HIGH EFFICIENCY ELECTRODIALYSIS FLUID PURIFICATION DEVICE AND METHOD
20220380236 · 2022-12-01
Inventors
- Aaron T. Timperman (Urbana, IL, US)
- Dayi Chen (Urbana, IL, US)
- Jin-Tae Kim (Savoy, IL, US)
- Leonardo P. Chamorro (Mahomet, IL, US)
Cpc classification
C02F2103/16
CHEMISTRY; METALLURGY
C02F2103/365
CHEMISTRY; METALLURGY
Y02A20/124
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
An electrodialysis fluid purification device includes a fluid output from an upper part of a first fluid reservoir. One or more ion permselective elements at a surface on or near the bottom of the first reservoir are arranged to provide one or more small area points or lines. A fluid connection to a second fluid reservoir is on an opposite side of the one or more ion permselective elements. Electrodes and a power supply create a voltage differential across the one or more ion permselective elements. Another fluid purification device includes a first reservoir with which an ion permselective element interfaces directly in a 2D to 3D relationship. A method employs small area ion permselective element interfaces at a surface on or near the bottom of the first reservoir such that ion transport creates a depleted zone that extends into the first fluid reservoir.
Claims
1. An electrodialysis fluid purification device, comprising a fluid output from an upper part of a first fluid reservoir; one or more ion permselective elements at a surface on or near the bottom of the first reservoir, the one or more ion permselective elements being arranged to provide one or more small area points or lines; a fluid connection to a second fluid reservoir on an opposite side of the one or more ion permselective elements; and electrodes and a power supply to create a voltage differential across the one or more ion permselective elements.
2. The device of claim 1, wherein the one or more ion permselective elements comprise a plurality of elements at each of a plurality of small area interfaces.
3. The device of claim 2, wherein the plurality of elements is arranged with edges of the elements facing a volume of the first reservoir.
4. The device of claim 1, wherein the one or more ion permselective elements are arranged in one or more microchannels between the first fluid reservoir and the fluid connection to the second fluid reservoir.
5. The device of claim 1, wherein the one or more ion permselective elements comprise an ion-permselective nanoporous gel.
6. The device of claim 1, wherein the wherein the one or more ion permselective elements is interfaced into a side surface of the first reservoir.
7. The device of claim 1, wherein the wherein the one or more ion permselective elements is arranged to create a depleted zone that extends into the first reservoir.
8. The device of claim 7, wherein the depleted zone extends up, away and around edges of the one or more ion permselective elements.
9. The device of claim 1, wherein the wherein the one or more ion permselective elements is configured to create a micro scale interface to a macroscale volume in the first reservoir.
10. The device of claim 1, wherein the one or more ion permselective elements comprises a discontinuous ion permselective element.
11. The device of claim 1, wherein the one or more ion permselective elements presents a small surface area compared to surface portions of a volume of the first reservoir to which it is exposed.
12. The device of claim 11, wherein the small surface area of the one or more ion permselective elements is 50% or less than the surface portions of the volume.
13. The device of claim 12, wherein the small surface area of the one or more ion permselective elements is 20% or less than the surface portions of the volume.
14. The device of claim 11, wherein the one or more ion permselective elements are arranged to present a microscale interface to a macroscale volume of the first fluid reservoir.
15. The device of claim 14, wherein the one or more ion permselective elements are arranged to present edges of the elements to a volume of the first reservoir.
16. The device of claim 15, wherein the microscale interface is a 1D interface and the macroscale volume is a 3D volume.
17. A fluid purification device, comprising a first reservoir with which an ion permselective element interfaces directly in a 2D to 3D relationship, an outlet channel for the clean water in an upper part of the first reservoir, a input channel into the first reservoir for raw water, an outlet channel at or near the bottom of the first reservoir to remove water that is enriched in contaminants, a second reservoir that is in fluid communication with the first reservoir through the ion permselective element, and electrodes to provide an applied electric field between the first and second reservoirs.
