Recycling of lead- and tin-based materials

Patent metadata

Field	Value
Publication number	US-11427478-B2
Application number	US-201917265113-A
Country	US
Kind code	B2
Filing date	Aug 2, 2019
Priority date	Aug 3, 2018
Publication date	Aug 30, 2022
Grant date	Aug 30, 2022

Abstract

This invention relates to a process for obtaining lead (Pb) and/or tin (Sn) from a lead- and/or tin-based material using a deep eutectic solvent.

First claim

The invention claimed is:

1. A method comprising:
combining a lead- or tin-based material, or a mixture thereof, and a compound comprising a carboxylic acid moiety in the presence of a deep eutectic solvent; and
precipitating lead or tin carboxylate;
wherein the lead-based material comprises Pb, PbO, PbO 2 , PbSO 4 , PbCO 3 , (PbCO 3 ) 2 .Pb(OH) 2 , PbTe, or APbX 3 , or a mixture thereof, wherein A is CH 3 NH 3 or HC(NH 2 ) 2 and each X is independently I, Br or Cl; and
wherein the tin-based material comprises ASnX 3 , wherein A is CH 3 NH 3 or HC(NH 2 ) 2 and each X is independently I, Br or Cl.

2. The method of claim 1 comprising:
combining a lead- or tin-based material, or a mixture thereof, with a deep eutectic solvent;
adding a compound comprising a carboxylic acid moiety; and
precipitating lead or tin carboxylate;
wherein the lead-based material comprises Pb, PbO, PbO 2 , PbSO 4 , PbCO 3 , (PbCO 3 ) 2 .Pb(OH) 2 , PbTe, or APbX 3 , or a mixture thereof, wherein A is CH 3 NH 3 or HC(NH 2 ) 2 and each X is independently I, Br or Cl; and
wherein the tin-based material comprises ASnX 3 , wherein A is CH 3 NH 3 or HC(NH 2 ) 2 and each X is independently I, Br or Cl.

3. The method of claim 1 comprising:
combining a lead- or tin-based material, or a mixture thereof, with a deep eutectic solvent comprising a compound comprising a carboxylic acid moiety; and
precipitating lead and/or tin carboxylate;
wherein the lead-based material comprises Pb, PbO, PbO 2 , PbSO 4 , PbCO 3 , (PbCO 3 ) 2 .Pb(OH) 2 , PbTe, or APbX 3 , or a mixture thereof, wherein A is CH 3 NH 3 or HC(NH 2 ) 2 and each X is independently I, Br or Cl; and
wherein the tin-based material comprises ASnX 3 , wherein A is CH 3 NH 3 or HC(NH 2 ) 2 and each X is independently I, Br or Cl.

4. The method of claim 1 , wherein the compound comprising a carboxylic acid moiety is a compound of formula:

wherein R is H or a straight or branched C 1-6 alkyl, substituted with 0-4 substituents selected from OH or COOH.

5. The method of claim 1 , wherein the compound comprising a carboxylic acid moiety is a compound comprising at least two carboxylic acid moieties, or a compound of formula:

wherein R′ is a straight or branched C 1-6 alkyl, substituted with 0-3 substituents selected from OH or COOH.

6. The method of claim 1 , wherein the compound comprising a carboxylic acid moiety is acetic acid, oxalic acid or citric acid or a mixture thereof.

7. The method of claim 1 , wherein the deep eutectic solvent comprises a hydrogen bond donor and an ammonium salt or a metal chloride hydrate and a hydrogen bond donor.

8. The method of claim 7 , wherein (a) the hydrogen bond donor is ethylene glycol, glycerol, propylene glycol, fructose, xylitol, erythritol, 1,6-hexanediol, urea, acetamide, 1-methyl urea, 1,3-dimethyl urea, 1,1-dimethyl urea, thiourea, benzamide, oxalic acid, malonic acid, benzoic acid, adipic acid, succinic acid, citric acid or water; (b) the ammonium salt is choline chloride; and/or (c) the metal chloride hydrate is lithium chloride, sodium chloride, aluminium trichloride, tin chloride or zinc chloride.

