Light Activated Cation Separation

Patent metadata

Field	Value
Publication number	US-2015122734-A1
Application number	US-201314406261-A
Country	US
Kind code	A1
Filing date	Jun 7, 2013
Priority date	Jun 8, 2012
Publication date	May 7, 2015
Grant date	—

Abstract

A method of separating one or more valuable metal cations from an ionic solution by (a) contacting the ionic solution with an activated photoisomerizable host molecule containing a photoisomerizable moiety and a host moiety, where the photoisomerizable moiety has first and second states, and where the host moiety has a greater affinity for a metal cation when the photoisomerizable moiety is in the first state (active binding state) than when the photoisomerizable moiety is in the second state (release state), so that an ion-host molecule association is formed, and (b) separating the ion-host molecule association from the ionic solution. Also disclosed are photoisomerizable host molecules, a method of recovering valuable metals from a waste stream using the photoisomerizable host molecules, and an apparatus comprising a photoisomerizable host molecule attached to a support.

First claim

What is claimed is:

1 . A method of separating one or more metal cations from an ionic solution, the method comprising the steps of:
(a) contacting said ionic solution with a photoisomerizable host molecule comprising a photoisomerizable moiety and a host moiety, wherein the photoisomerizable moiety has first and second states, and wherein the host moiety has a greater affinity for a metal cation when the photoisomerizable moiety is in the first state (active binding state) than when the photoisomerizable moiety is in the second state (release state), so that an ion-host molecule association is formed; and (b) separating said ion-host molecule association from said ionic solution.

2 . The method of claim 1 , further comprising the step of:
(c) recovering the bound metal cation from said ion-host molecule association.

3 . The method of claim 2 , further comprising the step of:
(d) recovering the photoisomerizable host molecule.

4 . The method of claim 1 , wherein said photoisomerizable host molecule has a structure selected from the group consisting of Formulae (Ia) to (Id):
A 1 -X 1 -A 2   (Ia)
A 1 -(X 1 -) n A 2   (Ib)
A 1 -((X 1 -) n A 2 ) n′   (Ic)
(A 1 -X 1 ) m -A 2 -((X 2 -) m A 3 ) n′ -(X 3 -A 4 ) m′   (Id)

wherein n and n′ are independently selected from an integer between 1 and 100, inclusive; m and m′ are independently selected from an integer between 0 and 100,000,000, inclusive; A 1 , A 2 , A 3 and A 4 are independently selected from the group consisting of host moieties that selectively bind or bond said one or more metal cations to be separated; and X 1 , X 2 , and X 3 are independently selected from the group consisting of groups that photoisomerize to or from an active binding state configuration in the presence or absence of light, as appropriate to said photoisomerizable group, in which at least one of said host moieties selectively binds or bonds said one or more metal cations.

5 . The method of claim 4 , wherein, when said photoisomerizable host molecule is in an active binding state configuration, said host moieties selectively bind or bond one or more metal cations selected from the group consisting of Group II metals, Group III metals, rare earth metals, transition metals, coinage metals, platinum group metals, metalloids, main group 13 metals, main group 14 metals, main group 15 metals, main group 16 metals and actinides.

6 . The method of claim 4 , wherein A 1 , A 2 , A 3 and A 4 are cation-binding moieties independently selected from the group consisting of macrocyclic molecules, chelating agents, complexing agents and metal organic frameworks that selectively bind said cations to be separated from said solution.

7 . The method of claim 6 , wherein A 1 , A 2 , A 3 and A 4 are macrocyclic molecules independently selected from the group consisting of crown ethers, cryptates, cryptands, and cyclodextrins.

8 . The method of claim 6 , wherein A 1 , A 2 , A 3 and A 4 are chelating agents independently selected from the group consisting of carboxylates, aminopolycarboxylates, polyalkene amines, acetoacetonates, diols, phosphonates, polyols, polyesters, and naturally occurring chelating agents.

