JP2021531158A - Faradick porous cell - Google Patents

Abstract

Applicant's Faradic Porous Cell combines the adsorption (physical and volumetric) of the target species with the Faradic immobilization by optimizing the porosity of the electrode, the applied E, and the Pourbaix working region. Is. The optimization parameters are (i) physical adsorption; (ii) volumetric adsorption; (iii) electrochemical pH control; (iv) electrochemical peroxide (H2O2) generation; (v) electrodeposition (eg, electroplating). , Electrochemical deposition); (vi) electrochemical oxidation or reduction; (vii) precipitation; (viii) pore size profile, and (ix) electrode spacing, and (xi) flow-by vs. flow-through vs. carbon block cell design. be. [Selection diagram] FIG. 4

Description

Detailed description of the invention

[Background of invention]
(Field of invention)
[001] The art of the present invention is the combination of selected faradic reactions with carbon electrode pore size profiling of metal ions, halide ions, metal and halide derivatives, and ionic particulate matter from solution. Removal, eg removal of lead from water.

[Definition]
[002] “Adsorption” means attracting ions in the input flow to the surface of the electrode and retaining the ions on the surface of the electrode.

[003] "Aggregation" means removing a metal ion, a halide ion, a metal or a derivative of a halide, or a particulate metal from the input stream to the cell by one or more of the following: (I) Physical adsorption; (ii) Capacitive adsorption; (iii) Electrochemical pH control and metal immobilization; (iv) Electrochemical peroxide (H ₂ O ₂ ) generation and metal oxidation; (v) Electrodeposition Or electroplating; (vi) electrochemical oxidation or reduction; (vii) precipitation; (viii) pore size profile, (ix) electrode treatment, (x) electrode spacing, and (xi) flow-by vs. flow-through vs. carbon block. Cell design.

[004] "BET surface area" means the surface area determined by the Brunauer-Emmett-Teller method, which is a physisorption-based method of determining the surface area of a material using nitrogen.

[005] The "break curve" means the course of the adsorption concentration of the effluent at the outlet of the fixed adsorber. The breakthrough curve allows the calculation of technically usable sorption capacity. The breakthrough curve typically plots the target species concentration vs. the treated volume. See, for example, FIG.

[006] A "carbon block" is an extruded carbon material in which carbon particles are bonded to a polymer to form a bulk solid. Typically used for dechlorination and particle filters. In the design of carbon block cells used in FPCs, each of one or more pure carbon blocks is typically split into two electrically isolated halves in the FPC; one half of each block. Is used as the anode and the other half of each block is used as the cathode.

[007] “Volume adsorption” means the adsorption of ions or other charged species to the electrodes as a result of electrical attraction.

[008] A "CCC" or "capacitive coagulation cell" or "CCC device" is a liquid (typically aqueous) input of metal ions, metal derivatives, or particulate metals, primarily using capacitive adsorption. It means a purification cell that is removed from the stream and produces an output stream with a metal, metal derivative, or particulate content below government-regulated limits. For example, the US EPA defines a lead content of 15 ppb as a "countermeasure level" for drinking or irrigation water.

[009] “CCC parameter” means an FPC parameter selected by the user in the CCC.

[0010] A "cell" generally means a plurality of electrodes exposed to an input flow (inflow), an outlet for an output flow (outflow) during operation, a short circuit switch or power supply attached to the electrode, It comprises a manual or computerized means of controlling the power supply and any inflow valve, and a sensor that monitors the operation of the cell and interfaces with the manual or computerized control means. The cell can optionally include additional means of controlling the input and output flows, for example, to select various output flow collection vessels or other arrangements during the operation of the cell. Unlike capacitive deionization cells, the FPC does not regenerate (also called desorption) the electrodes during operation to generate a waste distribution of the desorbed target species. Alternatively, for example, if the concentration of the target species in the output stream exceeds a user-selected threshold, the FPC containing the CCC or EDC will be replaced. Exchange criteria other than the target species concentration in the output stream may be specified, eg, the cumulative volume of the passing stream for a given FPC, and the presence of certain reaction by-products.

[0011] "Charging potential" means the voltage applied to a cell to perform a task.

[0012] "Conductivity" means the electrical conductivity of an input stream, a passing stream, an output stream, or a waste distribution. Conductivity is a surrogate measurement of the molar concentration of ions in the input stream, output stream, or waste distribution. Conductivity is directly proportional to the molar concentration of ions in such a liquid stream.

[0013] "CG" means carbon having a predominantly mesoporous structure and a nominal surface area of about 700 m ² / g. The CG was formulated by us using the pore size profile method disclosed herein and was made for us by Calgon Corporation (Naperville, IL). CG may be referred to as Calgon® in the table.

[0014] "CV" means a cyclic voltammogram.

[0015] "CX" means carbon xerogel. The CX electrode has a mesoporous structure and has a nominal surface area of about 200 m ² / g.

[0016] By "cycle" is meant a cycle of operation in which a series of positive and then negative or negative and then positive potentials are applied to the FPC electrode.

[0017] "DO" means dissolved oxygen.

[0018] "E" means a voltage and is also called an electric potential. In the case of direct current, E has a certain polarity (positive or negative).

[0019] "Electrode" means a conductive material, typically porous carbon.

[0020] "EDC" means an electrodehalogenated cell disclosed in the present application. EDC is a kind of water purification cell belonging to FPC.

[0021] "EDC parameter" means an FPC parameter selected by the user in EDC.

[0022] "EDX" means energy dispersive X-ray analysis.

[0023] "E _o " is the pair reference electrode potential when the electrode is short-circuited (that is, E _o is the potential in the short-circuited state).

[0024] "E _PZC " or "zero charge potential" means the potential of the electrode that minimizes ion adsorption on the surface. The E _PZC can be intentionally shifted by surface modification of the carbon electrode, or can be essentially displaced as a result of oxidation of the electrode surface by the extended applied potential or voltage. _{The EPZC} of a pure carbon electrode is typically between -0.1V and + 0.1V. The Epzc shift of the electrode due to surface modification is disclosed in detail in US Patent Application No. 62/702286 incorporated herein. _{The EPZC} of the FPC electrode for a given target species depends on the chemistry of the water and is determined experimentally.

[0025] “Faradic immobilization” means electron transfer to a target species in an electrolyte, or electron transfer to a species in an electrolyte, followed by a homogeneous reaction in solution with the target species of interest. The reaction product is then adsorbed on the electrode.

[0026] The "flow-by" cell design means that the flow through the FPC does not pass through the electrodes, but flows across the surface of the electrodes in the FPC. The flow-by-cell design can provide the following advantages over the flow-through cell design: low pressure drop, high flow rate, comparable degradation of carbon electrodes, equivalent generated for each pair of electrodes. pH range.

[0027] "Flow rate" means the flow rate of an input, throughput, output, or waste distribution, typically in units of L / hour, ml / min, and the like.

[0028] The "flow-through" cell design means that the passing flow in the FPC is forced to pass through the electrodes in the FPC. The flow-through cell design can provide the following advantages over the flow-by-cell design: extreme pH range, good control over outlet pH.

[0029] The "FPC" or "Faradic porous cell" or "FPC device" uses agglomeration to form a metal ion, halide ion, target metal or target halide from a liquid (typically aqueous) input stream. A purification cell that removes a derivative (eg, another species) of a metal, a halide, or a purifying cell that produces an output stream with a reduced content of metal, halide, or fine particles. Different species of FPC can be used in series or in parallel to remove multiple target species from the aqueous influx into the purification system. An "FPC system" is one or more FPCs and optionally other types of purification cells (see definition of "hybrid system"), such as capacitive deionization ("CDI") cells, membrane CDI. It means a water purification system containing a cell (“MCDI”), a reverse CDI (“i-CDI”) cell, and a non-electrochemical cell and a filter. Incorporation of CDI, MCDI, i-CDI cells, or similar detachable cells into the FPC system includes providing waste logistics and desorption from CDI, MCDI, i-CDI, and similar detachable cells to waste logistics. Control of the associated cells in the FPC system to accommodate is required. CCC and EDC are a type of FPC.

[0030] "FPC parameter" is, (i) physical adsorption; (ii) capacity adsorption; (iii) electrochemically pH adjusted; (iv) Electrochemical peroxide _{(H 2 O} 2) generation and target species Oxidation; (v) electrodeposition (eg, electroplating, electrophoresis deposition); (vi) electrochemical oxidation or reduction; (vii) precipitation; (viii) pore size profile, (ix) electrode treatment, (x) It means the electrode spacing and the value selected by the user in the FPC of (xi) flow-by vs. flow-through vs. carbon block cell design. One or more FPC parameters are selected or "adjusted" to remove the target species from the flow through, based on experimental data on the chemistry of a given input water.

[0031] "Halogen derivative" means a molecule or compound containing a halide.

[0032] "HE" means highly efficient mesoporous carbon. Electrodes made of HE carbon have a predominantly mesoporous structure with a nominal surface area of approximately 380 m ² / g. HE has a formulation in which mesoporous carbon exceeds 98% and the balance is macroporous carbon. HE is formulated using the pore size profile method disclosed in US Patent Application No. 62/702286 incorporated herein.

[0033] A "hybrid system" is an FPC (CCC or EDC) and at least one other type of water purification cell such as a peroxide cell, CDI, MCDI, i-CDI, or non-electrochemical cell. Or it means a water purification system that houses a filter. The minimum configuration of a hybrid system is series (FPC supplies other cell types or vice versa). Larger systems can be series-only or have parallel series passages (to increase throughput).

[0034] "immobilization" means adsorption of the target species to the FPC electrode without subsequent desorption into the purified output stream.

[0035] "Input flow" means a liquid containing various ions and metals, typically water, which is delivered through the inlet to the cell.

[0036] "KN" means microporous carbon sold as Kynol®, available from American Kynol, Inc. (Pleasantville, NY). The electrode made of KN carbon has a microporous structure and a nominal surface area of about 1800 m ² / g.

[0037] "Metal" has a Pourbe diagram, and As, Se, Pb, Ni, Zn, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb. , Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb , Dy, Ho, Er, Tm, Yb, and Lu means a metal containing a metal selected from the group, a metal ion, a metal complex, a metal particle, or a toxin.

[0038] "Metal derivative" means a molecule or compound containing a metal or metalloid.

[0039] "Speciation" means various chemical forms ("species") of a metal in a given environment. For example, As (III) and As (V) are arsenic species that can coexist in an aqueous solution at a given pH.

[0040] "NHE" means a normal hydrogen electrode.

[0041] By "output stream" is meant a liquid that has passed through the FPC and contains a target species with a lower molar concentration than the input stream.

[0042] "Parallel system architecture" means FPCs connected in parallel (and optionally other types of cells and filters), i.e., each FPC (and optionally other types of cells and filters). Exit provides system output. The parallel system architecture can be fixed or include multiple FPCs, process controllers, interconnect lines, sensors, and valves located on the lines and cells.

[0043] "Physisorption" means the physical capture of the target species into the electrode pores.

[0044] "PMD" means pore diameter, which is the diameter of the pores on the surface of the carbon electrode. The pores may be dead-end channels or through-channels within the carbon electrode and typically have a variable channel diameter.

[0045] "Inflow point" or "POE" means the place where the water supply facility supplies water to the water distribution system in a residential, commercial / industrial building, or other structure.

[0046] "Point of use" or "POU" means the place where water is distributed from the water distribution system to the consumer, beverage dispenser, kitchen equipment, or other end use.

[0047] "Polarity" means either the positive or negative polarity of the DC voltage.

[0048] A "porosity profile" is made according to the porosity profile method disclosed in U.S. Patent Application No. 62 / 702,286 and U.S. Patent Application No. 16 / 417,574 incorporated herein. It also means the volume ratio (s) of microporosity, mesoporosity, and macroporosity carbon in the electrode. Generally speaking, the larger the average pore diameter, the longer the useful life of the electrode and the higher the permeability of the electrode to the passing flow. The average pore size is controlled by the ratio of microporous, mesoporous, and macroporous carbon used to make a given carbon electrode.

[0049] "Pourbaix diagram" (potential / pH diagram, also referred to as E _H-pH diagram or pE / pH diagram) shows a possible stable (equilibrium) phase of the aqueous electrochemical systems. The predominant ionic boundaries are represented by lines. Therefore, the Pourbaix diagram can be read in the same way as a standard phase diagram with different sets of axes. Like the phase diagram, the Pourbaix diagram does not deal with reaction rates or rate effects. For soluble seeds, the lines of the Pourbaix diagram are usually drawn for concentrations of ^{1 M or 10-6 M.} For other densities, additional lines may be drawn.

[0050] The "Pourbaix working region" associates the pH at a given electrode in the FPC and the applied E with the Pourbaix diagram to select immobilization of the target species in a given water chemistry. Means that.

[0051] "Pure" associated with an electrode means that it has not been surface modified. For example, the Spectracarb ™ electrode is pure as supplied by the manufacturer.

[0052] A "process controller" monitors sensors located within the system of FPCs (and optionally other types of cells and filters) and one or more FPCs, and optionally one or more. Process control to sample input, passage, and / or output flow in a water purification system including multiple other types of water purification cells or filters, as well as the state of the FPC (and optionally other types of cells and filters). Means the computer that operates the application. The process controller activates a valve in the line that interconnects the source of the aqueous solution to be processed, the FPC (and optionally other types of cells and filters), and the system outlet, thereby various FPCs (and optionally). (Optionally, other types of cells and filters) can be configured with a series system architecture, a series-parallel system architecture, or a parallel system architecture. Based on the sensor data, the process controller can dynamically adjust the FPC parameters of the FPC in the system (and optionally adjust other cells and filters in the system).

