ACIDIFICATION OF SEAWATER IN AN ELECTROLYTIC - CATION EXCHANGE MODULE (E-CEM) DEVICE

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119 (e) to U.S. Provisional Application Ser. No. 63/698,243, titled “ACIDIFICATION OF SEAWATER IN AN ELECTROLYTIC-CATION EXCHANGE MODULE (β-CEM) DEVICE,” filed on Sep. 24, 2024, the subject matter of same being incorporated herein by reference in its entirety for all purposes.

GOVERNMENT LICENSE RIGHTS

This invention was made with government support under Contract No. N00014-21-C-1019 awarded by the Department of the Navy. The government has certain rights in the invention.

FIELD OF TECHNOLOGY

Aspects and embodiments disclosed herein relate to devices and methods for acidifying seawater to generate and capture carbon dioxide (CO₂) and hydrogen (H₂).

SUMMARY

In accordance with one aspect, there is provided an apparatus for generation of at least one of carbon dioxide or hydrogen from saline water. The apparatus comprises an anodic compartment having an inlet and an outlet, an anode disposed on a first side of the anodic compartment, a cathodic compartment having an inlet and an outlet, a cathode disposed on a first side of the cathodic compartment, a first cation permeable fluidic separator disposed on a second side of the anodic compartment, a second cation permeable fluidic separator disposed on a second side of the cathodic compartment, a center compartment defined between the first cation permeable fluidic separator and the second cation permeable fluidic separator, and a mixing chamber including an inlet fluidly connectable to or in fluid communication with the outlet of the anodic compartment and an outlet, the center compartment having one of an outlet fluidly connectable to or in fluid communication with the inlet of the mixing chamber or an inlet fluidly connectable to or in fluid communication with the outlet of the mixing chamber.

In some embodiments, the outlet of the mixing chamber is fluidly connectable to or in fluid communication with the inlet of the center compartment.

In some embodiments, the apparatus further comprises a deoxygenation apparatus configured and arranged to at least partially deoxygenate anolyte from the outlet of the anodic compartment prior to the anolyte from the outlet of the anodic compartment being introduced into the mixing chamber.

In some embodiments, the apparatus further comprises a source of fresh saline water fluidly connectable to or in fluid communication with the inlet of the mixing chamber.

In some embodiments, the apparatus further comprises a controller configured to regulate relative amounts of the anolyte from the output of the anodic compartment and the fresh saline water that are mixed in the mixing chamber to form an acidic saline water with a predetermined pH.

In some embodiments, the predetermined pH of the acidic saline water is less than about 6. The predetermined pH of the acidic saline water may be in a range of pH 3 to 5.

In some embodiments, the apparatus further comprises a pH sensor disposed at the outlet of the anodic compartment and in communication with the controller.

In some embodiments, the controller is further configured to regulate a flow rate of anolyte through the anodic compartment at a rate which maintains a pH of the anolyte from the outlet of the anodic compartment at a predetermined value. The predetermined level of pH of the anolyte from the outlet of the anodic compartment may be in a range of pH 2 to 3.

In some embodiments, the inlet of the center compartment is fluidly connectable to or in fluid communication with the outlet of the mixing chamber.

In some embodiments, the apparatus further comprises a controller configured to regulate relative amounts of anolyte from the output of the anodic compartment, effluent from the center compartment, and the fresh saline water introduced into the mixing chamber to produce a mixed product stream having a pH of less than about 5. The pH of the mixed product stream may be in a range of pH 3 to 5.

In some embodiments, the source of fresh saline water is a source of seawater.

In accordance with another aspect, there is provided a method of facilitating generation at least one of hydrogen or carbon dioxide from seawater. The method comprises providing an electrolytic cell including an anodic compartment having an inlet and an outlet, an anode disposed on a first side of the anodic compartment, a cathodic compartment having an inlet and an outlet, a cathode disposed on a first side of the cathodic compartment, a first cation permeable fluidic separator disposed on a second side of the anodic compartment, and a second cation permeable fluidic separator disposed on a second side of the cathodic compartment, the center compartment defined between the first cation permeable fluidic separator and the second cation permeable fluidic separator. The method further comprises providing instructions to flow anolyte through the anodic chamber to form an acidified anolyte, and to introduce the acidified anolyte from the outlet of the anodic chamber and fresh seawater into a mixing chamber including an inlet in fluid communication with the outlet of the anodic compartment. The center compartment includes one of an outlet in fluid communication with the inlet of the mixing chamber or an inlet in fluid communication with the outlet of the mixing chamber.

