ix for mining application
TRANSCRIPT
Selective Ion Exchange Resins
and
Their Applications for Mining
Dr. Guido Fries
Global Mining Manager, Ion Exchange Applications
Dr. Guido Fries20. Juni 20112
Overview
1) Production of Ion Exchange Resins
2) Selective Ion Exchange Resins
3) Metal recovery from dilute solutions
4) Selective removal of impurities from metal solution
Dr. Guido Fries20. Juni 20113
1) Production of Ion Exchange Resins
monomere
+
styrene DVB
starter
crosslinking agent crosslinked
polystyrene
functionalisation
Base for most IX-Materials: Crosslinked Polystyrene
Dr. Guido Fries20. Juni 20114
1) Production of Ion Exchange Resins
A) Heterodispersed Resins Production Process
water fill-in
monomers (e.g. styrene, DVB); emulsifying agents; (porogenes);Starter fill-in
polymerisation
filtration; (porogene stripping); drying
functionalisation
rinsing
Product
heat
Dr. Guido Fries20. Juni 20115
Column
reactor
additiveswater
styrene, DVB starterpore generating agent
B) Monodispersed Resins
Product
filtration; (porogene stripping); drying
functionalisation
rinsing
After-treatment
1) Production of Ion Exchange Resins
Dr. Guido Fries20. Juni 20116
heterodispersed (HD) beads monodispersed beads (uniform particle sized)
0102030405060708090
100V
olu
me (
%)
0.3
- 0
.45
0.4
5 -
0.5
5
0.5
5 -
0.6
5
0.6
5 -
0.8
5
0.8
5 -
1.0
1.0
- 1
.15
particle size (mm)
HD
MD
differential particle size distribution:
0
20
40
60
80
100
120
0 0,5 1 1,5
particle size (mm)
Vo
lum
e (
%)
HD
MD
integrale particle size distribution:
1) Different types of particle size distribution
Dr. Guido Fries20. Juni 20117
Example : Lewatit® TP 207
1) Stability Tests: heterodispersed vs. monodispersed
NaOH
HClResin – H-Form Resin – Na-Form
(35% swelling)
0
20
40
60
80
100
TP 207 HD TP 207 MD
Stability 40cycles
Stability 200cycles
Roll test
** f
N
CH2COOH
CH2COOH
Lewatit® TP 207 (H-form)
Dr. Guido Fries20. Juni 20118
0
10
20
30
40
50
60
1000 1400 1800 2200 2600 3000
Bed volume
Ca
(p
pb
)
TP 260 MD
+ 20%
NaCl: 300 g/l
Ca + Mg: 5 ppm
pH 10
Temperature: 60 °C
Specific flow rate: 20 BV / h TP 260 HD
1) Operating capacity: heterodispersed vs. monodispersed
Dr. Guido Fries20. Juni 20119
The world‘s most modern production Unit for monodispersed IX resins is operated
in Bitterfeld, Germany,
1) Production of Ion Exchange Resins
Dr. Guido Fries20. Juni 201110
CH2 - N
CH2-CO-ONa
CH2-CO-ONa
CH2 - N
CH2-CO-O
CH2-CO-O
Ni
+ 2 Na+
Ni2+
Mechanism of the Ion exchange process with chelating resins
• Ion-pair exchange combined with complex formation
Basic principle
• the free electron pair of nitrogen interacts with one d-orbital of the heavy metal
• only metals with an empty d-orbital can interact
• additional stability is gained by the chelating
effect (⇒⇒⇒⇒ entropy)• other important factors:
- charge density of the metal
- electron configuration ⇒⇒⇒⇒ coordination geometry
Only heavy metals and earth alkali metals
Chelating ligands have a higher selectivity compared to SAC
2) Selective Ion Exchange Resins
Dr. Guido Fries20. Juni 201111
pH
Influence of pH on Affinity of Metals to Lewatit® TP207
7
0
6
5
4
3
2
1
Mn2+
Zn2+
Ni2+
Cu2+
Fe3+
Ba2+
RH + M+ RM + H+
2) Selective Ion Exchange Resins
Dr. Guido Fries20. Juni 201112
Effect of Selectivity on Break-Through (C
on
ce
ntr
ati
on
mg
/L)
Breakthrough experiment from
multi-component adsorption
on Lewatit® TP 207
Selectivity Series:
Cu >> Zn > Pb > Ni > Cd >>> Ca
2) Selective Ion Exchange Resins
Dr. Guido Fries20. Juni 201113
CH2-CO-OH
CH2 - NCH2-CO-OH
Fe3+>Cu2+> H+> Hg2+ >Pb2+>Ni2+>Zn2+>Cd2+>Co2+>Fe2+>Mn2+>>Ca2+>Mg2+>Sr2+>Ba2+>>> Alkalis
CH2-CO-OH
CH2 - NCH2-CO-ONa
Fe3+>Cu2+> H+> Hg2+ >Pb2+>Ni2+>Zn2+>Cd2+>Co2+>Fe2+>Mn2+>>Ca2+>Mg2+>Sr2+>Ba2+>>> Alkalis
pH 1.2
pH 4.0
By adjusting the pH selective removal of metals is feasible!!
