Method of removing a metal ion from a water stream using organo-ceramic composite materials
The present invention relates to an organo-ceramic composite material useful for the extraction of metal ions from solution. The organo-ceramic composite material is formed according to a sol gel synthesis scheme by reacting a functional precursor silane and its homopolymers with either (i) a mixture of a cross-linking silane and its homopolymers or (ii) the cross-linking silane, under conditions effective to yield the composite material of the present invention. Further aspects of the present invention relate to methods of removing a metal ion from a water stream and recovering a metal ion from a water stream, both of which include contacting a water stream containing a metal ion with an organo-ceramic composite material of the present invention under conditions effective to remove the metal ion from the water stream.
1. A method of removing a metal ion from a water Stream comprising:
(i) providing a copolymer of formula (I)
wherein R 1 is independently H, an alkyl group having from 1 to 5 carbon atoms,
R 2 is independently H or an alkyl group having from 1 to 5 carbon atoms,
R 3 is independently R 2 ,
R 4 is a functional group with metal ion adsorption activity that has the structure
wherein a is an integer from 1 to 5 and X is
with W being sulfur or oxygen, and G being hydrogen or an alkyl group having from 1 to 5 carbon atoms,
or the structure
wherein b is an integer from 0 to 5, c is an integer from 1 to 5, and Y′ and Y″ are different and each is NH 2 or OH,
R 5 is independently R 2 or
n is an integer greater than 10 and m is an integer greater than 1, and
wherein the copolymer is characterized by clustering of the functional groups having adsorption activity as dimers, trimers, or higher oligomers integrated into the copolymer; and
(ii) contacting a water stream containing a metal ion with the copolymer under conditions effective to remove the metal ion from the water stream.
2. The method according to claim 1 , wherein the metal ion is selected from the group of heavy metal ions, rare earth metal ions, platinum group metal ions, and noble metal ions.
3. The method according to claim 2 , wherein the metal ion is a rare earth metal ion selected from the group of cerium, neodymium, and praseodymium.
4. The method according to claim 2 , wherein the metal ion is a noble metal ion selected from the group of silver and gold.
5. The method according to claim 2 , wherein the metal ion is a platinum group metal ion selected from the group of palladium, platinum, rhodium, ruthenium, osmium, iridium.
6. The method according to claim 2 , wherein metal ion is a heavy metal ion selected from the group of antimony, arsenic, beryllium, cadmium, chromium, copper, lead, mercury, selenium, thallium, tin, zinc, molybdenum, cobalt, technetium, rhenium, cesium, and strontium.
7. The method according to claim 1 , wherein the water stream comprises two or more metal ions and said contacting is carried out under conditions effective to remove the two or more metal ions from the water stream.
8. The method according to claim 7 , wherein said contacting is carried out under conditions effective to remove the two or more metal ions from the water stream exclusive of another metal ion in the water stream.
9. The method according to claim 8 , wherein the two or more metal ions are noble metal ions or platinum group metal ions.
10. The method according to claim 9 , wherein the functional group is
wherein a is an integer from 1 to 5 and
X is either
11. The method according to claim 1 , wherein the functional group is
wherein a is an integer from 1 to 5 and
X is
with W being sulfur or oxygen, and G being hydrogen or an alkyl group having from 1 to 5 carbon atoms.
12. The method according to claim 1 , wherein the copolymer comprises a plurality of pores having an average pore size of about 5 Å to about 200 Å.
13. The method according to claim 1 , wherein the copolymer has a functional group density of about 0.1 mmol/g to about 10 mmol/g.
14. The method according to claim 1 , wherein the copolymer is present in the form of a plurality of granules having an average particle diameter of about 10 μm to about 500 μm.
15. The method according to claim 1 , further comprising:
introducing the copolymer into a packed bed or a fluidized bed, wherein said contacting occurs in the packed bed or the fluidized bed.
16. The method according to claim 1 , wherein the functional group is
wherein b is an integer from 0 to 5, c is an integer from 1 to 5, and Y′ and Y″ are different and each is NH 2 or OH.
