Professional Documents
Culture Documents
Technical Review - Copper Solvent Extraction in Hydrometallurgy
Technical Review - Copper Solvent Extraction in Hydrometallurgy
Extraction in Hydrometallurgy
MTRL 557
Submitted to Dr. David Dreisinger
By Patrick Littlejohn
December 2007
Table of Contents
List of Figures............................................................................................................. 3
1.0 Introduction........................................................................................................ 4
2.0 SX Design Factors ........................................................................................... 5
2.1 SX Reagents.................................................................................................... 6
2.2 Acid Management ........................................................................................ 8
2.3 Liquor Temperature ................................................................................. 11
2.4 Crud Management ..................................................................................... 11
3.0 The Effect of Impurities and Additives............................................. 13
3.1 Leaching Aids ............................................................................................... 13
3.2 Nitrate .............................................................................................................. 14
3.3 Silica .................................................................................................................. 15
3.4 Chloride ........................................................................................................... 16
3.5 Manganese..................................................................................................... 17
3.6 Iron .................................................................................................................... 20
3.7 Antimony and Bismuth........................................................................... 21
4.0 Solvent Extraction Equipment ............................................................... 22
4.1 Mixer-Settlers .............................................................................................. 22
4.2 Pulsed Columns .......................................................................................... 23
4.3 Molecular Recognition Technology ................................................. 26
4.4 Non-Dispersive Solvent Extraction ................................................. 27
4.5 Emulsion Liquid Membranes ............................................................... 29
5.0 Summary............................................................................................................. 31
6.0 References ......................................................................................................... 34
List of Abbreviations
contactor
EW – Electrowinning
IX – Ion Exchange
SX – Solvent Extraction
List of Figures
Column
copper from a diverse range of leach liquors, from low tenor, low acid
producers. This paper will seek to cover several factors that must be
operating a copper SX-EW plant. First and foremost is the makeup and
processing heap leach liquor will be very different from those for a
affects the flowrate of the aqueous PLS (pregnant leach solution) – for
(Sole and Feather 2003). This relationship also determines the optimal
A/O ratio in extraction, and therefore will also affect the loading
will also affect the choice of extractant, as loading and stripping rates
operating and fine tuning a plant (Komulainen et al. 2006). The choice
2.1 SX Reagents
the reagent inventory an expensive part of the initial capital cost, but
plant flow sheet will also be affected because impurity control, loading
and ore body an SX reagent can be tailor made to best suit a circuit
which made them more effective for dilute acid low copper tenor
2003).
Over the next decade it was discovered that by using non chelating
several areas. Alkyl phenol was the first such modifier that allowed the
al. 2003). Ester modified aldoxime reagents are commonly used today,
particularly in new plants where flow sheet designs are not constrained
the efficiency of the plant in several ways. First and foremost, the
The pH of the PLS must be managed so that copper will move from the
the electrolyte.
Acid management can also be a challenge when treating high acid and
2+
2 RH Org + Cu aq ↔ R2 CuOrg + 2 H aq+ (Eq. 1)
For each mole of copper removed from the aqueous it is replaced with
The loading stage can also be split into multiple cells to allow partial
circuits.
2.3 Liquor Temperature
and pressure oxidation streams can be near boiling point when they
first leave the leach reactors. Even if cooling towers are used the
leach liquor entering the circuit will alter the chemical behavior and
the others. Elevated temperature will also increase the loss of organic
eventually spread to the rest of the circuit and can cause serious
in the context of a full circuit is complex. The solid particles that give
the emulsion stability are typically modeled as silica, but any fine solid
(<2 micron) that passes thickeners can cause crud formation. Clays,
jarosites, gypsum, quartz, and micas have all been linked to crud
et al. 1999).
Excessive mixing can also enhance crud formation through strong
shear forces that break droplets into micro droplets, which settle
Some copper processes use leaching aids during the leaching stage to
improve recovery and/or kinetics. Often these chemical aids are in the
(Kordosky and Virnig 2007). These chemicals are not removed from
the PLS before entering the SX-EW segment of the circuit and so they
time for settling and phase separation. This in turn can increase
3.2 Nitrate
and as such it can find its way into PLS solutions. Through recycle
slower (Kordosky and Virnig 2007). In any plant with the potential for
3.3 Silica
silicon in the copper ore or in the host rock. It can be present both as
case the presence of silica in the copper leach solution can cause
equation 2.
This colloidal silica gel is of low density and is difficult to separate from
the aqueous phase. The gel absorbs organic and does not compact
easily. This problem was studied in detail after silica issues in the
entrainment in the organic and decreased silica levels in the high acid
strip where silica precipitation was most prevalent (Readett and Miller
1995).
3.4 Chloride
such as the CLEAR process, CYMET, CESL, and the BHAS process
extraction. Chloride can also enter with the mineral, although this is
(de Maere and Winand 1995). However, excess chloride can cause
3.5 Manganese
not only wasted on these side oxidation reactions, but also because
1995).