9 . The method of claim 4 , wherein X 1 , X 2 and X 3 are independently selected from the group consisting of Formula (II):
R 1 —R 2 —B 1 ═B 2 —R 3 —R 4   (II)
wherein B 1 and B 2 are independently selected from CR or N, where R is H, lower alkyl, lower haloalkyl, halogen, lower alkoxy or lower haloalkoxy; R 1 and R 4 are independently selected from aryl or heteroaryl; and R 2 and R 3 are independently selected from a bond, O, S(O) n″ , where n″=0-2, NR, (CH 2 ) m″ , where m″=1-12, or (CH(R″)CH 2 O) m″ , where R″ is H or lower alkyl.

10 . The method of claim 9 , wherein X is —N═N—, —CH═CH—, —N═CH— or —CH═N—.

11 . The method of claim 1 , wherein said ionic solution further comprises alkali and/or alkaline earth and/or iron cations, and said host moieties have a greater binding affinity for at least one of the other cations in said solution.

12 . The method of claim 1 , wherein said photoisomerizable host molecule is covalently bonded to particles or a substrate support.

13 . The method of claim 12 , wherein said particles or substrate support comprises a metallic and/or a ceramic and/or a polymeric and/or an organic material.

14 . The method of claim 12 , wherein steps (a) and (b) are performed within a column containing said particles or support.

15 . The method of claim 1 , wherein said photoisomerizable host molecule is dissolved in, suspended in or supported by a medium that is immiscible with said ionic solution.

16 . The method of claim 15 , wherein said medium is a liquid membrane.

17 . The method of claim 15 , wherein said medium is a chromatography stationary phase.

18 . The method of claim 17 , wherein said stationary phase is an ion exchange resin.

19 . The method of claim 1 , wherein when said photoisomerizable host molecule is in said active binding state configuration, at least one host moiety selectively binds or bonds rare earth metal cations.

20 . The method of claim 19 , wherein at least one host moiety selectively binds or bonds ppm concentrations of rare earth metal cations in the presence of about 1% to about 10% by weight of other ionic species.

21 . The method of claim 20 , wherein said rare earth metal cation is scandium.

22 . The method of claim 1 , wherein when said photoisomerizable host molecule is in said active binding state configuration, at least one host moiety selectively binds or bonds ppm concentrations of transition metal cations in the presence of about 1% to about 10% by weight of other ionic species.

23 . The method of claim 1 , wherein when said photoisomerizable host molecule is in said active binding state configuration, at least one host moiety selectively binds or bonds ppm concentrations of actinide cations in the presence of about 1% to about 10% by weight of other ionic species.

24 . The method of claim 1 , wherein when said photoisomerizable host molecule is in said active binding state configuration, at least one host moiety selectively binds or bonds ppm concentrations of coinage metal cations in the presence of about 1% to about 10% by weight of other ionic species.

25 . The method of claim 1 , wherein when said photoisomerizable host molecule is in said active binding state configuration, at least one host moiety selectively binds or bonds ppm concentrations of platinum group metal cations in the presence of about 1% to about 10% by weight of other ionic species.

26 . The method of claim 9 , wherein R 1 and R 4 are phenyl, R 2 and R 3 are each a bond, and B 1 and B 2 are nitrogen.

27 . The method of claim 9 , wherein R 1 and R 4 are phenyl, R 2 and R 3 are each a bond, and B 1 and B 2 are CH.

28 . The method of claim 4 , wherein at least two host moieties are selected from the group consisting of [1.1.1]cryptand and [2.1.1]cryptand.

29 . The method of claim 28 , wherein at least two host moieties are selected from the group consisting of [3.3.2]cryptand and [3.3.3]cryptand.

30 . The method of claim 28 , wherein at least two host moieties are selected from the group consisting of cyclen and EDTA.

31 . The method of clai

Assignees

• Univ Rutgers

Inventors

• Riman Richard E
• Porter Brook

Classifications

• C02F1/42 Primary

  by ion-exchange (ion-exchange in general B01J) · CPC title

• C02F2001/425

  using cation exchangers · CPC title

• C22B3/0005 Primary

  Chemistry & Metallurgy · mapped topic

• C07D323/00 Primary

  Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms · CPC title

• C22B3/42

  by ion-exchange extraction · CPC title