18. A method for fluid purification through electrodialysis, comprising: providing a first reservoir for clean fluid collection and introduction of raw fluid; arranging small area ion permselective element interfaces at a surface on or near the bottom of the first reservoir such that ion transport creates a depleted zone that extends into the first fluid reservoir; introducing feed fluid to the interfaces in the first reservoir; creating ionic fluid transport across the interfaces into the second reservoir; and collecting clean fluid from an upper part of the first reservoir.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] FIGS. 1A-1B (Prior Art) are schematic diagrams of conventional electrodialysis systems;
[0032]
[0033] FIG. 1D (Prior Art) is the I-V curve of the FIGS. 1A-1B devices that has three distinct regions: i) Ohmic, ii) limiting, iii) and overlimiting;
[0034]
[0035]
[0036]
[0037]
[0038]
[0039]
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0040] A preferred embodiment is an electrodialysis fluid purification device. The device includes a feed fluid supply into a first fluid reservoir. A fluid output is taken from an upper part of the first fluid reservoir. One or more ion permselective elements are at a surface on or near the bottom of the first reservoir, the one or more ion permselective elements being arranged to provide one or more small area points or lines. A fluid connection to a second fluid reservoir is on an opposite side of the one or more ion permselective elements. Electrodes and a power supply create a voltage differential across the one or more ion permselective elements.
[0041] An electrodialysis fluid purification device of the invention includes a feed fluid supply into a first fluid reservoir. A fluid output is from an upper part of the first fluid reservoir. One or more ion permselective elements are at a surface on or near the bottom of the first reservoir. A fluid connection is to a second fluid reservoir on an opposite side of the one or more ion permselective elements. Electrodes and a power supply create a voltage differential across the one or more ion permselective elements. The one or more ion permselective elements are arranged to present a microscale interface to a macroscale volume of the first fluid reservoir.
[0042] A method for fluid purification through electrodialysis includes providing a first reservoir for clean fluid collection and introduction of raw fluid. The method also includes arranging small area ion permselective element interfaces at a surface on or near the bottom of the first reservoir such that ion transport creates a depleted zone that extends into the first fluid reservoir. Feed fluid is introduced to the interfaces in the first reservoir. Ionic fluid transport is created across the interfaces into the second reservoir. Clean fluid is collected from an upper part of the first reservoir.
[0043] An electrodialysis fluid purification device includes a channel/tube for removal of water that is enriched in the contaminants (referred to as the brine in desalination) in the first reservoir. A preferred device includes a first reservoir with which the ion permselective element interfaces directly in a 2D to 3D relationship, an outlet channel for the clean water near the top, a input channel for raw water, an outlet channel at or near the bottom to remove water that is enriched in contaminants, a second reservoir that is in fluid communication with the first reservoir through the ion permselective element, and electrodes to provide an applied electric field between the first and second reservoirs.
[0044] An ion permselective element, as used herein, can be a charged gel, charged membrane, or nanochannel etc. The ion permselective element must induce concentration polarization.
[0045] Preferred embodiments of the invention will now be discussed with respect to experiments and drawings. Broader aspects of the invention will be understood by artisans in view of the general knowledge in the art and the description of the experiments that follows.
[0046]
[0047] Preferred embodiments include a depleted zone emanating from microscale permselective element into a 3D macro reservoir as shown in
[0048] In preferred devices, the high resistance of the depleted zone is avoided by releasing the depleted zone from a small cross-sectional area into a larger reservoir (
[0049]
[0050] In preferred devices consistent with
[0051]
[0052] Preferred devices are formed as microfluidic devices in accordance with
[0053] Experimental water purification devices had two PDMS layers and a PET membrane as the ion-permselective element. The top layer has reservoirs and a 360 μm ID tubular channel, moulded with a 360 μm OD capillary, connecting the depleted zone reservoir and the purified water reservoir. a ˜300 μm thick PDMS layer was attached to the top layer via plasma before punching the reservoir, so that the center of the tubular channel is about 500 μm above the bottom of the reservoir. The bottom layer has microchannel (40 μm W×36 μm H) facing up. The smooth PET membrane covers the microchannel, and the top layer is positioned to have a 400 μm long microchannel section fluidically connected to the above reservoir. The microchannel length between the inlet reservoir and depleted zone reservoirs is 2.8 mm.
