Solvent Extraction (SX) reagent
selection for high temperature, high
acid, high chloride and high Cu
concentration leach solution at Port
Pirie and its impact on electrowinning
By
P. Crane, M. Urbani, K. Dudley, A. Horner and M. Virnig
Nyrstar Port Pirie Smelter
• The smelter is situated 230km north of Adelaide in South
Australia on the Spencer Gulf.
Port Pirie
Broken Hill
Rich lead
deposit
Courtesy Google
The smelter was built on a natural harbour
allowing ease of product export
Background
History: The smelter has been processing lead concentrates since 1889,
after the ore field in Broken Hill was discovered.
Much expansion occurred during the 1950s and 1960s.
Zinc production commenced in 1967
Copper production commenced in 1984
Production Capacity: Lead – 235,000 Tonnes
Zinc – 45,000 Tonnes
Silver – 11.5 million troy ounces (357 Tonnes)
Gold - 16,000 million troy ounces (497 kilos)
Sulphuric Acid – 80,000 Tonnes
Copper – 4,500 Tonnes
Copper plant Feedstock
mainly sourced from lead concentrates
NPPS New Copper Inputs (tpa)
External
Zinc External
Residues Lead
12% Residues
711 T 17%
1041 T
4338 T
Lead
Concentrates
71%
NPPS Copper Process
• Copper is recovered from the lead furnace in the form
of a matte, which is treated in the copper plant
• The Copper recovery process employs a unique mixed
chloride-sulphate leach technology (formerly known as
the BHAS process) developed by BHAS engineers.
• This aggressive chloride-assisted leach is followed by
conventional Cu SX / EW processes operated under
fairly harsh conditions.
Basic NPPS Copper Plant Circuit
Process description
Matte from
CDF Milling
Leach (primary and Residue/ Residue back to
secondary) Neutralisation Sinter Plant
Solvent Extraction
Electrowinning
•Ball Mill and Feed Hopper
Grinding
• A conventional ball mill in closed circuit with a spiral classifier, treating 12,000 tpa
matte.
• Product goes to Primary Leach after thickening and storage.
To
leach
Overall leach chemistry (effect of chloride not shown)
Cu2S + PbS + H2SO4 + 4H+ + 3/2 O2 PbSO4 + 2Cu2+ + 2S + 3H2O
Black Acid
Primary
Leach Thickener
Underflow
Secondary
To Neutralisation then
Sinter Plant
PLS
Underflow
PLS to
Clarifier
•Leach Reactors
2nd Stage Leach and washing
• Thickener U/F from 1st stage leach at 35-40% solids is pumped
to a one-stage repulp reactor.
• Salt, white acid and Oxygen added.
• 4-5 hrs residence time.
• 2nd stage leach discharge washed with raffinate in a repulp
mixer.
• Polysil added in repulp mixer for silica control, and Magnafloc
added to Repulp Thickener as a settling aid.
• Repulp slurry is thickened; solids are sent to neutralisation and
return to the sinter plant, whilst liquids go to 1st stage leach.
•Salt addition to repulp reactor
NaCl prevents precipitation of
CuS from Cu+ and S0.
•Preg Clarifier
•Leach Thickener
Copper SX
• Conventional 2E x 1W x 2S circuit.
E1 organic
Pregnant
Leach
Wash
aqueous Cu2+ Solution
Extraction
Water
Impurities E organic
2
Washing
aqueous Cu2+ Raffinate
aqueous
organic
organic Cu2+
S2 aqueous Spent
Electrolyte
Stripping
Wash
Water
Cu2+ organic
aqueous S1 Advance
Electrolyte
• Pregnant Leach Solution (PLS) containing approx. 40 g/L
Cu, 20 g/L acid and 20 g/L Cl- at >40 deg C.
•SX Mixer-settlers, S1 and S2
Electrowinning
• Two stage cascade systems in series with 15 cells per unit.
• Each cell has capacity for 40 stainless steel or titanium cathodes
and 41 antimonial lead anodes
• Cathodes and anodes are connected to two 10,000A rectifiers.
