The present disclosure relates to capacitive desalination systems and methods, and more particularly to systems and methods for flow through electrode, capacitive deionization (FTE-CDI) which incorporate a new electrode construction for effectively removing nitrate from a mixture of ions in fluid (water) flowing through the system.
The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
The current state-of-the-art for water desalination is reverse osmosis (RO). Reverse osmosis uses membranes that allow water, but not salt, to pass through the membranes. Pressure is applied to the feed side, pushing water across the membrane to overcome membrane resistance, as well as the osmotic pressure. Energy use in RO scales with the amount of water produced. For seawater, the energy efficiency of RO is unsurpassed, however at low salt concentration the energy efficiency of RO is significantly reduced. Furthermore, RO membranes are non-selective, which means that one must remove all ions to remove a particular contaminant. This further reduces the possible efficiency of using RO to treat water for specific trace contaminants.
Capacitive deionization (GDI) is a more recently developed technology. Unlike membrane-based methods, GDI removes salt with electric fields. The charged salt ions are attracted to the charged porous electrodes and thus removed from the water. The device is operated by applying a voltage to the two spaced apart electrodes, which act like plates of a supercapacitor. While water passes through the device, salt ions are attracted to the charged surface and thus removed from the feed water. The energy cost of GDI is proportional to the amount of salt removed, thus giving it the potential to be more energy efficient than RO in low salinity regimes. Because GDI is an inherently low-pressure operation and cell and electrode components are made from low-cost materials, the capital costs are also expected to be significantly less than RO.
Flow-through electrode capacitive deionization (FTE-CDI) is a technology that involves flowing feed water to be desalinated through the porous electrodes of a capacitive deionization system, rather than between the electrodes as in a conventional GDI device. The assignee of the present application is a leader in the development of this technology, as will be appreciated from the disclosure of U.S. Patent Publication No. 2012/0273359 A1, published Nov. 1, 2012, the disclosure of which is hereby incorporated by reference into the present disclosure. In view of the known advantages of an FTE-CDI system, significant interest exists in even further enhancing and improving the capabilities of such a system to even more effectively and efficiently perform desalination on salt water and/or to remove other types of ions from water.
In addition to general salinity reduction, a particular area of interest in GDI research is the selective removal of specific ionic contaminants for increased energy efficiency and to more effectively utilize removal capacity. One of the major contaminants of interest in present day GDI research is nitrate, which is regulated by the US Environmental Protection Agency to a maximum contaminant level in drinking water of 10 mg/L (as N) or 0.7 mM as NO3. The concentration of nitrate in groundwater is increasing by a reported 1-3 mg/L/yr due to a number of factors including human activities involving agriculture, for example from fertilizer runoff and disposal of municipal effluents by sludge spreading on fields. Other factors contributing to the increased concentration of nitrate found in groundwater include atmospheric emissions from energy production sources, as well as combustion engines of present day motor vehicles. Accordingly, there is a growing interest in developing systems for more effectively removing nitrates, in particular, from groundwater, making the development of effective treatment methods increasingly important.
In one aspect the present disclosure relates to a flow through electrode, capacitive deionization (FTE-CDI) system. The system may comprise a pair of electrodes arranged generally parallel to one another; a water permeable dielectric arranged between the electrodes so as to be sandwiched between the electrodes; and an electronic circuit for applying a direct current voltage across the electrodes. At least one of the electrodes may be formed from a carbon material having a hierarchical pore size distribution, the hierarchical pore size distribution including a first plurality of nano-sized pores having a width of no more than about 1 nm, and a second plurality of pores having micron-sized pores that enable a flow of water to be pushed through the electrode. The first plurality of pores form adsorption sites for nitrate molecules carried in the water flowing through the at least one electrode.
In another aspect the present disclosure relates to an ultramicroporous electrode for use in a flow through, capacitive deionization (FTE-CDI) system for adsorbing nitrate molecules contained in water being fed into the electrode for treatment. The electrode may comprise a carbon aerogel member having a hierarchical pore size distribution. The hierarchical pore size distribution may include a first plurality of ultramicropores randomly distributed throughout a thickness of the carbon aerogel member, and each forming a slit having a width of no more than about 1 nm; and a second plurality of micron-sized pores randomly distributed throughout the thickness of the carbon aerogel member. The micron-sized pores are sufficiently large to enable liquid flow paths to be formed through the entire thickness of the carbon aerogel member, which enable a flow of water to be pushed through the thickness of the carbon aerogel member. The first plurality of pores form adsorption sites for capturing nitrate molecules carried in the water flowing through the carbon aerogel member.
In still another aspect the present disclosure relates to a method for making a carbon aerogel electrode material. The method may comprise making a wet organic sol-gel form; carbonizing the sol-gel form at a temperature of from about 900° C. to about 1000° C., for from about 2 to about 4 hours; and activating the carbonized sol-gel under carbon dioxide flow, for from about 0.5 hours to about 1.5 hours, at from about 900° C. to about 1000° C.
Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.
1 and 3b1 are illustrations showing the distribution of solvating water molecules around the disc-like nitrate molecule, and wherein
The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. It should be understood that throughout the drawings, corresponding reference numerals indicate like or corresponding parts and features.
The present disclosure relates to FTE-CDI systems and methods which employ a new material in a new geometry to further increase the process rate compared to the typical flow between the electrodes of a GDI system. The present system and method introduces a FTE-CDI system which uses a new carbon material (CO2 activated AARF) for the electrodes of the system, described more fully in the following paragraphs, which has a hierarchical pore size distribution. The hierarchical pore size distribution includes a first plurality of sub-nanometer scale pores (“ultramicropores”) to provide adsorption sites, while a second plurality of pores are included which form micron-sized pores through which water can be pushed at relevant flow rates without requiring a substantial amount of energy. This material can now be used in a different geometry: rather than passing water between the electrodes, the water is pushed through the electrodes. Instead of relying on diffusion, the salt is actively pushed into and out of the capacitor, which reduces desalination time substantially.