In some embodiments, the method further comprises providing instructions to at least partially deoxygenate the anolyte from the outlet of the anodic chamber prior to introducing the anolyte from the outlet of the anodic chamber into the mixing chamber.

In some embodiments, the outlet of the mixing chamber is in fluid communication with the inlet of the center compartment and the method further comprises providing instructions to produce an acidified seawater from the anolyte from the outlet of the anodic chamber and the fresh seawater in the mixing chamber, and to flow the acidified seawater through the center compartment.

In some embodiments, the method further comprises providing instructions to remove hydrogen and carbon dioxide from the cathodic compartment and the center compartment, respectively.

In some embodiments, the method further comprises providing instructions to regulate relative amounts of the anolyte from the output of the anodic compartment and fresh seawater that are mixed in the mixing chamber to form the acidified seawater with a predetermined pH.

In some embodiments, the predetermined pH is less than about 6.

In some embodiments, the inlet of the mixing chamber is in fluid communication with the outlet of the center compartment and the method further comprises providing instructions to direct effluent from the outlet of the center compartment, anolyte from the outlet of the anodic compartment, and the fresh seawater into the mixing chamber to form a mixed product solution from which the carbon dioxide may be extracted.

In some embodiments, the method further comprises providing instructions to regulate relative amounts of the anolyte from the output of the anodic compartment, the effluent from the outlet of the center compartment, and the fresh saline introduced into the mixing chamber to produce the mixed product solution with a pH of less than about 5.

In accordance with another aspect, there is provided a method of retrofitting an apparatus for generation of at least one of carbon dioxide or hydrogen from a saline water source, the apparatus comprising an anodic compartment having an inlet and an outlet, a cathodic compartment having an inlet and an outlet, and a center compartment defined between the anodic compartment and the cathodic compartment. The method comprises connecting an inlet of a mixing chamber to the outlet of the anodic compartment, and one of connecting the outlet of the center compartment to the inlet of the mixing chamber or connecting an outlet of the mixing chamber to an inlet of the center compartment.

In some embodiments, the method further comprises fluidically connecting a source of fresh seawater to the mixing chamber.

In some embodiments, the method further comprises fluidically connecting an outlet of the mixing chamber to the inlet of the center compartment.

In some embodiments, the method further comprises fluidically connecting the outlet of the center compartment to the mixing chamber, fluidically connecting the outlet of the anodic compartment to the mixing chamber, and fluidically connecting a source of fresh seawater to the mixing chamber.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are not drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in the various figures is represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. In the drawings:

FIG. 1 is a schematic drawing of one example of an electrochemical cell;

FIG. 2 is a schematic drawing of another example of an electrochemical cell;

FIG. 3 is a diagram illustrating the equilibrium for inorganic carbonic species in seawater at 10° C.;

FIG. 4 is a schematic drawing of the E-CEM process;

FIG. 5 is a graph illustrating seawater effluent pH versus run time in an example of an E-CEM device;

FIG. 6A is a graph showing results of a run of an E-CEM process using an E-CEM device with a first seawater compartment thickness;

FIG. 6B is a graph showing results of a run of an E-CEM process using an E-CEM device with a second seawater compartment thickness;

FIG. 7 is a graph showing current density versus the inverse of residence time in an example of an E-CEM device;

FIG. 8 is a graph showing the theoretical amount of H⁺ ions that would be used to reduce the pH in synthetic seawater in an example of an E-CEM device;

FIG. 9A is a graph showing expected versus calculated current density at different pH levels in an E-CEM device with a first seawater compartment thickness;

FIG. 9B is a graph showing expected versus calculated current density at different pH levels in an E-CEM device with a second seawater compartment thickness;

FIG. 10 is a graph showing results of calculations to estimate excess H⁺ ion production in an example of an E-CEM device as a function of residence time at different pH levels;

FIG. 11 is a schematic diagram of an example of an E-CEM device as disclosed herein; and

FIG. 12 is a schematic diagram of another example of an E-CEM device as disclosed herein.

