SCC product where an oxidizing agent has been created and incorporated into the feed stream. Here the oxidative power of the target feed stream acts is leveraged as a leachant to dissolve the recovered SBS plated copper and create a concentrated target metal ion (here cupric ion) solution in the portion of the feed stream utilized to drive the solid SBS copper oxidation. At the reducing SBS surface of the plated copper STEP 1 product (SBS) ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²) while corroded copper dissolves as cupric (Cu⁺²) ions along with unreacted residual zinc which dissolves as zinc ions (Zr⁺²)—i.e. ferric is cementively reduced in STEP 2 (but to ferrous rather than a solid metal) by SBS copper and/or residual unreacted FBS zinc metal impurities. This lowers the oxidative power of the feed stream being treated and can raise the solution pH via release of hydroxide complexed during iron ion hydrolysis in addition to any direct proton consumption and resultant pH shift resulting from feed stream reaction with the STEP 1 SBS product and residual FBS. As the feed stream initial ferric concentration is typically much higher than the initial concentration of the target SBS metal being consumed (here copper), the sacrificial SBS metal solution concentration can be concentrated in solution relative to its initial target stream concentration; often significantly, in the treated stream and then be recovered in practical fashion from this concentrated stream by conventional methods. STEP 3 (Electroregeneration) 830 here utilizes electrowinning to further adjust the STEP 1 treated stream chemistry and concurrently regenerate or electroplate the STEP 1 FBS reducing agent (here zinc) in a suitable form to be re-used as the sacrificial reducing agent in 810 STEP 1. This may be performed directly at the cathode of an electrolytic cell or in directly through chemical means. This enables reuse of the captured and regenerated FBS metal and recycle of this substrate. Similarly, STEP 2 leachant feed solution oxidative power might also be augmented or refreshed by STEP 3 tailored to oxidize or re-oxidize species of interest for use as an oxidizing agent in the leachant feed stream for STEP 2.
Another alternative embodiment of a processing method in accordance with the above processing scheme [0047, 0048] has been illustrated in FIG. 9—Example 3: A=Sn/B=Cu. The method utilizes three main steps which are briefly summarized. STEP 1 (SBS formation reaction) 910 uses sacrificial fin corrosion as a reducing FBS to adjust the target stream chemistry in desirable ways. Here emphasis is on adjusting the pH and oxidative power of the target stream with copper recovery (SBS) as a secondary byproduct. At the reducing FBS surface ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²). This lowers the oxidative power of the stream being treated and can raise the solution pH via release of hydroxide complexed during iron ion hydrolysis. Also, direct proton consumption and hydrogen evolution from reaction of the reducing FBS surface with protons/acid in the solution can also occur and raise the solution pH. When the oxidative power of the target solution is sufficiently lowered, SBS metals such as copper present in the target feed stream being treated can be electrowon at the solid reducing FBS surface via cementive plating and then they can be readily separated using common solid/liquid separation techniques. STEP 2 (SBS consumption reaction) 920 employs the 910 STEP 1 captured copper product as a sacrificial reducing solid SBS surface and corrodes it with highly oxidizing target feed stream. This solution may represent untreated target stream, solution as shown in FIG. 9 or potentially electroregenerated SCC product where an oxidizing agent has been created and incorporated into the feed stream. Here the oxidative power of the target feed stream is leveraged as a leachant to dissolve the solid recovered copper SBS and concentrate it in a portion of the product stream. At the reducing SBS surface (here tin) ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²) while corroded copper dissolves as cupric (Cu⁺²) ions—i.e. ferric is reduced to ferrous with copper. This losers the oxidative power of the stream being treated and can raise the solution pH via release of hydroxide complexed during ferric iron ion hydrolysis. As the feed stream initial ferric concentration is typically much higher than the initial solution concentration of SBS metal being consumed (here copper), the sacrificial SBS metal can be concentrated relative to its concentration in the untreated feed target scream; often significantly, in the SBS consumption reaction treated product stream and then be recovered from this concentrated stream by conventional methods. STEP 3 (Electroregeneration) 930 utilizes electrowinning (EW) to further adjust the STEP 1 treated stream chemistry and concurrently electroplate the STEP 1 FBS reducing agent (tin) in a suitable form to be re-used as the sacrificial reducing FBS in 910 STEP 1. This may be performed directly at the cathode of an electrolytic cell or in directly through chemical means. This enables reuse of the captured and regenerated. FBS metal and recycle of this substrate.
Yet another alternative embodiment of a processing method in accordance with the above processing scheme [0047, 0048] has been illustrated in FIG. 10—Example 4: A=Sn/B=Sb. The method utilizes three main steps which are briefly summarized. STEP 1 (SBS formation reaction) 1010 uses sacrificial tin corrosion as a reducing FBS to adjust the target stream chemistry in desirable ways. Here emphasis is on adjusting the pH and oxidative power of the target stream with antimony recovery as a secondary byproduct. At the solid reducing FBS surface ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²). This lowers the oxidative power of the stream being treated and can raise the solution pH via release of hydroxide complexed during iron ion hydrolysis. Also, direct proton consumption and hydrogen evolution from reaction of the reducing FBS surface with protons/acid in the solution can also occur and raise the solution pH. When the oxidative power of the target solution is sufficiently lowered, SBS metals such as antimony present in the target feed stream being treated can be electrowon at the solid reducing FBS surface via cementive plating and then they can be readily separated using common solid/liquid separation techniques. STEP 2 (SBS consumption