IP Library Granted Patent US 11,369,944
Granted Patent B2
US 11,369,944 · App. 16/660,142 · Granted Jun 28, 2022

Organic polymer compositions for removal of oxoanions from aqueous solutions

Inventor: Santa Jansone-Popova (Knoxville, TN)
Assignee: UT-Battelle, LLC
B01J20/262B01J20/24B01J20/2808B01J20/3425C08L79/02
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Quick Facts
Patent No.
US 11,369,944
App. No.
16/660,142
Granted
Jun 28, 2022
Kind
B2
Abstract

An organic polymer composition (OPC) comprising guanidinium-containing A units interconnected with B units of the formula *—R *) r , wherein each asterisk (*) in A units denotes a connection point with an asterisk in B units; R is a hydrocarbon linking group containing at least one carbon atom; r is an integer of 1, 2, or 3; and the composition necessarily includes an anionic species X m− with a magnitude of charge m of at least 1, wherein the sum of negative charge provided by anionic species X m− counterbalances the total positive charge provided by the A units. Also described herein is a method for removing one or more oxoanions from an aqueous source by (i) contacting the aqueous source with the above described OPC to result in absorption of the oxoanion into the OPC to produce an oxoanion-containing OPC; and (ii) removing the oxoanion-containing OPC from the aqueous source.

Claims (96)

1. An organic polymer composition comprising the following structure:

A units:

*—R *) r   B units:

wherein:

the composition includes at least two A units and at least one B unit;

each asterisk (*) in the at least two A units denotes a connection point with an asterisk in the at least one B unit, provided that, in the event of surplus asterisks being present, the surplus asterisks are terminated by endcapping groups;

R is a hydrocarbon linking group containing at least one carbon atom;

the R 1 , R 2 , R 3 , R 4 , and R 5 groups are independently selected from hydrogen atoms and hydrocarbon groups containing 1-6 carbon atoms;

r is an integer of 1, 2, or 3; and

the composition necessarily includes an anionic species X m− with a magnitude of charge m of at least 1, wherein the sum of negative charge provided by anionic species X m− counterbalances the total positive charge provided by the at least two A units.

2. The composition of claim 1 , wherein the organic polymer composition comprises at least three A units and at least two B units.

3. The composition of claim 1 , wherein R is a ring-containing moiety.

4. The composition of claim 3 , wherein at least one ring in the ring-containing moiety is an aromatic ring.

5. The composition of claim 4 , wherein the aromatic ring is a benzene ring.

6. The composition of claim 1 , wherein the organic polymer composition is porous.

7. The composition of claim 6 , wherein the organic polymer composition possesses nanopores.

8. The composition of claim 7 , wherein the nanopores have a size within a range of 1-20 nm.

9. The composition of claim 1 , wherein r is 2 or 3.

10. The composition of claim 1 , wherein the R 1 , R 2 , R 3 , R 4 , and R 5 groups are hydrogen atoms.

11. The composition of claim 1 , wherein the at least two A units have the formula:

12. A method for removing an oxoanion from an aqueous source containing said oxoanion, the method comprising:

(i) contacting the aqueous source with an organic polymer composition to result in absorption of the oxoanion into the organic polymer composition to produce an oxoanion-containing organic polymer; and

(ii) removing the oxoanion-containing organic polymer from the aqueous source;

wherein the organic polymer composition comprises the following structure:

A units:

*—R *) r   B units:

wherein:

the composition includes at least two A units and at least one B unit;

each asterisk (*) in the at least two A units denotes a connection point with an asterisk in the at least one B unit, provided that, in the event of surplus asterisks being present, one of the more surplus asterisks are terminated by endcapping groups;

R is a hydrocarbon linking group containing at least one carbon atom;

the R 1 , R 2 , R 3 , R 4 , and R 5 groups are independently selected from hydrogen atoms and hydrocarbon groups containing 1-6 carbon atoms;

r is an integer of 1, 2, or 3; and

the composition necessarily includes an anionic species X m− with a magnitude of charge m of at least 1, wherein the sum of negative charge provided by anionic species X m− counterbalances the total positive charge provided by the at least two A units, provided that X m− is an anionic species exchangeable with the oxoanion in said aqueous source before said organic polymer composition contacts said oxoanion in step (i), and X m− is said oxoanion in the oxoanion-containing organic polymer.

13. The method of claim 12 , wherein the oxoanion is a tetrahedral oxoanion.

14. The method of claim 13 , wherein the tetrahedral oxoanion is selected from chromate, arsenate, perrhenate, pertechnetate, selenate, sulfate, molybdate, tungstate, perchlorate, perbromate, periodate, and phosphate.

15. The method of claim 13 , wherein the tetrahedral oxoanion is selected from chromate and arsenate.

16. The method of claim 15 , wherein, in step (i), the chromate or arsenate is selectively absorbed in the organic polymer composition when the chromate or arsenate is in the presence of one or more other types of oxoanions.

17. The method of claim 12 , further comprising: (iii) regenerating the organic polymer composition with concomitant release of the oxoanion by treating the oxoanion-containing organic polymer composition with a base to result in a deprotonated organic polymer composition, followed by re-protonation of the deprotonated organic polymer composition by treatment with an acid.

18. The method of claim 12 , wherein step (i) is achieved by passing the aqueous source solution through a column containing the organic polymer composition.

19. The method of claim 12 , wherein step (i) is achieved by adding the organic polymer composition to the aqueous source solution, agitating the aqueous source solution, and filtering the organic polymer composition from the aqueous source solution.

20. The method of claim 12 , wherein the organic polymer composition comprises at least three A units and at least two B units.

