BRPI0709789A2 - electrolytic apparatus with polymeric electrode and methods of preparation and use - Google Patents

Abstract

<B> ELECTROLYTIC APPLIANCE WITH POLYMERIC ELECTRODE AND METHODS OF PREPARATION AND USE <D> The present invention relates to low-cost methods and apparatus that use at least one carbon-charged polymer electrode to generate desirable products electrolytically.

Description

Report of the Invention Patent for "ELECTRONIC APPLIANCE WITH POLYMERIC ELECTRODE AND METHODS OF PREPARATION AND USE".

Background of the Invention

Field of the Invention

The present invention relates to an electrolytic apparatus having less than one polymer electrode and its construction and use methods, and specifically to an electrolytic apparatus comprising at least one polymeric electrode electrolytically generating oxidizing species.

Relative Technique Discussion

Electrolytically generated disinfectant solutions have been described. For example, Barger, et al., In U.S. Patent No. 6,255,270, describes cleaning and disinfecting compositions with an electrolyte disinfecting enhancer. Tremblay, et al., In U.S. Patent Application Publication Number 2003/0042134, describes a high efficiency electrolysis cell for generating oxidants in solutions. Indeed, Logan, in U.S. Patent No. 2,163,793, describes electrolytically producing chlorine dioxide.

Kadlec, et al., In U.S. Patent Number 6,869,518, describes electrochemical chlorine dioxide ageration. Chen, et al., U.S. Patent No. 6,921,521, describe a method for producing chlorine dioxide employing an alkaline chlorate in a urea mineral acid medium as a reducing agent. Scheper, et al., U.S. Patent No. 6,921,743, describes automatic dishwashing compositions containing a halogen dioxide salt and methods for use with electrochemical cells and / or electrolyte devices. Price, et al., In U.S. Patent Application Publication No. 2003/0213503, describes a signal-based electrochemical methods for automatic dishwashing.

Scheper, et al., In U.S. Patent Application Publication No. 2003/0213704, describes a self-contained, self-contained electrolytic device for improved automatic dishwashing performance.

Herrington, in U.S. Patent No. 7,008,523, describes an electrolyte cell for surface disinfection and point of use. Tremblay, et al., In U.S. Patent Application Publication No. 2004/0149571, describes an electrolytic cell for generating halogen dioxide in a utensil. Tremblay, et al., In U.S. Patent No. 7,048,842, describes an electrolyte cell for generating chlorine dioxide.

Roensch et al., U.S. Patent No. 7,077,995, describe a method for treating aqueous systems with locally generated chlorine dioxide.

Summary of the Invention

According to one or more embodiments, the invention relates to an electrolytic apparatus comprising an electrolytic cell that is less a carbon-filled polymeric electrode.

According to one or more embodiments, the invention relates to a method comprising providing an electrolyte cell having at least one carbon charged polymer electrode.

Brief Description of Drawing

The accompanying drawing is not intended to be drawn in scale. For the sake of clarity, not all components may be identified in the drawing.

In the drawing, Figure 1 illustrates an electrolytic apparatus according to one or more embodiments of the invention.

The present invention may provide an electrolyte apparatus, systems utilizing one or more electrolytic apparatus, as well as techniques involving such electrolytic devices. According to some aspects, one or more embodiments of the invention involve electrolytic devices having at least one polymeric electrode. In some cases, the electrolyte device of the invention may comprise a plurality of electrodospolymer. For example, the electrolytic device may have at least one electrode serving as a cathode comprised of a polymeric material and optionally one or more electrodes serving as an anode comprising the same or a different polymeric material. In some cases, the polymer electrode may be considered to be charged with electrically conductive components. In some aspects, the invention provides relatively low cost components compared to conventional electrodes but with comparable performance. The polymer electrode may be a carbon charged polymer electrode. Additional embodiments may involve using other components that facilitate the conduction or transport of an applied electric current through one or more polymer electrodes of the apparatus of the invention. The polymeric electrode may additionally comprise one or more electrical nuclei or components that provide electrical conductivity throughout the electrode body. For example, the electrolytic cell may have an anode and a cathode, and one or both may be a polymeric electrode with at least one metal core embedded in it. The metal core thus serves to conduct current electrically and reduces the likelihood of a resistive gradient across the electrode.