reaction) 1020 employs the 1010 STEP 1 captured plated antimony product as a sacrificial reducing SBS and corrodes it with highly oxidizing target feed stream. This solution may represent untreated target stream solution as shown in FIG. 10 or potentially electroregenerated SCC product where an oxidizing agent has been created and incorporated into the feed stream. Here the oxidative power of the target feed stream is leveraged as a leachant to dissolve the recovered SBS antimony and concentrate it in a portion of the product stream. At the reducing SBS surface ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²) while corroded antimony dissolves as (SbO⁺) ions—i.e. ferric is reduced to ferrous with antimony. This lowers the oxidative power of the stream being treated and can raise the solution pH via release hydroxide complexed during iron ion hydrolysis. As the feed stream initial ferric concentration is typically much higher than the initial solution concentration of SBS metal being consumed (here antimony), the sacrificial SBS metal can be concentrated in solution relative to its initial target stream concentration; often significantly, in the treated stream and then be recovered from this concentrated stream by conventional methods. STEP 3 (Electroregeneration) 1030 utilizes electrowinning (EW) to further adjust the STEP 1 treated stream chemistry and concurrently electroplate the STEP 1 FBS reducing agent (tin) in a suitable form to be re-used as the sacrificial reducing SBS in 1010 STEP 1. This may be performed directly at the cathode of an electrolytic cell or in directly through chemical means. This enables reuse of the captured and regenerated FBS metal and recycle of this substrate.
In addition, another alternative embodiment of a processing method in accordance with the above processing scheme [0047, 0048] has been illustrated in FIG. 11—Example 5: A=Zn/B=Sb. The method utilizes three main steps which are briefly summarized. STEP 1 (SBS formation reaction) 1110 uses sacrificial zinc corrosion as a solid reducing FBS to adjust the target stream chemistry in desirable ways. Here emphasis is on adjusting the pH and oxidative power of the target stream with solid SBS antimony recovery as a secondary byproduct. At the reducing FBS surface ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²). This lowers the oxidative power of the stream being treated and can raise the solution pH via release of hydroxide complexed during iron ion hydrolysis. Also, direct proton consumption and hydrogen evolution from reaction of the reducing FBS with protons/acid in the solution can also occur and raise the solution pH. When the oxidative power of the target solution is sufficiently lowered, SBS metals such as antimony present in the target feed stream being treated can be electrowon at the solid reducing FBS surface (here zinc) via cementive plating and then they can be readily separated using common solid/liquid separation techniques. STEP 2 (SBS consumption reaction) 1120 employs the 1110 STEP 1 captured solid antimony product as a sacrificial reducing SBS and corrodes it with highly oxidizing target feed water. This solution may represent untreated target stream solution as shown in FIG. 11 or potentially electroregenerated SCC product where an oxidizing agent has been created and incorporated into the feed stream. Here the oxidative power of the target feed stream is leveraged as a leachant to dissolve the recovered SBS antimony and concentrate it in a portion of the product stream. At the solid reducing SBS surface ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²) while corroded antimony dissolves as (SbO⁺) ions—i.e. ferric is reduced to ferrous with antimony. This lowers the oxidative power of the stream being treated and can raise the solution pH via release of hydroxide complexed during iron ion hydrolysis. As the feed stream initial ferric concentration is typically much higher than the initial dissolved concentration of SBS metal being consumed (here antimony), the sacrificial SBS metal in solution can be concentrated in solution relative to its initial target stream concentration; often significantly, in the treated stream and then be recovered from this concentrated stream by conventional methods. STEP 3 (Electroregeneration) 1130 utilizes electrowinning (EW) to further adjust the STEP 1 treated stream chemistry and concurrently electroplate the STEP 1 FBS reducing agent (zinc) in a suitable form to be re-used as the sacrificial reducing FBS surface in 1110 STEP 1. This may be performed directly at the cathode of an electrolytic cell or indirectly through chemical means. This enables reuse of the captured and regenerated FBS metal and recycle of this substrate.
Yet another additional alternative embodiment of a processing method in accordance with the above processing scheme [0047, 0048] has been illustrated in FIG. 12—Example 6: A=Fe/B=In. The method utilizes three main steps which are briefly summarized. STEP 1 (SBS formation reaction) 1210 uses sacrificial iron corrosion as a reducing FBS to adjust the target stream chemistry in desirable ways. Here emphasis is on adjusting the pH and oxidative power of the target stream with indium recovery as a SBS secondary byproduct. At the solid reducing FBS surface ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²). This lowers the oxidative power of the stream being treated and can raise the solution pH via release of hydroxide complexed during iron ion hydrolysis. Also, direct proton consumption and hydrogen evolution from reaction of the reducing FBS with protons/acid in the solution can also occur and raise the solution pH. When the oxidative power of the target solution is sufficiently lowered, SBS metals such as indium present in the target feed stream being treated can be electrowon at the solid reducing FBS surface via cementive plating and then they can be readily separated using common solid/liquid separation techniques. STEP 2 (SBS consumption reaction) 1220 employs the 1210 STEP 1 captured solid indium product as a sacrificial reducing SBS and corrodes it with highly oxidizing target feed stream. This solution may represent untreated target stream solution as shown in FIG. 12 or potentially electroregenerated SCC product where an oxidizing agent has been created and incorporated into the feed stream. Here the oxidative power of the target feed stream is leveraged as a leachant to dissolve the recovered solid SBS indium and concentrate it in a