2) Selective Ion Exchange Resins
Dr. Guido Fries20. Juni 201114
Ion Exchange – a versatile tool for problem solutions
Concentration(e.g. Resin-in-pulp;
Resin-in-column)
Purification(e.g. Ni / Co separation;protection of SX circuits)
Waste water processing(e.g. removal of metals
from mine decant water)
Applications
Ion Exchange Resins are versatile tools for the mining industry
Dr. Guido Fries20. Juni 201115
Ion Exchange Resins
for Copper, Nickel & Cobalt
Mining
Dr. Guido Fries20. Juni 201116
Ore
Crush / Grind
Concentration Gangue
Leach Leach Residue
Concentration /
PurificationBy-products
ReductionPure Metal or
Compound
Hydrometallurgy
Mineral Processing
Ion exchange
A principle flowsheet for a hydrometallurgical process
Dr. Guido Fries20. Juni 201117
Metal recovery from dilute solutions
using
Ion Exchange Resins
Dr. Guido Fries20. Juni 201118
3) The resin-in-pulp process
Metal bearing pulp
Barren pulp
Strippingcolumn
Pregnant metal solution
Counter-current movement
of the resin
Dr. Guido Fries20. Juni 201119
A Special Resin for Resin-in-Pulp applications
Lewatit® MonoPlus TP 207 XL
� Iminodiacetic acid functionality
� Macroporous type, monodisperse
� Bead size [mm]: ≈ 0,8 (uniformity coefficient: max. 1.1)
� Total Capacity [eq/L]: 2,0
� Water retention [wt.%]: 55 - 60
The especially enlarged bead size is combined with high mechanical
and osmotical stability and therefore very suitable for RIP applications
Fe3+> Cu2+> H+> Hg2+> Pb2+> Ni2+> Zn2+> Cd2+> Co2+> Fe2+> Mn2+>> Ca2+> Mg2+>>> Alkalis
Selectivity series
Dr. Guido Fries20. Juni 201120
0
10
20
30
40
0 50 100 150 200 250 300 350 400 450
Aqueous concentration mg/L
Re
sin
lo
ad
ing
g/L
(w
et
sett
led
re
sin
)
pH 4.5 pH 4.0 pH 3.5
(source UBC for IWC Oct.2006)
3) Effect of pH on loading of TP 207 by Ni at 45°C
Dr. Guido Fries20. Juni 201121
3) Copper loaded Lewatit® MonoPlus TP 207 XL
Copper loaded Lewatit® MonoPlus TP 207 XL from a RIP circuit
Dr. Guido Fries20. Juni 201122
A
B
C
A
B
C
Selective removal of impurities from metal solution
using
Ion Exchange Resins
Dr. Guido Fries20. Juni 201123
4) Purification of a Nickel/Cobalt solution; The flowsheet for Goro Nickel; New Caledonia
Feed Preparation
Pressure Acid Leach
Counter-current Decantation
Solution PurificationCopper Removal – Lewatit® TP 207
Primary SX – Ni/Co Recovery
Zinc Removal – Lewatit® MP 64
Secondary SX – Ni/Co Separation
Limonite Saprolite
Nickel Pyrohydrolysis
Nickel Oxide
Final Neutralization
Cobalt Carbonate
Cobalt Carbonate Precipitation
Tailing dam
Dr. Guido Fries20. Juni 201124
Copper removal from a Nickel sulfate solution before 1st solvent extraction
(WS-System)
Polishing positionPrimary position Regeneration re.