The electrodes 102 and 104 are arranged such that a flow of the feed water flows through the electrodes 102 and 104 and in a direction parallel to an electric field applied across the electrodes 102 and 104. While only a single pair of electrodes 102/104 is shown in
With further reference to
Header plates 150 and 152 are disposed to sandwich the electrodes 102 and 104 and the separator 114. The header plates 150 and 152 are made of, e.g., ultraviolet (UV) transparent acrylic material.
Alternative to acrylic, other transparent plastic materials may also be used (e.g., polycarbonate). The header plates 150 provides structural support to the electrodes 102 and 104 and the separator 114.
An epoxy 154 may be disposed between the header plates 150 and 152 and surrounding the electrodes 102 and 104 and the separator 114. The epoxy 154 may be, e.g., UV-curable epoxy. The header plates 150 and 152 and the epoxy 154 define a space that accommodates the electrodes 102 and 104 and the separator 114. In some embodiments, a combination of the header plates 150 and 152, the electrodes 102 and 104, the separator 114, the current collectors 138 and 140, and the epoxy 154 is referred to as a cell (e.g., an FTE-CDI cell, or a flow through cell). Again, it will be understood that in a commercial application, a large plurality of instances of the system 100 (with the system representing one “cell”) is likely to be used.
The FTE-CDI system 100 includes an input flow line 122 and an output flow line 124. In some embodiments, the input flow line 122 and the output flow line 124 are part of the system 100. In some embodiments, the system 100 may include multiple input flow lines and/or multiple output flow lines.
The header plate 150 includes one or more flow channels formed therein. For example, as shown in
Because the space accommodating the electrodes 102 and 104 and the separator 104 is sealed by the epoxy 154, water can only flow into and out of the cell through the flow lines 122 and 124. Thus, during operation, water flow into the FTE-CDI system 100 through the input flow line 122, the channel 151 of the header plate 150 (or multiple channels), the electrode 102, the separator 114, the electrode 104, the channel 153 of the header plate 152 (or multiple channels), and the output flow line 124.
In operation during a charging stage, as the water flows through the electrodes 102 and 104, ions from the water are attracted to the electrodes 102 and 104 and adsorb to the surfaces of the porous electrodes 102 and 104. During a discharging stage, to avoid ion saturation on the electrodes 102 and 104, the electrodes 102 and 104 are short-circuited or applied with a reverse electrical potential difference (e.g., by the electric circuit 110). As a result, ions previously adsorbed on the electrode surfaces are flushed into waste water flowing through the electrodes 102 and 104.
Electrode Construction
The electrodes 102 and 104 of the system 100 are new and effectively work to capture nitrate molecules from fluids (e.g., water) flowing through the electrodes. As shown in highly simplified representative form in FIG. 1a, each electrode 102 and 104 forms an ultramicroporous electrode (e.g., carbon aerogel). The terms “ultramicroporous” and “ultramicropores”, as used herein, mean a quantity of pores which are all below, or substantially all below, about 1 nm in width. These ultramicropores are designated by reference number 102a in
The ultramicropores 102a of the electrodes 102 and 104 are a highly important feature which enables the system 100 to selectively remove nitrate over other ions, especially common divalent species. The reason for this is that the ultramicropores 102a formed in the electrodes 102/104 (e.g., carbon aerogel) tend to have slit-shaped pores, as shown in highly simplified form in
The electrodes 102 and 104 were formed in the same manner, and therefore the following discussion will reference only the forming of the electrode 102. The flowchart 200 of
It is important to note that the resulting aerogel is activated to have the —0.3 cm3/g microporosity with pore sizes almost all being below 1 nm in width.
The electrosorption selectivity of the activated aerogel electrode 102 described above was measured in a flow-through electrode GDI cell, the results of which are shown in
While various embodiments have been described, those skilled in the art will recognize modifications or variations which might be made without departing from the present disclosure. The examples illustrate the various embodiments and are not intended to limit the present disclosure. Therefore, the description and claims should be interpreted liberally with only such limitation as is necessary in view of the pertinent prior art.
Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises,” “comprising,” “including,” and “having,” are inclusive and therefore specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed.
When an element or layer is referred to as being “on,” “engaged to,” “connected to,” or “coupled to” another element or layer, it may be directly on, engaged, connected or coupled to the other element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly engaged to,” “directly connected to,” or “directly coupled to” another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” versus “directly between,” “adjacent” versus “directly adjacent,” etc.). As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
Although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.
Spatially relative terms, such as “inner,” “outer,” “beneath,” “below,” “lower,” “above,” “upper,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Spatially relative terms may be intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the example term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
As used herein, the term “about,” when applied to the value for a parameter of a composition or method of this technology, indicates that the calculation or the measurement of the value allows some slight imprecision, resulting (for example) from manufacturing variability, without having a substantial effect on the chemical or physical attributes of the composition or method. If, for some reason, the imprecision provided by “about” is not otherwise understood in the art with this ordinary meaning, then “about” as used herein indicates a possible variation of up to 5% in the value.
This application is a divisional of and claims priority to U.S. patent application Ser. No. 16/268,154 filed on Feb. 5, 2019 (now allowed). The disclosure of the above application is incorporated herein by reference.
This invention was made with Government support under Contract No. DE-AC52-07NA27344 awarded by the United States Department of Energy. The Government has certain rights in the invention.
Number | Date | Country | |
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Parent | 16268154 | Feb 2019 | US |
Child | 17733860 | US |