portion of the product stream. At the solid reducing SBS surface ferric (Fe⁺³) iron is eliminated by reduction to ferrous (Fe⁺²) while corroded indium dissolves as (In⁺³) ions—i.e. ferric is reduced to ferrous with indium. This lowers the oxidative power of the stream being treated and can raise the solution pH via release of hydroxide complexed during iron ion hydrolysis. As the feed stream initial ferric concentration is typically much higher than the initial concentration of SBS metal being consumed (here indium), the sacrificial SBS metal can be concentrated in solution relative to its initial target stream concentration; often significantly, in the treated stream and then recovered from this concentrated stream by conventional methods. STEP 3 (Electroregeneration) 1230 employs electrowinning (EW) to further adjust the STEP 1 treated stream chemistry and concurrently electroplate the STEP 1 FBS reducing agent (iron) in a suitable form to be re-used as the sacrificial reducing FBS surface in 1210 STEP 1. This may be performed directly at the cathode of an electrolytic cell or in directly through chemical means. This enables reuse of the captured and regenerated FBS metal and recycle of this substrate.
Another alternative embodiment of a processing method in accordance with the above processing scheme [0047, 0048] has been illustrated in FIG. 13—Example 7: A=Fe/B=Re. The method utilizes three main steps which are briefly summarized. STEP 1 (SBS formation reaction) 1310 uses sacrificial iron corrosion as a reducing FBS to adjust the target stream chemistry in desirable ways. Here emphasis is on adjusting the pH and oxidative power of the target stream with rhenium recovery as a secondary SBS byproduct. At the solid reducing FBS surface ferric (Fe⁺³) iron is eliminated fay reduction to ferrous (Fe⁺²). This lowers the oxidative power of the stream, being treated and can raise the solution pH via release hydroxide complexed during iron ion hydrolysis. Also, direct proton consumption and hydrogen evolution from reaction of the reducing FBS with protons/acid in the solution can also occur and raise the solution pH. When the oxidative power of the target solution is sufficiently lowered, SBS metals such as rhenium present in the target feed stream, being treated can be electrowon at the solid reducing FBS surface via cementive plating and then they can be readily separated using common solid/liquid separation techniques. STEP 2 (SBS consumption reaction) 1320 employs the 1310 STEP 1 captured solid rhenium product as a sacrificial reducing SBS and corrodes if with highly oxidizing target feed stream. This solution may represent untreated target stream solution as shown in FIG. 13 or potentially electroregenerated SCC product where an oxidizing agent has been created and incorporated into the feed stream. Here the oxidative power of the target feed stream is leveraged as a leachant to dissolve the recovered solid SBS rhenium and concentrate it in a portion of the product stream. At the reducing SBS surface ferric (Fe⁺³) iron is eliminated toy reduction to ferrous (Fe⁺²) while corroded rhenium dissolves as perrhenate (ReO₄ ⁻) ions—i.e. ferric is reduced to ferrous with rhenium. This lowers the oxidative power of the stream being treated and can raise the solution pH via release of hydroxide complexed during iron ion hydrolysis. As the feed stream initial ferric solution concentration is typically much higher than the initial concentration of SBS metal being consumed (here rhenium), the sacrificial SBS metal can be concentrated in solution relative to its initial target stream concentration; often significantly, in the treated stream and then recovered from this concentrated stream by conventional methods. The STEP 3 (Electroregeneration) 1330 utilizes electrowinning (EW) to further adjust the STEP 1 treated stream chemistry and concurrently electroplate the STEP 1 FBS reducing agent (iron) in a suitable form to be re-used as the sacrificial reducing FBS in 1310 STEP 1. This may be performed directly at the cathode of an electrolytic cell or in directly through chemical means. This enables reuse of the captured and regenerated FBS metal and recycle of this substrate.
In addition, a variety (or mixture) of acids could be generated in the SCC units in different embodiments and could include but is not limited to sulfuric, sulfurous, hydrochloric, nitric, nitrous, phosphoric, phosphorous, perchloric, acetic, hydrosulfuric, boric, bydrobromic, hydroiodic, hydrofluoric, others. Embodiments generating sulfuric acid may be of particular interest since the raw target stream sources including sulfate may be very common. Also, embodiments including seawater application as the raw target stream (which the mining industry may be increasingly utilizing) may generate HCl—should that be of interest. Furthermore, the initial input stream could start at higher neutral or even alkaline pH with the process reversed—treatment lowers input stream pH to effect targeted separations within the anolyte and the “byproduct” may be now a strong base (catholyte) where Mx(OH)_Ncould be a variety of Mx and N combinations where Mx(OH)_Nmay be highly soluble (including alkali metals and ammonium or organics cations). An example and nonexclusive application embodiment would be the treatment of drainage from coal mining sites which is known to occur in many forms with a bimodal pH distribution, sometimes being acidic and other times being alkaline.
The present invention has been described with references to the exemplary embodiments arranged for different applications. While specific values, relationships, materials and components have been set forth for purposes of describing concepts of the invention, it will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the basic concepts and operating principles of the invention as broadly described. It should be recognized that, in the light of the above teachings, those skilled in the art can modify those specifics without departing from the invention taught herein. Having now fully set forth the preferred embodiments and certain modifications of the concept underlying the present invention, various other embodiments as well as certain variations and modifications of the embodiments herein shown and described will obviously occur to those skilled in the art upon becoming familiar with such underlying concept. It is intended to include all such modifications, alternatives and other embodiments insofar as they come within the scope of the appended claims or equivalents thereof. It should be understood, therefore, that the invention may be practiced otherwise than as specifically set forth herein. Consequently, the present embodiments are to be considered in all respects as illustrative and not restrictive.
