http://pubs.rsc.org/en/Content/ArticleLanding/2012/RA/c2ra20575k

Mechanochemical processing of serpentine with ammonium salts under ambient
conditions for CO2 mineralization

James Highfield, HuiQi Lim, Johan Fagerlund and Ron Zevenhoven

RSC Adv., 2012,2, 6542-6548

DOI: 10.1039/C2RA20575K

Abstract

This paper assesses the suitability of mechanochemistry as a convenient
low-energy processing option in CO2mineralization. Whereas some success has
been reported in milling alkaline earth-containing minerals under gaseous
CO2, this work focuses instead on a purely solid-state approach towards two
key objectives: (a) Mg extraction from serpentine using ammonium bisulfate;
and (b) direct or indirect CO2sequestration using ammonium bicarbonate in a
natural extension of its role as “CO2 carrier” in the chilled ammonia
scrubbing process. In Mg extraction work, dry milling of serpentine with
ammonium bisulfate gave respectable yields (>60% Mg) as boussingaultite
[(NH4)2Mg(SO4)2·6H2O] in 2 to 4 h. In CO2 sequestration, dry milling
anhydrous magnesium sulfate with ammonium bicarbonate yielded only mixed
sulfate products. Carbonation of the heptahydrate, epsomite, was found to
proceed via ammonium magnesium carbonate hydrate [(NH4)2Mg(CO3)2·4H2O],
which dissolves incongruently to yield nesquehonite [MgCO3·3H2O]. The
modest conversion (30%) is probably due to equipartition of Mg into the
double sulfate co-product. A similar route is followed in magnesia and
brucite, in which the existence of an amorphous native carbonate precursor
to nesquehonite in the same molar ratio (Mg:CO2 = 1) was inferred from
inconsistency in the XRD intensities. This was largely responsible for the
high carbonation yields in the unwashed products, 70% and 85% in MgO and
Mg(OH)2, respectively, as confirmed by TG-FTIR. The same intermediate is
probably formed in serpentine, but it is apparently soluble in the aqueous
mineral environment. When the unwashed product is subjected to mild thermal
consolidation, stable hydromagnesite [Mg5(CO3)4(OH)2·4H2O] is formed in 20%
yield after milling for 16 h. Possible identities for the amorphous
precursor are briefly considered.

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