Patent ID: 12187629

DETAILED DESCRIPTION

The following definitions are provided for the purpose of understanding the present subject matter and for construing the appended patent claims.

Definitions

Throughout the application, where compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings can also consist essentially of, or consist of, the recited components, and that the processes of the present teachings can also consist essentially of, or consist of, the recited process steps.

It is noted that, as used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise.

In the application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components. Further, it should be understood that elements and/or features of a composition or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present teachings, whether explicit or implicit herein.

The use of the terms “include,” “includes”, “including,” “have,” “has,” or “having” should be generally understood as open-ended and non-limiting unless specifically stated otherwise.

The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. In addition, where the use of the term “about” is before a quantitative value, the present teachings also include the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term “about” refers to a ±10% variation from the nominal value unless otherwise indicated or inferred.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently described subject matter pertains.

Where a range of values is provided, for example, concentration ranges, percentage ranges, or ratio ranges, it is understood that each intervening value, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the described subject matter. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and such embodiments are also encompassed within the described subject matter, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the described subject matter.

Throughout the application, descriptions of various embodiments use “comprising” language. However, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language “consisting essentially of” or “consisting of”.

For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

A system for treating reject brine and capturing carbon dioxide (CO2) produces multiple products with high purity from rejected brine and flue gas mixtures (10% CO2and 90% N2) emitted from an industrial plant. As shown inFIG.1, the system for treating reject brine and capturing carbon dioxide (CO2) includes a first electrodialysis (ED) stage, a second electrodialysis (ED) stage, and a freeze-dryer, as shown inFIG.1. Each of the first and second electro dialysis (ED) stages is configured to transport ions through a series of semi permeable membranes, under the influence of an electric potential. The membranes can be cation- or anion-selective. Accordingly, either positive ions or negative ions will flow through the membranes. With the first and second ED stages, the system can produce multiple products with high purity from rejected brine and flue gas mixtures (10% CO2and 90% N2). In an embodiment, the system can simultaneously capture CO2and treat rejected brine emitted from multistage flash desalination plants. Thus, pollutants of the desalination industry can be handled simultaneously onsite, with multiple products being produced with high purity.

As shown inFIGS.2and3, both the first ED stage and the second ED stage include a plurality of spaced, semi-permeable membranes positioned between an anode and a cathode. The space between adjacent membranes defines a cell. The anode and the adjacent membrane define an anolyte chamber. The cathode and the adjacent membrane define a catholyte chamber. In the first ED stage and second ED stage, groups of adjacent cells define chambers for receiving and processing brine and gas emissions from an industrial plant.

In the first ED stage, adjacent cell pairs can be grouped together to form chambers for receiving and processing brine or liquid emissions from an industrial plant. In an embodiment, liquid emissions from an industrial plant are transmitted to the multivalent ion chamber in a cell pair and water is transferred to an adjacent monovalent ion chamber in the same cell pair. Each chamber within a cell pair can be separated by an anion exchange membrane and adjacent cell pairs can be separated from one another by a cation exchange membrane. NaCl and monovalent ions from brine in the multivalent ion chamber can pass through the anion exchange membrane into the monovalent ion chamber, leaving water and a multivalent ion mixture in the multivalent ion chamber. Accordingly, each multivalent ion chamber can produce an outlet stream of standard irrigation water with a multivalent ion mixture and each monovalent ion chamber can produce an output stream of concentrated NaCl with monovalent ions. The standard irrigation water with the multivalent ion mixture can be collected and used for agricultural irrigation. The stream of concentrated NaCl can be transferred to the second ED stage.