[0053] By "purifying" is meant removing one or more target species from the passing stream. Purification involves metals (eg, As, Pb, Ni, Zn, Al, Cr, Mn, Fe, and Cu), halides (eg, Cl, Br, chloramines), organics, and biocompounds in which the Pourve diagram is present. Including removal of.

[0054] In the "winding cell design", a continuous separator and a porous carbon-based electrode material are physically wound in a spiral shape to form a plurality of, mainly flow-by passages, through the porous carbon electrode. It means the FCP cell design in which the cylinder to be provided is created. To manufacture a wound cell, a sheet of anode material, separator material, and cathode material is laminated and then wound to form a cylinder. Current collectors are typically mounted at multiple locations on the anode and cathode to reduce electrical loss.

[0055] "SC" means microporous carbon sold as Spectracarbo ™, available from Enginiered Fibers Technology, LLC (Shelton, Connecticut). Electrodes made of SC carbon have a microporous structure and a nominal surface area of approximately 1900 m ² / g.

[0056] "SCE" means a saturated calomel electrode, which is a standard reference electrode commonly used as a reference electrode in, for example, cyclic voltammetry.

[0057] "Series system architecture" means FPCs connected in series (and optionally other types of cells and filters), i.e., the exit of the first FPC supplies the inlet and the second FPC. Then, the exit of the second FPC supplies to the entrance and the third FPC, and so on. The serial system architecture can be fixed, multiple FPCs (and optionally other types of cells and filters), process controllers, sensors, interconnect supply lines, and one FPC exit and a second FPC inlet. It can also include valves located in the supply line between and.

[0058] A "serial-parallel system architecture" means a system in which FPCs (and optionally other types of cells and filters) can be connected in series or in parallel. The series-parallel system architecture can be fixed, multiple FPCs (and optionally other types of cells and filters), process controllers, interconnect supply lines, sensors, and one FPC exit and a second FPC. It can also include a valve located on the supply line between the inlet and the valve, which is operated by the process controller. A typical series-parallel system architecture includes a given set of cells of multiple ranks, thereby treating the flow through as well with increased throughput due to multiple series passages.

[0059] "SHE" means a standard hydrogen electrode.

[0060] "Shift" is an intentional or unintentional chemical or electrochemical modification of the electrode surface using the method disclosed in US Patent Application No. 62 / 702,286 incorporated herein. It means changing the potential (also called "position" _{) of the EPZC} of the electrode by quality (eg, electrochemical oxidation by applied potential or voltage).

[0061] "Seed" means a molecule, compound, or microparticle in a stream of water or adsorbed on a cell electrode.

[0062] "Speciation" means the distribution of elements between defined chemical species within a system or FPC. For example, uncharged metal particles, metal ions, and metal complexes of a given metal may coexist in a solution or suspension at a given pH, and their distribution will change as the pH changes. obtain.

[0063] In a "laminated cell design", separate pieces of separator and porous carbon electrode material are laminated layer by layer and multiple, predominantly flow-by passages, pass through and / or near the porous carbon electrode. It means FCP cell design that creates a cylinder with a road. Current collectors are typically mounted at multiple locations on the anode and cathode to reduce electrical loss. FIG. 23 shows a laminated cell design.

[0064] "Surface charge-enhanced surface" means an electrode surface to which a surface charge has been applied by a chemical or electrochemical method.

[0065] A "system" is a plurality of interconnected FPCs (and optionally other types of cells and filters), either manually or controlled by a process controller.

[0066] "Target metal" means one or more species of a given metal or metal derivative that is removed using CCC.

[0067] "Target species formation" is a function of E and pH applied to the cell electrode, as shown in the Pourbaix diagram of the target species, in some ionic states that the target species can take in an aqueous electrochemical cell. It means one of the complex formations.

[0068] By "target species" is meant a molecule, compound, or particulate that is removed using FPC. A "target species" is an FPC containing a molecule, compound, or microparticle as well as a molecule, compound, or microparticle detected in the input stream to the FPC (also referred to as "identified as a species in the Pourbaix diagram"). Also includes one or more intermediates and final reaction products produced in.

[0069] By "passing flow" is meant the liquid flow being processed in the cell. In other words, a passing flow means a liquid flow within the cell, between the inlet to the cell and the exit from the cell.

[0070] "Processing" means supplying an input stream to an operating FPC or a system accommodating the FPC and recovering the purified output stream.

[0071] By "processed electrode" is meant an electrode that has undergone electrode surface modification disclosed herein.

[0072] "TDS" means total dissolved solids. The general operational definition is that a solid must be small enough to withstand filtration through a filter with 2 micron pores.

[0073] "Untreated electrode" means an electrode that has not undergone electrode surface modification disclosed herein, i.e., a pure carbon electrode.

[0074] "voltage" and "potential" are synonymous herein. Voltage is direct current (“DC”) unless otherwise specified.

[0075] “Disposal logistics” passes through CDI, MCDI, i-CDI cells, reverse osmosis, ion exchange, or other water purification cells that repeat adsorption and desorption, with higher molar concentrations of ions than the input stream. It means the liquid contained. Deionized cells, such as capacitive deionized cells, can be used in systems accommodating FPCs. FPC has no waste logistics. The output flow from the FPC is purified water. Systems containing deionized cells that periodically desorb molecules include (i) a purified output stream from an adsorbed deionized cell combined with an FPC output stream, and (ii) desorption. It has a waste distribution from a deionized cell that operates in the state.

(Related technology)
[0076] Toxic metals in drinking water and crop irrigation water, especially lead, are a major global health problem. This problem, and its health effects, are rarely reported until a crisis occurs in which water in urban water systems becomes toxic due to lead pollution. Last year, at least 18 million Americans were at risk of drinking lead-contaminated water. Over 5,000 public water systems violated federal lead regulations. Elevated blood lead levels in children cause irreversible neurological and behavioral disorders and, even at low levels, have been associated with reduced IQ and lifetime achievement. The US Environmental Protection Agency (“EPA”) emphasizes that there are no safe levels of lead exposure. The most commonly used filters for lead reduction at residential use / inflow points (POU / POE), such as those using zeolites and ion exchange, are inadequate. They have a limited shelf life, lack substantial lead specificity, and are expensive.

[0077] Figure 1 shows the location of the United States where lead levels in urban drinking water are dangerously high and the frequency of elevated blood lead levels in infants in the United States, where infants have permanent brain damage. They are at risk of seizures, coma, and even death from lead poisoning. The US Natural Resources Conservation Council (“NRDC”) recently announced the EPA's Lead and Copper Regulations (https://www.epa.gov/dwreginfo/lead-and), a federal standard for monitoring lead and copper levels in water. We found 5,363 public water supply systems that violated -copper-rule). The NRDC report also finds 1,110 water systems that exceed lead countermeasure levels (15 ppb in at least 10 percent of tested homes). These systems serve a total of about 4 million people. The EPA is considering amending the 1991 lead and copper regulations to make the regulations more stringent, and EPA officials said the EPA "declares a war against lead" for an ambitious decade. He said he was working on a strategy and described lead in drinking water as "one of the greatest environmental threats we face as a nation."

A 2018 study of the urban water system in Flint, Michigan showed a lead level of 13,000 ppb, which is 866 times the EPA countermeasure level for lead in drinking water. People are becoming more aware and concerned about water quality in their homes, schools, and communities. Drinking fountains in public schools in New York, California, Ohio, and Illinois far exceeded the 15 ppb level of coverage in the test. Despite the anti-corrosion measures taken by public water authorities to minimize the risk of lead leaching from old infrastructure to drinking water systems, lead levels in drinking water are generally rising nationwide. There is. The most effective way to remove lead from drinking water is to replace the lead line, which costs an estimated $ 30 billion. A better POU / POE device for drinking water can be a much simpler and more cost effective solution. The problem of lead contamination has not been adequately addressed, as existing solutions are overwhelmed by high costs, inadequate effectiveness, and / or short device life.

[0079] Lead removal devices currently on the market lack specificity for lead, and device life is limited by the total volume of filtered water, regardless of lead concentration. With the passage of time, the pressure drop before and after the filter becomes large, and even if the adsorbent in the filter is not completely consumed, water cannot flow through the filter and becomes useless.

[0080] Chlorine and / or chloramines are routinely added to US drinking water supplies as disinfectants to control the growth of microorganisms. Although microbial removal is beneficial for human consumption, chlorine and / or chloramines contribute to the unpleasant taste and odor of tap water. Therefore, it is desirable to remove chlorine and chloramines before final use. Chlorine is more volatile than chloramines and can be easily removed by a typical consumer filter pitcher. However, to remove chloramines, a specially formulated filter containing activated carbon (catalytic carbon) is required. The presence of chlorine and / or chloramine is also detrimental to water purification processes that rely on polymer membranes, such as reverse osmosis (RO). Most membranes are not resistant to these disinfectants and will decompose when exposed, causing irreversible damage and replacement of expensive RO membranes. Drinking water and other waters used in thermoelectric plants and other industrial processes (“process water”) are chlorine, chloramine, and other halides (especially bromine and iodine) to reduce corrosion and contamination of the process system. ), As well as the halide derivative needs to be removed. The solution to the technical problem of reducing the use of activated carbon filters and removing both chlorine and chloramines from water sources without damaging the RO membrane not only reduces water purification costs, but is also drinkable. Improve water and process water quality. Oxidation of water pollutants as a water purification process is usually carried out using hydrogen peroxide or ozone. Oxidation of certain water pollutants promotes further decomposition and final destruction of the pollutants without further intervention.

The technical problems to be solved are: (i) more efficient and cheaper purification devices for producing purified water, especially devices that remove soluble and insoluble lead in drinking water to less than 15 ppb. To provide, the purification device is (ii) easily expandable for residential, urban, commercial, and industrial use. Applicants have developed a Faradic porous cell (“FPC”) that solves this technical problem by agglutination of target species. A novel electrodehalogenation technique, referred to herein as an electro-halogenation cell (“EDC”), is used to remove chlorine, other halides, chloramine disinfectants, and other halide derivatives from water. First species; and a second species that uses a novel capacitive coagulation technique, referred to herein as a capacitive coagulation cell (“CCC”), to remove metals, metal derivatives, and particulate metals. Two types of FPCs are disclosed herein. Applicant's Faradic porosity technique is significantly more effective in purifying water than commonly used processes such as chemical coagulation, ion exchange, and adsorbents. EDC solves the technical problem of reducing the cost and improving efficiency of removing chlorine, chloramines, and other halides and halide derivatives from drinking and process water. CCC solves the technical problem of reducing the cost and improving efficiency of removing metals, metal derivatives, and particulate metals from drinking water and process water.