DETAILED DESCRIPTION

The total carbon content of the world's oceans is approximately 38,000 gigatons (GT). Over 95% of this carbon is in the form of dissolved bicarbonate ion (HCO₃⁻). This bicarbonate ion, along with the carbonate ion (CO₃^2-), is responsible for buffering and maintaining the pH of the ocean which is relatively constant below the first 100 meters of ocean depth. The dissolved bicarbonate and carbonate ions present in the ocean are effectively bound CO₂, and the sum of the concentrations of these species, along with dissolved gaseous CO₂, represents the total carbon dioxide concentration [CO₂]_T, of seawater.

At a typical ocean pH of 7.8, kept relatively constant by a complex bicarbonate-carbonate buffer system, [CO₂]_T is about 2000 μmoles/kg near the surface and about 2400 μmoles/kg at depths below 300 meters. This equates to approximately 100 mg/L of [CO₂]_T. Of the total CO₂ in the ocean, about 2-3% is dissolved gaseous CO₂, about 1% is present as the dissolved carbonate ion, and the remainder, about 96%, is present as the dissolved bicarbonate ion. It is known that the equilibrium form and concentration of water containing CO₂ and its various ionic forms is dependent on the pH of the water. For example, at a seawater pH of 4.5, 99% of all carbonate species in seawater exist as carbonic acid, H₂CO₃. Thus, to convert HCO₃⁻ to H₂CO₃, the pH of seawater may be lowered.

CO₂ dissolved in water is in equilibrium with H₂CO₃ as shown in equation 1:

The hydration equilibrium constant is 1.70×10⁻³. This indicates that H₂CO₃ is not stable in water and gaseous CO₂ readily dissociates at pH of 4.5, allowing CO₂ to be easily removed by degassing or stripping once the seawater has been acidified to ensure that the unstable H₂CO₃ is deprotonated to the predominant carbonate species.

Electrochemical cells are used in marine, offshore, municipal, industrial, and commercial implementations. The design parameters of electrochemical cells, for example, inter-electrode spacing, thickness of electrodes and coating density, electrode areas, methods of electrical connections, etc., can be selected for different implementations. Aspects and embodiments disclosed herein are not limited to the number of electrodes, the space between electrodes, the electrode material, material of any spacers between electrodes, number of passes within the electrochemical cells, or electrode coating material.

An electrochemical device with ion exchange membranes can be designed to change the pH of a fluid stream while generating reaction products at the electrodes. FIGS. 1 and 2 show two variations of a device with three fluid streams separated by two ion exchange membranes of the same ionic selectivity. The electrode reactions depend on the composition of the electrolytes, electrode materials and operating conditions. Common reactions include:

In addition, chlorine gas evolution is possible at the anode if the anolyte contains chloride ions:

In FIG. 1, both membranes are cation exchange membranes (CEM), which preferentially pass cations. Under a DC voltage, H⁺ ions generated at the anode pass into the center compartment and acidifies the fluid stream by reacting with anions such as HCO₃⁻ or SO₄⁻². Excess H⁺ ions either continue into the cathode compartment, where they react with OH-ions to form water or are swept out of the center compartment by the fluid.

Conversely, in FIG. 2 both membranes are anion exchange membranes (AEM), which preferentially pass anions. OH-ions generated at the cathode pass into the center compartment and increases the pH of the fluid stream. Excess OH-ions either continue into the anode compartment, where they react with OH-ions to form water or are swept out of the center compartment by the fluid.

One use of the device in FIG. 1 is the E-CEM process to reduce seawater pH and convert dissolved bicarbonate ions to CO₂ gas while simultaneously producing hydrogen gas through electrolytic dissociation of water in the cathode compartment. The CO₂ and H₂ gas may be utilized as feedstock to a modified Fischer-Tropsch process to produce jet fuel.

The main reactions in the center (seawater) compartment are:

The pK₁ and pK₂ values are for seawater at 10° C. Other ions may react with the H⁺, such as conversion of borate to boric acid.

Seawater has a pH of ˜8. FIG. 3 shows the equilibrium diagram for inorganic carbonic species in seawater at 10° C. If the pH is reduced to less than ˜4, essentially all the carbonate and bicarbonate are converted to H₂CO₃.

The feeds to the anode and cathode compartments are conductive solutions, such as reverse osmosis (RO) product water with conductivity<200 μS/cm or sodium sulfate solution with conductivity of ˜200-3000 μS/cm.