The presence of MnO4- and other high valence manganese ions in the
spent electrolyte drives the solution potential up. This causes several
performance.
primarily causes problems via high valence ions increasing the solution
copper: iron selectivity (Sole et al. 2007). It is primarily ferric iron that
cyclical oxidation of iron (II) to iron (III). Iron in the electrolyte can be
case of leach solutions high in manganese but low in iron, iron can be
worse than those caused by iron. Iron (II) is also added to solutions as
a way to lower solution potential and reduce high other high valence
metal ions (Cupertino et al. 1999). Once in the electrolyte iron can be
removed via the recycle of a bleed stream back to the PLS. However,
solution is the use of ion exchange resins to treat a bleed from the
electrolyte and selectively remove iron. This is the Fenix Iron Control
them via an electrolyte bleed stream, they can gradually build up due
and bismuth removal ion exchange with phosphonic acid based resin
1995 (Dreisinger and Scholey 1995). Bismuth removal via MRT was
4.1 Mixer-Settlers
settler. The two phases are introduced into a tank with a fast moving
slower moving auxiliary mixer and given time for contact. Then the
dispersion is moved to a settling tank where the phases are given time
to separate. The less dense organic floats to the top and passes over a
spillway while the heavy aqueous sinks and leaves the cell through a
launder (See figure 2). Several design variables can improve the
distribution into the settler, roofs to seal the tanks and prevent
but only recently have they been applied to industrial scale copper
the column while the organic enters from the bottom. A pulse, typically
shaped baffles and rings force the fluids to travel in a serpentine path
rather than short circuiting down the center. At the top and bottom
decanters separate the phases and allow collection of the barren liquor
and the loaded organic (Nielson and Vancas 1999). A schematic design
continuous. For the former, the interface is in the bottom decanter and
to take place within a single column. This design was piloted in 2003
2003).
phase continuity, phase ratios, flux rate, and pulse intensity. The
separation.
Phase ratios are determined by the tenor of incoming liquor and the
loading capacity of the diluted extractant. The A/O ratio for heap leach
liquor will be higher than for high grade pressure oxidation liquor.
rate is the total flow rate per unit area. Typical pulsed column fluxes
are in the range of 30 to 50 m3/h/m2, roughly an order of magnitude
Lerner et al. 2003). This leads to a much smaller physical footprint for
higher.
nil and no particulate matter can enter the liquids. This is not only a
benefit for reagent consumption but also for safety since many SX
larger droplets than mixer settlers, less crud is formed, leading to less
conventional mixer-settlers.
recover dilute ions in the ppb range even the presence of high
antimony, and free chloride (Dale et al. 1999, Bruening et al. 2003).
<0.3 ppm. Once the ligand resin reaches capacity the bed is eluted
with strong sulphuric acid solution and the bismuth is recovered from
the eluate as a saleable salt (Izatt et al. 2000). MRT circuit flowsheets
of IX resin columns.
solvent extraction (see Figure 4). The cell operates with flow across
technology is that hollow fiber membrane cells can achieve high levels
coalescence, and crud issues. NDSX is best suited for use as a method
for the hydrocarbon processing industry, but since then they have also
shown potential for the solvent extraction of heavy metal ions (Li
extraction reagent while the aqueous phase within the droplet is the
within a single unit operation (see Figure 5). After the emulsion
the feed stream and demulsified. The metal in the separated strip
rupture likelihood. Strong mixer agitation in the cell will break the
emulsion layer with excessive shear stress. Rupture can also occur
costly problem as the high grade strip solution is lost and the pH of the
pregnant solution will be modified by the high acid strip solution. This
technology has been studied for use in low tenor ammoniacal solutions
5.0 Summary
can also affect the amount of siliceous crud formed through the circuit.
development but have not been shown to be feasible for industrial use
so far.
6.0 References
Bergh, L.G. and Yianatos, J.B. “Current status and limitations of copper
SX/EW plants control.” Minerals Engineering, 14.9 (2001): 975-985.
Cupertino, D.C., Charlton, M.H., Buttar, D., and Swart, R.M. “A study of
copper/iron separation in modern solvent extraction plants.” Copper,
Phoenix, Arizona, USA, 10-13 October, 1999. Ed. S.K. Young, D.B.
Dreisinger, R.P. Hackl, and D.G. Dixon. Montreal Quebec: Canadian
Institute of Mining, Metallurgy and Petroleum, 1999. 263-276.
Dale, J.B., Izatt, N.E., and Bruening, R.L. “Recent advances in the
application of molecular recognition technology (MRT) in the copper
industry.” Copper, Phoenix, Arizona, USA, 10-13 October, 1999. Ed.
S.K. Young, D.B. Dreisinger, R.P. Hackl, and D.G. Dixon. Montreal
Quebec: Canadian Institute of Mining, Metallurgy and Petroleum,
1999. 329-343.
Giralico, M., Gigas, B. and Preston, M. “Optimized mixer settler designs for
tomorrow’s large flow production requirements.” Copper, Santiago,
Chile, 30 November-3 December, 2003. Ed. P.A. Riveros, D.G. Dixon,
D.B. Dreisinger, and J.M. Menacho. Montreal Quebec: Canadian
Institute of Mining, Metallurgy and Petroleum, 2003. 775-794.