A map of counties where the water system violates EPA lead and copper regulations (left) and the number of children with high blood lead levels in 2012 (right), produced by the National Resource Defense Council. Schematic diagram of a part of the CCC core. The schematic shows two pairs of electrodes (anode and cathode per pair) in the CCC core. The CCC typically has more than 10 pairs of electrodes. Comparison of lead removal between the applicant's CCC device and a commercially available prior art POU device. The applicant's CCC, designated "PTW" in FIG. 2, tested the chemistry of various urban water services with lead content above EPA countermeasure levels. The applicant's CCC outperformed all prior art devices. FIG. 2 is a poolbed diagram of lead (Pb) in a carbonate solution showing the poolbe working region in the case of lead species removal at the intersection of E applied to the anode and cathode and the resulting pH near each electrode. Agglutination mechanism in the case of lead (Pb) removal, which indicates a route for lead speciation and immobilization of Pb species. Pourbaix diagram in the case of hypochlorite (Debiemme-Chouvy, Catherine & Hua, Y & Hui, F & Dual, Jean-Luc & Cachet, H. (2014). 28 (2011) pp. 10364-10370]. Electrochimica Acta. 121.461.10.1016 / j. Electta. 2014.01.130.). Pourbaix diagram for hypobromous acid (supra). Pourbaix diagram (www.sedimmentaryores.net/Pipe%20Scales/Chlorine-chloramine.html) in the case of monochloramine (NH _{2 Cl).} Commercially available microporous carbon [Spectracarbo (SC) and Kinol (KN)], mainly mesoporous carbon [Calgon (CG)], mesoporous carbon [Carbon xerogel (CX)] while repeating the applied voltage and short-circuit voltage. )], And the charge passed when using the inventor's high efficiency (HE) carbon electrode. The order of carbon types in the legend is also the order of traces of the starting specific charge (y-axis) that have passed, except that CX has a lower y-axis value than HE. It is the potential distribution in the case of the quinol electrode in the 4-electrode setting in 4.3 mM NaCl, where pure quinol was the anode and cathode, Pt was the counter electrode, and the standard caromel electrode (SCE) was the reference. The voltage was applied in 0.2V increments from 1.6V to 0.8V and returned to 1.6V. E _{0, avg} represents the open circuit voltage of the system. 8a-e show cyclic at a scanning rate of 0.5 mV / s in 4.3 mM NaCl using carbon as a working electrode, Pt-coated Ti as a counter electrode, and a standard calomel electrode (SCE) as a reference. The voltammogram (CV) is shown. CVs were collected using carbon electrodes (various types as shown) placed in the electrolyte and held at a constant voltage for the same experimental period. The voltage applied between the anode and cathode was increased at scan speed and then decreased, and the current response was recorded as CV. In addition to the CV of the pure (0h) electrode, each plot is the result of accelerated oxidation studies performed after using the electrode for 3 and 6 hours at a constant applied potential of 2.0 V (traces of 3 and 6 hours). Is shown. FIG. 8a shows the CV in the case of microporous SC. After 3 hours of electrochemical oxidation, the _EPZC shifted to the right, indicating that a covalent bond was formed between the oxygen-containing functional group and the carbon surface of the carbon electrode. After 6 hours, the zero charge (E _pzc ) potential is no longer present and the current drops significantly, indicating the collapse of the pores. The same tendency is observed in FIG. 8b for microporous KN. FIG. 8c shows CV in the case of CG which is mainly mesoporous carbon. After 3 and 6 hours of electrochemical oxidation, the _EPZC has shifted to the right, but the current is maintained due to the undisintegrated pores. FIGS. 8d and 8e, which are mesoporous CX and mesoporous HE, respectively, show the same tendency as observed for the CG of FIG. 8c, but HE has a large electrochemically active surface area, so that it is different from CX. By comparison, at 3 and 6 hours, they exhibit a larger area in the CV plot, thus achieving a larger current response. The pore size of CX is 10 times larger than that of HE, which is related to the stability and final life of the electrode. However, the larger the pore diameter of CX, the smaller the surface area than HE. Bench-scale capacitive coagulation device. SEM micrographs and EDX mappings showing the final state of the immobilized lead species. Carbon (C), lead (Pb), and oxygen (O) are mapped to the three panels below and are represented in the brightest contrast in each corresponding grayscale image. In the gray scale corresponding to the photograph, the carbon electrodes are shown in black and the copper is shown in gray. Color photographs of EDX mapping are available. Breakthrough curves in prior art activated carbon-filled columns (panel a) and applicant's CCC devices (panels b and c). The y-axis on the left is normalized to the initial lead concentration: (a) 126 ppb, (b) 296 ppb, and (c) 10,000 ppb. The y-axis on the right shows the total Pb removed relative to the treated volume in mg. DO reduction at 1.2V. DO reduction produces hydrogen peroxide, which is a powerful oxidant. Pourbaix diagram in the case of Pb (Schock, MR, Hyland, RN, and Welch, MM (2008). Occurs of Sci. Technology. 42 (12), pp. 4285-4291). Pourbaix diagram for Cu showing the removal method: (a) copper hydroxide [Cu (OH) ₂ ] formation, and (b) copper electrodeposition or electroplating [Cu _(s) ] (https://commons). .Wikimedia.org/wiki/File: Cu-copurbaix-diagram.svg). Pourbaix diagram for Ni (Ciesielczyk, F., Barticzak, P., Wieszczykka, K., Siwinska-Stephanska, K., Nowacka, M., and Jessionowski, T. (2013). from model solutions using co-precipitated inorganic oxides. Adsorption. 19, pp. 423-434). Pourbaix diagram in the case of Fe (https://comons.wikimedia.org/wiki/File:Pourbaix_Diagram_of_Iron.svg). Pourbaix diagram in the case of Mn (https://comons.wikimedia.org/wiki/File:Mn_pourbaix_diagram.png). Pourbaix diagram in the case of Al (https://corrosion-doctors.org/Corrosion-Thermodynamics / Potential-pH-diagram-aluminum.html). Pourbaix diagram in the case of Zn (https://comons.wikimedia.org/wiki/File: Zn-pourbaix-diagram.svg). Schematic diagram of an EDC device in a stacked cell design. The feed (inflow or input flow) flows into the bottom of the device, travels through the annular space near the wall of the cell housing, and then flows centered on the electrode surface into the axial channel. Then, it is discharged (outflow or output flow) to the FPC outlet through the axial channel. The feed spacer is optional; the feed spacer (shown in FIGS. 23 and 29) is an additional layer of material between the anode and cathode and is optional to create a larger flow path for the throughflow. It can be added by selection. Applied voltage and transient current as a function of volume processed at a flow rate of 300-500 ml / min in EDC experiments with Calgon as both electrodes. Current spikes at about 1500 and about 1600 gallons are due to noise (inadvertent physical movement of electrical leads) and are negligible. At about 1800 gallons, the operation was switched from applying a constant voltage to applying a constant current of about 0.2 A and observed as a straight line. The voltage decay seen under this condition (the voltage is read as negative, but the total cell voltage rises with a constant current) is the result of the application of a constant current. Subsequent switching was also done at constant current, but the voltage quickly reached the cutoff value and the system behaved as if it were essentially constant voltage. Copper deposits that occur at (a) cathodes and not (b) anodes at an applied potential of 1.2 V. In the grayscale equivalent in the photo, the carbon electrode is shown in black and the copper is shown in gray. Color photographs of copper deposited on the cathode are available. Rust-colored Fe oxide deposits on the separator on the cathode surface after the experiment. In the grayscale equivalent in the photo, the carbon electrode is black on the white separator and the iron is shown as a gray deposit. Color photographs of copper deposits on the cathode are available. (A) Scanning electron micrograph (SEM) micrograph of a carbon cloth with white precipitates and (b) a cloth showing Pb crystals. EDX mapping of Pb crystals from FIG. 27 confirming that the crystals are lead oxide due to the presence of both lead and oxygen. Carbon (C), lead (Pb), and oxygen (O) are mapped to the three panels on the right, represented by the brightest contrast in each corresponding grayscale image. Color photographs of EDX mapping are available. Outline of winding cell design in which a continuous separator and a porous carbon-based electrode material are physically wound in a spiral to create a cylinder having multiple, mainly flow-by passages, penetrating the porous carbon electrode. figure. EDC experiments with quinol as both electrodes. As a function of the volume processed at a flow rate of 500 ml / min, the concentration and applied voltage of total chlorine in the feed and product stream are shown. EDC experiments with quinol as both electrodes. As a function of the volume processed at a flow rate of 500 ml / min, the concentration of free chlorine and the applied voltage in the feed and product stream are shown. EDC experiments with quinol as both electrodes. As a function of the volume processed at a flow rate of 500 ml / min, the concentration of chloramine and the applied voltage in the feed and the product stream are shown. EDC experiments with quinol as both electrodes. As a function of the volume treated at a flow rate of 500 ml / min, the removal rate of total chlorine, free chlorine, chloramine and peroxide and the applied voltage after treating tap water with EDC are shown. An EDC experiment in which oxidized quinol was used as one electrode and Fuel Cell Earth was used as the other electrode. The concentration and applied voltage of total chlorine in the feed and product stream as a function of the volume processed at a flow rate of 300-500 ml / min. An EDC experiment in which oxidized quinol was used as one electrode and furcell earth was used as the other electrode. The concentration and applied voltage of free chlorine in the feed and product logistics as a function of the volume processed at a flow rate of 300-500 ml / min. An EDC experiment in which oxidized quinol was used as one electrode and furcell earth was used as the other electrode. The concentration and applied voltage of chloramines in the feed and product stream as a function of the volume processed at a flow rate of 300-500 ml / min. An EDC experiment in which oxidized quinol was used as one electrode and furcell earth was used as the other electrode. The removal rate and applied voltage of total chlorine, free chlorine, chloramine and peroxide after tap water as a function of the treated volume is treated with EDC. EDC experiment with Calgon as both electrodes. The concentration and applied voltage of total chlorine in the feed and product stream as a function of the volume processed at a flow rate of 300-500 ml / min. EDC experiment with Calgon as both electrodes. The concentration and applied voltage of free chlorine in the feed and product logistics as a function of the volume processed at a flow rate of 300-500 ml / min. EDC experiment with Calgon as both electrodes. The concentration and applied voltage of chloramines in the feed and product stream as a function of the volume processed at a flow rate of 300-500 ml / min. EDC experiment with Calgon as both electrodes. The removal rate and applied voltage of total chlorine, free chlorine, chloramine and peroxide after tap water as a function of the treated volume is treated with EDC.

[Outline of the invention]
[00123] In order to increase the efficiency of removing metal and halide contaminants from water using electrochemical devices that typically operate under constant applied potentials, Applicants have requested volume adsorption, near cell electrodes. Alternatively, the faradic reaction above and the electrode pore size profiling are combined to create a new type of electrochemical device, the faradic porous cell. The first consideration in Faradic porous cells is the selection of carbon-based materials that can react and change the pH over a long period of time at both the anode (carbon oxidation with water) and the cathode (dissolved oxygen reduction). And use. Carbon materials with appropriate porosity and bulk material properties can trigger these reactions over a long period of time, allowing for targeted reactions with incoming components (target species) to be removed from the aqueous solution. ..

[00124] The next design consideration is the spacing between the anode and the cathode. Reducing the spacing allows the reaction rate to be increased while maintaining electrical insulation between the electrodes, limiting the residence time required to achieve a particular "reaction and immobilization" process. .. The electrode spacing is typically less than 1 mm and must not cause an anode-cathode short circuit or an unacceptable pressure drop within the FPC (resulting in increased residence time and decreased flow rate). , It is desirable to be as close as possible. The preferred electrode spacing is less than 1 mm, preferably less than 200 microns, more preferably less than 50 microns, and most preferably less than 20 microns.

[00125] Some of the target species are adsorbed to the electrode by physical capture (“physical adsorption”) or by electrical attraction (“capacitive adsorption”). Other species of the target species are starting materials for reactions (typically oxidation) that directly or indirectly create new species of the target species that are immobilized on the electrodes. Immobilization removes the target species from the solution. Given spacing between electrodes and the characteristics of the corresponding carbon electrode material, the potentials applied to the anode and cathode are selected based on the Pourbaix diagram of the target species in the input stream. Examples of FPC parameters for various target species are shown in Table 1. For example, to remove copper, plating immobilization on the electrodes can occur at potentials in the range of about 0.3V to −0.4V against NHE in the pH range 0-14. In addition, at potentials above 0 V and pH values above 4 for NHE, precipitation can occur in the form of _{copper hydroxide (Cu (OH) 2) at the anode (see FIG. 17).} A total cell potential of about 0.4 V is desirable for copper removal in the Faradic porous cell.

[00126] Other target species have a similar mechanism but can be removed in different voltage regions. For example, lead precipitation can occur from the pH and potential generated on the electrode surface. At potentials negative than about -0.4 V to NHE and in the pH range 0-14, lead can be plated as a solid at the cathode. _{Precipitation at the anode can also occur as PbO 2} if the pH is kept above 1.5 and a potential above 0.5 V vs. NHE is used (FIG. 16). _{Finally, oxidation from H 2} O ₂ that occurs at the cathode can also cause precipitation of target species. The rate of reduction of dissolved oxygen (“DO”) near the cathode depends, for example, on the oxidation of the cathode carbon due to the oxidative shift of the _{cathode's EPZC or as a result of its use in situ.}

[00127] Pourbaix diagrams for materials can be used to define the pH and voltage required to remove the target species of interest in a Faradic porous cell. Faradic porous cells include a series of porous carbon anodes and cathodes, typically a reducing cathode (negative _EPZC and positive surface charge) and a pure anode (although the anode is positive during use). It _{consists of an} E PZC shift (subject to (negative surface charge)) and operates by applying a small voltage, eg 1.2V, across the electrodes. A schematic diagram of the CCC embodiment of the FPC is shown in FIG. The aqueous input stream to be purified is introduced into the FPC through the inlet to the cell, the electrodes in the FPC are immersed in the water stream and the target species are removed from the passing stream. After removal of the target species in the FPC, the passing stream is expelled from the cell through the outlet for use, storage, or further processing. The electrodes of the cell are connected to a power source that can apply E + or E- to a given electrode. The core inventive step of the FPC is the exact matching of E + applied to the cell anode and E-applied to the cell cathode, the pore size profile of the electrode material, and the pool bed operating region of choice. As a result, purification efficiency is improved and costs / benefits are improved. The Pourbaix diagram working region shows speciation based on the applied E and pH. In FPC, speciation is driven by the potentials E + and E− applied to the electrodes. Using electrodes with an optimized pore size distribution (“PMD”) profile and maintaining FPC operation in the selected Pourbaix operating region will remove target species far beyond conventional adsorption occurring on untreated electrodes. Will increase.

[00128] The preferred average pore diameter is in the range of 0.8 nm to 50 nm, and the more preferred average pore diameter is in the range of 2 nm to 20 nm. The applied potential causes a redox reaction of the target species (eg, plating, oxidation, reduction, peroxide, etc.) on a carbon electrode that changes the local pH range at the anode (acidic) and cathode (basic). Promote the Phaladic reaction in. The combination of the reaction of the target species and the change in pH is controlled by the applied potential. The applied E is typically a constant voltage and reaches a near constant current in a steady state. Generally speaking, the applied voltage determines what faradic reaction occurs in the FPC. FPC removes target species from the flow through without using treated (ie, shifted _EPZC ) electrodes, but using treated electrodes removes target species in certain water chemistries. Will increase. When using the processed electrode, using voltage window (the anode of _{E PZC} and the cathode potential difference _{E PZC)} is typically in the range of 0.3V～1.23V.

[00129] The invention of FPC is to optimize the porosity of the electrode, the applied E, and the working region of the adsorbate to accommodate the target species (eg, lead, iron, manganese, cadmium, chromium, chlorine, chloramine, etc.). It combines adsorption (physical and capacitive) with immobilization (also called coagulation) of the adsorbed target species. (I) Physical adsorption; (ii) Volumetric adsorption; (iii) Electrochemical pH control and target species immobilization; (iv) Electrochemical peroxide (H ₂ O ₂ ) generation; (v) Electrodeposition (eg) , Electroplating, electrophoresis deposition); (vi) electrochemical oxidation or reduction; (vii) precipitation; (viii) pore size profile; (ix) electrode treatment, (x) electrode spacing, and (xi) flow-by pair. Optimization of flow-through vs. carbon block cell design depends on the target species, the chemistry of the input flow water, and the chemistry of the passing flow water.

