Method for separation of adjacent lanthanide elements
Lanthanide complexing molecules having the following structure: wherein: R 1 , R 2 , R 4 , and R 5 are independently selected from hydrogen atom, alkyl groups containing 1-3 carbon atoms, and hydrophilic groups containing at least one oxygen atom; R 3 and R 6 are independently selected from hydrogen atom, alkyl groups containing 1-3 carbon atoms, and hydrophilic groups containing at least one oxygen atom; and R a and R b are independently selected from hydrogen atom, methyl group, halogen atoms, and hydrophilic groups containing at least one oxygen atom; wherein at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R a , and R b are said hydrophilic groups. Also described is a method of separating adjacent lanthanides by use of a two-phase extractant system that includes (i) an acidic aqueous solution containing the lanthanide complexing molecule (1) along with a mixture of at least two lanthanides, and (ii) an aqueous-insoluble hydrophobic solution containing a lipophilic lanthanide extractant compound.
1 . A lanthanide complexing molecule having the formula:
wherein:
R 1 , R 2 , R 4 , and R 5 are independently selected from hydrogen atom, alkyl groups containing 1-3 carbon atoms, and hydrophilic groups containing at least one oxygen atom; wherein optionally, R 1 and R 2 may interconnect to form a ring and/or R 4 and R 5 may interconnect to form a ring;
R 3 and R 6 are independently selected from hydrogen atom, alkyl groups containing 1-3 carbon atoms, and hydrophilic groups containing at least one oxygen atom; and
R a and R b are independently selected from hydrogen atom, methyl group, halogen atoms, and hydrophilic groups containing at least one oxygen atom;
wherein at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R a , and R b are said hydrophilic groups.
2 . The molecule of claim 1 , wherein at least four of R 1 , R 2 , R 3 , R 4 , and R 6 are said hydrophilic groups.
3 . The molecule of claim 1 , wherein said hydrophilic groups are selected from the group consisting of hydroxy-containing groups, ether-containing groups, groups containing both hydroxy and ether groups, carboxylic acid groups, sulfonic acid groups, and nitro groups.
4 . The molecule of claim 1 , wherein at least two of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 have the formula —(CH 2 CH 2 O) n —CH 2 CH 2 OH, wherein n is 0-6.
5 . The molecule of claim 4 , wherein n is 1-6.
6 . The molecule of claim 1 , wherein at least four of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 have the formula —(CH 2 CH 2 O) n —CH 2 CH 2 OH, wherein n is 0-6.
7 . The molecule of claim 6 , wherein n is 1-6.
8 . The molecule of claim 1 , wherein the molecule has the formula:
wherein:
R 1 , R 2 , R 4 , and R 5 are independently selected from hydrogen atom and hydrophilic groups containing at least one oxygen atom, wherein at least two of R 1 , R 2 , R 4 , and R 5 are said hydrophilic groups.
9 . The molecule of claim 8 , wherein at least two of R 1 , R 2 , R 4 , and R 5 have the formula —(CH 2 CH 2 O) n —CH 2 CH 2 OH, wherein n is 0-6.
10 . The molecule of claim 9 , wherein n is 1-6.
11 . The molecule of claim 8 , wherein each of R 1 , R 2 , R 4 , and R 5 has the formula —(CH 2 CH 2 O) n —CH 2 CH 2 OH, wherein n is 0-6.
12 . The molecule of claim 11 , wherein n is 1-6.
13 . A method for separating adjacent lanthanide elements, the method comprising:
(i) providing an acidified aqueous solution containing adjacent lanthanide elements complexed with a hydrophilic lanthanide complexing agent having the formula:
wherein:
R 1 , R 2 , R 4 , and R 5 are independently selected from hydrogen atom, alkyl groups containing 1-3 carbon atoms, and hydrophilic groups containing at least one oxygen atom; wherein optionally, R 1 and R 2 may interconnect to form a ring and/or R 4 and R 5 may interconnect to form a ring;
R 3 and R 6 are independently selected from hydrogen atom, alkyl groups containing 1-3 carbon atoms, and hydrophilic groups containing at least one oxygen atom; and
R a and R b are independently selected from hydrogen atom, methyl group, halogen atoms, and hydrophilic groups containing at least one oxygen atom;
wherein at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R a , and R b are said hydrophilic groups;
wherein said hydrophilic lanthanide complexing agent according to Formula (1) complexes more strongly with lighter lanthanide ions compared to heavier lanthanide ions and thereby more strongly retains lighter lanthanide ions in the acidified aqueous solution compared to heavier lanthanide ions;
(ii) contacting the acidified aqueous solution with an aqueous-insoluble hydrophobic solution comprising a lipophilic lanthanide extractant compound dissolved in an aqueous-insoluble hydrophobic solvent, wherein said lipophilic lanthanide extractant compound complexes more strongly with heavier lanthanide ions compared to lighter lanthanide ions, to result in said lipophilic lanthanide extractant compound more selectively extracting one or more heavier lanthanide ions from the acidified aqueous solution into the hydrophobic solution.
14 . The method of claim 13 , wherein the lipophilic lanthanide extractant compound has the following structure:
X-L-Y (2)
wherein:
X and Y are independently selected from —C(O)NR 2 and —P(O)R 2 , wherein R is independently selected, in each instance, from hydrocarbon groups containing 1-30 carbon atoms and optionally containing an ether or thioether linkage connecting between carbon atoms, provided that the total carbon atoms in X and Y combined is at least 12; and
L is a linker containing at least one carbon atom.
15 . The method of claim 14 , wherein the lipophilic lanthanide extractant compound has the following structure:
wherein:
R 7 , R 8 , R 9 , and R 10 are independently selected from alkyl groups containing 1-30 carbon atoms and optionally containing an ether or thioether linkage connecting between carbon atoms, provided that the total carbon atoms in R 7 , R 8 , R 9 , and R 10 is at least 12; and
R 11 and R 12 are independently selected from hydrogen atom and alkyl groups containing 1-3 carbon atoms;
wherein R 8 and R 11 optionally interconnect to form a lactam ring, and/or R 10 and R 12 optionally interconnect to form a lactam ring.
16 . The method of claim 13 , wherein at least four of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are said hydrophilic groups.
17 . The method of claim 13 , wherein said hydrophilic groups are hydroxy-containing groups, ether-containing groups, or groups containing both hydroxy and ether groups.
18 . The method of claim 13 , wherein at least two of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 have the formula —(CH 2 CH 2 O) n —CH 2 CH 2 OH, wherein n is 0-6.
19 . The method of claim 18 , wherein n is 1-6.
20 . The method of claim 13 , wherein at least four of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 have the formula —(CH 2 CH 2 O) n —CH 2 CH 2 OH, wherein n is 0-6.
21 . The molecule of claim 20 , wherein n is 1-6.
22 . The method of claim 13 , wherein the method separates adjacent lanthanide elements Ln1 and Ln2 with an Ln1/Ln2 selectivity of at least 2.
23 . The method of claim 13 , wherein the method separates adjacent lanthanide elements Ln1 and Ln2 with an Ln1/Ln2 selectivity of at least 3.
24 . The method of claim 13 , wherein the method separates Nd and Pr lanthanide elements with an Nd/Pr selectivity of at least 2.
25 . The method of claim 13 , wherein the method separates Eu and Sm lanthanide elements with an Eu/Sm selectivity of at least 2.
26 . The method of claim 13 , wherein the method separates Pm and Nd lanthanide elements with an Pm/Nd selectivity of at least 2.
27 . The method of claim 13 , wherein the method separates Sm and Pm lanthanide elements with an Sm/Pm selectivity of at least 2.