The electrolytic devices of the invention may be used for the electrocatalytic generation of one or more products of one or more precursor species. Some aspects of the invention involving various electrolyte devices of the invention may be directed to the generation of an oxidizing species. Specifically, some aspects of the invention may involve electrolytically generating one or more halogenated oxidizing agents. For example, one or more electrolyte embodiments of the invention may involve electrolytically generating a chlorinated, brominated, or fluorinated compound, or mixtures thereof, which may oxidize one or more target compounds, non-limiting examples of which include bacteria. In accordance with some specifically advantageous embodiments, the various electrolyte modalities of the invention may be used to generate one or more chlorine, hypochlorous species, and chlorine dioxide. Still, some embodiments of the invention provide an oxidizing species which may be present or charged in a locally generated disinfectant solution, typically for immediate delivery and use. As used herein, disinfecting at least partially refers to rendering organisms biologically inactive or inert or incapable of further reproduction or spread of colony.

Additional specific embodiments of the invention involve providing an electrolyte apparatus comprising at least one electrodopolymer. The following discussion involves the generation of chlorine dioxide but the invention is not limited thereto and may be used to generate other desirable species. The electrolyte apparatus, exemplarily illustrated in Figure 1, in one or more embodiments of the invention may have one or more electrolyte cells 110, one or more of which may comprise at least one cathode 112 and at least one anode 114. The electrolytic apparatus 100 may further comprise a or more electrolyte sources in fluid communication or at least capable of fluid communication with the electrolytic cell 110. A plurality of electrolyte fluid sources may be used to flexibly provide the features selectively chosen by an apparatus operator. Thus, for example, the electrolyte apparatus may comprise a first or primary source of a first electrolyte comprising one or more precursor compounds and an alternative or supplementary source of a second electrolyte comprising one or more alternative precursor compounds. The electrolyte may further comprise at least one oxidizing agent selected from the group consisting of chlorates, perchlorates, hypoalites, permanganates, chromates, and peroxides. In other cases, the electrolyte may consist of or consist essentially of a breath or halide such as a chlorite or chloride.

The electrolytic cell may be fluidly connected to an electrolyte fluid source through an inlet port 102. The cell 110 further comprises at least one outlet port 104 for supplying a generated product to a point of use. Cell 110 has a body 114 containing a cavity 106 which, during operation, is filled with electrolyte from one or more electrolyte sources having at least one precursor species therein. Cell 110 still has an anode 112 connected to a power source 130. Body 114 may also serve as a cathode and is illustrated as electrically connected to power source 130 via one or more metal cores, conductors 115 at least partially embedded within. Typically, a member 120 can electrically hold and isolate anode 112 from cathode body 114. Thus, some electrolyte cells of the invention may comprise a body which serves to contain the electrolyte and facilitates the electrolytic conversion of a precursor compound into one or more. more oxidizing compounds generated. In alternative modalities, the body of the electrolytic cell can serve as the year.

This aspect of the invention facilitates electrolytic cell production especially where polymeric materials are employed. Thus, some aspects of the invention may provide a fusible or moldable electrode configured to contain the electrolyte.

During operation, an applied current is conducted through the electrolytic cell to generate one or more desired compounds of one or more precursor compounds in the electrolyte fluid transferred into the cell. For example, chlorine dioxide may be generated at or near the electrode, typically at or near the anode, of the electrolyte cell, a species of precursor chlorite in the electrolyte. In some specific embodiments of the invention, the breath compounds may be electronically converted to provide a disinfectant or deodorant solution comprising chlorine dioxide. Other suitable desirable or auxiliary reactions may be facilitated including those that generate the hypochlorous species, chlorine, and other oxidizing species. As noted herein, however, auxiliary oxidizing species may also be present in the electrolyte.

Electric current may be provided by one or more electrical sources. In some cases, the power supply provides a direct current potential of less than about 6 volts but in some cases less than about 4.5 volts and in still other cases less than about 3 volts. Depending on the service, lower potentials may be used to provide sufficient generation of the desired product. Typically, however, a minimum potential, such as at least about 2 volts, may be preferred to provide a less partial conversion of the precursor compounds into one or more desirable oxidizing products. Specifically advantageous embodiments of the power source may involve conventional primary cells such as zinc - carbon, alkaline, or lithium based electrochemical cells or batteries as well as secondary or rechargeable batteries such as, but not limited to, nickel cadmium cells, or nickel metal hydride, or lithium deions. Preferably, the electrical source may comprise one or more cells such as those having the size designations of "AA", "A-AA", "C" and "D".