17. A method of recovering a metal ion from a water stream comprising:
(i) providing a copolymer of formula (I)
wherein R 1 is independently H, an alkyl group having from 1 to 5 carbon atoms,
R 2 is independently H or an alkyl group having from 1 to 5 carbon atoms,
R 3 is independently R 2 ,
R 4 is a functional group with metal ion adsorption activity that has the structure
wherein a is an integer from 1 to 5 and X is
with W being sulfur or oxygen, and G being hydrogen or an alkyl group having from 1 to 5 carbon atoms,
or the structure
wherein b is an integer from 0 to 5, c is an integer from 1 to 5, and Y′ and Y″ are different and each is NH 2 or OH,
R 5 independently R 2 or
n is an integer greater than 10 and m is an integer greater than 1, and
wherein the copolymer is characterized by clustering of the functional groups having adsorption activity as dimers, trimers, or higher oligomers integrated into copolymer;
(ii) contacting a water stream containing a metal ion with the copolymer under conditions effective for the copolymer to adsorb the metal ion from the water stream;
(iii) stripping the adsorbed metal ion from the copolymer under conditions effective to yield a concentrate of the metal ion; and
(iv) recovering the metal ion from the concentrate.
18. The method according to claim 17 , wherein the metal ion is selected from the group of heavy metal ions, rare earth metal ions, platinum group metal ions, and noble metal ions.
19. The method according to claim 18 , wherein the metal ion is a rare earth metal ion selected from the group of cerium, neodymium, and praseodymium.
20. The method according to claim 18 , wherein the metal ion is a noble metal ion selected from the group of silver and gold.
21. The method according to claim 18 , wherein the metal ion is a platinum group metal ion selected from the group of palladium, platinum, rhodium, ruthenium, osmium, iridium.
22. The method according to claim 18 , wherein the metal ion is a heavy metal ion selected from the group of antimony, arsenic, beryllium, cadmium, chromium, copper, lead, mercury, selenium, thallium, tin, zinc, molybdenum, cobalt, technetium, rhenium, cesium, and strontium.
23. The method according to claim 17 , wherein the water stream comprises two or more metal ions and said contacting is carried out under conditions effective to remove the two or more metal ions from the water stream.
24. The method according to claim 23 , wherein said contacting is carried out under conditions effective to remove the two or more metal ions from the water stream exclusive of another metal ion in the water stream.
25. The method according to claim 24 , wherein the two or more metal ions are noble metal ions or platinum group metal ions.
26. The method according to claim 25 , wherein the functional group is
wherein a is an integer from 1 to 5 and
X is either
27. The method according to claim 17 , wherein the functional group is
wherein a is an integer from 1 to 5 and
X is
with W being sulfur or oxygen, and G being hydrogen or an alkyl group having from 1 to 5 carbon atoms.
28. The method according to claim 17 , wherein the copolymer comprises a plurality of pores having an average pore size of about 5 Å to about 200 Å.
29. The method according to claim 17 , wherein the copolymer has a functional group density of about 0.1 mmol/g to about 10 mmol/g.
30. The method according to claim 17 , wherein the copolymer is present in the form of a plurality of granules having an average particle diameter of about 10 μm to about 500 μm.
31. The method according to claim 17 , further comprising:
introducing the copolymer into a packed bed or a fluidized bed, wherein said contacting occurs in the packed bed or the fluidized bed.
32. The method according to claim 17 , wherein said stripping comprises passing a stripping agent over the copolymer.
33. The method according to claim 17 , wherein said recovering comprises subjecting the concentrate to electrolysis under conditions effective to recover the metal ion.
34. The method according to claim 17 , wherein said recovering comprises precipitating from the concentrate an insoluble or weakly soluble salt of the metal.
35. The method according to claim 17 , wherein the functional group is
wherein b is an integer from 0 to 5, c is an integer from 1 to 5, and Y′ and Y″ are different and each is NH 2 or OH.