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Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal recovery from aqueous solutions

United States Patent

5,834,525
November 10, 1998
View the Complete Patent at the US Patent & Trademark Office
Lawrence Berkeley National Laboratory - Visit the Technology Transfer and Intellectual Property Management Department Website
The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe.sup.3+ ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+, Mg.sup.2+, Al.sup.3+, and Cr.sup.3+ ions at pH 1-3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe.sup.3+ (for example, Hg.sup.2+ at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe.sup.3+ Al.sup.3+ ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads used determined are useful as well as equilibrium selectivity coefficient (K.sub.m) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe.sup.3+ ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2,6-LICAMS series of polymer pendant ligands are more selective to divalent metal ions Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+, and Mg.sup.2+, than either PS-CATS or PS-3,3-LICAMS. However, Fe.sup.3+ ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe.sup.3+, the polymer ligand is selective for Al.sup.3+, Cu.sup.2+ or Hg.sup.2+. The changing of the cavity size from two CH.sub.2 groups to six CH.sub.2 groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion selectivity.
Fish; Richard H. (Berkeley, CA)
The Regents of the University of California (Oakland, CA)
08/ 839,359
April 17, 1997
ORIGIN OF THE INVENTION This invention was supported by the U.S. Department of Energy, Contract no. DE-AC03-76SF00098. The Government has certain rights in this invention.