According to an embodiment, a mixture of flue gases emitted from the industrial plant, the concentrated NaCl brine including monovalent ions from the first ED stage, along with two streams of water can be transferred to the second ED stage. The second ED stage can include a plurality of chambers defined by cell groups between anolyte and catholyte chambers. In an embodiment, the second ED stage can include a flue gas chamber for receiving the flue gas mixture from the industrial plant, a concentrated brine chamber for receiving the concentrated NaCl stream (with monovalent ion mixture) from the first ED stage, an acid chamber between the flue gas chamber and the concentrated brine chamber for producing acid, a carbonate chamber adjacent the concentrated brine chamber for producing carbonates. The second ED stage includes a bubble column reactor which receives one of the water streams and CO2emitted from the plant. The bubble column reactor dissolves the CO2to form CO3−2and HCO3−1ions which are then circulated continuously in the carbonate chamber. The other stream of water is provided to the acid chamber for acid collection. The sodium and chloride ions from the concentrated brine in the concentrated brine chamber can be shifted to different, adjacent chambers with the help of an electric current. In an embodiment, the chloride ions from the concentrated brine chamber combine with hydrogen ions in the acid chamber to form HCl, whereas sodium ions from the concentrated brine chamber combine with carbonate (CO3−2) and bicarbonate (HCO3−1) ions to form sodium carbonate (Na2CO3) and NaHCO3solution. CO3−2and HCO3−1ions formation occurs in the bubble column contactor with the dissolution of CO2in an alkaline solution.

The second ED stage can produce a high concentration of acid (over 90% concentration of HCl, the rest being sulphuric acid (H2SO4)), clean gas, a brine stream that is suitable for enhanced oil recovery, and a liquid mixture including Na2CO3and NaHCO3.

In an embodiment, the liquid carbonate mixture produced in the second stage can be freeze-dried to produce a solid powder mixture of Na2CO3and NaHCO3. According to an embodiment, a purity of HCl collected from the second ED stage can exceed about 92%. Thus, in addition to producing useable irrigation water in the first ED stage, the present system produces multiple useable products in the second ED stage.

The system can be configured for continuous circulation of an electrolyte. In the first stage, an electrolyte, e.g., sulphamic acid, can be recirculated through anolyte and catholyte chambers formed respectively between the anode and its adjacent membrane, defining the anolyte chamber, and the cathode and its adjacent membrane (the catholyte chamber). According to an embodiment, water can be formed from the combination of hydrogen ions (H+) generated at the anode and hydroxide ions (OH−) generated at the cathode. In the second ED stage, an anolyte (sulphamic acid) and a catholyte (sodium hydroxide) in the second ED stage can be circulated separately in the anolyte and catholyte chambers, respectively, and do not mix. One or more pumps can be provided to drive the brine through the system and then recycle the output back through the system again. According to an embodiment, a separate pump can be provided for cycling the electrolyte in the first ED stage. According to an embodiment, two separate pumps can be provided in the second ED stage for cycling the electrolyte in the anolyte and catholyte chambers separately, as shown inFIG.3.

In an embodiment, the industrial plant is a desalination plant. Since brine and CO2are the most common pollutants emitted by most industries, however, the present system can be integrated with other industries other than desalination plants, such as oil, fertilizer, and cement industries.

According to an embodiment, while the rejected brine from the first stage can include mostly NaCl, some monovalent ions from the original liquid emissions can also be present. In an embodiment, the rejected brine from the first stage can include, for example, sodium, chloride, calcium, magnesium, and potassium ions, initially present in the liquid emissions.

As shown inFIG.2, an exemplary embodiment of the first ED stage can include an anolyte chamber, a catholyte chamber, and twenty cell pairs therebetween. Each cell pair can define two chambers separated by a monovalent anion exchange membrane. The anion exchange membrane separates the monovalent ions (K+, Na+, Cl−) from the multivalent ions (Ca2+, Mg2+, SO42−) in the initial liquid emissions. Each of the cell pairs can be separated from one another by a cation exchange membrane. The cation exchange membrane can collect monovalent ions (Na+, Cl−). According to an embodiment, the first ED stage can include a total of 20 monovalent anion selective membranes, 19 monovalent cation selective membranes, and two end cation exchange membranes. In an embodiment, a rejected brine output from the first stage can include from about 20% to about 95% of the initial sodium chloride ions, calcium, magnesium, and potassium after being processed in the first stage for about 1 hour to about 2 hours. It is preferable that most multivalent ions in the first ED stage are collected by the ion selective membranes and prevented from passing to the second ED stage where they can be precipitated in the form of carbonates, thereby obstructing membrane pores.

