Diglycolamide derivatives for separation and recovery of rare earth elements from aqueous solutions

Patent metadata

Field	Value
Publication number	US-2022002229-A1
Application number	US-202117366172-A
Country	US
Kind code	A1
Filing date	Jul 2, 2021
Priority date	Jul 6, 2020
Publication date	Jan 6, 2022
Grant date	—

Abstract

Rare earth extractant compounds having the following structure:

wherein R 1 , R 2 , R 3 , and R 4 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 1 , R 2 , R 3 , and R 4 is at least 12; R 5 and R 6 are independently selected from hydrogen atom and alkyl groups containing 1-3 carbon atoms; and provided that at least one of the conditions (i)-(iv) apply as follows: presence of a distal branched group in at least one of R 1 -R 4 (condition i), asymmetry in R 1 -R 4 (condition ii), presence of amine-containing ring (condition iii), or presence of lactam ring (condition iv). Also described are hydrophobic water-insoluble solutions containing at least one extractant compound of Formula (1), as well as method for extracting rare earth elements from aqueous solution by contacting the aqueous solution with the water-insoluble solution.

First claim

What is claimed is:

1 . A rare earth extractant compound having the following structure:

wherein:
R 1 , R 2 , R 3 , and R 4 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 1 , R 2 , R 3 , and R 4 is at least 12; and R 5 and R 6 are independently selected from hydrogen atom and alkyl groups containing 1-3 carbon atoms; and provided that at least one of the following conditions apply:
(i) at least one of R 1 , R 2 , R 3 , and R 4 is a distal branched alkyl group constructed of a linear alkyl backbone having at least four carbon atoms with an alpha carbon atom of the linear alkyl backbone attached to a nitrogen atom shown in Formula (1), and the linear alkyl backbone contains a substituting hydrocarbon group at a gamma carbon or higher positioned carbon on the linear alkyl backbone, wherein the substituting hydrocarbon group contains at least one carbon atom, provided that the distal branched alkyl group contains a total of up to 30 carbon atoms;
(ii) R 1 and R 2 are equivalent and R 3 and R 4 are separately equivalent, while R 1 and R 2 are different from R 3 and R 4 , or alternatively, only one of R 1 , R 2 , R 3 , and R 4 is different, to result in an asymmetrical compound of Formula (1);
(iii) R 1 and R 2 interconnect to form a first amine-containing ring, and/or R 3 and R 4 interconnect to form a second amine-containing ring, and the first and second amine-containing rings are attached to an alkyl group containing at least three carbon atoms and optionally containing an ether or thioether linkage connecting between carbon atoms; and/or
(iv) R 2 and R 5 interconnect to form a first lactam ring, and/or R 4 and R 6 interconnect to form a second lactam ring.

2 . The compound of claim 1 , wherein condition (i) applies and wherein the distal branched alkyl group contains at least one substituting hydrocarbon group located at a gamma carbon of the linear alkyl backbone.

3 . The compound of claim 1 , wherein condition (i) applies and wherein the distal branched alkyl group contains at least one substituting hydrocarbon group located at a delta carbon of the linear alkyl backbone.

4 . The compound of claim 1 , wherein condition (i) applies and wherein the distal branched alkyl group contains at least one substituting hydrocarbon group located at an epsilon carbon of the linear alkyl backbone.

5 . The compound of claim 1 , wherein condition (i) applies and wherein the distal branched alkyl group contains at least two substituting hydrocarbon groups located at gamma or higher carbon positions of the linear alkyl backbone.

6 . The compound of claim 1 , wherein condition (ii) applies and wherein R 1 and R 2 are equivalent and each contains 1-3 carbon atoms, and R 3 and R 4 are separately equivalent and each contains 4-30 carbon atoms.

7 . The compound of claim 1 , wherein condition (ii) applies and wherein R 1 and R 2 are equivalent and each contains 1-3 carbon atoms, and R 3 and R 4 are separately equivalent and each contains 6-30 carbon atoms.

8 . The compound of claim 1 , wherein condition (ii) applies and wherein R 1 and R 2 are equivalent and each contains 1-3 carbon atoms, and R 3 and R 4 are separately equivalent and each contains 8-30 carbon atoms.

9 . The compound of claim 1 , wherein condition (iii) applies and wherein said first or second amine-containing ring is a five-membered ring.

10 . The compound of claim 1 , wherein condition (iii) applies and wherein said alkyl group contains at least three carbon atoms and an ether or thioether linkage connecting between carbon atoms.

11 . The compound of claim 1 , wherein condition (iii) applies and wherein said alkyl group contains at least six carbon atoms and an ether or thioether linkage connecting between carbon atoms.

12 . The compound of claim 1 , wherein condition (iv) applies.

13 . A liquid solution useful for extracting rare earth elements from aqueous solutions, the solution comprising a rare earth extractant compound dissolved in an aqueous-insoluble hydrophobic solvent, wherein the rare earth extractant compound has the following structure:

wherein:
R 1 , R 2 , R 3 , and R 4 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 1 , R 2 , R 3 , and R 4 is at least 12; and R 5 and R 6 are independently selected from hydrogen atom and alkyl groups containing 1-3 carbon atoms; and provided that at least one of the following conditions apply:
(i) at least one of R 1 , R 2 , R 3 , and R 4 is a distal branched alkyl group constructed of a linear alkyl backbone having at least four carbon atoms with an alpha carbon atom of the linear alkyl backbone attached to a nitrogen atom shown in Formula (1), and the linear alkyl backbone contains a substituting hydrocarbon group at a gamma carbon or higher positioned carbon on the linear alkyl backbone, wherein the substituting hydrocarbon group contains at least one carbon atom, provided that the distal branched alkyl group contains a total of up to 30 carbon atoms;
(ii) R 1 and R 2 are equivalent and R 3 and R 4 are separately equivalent, while R 1 and R 2 are different from R 3 and R 4 , or alternatively, only one of R 1 , R 2 , R 3 , and R 4 is different, to result in an asymmetrical compound of Formula (1);
(iii) R 1 and R 2 interconnect to form a first amine-containing ring, and/or R 3 and R 4 interconnect to form a second amine-containing ring, and the first and second amine-containing rings are attached to an alkyl group containing at least three carbon atoms and optionally containing an ether or thioether linkage connecting between carbon atoms, wherein the total number of carbon atoms in the first or second amine-containing ring and attached alkyl group is up to 30 carbon atoms; and/or
(iv) R 2 and R 5 interconnect to form a first lactam ring, and/or R 4 and R 6 interconnect to form a second lactam ring.

14 . The liquid solution of claim 13 , wherein the aqueous-insoluble hydrophobic solvent is a hydrocarbon solvent.

15 . The liquid solution of claim 13 , wherein the liquid solution further comprises an organoamine soluble in the aqueous-insoluble hydrophobic solvent.

16 . The liquid solution of claim 15 , wherein the organoamine contains at least one hydrocarbon group containing at least four carbon atoms.

17 . The liquid solution of claim 13 , wherein the liquid solution further comprises an alcohol soluble in the aqueous-insoluble hydrophobic solvent, and wherein the alcohol contains at least six carbon atoms.

Assignees

• Ut Battelle Llc

Inventors

• Jansone-Popova Santa
• Popovs Ilja
• Moyer Bruce A

Classifications

• Y02P10/20

  Recycling · CPC title

• C01F17/17

  involving a liquid-liquid extraction · CPC title

• C22B3/282

  Aliphatic amines · CPC title

• C22B3/32

  Carboxylic acids · CPC title

• C22B59/00 Primary

  Obtaining rare earth metals · CPC title