[0054] The
[0055] As controls, devices with no-membrane and 400 nm pore membrane that does not induce CP are used. The no-membrane and 400 nm pore membrane devices produce currents of (4.2±0.3) μA and (3.3±0.2) μA, while the CP inducing water purification device produces a current of (474±31) μA, which is more than 100-fold greater than both controls.
[0056] The purity of the clean water is proportional to the flowrate. As shown in
[0057] The ion permselective elements used in preferred embodiments can be commercial membranes, such as membranes from 10 nm pore size polyester (PET) membrane (23 μm thick with pore density of 4E09.Math.cm.sup.−2) was from it4ip S.A. (Belgium). Generally, the ion-permselective element can be any charged nanoporous material. Nanoporous gels can also be used as ion permselective elements, as in
[0058] Experiments Regarding Depleted Zone
[0059] The following experiments and discussion of the same demonstrate the creation of depleted zones in preferred devices and methods of the invention.
[0060] In preferred embodiments, to obtain high currents, an ion permselective element with a microscale cross-section is interfaced with a macroscale reservoir. Confocal fluorescence microscopy and microparticle tracking velocimetry (μ-PTV) were used to characterize the depleted zone that emanates vertically from the CP inducing nanoporous gel into the macroscale reservoir. The shape and growth of depleted zone and velocity in the surrounding bulk solution are consistent with natural convection being the driver of the depleted zone morphology and eliminates the high resistance created by the depleted zone in 1D and 2D systems. Once the resistance of the depleted zone is negated, the high currents are believed to result from enhancement of counter-ion concentration in the nanoporous gel-filled microchannel. In contrast with conventional systems, the current increases monotonically and remains stable at a high quasi-steady level in the reported systems. These results may be used to increase the efficiency and performance of future devices that utilize CP, while the ability to collect purified water with this geometry is demonstrated.
[0061] Experiments were conducted regarding the CP and depleted zone with the micro to macroscale interface used in example water purification devices. We used nanoporous gel as the ion-permselective element to fill the microchannel that connects to the 3D reservoir with different lengths to elucidate the mechanism. The planar design of the system allowed for imaging of the depleted zone and characterization of advection using micro-particle tracking velocimetry (μ-PTV). The depleted zone shape and currents were measured with the device in upright and upside-down orientations to probe the effects of buoyancy-driven flow on the shape of the depleted zone. We demonstrated a greater than one order of magnitude increase in current, and also through confocal imaging and μ-PTV, provided substantial insight into the mechanisms that provide improved current and mass transport. Based on this mechanism, we fabricated the micro water purification system with a 10 nm pore polyester (PET) membrane as the ion-permselective element shown in
[0062] Microfluidic devices were fabricated using PDMS as previously with a curing time of a least 3 days according to known techniques. Schematics of the devices are shown in
[0063] The negatively charged nanoporous gel was formed via in-situ photopolymerization.
