IP Library Granted Patent US 7,419,602
Granted Patent B2
US 7,419,602 · App. 11/284,856 · Granted Sep 2, 2008

Selenium removal from water

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Quick Facts
Patent No.
US 7,419,602
App. No.
11/284,856
Granted
Sep 2, 2008
Kind
B2
Abstract

A process for removing selenium from a water stream, in particular a waste water stream, by: 1) the addition thereto of a ferric salt, followed by 2) the addition of a cupric salt and pH adjustment to a pH value in the range of from about 6.5 to about 8.0, thereby forming a copper-and-selenium-containing precipitate, and 3) removing the copper-and-selenium-containing precipitate to thereby form a treated water stream, is disclosed. The optional precipitation and removal of excess copper ions is also disclosed.

Claims (27)

1. A process comprising:

adding a ferric salt to a feed stream comprising water and selenocyanate to thereby form a first intermediate stream, wherein at least about 0.003 milligrams of said ferric salt are added to said feed stream;

adding a cupric salt to said first intermediate stream to thereby form a second intermediate stream;

adjusting the pH of said second intermediate stream to a pH value in the range of from about 6.5 to about 8.0 in order to maximize the reaction of said cupric salt with said selenocyanate to thereby form a copper-adding a polymer to said second intermediate stream for flocculation with said copper-and-selenium-containing precipitate thereby forming a third intermediate stream comprising floccules of said polymer and said copper-and-selenium-containing precipitate; and-selenium-containing precipitate; and

removing said floccules-and-selenium-containing floccules from said third intermediate stream to thereby form a treated water stream.

2. A process in accordance with claim 1 wherein said ferric salt comprises a salt selected from the group consisting of ferric halide, ferric nitrate, or ferric sulfate, and combinations thereof.

3. A process in accordance with claim 1 wherein said ferric salt is ferric chloride.

4. A process in accordance with claim 1 wherein said cupric salt comprises a salt selected from the group consisting of cupric halide, cupric nitrate and cupric sulfate.

5. A process in accordance with claim 1 wherein said cupric salt is cupric chloride.

6. A process in accordance with claim 1 wherein said cupric salt is cupric sulfate.

7. A process in accordance with claim 1 wherein said cupric salt is added to said first intermediate stream in a stoichiometric excess relative to the amount of said selenocyanate present in said first intermediate stream.

8. A process in accordance with claim 1 wherein in the range of from about 0.003 milligrams to about 0.07 milligrams of said ferric salt are added per milliliter of said feed stream.

9. A process in accordance with claim 1 wherein the pH of said second intermediate stream is adjusted by either adding an acid or a base to said second intermediate stream.

10. A process in accordance with claim 9 wherein said acid comprises a member selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and combinations thereof, and wherein said base comprises a member selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and combinations thereof.

11. A process in accordance with claim 1 wherein the pH of said second intermediate stream is adjusted to a pH value in the range of from about 7.0 to about 8.0.

12. A process in accordance with claim 1 wherein the selenium concentration of said feed stream is greater than about 500 ppbw, on an elemental selenium basis.

13. A process in accordance with claim 1 wherein the selenium concentration of said treated stream is less than about 20 ppbw, on an elemental selenium basis.

14. A process in accordance with claim 1 wherein the step of removing said copper-and-selenium-containing precipitate comprises the steps of:

a polymer to said second intermediate stream for flocculation with said copper-and-selenium-containing thereby forming a third intermediate stream comprising floccules of said polymer and said copper-and-selenium-containing

passing said third intermediate stream to a dissolved air flotation unit;

introducing fine air bubbles to said air flotation unit for passage up through said third intermediate stream for contact with said floccules to thereby form a froth comprising said floccules which rises to the top of said air flotation unit; and

removing said froth from said third intermediate stream to thereby form said treated water stream.

15. A process in accordance with claim 1 wherein:

a water soluble compound, having an ion which reacts with cupric or cuprous ions, is added to said treated water stream in a stoichiometric excess based on the amount of unreacted cupric or cuprous ions present in said treated water stream thereby forming a copper precipitate; and

said copper precipitate is removed from said treated water.

16. A process in accordance with claim 15 wherein said water soluble compound comprises a compound selected from the group consisting of a sulfide salt, a carbamate, a thiocarbonate, and combinations thereof.

17. A process in accordance with claim 16 wherein said sulfide salt comprises a compound selected from the group consisting of ferrous sulfide, ammonium sulfide, sodium sulfide, sodium polysulfide, potassium sulfide, magnesium sulfide, calcium sulfide, barium sulfide, and combinations thereof.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 15, 2012
From: CONOCOPHILLIPS COMPANY
To: PHILLIPS 66 COMPANY
Reel/Frame 028213/0824 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 10, 2006
From: MITCHELL, STEVEN C.; ROOSEVELT, ALEXANDER; LORD, CHARLES J.
To: CONOCOPHILLIPS COMPANY
Reel/Frame 017332/0158 →