Possible Embodiment Combinations of Method: Each linked and balanced instantiation combination 1n:2n:3 for the method where n=A or B can use a range of reduction targets and a range of oxidation targets X, X′, Y1, Y2, and Z, each of which may consist of one or more specific substances in combination (see, for example, FBS and SBS options A and B respectively as listed in paragraphs [0047 and 0043]), where X is the reduced form of the STEP 1 (Remove) target product SBS and X′ is its oxidized form, Y1 is the reduced form of the STEP 1 target feedstock FBS and the STEP 3 (Electroregenerate) reduction reaction target product when recycling FBS, Y2 is the target feedstock used in STEP 2 (Concentrate) to facilitate the re-oxidation of X into X′ and X2 can be an oxidized form of Y1 or another species, and Z is an appropriately selected product(s) of the STEP 3 oxidation reaction (and could be Y2 when appropriate). FIG. 14 summarizes possible combinations for different embodiments of the method presented. For the Chemical Method options (n=A), the redox chemistry must be selected to be spontaneous whereas for the electrochemical options (n=B) reactions are effected by an electrochemical cell and may be either spontaneous or non-spontaneous (externally driven), selected as appropriate for specific processing goals and conditions. STEP 3 denotes potential conversion of one or more species into the desired FBS and SBS feedstock or feedstock precursor targets (Y1) or (Y2) respectively for consumption in STEP 1 or STEP 2 respectively by redox chemistry effected by various potential means including but not limited to electrolysis by an electrochemical cell as illustrated here to provide a representative but not restrictive instant example of the method. For embodiment 1B:2B:3 (STEP 1 and STEP 2 SCC electrolysis cell reactors), a special case exists where the reduced form of Y2=Y1 and the oxidized form of Y1=Y2 and STEP 3 may become superfluous reducing the treatment embodiment to 1B:2B with the Y1/Y2 redox couple acting as a reversible electron shuttle between the linked and balanced STEP 1 and STEP 2 reactions.
Method Embodiment Special Case-A: FIG. 15 illustrates one example of instantiating the embodiment special case noted above in paragraph [0060] where the complete integrated 3-STEP treatment is accomplished in two coupled electrolysis processes (effected by one or more SCC cells). Here two integrated SCC electrolysis cell assemblies embodying the full generality of instantiating specific examples of SCC cells as more fully discussed in relevant patents such as noted in the CROSS REFERENCE TO RELATED APPLICATIONS is encompassed with this description emphasizing central aspects of linking and balancing chemistries and target reactions for process integration for a specific simple and illustrative instantiation case without limiting the range of associated and obvious extensions included by these teachings. For example, each SCC cell assembly respectively may include of one or more anodes 1508, 1548 coupled to one or more cathodes 1504, 1544, here where one is in the form of a high surface area moving particulates bed (cathode 1504 and anode 1548 respectively), contained respectively in cathode cell chambers 1532, 1574 and anode cell chambers 1534, 1572 (which contain the respective associated electrodes and electrolytes and shown here for the well-known double chamber planar configuration) each pair of which is separated by a separator 1590, 1592 allowing ionic conduction (a porous or selective membrane for example) and which directs the bulk flows of electrolytes (catholyte 1510, 1519 and anolyte 1518, 1514) while maintaining intimate electrochemical contact between the separated cathodes 1504, 1544 and anodes 1508, 1548 via ionic conduction. In a first SCC cell assembly, catholyte flow of feed stream liquid electrolyte catholyte 1510 containing oxidized SBS form X′, is directed into cathode cell chamber 1532 and then through the high surface cathode 1504, to achieve vigorous convection in the particulates bed to facilitate a high degree of electrode utilization and the oxidized precursor SBS target X′ is reduced to the SBS target X and plated onto particulates electrode substrate $ and denoted as plated product X/S (Treatment STEP 1: Remove) and where X is a suitable substance selected from lists B seen in paragraphs [0047, 0048]. The catholyte/cathode mixture is removed from the cathode cell chamber 1532, directed through separating unit 1582 where the treated electrolyte stream 1512 and sufficiently SBS plated (“ripened”) particulates electrode elements 1520 which are plated with SBS material X on substrate S and denoted X/S are separated and treated solution product 1512 is discharged and ripe particulates 1520 are passed to the anode cell chamber 1572 of the second SCC cell assembly for anodic SBS harvesting (“Stripping”) and generation of oxidation product X′ and stripped particulates electrode substrate S (Treatment STEP 2: Concentrate). Anolyte 1518 is passed through first SCC cell assembly anode cell chamber 1534 where reduced FBS form Y1′ is oxidized to Y1 and treated anolyte product 1519 passed to the cathode cell chamber 1574 of a second SCC cell assembly and where Y1 is a suitable substance selected from lists A seen in paragraphs [0047, 0048]. In the second SCC cell assembly the product 1519 containing the oxidized FBS form Y1 is introduced into the cathode cell chamber 1574 and reduced to form product Y1′. The treated catholyte product 1518 then exits the cathode cell chamber and is directed to the first SCC cell assembly anode cell chamber where it acts as the anolyte feedstream and Y1′ gets re-oxidized to Y1, completing the Y1/Y1′ redox cycle and electroregeneration (Treatment STEP 3: ERG). The separated ripened X/S particulates electrodes elements 1520 get combined with the second SCC cell assembly anolyte makeup stream 1514 and the mixture gets introduced into the anode cell chamber 1572 to create a high surface area moving particulates bad where plated SBS material X gets oxidized and stripped from plated X/S particulates to generate stripped particles substrates S and targeted treatment product containing