[00130] Reduction occurs only at the cathode of the FPC. Electrochemical reduction is usually described as the potential applied to the cell. The voltage distribution between the anode and cathode occurs spontaneously based on the amount of voltage applied, the material properties of the electrodes, and the chemistry of the aqueous solution.

[00131] One embodiment of the present invention is a metal ion or particulate metal in which a pool bed diagram is present, such as As, Se, Pb, Ni, Zn, Al, Sc, Ti, V, Cr, Mn, Fe, Co. , Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ce, Pr, Nd , Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu are removed from the input stream by one or more of the following methods, each of which is a CCC parameter. Capacitive coagulation systems and methods that use multiple capacitive coagulation cells: (i) physical adsorption; (ii) capacitive adsorption; (iii) electrochemical pH control and metal immobilization; (iv) electrochemical over. Oxide (H ₂ O ₂ ) generation and metal oxidation; (v) electrodeposition (eg, electrochemical deposition, electrophoresis deposition); (vi) electrochemical oxidation or reduction; (vii) precipitation; (viii) pore diameter Profiles; (ix) electrode treatment, (x) electrode spacing, and (xi) flow-by vs. flow-through vs. carbon block cell design. The CCC can remove lead from water to produce water with a lead concentration of less than 15 ppb, which is the EPA countermeasure level for drinking or irrigation water.

[00132] Compared to prior art devices, Applicant's CCC has higher specificity for lead and other metals, dissolves and removes both lead and other metals in particulates, rather than on a daily or weekly basis. Uses low cost materials with a device life that can be measured on a yearly basis. Applicant's CCC is a system that combines electrochemical and carbon materials and is not saturated, contaminated, or inhibited by other components in water, such as iron, volatile organic compounds (VOCs), particulate matter and natural organics (NOMs). By providing, achieve its long life and efficiency. The life of the applicant's device is several times longer than the prior art of carbon filtration, ion exchange filtration, zeolite adsorbents, and reverse osmosis (RO).

[00133] In the CCC, the combination of optimized PMD, applied E, chemical manipulation, and electrochemical manipulation facilitates the immobilization (solidification) of lead to the carbon electrode. The adsorbed lead is permanently removed from the solution (FIG. 13). This methodology is readily applicable and applicable to the treatment of iron, manganese, cadmium, chromium, as well as other metals and metal derivatives. "Adjusting" the CCC is primarily based on (ii) analyzing and selecting the working region in the Pourbaix diagram of the target species, and (i) selecting the voltage applied between the CCC anode and cathode. It means selecting the pore size profile of the CCC carbon electrode that maximizes the removal of (iii) target species. The effluent from the CCC can be used without further treatment or sent to one or more EDCs, CCCs, or prior art water purification cells for further removal of other target species. can. The adjustment is optional and can be further optimized by electrode treatment.

[00134] Utilizing the seed formation and chemistry of metals, it is possible to selectively remove lead (and other target metals) from water with high efficacy and selectivity, regardless of the chemistry of water. can. This operation allows Applicant's CCC to (i) remove lead and other target species from drinking water sources electrochemically, chemically, and physically, as is currently required and in the state of input flow. And eliminate the need for numerous separation techniques driven by varying pH, (ii) more efficient, cheaper and expandable devices for purifying drinking and process water, especially soluble. And solve the technical problem of providing a device that removes insoluble lead to less than 15 ppb. Adjustment of the pH of the input stream may be necessary to improve the aggregation of the target species, especially for the removal of metals.

[00135] In an EDC embodiment of the FPC technique, the EDC parameter is "adjusted" to remove other non-metal target species such as chlorine, chloramines, and other halides and halide derivatives from the EDC influx. Will be done. "Adjusting" the EDC is primarily based on (ii) analyzing and selecting the working region in the Pourbaix diagram of the target species, and (i) selecting the voltage applied between the EDC anode and cathode. It means selecting the pore size profile of the EDC carbon electrode that maximizes the removal of (iii) target species. The effluent from the EDC can be used without further treatment or sent to one or more EDCs, CCCs, or prior art water purification cells for further removal of other target species. can. The adjustment is optional and can be further optimized by electrode treatment. The features and advantages of the device are listed below and in Tables 2 and 3 of the drawing.

[00136] The EDC or CCC optionally uses a treated anode and cathode made of carbon in which the Epzc of one or both electrodes is shifted compared to the Epzc of a pure electrode. Shifting the Epzc of the electrodes can change the rate of the reaction that occurs (either in the positive direction or in the negative direction). Whether to shift only the anode, only the cathode, both types of electrodes, and how much Epzc shift is used depends on the chemistry of the input water and the target species.

[00137] The carbon electrode is superior to the metal electrode in that it avoids or reduces electrolysis or water splitting when a high potential of 3 V is applied to the electrode. An applied potential above 1.23 V (“overpotential”) can cause electrolysis of water, which produces dangerous hydrogen gas. Metal electrodes can cause the production of hydrogen gas below 2V. In contrast, carbon electrodes can withstand higher applied voltages while avoiding substantial water electrolysis.

[00138] EDC advances include (i) reduction of power consumption required to reduce chlorine and chloramine (causes of taste and odor) with specific carbon electrodes and applied voltage, (ii) on-demand or continuous processing. It can be used as (iii) a highly expandable and simple design that enables significantly lower cost POU / POE devices and lower cost urban, commercial, and industrial large-scale systems. (Iv) Performance similar to conventional carbon blocks (eg activated carbon / activated carbon), but significantly less carbon required, (v) Similar free chlorine removal performance with much shorter residence time, (Vi) Low carbon used, (vii) long electrode life, especially in the case of chlorine and chloramine removal, (viii) finer control over specific removal amounts and output water quality, (ix) target species Better control over the rate at which the removal vs. electrode life is balanced, and (x) the choice of carbon for the FPC electrode can regulate the cost / benefit of the FPC.

[Detailed Description of Preferred Embodiment]
[00139] During the capacitive charging process, a constant current or voltage is used to charge the electrode surface for energy storage, desalting, or other useful capacitive techniques. Electrode charging and subsequent discharging are often done in thousands of cycles over a range of voltages and currents, depending on the intended use. Carbon electrodes made of activated carbon have (i) a large specific surface area, resulting in a large capacitance, and (ii) the addition of functional groups, among other things, the removal of metals and other target species, energy. It is often used in these capacity-based charging and discharging processes because of the opportunity to perform storage and surface modifications to improve deionization (eg, desalting of seawater or steam water). Activated carbon is in the form of carbon treated to have a large number of small, low volume pores that increase the surface area available for adsorption or chemical reactions. FPC is waste water, cooling water, washing waste water, water to be purified for human consumption, water to be purified for agriculture, water to be purified for gardening, water to be purified for use in food, softening. Water to be purified, seawater to be purified for human consumption, water to be purified for laboratory use, brackish water to be purified for human consumption or agricultural use, and medical use It can be used to purify water that should be purified.

[00140] The distribution of the pore size in the carbon electrode is an important FPC parameter that has been overlooked in conventional water purification techniques.

[00141] The electrode characteristics are shown in Table 4. The source of the electrodes is listed in the first column of Table 4. The pore diameter, or pore diameter (“PMD”), is crucial in maintaining the charge passing through and is directly related to the lifetime of the EDC electrode. The PMD is typically used as a representative of the diameter of the associated pore channel within the carbon electrode. FIG. 9 shows the effect of PMD on the stability of the passing charge. After repeated cycles of voltage or potential application followed by reverse voltage or potential (or short circuit or open circuit of anode (s) and cathode (s)), the pore channel (and even the pore opening) ) May "collapse" (more precisely, the pores are blocked). The pore openings become "covered" and / or the pore channels become "closed", reducing the surface area of carbon (particularly the diameter and length of the pore channels), so that the pores are no longer effective. Does not work. A "covered" pore opening blocks access to the inside of the pore. Roof formation of pore openings and collapse of pore channels cause deterioration of electrode performance and final failure of prior art cells.

[00142] In FPC, if the target species is ionized, charged, or partially charged due to the asymmetric distribution of electrons in the chemical bond, carbon due to the applied potential. It can be attracted to the electrode, which creates a driving force that brings the target species closer to (or comes into contact with) the carbon electrode. Nonionic and uncharged target species can collide with the electrode surface. Contact with the electrode surface can result in multiple routes to immobilization of the target species. Local and large pH fluctuations can be controlled to electrochemically create an alkaline environment, which, for example, produces insoluble metal oxides that precipitate near or above the electrodes and are fine. It is captured in the hole. A faradic reaction, such as an oxygen reduction reaction at the cathode, can produce hydrogen peroxide, which can diffuse from the electrode and oxidize nearby target metal molecules. Hydrogen peroxide carries out indiscriminate oxidation. The higher the local concentration of the target species closer to the electrode, the higher the statistical probability that hydrogen peroxide will oxidize the target species. Other faradic reactions, such as direct electron transfer (reduction or oxidation) between the target species and the electrode, can also occur. When the target species is attracted to the surface of the electrode, the carbon electrode either (1) transfers electrons (s) from the electrode to the target species to reduce the target species and deposits them on the electrode (2). More reactions that can be immobilized by transferring electrons (s) from the target species to the carbon electrode to oxidize the target species into either an insoluble oxide or hydroxide, or by an additional electron transfer reaction or pH control. It can be a highly sexual species. Precipitated and electrically attracted seeds are trapped in the electrode pores.

[00143] The actual size and volume of the pores in the activated carbon depends on the shape of the given pores, the tortuosity (usually associated with changes in pore diameter), and the channel length. Based on micrographs of activated charcoal, the pores in the activated carbon may be tubular channels, polygonal channels, spheroidal chambers, surface slits, etc., depending on the activation and / or synthesis procedure. The channel and chamber can be a "dead end" or "penetration" (ie, a channel or chamber having two surface appearances also called "pore openings" and having channel continuity between the two pore openings). .. The pores in the activated carbon are generalized as tubular channels having an average pore channel diameter (hereinafter, "pore channel diameter") and an average pore diameter. Measuring the actual pore channel diameter of billions of pores, which rarely have a constant pore channel diameter in a mass of activated carbon, is a very difficult task and is not reported here. As a generalization, the pore channel diameter is assumed to be the same as the pore diameter.

[00144] The diameter of the pore opening, i.e., the opening of the pore to the electrolyte, has a significant effect on the utilization of the pore for adsorption and the multicycle performance in capacitive coagulation, with small pore diameters. , The influence is dominant. The larger the pore diameter (and thus the pore surface area), the more significant contact area is provided between the pore channel and the electrolyte. Small pore diameters have a more limited contact area (ie, "pore mouth surface area"). Porosity is defined by IUPAC as microporous, mesoporous, and macroporous with pore diameters of less than 2 nm, 2-50 nm, and more than 50 nm, respectively. The lifetime of the adsorption medium has a direct correlation with the pore size present on the surface of the material. The concept and effect of "pore mouth roof formation", which is also called pore mouth blockage, after repeating the adsorption and desorption cycle using the activated carbon electrode will be described below. After repeated FPC polarity reversal cycles, the pore openings "roof" or "close" and the pore channels "collapse", so that the surface area of the pores is effective in capturing and adsorbing the target species. Does not work.

[00145] The applicant's device incorporating the capacitive coagulation technology can remove soluble (dissolved) and insoluble (fine particles) lead species from tap water of a sample mixed with a lead concentration of up to about 300 ppb, far from the EPA countermeasure level. It was removed until it fell below the water level. Efficient lead removal was demonstrated even when the concentration of lead in the input stream was as low as 5 ppb, well below the countermeasure level. The prototype device achieved a specificity of more than 90%, and often more than 99%, for lead removal over other components commonly found in tap water, such as calcium (Ca ^2+). The applicant's invention of capacitive coagulation was able to achieve this performance in hard alkaline water, where lead species tend to form complex-forming species that are difficult to remove with off-the-shelf products on the market. CCC can also unexpectedly remove both soluble (dissolved) and insoluble (fine particles) lead, arsenic, nickel, and copper species.

[00146] Applicant's invention of capacitive coagulation, in one embodiment for lead removal, is 1 gallon per minute (gpm) regardless of the input water source conditions, ie hardness, pH, alkalinity, and type of disinfection. Provided is a POU / POE water purification device capable of satisfying NSF / ANSI53 and 61 certifications at the minimum flow rate of. In addition, the device is (i) highly specific for target metals such as arsenic, lead, nickel, copper, cadmium, lead, manganese, mercury, and radioactive metals, and is more specific than the latest solutions ( ii) Reliable, (iii) efficient, and (iv) long lasting. Applicant's capacitive coagulation cell removes soluble and insoluble lead to less than 15 ppb, making it more efficient and cheaper, suitable not only for residential use but also for scaling to higher throughput systems. , Realize a highly expandable water purification device. The following detailed examples focus on lead removal using capacitive coagulation cells, but by adjusting the CCC parameters, the CCC is "adjusted" to any other metal for which a Pourve diagram is present. Or metal derivatives such as arsenic, cadmium, manganese, and mercury, as well as Se, Ni, Zn, Al, Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru. , Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , Yb, and Lu can be removed.

[00147] In the direct comparison shown in FIG. 3, the applicant's CCC is a commercially available POU / POE water purification device such as Brita® Longlast® and Brita® PUR. It was superior to the filter as well as the Calgon GAC filter material. Brita® Longlast® Pitcher Filters have extremely different performance when tested on different two days based on changes in the chemistry of water supplied by the Lexington Urban Water System, Kentucky. Met. This different performance underscores the need for more reliable devices that work well with the ever-changing chemistry of water. The applicant's invention was superior to the Brita® Long Last® device in both cases.

