XXXI International Mineral Processing Congress 2024 Proceedings/Washington, DC/Sep 29–Oct 3 1731
(pH 2–8). Detailed experimental and solution chemistry
analyses showed that increasing gas flow rate, temperature,
and stirring rate resulted in enhanced Co-Mn recovery.
However, the increase was not significantly different for a
lower range of gas flow rate, stirring rate, and temperature
within a 95% confidence level. Our kinetic rate and activa-
tion energy results for the oxidative precipitation reaction
for the first 30 seconds (i.e., EaCo= 21.6kJ/mol &EaMn=
–13.9kJ/mol), and 30 minutes (i.e., EaCo= 27.3kJ/mol &
EaMn= 26.7kJ/mol) period of the reaction fit well with the
Pseudo-homogeneous model. The specific mechanism for
Co-Mn oxidative precipitation using ozone was not identi-
fied due to the complexity of the process and the interplay
of various phenomena involving the mass transfer of ozone,
co-precipitation and adsorption effects on precipitates of
elements, and competing reactions. However, the effect of
process parameters and calculated activation energy values
suggest that the oxidative precipitation of Co-Mn is primar-
ily a diffusion-controlled reaction. Future research in this
area would focus on understanding the interactive effect of
process parameters, and validating the scaleup parameters
of this method.
REFERENCES
Balintova, M., Petrilakova, A. 2011. Study of pH influence
on selective precipitation of heavy metals from acid
mine drainage. Chem. Eng. Trans. 25:345–350
Cruz-Díaz, M.R., Arauz-Torres, Y., Caballero, F., Lapidus,
G.T., &González, I. 2015. Recovery of MnO2 from
a spent alkaline battery leach solution via ozone treat-
ment. Journal of Power Sources, 274:839–845. doi:
10.1016/j.jpowsour.2014.10.121
Freitas, R.M., Perilli, T.A., &Ladeira, A.C.Q. 2013.
Oxidative precipitation of manganese from acid mine
drainage by potassium permanganate. Journal of
chemistry, 287257.
Ichlas, Z.T., Mubarok, M.Z., Magnalita, A., Vaughan,
J., &Sugiarto, A.T. 2020. Processing mixed nickel-
cobalt hydroxide precipitate by sulfuric acid leaching
followed by selective oxidative precipitation of cobalt
and manganese. Hydrometallurgy, 191. doi: 10.1016/j.
hydromet.2019.105185
International Energy Agency (IEA). 2023. Critical
Minerals Market Review. Accessed at: https://iea.blob
.core.windows.net/assets/c7716240-ab4f-4f5d-b138
–291e76c6a7c7/CriticalMineralsMarketReview2023
.pdf
Jing, Q.K., Liu, X.Y., &Wen, J.K. 2014. A novel iron
oxidation process in zinc leaching solution by ozone.
Advanced Materials Research, 900:35–38. doi: 10.4028/
www.scientific.net/AMR.900.35
Joo, S.H., Kang, J., Woong, K., &Shin, S.M. 2013.
Production of chemical manganese dioxide from
lithium ion battery ternary cathodic material by selec-
tive oxidative precipitation of manganese. Materials
Transactions, 54(5): 844–849.
Johnson, D.B., &Hallberg, K.B. 2005. Acid mine drain-
age remediation options: a review. Science of the total
environment, 338(1‑2): 3–14.
Kim, Y.W., &Baird, J.K. 2005. Chemical equilibrium
and critical phenomena: The solubilities of manganese
dioxide and aluminum oxide in isobutyric acid +water
near its consolute point. Journal of Physical Chemistry
B, 109(36):17262–17266. doi: 10.1021/jp058170r
Lewis, A., Seckler, M., Kramer, H. and Van Rosmalen,
G. 2015. Industrial crystallization: fundamentals and
applications. Cambridge University Press.
Myerson, A., 2002. Handbook of industrial crystallization.
Butterworth-Heinemann.
Oruê, B.P., Botelho Junior, A.B., Tenório, J.A.S.,
Espinosa, D.C.R., &Baltazar, M. dos P.G. 2021.
Kinetic Study of Manganese Precipitation of Nickel
Laterite Leach Based-solution by Ozone Oxidation.
Ozone: Science and Engineering, 43(4): 324–338. doi:
10.1080/01919512.2020.1796580
Qu, B., Li, T., Yang, Z., Deng, H., Wu, M., &Chen,
S. 2022. Kinetics Analysis of Ozonation Process of
Recovering Manganese Dioxide from Aqueous Phase in
the Presence of Manganese. Dithionate. doi: 10.21203
/rs.3.rs-2265190/v1
Rezaee, M., Shekarian, Y., &Pisupati, S. 2022. Ozone
Oxidative Precipitation of Elements from Aqueous
Streams (Pending Patent No. 63/392 2022 330).
Rezaee, M., Vaziri Hassas, B., Pisupati, S.V. 2021. Recovery
of rare earth elements from acidic solutions, U.S. pend-
ing patent, WO2021155224A1.
Rozelle, P.L., Mamula, N., Arnold, B.J., O’Brien, T.,
Rezaee, M., Pisupati, S.V. 2021. Secondary cobalt and
manganese resources in Pennsylvania: quantities, link-
age with mine reclamation, and preliminary flowsheet
evaluation for the U.S. domestic lithium-ion battery
supply chain. The Pennsylvania State University Center
for Critical Minerals. https://www.c2 m.psu.edu/sites
/default/files/publications/2021/Cobalt%20
Study%20Report%20Dec%202021.pdf
(pH 2–8). Detailed experimental and solution chemistry
analyses showed that increasing gas flow rate, temperature,
and stirring rate resulted in enhanced Co-Mn recovery.