Where the electrolyte apparatus comprises a plurality of electrolytic cells, one or more of at least one source of electrolytic fluid may be fluidly connected, or be connectable to any of the electrolytic cells. In some embodiments of the invention, one or more components of the electrolyte apparatus may be removed and replaced. For example, the electrolyte source may be removed, accessed or otherwise filled with fresh electrolyte. Similarly, the power source may be replaced or recharged or otherwise reenergized and thereby further provide an electric current to the cell.

At least a portion of the generated product solution can then be used to at least partially disinfect or deodorize a point of use such as a surface. Supply of the product solution comprising the one or more generated oxidizing agents may be effected using any suitable technique. For example, the generated disinfectant or deodorant solution may be aerated as an aerosol or sprayed on at least a portion of the desired surface to be decontaminated. In other cases, the generated solution comprising one or more oxidizing agents may be transferred into a herd comprising the same or different desirable oxidizing agents. The target article may then be immersed therein to facilitate oxidation or deactivation of the target compounds by one or more oxidizing species.

The polymeric electrode may utilize any suitable binder component or matrix. For example, the electrode may comprise thermoplastic or thermostable polymeric materials with electroconductive or electroactive components, non-limiting examples include graphite and electrically conductive carbon. The polymeric electrode may be formed by injection molding or similar techniques used to manufacture polymeric components. Indeed, the moldability of polymeric materials can provide low cost electrodes having increased surface areas relative to conventional non-polymer based electrodes, thereby reducing the effective current density and, in some cases, decreasing the voltage of the electrodes. operation. For example, the polymer electrodes may be configured to have ribs that increase the effective surface area. In addition, perfected cell fluid dynamics can be accomplished by fusing at least a portion of the cell with smooth surfaces and a surface profile that enhances mass transfer across the cell and, in some cases, also reduces any precipitation precipitation tendency. Non-limiting examples of polymeric binders include polyethylene, polypropylene, opolystyrene, polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride, polycarbonate, nylon, polymethyl methacrylate, and mixtures thereof or copolymers. The polymeric binder may further comprise reinforcing agents such as fibers. In some cases, the reinforcing component may also serve to facilitate electrical conductivity. For example, the electrode may comprise a reinforcing metal core comprised, for example, of copper, connected to the power source. In some cases at least a portion of the polymer electrodes may further comprise an electrocatalytic coating. Non-limiting examples of which include valve metals, precious metals, deplatin group metals, as well as their oxides and mixtures. Other coating materials that may be used include, for example, C0O2 and Μηθ2 ·

The electrode may further utilize a crosslinked or teladent substrate of the molded electrode. For example, the polymeric material may be molded with a titanium screen. The conductive characteristics of the cell can be improved by facilitating additional electrical contact points, for example by utilizing high pressure points and also by the use of crosslinked structures to further improve contact characteristics. The crosslinked structures may be comprised, for example, of copper, nickel, aluminum, and silver.

The various systems and techniques of the invention may be used in applications other than in the exemplary described chlorine dioxide generation modalities including, for example, in electrochlorination, mixed oxidant generation, and pool chlorinators. Other applications include use as electrodeionization cathodes.

The function and advantages of these and other embodiments of the invention may be further understood from the examples below, which illustrate the benefits and / or advantages of the one or more systems and techniques of the invention but do not exemplify the full scope of the invention.

Example 1

This example compares the performance of an electrolytic cell comprising a carbon-loaded polyethylene electrode from Co-valence Specialty Materials Corp. (Franklin, Massachusséts), in relation to a cell with a bare titanium electrode. The anode in both cells is a titanium screen electrode with an OPTIMA®RUA-SW electroactive coating from Siemens Corporation (Union, New Jersey). The electrode clearance is 2 mm. The electrolyte solution used is 1 M sodium chloride.

Table 1 lists the potential measured at various operating current densities. The data show a specific resistivity plus higher carbon-loaded polyethylene electrodes relative to titanium cathodes.

Table 1. Cell voltage measured in volts using a carbon-loaded polyethylene cathode or a titanium cathode. <table> table see original document page 10 </column> </row> <table>

Example 2

In this example, the polymer electrodes of example 1 have been modified to improve performance by utilizing metal components, four aluminum bars, and having multiple contact points.