solubilized X′. The treated anolyte and particulates S mixture exit the anode cell chamber 1572 and are directed to separator unit 1584 where the concentrated product stream 1516 containing X′ is separated for collection and 1522 the stripped particulates S are returned to the first SCC cell assembly and mixed with the catholyte feed stream 1510 for re-injection back into cathode cell chamber 1532 to complete the recycle and refresh loop for the particulates electrode elements. To drive the target reactions, unidirectional current is fed into the cell, via anode current feeds 1506, 1546(+) and out via cathode current feeds 1502, 1542 (−) respectively for the first and second SCC cell, assemblies. Practitioners may note that other cell, configurations (stacked, cylindrical, etc.) may also be employed, and that cells employing multiple and/or additional chambers may be of similar or different configurations and employ similar or different cathodes 1504, 1544, anodes 1508, 1548, and separators 1590, 15S2 as may be chosen in specific embodiments. Recirculation may be employed so that the individual SCC cells and chamber might be operated in a range of electrolyte recirculation conditions spanning the extremes from, single-pass flow-through (no recirculation, as depicted) through batch (infinite recirculation) processing modes. It is understood that partial removal or stripping of plated “ripe” X/S particles 1520 may occur such that “stripped” S particles 1522 may only have a portion of X removed from them.
Method Embodiment Special Case-B: FIG. 16 illustrates another example of Instantiating the embodiment special case noted above in paragraph [0060] where the complete integrated 3-STEP treatment is accomplished in two coupled electrolysis processes (effected by one or more SCC cells). Here two integrated SCC electrolysis cell assemblies embodying the full generality of instantiating specific examples of SCC cells as more fully discussed in relevant patents such as noted in the CROSS REFERENCE TO RELATED APPLICATIONS is encompassed with this description emphasizing central aspects of linking and balancing chemistries and target reactions for process integration for a specific simple and illustrative instantiation case without limiting the range of associated and obvious extensions included by these teachings. For example, each SCC cell assembly respectively may include of one or more anodes 1608, 1648 coupled to one or more cathodes 1604, 1644, here where one is in the form of a high surface area moving particulates bed (cathode 1604 and anode 1648 respectively), contained respectively in cathode cell chambers 1632, 1674 and anode cell chambers 1634, 1672 (which contain the respective associated electrodes and electrolytes and shown here for the well-known double chamber planar configuration) each pair of which is separated by a separator 1690, 1692 allowing ionic conduction (a porous or selective membrane for example) and which directs the bulk flows of electrolytes (catholyte 1610, 1619 and anolyte 1618, 1614) while maintaining intimate electrochemical contact between the separated cathodes 1604, 1644 and anodes 1608, 1648 via ionic conduction. In a first SCC cell assembly, catholyte flow of 1619, is directed into cathode cell chamber 1632 and then through the high surface cathode 1604, to achieve vigorous convection in the particulates bed to facilitate a high degree of electrode utilization and the oxidized precursor SBS target X′ is reduced to the SBS target X and plated onto particulates electrode substrate S and denoted as plated product X/S (Treatment STEP 1: Remove) and where X is a suitable substance selected from lists B seen in paragraphs [0047, 0048]. The catholyte/cathode mixture is removed from the cathode cell chamber 1632, directed through separating unit 1682 where the treated electrolyte stream: 1618 and sufficiently SBS plated (“ripened”) particulates electrode elements 1620 which are plated with SBS material X on substrate S and denoted X/S are separated and treated solution 161S is directed to anode cell chamber 1634 and ripe X/S plated particulates 1620 are passed to the anode cell chamber 1672 of the second SCC cell assembly for anodic SBS harvesting (“Stripping”) and generation of oxidation product X′ and stripped particulates electrode substrate S (Treatment STEP 2: Concentrate). Anolyte feedstream 1618 is passed through anode cell chamber 1634 where reduced FBS form Y1′ is re-oxidized to Y1 completing the Y1/Y1′ redox cycle and regeneration (Treatment STEP 3: ERG) where Y1 is a suitable substance selected from lists A seen in paragraphs [0047, 0048] and treated anolyte product stream 1612 containing Y1 is discharged. Feed stream liquid electrolyte catholyte 1610 and containing oxidized FBS form Y1 and oxidized SBS form X′ is introduced to cathode cell chamber 1674 of a second SCC cell assembly where Y1 is reduced, to form product Y1′. The treated catholyte product 1619 containing oxidized SBS form X′ then exits the cathode cell chamber 1674 and is directed to the first SCC cell assembly cathode cell chamber 1632 and mixed with 1622, the stripped particulates S, for re-injection back into cathode cell chamber 1632 to complete the recycle and plate/strip loop for the particulates electrode elements S and to reduce X′ to X (Treatment STEP 1: Remove) and to plate X′ onto the particulates electrode substrate X/S. The separated ripened X/S particulates electrodes elements 1620 get combined with the second SCC cell assembly anolyte makeup stream 1614 and the mixture gets introduced into the anode cell chamber 1672 to create a high surface area moving particulates bed where plated SBS material X gets oxidized and stripped from ripened X/S particulates to generate stripped particles substrates S and targeted treatment product containing solubilized X′ (Treatment STEP 2: Concentrate). The treated anolyte and particulates S mixture exit the anode cell chamber 1672 and are directed to separator unit 1684 where the concentrated product stream 1616 containing X′ is separated for collection and 1622 the stripped particulates S are returned to the first SCC cell assembly for re-injection back into cathode cell chamber 1632 to complete the recycle and refresh loop for the particulates electrode elements. To drive the target reactions, unidirectional current is fed into the cell via anode current feeds 1606, 1646 (+) and out via cathode current feeds 1602, 1642 (−) respectively for the first and second SCC cell assemblies. Practitioners may note that other cell configurations (stacked, cylindrical, etc.) may also be employed and that cells employing multiple and/or additional chambers may be of similar or different configurations and employ similar or different cathodes 1604, 1644, anodes 1608, 1648, and separators 1690, 1692 as may be chosen in specific embodiments. Recirculation may be employed so that the individual SCC cells and chamber might be operated in a range of electrolyte recirculation conditions spanning the extremes from single-pass flow-through (no recirculation, as depicted) through batch (infinite recirculation) processing modes. It is understood that partial removal, or stripping of plated “ripe” X/S particles 1620 may occur such that “stripped” S particles 1622 may only have a portion of X removed from them.
