Ae. Gash et al., EFFICIENT RECOVERY OF ELEMENTAL MERCURY FROM HG(II)-CONTAMINATED AQUEOUS-MEDIA USING A REDOX-RECYCLABLE ION-EXCHANGE MATERIAL, Environmental science & technology, 32(7), 1998, pp. 1007-1012
The use of lithium-intercalated transition metal dichalcogenides, LixE
S2, as redox-recyclable ion-exchange materials for the extraction of t
he aqueous heavy metal ions Hg2+, Pb2+, Cd2+ and Zn2+ was investigated
(0.25 less than or equal to x less than or equal to 1.9, E = Mo, W, T
i, Ta). For LixTiS2 and LixTaS2, hydrolysis produced S2-(aq) ions, whi
ch precipitated Hg(II) as HgS(s). In contrast, the materials LixMoS2 a
nd LixWS2 did not undergo hydrolysis to form S2- ions. Instead, ion-ex
changed materials such as Hg0.50MoS2 and Pb0.15MoS2 were isolated. The
selectivity of LixMoS2 for the heavy metal ions was Hg2+, Pb2+ > Cd2 > Zn2+. The affinities for the latter three ions but not for Hg2+ inc
reased when the extractions were performed under anaerobic conditions.
When HgyMoS2 was heated under vacuum at 425 degrees C, an entropy-dri
ven internal redox reaction resulted in deactivation of the extractant
, producing essentially mercury-free MoS2 and a near-quantitative amou
nt of mercury vapor (collected in a cold trap). The ratio of the volum
e of metallic mercury (secondary waste) to the volume of 10.0 mM Hg2+(
aq) (primary waste) was 1.5 x 10(-4). Samples of MoS2 produced by heat
ing HgyMoS2 were reactivated to LixMoS2 by treatment with n-butyllithi
um. Some samples were used for three cycles of extraction, deactivatio
n/recovery, and reactivation with a primary waste simulant consisting
of 10 mM Hg2+(aq) in 0.1 M HNO3 with no loss in ion-exchange capacity.
When the Mo/Hg molar ratio was 5.0 and the initial [Hg2+(aq)] = 1 mM,
only 0.033(2) mu M mercury (6.5 ppb) was detected in the filtrate aft
er the extraction step. The highest observed capacity of LixMoS2 for H
g2+(aq) was 580 mg of mercury/g of Li1.9MoS2.