In an embodiment, the first ED is a closed-loop process in which an electrolyte is circulated between anolyte and catholyte chambers. In an embodiment, the electrolyte is sulphamic acid. In an embodiment, 0.5 M of sulphamic acid is used as an electrolyte in the first ED stage.

In the first ED stage, OH−generated at the catholyte combines with the anolyte stream, creating H+to form water. This continuous combination of the catholyte and anolyte stream maximizes the utilization of current density for the separation of monovalent ions from multivalent ions.

In an embodiment, the first ED stage collects most of the multivalent ions that were present in the liquid emissions, leaving an NaCl-rich outlet stream with some monovalent ions to be transferred to the second ED stage. The NaCl produced from the first ED stage can have a purity exceeding about 90%, e.g., about 92%. According to an embodiment, the processing in the first ED stage can last for a first period of time ranging from about 1 hour to about 2 hours, e.g., about 92 minutes.

FIG.3is a schematic diagram of an exemplary second ED stage having a total of five cell groups between the anolyte and catholyte chambers. As shown inFIG.3, the flue gas chamber and the carbonate chamber can be separated by an anion exchange membrane. The carbonate chamber and the concentrated brine chamber can be separated by cation exchange membrane. The concentrated brine chamber and the acid chamber can be separated by an anion exchange membrane. The acid chamber can be separated from an adjacent flue gas chamber by a bipolar membrane. In the first cell group, the flue gas chamber can be separated from the catholyte chamber by a bipolar membrane. In the fifth cell group, the acid chamber can be separated from the anolyte chamber by an end cation exchange membrane. According to an embodiment, the second ED stage can include a total of 5 standard cation exchange membranes, 10 standard anion exchange membranes, 5 bipolar membranes, and 1 end exchange membrane.

In an embodiment, an electrolyte is separately circulated in the anolyte and catholyte chambers of the second ED stage. In an embodiment, the electrolyte in the anolyte chamber is sulphamic acid. In an embodiment, 0.5M of sulphamic acid is used as an electrolyte in the anolyte chamber. In an embodiment, the electrolyte in the catholyte chamber is sodium hydroxide. In an embodiment, 0.1 M of sodium hydroxide is circulated in the catholyte chamber.

In an embodiment, each of the first and second ED stages can be operated using about 0.5 A to about 0.9 A of current, about 5 to about 20 cells, about 5 L/hr to about 15 L/hr of diluate/concentrate flow, and about 25 L/hr to about 75 L/hr of electrolyte flow.

The average CO2removal efficiency in the second ED stage can range from about 50% to about 70% with an inlet gas flow rate ranging from about 0.3 l/min to about 0.1 l/min. Due to efficient mixing with the help of the bubble column contactor, the proposed process can capture CO2from a dilute gas mixture (less concentration of CO2in a gas mixture); therefore, the CO2removal efficiency can be further increased by recirculating the released gas from the second ED stage. In an embodiment, the concentration of CO3−2and HCO3−1ions in the liquid mixture from the carbonate chamber can be about 0.103 M to about 0.093 M, respectively, after about 420 minutes of operation at optimum conditions.

A schematic of the bubble column contactor of the second ED stage is shown inFIG.4. The flue gas mixture, which can include 10% CO2and 90% N2, for example, can be transferred into the contactor containing a Na2CO3solution with, e.g., an initial conductivity of about 10 mS/cm, to overcome the initial resistance. Bubbles of gas can be introduced through a diffuser into the contactor, containing inert mixing particles. In an embodiment, the inert mixing particles can include polymethylmethacrylate (PMMA). The mixing particles break can down larger gas molecules into smaller molecules, which increases mass transfer between phases. The mixing particles can also increase the gas holdup, resulting in more CO2dissolution into the solution. Upon dissolving CO2into the solution, CO3−2and HCO3−1ions can pass through the anion exchange membrane into the carbonate chamber to form a mixture of NaHCO3and Na2CO3with small amounts of potassium and chloride. Chloride and sulfate ions can be transferred from the NaCl chamber into the acid chamber through the anion exchange membrane, forming an acid mixture including HCl and H2SO4. The acid mixture can include more than about 90% HCl.