FIG. 4 is a schematic of the E-CEM process. A fraction of the H⁺ ions generated at the anode lower the pH in the anolyte and exits the device in the effluent from the anode compartment. The remaining H⁺ ions enter the seawater compartment through the first CEM. A fraction of these H⁺ ions react with HCO₃⁻ in the seawater to form H₂CO₃. The remaining H⁺ ions pass unreacted through the center compartment and enter the cathode compartment or is transported out the center compartment with the seawater. The unreacted H⁺ ions can be considered “losses” in the E-CEM process that reduce its energy efficiency, i.e. it increases the kWh required per mol of H₂CO₃ in the seawater effluent.

The present disclosure proposes a method to acidify the seawater feed and effluent in an Electrolytic—Cation Exchange Module (E-CEM) device.

The E-CEM process was tested in the laboratory using a module with the following specifications:

• • Flow compartment width: 1.25 in (3.18 cm)
  • Flow compartment length: 7.0 in (17.8 cm)
  • Electrode compartment thickness: 0.06 in (0.15 cm)
  • Seawater compartment thickness: 0.375 in (0.95 cm) or 0.75 in (1.9 cm)
  • Active membrane area: 8.75 in² (56.45 cm²)
  • Electrodes: Platinum coated titanium plate
  • Membranes: Ionpure® heterogeneous CEM

Hereinafter, seawater compartment thickness of 0.375 inches will be referred to as “1× thickness” and thickness of 0.75 inches will be referred to as “2× thickness”. An example of a test run is shown in FIG. 5. After the DC voltage is applied, the pH in the seawater effluent decreases until it reaches a steady state value of about 4. The seawater compartment thickness was 0.375 in (0.95 cm).

The operating conditions were:

• • Seawater feed: synthetic Instant Ocean® seawater with conductivity of 49.05 mS/cm and HCO₃ concentration of 194 ppm (higher than typical seawater)
  • Anolyte and catholyte feed: 270 μS/cm Na₂SO₄ solution in deionized water
  • Current density: 317 A/m² (1.79 A)
  • Anolyte flow rate: 0.15 l/min (residence time T=3.4 sec)
  • Seawater flow rate: 0.30 l/min (residence time T=10.8 sec)
  • Catholyte flow rate: 0.15 l/min (residence time T=3.4 sec)

FIGS. 6A and 6B show the results for additional runs at different seawater compartment thickness; the steady pH in the seawater effluent is plotted vs. 1/residence time at different current densities.

From the regression equations, the current density utilized at different residence times (or vice versa) to achieve a given steady state pH can be calculated. FIG. 7 shows current density vs. inverse of residence time (1/sec) so that the data points can be fitted with linear curves.

FIG. 8 shows the theoretical amount of H⁺ ions used to reduce the pH in synthetic seawater, assuming the pK₁ and pK₂ values in Equations 3 and 4. Reactions of H⁺ ions with other ions in seawater are ignored for the following analysis.

From the applied current the amount of H⁺ ions generated at the anodes (in mol/s) can be estimated for the test runs using the Faraday constant. FIGS. 9A and 9B show that the amount of H⁺ ions generated exceed the theoretical amount necessary for titration in most of the tests (the ratios less than 1.0 may be due to inaccuracies in measurements).

The pH of the anolyte effluent varies from 2.6-3.0, averaging around 2.8. Based on the reduction in pH from the inlet to the outlet and the flow rate, the amount of H⁺ ions used to reduce the pH in the anolyte can be estimated.

Calculations were used to estimate the amount of excess H⁺ ions that are “wasted” in the seawater compartment. The results are shown in FIG. 10. Note that the percent of excess H⁺ ions in the seawater compartments increase as the residence time is decreased and can reach 25% to 30% at the lowest residence times. Additional tests and analysis may be performed to improve the accuracy of the estimates.

The overall indication is that a significant percentage of the H⁺ ions generated is underutilized, particularly as the residence time decreases. Aspects and embodiments disclosed herein include modifications of the E-CEM devices to increase the utilization rate and thereby reduce the energy consumption of the process in terms of kWh supplied from the DC power supply per mol of H₂CO₃ removed from seawater.

