IP Library Granted Patent US 11,220,443
Granted Patent B2
US 11,220,443 · App. 17/249,345 · Granted Jan 11, 2022

Removal of phosphorus and nitrogen from water

Inventors: Carlos Borras (Ruskin, FL); Donald A. Luke (Valrico, FL)
Assignee: Phosphorus Free Water Solutions, LLC
C02F1/46176C02F1/001C02F1/4676C02F1/5254C02F1/586C02F1/66C25B1/00C25B1/20C25B1/50C25B9/65C02F2001/46119C02F2001/46133C02F2101/105C02F2101/16C02F2101/20C02F2209/06
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Quick Facts
Patent No.
US 11,220,443
App. No.
17/249,345
Granted
Jan 11, 2022
Kind
B2
Abstract

Various embodiments relate to methods and systems for removing phosphorus and/or nitrogen from water. A method of removing phosphorus and nitrogen from water includes passing starting material water including nitrogen and phosphorus through an elevated pH phosphorus removal stage. The method includes passing the water through an electrolytic nitrogen removal stage. The method includes passing the water through a galvanic phosphorus removal stage. The water produced by the method has a lower phosphorus concentration and a lower nitrogen concentration than the starting material water.

Claims (105)

1. A method of removing phosphorus and nitrogen from starting material water, the method comprising:

passing the starting material water having a pH of less than 7.5 and comprising both nitrogen and phosphorus through an elevated pH phosphorus removal stage comprising

raising pH of the starting material water to greater than or equal to 7.5 to precipitate a phosphorus salt therefrom; and

removing the precipitated phosphorus salt from the starting material water, to form water from the elevated pH phosphorus removal stage;

passing the water from the elevated pH phosphorus removal stage through an electrolytic nitrogen removal stage comprising

passing the water from the elevated pH phosphorus removal stage through an electrolytic cell to remove nitrogen therefrom as nitrogen gas, to form water from the electrolytic nitrogen removal stage; and

passing the water from the electrolytic nitrogen removal stage through a galvanic phosphorus removal stage comprising

immersing a galvanic cell in the water from the electrolytic nitrogen removal stage to form treated water comprising a salt that comprises phosphorus from the water from the electrolytic nitrogen removal stage, the galvanic cell comprising

an anode comprising Mg, Al, or a combination thereof,

a cathode having a different composition than the anode, the cathode comprising Cu, and

a conductive connector that electrically connects the anode and the cathode, the conductive connector comprising Cu, Zn, Fe, Cd, Ni, Sn, Pb, or a combination thereof, and

separating the salt comprising the phosphorus from the treated water, to form water from the galvanic phosphorus removal stage;

wherein the water from the galvanic phosphorus removal stage has a lower phosphorus concentration and a lower nitrogen concentration than the starting material water.

2. The method of claim 1 , wherein the starting material water is water originated from a process of dissolving phosphate-containing rock to produce phosphoric acid.

3. The method of claim 1 , wherein the starting material water has a chloride concentration of 200 ppm to 10,000 ppm.

4. The method of claim 1 , wherein the water from the galvanic phosphorus removal stage has a total phosphorus concentration, a dissolved phosphorus concentration, a reactive phosphorus concentration as measured according to US EPA Method 365.1, or a combination thereof, of 0.0001 ppm to 0.1 ppm, and a total nitrogen concentration, a dissolved nitrogen concentration, or a combination thereof, of about 0 ppm to about 1 ppm.

5. The method of claim 1 , wherein raising pH of the starting material water to precipitate the phosphorus salt therefrom comprises raising the pH of the starting material water to 8.5 to 9.5.

6. The method of claim 1 , wherein the precipitated phosphorus salt comprises struvite, calcium phosphate, or a combination thereof.

7. The method of claim 1 , wherein the electrolytic cell comprises a cathode comprising titanium, stainless steel, or a combination thereof.

8. The method of claim 1 , wherein the electrolytic cell comprises an anode comprising

titanium oxide, ruthenium oxide, and iridium oxide supported on titanium (TiO 2 —RuO 2 —IrO 2 /Ti), or

titanium oxide and ruthenium oxide supported on titanium (TiO 2 —RuO 2 /Ti), or

titanium and platinum (Ti—Pt), or

a combination thereof.

9. The method of claim 1 , wherein passing the water from the elevated pH phosphorus removal stage through the electrolytic nitrogen removal stage produces hypochlorite which reacts with ammonia in the water from the elevated pH phosphorus removal stage to form the nitrogen gas that is removed during the electrolytic nitrogen removal stage.

10. The method of claim 1 , wherein the salt comprising the phosphorus comprises a material from the anode of the galvanic cell.

