Intercalation-Based Materials and Processes for Softening Water
20200148560 ยท 2020-05-14
Inventors
- Sondra Hellstrom (Palo Alto, CA, US)
- Michael Metzger (Sunnyvale, CA, US)
- Saravanan Kuppan (Sunnyvale, CA, US)
- Jake CHRISTENSEN (Elk Grove, CA, US)
Cpc classification
C02F2201/46115
CHEMISTRY; METALLURGY
Y02A20/131
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
C02F1/46104
CHEMISTRY; METALLURGY
C02F2001/46138
CHEMISTRY; METALLURGY
International classification
Abstract
A device for removing ions from a flow of water includes a first electrode and a counter-electrode opposite the first electrode in the flow of water. The first electrode contains at least one material which is capable of intercalating one or both of Mg.sup.2+ and Ca.sup.2+ ions in the flow of water. The counter-electrode can include a material capable of binding to anions in the flow of water.
Claims
1. A device for removing ions from a flow of water comprising: a first electrode connectable to a current source and configured to be arranged in a flow of water; and a counter-electrode connectable to the current source and configured to be arranged in the flow of water opposite said first electrode, wherein said first electrode contains at least one material which is capable of intercalating one or both of Mg.sup.2+ and Ca.sup.2+ ions in the flow of water.
2. The device of claim 1, wherein the at least one material is selected from the group consisting of: A.sub.xCuFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xMnFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xMnMn(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xZnFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xBaFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xFeFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xNiFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; Ti.sub.xFe.sub.1-x[Fe(CN).sub.6].sub.0.96 0x1; polyimide; FePO.sub.4; NaMnFe.sub.2(PO.sub.4).sub.3; Na.sub.3Fe.sub.3(PO.sub.4).sub.4; Na(M)PO.sub.4, M=Fe, Mn, or Fe.sub.xMn.sub.1-x0x1; MnO.sub.2; Na.sub.xMnO.sub.2, 0x1; ZnMn.sub.2O.sub.4; MgFeSiO.sub.4/C; Mg.sub.xMn.sub.2-xSiO.sub.4, 0x2; Mg.sub.0.5Ti.sub.2(PO.sub.4).sub.3; LiTi.sub.2(PO.sub.4).sub.3; Ti.sub.xAl.sub.2-x(PO.sub.4).sub.3, 0x2; TiP.sub.2O.sub.7; Na.sub.3MnTi(PO.sub.4).sub.3; K.sub.2Ti.sub.4O.sub.9; TiS.sub.2; FeS.sub.2; CaMO.sub.3 (M=Mn and/or Fe); potassium terephthalate; 2,5-pyridinedicarboxylate (K.sub.2PC); KFeF.sub.3; K.sub.0.3MnO.sub.2; KMg.sub.xFe.sub.2-x(PO.sub.4).sub.2, 0x2; NaTi.sub.2(PO.sub.4).sub.3; Na.sub.2FeP.sub.2O.sub.7, TiO.sub.2, and Na.sub.2Ti.sub.3O.sub.7.
3. The device of claim 1, wherein the counter-electrode includes a material capable of binding anions in the flow of water to the counter-electrode.
4. The device of claim 3, wherein the counter-electrode material is capable of binding one or both of Cl.sup. and Co.sub.3.sup.2 anions in the flow of water to the counter-electrode.
5. The device of claim 4, wherein the counter-electrode material includes a porous carbon layer.
6. The device of claim 3, wherein the counter-electrode includes an ion-selective membrane arranged on said counter-electrode to be between the counter-electrode material and the flow of water.
7. The device of claim 1, further comprising a non-conductive water permeable separator arranged to be disposed in the flow of water between said first electrode and said counter-electrode.
8. The device of claim 1, wherein said counter-electrode contains at least one material which is capable of intercalating one or both of Mg.sup.2+ and Ca.sup.2+ ions in the flow of water.