Method Embodiment Special Case-C: PIG. 17 illustrates another example of instantiating the embodiment special case noted above in paragraph [0060] where the complete integrated 3-STEP treatment is accomplished in two coupled electrolysis processes (effected, by one or more SCC cells). Here two integrated SCC electrolysis cell assemblies embodying the full generality of instantiating specific examples of SCC cells as more fully discussed in relevant patents such as noted in the CROSS REFERENCE TO RELATED APPLICATIONS is encompassed with this description emphasizing central aspects of linking and balancing chemistries and target reactions for process integration for a specific simple and illustrative instantiation case without limiting the range of associated and obvious extensions included by these teachings. For example, each SCC cell assembly respectively may include of one or more anodes 1708, 1748 coupled to one or more cathodes 1704, 1744, here where one is in the form, of a high surface area, moving particulates bed. (cathode 1704 and anode 1748 respectively), contained respectively in cathode cell chambers 1732, 1774 and anode cell chambers 1734, 1772 (which contain the respective associated electrodes and electrolytes and shown here for the well-known double chamber planar configuration) each pair of which is separated by a separator 1790, 1792 allowing ionic conduction (a porous or selective membrane for example) and which directs the bulk, flows of electrolytes (catholyte 1710, 1719 and anolyte 1718, 1714) while maintaining intimate electrochemical contact between the separated cathodes 1704, 1744 and anodes 1708, 1748 via ionic conduction. In a first SCC cell assembly, catholyte flow of feed stream liquid electrolyte catholyte 1710 containing oxidized SBS form X′ and a soluble reduced FBS form Y1′, is directed into cathode cell chamber 1732 and then through the high surface cathode 1704, to achieve vigorous convection in the particulates bed to facilitate a high degree of electrode utilization and the oxidized precursor SBS target X′ is reduced to the SBS target X and plated onto particulates electrode substrate S and denoted as plated product X/S (Treatment STEP 1: Remove) and where X is a suitable substance selected from lists B seen in paragraphs [0045, 0048]. The catholyte/cathode mixture is removed from the cathode cell chamber 1732, directed through separating unit 1782 where the treated electrolyte stream 1718 and sufficiently SBS plated (“ripened”) particulates electrode elements 1720 which are plated with SBS material X on substrate S and denoted X/S are separated and treated solution product 1718 is injected into anode cell chamber 1734 and ripe particulates 1720 are passed to the anode cell chamber 1772 of the second SCC cell assembly for anodic SBS harvesting (“Stripping”) and generation of oxidation product X′ and stripped particulates electrode substrate S (Treatment STEP 2: Concentrate). Anolyte 1718 (now with X′ removed) is passed through anode cell chamber 1734 where reduced FBS form Y1′ is oxidized to Y1 and treated anolyte product 1719 removed and passed to the cathode cell chamber 1774 of a second SCC cell assembly and where Y1 is a suitable substance selected from lists A seen in paragraphs [0047, 0048]. In the second SCC cell assembly the product 1719 containing the oxidized FBS form Y1 is introduced into the cathode cell chamber 1774 and reduced to form product Y1′ and regenerated (Treatment STEP 3: ERG). The treated catholyte product 1712 then exits the cathode cell chamber and is discharged as the treated stream. The separated ripened X/S particulates electrodes elements 1720 get combined with the second SCC cell assembly anolyte makeup stream 1714 and the mixture gets introduced into the anode cell chamber 1772 to create a high surface area moving particulates bed where plated SBS material X gets oxidized and stripped from ripened X/S particulates to generate stripped particles substrates S and targeted treatment product containing solubilized X′ (Treatment STEP 2: Concentrate). The treated anolyte and particulates S mixture exit the anode cell chamber 1772 and are directed to separator unit 1784 where the concentrated product stream 1716 containing X′ is separated for collection and 1722 the stripped particulates S are returned to the first SCC cell assembly and mixed with the catholyte feed stream 1710 for re-injection back into cathode cell chamber 1732 to complete the recycle and refresh loop for the particulates electrode elements. To drive the target reactions, unidirectional current is fed into the cell via anode current feeds 1706, 1746(+) and out via cathode current feeds 1702, 1742 (−) respectively for the first and second SCC cell assemblies. Practitioners may note that other cell configurations (stacked, cylindrical, etc.) may also be employed and that cells employing multiple and/or additional chambers may be of similar or different configurations and employ similar or different cathodes 1704, 1744, anodes 1708, 1748, and separators 1790, 1702 as may be chosen in specific embodiments. Recirculation may be employed so that the individual SCC cells and chamber might be operated in a range of electrolyte recirculation conditions spanning the extremes from single-pass flow-through (no recirculation, as depicted) through batch (infinite recirculation) processing modes. It is understood that partial removal or stripping of plated “ripe” X/S particles 1720 may occur such that “stripped” S particles 1722 may only have a portion of X removed, from them.