21. The method of claim 12 , wherein R is a ring-containing moiety.

22. The method of claim 21 , wherein at least one ring in the ring-containing moiety is an aromatic ring.

23. The method of claim 22 , wherein the aromatic ring is a benzene ring.

24. The method of claim 12 , wherein the organic polymer composition is porous.

25. The method of claim 24 , wherein the organic polymer composition possesses nanopores.

26. The method of claim 24 , wherein the nanopores have a size within a range of 1-20 nm.

27. The method of claim 12 , wherein r is 2 or 3.

28. The method of claim 12 , wherein the R 1 , R 2 , R 3 , R 4 , and R 5 groups are hydrogen atoms.

29. The method of claim 12 , wherein the at least two A units have the formula:

30. An organic polymer composition comprising the following structure:

A units:

*—R *) r   B units:

wherein:

the composition includes at least three A units and at least two B units;

each asterisk (*) in the at least three A units denotes a connection point with an asterisk in the at least two B units, provided that, in the event of surplus asterisks being present, the surplus asterisks are terminated by endcapping groups;

R is a hydrocarbon linking group containing at least one carbon atom;

the R 1 , R 2 , R 3 , R 4 , and R 5 groups are independently selected from hydrogen atoms and hydrocarbon groups containing 1-6 carbon atoms;

r is an integer of 1, 2, or 3; and

the composition necessarily includes an anionic species X m− with a magnitude of charge m of at least 1, wherein the sum of negative charge provided by anionic species X m− counterbalances the total positive charge provided by the at least three A units.

31. An organic polymer composition comprising the following structure:

A units:

*—R *) r   B units:

wherein:

the composition includes at least two A units and at least one B unit;

each asterisk (*) in the at least two A units denotes a connection point with an asterisk in the at least one B unit, provided that, in the event of surplus asterisks being present, the surplus asterisks are terminated by endcapping groups;

R has the structure —(CH 2 ) t —, wherein t is at least 1 and up to 30, and each hydrogen atom is optionally and independently substituted with a methyl or ethyl group;

the R 1 , R 2 , R 3 , R 4 , and R 5 groups are independently selected from hydrogen atoms and hydrocarbon groups containing 1-6 carbon atoms;

r is an integer of 1, 2, or 3; and

the composition necessarily includes an anionic species X m− with a magnitude of charge m of at least 1, wherein the sum of negative charge provided by anionic species X m− counterbalances the total positive charge provided by the at least two A units.

32. A method for removing an oxoanion from an aqueous source containing said oxoanion, the method comprising:

(i) contacting the aqueous source with an organic polymer composition to result in absorption of the oxoanion into the organic polymer composition to produce an oxoanion-containing organic polymer; and

(ii) removing the oxoanion-containing organic polymer from the aqueous source;

wherein the organic polymer composition comprises the following structure:

A units:

*—R *) r   B units:

wherein:

the composition includes at least three A units and at least two B units;

each asterisk (*) in the at least three A units denotes a connection point with an asterisk in the at least two B units, provided that, in the event of surplus asterisks being present, one of the more surplus asterisks are terminated by endcapping groups;

R is a hydrocarbon linking group containing at least one carbon atom;

the R 1 , R 2 , R 3 , R 4 , and R 5 groups are independently selected from hydrogen atoms and hydrocarbon groups containing 1-6 carbon atoms;

r is an integer of 1, 2, or 3; and

the composition necessarily includes an anionic species X m− with a magnitude of charge m of at least 1, wherein the sum of negative charge provided by anionic species X m− counterbalances the total positive charge provided by the at least three A units, provided that X m− is an anionic species exchangeable with the oxoanion in said aqueous source before said organic polymer composition contacts said oxoanion in step (i), and X m− is said oxoanion in the oxoanion-containing organic polymer.

33. A method for removing an oxoanion from an aqueous source containing said oxoanion, the method comprising:

(i) contacting the aqueous source with an organic polymer composition to result in absorption of the oxoanion into the organic polymer composition to produce an oxoanion-containing organic polymer; and

(ii) removing the oxoanion-containing organic polymer from the aqueous source;

wherein the organic polymer composition comprises the following structure:

A units:

*—R *) r   B units:

wherein:

the composition includes at least two A units and at least one B unit;

each asterisk (*) in the at least two A units denotes a connection point with an asterisk in the at least one B unit, provided that, in the event of surplus asterisks being present, one of the more surplus asterisks are terminated by endcapping groups;

R has the structure —(CH 2 ) t —, wherein t is at least 1 and up to 30, and each hydrogen atom is optionally and independently substituted with a methyl or ethyl group;

the R 1 , R 2 , R 3 , R 4 , and R 5 groups are independently selected from hydrogen atoms and hydrocarbon groups containing 1-6 carbon atoms;

r is an integer of 1, 2, or 3; and

the composition necessarily includes an anionic species X m− with a magnitude of charge m of at least 1, wherein the sum of negative charge provided by anionic species X m− counterbalances the total positive charge provided by the at least two A units, provided that X m− is an anionic species exchangeable with the oxoanion in said aqueous source before said organic polymer composition contacts said oxoanion in step (i), and X m− is said oxoanion in the oxoanion-containing organic polymer.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 5, 2021
From: JANSONE-POPOVA, SANTA
To: UT-BATTELLE, LLC
Reel/Frame 056141/0802 →
CONFIRMATORY LICENSE Recorded Jan 29, 2020
From: UT-BATTELLE, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 051663/0554 →
Continuity (2)
Provisional Application 62749278 · Oct 23, 2018
Related Publication 20200122118A1 · Apr 23, 2020
Cited By (1)
US 12,662,403