Sulphur-Mediated Precipitation of Pt/Fe/Co/CrIons in Liquid-Liquid and Gas-Liquid Chloride Systems
The proof of concept experiments were conducted to
determine the feasibility of using small amounts of Dissolved
Sulphur (DS) from the gaseous phase to precipitate platinum ions in
chloride media. Two sets of precipitation experiments were
performed in which the source of sulphur atoms was either a
thiosulphate solution (Na2S2O3) or a sulphur dioxide gas (SO2). In
liquid-liquid (L-L) system, complete precipitation of Pt was achieved
at small dosages of Na2S2O3 (0.01 – 1.0 M) in a time interval of 3-5
minutes. On the basis of this result, gas absorption tests were carried
out mainly to achieve sulphur solubility equivalent to 0.018 M. The
idea that huge amounts of precious metals could be recovered
selectively from their dilute solutions by utilizing the waste SO2
streams at low pressure seemed attractive from the economic and
environmental point of views. Therefore, mass transfer characteristics
of SO2 gas associated with reactive absorption across the gas-liquid
(G-L) interface were evaluated under different conditions of pressure
(0.5 – 2 bar), solution temperature ranges from 20 – 50 oC and acid
strength (1 – 4 M, HCl). This paper concludes with information about
selective precipitation of Pt in the presence of cations (Fe2+, Co2+,
and Cr3+) in a CSTR and recommendation to scale up laboratory data
to industrial pilot scale operations.
[1] S. Ebrahimi, R. Kleerebezem, M. C. M. van Loosdrecht, and J. J.
Heijnen, "Kinetics of the reactive absorption of hydrogen sulphide into
aqueous ferric sulphate solutions," Chem. Eng. Sci., vol. 58, pp. 417 -
427, 2003.
[2] H. Ter Maat, J. A. Hogendoorn, and G. F. Versteeg, "The removal of
hydrogen sulphide from gas stream using an aqueous metal sulphate
absorbent. Part I. The absorption of hydrogen sulphide in metal sulphate
solutions," Sep. Purif. Technol., vol. 43, pp. 183 - 197, 2005.
[3] M. Al-Tarazi, A. B. M. Heesink, and G. F. Versteeg, "Precipitation of
metal sulphides using gaseous hydrogen sulphide: mathematical
modelling," Chem. Eng. Sci., vol. 59, pp. 567 - 579, 2004.
[4] N. Karbanee, "Investigation towards controlled precipitation of nickel
using H2S gas by harnessing pH dependent sulphide speciation," M.Sc
in Eng. Thesis, University of Cape Town, South Africa, 2007,
unpublished.
[5] V. Menard, and G. P. Demopoulos, "Gas transfer kinetics and redox
potential consideration in oxidative precipitation of manganese from an
industrial zinc sulphate solution with SO2/O2," Hydrometallurgy, vol.
89, pp. 357 - 368, 2007.
[6] F. L. Bernardis, R. A. Grant, and D. C. Sherrington, "A review of
methods of separation of the platinum-group metals through their
chloro-complexes," React. & Fun. Poly., vol. 65, pp. 205 - 217, 2005.
[7] D. Dreisinger, W. Murray, D. Hunter, K. Baxter, J. Ferron and C.
Fleming," The Application of the PLATSOL™ Process to Copper-
Nickel-Cobalt-PGE/PGM Concentrates from PolyMet Mining's
NorthMet Deposit", Presented at ALTA 2005, Perth, WA, May, 2005,
unpublished.
[8] H. Kasaini, "Enrichment process for PGM-metals containing stream,"
South Africa Patent PCT/ZA2008/000067, July 28, 2008.
[9] J. I. Kroschwitz and M. Howe-Grant,"Encyclopaedia of chemical
technology, Kirk-Othmer 4th ed.," Wiley & Sons. New York, 1991.
[10] K. K. Mishra and M. L. Kapoor, "Kinetics of liquid-gas reactions
through bubbles," Hydrometallurgy, vol. 3, pp. 75-83, 1978.
[11] R. Higbie, "The rate of absorption of a pure gas into a still liquid during
short periods of exposure," Trans. Am. Inst. Chem. Eng., Vol. 35, pp.
36-60, 1935.
[12] C. Oktaybas, E. Acma, C. Arslan, and O. Addemir, "Kinetics of copper
precipitation by H2S from Sulphate solutions," Hydrometallurgy, vol.
35, pp. 129-37, 1994.
[13] R. R. Broekhuis, D. J. Koch, and S. Lynn,"A medium temperature
process for removal of hydrogen sulphide from sour gas streams with
aqueous metal sulphate solutions," Ind. Eng. Chem. Res., vol. 31 pp.
2635-42, 1992.