The anode used is a titanium plate with an electroactive coating OPTIMA® RUA from Siemens Corporation. The electrode clearance is 1.6 mm and the electrolyte solution is 1 M sodium chloride.

Table 2 lists the measured potential with multiple contact points and shows that increased contact points can improve cell characteristics because charged carbon can in some cases be considered as carbon particle loaded polyethylene in contact with others to provide a conductive path and electrode surface.

Table 2. Cell potential measured using a carbon-loaded polyethylene cathode with multiple contact points.

<table> table see original document page 10 </column> </row> <table>

Example 3

This example shows the performance of a cell utilizing the carbon-loaded polyethylene method of example 1 and further comprising a silver crosslinked structure to facilitate electrical conduction.

The anode is comprised of titanium plate catalyzed with an OPTIMA® RUA coating. The electrode clearance is 1.6 mm and the electrolyte and sodium chloride at 1 M. Table 3 lists the measured potential with and without the cross-linked conductor and shows improved performance.

Table 3. Cell potential measured using a carbon-charged polyethylene cathode with and without a cross-linked conductor.

<table> table see original document page 11 </column> </row> <table>

Example 4

To further enhance performance, the carbon-loaded polyethylene cathode of Example 1 was treated with surface tension reducing agents. The anode used is a catalyzed titanium plate with an OPTIMA® RUA coating. The electrode clearance is 1.6 mm and the electrolyte is sodium chloride. The carbon-loaded polyethylene cathode was used with two aluminum bars and two cross-linked foam silver strips, and the data presented in table 4 show that such components facilitate electrical contact by decreasing cell potential,

Table 4. Cell potential measured using a carbon-loaded polyethylene cathode with various surface treatments.

<table> table see original document page 11 </column> </row> <table>

Example 5

In this example, an alternate carbon-based material, a GRAFCELL® graphite plate from GrafTech International Ltd. (Parma, Ohio) was used as the cathode. It is believed that the higher carbon content relative to the carbon-loaded electrode should provide improved specific resistivity and lower contact resistance. The anode is comprised of a titanium plate with an OP-TlMA® coating. The electrode clearance is 1.6 mm and the electrolyte solution is sodium chloride.

Table 5 shows the performance of this configuration, table 5. Cell performance using a GRAFCELL® graphite plate cathode over time.

<table> table see original document page 12 </column> </row> <table> Example 6

In this example, the anode and cathode of example 4 were modified to evaluate alternative contact configurations. As in example 4, the anode comprised of titanium plate and catalyzed with an OPTIMA® coating was sandblasted and connected at two contact points without using the aluminum contact bars. The GRAFCELL® Graffiti Plate Cathode has been similarly configured to have two contact points. A titanium plate was also used to provide a comparative base.

Table 6 lists the potentials measured at various densities resulting from the GRAFCELL® graphite plate cathode and the titanium sheet cathode. The electrolyte is 3 sódio sodium chloride solution. GRAFCELL® placade was pretreated for 40 hours at 0.5 A / m2. The data show comparable performance between the graphite plate cathode and the conventional titanium cathode.

Table 6. Cell potential, in volts, using a GRAFCELL® graphite plate cathode compared to a titanium cathode. <table> table see original document page 13 </column> </row> <table>

Example 7

In this example, the cell was assembled using a GRAFCELL® graphite plate as the cathode as well as the anode. The electrode gap is 1.6 mm and the solution is sodium chloride. At 0.2 kA / m2, the operating potential is 3.37 volts. This example thus shows that cells comprising carbon-charged electrodes may be used in accordance with some aspects of the invention.

Example 8

In this example, the cell as in example 7 was further modified by platinizing the graphite plate anode. Under the same operating configuration, the operating voltage was measured to be approximately 2.99 volts thereby decreasing the overvoltage potential.

Having now described some illustrative embodiments of the invention, it should be apparent to those skilled in the art that the above is merely illustrative and non-limiting, having been given as examples only. Numerous modifications and other embodiments are within the scope of one of ordinary skill in the art and are contemplated as falling within the scope of the invention. For example, the electrolytic cell anode may comprise a carbon-loaded polymeric material. Specifically, while many of the examples presented herein involve specific combinations of method acts or system elements, it should be understood that these acts and elements may be combined in other ways to achieve the same objectives.