9. The device of claim 8, wherein the at least one material of the counter-electrode is selected from the group consisting of: A.sub.xCuFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xMnFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xMnMn(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xZnFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xBaFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xFeFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xNiFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; Ti.sub.xFe.sub.1-x[Fe(CN).sub.6].sub.0.960x1; polyimide; FePO.sub.4; NaMnFe.sub.2(PO.sub.4).sub.3; Na.sub.3Fe.sub.3(PO.sub.4).sub.4; Na(M)PO.sub.4, M=Fe, Mn, or Fe.sub.xMn.sub.1-x0x1; MnO.sub.2; Na.sub.xMnO.sub.2, 0x1; ZnMn.sub.2O.sub.4; MgFeSiO.sub.4/C; Mg.sub.xMn.sub.2-xSiO.sub.4, 0x2; Mg.sub.0.5Ti.sub.2(PO.sub.4).sub.3; LiTi.sub.2(PO.sub.4).sub.3; Ti.sub.xAl.sub.2-x(PO.sub.4).sub.3, 0x2; TiP.sub.2O.sub.7; Na.sub.3MnTi(PO.sub.4).sub.3; K.sub.2Ti.sub.4O.sub.9; TiS.sub.2; FeS.sub.2; CaMO.sub.3 (M=Mn and/or Fe); potassium terephthalate; 2,5-pyridinedicarboxylate (K.sub.2PC); KFeF.sub.3; K.sub.0.3MnO.sub.2; KMg.sub.xFe.sub.2-x(PO.sub.4).sub.2, 0x2; NaTi.sub.2(PO.sub.4).sub.3; Na.sub.2FeP.sub.2O.sub.7, TiO.sub.2, and Na.sub.2Ti.sub.3O.sub.7.
10. The device of claim 1, further comprising an ion exchange membrane between said first electrode and said counter-electrode.
11. The device of claim 10, wherein the ion exchange membrane is an anion exchange membrane.
12. The device of claim 10, wherein the ion exchange membrane is a cation exchange membrane.
13. The device of claim 1, wherein said first electrode includes: a conductive substrate; and a layer on said substrate including said at least one material, an electrically conductive additive and a binder.
14. The device of claim 13, wherein said electrically conductive additive is a carbon composition.
15. The device of claim 13, wherein said binder is a polyvinylidene di-fluoride (PVDF).
16. The device of claim 15, wherein said layer includes said at least one material in 60-85 wt. %, said PVDF binder in 5-35 wt. % and a carbon composition as said electrically conductive additive in 3-10 wt. %.
17. A method for removing ions from a flow of water comprising: positioning a device in the flow of water, the device comprising a first electrode and a counter-electrode opposite said first electrode, wherein said first electrode contains at least one material which is capable of intercalating one or both of Mg.sup.2+ and Ca.sup.2+ ions in the flow of water; applying a positive voltage to the first electrode to intercalate one or both of the Mg.sup.2+ and Ca.sup.2+ ions from the flow of water into the first electrode.
18. The method of claim 17, further comprising discharging the water with one or both of the Mg.sup.2+ and Ca.sup.2+ ions removed from the device.
19. The method of claim 17, wherein the positive voltage is within the stability window of water.
20. The method of claim 17, further comprising applying a negative voltage to the first electrode to release the one or both of the Mg.sup.2+ and Ca.sup.2+ ions intercalated in the first electrode from the first electrode.
21. The method of claim 20, wherein the negative voltage is within the stability window of water.
22. The method of claim 20, further comprising releasing the one or both of the Mg.sup.2+ and Ca.sup.2+ ions into a flow of water discharged from the device.
23. The method of claim 22, further comprising discharging the water with one or both of the Mg.sup.2+ and Ca.sup.2+ ions removed from the device separate from the flow of water discharged from the device in which the one or both of the Mg.sup.2+ and Ca.sup.2+ ions have been released.
24. The method of claim 17, wherein: the counter-electrode of the device includes a material capable of binding anions; and the step of applying a positive voltage to the first electrode includes applying a negative voltage to the counter-electrode to bind the anions in the flow of water to the counter-electrode.
25. The method of claim 24, wherein counter-electrode material is capable of binding one or both of Cl.sup. and Co.sub.3.sup.2 anions in the flow of water to the counter-electrode.