Stand-byWORKING FILTERS
4) Purification: Lewatit® TP 207 for Cu removal before 1st SX
TP207
TP207
TP207
TP207
pH – adjustment
pH ≈ 2 - 2.5
[Cu2+]
< 50 ppb
H2SO4
2 BV, 15%
[Cu2+] ≈ 30 – 35 g/l
⇒ Electrowinning
Acid reuse for regeneration
Merry-go-round
Ni2+, Co2+, Cu2+, Zn2+
to solvent extraction
Dr. Guido Fries20. Juni 201125
4) Primary SX: Stripping and its chemistry
Stripping agent (HCl)
Metal-loaded SX
Emulsion overflow
Mixer chamber
Settling chamber
Aqueous layer
Solvent extractant
Ni2+
Co2+
Zn2+
Ni2+
[CoCl4]2-
[ZnCl4]2-
HCl
Chemistry of stripping:
to be removed
Dr. Guido Fries20. Juni 201126
Zink removal from a Nickel/Cobalt chloride solution before 2nd solvent extraction
Polishing position1st position Regeneration re.
Stand-byWORKING FILTERS
4) Purification: Lewatit® MP64 for Zn removal before 2nd SX
2nd position
TP207
MP 64
Feed with high [HCl]
[Zn]< 50 ppb
1. HCl (≈100g/L)Merry-go-round
Ni2+, [CoCl4]2-, [ZnCl4]
2-
MP 64 MP 64
[CoCl4]2-
Zn2+ + 4 Cl-
MP 64
2. waterto solvent extraction
Dr. Guido Fries20. Juni 201127
A
B
C
A
B
C
Selective removal of impurities from mining waste water
using
Ion Exchange Resins
Dr. Guido Fries20. Juni 201128
4) Precipitation metals in an alkaline environment
pH
Fe3+
Sn2+
Al3+
Cr3+
Cu2+
Fe2+
Zn2+
Ni2+
Cd2+
Pb2+
pH
< 3,0 mg/L
< 2,0 mg/L
< 3,0 mg/L
< 0,5 mg/L
< 0,5 mg/L
< 3,0 mg/L
< 2,0 mg/L
< 0,5 mg/L
< 0,2 mg/L
< 0,5 mg/L
1211109876543
1211109876543
NaOH
Na2CO3
CaCO3
• Precipitation is only economically if the metal concentration is high
• Ion Exchange provides benefits at low metal concentrations
Dr. Guido Fries20. Juni 201129
C NBBe
Al Si P
Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As
Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb
Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi
Mg
LaTl+ ≈3,7
Be2+ ≈3,5
Al3+ ≈2,2Mg2+ ≈4,6
Ca2+ ≈4,4
Sr2+ ≈4,7
Ba2+ ≈4,8 Pb2+ ≈1,8
Sc3+ ≈2,0
La3+ ≈2,1
Mn2+ ≈4,0 Co2+ ≈2,6 Ni2+ ≈2,2 Cu2+ ≈1,0 Zn2+ ≈2,5VO2+ ≈1,6TiO2+ ≈1,2
Sn2+ <2,0
The Decomplexation-pH-value is the hydrogen concentration, at wich adsorption and desorption are at equilibrium
• Feed-pH-value approx. 0,5...1 Units above the DpH
⇒ limited uptake is possible
• Feed-pH-value approx. 2 Units above DpH or higher:
⇒ Maximum of the capacity for a metal cation is nearly attainable
Lewatit® TP207 can be used to remove different metals from mining water selectively
rest concentrations of < 0,1 ppm are achievable
4) Lewatit® TP 207 for selective removal of metals
Dr. Guido Fries20. Juni 201130
4) Example: Ion Exchange for mining waste water polishing
Mining waste water
Lime or NaOH
Thickenerheavy metals
landfill
IX IX
precipitation
regenerant,rinse
eluate back toprecipitation
heavy metal sludge
Dr. Guido Fries20. Juni 201131
4) Example: Ion Exchange for mining waste water
Mining waste water from tailings ponds
heavy metals
IX IX
regenerant,rinse
eluate waste water plant
• Precipitation is only economically if the metal concentration is high
• Ion Exchange provides benefits at low metal concentrations
Thank you very muchfor your attention.
Dr. Guido Fries20. Juni 201133
Dr. Guido Fries20. Juni 201134
Disclaimer
This information and our technical advice – whether verbal, in writing or by way of trials – are given in good faith but without warranty, and this also applies where proprietary rights of third parties are involved. Our advice does not release you from the obligation to check its validity and to test our products as to their suitability for the intended processes and uses. The application, use and processing of our products and the products manufactured by you on the basis of our technical advice are beyond our control and, therefore, entirely your own responsibility. Our products are sold in accordance with the current version of o u r G e n e r a l C o n d i t i o n s o f S a l e a n d D e l i v e r y .
LEWATIT® and IONAC® are registered trademarks of LANXESS AG