[00148] Soluble lead ions are adsorbed to the carbon electrode by physical and / or chemisorption, and this process has been well documented (J. Chem. Technology. Biotechnol. 2002, 77, 458-464). , Shekinah, P .; Kadirvelu, K .; Kanmani, P .; Senthirkumar, P .; Subburam, V. and Carbon. 2004, 42, 3057-3069, Switakowski, A .; Pakula, M .; Bina. .; Walkzyk, M.), under applied potential, undergoes further electrical adsorption to the cathode. pH regulation can also be used to control lead speciation in tap water. At an operating voltage of 1.2V (as shown in FIG. 4), the potential distribution across the device yields +0.9V at the anode and -0.3V at the cathode, with pH fluctuating between the electrodes, almost medium overall. Sexual pH is produced. However, although the overall pH remains relatively constant, there are significant pH fluctuations (also called "plugs") from acidic pH 2 to alkaline pH 10, which contributes to the acid / base chemistry on the electrode surface. Make a big difference. By associating the voltage and pH at each electrode with the Pourbaix diagram, operating conditions can be selected to obtain the desired lead species formation in the chemistry of a given water (FIG. 4, DIC in the figure). Dissolved inorganic carbon). Boric acid is removed using capacitive deionization (CDI), utilizing a similar approach of manipulating pH. Electrochimica Acta. 2011, 56, 248-54, Avraham, E. et al. Noked, M. et al. Soffer, A. Aurora, D. In most residential and commercial applications, the input flow pressure is less than 60 psi and the porosity of the electrodes typically avoids a drop of more than 20 psi at the FPC outlet compared to the inlet pressure.

[00149] In the CCC, there are multiple mechanisms of action for lead removal during operation: physical and electrochemical adsorption, pH regulation to produce acid / basic chemistry, and electricity to produce lead oxide and other insoluble species. Chemical / chemical oxidation occurs at the same time. The effect of applied potential and H ₂ O ₂ generated for lead removal from tap water, was verified by experimental data. As shown in Table 5, some degree of physical adsorption of lead occurs in the carbon electrode in the open circuit. With a short circuit, there is a slight improvement in lead removal, but the most dramatic result occurs at an applied voltage of 1.2 V, with the lead concentration dropping to almost 0 ppb. In the CCC used in the experiment, "supply" is the input stream and "processed" is the output stream.

[00150] FIG. 4 shows a Pourbaix working region for lead species removal at the CCC at the intersection of E applied to the anode and cathode in the Pourbaix diagram of lead (Pb) in an aqueous carbonate solution. .. In the flow-through cell, FIG. 2 shows that the pH range at the start of the cathode is acidic (pH 2-3), whereas the pH range at the start of the anode is basic (pH 9-10). .. In the flow-through cell design (FIG. 2), these pH ranges are the result of reactions occurring on the electrode surface, resulting in pH variations of 2-10. In FIG. 4, Pb ²⁺ is in solution equilibrium in most white regions (about pH 7) between the dark PbO _{2 (s) and Pb (s) regions.} However, in the solution closest to the anode and cathode, Pb ²⁺ becomes (i) reactive or (ii) immobilized as another Pb species. FIG. 5 shows the reaction mechanism by which Pb is removed from the solution. Flow In-through cell, (in E the applied of 0.9V, generated from pH resulting from the cathode) anode Near alkaline (PH9～pH10) region ^{in, Pb} 2+ _{is, PbCO 3 -2Pb (OH) 2} , 2Pb Immobilized as (OH) ₂ and PbO ₂ (adsorbed to the anode). In the alkaline region near the anode, Pb ²⁺ also forms lead hydroxide with ionic compounds (as shown in the central box in FIG. 5), which are then oxidized to PbO _2, Pb ₃ O ₄ , and Pb. (OH) ₂ and then these reaction products are immobilized (adsorbed). Also, in the flow-through cell, hydrogen peroxide, which is generated at the cathode by the reduction of dissolved oxygen and combined with the acidic pH (pH2 to pH3) generated from the anode at E applied at -0.4 V, is a powerful oxidant. Is. Hydrogen peroxide diffuses into the passing stream containing the region near the anode where it oxidizes lead species in the above intermediate reactions. This removes the immobilized lead species from the solution. Additional lead species are more likely to be immobilized by reaction with hydrogen peroxide generated by oxygen reduction at the cathode (“peroxide cell”). Water Research. 2017, 120, pp. 229-237, Tang, W. et al. He, D. Zhang, C.I. Kovalsky, P. et al. Waite, T.I. D. In hybrid systems, FPCs can be used in series with cells peroxide to achieve increased lead removal.

[00151] In EDC, a chemistry-electrochemical-chemical-electrochemical reaction cascade chain occurs, decomposing free chlorine and chloramines. pH and working voltage are correlated via a Pourbaix diagram for the target species. Examples of hypochlorite, hypobromous acid, and monochloramine are shown below and are shown in FIGS. 6, 7 and 8, respectively. Target speciation can be controlled by selecting the pH and the voltage to be applied based on the pH and potential distribution at each electrode. This calibration process determines and controls which species are decomposed at what voltage in the chemistry of the water of a given influx. In FIGS. 6-8, the y-axis is the counter-standard hydrogen electrode (SHE) voltage applied between the anode and the cathode, and the x-axis is the pH.

[00152] Referring to FIG. 6, at an anode potential of less than 1.5 V relative to NHE and a total cell potential of less than 2.5 V applied across the anode and cathode, the electrochemically generated hydrogen hydrogen is generated. Reacts with "free chlorine" in solutions with a pH above 7. Direct electrochemical reduction of hypochlorous acid (HOCl) and hypochlorite ion (OCl ⁻ ) from the carbon cathode converts them to free chloride ions and water. The chloride ion is then capacitively adsorbed (immobilized). There is no upper limit to the pH (e.g., it can be dechlorinated effluent from caustic / chlorine odor cleaning apparatus using H ₂ O _2), as a practical matter, to achieve instantaneous reaction Is preferably pH 8.5.

[00153] With reference to FIG. 7, which is a Pourbe diagram for hypochlorite, the anode potential with respect to NHE is less than 1.2 V, the cathode potential with respect to NHE is greater than −1.0 V, and the anode and cathode. At a total cell potential of less than 2.2 V applied to both ends, the electrochemically generated anode reacts with "free bromine" in a solution having a pH above 7. Direct electrochemical reduction of hypobromous acid (HOBr) and hypobromous acid ion (OBr ⁻ ) from the carbon cathode converts them to free chloride ions and water. The bromine ion is then capacitively adsorbed (immobilized).

[00154] With reference to FIG. 8, which is a pool diagram for monochromamine, an anode potential of less than 1.4 V with respect to NHE, a cathode potential of more than −1.0 V with respect to NHE, and applied to both ends of the anode and cathode. At total cell potentials below 2.4 V, direct electrochemical changes in chloramine under acidic conditions produce ammonium salts. The electrochemically generated hydrogen peroxide (at the EDC cathode) reacts directly with chloramines to produce a product, a mixture of chloride ions, nitrite ions, protons (acids), and water. Chloramine reacts with electrochemically generated hydrogen to produce ammonia, and ammonia reacts with 1) electrochemically generated hydrogen to produce nitrogen, hydrogen gas and water, or 2 ) It reacts with an acid to produce an ammonium salt, which is further reacted by two methods. Chloramine also reacts directly with electrochemically generated acids in a cascade process to produce trichloramine, which is converted to hypochlorous acid in water.

[00155] The EDC typically operates at a total cell potential of less than 3.0 V applied across the anode and cathode. Depending on the target species and the chemistry of the input water, the total cell potential below 3.0 V applied across the anode and cathode in the EDC is typically between 1.0 V and 3.0 V.

[00156] As shown in FIG. 9, the active surface area of the SC, KN, and CG carbon electrodes is reduced by exposure to the cycle of applied voltage. The specific charge that the CX passes through is stable over repeated cycles, but is lower than the other carbons tested. In contrast, the applicant's HE electrode formulated with the PMD functions better than the other electrodes after about 220 cycles and maintains excellent performance. In SC, KN, CG, and CX electrodes, oxide groups are formed on the surface, causing pore roof formation and pore collapse, leading to increased resistance (bulk oxidation). Alternatively, the oxide group may form a resistant oxide layer (surface oxidation). In both scenarios, according to Ohm's law, it is necessary to increase the applied voltage in order to maintain the same amount of current and compensate for this increase in resistance: V = IR, in the equation, V is the voltage (V). ), I is the current (A), and R is the resistance (Ω).

[00157] FIG. 10 shows that at a given applied voltage, there is a potential distribution between the anode and cathode in the CCC. The voltage is split between the electrodes but may not be equal. For example, when 1.6V is applied to the FPC, the cathode can be -0.9V vs. SCE and the anode can be +0.7V vs. SCE (FIG. 10). This in turn affects the operating parameters of the FPC and the frequency of polarity switching performed in each cycle of operation in the EDC. The active surface area, carbon material, and applied voltage affect the potential distribution, among other things. The Epzc of the electrode affects the distribution of E applied during the first use of the electrode, and the potential distribution changes slightly. Balancing the faradic reaction rate at the anode and cathode ultimately stabilizes the potential distribution.

The accelerated oxidation study shown in FIG. 11 shows the effect of pore "collapse and roof formation" observed in microporous carbon. This emphasizes that mesoporous carbon can handle large applied voltages while maintaining charge efficiency and avoiding the effects of pore collapse and roof formation. Careful selection of PMDs for FPC devices can significantly improve device reliability and life, thereby reducing water treatment costs.

[00159] A bench-scale CCC system is shown in FIG. Capacitive solidification systems provide over 50% lead removal selectivity for non-metal ions. With CCCs (“lead removal CCCs”) tuned to remove lead (using CCC parameters), lead removal can approach 100%. In one embodiment of the lead-removing CCC, various oxygen-based surface groups are added to the electrodes and at a CCC operating voltage of 1.2 V, lead is less than 15 ppb in all cases for a tap water input stream of about 50 ppb. Lead removal is achieved. Using a carboxyl-functionalized electrode (also referred to as a treated electrode) as described in US Patent Application No. 62/702286 incorporated herein, the lead-removing CCC has a low lead concentration in the output stream. Reduced to 0.05 ppb, which corresponds to a removal efficiency of 99.9%.

[00160] Confirmed by ICP-MS and calculated as the seed removal rate, the removal selectivity of dissolved lead is higher than that of Ca ^{2+ in} the treatment of continuous 5 gallons of tap water with a high lead concentration of about 10 ppm. It was consistently above 99% (Table 6). FIG. 13 shows scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) analysis of the electrodes after filtration with confirmed lead immobilization.

[00161] In order to further study the effect of the applied potential on lead removal, tap water mixed with lead was filtered with a packed column filled with activated carbon without applying the potential (passive filtration / physical adsorption). Compared to CCC (active filtration / capacitive coagulation) operated at 1.2 V. Equal amounts of carbon and flow were used in both experiments. The breakthrough curves for these studies are shown in FIG. The packed column initially adsorbed lead, as indicated by the sharp drop in concentration, but after only about 0.3 L of water had passed through the carbon, it began to saturate. In contrast, the CCC was able to filter 5 gallons (about 19 L) of water to an astonishing 10,000 ppb to maintain performance and consistently remove lead below concentrations of 2 ppb. This is an estimated device capacity that, when extrapolated, removes more than 1 g of lead per gram of carbon electrode. The prototype device shown in FIG. 9 produces an overall volume of lead of 500 g or more, which corresponds to a theoretical volume capacity of about 8.8 million gallons, assuming an input flow concentration of 150 ppb lead. Other factors also affect the CCC performance of the POU configuration, resulting in a predicted CCC volume capacity of 100,000 gallons. In contrast, current POU filters have a volume capacity of only about 1,500 gallons.

[00162] In addition, dissolved oxygen (DO) drops to about 10% of saturation, which corresponds to less than 1 ppm DO and 1.25 ppm H ₂ O _{2 after filtration at an applied potential of 1.2 V.} Was measured (Fig. 15). These observations lead removal, it reveals that affected by a combination of potential and H ₂ O ₂ generation. The Pourbaix diagram of FIG. 4 emphasizes how lead speciation is susceptible to slight changes in water chemistry, such as changes in pH and voltage. The combination of these mechanisms produces the advantages observed in the capacitive coagulation used in CCC.

[00163] To test the limits of the applicant's CCC device, tap water with a low lead concentration of 5 ppb and tap water with a high lead concentration of 10,000 ppb were treated with CCC. Lead was successfully removed in all cases at an applied voltage of 1.2 V (Table 7). Even under extremely dilute conditions, which are difficult with passive filtration consisting of equilibrium-based adsorption, the active filtration process of capacitive coagulation is predominant and the selectivity is 99% or better (Table 6).
Significant improvements in CCC device performance over prior art devices:
99.9% Lead Removal 99% or More Selectivity Maintained Up to Approximately 5 ppb Lead Developed Active Lead Filtration System (Capacitive Coagulation)
Permanent lead removal

[00164] Higher throughput CCC systems are made by adding more capacitive coagulation cells and / or by using larger electrodes in each cell. Such a large system realizes lead removal effectiveness of 150 ppb to 10 ppb or less at a flow rate of 1 gpm or more.

[00165] Preferred applied for removal of Al, Ag, Au, Br, Cl, Co, Cu, Fe, Hg, Ir, Mn, Pb, Pd, Pt, Ni, Zn, and chloramine using FPC. E is shown in Table 1.

[00166] The CCC system removes lead below EPA countermeasure levels, even when the input stream has various combinations of lead content, water hardness, alkalinity, disinfectant, and pH. The chemistry of water affects lead seed formation (eg, the chemistry of urban waterworks varies from day to day, the effect of which is shown in Figure 4 above). Currently, there is no single device that can handle all forms of lead. Prior art devices typically use physical capture at higher pH and zeolite media at lower pH. In contrast, CCC is capable of removing all forms (species) of lead commonly found in drinking water sources.

