Coal byproducts could be a promising
feedstock to alleviate the
supply risk of critical rare earth elements (REEs) due to their abundance
and REE content. Herein, we investigated the economic and environmental
potential of producing REEs from coal fly ash and lignite through
an integrated process of leaching, biosorption, and oxalic precipitation
on the basis of experimental data and modeling results. Two microbe
immobilization systems (polyethylene glycol diacrylate (PEGDA) microbe
beads and Si sol–gels) were examined for their efficiency in
immobilizing Arthrobacter nicotianae to selectively recover REEs. Techno-economic analysis revealed that
North Dakota lignite could be a profitable feedstock when Si sol–gel
is used due to its high cell loading and REE adsorption capacity as
well as high reuse cycles. Life cycle analysis revealed that Si sol–gel-based
biosorption could be more environmental friendly than the prevailing
REE production in China due to the use of less toxic chemicals. However,
fly ash sourced from Powder River Basin coals was neither profitable
nor environmentally sustainable, primarily due to low solubility of
high-value scandium at an economical pulp density (100 g ash/L of
acid solution). To further improve the proposed biotechnology, future
research could focus on scandium recovery, leaching efficiency at
a high pulp density, and reuse cycles of the immobilized microbes.
Low-grade residuals such as mine
wastes and combustion ash are
potential sources of critical metals such as rare-earth elements (REEs).
Major challenges in the efficient recovery of REEs are the matrix
interferences in the waste extracts that impede subsequent purification
steps. This study evaluated feedstock matrix variables such as aqueous
aluminum (Al), iron (Fe), and pH for their impact on neodymium (Nd)
and erbium (Er) recovery flux by supported liquid membrane (SLM) separations,
a type of liquid–liquid extraction method. We initially hypothesized
that REE mass transfer would be lower at low [REE]/[Fe] and [REE]/[Al]
molar ratios due to increased competition for chelation sites at the
membrane interface. However, the results showed that the absolute
Fe and Al concentrations, not the molar ratios, controlled Nd and
Er mass transfer. The permeability coefficients of Nd and Er were
most sensitive to the feedstock concentration of Fe3+ relative
to Al3+ and Fe2+. The threshold Fe3+ concentration that resulted in reduced Nd and Er permeability was
more than 100 times lower than the concentrations required for Al
or Fe2+ to decrease REE permeability. REE recovery rates
also increased with increasing pH of the feedstock. Separations performed
with excess Fe3+ did not result in observable fouling at
the membrane interface. Instead, the pH gradient across the membrane
and the relative cation affinity for the chelator were the major drivers
of mass transfer. These results provide insights for predicting REE
mass transfer rates and SLM separation performance for extractions
of low-grade feedstocks.
Scandium (Sc) has great potential
for use in aerospace and clean
energy applications, but its supply is currently limited by a lack
of commercially viable deposits and the environmental burden of its
production. In this work, a biosorption-based flow-through process
was developed for extraction of Sc from low-grade feedstocks. A microbe-encapsulated
silica gel (MESG) biosorbent was synthesized through sol–gel
encapsulation of Arthrobacter nicotianae, a bacterium that selectively adsorbs Sc. Microscopic imaging revealed
a high cell loading and macroporous structure, which enabled rapid
mass transport and adsorption/desorption of metal ions. The biosorbent
displayed high Sc selectivity against lanthanides and major base metals,
with the exception of Fe(III). Following pH adjustment to remove Fe(III)
from an acid leachate prepared from lignite coal, a packed-bed column
loaded with the MESG biosorbent exhibited near-complete Sc separation
from lanthanides; the column eluate had a Sc enrichment factor of
10.9, with Sc constituting 96.4% of the total rare earth elements.
The MESG biosorbent exhibited no significant degradation with regard
to both adsorption capacity and physical structure after 10 adsorption/desorption
cycles. Overall, our results suggest that the MESG biosorbent offers
an effective and green alternative to conventional liquid–liquid
extraction for Sc recovery.
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