Method Embodiment Special Case-D: FIG. 18 illustrates another example of instantiating the embodiment special case noted above in paragraph [0060] where the complete integrated 3-STEP treatment is accomplished in two coupled electrolysis processes (effected by one or more SCC cells). Here two integrated SCC electrolysis cell assemblies embodying the full generality of instantiating specific examples of SCC cells as more fully discussed in relevant patents such as noted in the CROSS REFERENCE TO RELATED APPLICATIONS is encompassed with this description emphasizing central aspects of linking and balancing chemistries and target reactions for process integration for a specific simple and illustrative instantiation case without limiting the range of associated and obvious extensions included by these teachings. For example, each SCC cell assembly respectively may include of one or more anodes 1808, 1848 coupled, to one or more cathodes 1804, 1844, here where both anode and cathode are separately in the form of a high surface area moving particulates bed ( cathodes 1804, 1844 substrate S and anodes 1808, 1848 substrate S& respectively), contained respectively in cathode cell chambers 1832, 1874 and anode cell chambers 1834, 1872 (which contain the respective associated electrodes and electrolytes and shown here for the well-known double chamber planar configuration) each pair of which is separated by a separator 1890, 1892 allowing ionic conduction (a porous or selective membrane for example) and which directs the bulk, flows of electrolytes (catholyte 1810, 1819 and anolyte 1818, 1814) while maintaining intimate electrochemical contact between the separated cathodes 1804, 1844 and anodes 1808, 184 8 via ionic conduction. In a first SCC cell assembly, catholyte flow of feed stream liquid electrolyte catholyte 1810 containing oxidized SBS form X′ and solid reduced FBS form Y1′, is directed into cathode cell chamber 1832 and then through the high surface cathode 1804, to achieve vigorous convection in the particulates bed to facilitate a high degree of electrode utilization and the oxidized precursor SBS target X′ is reduced to the SBS target X and plated onto particulates electrode substrate S and denoted as plated product X/S (Treatment STEP 1: Remove) and where X is a suitable substance selected from lists B seen in paragraphs [0047, 0048]. The catholyte/cathode mixture is removed from the cathode cell chamber 1832, directed through separating unit 1882 where the treated electrolyte stream 1818 and sufficiently FBS plated (“ripened”) particulates electrode elements 1820 which are plated with SBS material X on substrate S and denoted X/S are separated and treated solution product (now with X′ removed) 1818 is injected into anode cell chamber 1834 and ripe particulates 1820 are passed to the anode cell chamber 1872 of the second SCC cell assembly for anodic SBS harvesting (“Stripping”) and generation of oxidation product X′ and stripped particulates electrode substrate S (Treatment STEP 2: Concentrate). Anolyte 1813 is passed through anode cell chamber 1834 where reduced FBS form Y1′ on the particulates electrode substrate SA and denoted as Y1′/SA is oxidized to Y1 and stripped into the anolyte from electrode substrate SA and a particulates anode/anolyte mixture exits the anode cell chamber and is passed to separator unit 1888 where the particulates electrode 1826 elements substrate S& are separated and passed to the cathode cell chamber 1874 of a second SCC cell assembly substantially independently from anolyte 1819 and treated anolyte product 1819 is separately passed to the cathode cell chamber 1874 of a second SCC cell assembly and where Y1 is a suitable substance selected from lists A seen in paragraphs [0047, 0048]. In the second SCC cell assembly the product 1819 containing the oxidized FBS form Y1 is combined with particulates electrode 1826 and introduced into the cathode cell chamber 1874 and reduced to form product Y1′ upon particulates electrode substrate SA to regenerate the FBS material and are denoted as Y1′/SA (Treatment STEP 3: ERG). The treated particulates cathode/catholyte mixture exits the cathode cell chamber, is passed to separator unit 1886 where the catholyte product 1812 and the “ripe” particulates electrodes Y1′/SA are separated and the ripe particle flow 1824 is directed to the first SCC cell assembly anode cell chamber where Y1′ gets re-oxidized to Y1, completing the Y1/Y1′ redox cycle and regeneration (Treatment STEP 3: ERG) and the treated catholyte product 1812 gets discharged. The separated ripened X/S particulates electrodes elements 1820 get combined with the second SCC cell assembly anolyte makeup stream 1814 and the mixture gets introduced into the anode cell chamber 1872 to create a high surface area moving particulates bed where plated SBS material X gets oxidized and stripped from, ripened X/S particulates to generate stripped particles substrates S and targeted treatment product containing solubilized X′ (Treatment STEP 2: Concentrate). The treated anolyte and particulates S mixture exit the anode cell chamber 1872 and are directed to separator unit 1884 where the concentrated product stream 1816 containing X′ is separated for collection and 1822 the stripped particulates S are returned to the first SCC cell assembly and mixed with the catholyte feed stream 1810 for re-injection back into cathode cell chamber 1832 to complete the recycle and refresh loop for the S particulates electrode elements. To drive the target reactions, unidirectional current is fed into the cell via anode current feeds 1806, 1846 (+) and out via cathode current feeds 1802, 1842 (−) respectively for the first and second SCC cell assemblies. Practitioners may note that other cell configurations (stacked, cylindrical, etc.) may also be employed and that cells employing multiple and/or additional chambers may be of similar or different configurations and employ similar or different cathodes 1804, 1844, anodes 1808, 1848, and separators 1890, 1892 as may be chosen in specific embodiments. Recirculation may be employed so that the individual SCC cells and chamber might be operated in a range of electrolyte recirculation conditions spanning the extremes from single-pass flow-through (no recirculation, as depicted) through batch (infinite recirculation) processing modes. It is understood that partial removal or stripping of plated “ripe” X/S particles 1820 and Y1′/SA particles 1824 may occur such that “stripped” S particles 1822 and SA particles 1826 may only have a portion of X and Y1′, respectively, removed from them.