Spent
Electrolyte
to S2 after
cooling
Advance Electrolyte
•Cell house
Process Difficulties
The use of the highly effective chloride – sulphate leach process
results in several challenges for the operation of the Cu SX-EW
plant, namely it:
• Produces a hot PLS, high in acid, chloride and copper content;
• Requires effective silica control and solids liquid separation;
• Requires a high SX extractant concentration and high O/A ratios;
• Requires careful monitoring of organic health and regular,
effective, organic treatment.
Cognis Involvement
Cognis visited Port Pirie in mid 2003 to view the plant operation
and offer technical assistance. Main observations:
• Operating with high concentration of Acorga® M5640 (C9
aldoxime with TXIB modifier) and high O/A ratio.
• No phase separation under Organic Continuous conditions
Forced Aqueous Continuous operation.
• Evidence of silica-based crud.
• Re-oximation stage due to high reagent degradation rate.
• Viscous organic with dark colouration after strong acid strip.
• High entrainment and resultant high Cl transfer to electrolyte
(consistently >200 ppm Cl in electrolyte) titanium plates.
• Poor atmospheric environment in EW (low levels Cl2 gas).
Cognis Involvement, cont.
In August 2003, a sample of Port Pirie plant organic was
analysed in Cognis’ Tucson laboratory. The main findings were:
• Extremely poor OC phase break >15 minutes at 25C
• Slow stripping kinetics – 62% after 30 sec (typically 95%)
• High nitro-C9 aldoxime level (16.2 % of total oxime)
• Excessive levels of hydrolysis product (aldehyde)
• High TXIB : C9 aldoxime ratio (0.38 compared to 0.28 in
Acorga M5640)
• Presence of 2-cyano-4-nonylphenol and 5-nonylsalicylamide
• The organic did not respond to clay treatment
33%(v/v) LIX® 674N- Stripping
LV in SX 12 after a few
load strip cycles then tests
completely stripped. indicated the
Note the clarity. scale of the
problem
33%(v/v) LIX® 674N-
LV in SX 12 after a few
load strip cycles then Red colour
completely stripped. warning
signs of
nitration
Port Pirie plant sample
completely stripped – 4
contacts with 250 g/L
acid, O/A 2:1.
Nitration of oximes
Requires acid, nitrate and high ORP
HNO3 + H NO2 + H2O
OH NOH OH NOH
O2N
H H
NO2 +
R R
C9 Aldoxime Nitro C9 Aldoxime
Catalysed by presence of modifiers
(Virnig, et. al. Copper2003)
Effect of modifiers on oxime
Effect ofdegradation
Modifiers in presence of nitrate
LIX 622N M5640 LIX 984N LIX 84-I LIX 84-I & TDA
2
1.8
1.6
% (w/v) Aldehyde or Ketone
Aldoxime + TDA
1.4
1.2
Aldoxime + TXIB
1
0.8
Ketoxime + TDA
0.6
0.4
Ketoxime + Aldoxime
0.2
Ketoxime
0
0 10 20 Days 30 40 50
Stripped organic phases of all modified reagents: LIX 622N, M5640
and LIX 84-I + TDA; were red in colour
Cognis Manufactured Oximes
INCREASING REAGENT STABILITY
OH OH OH
OH N OH N OH N
C C C
H H CH3
C9H19 C12H25 C9H19
C9 Aldoxime C12 Aldoxime C9 Ketoxime
Acorga M5640 (incl. TXIB modifier) LIX 984
© Copyright, Cognis Corporation, 2005
Cognis recommendations
• Convert reagent to a more stable non-modified reagent type to:
– Reduce rate of nitration
– Reduce rate of degradation
– Reduce viscosity of organic phase
• Cease re-oximation of the organic, since:
– Re-oximated organics demonstrate poor physical performance
– Re-oximated organics are typically difficult to clean up
– Hydroxylamine may have been at least a partial source of the
nitrogen oxide species
Recommendations were all intended to improve the
physical state and the performance of the organic phase.
