Organic polymer compositions for removal of oxoanions from aqueous solutions

Patent metadata

Field	Value
Publication number	US-11369944-B2
Application number	US-201916660142-A
Country	US
Kind code	B2
Filing date	Oct 22, 2019
Priority date	Oct 23, 2018
Publication date	Jun 28, 2022
Grant date	Jun 28, 2022

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 Xm− with a magnitude of charge m of at least 1, wherein the sum of negative charge provided by anionic species Xm− 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.

First claim

What is claimed is:

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 ast

Assignees

• Ut Battelle Llc

Inventors

• Jansone-Popova Santa

Classifications

• B01J20/3425

  of sorbents or filter aids comprising organic materials · CPC title

• B01J41/04 Primary

  Processes using organic exchangers · CPC title

• C02F2101/22

  Chromium or chromium compounds, e.g. chromates · CPC title

• B01J20/262 Primary

  obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation (macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G) · CPC title

• C02F2101/101

  Sulfur compounds · CPC title