[00167] Various operating parameters are considered depending on the type of water. Corrosion of internal materials is a common concern in electrochemical-based systems, but little evidence of corrosion has been observed in FPC systems. The internal components are designed and the materials are selected to be extremely robust, stable and inert to electrolytic and chemical corrosion. In one embodiment of the invention, the FPC system shall be designed to switch to an open circuit or small potential when not in use if lead leaching is found after an on / off operation or by the addition of chloramines. And an inexpensive carbon block pre-filter is added to remove chloramines. If it is discovered that a small piece of carbon cloth has fallen off over time, an optional post-filter is added.

[00168] Operational adjustments for specific water chemistries. Analysis of the typical input flow supplied to a given FPC device allows adjustments to optimize operating parameters for specific water chemistries (adjustments are the physical and electrical of lead). To optimize chemical adsorption, pH regulation, and oxidation to lead oxide and other insoluble species). Typical operating parameters are adjusted as follows:

[00169] Operating voltage. A three-electrode configuration with cathode, anode, and standard caromel electrode (SCE) as a reference is used to obtain the potential distribution. The potential at each electrode is recorded up to a voltage of 1.4V in open circuit, short circuit, and 0.2V increments. The pH and the working voltage are interrelated via the Pourbaix diagram. Lead speciation can be controlled by selecting the applied voltage based on the pH and potential distribution at each electrode. This calibration process determines and controls which lead species are deposited at what voltage in the chemistry of water in a given input stream.

[00170] Oxygen reduction and H ₂ O ₂ generation. Oxygen reduction at the cathode produces H ₂ O _{2, which} can react with lead species to promote the formation of lead oxide. At an applied voltage of 1.2 V, DO is significantly reduced and 1.25 ppm H ₂ O ₂ is measured in filtered water. The working voltage is controlled to amplify this reaction and maximize lead removal. Open circuit, short circuit, and conducted experiments to the maximum voltage 1.4V in 0.2V increments, pH at the outlet, DO, and _H 2 _{O 2} concentration, typically remove lead to below EPA action level ..

[00171] Carbon conductivity. FPC devices typically use microporous carbon (Carbon B in Table 8) with moderate conductivity. In order to elucidate the effect of capacitive solidification on lead removal, a comparative study of carbons with different characteristics in Table 8 was conducted.

[00172] CCC lead removal techniques include (i) physical adsorption; (ii) volumetric adsorption; (iii) electrochemical pH control and metal immobilization; (iv) electrochemical peroxide (H ₂ O ₂ ) generation. & Metal Oxidation; (v) Electrodeposition (eg, Electroplating, Electromagnetic Deposit); (vi) Electrochemical Oxidation; (vii) Precipitation; (viii) Pore Diameter Profile, (ix) Electrode Treatment, (x) Depends on electrode spacing and (xi) flow-by vs. flow-through vs. carbon block cell design. The combination of these factors, or the cascade of these factors, causes speciation and immobilization of the target species captured in the pore network of the carbon electrode, thereby resulting in a purified effluent. It is essential that the carbon electrode is conductive. The higher the conductivity of the carbon material, the current distribution across the electrodes is uniform, typically results in more efficient lead removal process with an increased occurrence H ₂ O _2. Pore diameter and surface area are related to the adsorption capacity and tortuosity of the material. Pore diameter and surface area also affect _{H 2} O _{2 generation in FPC devices.}

[00173] POU / POE device design. The design parameters for POU / POE FPC products are: (1) device residence time and size specified to achieve a flow rate of 1.5 gpm; and (2) treating at least 150 gallons of water at 1.5 gpm. Includes effective lead removal as defined by the reduction of dissolved lead levels from 150 ppb to 10 ppb or less and removal selectivity of more than 90% for non-metal divalent ions.

Water Dwelling Time: Dwelling time is a measure of the average time (volume / flow rate) that a volume of water stays in the device. In other words, the time required to filter a given amount of water. The dwell time is determined by the internal volume and flow rate of the device. Bench-scale CCC devices typically provide the desired removal at a flow rate of 20 ml / min with a residence time of 5 minutes. The dwell time at the peak performance flow rate is selected as a design specification and the device is sized appropriately.

[00175] Pressure drop: The pressure drop before and after the FPC device becomes more and more important as the flow rate increases. Pressure drops below 20 psi are considered acceptable and are below the normal inlet water pressure for residential and urban buildings of about 45 psi.

[00176] Extreme capacity of the FPC device. NSF / ANSI certification requires the lead concentration to be reduced from 150 to 10 ppb, and POU systems on the market are rated to treat up to 120 gallons of water. This means that for pitcher systems, about 1 gallon of water is treated per gram of carbon, and for subsink systems, about 1.6 gallons of water is treated per gram of carbon. One embodiment of the CCC device can treat 2 gallons of water at 1.5 gpm to bring lead levels from 150 ppb to 10 ppb or less. The ultimate capacity of the system is obtained from the lead removal curve. The problem of pressure drop typically arises after removing more than 1 g of lead per gram of FPC carbon electrode. CCC embodiments for POU / POE use can include lead sensors and / or pressure drop sensors to warn the user of device replacement.

[00177] FPC exchange threshold range for various embodiments. In general, CCCs are exchanged when the target metal concentration in the output stream exceeds the relevant threshold level, eg, 15 ppb for lead concentration and 1.3 ppm for copper (regulation published by EPA in 1991). See The Lead and Copper Rule (https://www.epa.gov/ground-water-and-drinking-water/national-primary-drinking-water-regulations). The threshold level (also called the harbor capacity) can be specified by a government agency or selected by the user. Urban and industrial wastewater emission limits are different from drinking water limits. The metal concentration threshold is typically higher. There are drainage guidelines for various industries (https://www.epa.gov/eg).

[00178] Playback of FPC. When the metal concentration in the FPC output stream is above the threshold level, instead of replacing the FPC, certain FPCs regenerate (eg, in the CCC, the adsorbed metal ions and particles are desorbed from the CCC electrode (eg, in the CCC). Can be removed). One method of CCC regeneration is to flow an acid through the cell to dissolve the solidified metal and regenerate the electrode. During this "acid regeneration" process, the output stream is sent to a container where highly concentrated waste logistics are collected for other processing. After the acid regeneration step, the CCC is flushed with water until the output stream reaches pH 7 (or other target pH), followed by normal CCC operations (ie, removal of metal ions and particles from the passing stream). It will be resumed. Another method of CCC regeneration is by electrolysis or electrochemical regeneration in an acidic solution. Electrolytic (also called electrochemical) regeneration converts metal oxides into soluble metal ions, rinses them with water from the CCC, and collects them in waste containers. Electrolysis is an electrochemical reaction that requires the application of an external voltage to promote an involuntary reaction. Any insoluble metal species formed on the electrodes can be dissolved in solution using a small voltage applied across the CCC, typically 5 V or less. CCC regeneration can also be a sequence of acid regeneration followed by electrolysis, or vice versa.

[00179] Multiple FPCs in series, each targeting the same or different species. Multiple FPCs connected in series (outlet to inlet), tuned to eliminate the same target species, can continuously concentrate the target species once the input stream is passed through the FPCs connected in series. Acts to reduce (achieves the same level of target species removal as operating a single cell in batch mode multiple times). By adjusting the FPC parameters of multiple cells connected in series, such as the pH of the passing flow and the voltage applied to the cell electrodes of a given cell, to different FPC and EDC parameters, in some cases 1 Each pass allows each cell in series to remove different target species from the pass stream. Pourbaix diagrams showing speciation of target species at a given voltage and pH best explain the concept of "cell series". Pourbaix diagrams for lead (FIG. 16) and copper (FIG. 17) are used to illustrate the immobilization of different metals in the CCC series. The horizontal dashed line represents the applied voltage, which can move along the vertical axis. The vertical dashed line represents pH, which can move along the horizontal axis. The area where these lines intersect represents the metal species present under these conditions. The operating conditions shown in FIGS. 16 and 17a are that Pb and Cu are immobilized (adsorbed to the CCC electrode) as _{PbO 2 (s)} (FIG. 16) and Cu (OH) _{2 (s) (FIG. 17), respectively.} Effectively removes metal from the supply logistics. Under the operating conditions shown in FIG. 17b, Cu is electrodeposited or electroplated on the _{electrodes as Cu (s).} Pourbaix diagrams for nickel, iron, manganese, aluminum, and zinc are also included (FIGS. 18-22). Similar approaches can be used to manipulate the applied voltage and pH to remove these metals. The operating conditions selected to form an insoluble species may vary from target species to target species, and there are several possibilities for a given target species, depending on the speciation illustrated in the Pourbaix diagram. obtain.

[00180] As described below, using the Pourbaix diagrams shown in FIGS. 18-22, respectively, the applied voltage and electrochemical pH control CCC target species of Ni, Fe, Mn, Al, and Zn. Selected for removal from influx. One of ordinary skill in the art can choose the applied voltage and electrochemical pH adjustment to remove a given species of target element or complex. Copper is removed by CCC by electrodeposition, hydroxide precipitation, and / or oxidation to copper oxide.

[00181] FPC control system. FPC parameters for a given FPC are monitored and controlled using a computer system that monitors and / or controls various sensors, interfaces, valves, and peripherals, which is commonly referred to as a process control computer (also referred to as a process controller). ), Which is generally a computer associated with continuous or semi-continuous production activities related to materials such as chemicals and petroleum, whether liquid, solid or vapor phase. The process control computer allows the FPC parameters to be applied to one or more FPCs in the system and to change the path of the throughflow, eg, to convert a series system architecture to a series-parallel system architecture.

[00182] Extension of FPC design to other target species in which Pourbaix diagram exists. In addition to Pb, Ni, Zn, Al, Cu, Fe, Mn, Cl, Br, and chloramine, the FPC parameters and the systems and methods disclosed above include As, Se, Sc, Ti, V, Cr, Co. , Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and other halides can be applied to the removal of metal and halide species identified in the Pourbe diagram.

[00183] [Example]
[00184] EDC performance tests were performed to verify the removal of total chlorine, free chlorine, chloramines, and peroxide (H ₂ O _{2) using carbon electrodes and voltages below 3.0 V.} The measurements were made using an analytical test kit. The experiment was performed using a flow-by-cell design and 14 pairs of electrodes alternating with the anode-cathode-anode-cathode (variable number of anode-cathode repetitions) anode-cathode (FIG. 23). In the flow-by design shown in FIG. 23, the input flow travels through an annular space near the wall of the cell vessel, then flows centered on the electrode surface into the axial channel and then through the axial channel. Is discharged to the FPC exit. A positive voltage is applied to the anode and a negative voltage is applied to the cathode. To ensure that all electrodes deteriorate at the same rate and extend the life of the EDC device, the polarity of the voltage applied to a given electrode is periodically switched (each anode as the cathode, each cathode as the anode). Convert to). An example is shown in FIG. The interval of polarity switching for a given EDC can be set arbitrarily (eg, hourly) or with one or more EDC parameters such as current threshold, voltage threshold, current reduction at constant voltage. It can also be set based on the rate, the rate of decrease in current at constant voltage, the rate of decrease in voltage at constant current, the rate of decrease in voltage at constant current, the total volume processed, and the concentration of the target species in the EDC effluent. Preferred polarity switching points are (i) the rate of decrease in current at a constant applied voltage, (ii) the rate of increase in voltage at a constant applied current, (iii) the total volume treated, and (iii) in the effluent. The concentration of the target species. Depending on the target species, a decrease or rate of increase may be detected before an increase in the concentration of the target species in the effluent is detected, and vice versa (V vs. concentration of the target species in the effluent is plotted. See the figure below). Three types of carbon were examined. The electrode characteristics are shown in Table 4.

[00185] Capacitive solidification experiments were performed and Cu removal was tested using 16 pairs of carbon electrodes (about 13 g of carbon). The cathode was pure SC and the anode was SC oxidized with nitric acid. The FPC was operated with a short circuit (0V). Direct injected ( "DI") was in _{H 2} O _{Cu [Cu (NO 3) 2} ] is the feed solution 1L of about 100ppm was treated with 20 ml / min flow rate. Samples were analyzed by inductively coupled plasma (ICP) using an optical emission spectrometer (OES) and the results in Table 9 show that about one-third of Cu was removed in a single pass.

[00186] Capacitive solidification experiments were performed and Cu removal was tested using 12 pairs of carbon electrodes (about 10 g of carbon). Both the cathode and the anode were pure SC. The FPC was operated at an applied potential of 1.2 V to the cathode. 18.5 L of the feed solution containing about 50 ppm Cu [Cu (NO ₃ ) ₂ ] and about 50 ppm Ca (CaCl ₂ ) in DIH ₂ O was treated at a flow rate of 20 ml / min. During operation, Cu is plated from the solution to the cathode and is shown as a greyish deposit in FIG. 25a.

[00187] A flow-by capacitive solidification experiment was performed using 14 pairs of carbon electrodes (about 30 g of carbon) to test Cu removal. The cathode was KN oxidized with nitric acid and the anode was pure carbon. The FPC was operated at applied potentials of 0.8, 1.0, and 1.2 V. 1.5 L of a feed solution containing about 2 ppm Cu [Cu (NO ₃ ) ₂ ] in water H ₂ O was treated at a flow rate of 100 mL / min. Samples were taken before and after filtration in the cell and the Cu ²⁺ concentration was measured by ICP-OES. Approximately 78% Cu removal was achieved under all conditions tested (Table 10).