Maes, C., Tinkler, O., Moore, T., and Mejias, J. “The evolution of modified
aldoxime copper extractants.” Copper, Santiago, Chile, 30 November-3
December, 2003. Ed. P.A. Riveros, D.G. Dixon, D.B. Dreisinger, and
J.M. Menacho. Montreal Quebec: Canadian Institute of Mining,
Metallurgy and Petroleum, 2003. 753-760.
Menacho, J. and Zivkovic, Y. “Control of emulsions in solvent extraction
processes.” Hydro-metallurgical congress on copper, Valparaiso, Chile,
1994.
Miller, G.M. “The problem of manganese and its effects on copper SX-EW
operations.” Copper, Santiago, Chile, 26-29 November 1995. Ed. W.C.
Cooper, D.B. Dreisinger, J.E. Dutrizac, H. Hein, and G. Ugarte.
Montreal, Quebec: Canadian Institute of Mining Metallurgy and
Petroleum, 1995. 649-663.
Nielson, M.C. and Vancas, M.F. “Pulsed column application in copper solvent
extraction.” Copper, Phoenix, Arizona, USA, 10-13 October, 1999. Ed.
S.K. Young, D.B. Dreisinger, R.P. Hackl, and D.G. Dixon. Montreal
Quebec: Canadian Institute of Mining, Metallurgy and Petroleum,
1999. 319-327.
Pekkala, P. et al. “Solvent extraction – how to get over hard times.” Copper,
Phoenix, Arizona, USA, 10-13 October, 1999. Ed. S.K. Young, D.B.
Dreisinger, R.P. Hackl, and D.G. Dixon. Montreal Quebec: Canadian
Institute of Mining, Metallurgy and Petroleum, 1999. 305-318.
Reddy, B.R., Park, K.H., and Mohapatra, D. “Process development for the
separation and recovery of copper from sulphate leach liquors of
synthetic Cu-Ni-Co-Fe matte using LIX 84 and LIX 973N.”
Hydrometallurgy 87 (2007): 51-57.
Readett, D.J. and Miller, G.M. “The impact of silica on solvent extraction:
Girilambone Copper Company case study.” Copper, Santiago, Chile,
26-29 November 1995. Ed. W.C. Cooper, D.B. Dreisinger, J.E.
Dutrizac, H. Hein, and G. Ugarte. Montreal, Quebec: Canadian
Institute of Mining Metallurgy and Petroleum, 1995. 679-690.
Robinson, T. “Innovations in Solvent Extraction.” Copper, Toronto, Canada,
26-29 August 2007. Ed. P.A. Riveros, D.G. Dixon, D.B. Dreisinger, M.J.
Collins. Montreal, Quebec: Canadian Institute of Mining Metallurgy and
Petroleum, 2007.
Shaw, R., Vance, S., Illescas, J., Dreisinger, D., and Wassink, B. “Ion
exchange for iron impurity control in the base metal industry.” Iron
Control Technologies, Montreal, Canada, 2006. Ed. J.E. Dutrizac and
P.A. Riveros. 757-769.
Sole, K.C., and Feather, A.M. “Solvent extraction of copper from high-tenor
pressure leach solutions using new modified aldoximes.” Copper,
Santiago, Chile, 30 November-3 December, 2003. Ed. P.A. Riveros,
D.G. Dixon, D.B. Dreisinger, and J.M. Menacho. Montreal Quebec:
Canadian Institute of Mining, Metallurgy and Petroleum, 2003. 691-
705.
Van de Voorde, I. et al. “Influence of acetate ions and the role of the
diluents on the extraction of base metals with different types of
extractants.” Hydrometallurgy 78 (2005): 92-106.
Virnig, M., Boley, T., and Thompsen, J. “Copper Solvent Extraction and
Concentrate Leach Solutions.” Copper, Toronto, Canada, 26-29 August
2007. Ed. P.A. Riveros, D.G. Dixon, D.B. Dreisinger, M.J. Collins.
Montreal, Quebec: Canadian Institute of Mining Metallurgy and
Petroleum, 2007.
Virnig, M.J. et al. “Crud formation: field studies and fundamental studies.”
Copper, Toronto, Canada, 26-29 August 2007. Ed. P.A. Riveros, D.G.
Dixon, D.B. Dreisinger, M.J. Collins. Montreal, Quebec: Canadian
Institute of Mining Metallurgy and Petroleum, 2007. 291-303.
Virnig, M., Eyzaguirre, D., Jo, M., and Calderon, J. “Effects of nitrate on
copper SX circuits: A case study.” Copper, Santiago, Chile, 30
November-3 December, 2003. Ed. P.A. Riveros, D.G. Dixon, D.B.
Dreisinger, and J.M. Menacho. Montreal Quebec: Canadian Institute of
Mining, Metallurgy and Petroleum, 2003. 795-810.