Claims

We claim:

1) A method for chemical modification of concentrations of constituents of at least one liquid stream containing organic or inorganic constituents comprising of following steps:

providing at least one reactor device having one or more reaction chambers that include at least one first boundary substance and containing at least one organic or inorganic constituent of the at least one liquid stream;

generating at least one second boundary substance from the at least one first boundary substance and the at least one organic or inorganic constituent of the at least one liquid stream;

dissolving the at least one second boundary substance in at least one another liquid stream and generating a solution of greater dissolved second boundary substance concentration than the respective constituent initial occurrence in the at least one liquid stream;

regenerating the at least one first boundary substance for subsequent generation of the at least one second boundary substance.

2) The method of claim 1, wherein the at: least one reactor device having one or more reaction chambers is a chemical reactor.

3) The method of claim 1, wherein the at least one reactor device having one or more reaction chambers is an electrochemical reactor.

4) The method of claim 3, wherein the electrochemical reactor is a split compartment cell.

5) The method of claim 4, wherein the split compartment cell is a Moving Bed Electrode cell.

6) The method of claim 1, wherein the at least one first, boundary substance is a metal selected from the group of metals consisting of Rh, Re, Cu, Bi, As, Sb, Bi, Ir, Te, W, Pb, Sn, Ni, V, Co, Tl, In, Se, Cd, Fe, Cr, Ga, Zn, Ti, Mn, Pd, Ag, Au, Pt.

7) The method of claim 1, wherein the at least one second boundary substance is a metal selected from the group of metals consisting of Rh, Re, Cu, Bi, As, Sb, Bi, Ir, Te, W, Pb, Sn, Ni, V, Co, Tl, In, Se, Cd, Fe, Cr, Ga, Zn, Ti, Mn, Pd, Ag, Au, Pt.

8) The method of claim 1, wherein the at least one first boundary substance is an alloys, mixtures of metals, or a non-metallic solid.

9) The method of claim 1, wherein the at least one first boundary substance is a gas, a liquid, or a dissolved species selected from the group consisting of H₂, SO₂, NO, NO₂, N₂O, N₂O₂ ⁻², CO, ClO₂, H₂S, H₂O, H₂O₂, HO₂ ⁻, NH₃, N₂O₄, NH₄OH, CH₄, C₂H₆, MeOH, EtOH, Propanol, HCOOH, and other hydrocarbons, V⁺², V⁺³, U⁺⁴, UO₂ ⁺, Tc⁺², Ru⁺², Bi⁺, H₂SO₃, S₂O₃ ⁻², S₂O₈ ⁻², HNO₂, MnO₂, Cu₂O, RuO₄ ⁻², ClO₃ ⁻, ClO₂ ⁻, PbO, In⁺, In⁺², Sn⁺², Fe⁺², Cu⁺, Co⁺², OH⁻, Br⁻, I⁻, IO⁻, SO₃ ⁻³.

10) The method of claim 1, wherein the steps of generating at least: one second boundary substance and dissolving and concentrating the at least one second boundary substance in a pregnant liquid solution are at least in part coupled, balanced, and matched such that component mass flows and the charge exchanges during generation of the second boundary substance correspond to the mass flows and the charge exchanges during the dissolving and concentrating of the at least one second boundary substance.

11) A method of chemical modification of concentrations of constituents of at least one liquid stream containing organic or inorganic constituents comprising of following steps:

providing at lease one reactor device having one or more reaction chambers that include at least one first boundary substance and containing at least one organic or inorganic constituent of the at least one liquid stream;

dissolving and concentrating the at least one second boundary substance in a pregnant liquid solution;

electroregenerating the at least one first boundary substance for subsequent generation of the at least one second boundary substance.

12) The method of claim 11, wherein the electroregenerating includes electrowinning facilitated by injection of electrons from at least one external source to plate the at least one first boundary substance for subsequent consumption in the at least one reactor device.

13) The method of claim 11, wherein the at least one reactor device having one or more reaction chambers is a chemical reactor.

14) The method of claim 11, wherein the at least one reactor device having one or more reaction chambers is an electrochemical reactor.

15) The method of claim 14, wherein the electrochemical reactor is a split compartment cell.

16) The method of claim 15, wherein the split compartment cell is a Moving Bed Electrode cell.

17) The method of claim 11, wherein the at least one first boundary substance is a metal selected from the group of metals consisting of Rh, Re, Cu, Bi, As, Sb, Bi, Ir, Te, W, Pb, Sn, Ni, V, Co, Tl, In, Se, Cd, Fe, Cr, Ga, Zn, Ti, Mn, Pd, Ag, Au, Pt.

18) The method of claim 11, wherein the at least one second boundary substance is a metal selected from the group of metals consisting of Rh, Re, Cu, Bi, As, Sb, Bi, Ir, Te, W, Pb, Sn, Ni, V, Co, Tl, In, Se, Cd, Fe, Cr, Ga, Zn, Ti, Mn, Pd, Ag, Au, Pt.

19) The method of claim 11, wherein the at least one first boundary substance is an alloys, mixtures of metals, or a non-metallic solid.

20) The method of claim 11, wherein the at least one first boundary substance is a gas, a liquid, or a dissolved species selected from the group consisting of H₂, SO₂, NO, NO₂, N₂O, N₂O₂ ⁻², CO, ClO₂, H₂S, H₂O, H₂O₂, HO₂ ⁻, NH₃, N₂O₄, NH₄OH, CH₄, C₂H₄, MeOH, EtOH, Propanol, HCOOH, and other hydrocarbons, V⁺², V⁺³, U⁺⁴, UO₂ ⁺, Tc⁺², Ru⁺², Bi⁺, H₂SO₃, S₂O₃ ⁻², S₂O₆ ⁻², HNO₂, MnO₂, Cu₂O, RuO₄ ⁻², ClO₃ ⁻, ClO₂ ⁻, PbO, In⁺, In⁺², Sn⁺², Fe⁺², Cu⁺, Co⁺², OH⁻, Br⁻, I⁻, IO⁻, SO₃ ⁻².