However, the increase was not significantly different for a
lower range of gas flow rate, stirring rate, and temperature
within a 95% confidence level. Our kinetic rate and activa-
tion energy results for the oxidative precipitation reaction
for the first 30 seconds (i.e., EaCo= 21.6kJ/mol &EaMn=
–13.9kJ/mol), and 30 minutes (i.e., EaCo= 27.3kJ/mol &
EaMn= 26.7kJ/mol) period of the reaction fit well with the
Pseudo-homogeneous model. The specific mechanism for
Co-Mn oxidative precipitation using ozone was not identi-
fied due to the complexity of the process and the interplay
of various phenomena involving the mass transfer of ozone,
co-precipitation and adsorption effects on precipitates of
elements, and competing reactions. However, the effect of
process parameters and calculated activation energy values
suggest that the oxidative precipitation of Co-Mn is primar-
ily a diffusion-controlled reaction. Future research in this
area would focus on understanding the interactive effect of
process parameters, and validating the scaleup parameters
of this method.
REFERENCES
Balintova, M., Petrilakova, A. 2011. Study of pH influence
on selective precipitation of heavy metals from acid
mine drainage. Chem. Eng. Trans. 25:345–350
Cruz-Díaz, M.R., Arauz-Torres, Y., Caballero, F., Lapidus,
G.T., &González, I. 2015. Recovery of MnO2 from
a spent alkaline battery leach solution via ozone treat-
ment. Journal of Power Sources, 274:839–845. doi:
10.1016/j.jpowsour.2014.10.121
Freitas, R.M., Perilli, T.A., &Ladeira, A.C.Q. 2013.
Oxidative precipitation of manganese from acid mine
drainage by potassium permanganate. Journal of
chemistry, 287257.
Ichlas, Z.T., Mubarok, M.Z., Magnalita, A., Vaughan,
J., &Sugiarto, A.T. 2020. Processing mixed nickel-
cobalt hydroxide precipitate by sulfuric acid leaching
followed by selective oxidative precipitation of cobalt
and manganese. Hydrometallurgy, 191. doi: 10.1016/j.
hydromet.2019.105185
International Energy Agency (IEA). 2023. Critical
Minerals Market Review. Accessed at: https://iea.blob
.core.windows.net/assets/c7716240-ab4f-4f5d-b138
–291e76c6a7c7/CriticalMineralsMarketReview2023
Jing, Q.K., Liu, X.Y., &Wen, J.K. 2014. A novel iron
oxidation process in zinc leaching solution by ozone.
Advanced Materials Research, 900:35–38. doi: 10.4028/
www.scientific.net/AMR.900.35
Joo, S.H., Kang, J., Woong, K., &Shin, S.M. 2013.
Production of chemical manganese dioxide from
lithium ion battery ternary cathodic material by selec-
tive oxidative precipitation of manganese. Materials
Transactions, 54(5): 844–849.
Johnson, D.B., &Hallberg, K.B. 2005. Acid mine drain-
age remediation options: a review. Science of the total
environment, 338(1‑2): 3–14.
Kim, Y.W., &Baird, J.K. 2005. Chemical equilibrium
and critical phenomena: The solubilities of manganese
dioxide and aluminum oxide in isobutyric acid +water
near its consolute point. Journal of Physical Chemistry
B, 109(36):17262–17266. doi: 10.1021/jp058170r
Lewis, A., Seckler, M., Kramer, H. and Van Rosmalen,
G. 2015. Industrial crystallization: fundamentals and
applications. Cambridge University Press.
Myerson, A., 2002. Handbook of industrial crystallization.
Butterworth-Heinemann.
Oruê, B.P., Botelho Junior, A.B., Tenório, J.A.S.,
Espinosa, D.C.R., &Baltazar, M. dos P.G. 2021.
Kinetic Study of Manganese Precipitation of Nickel
Laterite Leach Based-solution by Ozone Oxidation.
Ozone: Science and Engineering, 43(4): 324–338. doi:
10.1080/01919512.2020.1796580
Qu, B., Li, T., Yang, Z., Deng, H., Wu, M., &Chen,
S. 2022. Kinetics Analysis of Ozonation Process of
Recovering Manganese Dioxide from Aqueous Phase in
the Presence of Manganese. Dithionate. doi: 10.21203
/rs.3.rs-2265190/v1
Rezaee, M., Shekarian, Y., &Pisupati, S. 2022. Ozone
Oxidative Precipitation of Elements from Aqueous
Streams (Pending Patent No. 63/392 2022 330).
Rezaee, M., Vaziri Hassas, B., Pisupati, S.V. 2021. Recovery
of rare earth elements from acidic solutions, U.S. pend-
ing patent, WO2021155224A1.
Rozelle, P.L., Mamula, N., Arnold, B.J., O’Brien, T.,
Rezaee, M., Pisupati, S.V. 2021. Secondary cobalt and
manganese resources in Pennsylvania: quantities, link-
age with mine reclamation, and preliminary flowsheet
evaluation for the U.S. domestic lithium-ion battery
supply chain. The Pennsylvania State University Center
for Critical Minerals. https://www.c2 m.psu.edu/sites
/default/files/publications/2021/Cobalt%20
Study%20Report%20Dec%202021.pdf