[14] H. Maat Ter, J. A. Hogendoorn, and G. F. Versteeg,"The removal of
hydrogen sulphide from gas stream using an aqueous metal sulphate
absorbent: Part I The absorption of H2O in metal sulphate solutions,"
Separation and Purification Technology, vol. 4, pp. 183 - 197, 2005
[15] F. Habashi, "Principles of Extractive Metallurgy, Vol. 2" Gordon and
Breach, Science Publishers, Inc. New York, pp. 203, 1970.
[16] G. Schreier, and C. Edtmaier, "Separation of Ir, Pd, and Rh from
secondary Pt scrap by precipitation and calcinations," Hydrometallurgy,
vol. 68, pp. 69 - 75, 2003.
[17] H. G. Julsing, and R. I. McCrindle, "The use of sodium formate for the
recovery of precious metals from acidic base metal effluents," Journal of
Chem. Technol. & Biotechnology., vol. 76(4), pp. 349 - 354(6), 2001.
[18] H. Kasaini, R. C. Everson, and O. S. L. Bruinsma, "Selective Adsorption
of Platinum from Mixed solutions Containing Base Metals Using
Chemically Modified Activated Carbons," Separation Science and
Technology, vol. 40, pp. 507 - 523, 2005.
[19] A. E. Nielsen, "Kinetics of nucleation," Pergamon Press Ltd.
[20] O. Söhnel, and J. Garside, "Precipitation, basic principles and industrial
Applications," Butterworth Heinemann Ltd., Oxford.
[21] O. Levenspiel, "Chemical Reaction Engineering, 3rd ed.," John Wiley &
Sons, Inc., New York, 1999, pp. 38 - 76.
[22] Y. E. Kenig, U. Wiesner, and A. Gorak, "Modelling of reactive
Absorption Using the Maxwell-Stefan Equations," Ind. Eng. Chem.
Res., vol. 36, pp. 4325 - 4334, 1997.
[23] L. Rodriguez-Sevilla, M. Alvarez, G. Liminana, and M. C. Diaz, "Dilute
SO2 Absorption Equilibrium in Aqueous HCl and HCl Solution at
298.15 K," J. Chem. Eng. Data, vol. 47, pp. 1339 - 1345, 2002.
[24] V. M. Dagaonkar, A. A. C. M. Beenackers, and V. G. Pangarkar,
"Enhancement of gas-liquid mass transfer by small reactive particles at
realistically high mass transfer coefficients: absorption of sulphur
dioxide into aqueous slurries of Ca(OH)2 and Mg(OH)2 particles,"
Chem. Eng. J., vol. 81, pp. 203 - 212, 2001.
[25] H. Kasaini, M. Goto, and S. Furisaki, "Separation of Pd(II), Rh(III) and
Ru(III) ions from a Mixed Chloride Solution Using Activated Carbon
Pellets," Sep. Sci. Technol., vol.35(9), pp. 1307 - 1327, 2000.
[26] H. Kasaini, R. C. Everson, and O. S. L. Bruinsma, "Selective Adsorption
of Platinum from mixed Solution Containing Base Metals using
Chemically Modified Activated Carbons," Sep. Sci. Technol., vol. 40,
pp. 507 - 523, 2005.
[27] M. Cox, "Solvent Extraction in Hydrometallurgy, Principles and
Practices," In Principles and Practices of Solvent Extraction; J. Rydberg,
C. Musikas, G. R. Choppin, Eds.; Marcel Dekker, Inc.: New York, pp.
381 - 393, 1992.
[28] M. Cox, "Liquid-Liquid Extraction in Hydrometallurgy," In Science and
Practice of Liquid-Liquid Extraction; Thornton, J. D., Ed.; Clarendon
Press: Oxford 2, pp. 57, 1992.
[29] A. Koliadima, J. Kapolos, and L. Farmakis, "Diffusion Coefficients of
SO2 in Water and Partition Coefficients of SO2 in Water-Air Interface at
Different Temperature and pH Values," Instrument. Sci. And Technol.,
vol. 37, pp. 274 - 283, 2009.
[30] D. G. Leaist, "Diffusion Coefficient of Aqueous Sulphur Dioxide at
25┬░C," J. Chem. Eng. Data, vol. 29, pp. 281 - 282, 1984.
[31] J. Boniface, Q. Shi, Y. Q. Li, J. L. Cheung, O. V. Rattigan, P.
Davidovits, D. R. Worsnop, S. T. Jayne, and C. E. Kolb, " Uptake of
gas-phase SO2, H2S and CO2 by aqueous solutions," J. Phys. Chem. A
vol. 104 (32), pp. 7502-7510, 2000.
[1] S. Ebrahimi, R. Kleerebezem, M. C. M. van Loosdrecht, and J. J.
