IP Library Granted Patent US 11,001,554
Granted Patent B2
US 11,001,554 · App. 16/369,922 · Granted May 11, 2021

Lipophilic guanidinium compounds for removal of oxyanions from aqueous solutions

Inventors: Neil J. Williams (Knoxville, TN); Radu Custelcean (Beavercreek, OH); Charles A. Seipp (Beavercreek, OH); Bruce A. Moyer (Oak Ridge, TN); Ross Ellis (Moss, NO); Carter W. Abney (Califon, NJ)
Assignee: UT-Battelle, LLC
C07C281/16B01D11/0492B01J41/07B01J41/09C02F1/26C02F1/42C07C281/18C22B3/0013C22B3/0016B01D2257/70B01J41/04C07C29/76C22B3/001C22B3/0006
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Quick Facts
Patent No.
US 11,001,554
App. No.
16/369,922
Granted
May 11, 2021
Kind
B2
Abstract

Methods for removing an oxyanion from an aqueous source containing said oxyanion, comprising contacting said aqueous source with an aqueous-insoluble hydrophobic solution containing an oxyanion extractant compound dissolved in an aqueous-insoluble hydrophobic solvent to result in formation of an oxyanion salt of said extractant compound and extraction of said oxyanion salt into said aqueous-insoluble hydrophobic solution, wherein said extraction results in an extraction affinity (D) of said oxyanion of at least 1, wherein D is the concentration ratio of said oxyanion in the organic phase divided by the concentration of said oxyanion in the aqueous phase; wherein said extractant compound has the following composition: wherein at least one of R 1 -R 10 is or contains a hydrocarbon (R) group containing at least 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

Claims (42)

1. A compound having the following structure:

wherein:

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from (i) hydrogen atom, (ii) hydrocarbon groups (R) containing 1-30 carbon atoms and optionally substituted with one or more fluorine atoms, (iii) —OR′ groups, and (iv) —NR′ 2 groups, wherein R′ groups are independently selected from R groups and hydrogen atoms, provided that at least four of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms;

R 11 and R 12 are independently selected from hydrogen atom and methyl group;

X m− is an anionic species with a magnitude of charge m, where m is an integer of at least 1; and

n is a number, provided that n×m=1.

2. The compound of claim 1 , provided that at least four of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms.

3. The compound of claim 1 , provided that:

(i) at least two of R 1 , R 2 , R 3 , R 4 , and R 5 are selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms, and

(ii) at least two of R 6 , R 7 , R 8 , R 9 , and R 10 are selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms.

4. The compound of claim 1 , provided that:

(i) at least two of R 1 , R 2 , R 3 , R 4 , and R 5 are selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms, and

(ii) at least two of R 6 , R 7 , R 8 , R 9 , and R 10 are selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms.

5. The compound of claim 1 , wherein X m− is halide or nitrate.

6. The compound of claim 1 , wherein X m− is sulfate or phosphate.

7. A method for removing an oxyanion from an aqueous source containing said oxyanion, the method comprising contacting said aqueous source with an aqueous-insoluble hydrophobic solution containing an oxyanion extractant compound dissolved in an aqueous-insoluble hydrophobic solvent to result in formation of an oxyanion salt of said oxyanion extractant compound and extraction of said oxyanion salt of said oxyanion extractant compound into said aqueous-insoluble hydrophobic solution, wherein said extraction results in an extraction affinity (D) of said oxyanion of at least 1, wherein D is the concentration ratio of said oxyanion in the organic phase divided by the concentration of said oxyanion in the aqueous phase;

wherein said oxyanion extractant compound has the following structure:

wherein:

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from (i) hydrogen atom, (ii) hydrocarbon groups (R) containing 1-30 carbon atoms and optionally substituted with one or more fluorine atoms, (iii) —OR′ groups, and (iv) —NR′ 2 groups, wherein R′ groups are independently selected from R groups and hydrogen atoms, provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms;

R 11 and R 12 are independently selected from hydrogen atom and methyl group;

X m− is an anionic species with a magnitude of charge m, where m is an integer of at least 1, provided that X m− is an anionic species exchangeable with the oxyanion in said aqueous source before said oxyanion extractant compound contacts said aqueous source, and X m− is said oxyanion in the oxyanion salt of said oxyanion extractant compound; and

n is a number, provided that n×m=1.

8. The method of claim 7 , wherein said oxyanion is selected from the group consisting of sulfate, nitrate, selenate, tellurate, phosphate, arsenate, carbonate, bicarbonate, perchlorate, and metal oxyanions.

9. The method of claim 7 , wherein said oxyanion is sulfate or phosphate.

10. The method of claim 7 , wherein X m− is halide or nitrate before said oxyanion extractant compound contacts said aqueous source.

11. The method of claim 7 , provided that at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms.

12. The method of claim 7 , provided that at least four of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms.

13. The method of claim 7 , provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms.

14. The method of claim 7 , provided that at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms.

15. The method of claim 7 , provided that at least four of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms.

16. The method of claim 7 , provided that:

(i) at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms, and

(ii) at least one of R 6 , R 7 , R 8 , R 9 , and R 10 is selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms.

17. The method of claim 7 , provided that:

(i) at least two of R 1 , R 2 , R 3 , R 4 , and R 5 are selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms, and

(ii) at least two of R 6 , R 7 , R 8 , R 9 , and R 10 are selected from: R groups containing 4-30 carbon atoms, or —OR groups with R containing 4-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 4-30 carbon atoms.

18. The method of claim 7 , provided that:

(i) at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms, and

(ii) at least one of R 6 , R 7 , R 8 , R 9 , and R 10 is selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms.

19. The method of claim 7 , provided that:

(i) at least two of R 1 , R 2 , R 3 , R 4 , and R 5 are selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms, and

(ii) at least two of R 6 , R 7 , R 8 , R 9 , and R 10 are selected from: R groups containing 6-30 carbon atoms, or —OR groups with R containing 6-30 carbon atoms, or —NR′ 2 groups with at least one R′ group being R containing 6-30 carbon atoms.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 25, 2021
From: OAK RIDGE ASSOCIATED UNIVERSITIES
To: UT-BATTELLE, LLC
Reel/Frame 056664/0938 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 29, 2021
From: SEIPP, CHARLES A.
To: OAK RIDGE ASSOCIATED UNIVERSITIES
Reel/Frame 056080/0321 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 20, 2021
From: WILLIAMS, NEIL J.; CUSTELCEAN, RADU; MOYER, BRUCE A.; ELLIS, ROSS; ABNEY, CARTER W.
To: UT-BATTELLE, LLC
Reel/Frame 055969/0946 →
CONFIRMATORY LICENSE Recorded Jul 31, 2019
From: UT-BATTELLE, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 049915/0625 →
Continuity (2)
Provisional Application 62649801 · Mar 29, 2018
Related Publication 20190299124A1 · Oct 3, 2019
Cited By (1)
US 12,662,403