Those skilled in the art should appreciate that the parameters and configurations described herein are exemplary and that the actual parameters and / or configurations will depend on the specific application in which the systems and techniques of the invention are used. Those skilled in the art should also recognize or be able to evaluate, using no more than routine experience, equivalents to the specific embodiments of the invention. It is therefore to be understood that the foregoing embodiments are given by way of example only and that, within the scope of the appended claims and their equivalents, the invention may be otherwise practiced as specifically described.

Further, it should also be appreciated that the invention is directed to each feature, system, subsystem, or technique described herein and any combination of two or more features, systems, subsystems, or techniques described herein and any combination of two or more features, systems, subsystems, and / or methods, if such features, systems, subsystems, and techniques are not mutually inconsistent, it is considered to be within the scope of the invention to be incorporated into the claims. Yet acts, elements, and characteristics discussed only in connection with one embodiment are not intended to be excluded from a similar role and other embodiments.

As used herein, the term "plurality" refers to two more items or components. The terms "comprising", "including", "performing", "having", "containing", and "involving", both in the written description of these claims and the like, are open terms, that is, they mean "including" but not limited to ". Thus, the use of such terms means to include the items listed below, and their equivalents, as well as additional items. Only the transitional phrases "consisting of" and "consisting essentially of" are closed or semi-closed transition sentences, respectively, with reference to the claims. The use of ordinal terms such as "first", "second", "third", and the like in the king claims to modify a claim element does not in itself confer any priority, precedence, or order of a claim element. claim over another or the temporal order in which the acts of a method are performed but are merely used as identifiers to distinguish a claim element that has a certain name from another element that has the same name (but for use of the ordinal term) to distinguish the claim elements.

Claims (22)

1. Electrolytic apparatus comprising an electrolytic cell that has at least one carbon charged polymer electrode. The electrolytic apparatus of claim 1, wherein the at least one carbon-charged polymer electrode comprises an electrically conductive carbon disposed within a thermoplastic polymeric binder. The electrolytic apparatus of claim 2, wherein the polymeric binder comprises polyethylene. Electrolytic apparatus according to claim 1, further comprising a body containing at least a portion of the electrolytic cell, at least a portion of the body comprising the carbon disposed within a polymeric binder. The electrolyte apparatus of claim 4, wherein at least a portion of the body serves as at least one electrolyte cell electrode. The electrolyte apparatus of claim 1, further comprising a source of an electrolyte comprising at least one of a breath and a halide. The electrolyte apparatus according to claim 6, wherein the electrolyte comprises a chlorite. The electrolyte apparatus of claim 6, wherein the electrolyte comprises a chloride. The electrolyte apparatus of claim 6, wherein the electrolyte further comprises at least one oxidizing agent selected from the group consisting of chlorates, perchlorates, hypoalites, permanganates, chromates, and peroxides. An electrolytic apparatus according to claim 1, further comprising an electrical potential source connected to at least one carbon-charged polymer electrode and providing less than approximately 3 volts for the electrolytic cell. The electrolytic apparatus of claim 10, further comprising a circuit constructed to regulate the electrical potential for the electrolytic cell to at least approximately 2 volts. Electrolytic apparatus according to claim 1, wherein at least one carbon charged polymer electrode serves as a cathode. Electrolytic apparatus according to claim 1, wherein the at least one carbon-charged polymer electrode comprises at least one metal core. The electrolytic apparatus of claim 1, wherein the at least one carbon charged polymer electrode comprises an electrocatalytic coating disposed on at least a portion of a surface thereof. A method comprising providing an electrolytic cell having at least one carbon charged polymer electrode. The method of claim 15, further comprising establishing an electric current through at least one carbon charged electrodopolymer. The method of claim 16, wherein establishing the electric current comprises providing a current with a potential of less than approximately 3 volts. The method of claim 17, wherein establishing the electric current comprises providing a current with a potential of less than approximately 2 volts. The method of claim 16, wherein establishing the electric current comprises connecting a terminal of an electrical source to a carbon charged polymer cathode of the electrolytic cell. The method of claim 16, wherein establishing the electric current further comprises connecting a terminal of an electrical source to a carbon-charged polymer electrode having an electroactive coating disposed on at least a portion of an overlay. surface of it. The method of claim 16, wherein establishing the electric current comprises connecting an electrical source to a carbon charged electrodopolymer having a metal core. The method of claim 16, wherein establishing the electric current comprises conducting the current from an electrical source to a carbon-charged polymer electrode through an electrically conductive member containing at least a portion of the carbon-charged polymer electrode.