According to an embodiment, a method of desalinating reject brine and flue gas emitted from an industrial plant can include providing a first electrodialysis (ED) stage including an anolyte chamber, a catholyte chamber, and a plurality of cell pairs therebetween, each cell pair including a multivalent ion chamber and a monovalent ion chamber separated by a monovalent anion exchange membrane; providing reject brine to a multivalent ion chamber and water to the monovalent ion chamber of each cell pair in the first ED stage; transporting ions from the reject brine in the multivalent ion chamber through the anion exchange membrane to the monovalent ion chamber; collecting a stream of irrigation quality water in a first output stream from the multivalent ion chamber and a concentrated NaCl rejected brine in a second output stream from the monovalent ion chamber; providing a second ED stage including a plurality of cell groups between anolyte and catholyte chambers, each of the cell groups including a flue gas chamber, a carbonate chamber, an anion exchange membrane separating the flue gas chamber and the carbonate chamber, a concentrated brine chamber, a cation exchange membrane separating the carbonate chamber and the concentrated brine chamber, an acid chamber, and an anion exchange membrane separating the concentrated brine chamber and the acid chamber; providing concentrated NaCl reject brine from the first ED stage to the concentrated brine chamber; providing water to the acid chamber, dissolving CO2from flue gas from an industrial plant to provide CO3−2and HCO3−1ions using a bubble column contactor; transporting the CO3−2and HCO3−1ions to the carbonate chamber, transporting sodium ions from the concentrated brine chamber to the carbonate chamber through the cation exchange membrane to produce a sodium carbonate mixture; transporting Cl ions from the concentrated brine chamber to the acid chamber through the anion exchange membrane to produce an acid mixture. In an embodiment the carbonate mixture includes a mixture of Na2CO3and NaHCO3. In an embodiment, the acid mixture can include HCl or HCl and H2SO4. In an embodiment, the Na2CO3and NaHCO3mixture is transferred to a freeze drier to produce a solid powder mixture of Na2CO3and NaHCO3.

In an embodiment, the flue gas includes about 10% CO2and about 90% N2. In an embodiment, the industrial plant is a desalination plant and the present method is used onsite for desalination of rejected brine from desalination emissions and for CO2recapture. As is conventionally known, a recirculating electrolyte stream may flow through the anode and cathode chambers formed respectively between the anode and its adjacent membrane and the cathode and its adjacent membrane.

The present method can eliminate pollutants with no environmental impact. In an embodiment, water used in the first ED stage and the second ED stage is selected from brackish water, seawater, and distilled water. In an embodiment, an inlet of the second ED stage includes two streams of water and one stream of concentrated NaCl brine transferred from the first ED stage. In an embodiment, producing an acid mixture and a liquid mixture including Na2CO3and NaHCO3in the second ED stage includes dissolving CO2into a bubble column reactor to form CO3−2and HCO3−1ions, with the dissolved CO2being circulated continuously in a separate chamber while the other stream of distilled water is used for acid collection in the acid chamber.

According to an embodiment, output from the second ED stage includes high concentrations of acid (over 90% concentration of HCl, the rest being sulphuric acid (H2SO4)), clean gas, a brine stream that is suitable for enhanced oil recovery, and a liquid mixture containing Na2CO3and NaHCO3with small impurities.

According to an embodiment, a solid powder mixture of Na2CO3and NaHCO3is formed by freeze-drying the liquid carbonate mixture. The water removed from the freeze-drying operation can be pure water without any ions and can be reused in the second ED stage in the carbonate chamber.