11. The method of claim 1 , wherein the cathode comprises Cu and the anode comprises Mg.

12. The method of claim 1 , wherein the cathode comprises Cu and the anode comprises Al.

13. The method of claim 1 , wherein:

the water from the electrolytic nitrogen removal stage immersing the galvanic cell has a pH of about 5 to about 7;

the anode of the galvanic cell comprises Al, wherein the anode is about 90 wt % to about 100 wt % Al;

the cathode of the galvanic cell comprises Cu, wherein the cathode is about 90 wt % to about 100 wt % Cu;

the galvanic cell comprises a conductive connector that electrically connects the anode and the cathode, the conductive connector comprising an alloy comprising Cu and Zn; and

the salt comprising the phosphorus formed in the galvanic phosphorus removal stage comprises

AlPO 4 or a hydrate thereof, the AlPO 4 comprising the phosphorus and Al from the anode,

aluminum hydroxide or a hydrate thereof, the aluminum hydroxide comprising Al from the anode, or

a combination thereof.

14. The method of claim 1 , wherein:

the water from the electrolytic nitrogen removal stage immersing the galvanic cell has a pH of about 10 to about 11;

the anode of the galvanic cell comprises Mg, wherein the anode is about 90 wt % to about 100 wt % Mg;

the cathode of the galvanic cell comprises Cu, wherein the cathode is about 90 wt % to about 100 wt % Cu; and

the galvanic cell comprises a conductive connector that electrically connects the anode and the cathode, the conductive connector comprising an alloy comprising Cu and Zn; and

the salt comprising the phosphorus formed in the galvanic phosphorus removal stage comprises

magnesium phosphate, magnesium potassium phosphate, a hydrate thereof, or a combination thereof,

NH 4 MgPO 4 or a hydrate thereof, the NH 4 MgPO 4 comprising the phosphorus and Mg from the anode,

Mg(OH) 2 comprising Mg from the anode, or

a combination thereof.

15. The method of claim 1 , further comprising further removing nitrogen from the water from the galvanic phosphorus removal stage.

16. A method of removing phosphorus and nitrogen from starting material water, the method comprising:

passing the starting material water having a pH of less than 8.5 and comprising both nitrogen and phosphorus through an elevated pH phosphorus removal stage, comprising

raising pH of the starting material water using one or more bases to 8.5 to 9.5 to precipitate a phosphorus salt therefrom comprising struvite, calcium phosphate, or a combination thereof; and

removing the precipitated phosphorus salt from the starting material water to form water from the elevated pH phosphorus removal stage, wherein the elevated pH phosphorus removal stage removes 90-98% of reactive phosphorus in the starting material water, wherein reactive phosphorus is measured according to US EPA Method 365.1;

passing the water from the elevated pH phosphorus removal stage through an electrolytic nitrogen removal stage comprising

passing the water from the elevated pH phosphorus removal stage through an electrolytic cell to remove nitrogen therefrom as nitrogen gas to form water from the electrolytic nitrogen removal stage, the electrolytic cell comprising a cathode comprising stainless steel and an anode that comprises titanium oxide, ruthenium oxide, and iridium oxide supported on titanium (TiO 2 —RuO 2 —IrO 2 /Ti), wherein passing the water from the elevated pH phosphorus removal stage through the electrolytic nitrogen removal stage removes 80-100% of ammonia therefrom; and

passing the water from the electrolytic nitrogen removal stage through a galvanic phosphorus removal stage comprising

immersing a galvanic cell in the water from the electrolytic nitrogen removal stage to form treated water comprising a salt that comprises phosphorus from the water from the electrolytic nitrogen removal stage, the salt comprising

AlPO 4 or a hydrate thereof, the AlPO 4 comprising the phosphorus and Al from the anode,

aluminum hydroxide or a hydrate thereof, the aluminum hydroxide comprising Al from the anode, or

a combination thereof;

the galvanic cell comprising

an anode comprising Al, wherein the anode is about 90 wt % to about 100 wt % Al,

a cathode comprising Cu, wherein the cathode is about 90 wt % to about 100 wt % Cu,

a conductive connector that electrically connects the anode and the cathode, the conductive connector comprising an alloy comprising Cu and Zn; and

separating the salt comprising the phosphorus from the treated water, to form water from the galvanic phosphorus removal stage;

wherein the water from the galvanic phosphorus removal stage has a lower phosphorus concentration and a lower nitrogen concentration than the starting material water, wherein the water from the galvanic phosphorus removal stage has

a total phosphorus concentration of about 0.0001 ppm to 0.05 ppm, and

a total nitrogen concentration of about 0 ppm to about 1 ppm.

