Metal-supported anion exchange resins and method of remediating toxic anions using the same

Patent metadata

Field	Value
Publication number	US-9844776-B2
Application number	US-201514664640-A
Country	US
Kind code	B2
Filing date	Mar 20, 2015
Priority date	Mar 20, 2014
Publication date	Dec 19, 2017
Grant date	Dec 19, 2017

Abstract

Provided are a method of removing a perchlorate ion (ClO 4 − ) and a nitrate ion (NO 3 − ) which are toxic anions in wastewater using an anion-exchange resin on which a metal is supported, and more particularly an anion-exchange resin on which a hydrogen activating metal is supported or a hydrogen activating metal and a secondary metal are supported together and a method of removing toxic anions using the same. The toxic anions may be efficiently ion-exchanged and removed using an anion-exchange resin supporting a reduction catalyst, the regeneration of the anion-exchange resin may be facilitated, and the consumption of energy and the reducing agent may be reduced, thereby being usable in removal of toxic anions from an actual water purification system.

First claim

What is claimed is:

1. An anion-exchange resin on which a hydrogen activating metal, or a hydrogen activating metal and a secondary metal is supported, in form of M/IX-L or M-S/IX-L, wherein M is a hydrogen activating metal; IX is an anion-exchange resin; L is a reducing agent which reduces a hydrogen activating metal supported on the anion-exchange resin; and S is a secondary metal belonging to non-noble metal.

2. The anion-exchange resin of claim 1 , wherein the hydrogen activating metal (M) is one or more selected from the group consisting of Groups IB, VIIB and VIII metals.

3. The anion-exchange resin of claim 2 , wherein the hydrogen activating metal (M) is one or more selected from the group consisting of Pd, Rh, Ir and Pt.

4. The anion-exchange resin of claim 1 , wherein the secondary metal (S) is one or more selected from the group consisting of Ag, Fe, Hg, Ni, Cu, Zn, Sn and In.

5. The anion-exchange resin of claim 1 , wherein the reducing agent (L) is a hydride or alcohol.

6. The anion-exchange resin of claim 5 , wherein the hydride is one or more selected from the group consisting of hydrogen gas, carbon monoxide, sodium borohydride and sodium citrate.

7. The anion-exchange resin of claim 1 , wherein the alcohol is one or more selected from the group consisting of methanol, ethanol, ethylene glycol and glycerol.

8. The anion-exchange resin of claim 1 , wherein an ion-exchange group having an ion exchange function is stably bonded to a parent polymer having a three-dimensional structure by a covalent bond, so as to be evenly fixed and distributed on a resin surface.

9. The anion-exchange resin of claim 1 , wherein the hydrogen activating metal is in a ratio of 0.01 to 50 wt %.

10. The anion-exchange resin of claim 8 , wherein the parent polymer of the anion-exchange resin corresponds to a parent body to introduce a hybrid polymer or an ion exchange group therein.

11. The anion-exchange resin of claim 10 , wherein the hybrid polymer is acryl and styrene, or styrene and divinylbenzene.

12. The anion-exchange resin of claim 8 , wherein an ion-exchange material to be introduced to a parent body of the anion-exchange resin is one or more selected from the group consisting of weak basic groups including a primary amine group, a secondary amine group and a tertiary amine group, and a strong basic groups including a quaternary ammonium group.

13. A method of preparing an anion-exchange resin on which a hydrogen activating metal, or a hydrogen activating metal and a secondary metal is supported, the method comprising:
(a) exchanging a negatively charged hydrogen activating metal precursor or a hydrogen activating metal precursor and a secondary metal precursor with an anion present in an anion-exchange resin, thereby supporting the metal on the anion-exchange resin; and
(b) reducing the hydrogen activating metal or the hydrogen activating metal and the secondary metal supported on the anion-exchange resin using a reducing agent.

14. The method of preparing an anion-exchange resin of claim 13 , an anion present in the anion-exchange resin is a chloride ion (Cl − ) or a hydroxide ion (OH − ).

