Lipophilic guanidinium compounds for removal of oxyanions from aqueous solutions

Patent metadata

Field	Value
Publication number	US-11001554-B2
Application number	US-201916369922-A
Country	US
Kind code	B2
Filing date	Mar 29, 2019
Priority date	Mar 29, 2018
Publication date	May 11, 2021
Grant date	May 11, 2021

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.

First claim

What is claimed is:

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 g

Assignees

• Ut Battelle Llc

Inventors

• Williams Neil J
• Custelcean Radu
• Seipp Charles A
• Moyer Bruce A
• Ellis Ross
• Abney Carter W

Classifications

• C22B3/26

  by liquid-liquid extraction using organic compounds · CPC title

• C07C281/18 Primary

  the other nitrogen atom being further doubly-bound to a carbon atom, e.g. guanylhydrazones · CPC title

• C22B3/282

  Aliphatic amines · CPC title

• C02F1/26

  by extraction · CPC title

• C07C281/16 Primary

  Compounds containing any of the groups [IMAGE cpc-sch-C07C-0974.gif], e.g. aminoguanidine · CPC title