[0064] Current Measurement
[0065] The microfluidic devices were filled with buffer containing 3 mM Na.sub.2HPO.sub.4, 2 mM NaH.sub.2PO.sub.4, and 5 mM NaHCO.sub.3 with a pH of 7.5. The NaHCO.sub.3 inhibits water hydrolysis and reduces bubble formation at the electrodes. Large plastic reservoirs that hold 1 mL buffer were added to the top of each device operated in the normal (upright) orientation (
[0066] Imaging
[0067] A confocal microscope system (Leica SP8) was used to image the ion depleted zone in the reservoir. Both XYZT and YZT scan modes were used (
TABLE-US-00001 TABLE 1 Experimental details of confocal fluorescent imaging. Experiment #1 #2 #3 #4 y-z μ-PTV Fluorescent 8 μM 100 nM 100 nM 500 nM Carboxylate- tracer Rhodamine Alexa Fluor Alexa Fluor Alexa Fluor modified 6G 594 594 594 1.0 μm 5 μM fluorescent Alexa Fluor microspheres 594 (7.2 × 10.sup.7/mL) and 100 nM Alexa Fluor 594 Scan type XYZT XYZT YZT XYZT YZT YZT Scan size.sup.1 600 × 600 1550 × 1550 400 × 400 1550 × 1550 400 × 400 (μm × μm) (XYZT) 400 × 400 (YZT) Spatial 1.17 × 1.17 3.03 × 3.03 0.783 × 0.783 3.03 × 3.03 0.783 × 0.783 resolution 1.52 × 1.52 (XYZT) (μm × μm) 0.783 × 0.783 (YZT) Scan range at 50 1800 1332 z-axis in XYZT.sup.2 (μm) Scan time 39 s/stack 53 s/stack 1.49 s/frame 39 s/stack 0.72 s/frame (XYZT) 1.49 s/frame (YZT) .sup.1It's x-y plane for XYZT scan and y-z plane for YZT scan. .sup.2All of the XYZT scans have z-axis step size of 36 μm except experiment#1, which is 5 μm.
[0068] First, 8 μM Rhodamine 6G (R6G) and 5 μM Alexa Fluor 594, as cation and anion tracers, respectively, were imaged simultaneously. A series voltage (0 V, 5 V, 15 V, 30 V, 50 V, 75 V, and 100 V) was applied with long microchannel devices, and each lasted for 5 min. The dyes were excited with 488 nm, 514 nm, and 561 nm laser lines. Three photomultipliers (PMT) were used to simultaneously collect light from R6G (571-595 nm), Alexa Fluor 594 (620-751 nm), and bright-field channels. Second, the time-dependent size and shape of the depleted zone were acquired with XYZT scans with 100 nM Alexa Fluor 594. One stack with 0 V images was taken before the voltage was applied. A potential of 30 V was applied to short microchannel devices for 60 min, and 100 V was applied to long microchannel devices for 90 min followed by the application of 5 V for 15 min. Third, the depleted zone shape was imaged in the vertical plane through the center of the reservoir and microchannel using YZT scans with Alexa Fluor 594. A series of voltages (5 V, 15 V, and 30 V) were applied for at least 11 min respectively in short microchannel devices. Each voltage step was separated by steps of 0 V for at least 5 min to allow for re-equilibration. Fourth, the effects of flipping the vertical orientation of the device were investigated by imaging the distribution of Alexa Fluor 594 with the device in upright and upside-down orientations. The devices with long microchannel and 2 mm device thickness were examined at 100 V. With the smaller reservoirs (˜20 μL), the cohesive forces/surface tension holds the liquid in the PDMS reservoir in the upside-down orientation. A 100 μm thick PDMS membrane was used to cover the reservoirs to prevent solution evaporation. After each experiment, the devices were stored in water for 3 days to provide time for re-equilibration.
[0069] μ-PTV
[0070] The advection in the macroscale reservoir in horizontal planes was characterized using x-y plane μ-PTV at a potential of 100 V with 75 μL reservoirs. Carboxylate-modified 1.0 μm fluorescent microspheres with a density of 7.2×10.sup.7/mL were used as tracers. The μ-PTV setup included an inverted microscope, halogen lamp, a 10× magnification objective, a 4MP Miro 340 camera (Amtek), and an 80 W diode-pumped laser. Images were collected at 100 fps with a distance-to-pixel ratio of 0.5 μm/pixel. A stair-shaped target of layered PDMS was used to calibrate the z-axis height. The μ-PTV were collected at two z-axis heights (20 μm and 100 μm). The devices were re-equilibrated for 3 days between collecting data at a different height. At each height, the data series were 950 frames each, beginning at 13 min, 27 min, 36 min, and 42 min, corresponding to current about 8 μA, 13 μA, 24 μA, and 33 μA, respectively.
