3420 XXXI International Mineral Processing Congress 2024 Proceedings/Washington, DC/Sep 29–Oct 3
HPMSM production. Records showed that in 2021, 92.5%
of HPMSM used in battery industry came from Mn ore
processing and balance amount by HPEMM dissolution in
H2SO4 acid (Jephcott, 2023). The former option requires
beneficiation, reduction (for oxide ores), leaching, impu-
rity removal from leachate and crystallisation steps to pro-
duce HPMSM. The process route relies on the mineralogy
and quality of the ore being processed. The latter option is
expensive as raw material price is high due to electrowin-
ning process and HPEMM price is fluctuating frequently.
Currently China dominates the HPMSM production for
battery use with a 91% market share in 2021 (Jephcott,
2023).
The demand for Mn in LIB battery industry in 2021
was 2% and it is expected to grow up to 10% in 2040.
Currently two types of LIBs use HPMSM in the cathode,
NMC (Nickle-Manganese-Cobalt) and LNMO (lithium-
Nickle-Manganese Oxide). NMC is the market dominator
holding 44% of the rechargeable battery market and esti-
mated to reach 47%–50% in 2035 (Jephcott, 2023).
A rigorous PLS purification route is required to meet
the final product specifications of HPMSM. Precipitation
and solvent extraction are promising methods to purify
Mn solutions. Precipitation of metals as their respective
hydroxides is widely used in hydrometallurgical processes
(Monhemius, 1977). As illustrated in Figure 1, differ-
ent metals precipitates at different pH values, thus this
method is useful for the separation of metals. It is obvi-
ous that Fe, Al, Pb and Zn can be separated from Mn
but separation from Ni, Co and Mg is hard. Therefore, in
most cases, hydroxide precipitation itself is insufficient for
PLS purification. Solvent extraction plays a vital role in
impurity removal from Mn solutions (Zhang and Cheng,
2007). Few different types of extractants are mainly used
for Mn recovery. Phosphoric acid based extractants such
as D2EHPA are widely used. Moreover, phosphonic acid
extractants and phosphinic acid extractants such as Cyanex
272 are used for Mn separation from Ca and Mg. As shown
in Figure 2, the separation is pH dependant. A comparison
of Cyanex 272 and D2EHPA was performed by Pakarinen
and Paatero (2011). Cyanex 272 was selective for Mn over
Ca than D2EHPA. A temperature of 40°C at A/O ratio
of 2/3 was the promising conditions with Cyanex 272 for
selective Mn extraction.
A high-level Mn leach and PLS purification process
flow is schematically represented in Figure 3 (Zhang and
Cheng 2007, Yan and Qiu 2014, Mendonça de Araujo et
al. 2006). The PLS purification process depends on the
impurities available and the end product specifications.
This may include, but not limited to, precipitation, IX resin
adsorption, and solvent extraction. The precipitation can
be hydroxide, fluoride and/or sulphide.
High carbon ferromanganese (HCFM) production
process produces different wastes mainly, furnace dusts
and slags. The average slag to metal ratio in ferromanga-
nese production process is known to be 0.9 (Zhdanov et al.,
2015). In majority of cases, these wastes are accumulated
in landfills. Those wastes contain considerable amount of
manganese which can be recovered for further use. There
are several treatment methods available as summarised in
Table 1 by Gaal et al. (2010). The recycling of Mn slags
and dusts back to furnace for ferroalloy production was
Figure 1. Solubility diagram of metal hydroxides at a temperature of 25 °C derived from (Zhang and Cheng, 2007)
HPMSM production. Records showed that in 2021, 92.5%
of HPMSM used in battery industry came from Mn ore
processing and balance amount by HPEMM dissolution in
H2SO4 acid (Jephcott, 2023). The former option requires
beneficiation, reduction (for oxide ores), leaching, impu-
rity removal from leachate and crystallisation steps to pro-
duce HPMSM. The process route relies on the mineralogy
and quality of the ore being processed. The latter option is
expensive as raw material price is high due to electrowin-
ning process and HPEMM price is fluctuating frequently.
Currently China dominates the HPMSM production for
battery use with a 91% market share in 2021 (Jephcott,
2023).
The demand for Mn in LIB battery industry in 2021
was 2% and it is expected to grow up to 10% in 2040.
Currently two types of LIBs use HPMSM in the cathode,
NMC (Nickle-Manganese-Cobalt) and LNMO (lithium-
Nickle-Manganese Oxide). NMC is the market dominator
holding 44% of the rechargeable battery market and esti-
mated to reach 47%–50% in 2035 (Jephcott, 2023).
A rigorous PLS purification route is required to meet
the final product specifications of HPMSM. Precipitation
and solvent extraction are promising methods to purify
Mn solutions. Precipitation of metals as their respective
hydroxides is widely used in hydrometallurgical processes
(Monhemius, 1977). As illustrated in Figure 1, differ-
ent metals precipitates at different pH values, thus this
method is useful for the separation of metals. It is obvi-
ous that Fe, Al, Pb and Zn can be separated from Mn
but separation from Ni, Co and Mg is hard. Therefore, in
most cases, hydroxide precipitation itself is insufficient for
PLS purification. Solvent extraction plays a vital role in
impurity removal from Mn solutions (Zhang and Cheng,
2007). Few different types of extractants are mainly used
for Mn recovery. Phosphoric acid based extractants such
as D2EHPA are widely used. Moreover, phosphonic acid
extractants and phosphinic acid extractants such as Cyanex
272 are used for Mn separation from Ca and Mg. As shown
in Figure 2, the separation is pH dependant. A comparison
of Cyanex 272 and D2EHPA was performed by Pakarinen
and Paatero (2011). Cyanex 272 was selective for Mn over
Ca than D2EHPA. A temperature of 40°C at A/O ratio
of 2/3 was the promising conditions with Cyanex 272 for
selective Mn extraction.
A high-level Mn leach and PLS purification process
flow is schematically represented in Figure 3 (Zhang and
Cheng 2007, Yan and Qiu 2014, Mendonça de Araujo et
al. 2006). The PLS purification process depends on the
impurities available and the end product specifications.
This may include, but not limited to, precipitation, IX resin
adsorption, and solvent extraction. The precipitation can
be hydroxide, fluoride and/or sulphide.
High carbon ferromanganese (HCFM) production
process produces different wastes mainly, furnace dusts
and slags. The average slag to metal ratio in ferromanga-
nese production process is known to be 0.9 (Zhdanov et al.,
2015). In majority of cases, these wastes are accumulated
in landfills. Those wastes contain considerable amount of
manganese which can be recovered for further use. There
are several treatment methods available as summarised in
Table 1 by Gaal et al. (2010). The recycling of Mn slags
and dusts back to furnace for ferroalloy production was
Figure 1. Solubility diagram of metal hydroxides at a temperature of 25 °C derived from (Zhang and Cheng, 2007)