17. The method of claim 1 , wherein the conductive connector comprises Cu and Zn.

18. The method of claim 1 , wherein the conductive connector comprises brass.

19. The method of claim 1 , wherein the conductive connector comprises a screw, a bolt, or a combination thereof.

20. A method of removing phosphorus and nitrogen from starting material water, the method comprising:

passing the starting material water having a pH of less than 7.5 and comprising both nitrogen and phosphorus through an elevated pH phosphorus removal stage comprising

raising pH of the starting material water to greater than or equal to 7.5 to precipitate a phosphorus salt therefrom; and

removing the precipitated phosphorus salt from the starting material water to form water from the elevated pH phosphorus removal stage;

passing the water from the elevated pH phosphorus removal stage through an electrolytic nitrogen removal stage comprising

passing the water from the elevated pH phosphorus removal stage through an electrolytic cell to remove nitrogen therefrom as nitrogen gas to form water from the electrolytic nitrogen removal stage; and

passing the water from the electrolytic nitrogen removal stage through a galvanic phosphorus removal stage comprising

immersing a galvanic cell in the water from the electrolytic nitrogen removal stage having a pH of about 5 to about 7 to form treated water comprising a salt that comprises phosphorus from the water from the electrolytic nitrogen removal stage, the galvanic cell comprising

an anode comprising Al, wherein the anode is about 90 wt % to about 100 wt % Mg,

a cathode comprising Cu, wherein the cathode is about 90 wt % to about 100 wt % Cu, and

a conductive connector that electrically connects the anode and the cathode, the conductive connector comprising an alloy comprising Cu and Zn; and

separating the salt comprising the phosphorus from the treated water, to form water from the galvanic phosphorus removal stage;

wherein the water from the galvanic phosphorus removal stage has a lower phosphorus concentration and a lower nitrogen concentration than the starting material water, and

wherein the salt comprising the phosphorus formed in the galvanic phosphorus removal stage comprises

AlPO 4 or a hydrate thereof, the AlPO 4 comprising the phosphorus and Al from the anode,

aluminum hydroxide or a hydrate thereof, the aluminum hydroxide comprising Al from the anode, or

a combination thereof.

21. A method of removing phosphorus and nitrogen from starting material water, the method comprising:

passing the starting material water having a pH of less than 7.5 and comprising both nitrogen and phosphorus through an elevated pH phosphorus removal stage comprising

raising pH of the starting material water to greater than or equal to 7.5 to precipitate a phosphorus salt therefrom; and

removing the precipitated phosphorus salt from the starting material water to form water from the elevated pH phosphorus removal stage;

passing the water from the elevated pH phosphorus removal stage through an electrolytic nitrogen removal stage comprising

passing the water from the elevated pH phosphorus removal stage through an electrolytic cell to remove nitrogen therefrom as nitrogen gas to form water from the electrolytic nitrogen removal stage; and

passing the water from the electrolytic nitrogen removal stage through a galvanic phosphorus removal stage comprising

immersing a galvanic cell in the water from the electrolytic nitrogen removal stage having a pH of about 10 to about 11 to form treated water comprising a salt that comprises phosphorus from the water from the electrolytic nitrogen removal stage, the galvanic cell comprising

an anode comprising Mg, wherein the anode is about 90 wt % to about 100 wt % Mg,

a cathode comprising Cu, wherein the cathode is about 90 wt % to about 100 wt % Cu, and

a conductive connector that electrically connects the anode and the cathode, the conductive connector comprising an alloy comprising Cu and Zn; and

separating the salt comprising the phosphorus from the treated water, to form water from the galvanic phosphorus removal stage;

wherein the water from the galvanic phosphorus removal stage has a lower phosphorus concentration and a lower nitrogen concentration than the starting material water, and

wherein the salt comprising the phosphorus formed in the galvanic phosphorus removal stage comprises

magnesium phosphate, magnesium potassium phosphate, a hydrate thereof, or a combination thereof,

NH 4 MgPO 4 or a hydrate thereof, the NH 4 MgPO 4 comprising the phosphorus and Mg from the anode,

Mg(OH) 2 comprising Mg from the anode, or

a combination thereof.

Assignments (2)
CHANGE OF NAME Recorded May 30, 2023
From: PHOSPHORUS FREE WATER SOLUTIONS, LLC
To: NUQUATIC, LLC
Reel/Frame 063801/0518 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 19, 2021
From: BORRAS, CARLOS; LUKE, DONALD A.
To: PHOSPHORUS FREE WATER SOLUTIONS, LLC
Reel/Frame 055655/0126 →
Continuity (3)
Continuation PCTUS2020037407 · Jun 12, 2020
Provisional Application 62860433 · Jun 12, 2019
Related Publication 20210179456A1 · Jun 17, 2021
Cited By (4)
US 12,215,044 US 12,240,772 US 12,351,492 US 12,492,137