A first embodiment of an improved apparatus for generation of carbon dioxide and hydrogen from a saline water source (an E-CEM device) is illustrated generally at 100 in FIG. 11. The E-CEM device 100 includes an anodic compartment 110 having an inlet 110A and an outlet 110B and an anode 120 disposed on a first side of the anodic compartment 110. The anodic compartment inlet 110A is supplied with anolyte (anode feed) 165, for example, deionized water or an aqueous sodium sulfate solution. The E-CEM device 100 further includes a cathodic compartment 130 having an inlet 130A and an outlet 130B, and a cathode 140 disposed on a first side of the cathodic compartment 130. The cathodic compartment inlet 130A is supplied with catholyte (cathode feed) 170, for example, deionized water or an aqueous sodium sulfate solution. A first cation permeable fluidic separator CEM is disposed on a second side of the anodic compartment 110 and a second cation permeable fluidic separator CEM is disposed on a second side of the cathodic compartment 130. A center compartment 150 is defined between the first cation permeable fluidic separator CEM and the second cation permeable fluidic separator CEM.

In the E-CEM device 100, O₂ gas in the anolyte effluent 160 is removed by vacuum, by membrane degasification or by purging with air, by a degasification/deoxygenation system 165 as shown in FIG. 11. The degassed/deoxygenated effluent 160 is then mixed with fresh seawater 175, or another form of fresh saline water, in a mixing chamber 180 to produce an acidic saline water with a predetermined pH that is utilized as pre-acidified seawater feed 185 that is directed into the center compartment 150. In some embodiments, the predetermined pH may be less than 6 or less than about 6.

The E-CEM device 100 may include a controller, for example, a general purpose computer, ASIC, PLC or other form of controller known in the art, configured to regulate relative amounts of the at least partially deoxygenated anolyte from the output 110B of the anodic compartment 110 and the fresh seawater 175 that are mixed to form the pre-acidified seawater feed 185 to maintain a predetermined pH of the pre-acidified seawater feed 185 using one or more pumps or valves (not shown so as not to obscure the figure).

A pH sensor pH may be disposed at the outlet 110B of the anodic compartment 110 (or in another location in a fluid line carrying the anolyte from the outlet 110B of the anodic compartment 110) and in communication with the controller. Another pH sensor pH may be disposed in a fluid line carrying the pre-acidified seawater feed 185. Communication lines to the controller are not illustrated so as not to complicate the figure. The controller may utilize measurements of pH of the anolyte from the outlet 110B of the anodic compartment 110 and/or measurements of the pH of the pre-acidified seawater feed 185 to determine how to regulate relative amounts of the at least partially deoxygenated anolyte from the output 110B of the anodic compartment 110 and the fresh seawater 175 that are mixed to form the pre-acidified seawater feed 185 to maintain the predetermined pH of the pre-acidified seawater feed 185. The controller may further regulate a flow rate of the anolyte through the anolyte chamber to provide the anolyte from the outlet 110B of the anodic compartment 110 with a predetermined pH. A desired range of pH for the anolyte effluent may be a pH range of 2-3 or a pH range of 1-2.

In a second embodiment, indicated generally at 200 in FIG. 12, the degassed anolyte effluent is mixed in a tank 180 with seawater effluent 190 from the outlet of the center compartment 150 and fresh seawater 175. This mixture results in an increased volume of acidified seawater 195 for CO₂ extraction. The E-CEM device 200 is substantially the same as the E-CEM device 100, with like reference numbers indicating like features, except that there is no pre-acidified seawater 185 directed into the center compartment 150. Rather, in the E-CEM device 200, mixing seawater effluent 190 of pH<3 and anolyte effluent 160 of pH<2 with fresh seawater 175 of pH<8 can result in acidified seawater 195 of pH<5. If the pH is reduced to less than about 4, essentially all the carbonate and bicarbonate are converted to H₂CO₃. Thus, the mixing volumes of fresh seawater and the seawater and anolyte effluents can be adjusted to achieve the desired final pH, which can then be sent to the Fischer-Tropsch reactor for CO₂ extraction. This embodiment provides for production of a higher volume of acidified seawater than convention E-CEM devices.

In the E-CEM device 200, the controller is configured to regulate relative amounts of the seawater effluent 190, anolyte effluent 160, and fresh seawater 175 to mix in the mixing chamber 180 to produce the acidified seawater 195 with a predetermined pH, for example, based on readings from pH meter(s) on or within conduit(s) through which any one or more of the seawater effluent 190, anolyte effluent 160, and/or acidified seawater 195 passes.