[00188] A flow-by capacitive coagulation experiment was performed using 14 pairs of carbon electrodes (about 30 g of carbon) to test Cu removal at low pH. The cathode was KN oxidized with nitric acid and the anode was pure carbon. The FPC was operated at 1.2V. 1.5 L of a feed solution containing about 10 ppm Cu [Cu (NO ₃ ) ₂ ] in water H ₂ O was treated at a flow rate of 100 mL / min. The pH was adjusted to 2.8 using _{concentrated H 2} SO _4. Samples were taken before and after filtration in the cell and the Cu ²⁺ concentration was measured by ICP-OES. Cu was removed very effectively (Table 11), with 99.8% removal.

[00189] A flow-by capacitive solidification experiment was performed using 14 pairs of carbon electrodes (about 30 g of carbon) to test Ni removal. The cathode was KN oxidized with nitric acid and the anode was pure carbon. The FPC was operated at applied potentials of 0.8, 1.0, and 1.2 V. 1.5 L of the feed solution containing about 50 ppm of Ni [Ni (Cl) ₂ ] in the water H ₂ O was treated at a flow rate of 100 mL / min. Samples were taken before and after filtration in the cell and the Ni ²⁺ concentration was measured by ICP-OES. A maximum removal of about 63% was achieved at 1.2 V (Table 12).

[00190] Capacitive solidification experiments were performed using 16 pairs of carbon electrodes (about 14 g of carbon) to test Fe removal. The cathode was pure SC and the anode was SC oxidized with nitric acid. The cell was operated with a short circuit (0V). 18.5 L of the feed solution containing 100 ppm Fe [Fe (Cl) _{3 ] or 25 ppm FeCl 3 in} DIH ₂ O was treated at a flow rate of 20 ml / min. The concentration of Fe was steadily decreased by the treatment, and the results of ICP-OES are shown in Table 13. For high concentration experiments (Fe 100 ppm), Fe oxides are formed on the separator as rusty precipitates at the cathode and are shown as greyish deposits (FIG. 26).

[00191] A flow-by capacitive solidification experiment was performed using 14 pairs of carbon electrodes (about 30 g of carbon) to test Fe removal. The cathode was KN oxidized with nitric acid and the anode was pure carbon. The FPC was operated at applied potentials of 0.8, 1.0, and 1.2 V. Water in _{H 2} O Fe [Fe _{(Cl) 3]} is the feed solution 1.5L approximately 15ppm was treated with 100 mL / min flow rate. Samples were taken before and after filtration in the cell and Fe ³⁺ concentration was measured by ICP-OES. Approximately 99.9% Fe removal was achieved under all conditions tested (Table 14).

[00192] A flow-by capacitive solidification experiment was performed using 14 pairs of carbon electrodes (about 30 g of carbon) to test Mn removal. The cathode was KN oxidized with nitric acid and the anode was pure carbon. The FPC was operated at applied potentials of 0.8, 1.0, and 1.2 V. 1.5 L of the feed solution having Mn [Mn (SO ₄ )] of about 20 ppm in water H ₂ O was treated at a flow rate of 100 mL / min. Samples were taken before and after filtration in the cell and the Mn ²⁺ concentration was measured by ICP-OES. Approximately 99.8% Mn removal was achieved at 1.2 V (Table 15).

[00193] A flow-by capacitive solidification experiment was performed using 14 pairs of carbon electrodes (about 30 g of carbon) to test Al removal. The cathode was KN oxidized with nitric acid and the anode was pure carbon. The FPC was operated at applied potentials of 0.4, 0.8, and 1.2 V. 1.5 L of the feed solution containing about 30 ppm Al from the wastewater sample was treated at a flow rate of 100 mL / min. Samples were taken before and after filtration in the cell and the Al ³⁺ concentration was measured by ICP-OES. Approximately 99.9% Al removal was achieved at 0.4 V (Table 16).

[00194] A flow-by capacitive solidification experiment was performed using 14 pairs of carbon electrodes (about 30 g of carbon) to test Zn removal. The cathode was KN oxidized with nitric acid and the anode was pure carbon. The FPC was operated at applied potentials of 0.4, 0.8, and 1.2 V. 1.5 L of the feed solution containing about 35 ppm of Zn [Zn (Cl ₂ )] in the water H ₂ O was treated at a flow rate of 100 mL / min. Samples were taken before and after filtration in the cell and the Zn ²⁺ concentration was measured by ICP-OES. Approximately 40.8% Zn removal was achieved at 1.2 V (Table 17).

[00195] To investigate the physical adsorption of Pb to pure and oxidized quinol, the packed column is filled with about 5 g of carbon and 1 L, 20 ml _{of DIH 2 O with a Pb [Pb (NO 3} ) ₂ ] of about 100 ppm. Filtered at a flow rate of / min. The results in Table 18 provide evidence that Pb is physically adsorbed on carbon. In addition, after filtration, a significant amount of white precipitate was present on the pure Kinol electrode (FIG. 27) and was confirmed to be lead oxide by energy dispersive X-ray spectroscopy (EDX) (FIG. 27). 28).

[00196] Flow-through capacitance using 1 L of feed solution with about 50 ppb of Pb [Pb (NO ₃ ) ₂ ] in water H ₂ O, 12 pairs of pure carbon electrodes (about 10 g) and a flow rate of 20 mL / min. Coagulation experiments showed Pb removal well below federal countermeasure level 15 ppb in a single pass (Tables 19 and 20). The cell was operated with a short circuit (0V) and applied potentials of 0.8 and 1.2V. Pb was mixed several times to test the removal. The experiments in Table 20 were performed at 1.2 V using a pure anode and a cathode oxidized with nitric acid. Samples were taken before and after filtration through the cell and Pb ²⁺ concentrations were measured by ANDallyze handheld sensors and / or inductively coupled plasma mass spectrometry (ICP-MS). "\" In the table means "not measured".

[00197] Pb [Pb (NO ₃ ) ₂ ] in tap water H ₂ O was oxidized with 1.5 L of feed solution of about 5 to about 275 ppb, 14 pairs of carbon electrodes (about 30 g), pure anode and nitric acid. Flow-by capacitive coagulation experiments using the cathode and a flow rate of 100 mL / min also showed Pb removal well below federal countermeasure level 15 ppb in a single pass (Table 21). The cell was operated at an applied potential of 1.2 V. Samples were taken before and after filtration in the cell and Pb ²⁺ concentrations were measured with an ANDalize handheld sensor and / or ICP-MS. The results revealed that Pb was permanently removed from the solution.

[00198] Flow-through capacitive coagulation using 1 L of feed solution with about 50 ppb of Pb [Pb (NO ₃ ) ₂ ] in tap water H ₂ O, 12 pairs of carbon electrodes (about 10 g), and a flow rate of 20 mL / min. Experiments were performed with open circuit voltage (OCV), short circuit (0V), and applied potentials of 0.4-1.4V in 0.2V increments. Various oxygen-containing surface groups and carbons with different properties were tested. A sample was taken after passing through the cell once and the Pb ²⁺ concentration was measured by an ANDalize handheld sensor and / or ICP-MS.

[00199] The experimental results in Table 22 are for a pure anode and a cathode oxidized with citric acid. Pb was removed by OCV and short circuit, but was removed more effectively under the applied potential. Best results were obtained at 1.2V with 92% Pb removed.

[00200] The experimental results in Table 23 are for a pure anode and a cathode oxidized with nitric acid. The measured concentration of Pb is below the mixed value of about 50 ppb. The pH was close to 9, and it was possible that the measurement did not contain insoluble Pb species. An orange precipitate was also observed on the last pure carbon piece (anode) and was found around the filter paper.

[00201] The experimental results in Table 24 are for a pure anode and a cathode oxidized at 340 ° C. for 72 hours in an oven. Pb removal was observed at short circuit and 1.2V. Dissolved oxygen (DO) is also monitored throughout the experiment, and decreases with the applied voltage, it suggests that oxygen is reduced to H ₂ O ₂ (Table 25).

[00202] Three carbons, Kynol, Zorflex, and Fuelcell Earth, were tested. These characteristics are listed in Table 26. The results of using Zoflex are shown in Tables 27 and 28. The applied voltage reduced DO and improved lead removal.

[00203] The results of using quinol are shown in Tables 18-24 and Table 29, Table 32 and Table 36 below. In the results shown in Table 29, only OCV, short circuit, and 1.2V applied potentials were tested. Lead removal to very low levels was achieved even at a starting concentration of about 10 ppb, and the DO concentration dropped to less than 6% at 1.2 V. Pb deposition on the electrodes was confirmed by SEM / EDX (FIG. 13).

[00204] Fuelcell earth (www.feelcellstore.com) is a graphite cloth and is highly conductive. The results are shown in Tables 30 and 31. Due to the very small surface area, there was no measurable current in either case. When the cells were disassembled after the first experiment (Table 30), there were orange precipitates on all filter papers, regardless of their position within the cells. Experiments were repeated with pure carbon on both the anode and cathode, and samples were taken after 3 hours of repetition rather than a single pass (Table 31). In this case, lead was not removed in the open circuit, somewhat in the short circuit, and much more in the applied potential of 1.2V. DO remained unchanged regardless of the applied potential, and H ₂ O ₂ was measured to be 0 ppm at 1.2 V. Pb removal, rather than caused by reaction with H ₂ O _2, can occur by pH change at the electrode surface.

[00205] Pb was mixed with synthetic tap water and the same series of experiments as above was performed (Tables 32 and 33). This water did not contain carbonate and the concentration of other ionic species was similar to our tap water. Pb removal was observed at OCV and short circuit, with slightly more removal at 1.2V. The DO concentration was low throughout the experiment.

[00206] Obtaining a breakthrough curve for a pure or nitric acid oxidized carbon (about 5 g) packed column, 20 mL / min of _{water H 2 O 1 L with a Pb [Pb (NO 3} ) ₂ ] of about 150 ppb. Filtered by flow rate (Tables 34 and 35). In this case, Pb removal is caused by physical adsorption (passive filtration) rather than capacity adsorption and coagulation (active filtration) by our device. The initial Pb concentration drops dramatically, but after treating about 0.3 L of water, both carbons rapidly saturate and become ineffective. Under the conditions tested, pure carbon appears to be more effective by physisorption of lead compared to oxidized carbon. To determine when the flow-through embodiment of the FPC device saturates, 12 pairs of electrodes (about 10 g) were used and 5 gallons of water per pass was treated at 1.2 V at 20 mL / min. Sustainable performance was obtained for treated 5 gallons of water (Table 36). The concentration of lead after filtration remained low, while ^{the concentration of calcium (Ca 2+} ) was nearly constant, demonstrating a selectivity of over 99% for lead. This experiment was repeated using a flow-by device and treated with 5 gallons of water at 1.2 V at 100 mL / min in a single pass using 14 pairs of electrodes (about 30 g) (Table 37). Pb removal was maintained for the total volume passed, even from extremely high starting Pb concentrations.

[00207] Flow-by capacitance using 1.5 L of feed solution with about 150 ppb of Pb [Pb (NO ₃ ) ₂ ] in water H ₂ O, 14 pairs of carbon electrodes (about 30 g), and a flow rate of 300 mL / min. The solidification experiment was performed at an applied potential of 1.2 V (Table 38). Samples were taken before and after passing through the cell once, and the Pb ²⁺ concentration was measured with an ANDalize handheld sensor. The processed sample was the detection limit of the sensor.

[00208] 1.5 L of feed solution with about 150 ppb of Pb [Pb (NO ₃ ) _{2 ] in tap H 2} O at pH 2.83 adjusted with _{concentrated H 2} SO ₄ , 14 pairs of carbon electrodes (about 30 g), And a flow-by capacitive coagulation experiment using a flow rate of 100 ml / min was performed at an applied potential of 1.2 V (Table 39). Samples were taken before and after passing through the cell once, and the Pb ²⁺ concentration was measured with an ANDalize handheld sensor. The processed sample was below the detection limit of the sensor.

[00209] A flow-by capacitive coagulation experiment using 1.5 L of a feed solution of a wastewater sample from a Pb acid battery manufacturer with a Pb of about 150 ppb, 14 pairs of carbon electrodes (about 30 g), and a flow rate of 100 ml / min. This was performed at an applied potential of 1.2 V (Table 40). Samples were taken before and after passing through the cell once, and the Pb ²⁺ concentration was measured with an ANDalize handheld sensor. The effluent was well below the assigned Pb emission limit of 0.6 ppm.

[00210] 1.5 L of feed solution with Pb [Pb (NO ₃ ) ₂ ] in tap water H ₂ O of about 150 ppb, about 14 g of carbon electrode, pure anode and cathode oxidized with nitric acid, and 50, 100, And a wound cell design was used in the capacitive coagulation experiment with a flow rate of 200 ml / min, all showing Pb removal to less than the federal countermeasure level of 15 ppb in one pass (Table 41). The cell was operated at an applied potential of 1.2 V. Samples were taken before and after filtration in the cell and the Pb ²⁺ concentration was measured with an ANDalize handheld sensor.

[00211] For a capacitive coagulation experiment using 1.5 L of a feed solution in which Pb [Pb (NO ₃ ) ₂ ] in tap water H ₂ O is about 50 ppb and Pb is 2.5 ppm, and Cu in tap water is about 10 ppm. A winding cell design was used. Pb removal was less than federal countermeasure level 15 ppb at low concentrations and less than 1 ppm at high concentrations (Table 42). Cu removal was over 99% (Table 43). A schematic diagram of the winding cell is shown in FIG.