An exemplary embodiment of the first ED stage can include a total of 20 monovalent anion selective membranes, 19 monovalent cation selective membranes, and 2 end cation exchange membranes. The membranes can be acquired from PCCELL GMBH. The end membranes in the first and second ED stages can be selected based on two properties: their resistance to oxidation media produced at the anode (traces of Cl2, H2O2, oxidized sulfates, etc.) and their ability to withstand high-pressure differences. The end membranes in the first and second ED stages can be made from sulphonic acid reinforced with polyethylene. The monovalent anion selective membranes can include ammonium with polyester reinforcement. The monovalent cation selective membranes can include sulfonic acid with polyester reinforcement. Polyester spacers can be used between the membranes in the first and second ED stages. Each of the chambers between the anolyte and catholyte chambers can have a circulation cylinder or pump. A separate cylinder or pump can be provided for continuous electrolyte in the anolyte and catholyte chambers. Water can be formed from the combination of hydrogen ions (H+) generated at the anode and hydroxide ions (OH−) generated at the cathode in the first ED stage.

An exemplary embodiment of the second ED stage can include a total of 5 standard cation exchange membranes, 10 standard anion exchange membranes, 5 bipolar membranes, and 1 end exchange membrane. The membranes can be acquired from PCCell GMBH. The anion exchange membranes can include ammonium with polyester reinforcement. The cation exchange membranes can include sulfonic acid with polyester reinforcement.

The system for treating reject brine and capturing carbon dioxide (CO2) can operate at room temperature and standard pressure to simultaneously capture CO2from the flue gas mixture and treat real rejected brine. An efficiency of the system can be enhanced by increasing the number of cell pairs or cell groups between the catholyte and anolyte chambers. As described herein, the system can produce multiple by-products with relatively high purity and zero environmental discharge.

Stage 1 and 2 processes can be carried out in a batch or continuous mode (for liquids and dissolved gas streams). Both of the ED stages can use titanium electrodes. In an embodiment, the anode can be coated with platinum and iridium oxide.

According to various embodiments, the rejected brine from the desalination plant can include 17000 ppm sodium, 31000 ppm chloride, 5352 ppm sulfate, 2460 ppm magnesium, 810 ppm potassium, and 586 ppm calcium. After the first ED stage, the rejected brine can include 4680 ppm sodium, 10400 ppm chloride, 3784 ppm sulfate, 2305 ppm magnesium, 184 ppm potassium, and 500 ppm calcium. Maximum removal of the fouling-prone species, such as calcium and magnesium can be obtained in the first ED stage before shifting the NaCl dominant stream to the second ED stage. The conductivity of rejected brine in the first ED stage can be reduced from 80 mS/cm to 30 mS/cm. Overall, 94%, 85%, and 71% rejection of magnesium, calcium, and sulfate ions can be obtained in the first ED stage at the end of 92 minutes.

According to an embodiment, the liquid carbonate mixture from the carbonate chamber can be freeze-dried at −70° C. and ˜1 Pa vacuum pressure to form a solid carbonate mixture.

In experiment, when the conductivity of the NaCl chamber in the second ED reached 20 mS/cm, the fraction of CO3−2and HCO3−1ions in the carbonate chamber was determined using a 2 step titration method and found to be 0.103 M CO3−2 and 0.093 M HCO3−1.

In the second ED stage, when conductivity of the NaCl chamber reached 20 mS/cm, calcium, magnesium, and sulfate, which are leaked from the brine chamber to the monovalent ion chamber in the first ED stage, were further reduced by 31%, 76%, and 50%, respectively.

In the second ED stage, the average CO2removal efficiency was 50%, and the pH decreased from 11.1 to 9.64 when the NaCl chamber conductivity reached 20 mS/cm. It took 414 minutes for the NaCl chamber conductivity to reach 20 mS/cm. A total of 9243 ppm of HCl was produced when the conductivity reached 20 mS/cm in the NaCl chamber.

Many conventional treatment systems for industrial waste and emissions are associated with significant precipitation of multivalent ions which lower the purity and quantity of products. The present system, however, removes multivalent ions in the first ED stage as a liquid by-product, thereby preventing precipitation in the second ED stage.