Port Pirie accepted the Cognis offer.
LIX 984 was selected because:
• 50/50 blend of LIX 84-I (ketoxime) and LIX 860-I (C12
aldoxime), both of which are more stable than the C9 aldoxime
present in Acorga M5640.
• LIX 984 contains no modifier Modifiers promote nitration.
• LIX 984 showed good chemical performance in initial
screening tests.
Pre-LIX reagent addition plant profile (April 2004)
• Cu Mass balance OK
• High oxime concentration (43%(v/v))
• Low Cu net transfer (0.14 g/L Cu / % oxime)
• Low % Cu max load
• Laboratory PDT’s – aqueous continuous - 126 seconds, organic
continuous - no separation after 15 minutes
• Again clay treatment had no effect, organic not filterable
• Extremely high viscosity (26.5 cSt compared to 3.9 cSt for fresh
LIX reagent at 43%(v/v)
Acorga addition stopped in April 2004 and LIX addition
commenced.
Regular plant monitoring involved:
• Chemical composition –C9 and C12 aldoxime, ketoxime,
TXIB, hydrolysis and nitration products
• Chemical performance – Cu recovery, % Cu ML, Cu net
transfer (g/L Cu / % oxime), extraction and stripping kinetics
• Physical performance – Plant PDTs, mixer continuity, temp,
laboratory PDTs, Effect of clay treatment, viscosity
• Monitoring the Cl- concentration in the electrolyte
CONCENTRATION OF REAGENTS IN NPPS PLANT ORGANIC SINCE THE ADDITION OF LIX REAGENT
80
75
70
65 TXIB
% of Total Components by Volume
60 C9 Aldoxime
C12 Aldoxime
55
Ketoxime Conversion rate
50 C9 nitro aldoximes
45
tracked by
40 decline in TXIB
35 content
30
25
20
15
10
5
-
04
04
05
05
05
06
06
06
07
07
07
08
08
4
7
/0
/0
/0
/0
1/
1/
1/
1/
1/
1/
1/
1/
1/
1/
1/
1/
1/
/1
/1
/1
/1
5/
8/
2/
5/
8/
2/
5/
8/
2/
5/
8/
2/
5/
11
11
11
11
Month
Plant chemical performance
Survey Date
Parameter
May- Nov- Jun- Nov - Apr - Oct - Sept -
Jan-05
04 04 05 06 07 07 08
PLS Cu(g/L) 41.0 45.8 44.6 42.3 45.0 51.9 32.0 45.2
Raffinate Cu(g/L) 12.9 15.4 13.9 15.0 15.5 14.8 8.1 10.9
Cu recovery (%) 68.5 66.4 68.8 64.5 65.6 70.7 65.5 75.8
Reagent Conc. (vol%) 45.0 34.0 30.0 25.8 32.6 33.5 33.3 30.0
Net Transfer (g/L Cu/vol%) 0.150 0.220 0.234 0.255 0.229 0.273 0.174 0.211
% max load 59.0 66.4 65.5 83.9 81.5 88.2 65.5 74.6
Plant chemical performance
Survey Date
Parameter
May- Nov- Jun- Nov - Apr - Oct - Sept -
Jan-05
04 04 05 06 07 07 08
PLS Cu(g/L) 41.0 45.8 44.6 42.3 45.0 51.9 32.0 45.2
Raffinate Cu(g/L) 12.9 15.4 13.9 15.0 15.5 14.8 8.1 10.9
Cu recovery (%) 68.5 66.4 68.8 64.5 65.6 70.7 65.5 75.8
Reagent Conc. (vol%) 45.0 34.0 30.0 25.8 32.6 33.5 33.3 30.0
Net Transfer (g/L Cu/vol%) 0.150 0.220 0.234 0.255 0.229 0.273 0.174 0.211
% max load 59.0 66.4 65.5 83.9 81.5 88.2 65.5 74.6
Plant chemical performance
Survey Date
Parameter
May- Nov- Jun- Nov - Apr - Oct - Sept -
Jan-05
04 04 05 06 07 07 08
PLS Cu(g/L) 41.0 45.8 44.6 42.3 45.0 51.9 32.0 45.2
Raffinate Cu(g/L) 12.9 15.4 13.9 15.0 15.5 14.8 8.1 10.9
Cu recovery (%) 68.5 66.4 68.8 64.5 65.6 70.7 65.5 75.8
Reagent Conc. (vol%) 45.0 34.0 30.0 25.8 32.6 33.5 33.3 30.0
Net Transfer (g/L Cu/vol%) 0.150 0.220 0.234 0.255 0.229 0.273 0.174 0.211
% max load 59.0 66.4 65.5 83.9 81.5 88.2 65.5 74.6
Laboratory extraction and stripping kinetics
Kinetics Aug 03 Jul 05 Mar 06 Jun 06 Dec 06 Feb 07 Sept 08
Extraction - - 86 % 90 % 90 % 96 % 92%
@ 30 sec
Strip @ 30 62 % 71 % 78 % 90 % 92 % 96 % 97%
sec
Plant physical performance
Laboratory PD tests using plant organic and plant PLS.