26. The method of claim 17, wherein the at least one material is selected from the group consisting of: A.sub.xCuFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xMnFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xMnMn(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xZnFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xBaFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xFeFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; A.sub.xNiFe(CN).sub.6 (A=Li,Na,K,Cs) 0x1; Ti.sub.xFe.sub.1-x[Fe(CN).sub.6].sub.0.96 0x1; polyimide; FePO.sub.4; NaMnFe.sub.2(PO.sub.4).sub.3; Na.sub.3Fe.sub.3(PO.sub.4).sub.4; Na(M)PO.sub.4, M=Fe, Mn, or Fe.sub.xMn.sub.1-x0x1; MnO.sub.2; Na.sub.xMnO.sub.2, 0x1; ZnMn.sub.2O.sub.4; MgFeSiO.sub.4/C; Mg.sub.xMn.sub.2-xSiO.sub.4, 0x2; Mg.sub.0.5Ti.sub.2(PO.sub.4).sub.3; LiTi.sub.2(PO.sub.4).sub.3; Ti.sub.xAl.sub.2-x(PO.sub.4).sub.3, 0x2; TiP.sub.2O.sub.7; Na.sub.3MnTi(PO.sub.4).sub.3; K.sub.2Ti.sub.4O.sub.9; TiS.sub.2; FeS.sub.2; CaMO.sub.3 (M=Mn and/or Fe); potassium terephthalate; 2,5-pyridinedicarboxylate (K.sub.2PC); KFeF.sub.3; K.sub.0.3MnO.sub.2; KMg.sub.xFe.sub.2-x(PO.sub.4).sub.2, 0x2; NaTi.sub.2(PO.sub.4).sub.3; Na.sub.2FeP.sub.2O.sub.7, TiO.sub.2, and Na.sub.2Ti.sub.3O.sub.7.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0012]
[0013]
[0014]
[0015]
[0016]
[0017]
[0018]
DETAILED DESCRIPTION
[0019] For the purpose of promoting an understanding of the principles of the disclosure, reference will now be made to the embodiments illustrated in the drawings and described in the following written specification. It is understood that no limitation to the scope of the disclosure is thereby intended. It is further understood that the disclosure includes any alterations and modifications to the illustrated embodiments and includes further applications of the principles of the disclosure as would normally occur to one skilled in the art to which this disclosure pertains.
[0020]
[0021] The intercalation host material 112 of the electrode 104 disclosed herein is one or more of the compounds identified in Table 1 below:
TABLE-US-00001 TABLE 1 A.sub.xCuFe(CN).sub.6, where A = Li, Na, K, Cs and 0 x 1 A.sub.xMnFe(CN).sub.6, where A = Li, Na, K, Cs and 0 x 1 A.sub.xMnMn(CN).sub.6, where A = Li, Na, K, Cs and 0 x 1 A.sub.xZnFe(CN).sub.6, where A = Li, Na, K, Cs and 0 x 1 A.sub.xBaFe(CN).sub.6, where A = Li, Na, K, Cs and 0 x 1 Ti.sub.xFe.sub.1x[Fe(CN).sub.6].sub.0.96, where 0 x 1 Polyimide (PNDIE) FePO.sub.4 NaMnFe.sub.2(PO.sub.4).sub.3 Alluaudite Na.sub.3Fe.sub.3(PO.sub.4).sub.4 Na(M)PO.sub.4, where M = Fe, Mn, or Fe.sub.xMn.sub.1x and 0 x 1 MnO.sub.2 Na.sub.xMnO.sub.2, where 0 x 1 ZnMn.sub.2O.sub.4 MgFeSiO.sub.4/C Mg.sub.xMn.sub.2xSiO.sub.4, where 0 x 2 Mg.sub.0.5Ti.sub.2(PO.sub.4).sub.3 LiTi.sub.2(PO.sub.4).sub.3 Ti.sub.xAl.sub.2x(PO.sub.4).sub.3, where 0 x 2 TiP.sub.2O.sub.7 Na.sub.3MnTi(PO.sub.4).sub.3 K.sub.2Ti.sub.4O.sub.9 TiS.sub.2 FeS.sub.2 CaMO.sub.3, where M = Mn and/or Fe) potassium terephthalate 2,5-pyridinedicarboxylate (K.sub.2PC) KFeF.sub.3 K.sub.0.3MnO.sub.2 KMg.sub.xFe.sub.2x(PO.sub.4).sub.2, where 0 x 2 A.sub.xFeFe(CN).sub.6, where A = Li, Na, K, Cs and 0 x 1 A.sub.xNiFe(CN).sub.6, where A = Li, Na, K, Cs and 0 x 1 NaTi.sub.2(PO.sub.4).sub.3 Na.sub.2FeP.sub.2O.sub.7 TiO.sub.2 Na.sub.2Ti.sub.3O.sub.7
[0022] In one embodiment, the electrode 104 includes material 112 disposed on the substrate 108 includes one or more of the intercalation host materials from Table 1, a carbon additive to improve electrical conductivity, and a binder. In one specific embodiment, the intercalation host materials are provided in an amount 60-85 wt %, the carbon additive provided in an amount 3-10 wt %, and a polyvinylidene di-fluoride (PVDF) is provided as the binder in an amount 5-35 wt %. To produce the electrode 104 having the intercalation host material 112, the carbon additive, and the polymeric binder are well-mixed as a slurry in an appropriate solvent, such as N-Methyl-2-Pyrrolidone (NMP), and then blade-cast, roll cast, or airbrushed onto the substrate 108 of the electrode 104.