[00212] A series cell architecture was used in a capacitive coagulation experiment using a solution with Pb [Pb (NO ₃ ) _{2 ] in 2.5 ppm in water H 2 O and a carbon electrode of about 30 g at 1.2 V.} Continuously treated with 5 gallons of water, the concentration was consistently less than 48 ppb (Table 44).

[00213] A carbon block was used in a capacitive coagulation experiment using 1.5 L of a feed solution in which Pb [Pb (NO ₃ ) _{2 ] in water H 2 O was about 50 ppb (Table 45).} Pb removal was less than the federal response level of 15 ppb.

[00214] Industrial wastewater containing a plurality of metal species, Cu, Fe, and Mn at concentrations in the ppm range was used in the flow-by volumetric solidification experiment. Flow rates of 0.5, 1.0, and 1.5 L / min were tested at 1.2 V. Cu decreased by more than 98%, Fe decreased by more than 14%, and Mn decreased by more than 87% (Table 46).

[00215] Reverse osmosis (RO) concentrates or brines containing multiple metal species, Cu, Fe, and Mn at concentrations in the ppb range were used in flow-by capacitive coagulation experiments. Flow rates of 0.1, 0.5, and 1.0 L / min were tested at 1.2 V. Cu decreased by more than 99%, Fe decreased by more than 99%, and Mn decreased by more than 74% (Table 47).

[00216] Total chlorine and free chlorine were measured before and after treatment with EDC prepared for chlorine removal. Chloramine was estimated from the difference between total chlorine and free chlorine. More than 99% free chlorine removal and up to 99% chloramine removal were obtained. During operation, a voltage of less than 3.0 V was applied to the cell. A flow rate of 100-500 ml / min was tested. Strictly speaking, a total of about 210 gallons of water was treated before performance degradation due to charge loss due to pore collapse was observed.

[00217] When V> 0, oxidized quinol (nitric acid treatment) was used as an anode, pure quinol was used as a cathode, and when V <0, the electrodes were switched. Total chlorine in the feed (inflow) and product (outflow) streams is shown in FIG. A clear reduction in total chlorine in the effluent was observed. 31 and 32 show the concentrations of free chlorine and chloramine in the feed and product stream, respectively. FIG. 33 shows the percentage of removal of each disinfectant. More than 99% free chlorine removal and about 80% chloramine removal were obtained. Up to 100% peroxide removal was also achieved after treatment with EDC.

[00218] Oxidized quinol (nitric acid treatment) was used as the cathode and furcell earth was used as the anode. The total chlorine in the feed and product distribution is shown in FIG. A clear reduction in total chlorine in the effluent was observed at an applied voltage of 2.0 V. 35 and 36 show the concentrations of free chlorine and chloramines in the feed and product stream, respectively. FIG. 37 shows the removal% of each disinfectant. More than 99% free chlorine removal and about 40% chloramine removal were obtained. After treatment with EDC, about 60% peroxide removal was also achieved.

[00219] When V> 0, oxidized calgon (nitric acid and electrochemical treatment) was used as the anode and as a pure calgon cathode, and when V <0, the electrodes were switched. Total chlorine in the feed and product distribution is shown in FIG. 38. A clear reduction in total chlorine in the effluent was observed. 39 and 40 show the concentrations of free chlorine and chloramines in the feed and product stream, respectively. FIG. 41 shows the removal% of each disinfectant. Up to 96% free chlorine removal and about 57% chloramine removal were obtained. After treatment with EDC, about 57% peroxide removal was also achieved.

[wrap up]
[00220] In summary, the invention of FPC is an electrochemical device for purifying an aqueous solution, with at least one carbon-based anode and at least one carbon-based cathode (the anode and cathode, respectively, without Epzc shifts). (Pure electrodes) are alternated within the container, said container comprising at least one inlet for supplying the aqueous solution to the vessel and at least one outlet for draining purified output from the vessel. At least one target species to be removed by supplying a DC constant voltage or constant current to the carbon-based electrode and a power supply with associated wiring, with a separator located between each electrode. An aqueous solution containing the above is pumped through an inlet to an exhaust channel that passes by or through an electrode and connects to at least one outlet, and is applied to a DC voltage applied to at least one anode and to at least one cathode. The DC voltage is shown in the pool bed diagram of at least one target species and is at least one by a mechanism selected from the group consisting of capacitive adsorption, faradic immobilization, and both capacitive adsorption and faradic immobilization. Includes a device, which is a DC voltage that aggregates the target species of. Aggregation of at least one target species is caused by oxidation of the target species in the pH range less than 4 near at least one anode. Alternatively, aggregation of at least one target species is caused by oxidation of the target species in a pH region of less than 4 near at least one anode, and oxidation is oxidation in a pH region greater than 10 near at least one cathode. It results from the production of the agent. The power supply is controlled by the process controller or manually. The materials used to make the electrodes are highly permeable, activated carbon cloth, a mixture of microporous and mesoporous activated carbon, a mixture of mesoporous and macroporous activated carbon, and microporous and mesoporous. Selected from the group consisting of a mixture of macroporous activated carbon. The thickness of the separator is selected from the group consisting of 1 nm to 100 microns, 2 nm to 50 microns, 2 nm to 30 microns, 1 to 100 microns, 1 to 50 microns, and 1 to 30 microns. The DC voltage used to achieve faradic immobilization is selected from the group consisting of less than 0.6V, less than 1.2V, and less than 2.0V. The electrodes may optionally be separated by an impermeable insulator, in which case the passing flow flows only through the porous electrode and reaches the discharge channel, or is permeable. It may be separated by a separator, in which case the passing flow will flow by the electrode and through the separator to the discharge channel. An ion exchange membrane can optionally cover at least one anode, at least one cathode, or both electrodes. The zero charge potential of at least one carbon-based electrode can be shifted by a mechanism selected from the group consisting of cathode reduction, cathode oxidation, anode reduction, and anode oxidation. The spacing between the electrodes is selected from the group consisting of less than 1 mm, less than 200 microns, less than 50 microns, and less than 20 microns. The cell design of the FPC can be wound or laminated.

[00221] The anode in the FPC is a microporous activated carbon of 0% to 30%, a microporous activated carbon containing carbon having a conductivity value of more than 10 S / cm, and a 70% to 100% mesoporous activated carbon. 2.0-10 nm average porosity and 0% -20% macroporous activated carbon and 80% -100% mesoporous activated carbon achieved using the pore caliber profile of. It is possible to have an average pore diameter selected from the group consisting of an average pore diameter of 2.5-10 nm achieved using the pore diameter profile of mesoporous activated carbon with a rate value greater than 10 S / cm. The cathode in the FPC is 0% to 30% microporous activated carbon, and the pores of the microporous activated carbon containing carbon having a conductivity value of more than 10 S / cm and the pores of 70% to 100% mesoporous activated carbon. Average pore diameter of 2.0-10 nm achieved using the caliber profile, and 0% -20% macroporous activated carbon and 80% -100% mesoporous activated carbon with conductivity values. It is possible to have an average pore diameter selected from the group consisting of an average pore diameter of 2.5 to 10 nm achieved using a pore size profile of mesoporous activated carbon above 10 S / cm.

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Claims (18)

An electrochemical device for purifying an aqueous solution,
At least one carbon-based anode and at least one carbon-based cathode (each of _{which is a pure electrode without an EPZC} shift) are arranged alternately in the container, and the container contains an aqueous solution. It is configured with at least one inlet to supply the container and at least one outlet to drain the purified output from the container, with a separator located between each electrode and associated wiring. The provided power supply supplies a DC constant voltage or a constant current to the carbon-based electrode.
An aqueous solution containing at least one target species to be removed is fed through the inlet and reaches a discharge channel that passes by or through the electrode and leads to the at least one outlet.
The DC voltage applied to the at least one anode and the DC voltage applied to the at least one cathode are associated with a pool bed diagram of the at least one target species, capacitive adsorption, faradic immobilization, and the like. And a DC voltage that aggregates at least one target species onto the electrode by a mechanism selected from the group consisting of both capacitive adsorption and faradic immobilization.
device. The device of claim 1, wherein the aggregation of the at least one target species is caused by oxidation of the target species in a pH region of less than 4 near the at least one anode. The aggregation of the at least one target species is caused by the oxidation of the target species in a pH region of less than 4 near the at least one anode, and the oxidation exceeds 8 near the at least one cathode. The device of claim 1, which results from the production of an oxidant in the pH range. The device of claim 1, wherein the power source is controlled by a process controller or manually. The material for making the electrode has high water permeability, activated carbon cloth, a mixture of microporous and mesoporous activated carbon, a mixture of mesoporous and macroporous activated carbon, and microporous and mesoporous. The device according to claim 1, which is selected from the group consisting of a mixture of activated carbon and macroporous activated carbon. Claim 1 in which the thickness of the separator is selected from the group consisting of 1 nm to 100 microns, 2 nm to 50 microns, 2 nm to 30 microns, 1 to 100 microns, 1 to 50 microns, and 1 to 30 microns. The device described in. The device of claim 1, wherein the DC voltage used to achieve faradic immobilization is selected from the group consisting of less than 0.6V, less than 1.2V, and less than 2.5V. The device of claim 1, wherein the electrodes are separated by an impermeable insulator so that the passing flow flows only through the porous electrodes and reaches the discharge channel. The device according to claim 1, wherein the electrodes are separated by a permeable separator, and a passing flow flows by the electrodes and reaches the discharge channel through the separator. The device of claim 1, wherein the ion exchange membrane covers the at least one anode, the at least one cathode, or both electrodes. The device of claim 1, wherein the zero charge potential of at least one carbon-based electrode is shifted by a mechanism selected from the group consisting of cathode reduction, cathode oxidation, anode reduction, and anode oxidation. .. At least one carbon-based anode
Using a pore size profile of 0% to 30% microporous activated carbon containing carbon with a conductivity value greater than 10 S / cm and 70% to 100% mesoporous activated carbon. Achieved average porosity of 2.0-10 nm,
Achieved using a pore size profile of 0% to 20% macroporous activated carbon and 80% to 100% mesoporous activated carbon with a conductivity value greater than 10 S / cm. Average porosity 2.5-10 nm
The device according to claim 1, which has an average pore diameter selected from the group consisting of. At least one carbon-based cathode
Using a pore size profile of 0% to 30% microporous activated carbon containing carbon with a conductivity value greater than 10 S / cm and 70% to 100% mesoporous activated carbon. Achieved average porosity of 2.0-10 nm,
Achieved using a pore size profile of 0% to 20% macroporous activated carbon and 80% to 100% mesoporous activated carbon with a conductivity value greater than 10 S / cm. Average porosity 2.5-10 nm
The device according to claim 1, which has an average pore diameter selected from the group consisting of. The device of claim 1, wherein the distance between the electrodes is selected from the group consisting of less than 1 mm, less than 200 microns, less than 50 microns, and less than 20 microns. The device of claim 1, wherein the cell design is winding, laminating, or carbon block. The average pore size distribution range is 0 to 50 nm, and the target species and FPC parameters are
An anode voltage range with FPC parameters from 0 to 1.2 V, a cathode voltage below -1.1, and manganese, which is the preferred operating voltage of 1.2 V;
Iron with FPC parameters in the anode voltage range from 0 to 1.2 V, cathode voltage below -0.5 V, and preferred operating voltage range from 0.4 to 1.2 V;
Cobalt with Anode voltage range with FPC parameters above 0V and cathode voltage below -0.5V;
Anode voltage range with FPC parameters from 0 to 1.0 V, cathode voltage below -0.4 V, and nickel, which is the preferred operating voltage of 1.2 V;
Anode voltage with FPC parameters above 0V, cathode voltage below 0V, and copper in the preferred operating voltage range of 0.8-1.2V;
Anode voltage with FPC parameters above 0V, cathode voltage below -0.8V, and zinc in the preferred operating voltage range of 0.8-1.2V;
Anode voltage with FPC parameters above 0V, cathode voltage below -1.3V, and aluminum, which is the preferred operating voltage of 0.4V;
Anode voltage with FPC parameters above 0.5V, cathode voltage below -0.4V, and lead, which is the preferred operating voltage of 1.2V;
Palladium whose FPC parameters are the anode voltage above 0V and the cathode voltage below 0V;
Anode voltage with FPC parameters above 0V, and silver with a cathode below 0V;
Anode voltage with FPC parameters above 0.4V and cathode voltage below 0V Iridium;
Platinum with Anode voltage with FPC parameters above 0V and cathode voltage below 0V;
Gold with Anode voltage with FPC parameters above 0.8V and cathode voltage below 0V;
Anode voltage with FPC parameters above 0.3V and cathode voltage below 0V mercury;
Chlorine with an Anode potential of less than 1.5 V for NHE with FPC parameters and a total cell potential of less than 2.5 V applied across the anode and cathode;
An anode potential with an FPC parameter of less than 1.2 V for NHE, a cathode potential of more than -1.0 V for NHE, and a total cell potential of less than 2.2 V applied across the anode and cathode; and FPC. Chloramine, whose parameters are an anode potential of less than 1.4 V for NHE, a cathode potential of more than -1.0 V for NHE, and a total cell potential of less than 2.4 V applied across the anode and cathode.
The device according to claim 1, which is selected from the group consisting of. A method of purifying an aqueous solution, wherein a faradic porous cell configured with FPC parameters for the target species has an input flow of solution to be purified and an output flow of purified water. .. The aqueous solution is purified for use in power plant wastewater, power plant cooling water, washing wastewater, water to be purified for human consumption, water to be purified for agriculture, water to be purified for gardening, and food. Water to be purified, water to be softened, seawater to be purified for human consumption, water to be purified for laboratory use, brackish water to be purified for human consumption or agricultural use, and 17. The method of claim 17, selected from the group consisting of water to be purified for medical use.

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