Date PDT (seconds)
OC AC
Apr 2004 No break 126
Jan 2005 No break 130
July 2005 No break 110
October 2005 >600 90
March 2006 >600 72
June 2006 600 100
December 2006 600 93
February 2007 474 109
April 2007 114 201
Oct 2007 49 26
Feb 2009 90 30
PD time before and after clay treatment.
Extraction (OC) sec Strip (AC) (sec)
Pre CT Post CT Pre CT Post CT
April 04 No break No break - -
March 06 920 22 72 20
June 06 627 22 100 20
Viscosity of the plant organic
Apr Sep Jan Jul 05 Oct Mar Jun Dec Feb May Sept
04 04 05 05 06 06 06 07 08 08
Visc @
26.48 19.43 15.06 15.13 13.15 13.90 12.20 9.50 8.93 7.72 6.66
25oC (cSt)
Chloride in electrolyte (and PLS)
200 100
180 90
160 80
Percent LIX reagent in circuit (%)
Cl in electrolyte
Chloride in electrolyte (mg/L)
140 70
Cl in repulp O/F
and repulp O/F (g/L)
120 Percent LIX in circuit 60
100 50
80 40
60 30
40 20
20 10
0 0
/0
4 04 05 05 05 06 06 07 07 07 08 /0
8
04 8/ 1/ 6/ 1/ 4/ 9/ 2/ 7/ 2/ 5/ 10
3/ /0 /0 /0 /1 /0 /0 /0 /0 /1 /0 9/
31 28 27 24 23 20 17 17 14 12
EW Chloride vs TXIB in organic
200 30
180 27
TXIB - Percent of total reagent in circuit
160 Cl in electrolyte 24
Cl in repulp O/F
Chloride in electrolyte (mg/L)
140 21
TXIB (Percent of total reagent component)
and repulp O/F (g/L)
120 18
100 15
80 12
60 9
40 6
20 3
0 0
4 4 5 5 5 6 6 7 7 7 8 8
/0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0
04 08 01 06 11 04 09 02 07 12 05 10
3/ 3 1/ 2 8/ 2 7/ 2 4/ 2 3/ 2 0/ 1 7/ 1 7/ 1 4/ 1 2/ 9/
Conclusions
The conversion of Acorga modified reagent to the more stable
LIX non-modified reagent resulted in:
• reduction in reagent concentration to <35vol% (now at 30%).
• improvement in extraction and strip kinetics.
• higher net transfer (>0.2gplCu/vol%).
• very significant improvement in phase separation behaviour.
• organic phase viscosity reduced by 75%.
• very significant decrease in chloride transfer to EW.
• reduction in electrolyte chloride level by ~90%.
• much easier plant operation.
Acknowledgements
Nyrstar Port Pirie
Cognis
Co-authors and investigators: Kym
Dudley, Mark Urbani, Dr Michael Virnig
and Anissa Horner
Questions?