[0023] The device 100 in some embodiments is arranged in a water supply system for a dwelling or other building (not shown) that includes various pumps, conduits, valves, and related components to transport water from an external water supply to water distribution branch circuits within the dwelling or building. Water flow 120 enters the device 100 at an input side 124 and exits the device 100 at an output side 128. The device 100 can be incorporated into a housing having an inlet, at the input side 124 of the device, which is in fluid-tight engagement with an input line connected to the external water supply, and an outlet, at the output side 128 of the device, which is in fluid-tight engagement with an inlet to the water distribution branch circuits.
[0024] As the water moves in a flow direction 132 through the device 100 and over the intercalation host material 112 on the electrode 104, the device 100 is configured to have different operating states so as to enable it to selectively remove the first target ions 116 from the water flow 120. The flow direction 132 shown in
[0025]
[0026]
[0027]
[0028] The voltage applied to the electrode 104 in the second and third operating states is configured to be within the stability window of water (i.e., 0.401 to +1.23 V vs. SHE) so as to avoid water electrolysis. As such, the intercalation host materials 112 identified in Table 1 are configured to intercalate and release the first target ions 116 at voltages within the stability window of water.
[0029] With continued reference to
[0030] When the device 100 is in the first operating state as shown in
[0031] When the device 100 is in the second operating state as shown in
[0032] When the device 100 is in the third operating state as shown in
[0033] In some embodiments, the electrode 104 can be paired with one more auxiliary electrodes that reversibly react with other ions. For instance, the auxiliary electrode(s) can be formed from materials such as Ag/AgCl or BiOCl that reversibly react with chloride ions.
[0034] In one embodiment, the device 100 can be provided in the form of a cartridge 150 mounted within a housing 152, as illustrated in
[0035]
[0036] The device 200 in some embodiments is arranged in a water supply system (not shown) that includes various pumps, conduits, valves, and related components to transport water from a source to an end user. The device 200 is arranged in the water supply system such that the water 120 enters the device 200 at an input side 224 and exits the device 200 at an output side 228. As the water moves in a flow direction 232 through the device 200 and over the intercalation host material 112 on the electrodes 204, the device 200 is configured to have different operating states so as to enable it to selectively remove the first target ions 116 from the water 120.
[0037]
[0038]
[0039] The device 200 can be provided as a cartridge 201 mounted within a housing 260 configured to be integrated into the water supply system of a dwelling or building, in a manner similar to the housing 152 described above. However, since the device 200 includes two discrete regions 250, 254 that alternate between a softened water flow path and a waste flow path, the housing 260 defines two discrete chambers 261, 265, each having a respective inlet fitting 262, 266 and outlet fitting 263, 267. The housing is configured to preserve the integrity of the two chambers and regions 250, 254 to prevent cross-contamination. A controller 268 is provided that is connected to a current source V.sub.IN and to each of the electrodes 204 to selectively apply a positive voltage, negative voltage or no voltage to the electrodes according to one of the three operating states described above. Since the two regions alternatively flow softened water and waste water through them, depending on the operating state, the outputs of the two chambers 261, 265 of the housing are fed to a two position valve assembly 270. A first element 271 of the valve assembly provides a direct connection 271a between the left chamber 261 and a waste outlet W, and a direct connection 271b between the right chamber 265 and a soft water outlet S. The second element 272 of the valve assembly crosses the connections, thereby providing a direct connection 272a between the left chamber 261 and a softened water outlet S, and a direct connection 272b between the right chamber 265 and a waste outlet W. A valve controller 273, such as an electrical solenoid, is provided to selectively move the valve assembly into one of the two positions. The valve controller 273 is tied to the controller 268 that selectively energizes the electrodes 204 to coordinate the action of the electrodes with the action of the valve assembly for each operating state. Thus, when the device 200 is in the second operating state shown in
[0040] While the disclosure has been illustrated and described in detail in the drawings and foregoing description, the same should be considered as illustrative and not restrictive in character. It is understood that only the preferred embodiments have been presented and that all changes, modifications and further applications that come within the spirit of the disclosure are desired to be protected.