9. The method of claim 1 , wherein the deep eutectic solvent is selected from:
a) a mixture of choline chloride and urea, wherein the molar ratio is about 4:1 to 1:6;
b) a mixture of choline chloride and ethylene glycol, wherein the molar ratio is about 5:1 to 1:20;
c) a mixture of choline chloride and propylene glycol, wherein the molar ratio is about 5:1 to 1:20;
d) a mixture of choline chloride and butanediol, wherein the molar ratio is about 5:1 to 1:20;
e) a mixture of choline chloride and glycerol, wherein the molar ratio is about 5:1 to 1:20;
f) a mixture of choline chloride and acetic acid, wherein the molar ratio is about 5:1 to 1:10;
g) a mixture of choline chloride and malonic acid, wherein the molar ratio is about 4:1 to 1:6;
h) a mixture of oxalic acid and choline chloride, wherein the molar ratio is about 2:1 to 1:2;
i) a mixture of choline chloride and glucose, wherein the molar ratio is about 6:1 to 1:6;
j) a mixture of choline chloride and fructose, wherein the molar ratio is about 6:1 to 1:6;
k) a mixture of choline chloride and xylitol, wherein the molar ratio about 6:1 to 1:6;
l) a mixture of choline chloride and erythritol, wherein the molar ratio is about 6:1 to 1:6;
m) a mixture of lithium chloride and ethylene glycol, wherein the molar ratio is about 4:1 to 1:4;
n) a mixture of sodium chloride and ethylene glycol, preferably wherein the molar ratio is about 4:1 to 1:4;
o) a mixture of lithium chloride and water, wherein the molar ratio is about 4:1 to 1:4;
p) a mixture of aluminium trichloride and acetamide, wherein the molar ratio is about 4:1 to 1:4;
q) a mixture of aluminium trichloride and urea, wherein the molar ratio is about 4:1 to 1:4; or
r) a mixture of tin chloride dihydrate and ethylene glycol, wherein the molar ratio is about 4:1 to 1:4.

10. The method of claim 1 , wherein the deep eutectic solvent comprises oxalic acid and choline chloride or ethylene glycol and choline chloride.

11. The method of claim 1 , wherein the deep eutectic solvent is a natural deep eutectic solvent comprising: an acid and quaternary ammonium salt; an acid and betaine an acid and an amino acid; an acid and a sugar, wherein the acid, amino acid, sugar and quaternary ammonium salt are selected from the group consisting of choline chloride, choline bitartrate, betaine, lactic acid, DL-malic acid, citric acid, phytic acid sodium, D/L-proline, D-proline, L-proline, L-serine, L-glutamic salt, D-(+)-glucose, D-(−)-fructose, -alanine, malonic acid, maleic acid, aconitic acid, L-(+)-tartaric acid, glycol, 1,2-propanediol, glycerol, meso-erythritol, xylitol, adonitol, ribitol, D-sorbitol, D-xylose, A-L-rhamnose, sorbose, D-mannose, D-(+)-galactose, sucrose, D-(+)-trehalose, maltose, raffinose, proline, oxalic acid, lactose, inositol, and proline.

12. The method of claim 1 , wherein the deep eutectic solvent is a natural deep eutectic solvent selected from the group consisting of choline chloride, choline bitartrate, betaine, lactic acid, DL-malic acid, citric acid, phytic acid sodium, D/L-proline, D-proline, L-proline, L-serine, L-glutamic salt, D-(+)-glucose, D-(−)-fructose, -alanine, malonic acid, maleic acid, aconitic acid, L-(+)-tartaric acid, glycol, 1 , 2 -propanediol, glycerol, meso-erythritol, xylitol, adonitol, ribitol, D-sorbitol, D-xylose, A-L-rhamnose, sorbose, D-mannose, D-(+)-galactose, sucrose, D-(+)-trehalose, maltose, raffinose, proline, oxalic acid, lactose, inositol, and proline.

13. The method of claim 1 wherein the lead-based material is a de-sulfurised lead-based material.

14. The method of claim 1 , wherein the lead-based material comprises Pb, PbO, PbO 2 , PbCO 3 , or (PbCO 3 ) 2 .Pb(OH) 2 , or a mixture thereof.

15. The method of claim 1 , wherein a concentration of lead- and/or tin-based material of about 1 gL −1 to about 100 gL −1 is dissolved in the deep eutectic solvent.

16. The method of claim 1 , wherein a concentration of lead- and/or tin-based material of about 0.005 mol L −1 to about 0.5 mol L −1 is dissolved in the deep eutectic solvent.

17. The method of claim 1 , further comprising the step of filtering the precipitated lead and/or tin carboxylate.

18. The method of claim 17 , further c

Assignees

• Imperial College Innovations Ltd

Inventors

• Hekselman Aleksandra Katarzyna
• Payne David
• Wang Yanying
• Ballantyne Andrew

Classifications

• C22B25/06

  from scrap, especially tin scrap (by electrolytic procedure C25C1/14) · CPC title

• C22B13/045 Primary

  Recovery from waste materials · CPC title

• C22B7/006

  Wet processes · CPC title

• C22B3/44

  by chemical processes (treatment or purification of solutions by liquid-liquid extraction C22B3/26, by ion-exchange extraction C22B3/42) · CPC title

• C01G21/02 Primary

  Oxides · CPC title