Heijnen, "Kinetics of the reactive absorption of hydrogen sulphide into
aqueous ferric sulphate solutions," Chem. Eng. Sci., vol. 58, pp. 417 -
427, 2003.
[2] H. Ter Maat, J. A. Hogendoorn, and G. F. Versteeg, "The removal of
hydrogen sulphide from gas stream using an aqueous metal sulphate
absorbent. Part I. The absorption of hydrogen sulphide in metal sulphate
solutions," Sep. Purif. Technol., vol. 43, pp. 183 - 197, 2005.
[3] M. Al-Tarazi, A. B. M. Heesink, and G. F. Versteeg, "Precipitation of
metal sulphides using gaseous hydrogen sulphide: mathematical
modelling," Chem. Eng. Sci., vol. 59, pp. 567 - 579, 2004.
[4] N. Karbanee, "Investigation towards controlled precipitation of nickel
using H2S gas by harnessing pH dependent sulphide speciation," M.Sc
in Eng. Thesis, University of Cape Town, South Africa, 2007,
unpublished.
[5] V. Menard, and G. P. Demopoulos, "Gas transfer kinetics and redox
potential consideration in oxidative precipitation of manganese from an
industrial zinc sulphate solution with SO2/O2," Hydrometallurgy, vol.
89, pp. 357 - 368, 2007.
[6] F. L. Bernardis, R. A. Grant, and D. C. Sherrington, "A review of
methods of separation of the platinum-group metals through their
chloro-complexes," React. & Fun. Poly., vol. 65, pp. 205 - 217, 2005.
[7] D. Dreisinger, W. Murray, D. Hunter, K. Baxter, J. Ferron and C.
Fleming," The Application of the PLATSOL™ Process to Copper-
Nickel-Cobalt-PGE/PGM Concentrates from PolyMet Mining's
NorthMet Deposit", Presented at ALTA 2005, Perth, WA, May, 2005,
unpublished.
[8] H. Kasaini, "Enrichment process for PGM-metals containing stream,"
South Africa Patent PCT/ZA2008/000067, July 28, 2008.
[9] J. I. Kroschwitz and M. Howe-Grant,"Encyclopaedia of chemical
technology, Kirk-Othmer 4th ed.," Wiley & Sons. New York, 1991.
[10] K. K. Mishra and M. L. Kapoor, "Kinetics of liquid-gas reactions
through bubbles," Hydrometallurgy, vol. 3, pp. 75-83, 1978.
[11] R. Higbie, "The rate of absorption of a pure gas into a still liquid during
short periods of exposure," Trans. Am. Inst. Chem. Eng., Vol. 35, pp.
36-60, 1935.
[12] C. Oktaybas, E. Acma, C. Arslan, and O. Addemir, "Kinetics of copper
precipitation by H2S from Sulphate solutions," Hydrometallurgy, vol.
35, pp. 129-37, 1994.
[13] R. R. Broekhuis, D. J. Koch, and S. Lynn,"A medium temperature
process for removal of hydrogen sulphide from sour gas streams with
aqueous metal sulphate solutions," Ind. Eng. Chem. Res., vol. 31 pp.
2635-42, 1992.
[14] H. Maat Ter, J. A. Hogendoorn, and G. F. Versteeg,"The removal of
hydrogen sulphide from gas stream using an aqueous metal sulphate
absorbent: Part I The absorption of H2O in metal sulphate solutions,"
Separation and Purification Technology, vol. 4, pp. 183 - 197, 2005
[15] F. Habashi, "Principles of Extractive Metallurgy, Vol. 2" Gordon and
Breach, Science Publishers, Inc. New York, pp. 203, 1970.
[16] G. Schreier, and C. Edtmaier, "Separation of Ir, Pd, and Rh from
secondary Pt scrap by precipitation and calcinations," Hydrometallurgy,
vol. 68, pp. 69 - 75, 2003.
[17] H. G. Julsing, and R. I. McCrindle, "The use of sodium formate for the
recovery of precious metals from acidic base metal effluents," Journal of
Chem. Technol. & Biotechnology., vol. 76(4), pp. 349 - 354(6), 2001.
[18] H. Kasaini, R. C. Everson, and O. S. L. Bruinsma, "Selective Adsorption
of Platinum from Mixed solutions Containing Base Metals Using
Chemically Modified Activated Carbons," Separation Science and
Technology, vol. 40, pp. 507 - 523, 2005.
[19] A. E. Nielsen, "Kinetics of nucleation," Pergamon Press Ltd.
[20] O. Söhnel, and J. Garside, "Precipitation, basic principles and industrial
Applications," Butterworth Heinemann Ltd., Oxford.
[21] O. Levenspiel, "Chemical Reaction Engineering, 3rd ed.," John Wiley &
Sons, Inc., New York, 1999, pp. 38 - 76.