[0071] The Leica SP8 confocal system was used to acquire y-z plane μ-PTV data at 1.39 fps. Carboxylate-modified 1.0 μm fluorescent tracer beads with a density of 7.2×10.sup.7/mL and 100 nM Alexa Fluor 594 were added to the buffer. The microspheres and dye were excited by 514 nm and 561 nm laser lines, and emission collected from 520-750 nm.
[0072] Matlab was used to analyze the XYZT stacks from the confocal imaging by calculating the area, volume, and height of the depleted zone. All the images were compared to the 0 V images at the same z-height with 2×2 binning. To determine the depleted zone area, a pixel was considered part of the depleted zone when both: its intensity at high voltage is less than 50% of its intensity at 0 V, and at least four of the eight surrounding pixels that meet the intensity criterion. The depleted zone volume was integrated using the trapz function along the z-direction. The depleted zone height was defined as the height that 95% depleted zone volume lies below.
[0073] Image series that monitors the concentration change in the pipe in water purification systems were also analyzed with Matlab. Because the pipe has a cylinder shape, the solution thickness is increased from the two edges to the center, corresponding to the maximum fluorescent intensity in the center. After flat field correction, the initial intensity (raw water fluorescence) of each pixel in the pipe is used to calculate its solution thickness coefficient, which is used as the weight when adding up concentration change at each pixel to calculate the overall concentration change percentage. After the syringe pump started, output water passed through the pipe at set flow rates. Only the images taken at the last minute of a certain flow rate are counted. Output water purity (%)=((raw water fluorescence—output water fluorescence)/raw water fluorescence)×100.
[0074] For the x-y plane μ-PTV after preprocessing sequences to remove the background using ImageJ, the position of each tracer bead is determined at the sub-pixel resolution, tracked using the Hungarian algorithm, and linked with three-frame gap closing for longer trajectories in Matlab. The reconstructed trajectories were filtered using fourth-order B splines to minimize the noise in the position detection. The process allows obtaining individual trajectories with the information of Lagrangian velocity and acceleration.
[0075] Our experiments and modelling showed that present devices are able to approach the Ohmic scaling limit by negating the resistance of the depleted zone by having depleted zone side boundary of the microscale ion-permselective element interface with a macroscale fluid reservoir. The ion-permselective element is made by filling a microchannel with an ion-permselective nanoporous gel and thus has a microscale cross-section.
[0076] The experiments showed that location of the nanoporous gel within the microchannel plays an important role in the current response. We considered four general locations for the nanoporous gel in both long (25 mm) and short (5mm) microchannel devices, as represented in
[0077] The results indicate the conductivity of the ion permselective material increases with CP. The increased conductivity can contribute to the high currents observed. The nanoporous gel properties are important as the length and charge both affect the current, as discussed previously. In addition to the high measured currents, the concentration of a cationic dye R6G was observed to increase in the nanoporous gel as a function of time and the high cationic dye concentration was observed. Additionally, the anionic dye is depleted in the gel and both cationic and anionic dyes are excluded from the depleted zone as expected, indicating that nearly all of the current is carried by cations.
[0078] While specific embodiments of the present invention have been shown and described, it should be understood that other modifications, substitutions and alternatives are apparent to one of ordinary skill in the art. Such modifications, substitutions and alternatives can be made without departing from the spirit and scope of the invention, which should be determined from the appended claims.
[0079] Various features of the invention are set forth in the appended claims.