Due to the low generation of fouling-prone species, such as calcium and magnesium, seawater can be used instead of distilled water in the first and second ED stages. The irrigation water collected from the first ED stage can be an ideal fertilizer liquid after the reduction of NaCl concentration (and accumulation of calcium and magnesium ions). In the second ED stage, the NaCl concentration from the brine collected from the first ED stage can be reduced, and the processed seawater stream can be ideally used for enhanced oil recovery since a higher concentration of NaCl reduces oil recovery.

FIGS.5A-5Cillustrate the conductivity and CO2removal efficiency of different chambers over time. In the first ED stage, after 92 minutes of maintaining the flow rates of both chambers at 15 l/hr, the electrolyte flow rate at 72.91 l/hr, and the number of cell pairs at 20, the conductivity of rejected brine drops to 30 mS/cm, whereas the conductivity of NaCl chambers increases to 55 mS/cm, as shown inFIG.5A. In the second ED stage, the acid (HCl) chamber's conductivity increased to 413 mS/cm, while the NaCl (concentrated brine) chamber's conductivity decreased to 20 mS/cm after 420 minutes. As shown inFIG.5B, the conductivity of the carbonate chamber increased to 24 mS/cm while the conductivity of the flue gas chamber remained constant, indicating that absorption is constant.FIG.5(C)illustrates that CO2absorption becomes constant after an initial fluctuation.

FIG.6shows the rejection rate of multivalent ions in the first ED stage over time by keeping the current at 0.7 A, cell pairs at 20, dilute/concentrate flow rate at 15 l/hr, and electrolyte flow rate at 72.91 l/hr. The rejection of all multivalent ions present in the rejected brine declines with time as the concentration of NaCl (major ions in rejected brine) decreases sharply. When NaCl concentrations decrease, multivalent ions tend to make contact with membrane surfaces more frequently, which causes leakage of ions. The rejection rate for magnesium, calcium, and sulfate ions is 94%, 85%, and 71%, respectively, after 92 minutes in stage 1. Magnesium and calcium have a higher hydrated radius than sulfate, which accounts for their higher rejection rates.

FIGS.7A-7Dshow SEM images of a freeze-dried solid carbonates mixture at different resolutions. SEM images are taken at 20 kV and 10 kV acceleration potentials, which according to the instrument's specifications, provide a resolution of 100 μm, 50 μm, and 40 μm. Agglomerates of particles can be seen in the images. Absorption of water into soluble compounds can increase molecular mobility, resulting in liquid bridges between neighboring particles, causing caking and agglomeration. Particle agglomeration can be prevented by applying high freezing rates before freeze-drying.

Table 1 andFIG.7(e)show the results of the EDX analysis. EDX is coupled with SEM using mixed BSE (back scatter electron) and LSE (lateral secondary electron) detectors. EDX analysis shows the atomic weight % of various elements in the freeze-dried carbonate mixture. Sodium, oxygen, carbon, potassium, chlorine, and gold are detected in the EDX analysis. Due to the gold coating deposited on the samples before SEM-EDX analysis, gold peaks have been observed in EDX analysis. In the carbonate chamber, chlorine diffusion is about 2-4%, while potassium leakage is less than 2%. In the first ED stage, potassium can pass through a monovalent selective membrane due to its monovalency. Due to the lower potassium concentration in the brine sample, however, potassium interacts less with the membrane surface, resulting in lower potassium passage. As a result, only 2% of potassium is detected in the final carbonate sample. EDX analysis in Table 1 indicates that sodium-based carbonate mixtures can be produced with high purity due to carbon, sodium, and oxygen atomic weight percentages exceeding 94%.

TABLE 1The atomic weight percentage of elementsPointsCONaClKAu113.0658.0823.393.781.690.00211.5761.7426.410.090.19311.3460.7924.402.241.21

It is to be understood that the system for treating reject brine and capturing carbon dioxide (CO2) is not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.