Both E-CEM device embodiments 100, 200 benefit by reducing the total power consumption and reduced number of modules required for producing acidified seawater. This also lowers the footprint of the overall unit.

The present disclosure also contemplates a method of facilitating generation of at least one of hydrogen or carbon dioxide from seawater. The method includes providing an electrolytic cell including an anodic compartment having an inlet and an outlet, an anode disposed on a first side of the anodic compartment, a cathodic compartment having an inlet and an outlet, a cathode disposed on a first side of the cathodic compartment, a first cation permeable fluidic separator disposed on a second side of the anodic compartment, and a second cation permeable fluidic separator disposed on a second side of the cathodic compartment, the center compartment defined between the first cation permeable fluidic separator and the second cation permeable fluidic separator. The method further includes providing instructions to flow anolyte through the anodic chamber to form an acidified anolyte, and to introduce the acidified anolyte from the outlet of the anodic chamber and fresh seawater into a mixing chamber including an inlet in fluid communication with the outlet of the anodic compartment, the center compartment having one of an outlet in fluid communication with the inlet of the mixing chamber or an inlet in fluid communication with the outlet of the mixing chamber.

The method may further include providing instructions to at least partially deoxygenate the anolyte from the outlet of the anodic chamber prior to introducing the anolyte from the outlet of the anodic chamber into the mixing chamber.

In some embodiments, the outlet of the mixing chamber is in fluid communication with the inlet of the center compartment and the method further includes providing instructions to produce an acidified seawater from the anolyte from the outlet of the anodic chamber and the fresh seawater in the mixing chamber, and flow the acidified seawater through the center compartment.

The method may further include providing instructions to remove hydrogen and carbon dioxide from the cathodic compartment and the center compartment, respectively, and may further include providing instructions to regulate relative amounts of the anolyte from the output of the anodic compartment and fresh seawater that are mixed in the mixing chamber to form the acidified seawater with a predetermined pH.

The predetermined pH may be less than about 6.

In some embodiments, the inlet of the mixing chamber is in fluid communication with the outlet of the center compartment and the method further includes providing instructions to direct effluent from the outlet of the center compartment, anolyte from the outlet of the anodic compartment, and the fresh seawater into the mixing chamber to form a mixed product solution from which the carbon dioxide may be extracted.

The method may further include providing instructions to regulate relative amounts of the anolyte from the output of the anodic compartment, the effluent from the outlet of the center compartment, and the fresh saline introduced into the mixing chamber to produce the mixed product solution with a pH of less than about 5.

The present disclosure further contemplates a method of retrofitting an apparatus for generation of at least one of carbon dioxide or hydrogen from a saline water source, the apparatus comprising an anodic compartment having an inlet and an outlet, a cathodic compartment having an inlet and an outlet, and a center compartment defined between the anodic compartment and the cathodic compartment. The method includes connecting an inlet of a mixing chamber to the outlet of the anodic compartment, and one of connecting the outlet of the center compartment to the inlet of the mixing chamber or connecting an outlet of the mixing chamber to an inlet of the center compartment.

The method may further include fluidically connecting a source of fresh seawater to the mixing chamber.

The method may further include fluidically connecting an outlet of the mixing chamber to the inlet of the center compartment.

The method may further include fluidically connecting the outlet of the center compartment to the mixing chamber, fluidically connecting the outlet of the anodic compartment to the mixing chamber, and fluidically connecting a source of fresh seawater to the mixing chamber.

The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term “plurality” refers to two or more items or components. The terms “comprising,” “including,” “carrying,” “having,” “containing,” and “involving,” whether in the written description or the claims and the like, are open-ended terms, i.e., to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of” and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as “first,” “second,” “third,” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.

Having thus described several aspects of at least one embodiment, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Any feature described in any embodiment may be included in or substituted for any feature of any other embodiment. Such alterations, modifications, and improvements are intended to be part of this disclosure and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only.

Those skilled in the art should appreciate that the parameters and configurations described herein are exemplary and that actual parameters and/or configurations will depend on the specific application in which the disclosed methods and materials are used. Those skilled in the art should also recognize or be able to ascertain, using no more than routine experimentation, equivalents to the specific embodiments disclosed.