[22] Y. E. Kenig, U. Wiesner, and A. Gorak, "Modelling of reactive
Absorption Using the Maxwell-Stefan Equations," Ind. Eng. Chem.
Res., vol. 36, pp. 4325 - 4334, 1997.
[23] L. Rodriguez-Sevilla, M. Alvarez, G. Liminana, and M. C. Diaz, "Dilute
SO2 Absorption Equilibrium in Aqueous HCl and HCl Solution at
298.15 K," J. Chem. Eng. Data, vol. 47, pp. 1339 - 1345, 2002.
[24] V. M. Dagaonkar, A. A. C. M. Beenackers, and V. G. Pangarkar,
"Enhancement of gas-liquid mass transfer by small reactive particles at
realistically high mass transfer coefficients: absorption of sulphur
dioxide into aqueous slurries of Ca(OH)2 and Mg(OH)2 particles,"
Chem. Eng. J., vol. 81, pp. 203 - 212, 2001.
[25] H. Kasaini, M. Goto, and S. Furisaki, "Separation of Pd(II), Rh(III) and
Ru(III) ions from a Mixed Chloride Solution Using Activated Carbon
Pellets," Sep. Sci. Technol., vol.35(9), pp. 1307 - 1327, 2000.
[26] H. Kasaini, R. C. Everson, and O. S. L. Bruinsma, "Selective Adsorption
of Platinum from mixed Solution Containing Base Metals using
Chemically Modified Activated Carbons," Sep. Sci. Technol., vol. 40,
pp. 507 - 523, 2005.
[27] M. Cox, "Solvent Extraction in Hydrometallurgy, Principles and
Practices," In Principles and Practices of Solvent Extraction; J. Rydberg,
C. Musikas, G. R. Choppin, Eds.; Marcel Dekker, Inc.: New York, pp.
381 - 393, 1992.
[28] M. Cox, "Liquid-Liquid Extraction in Hydrometallurgy," In Science and
Practice of Liquid-Liquid Extraction; Thornton, J. D., Ed.; Clarendon
Press: Oxford 2, pp. 57, 1992.
[29] A. Koliadima, J. Kapolos, and L. Farmakis, "Diffusion Coefficients of
SO2 in Water and Partition Coefficients of SO2 in Water-Air Interface at
Different Temperature and pH Values," Instrument. Sci. And Technol.,
vol. 37, pp. 274 - 283, 2009.
[30] D. G. Leaist, "Diffusion Coefficient of Aqueous Sulphur Dioxide at
25┬░C," J. Chem. Eng. Data, vol. 29, pp. 281 - 282, 1984.
[31] J. Boniface, Q. Shi, Y. Q. Li, J. L. Cheung, O. V. Rattigan, P.
Davidovits, D. R. Worsnop, S. T. Jayne, and C. E. Kolb, " Uptake of
gas-phase SO2, H2S and CO2 by aqueous solutions," J. Phys. Chem. A
vol. 104 (32), pp. 7502-7510, 2000.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:58847", author = "J. Siame and H. Kasaini", title = "Sulphur-Mediated Precipitation of Pt/Fe/Co/CrIons in Liquid-Liquid and Gas-Liquid Chloride Systems", abstract = "The proof of concept experiments were conducted to
determine the feasibility of using small amounts of Dissolved
Sulphur (DS) from the gaseous phase to precipitate platinum ions in
chloride media. Two sets of precipitation experiments were
performed in which the source of sulphur atoms was either a
thiosulphate solution (Na2S2O3) or a sulphur dioxide gas (SO2). In
liquid-liquid (L-L) system, complete precipitation of Pt was achieved
at small dosages of Na2S2O3 (0.01 – 1.0 M) in a time interval of 3-5
minutes. On the basis of this result, gas absorption tests were carried
out mainly to achieve sulphur solubility equivalent to 0.018 M. The
idea that huge amounts of precious metals could be recovered
selectively from their dilute solutions by utilizing the waste SO2
streams at low pressure seemed attractive from the economic and
environmental point of views. Therefore, mass transfer characteristics
of SO2 gas associated with reactive absorption across the gas-liquid
(G-L) interface were evaluated under different conditions of pressure
(0.5 – 2 bar), solution temperature ranges from 20 – 50 oC and acid
strength (1 – 4 M, HCl). This paper concludes with information about
selective precipitation of Pt in the presence of cations (Fe2+, Co2+,
and Cr3+) in a CSTR and recommendation to scale up laboratory data
to industrial pilot scale operations.", keywords = "CSTR, diffusivity, platinum, selective precipitation,sulphur dioxide, thiosulphate.", volume = "4", number = "9", pages = "584-10", }