15. The method of preparing an anion-exchange resin of claim 13 , wherein the reducing agent (L) is hydride or alcohol.

16. The method of preparing an anion-exchange resin of claim 15 , wherein the hydride is one or more selected from the group consisting of hydrogen gas, carbon monoxide, sodium borohydride and sodium citrate.

17. The method of preparing an anion-exchange resin of claim 13 , wherein the alcohol is one or more selected from the group consisting of methanol, ethanol, ethylene glycol and glycerol.

18. The method of preparing an anion-exchange resin of claim 13 , further comprising after the step (a), a step of placing the anion-exchange resin on which the hydrogen activating metal is supported in a solution containing NaOH or KOH, and stirring the solution.

19. The method of preparing an anion-exchange resin of claim 13 , wherein in the step (b), organic polymerizates or an oligomer material which is a metal stabilizing material, is further added.

20. The method of preparing an anion-exchange resin of claim 19 , the organic polymerizates is one or more selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl ether and cyclodextrine.

21. The method of preparing an anion-exchange resin of claim 19 , a concentration of the metal stabilizing material is 0.1-100 equivalent to the supported metal concentration.

22. The method of preparing an anion-exchange resin of claim 13 , the step (b) is carried out at 20 to 150° C.

23. The method of preparing an anion-exchange resin of claim 13 , the hydrogen activating metal is one or more metals selected from the group consisting of Groups IB, VIIB and VIII metals.

24. The method of preparing an anion-exchange resin of claim 13 , wherein the hydrogen activating metal is one or more selected from the group consisting of Pd, Rh, Ir and Pt.

25. The method of preparing an anion-exchange resin of claim 13 , wherein the secondary metal is one or more selected from the group consisting of Ag, Fe, Hg, Ni, Cu, Zn, Sn and In.

26. A method of removing toxic anions, the method comprising:
(a) carrying out ion-exchange of toxic anions using the anion-exchange resin according to claim 1 ; and
(b) reducing the anion-exchange resin using a reducing agent, when the anion exchange capacity of the anion-exchange resin on which the hydrogen activating metal is supported is saturated.

27. The method of removing toxic anions of claim 26 , wherein the steps (a) and (b) is repetitively carried out, using the anion-exchange resin on which the hydrogen activating metal is supported, reduced in the step (b).

28. The method of removing toxic anions of claim 26 , wherein the toxic anion is a perchlorate ion (ClO 4 −) or a nitrate ion (NO 3 −).

29. The method of removing toxic anions of claim 26 , wherein the toxic anion further comprises one or more oxyanion selected from the group consisting of NO 3 −, NO 2 −, BrO 3 −, ClO 3 − and ClO 4 −.

30. The method of removing toxic anions of claim 26 , being carried out with batch-type or in a column-type.

31. The method of removing toxic anions of claim 26 , wherein the reducing agent in the step (b) is a hydrogen gas or formic acid.

32. The method of removing toxic anions of claim 26 , wherein the reducing agent further comprises an acidic material selected from the group consisting of CO 2 , HCOOH and CH 3 COOH.

33. The method of removing toxic anions of claim 26 , wherein the step (b) is carried out at 20 to 150° C.

34. The method of removing toxic anions of claim 26 , wherein the step (b) is carried out under a dry or wet condition.

35. The method of removing toxic anions of claim 34 , wherein a solvent under the wet condition is one or more selected from the group consisting of water, methanol, ethanol and a solvent having lower polarity or lower dielectric constant than water.

Assignees

• Korea Advanced Inst Sci & Tech

Inventors

• Choi Minkee
• Kim You-Na

Classifications

• B01J41/08

  Use of material as anion exchangers; Treatment of material for improving the anion exchange properties · CPC title

• B01J41/12 Primary

  Macromolecular compounds · CPC title

• C02F2101/163

  Nitrates · CPC title

• C08J5/20

  Manufacture of shaped structures of ion-exchange resins · CPC title

• B01J23/72

  Copper · CPC title