Selective Ion Exchange Resins and Their Applications for Mining

Dr. Guido Fries Global Mining Manager, Ion Exchange Applications guido.fries@lanxess.com

Overview

1) 2) 3) 4)

Production of Ion Exchange Resins Selective Ion Exchange Resins Metal recovery from dilute solutions Selective removal of impurities from metal solution

Dr. Guido Fries 20. Juni 2011

1) Production of Ion Exchange Resins

monomere

starter

+
styrene DVB

functionalisation

crosslinking agent

crosslinked polystyrene

Base for most IX-Materials: Crosslinked Polystyrene

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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 heat polymerisation

filtration; (porogene stripping); drying

functionalisation

rinsing

Product

Dr. Guido Fries 20. Juni 2011

1) Production of Ion Exchange Resins B) Monodispersed Resins

Column reactor

After-treatment

filtration; (porogene stripping); drying

functionalisation

rinsing

Product

water styrene, DVB 5

Dr. Guido Fries 20. Juni 2011

additives starter pore generating agent

1) Different types of particle size distribution

differential particle size distribution:
100 90 80 70 60 50 40 30 20 10 0

integrale particle size distribution:

120 100

Volume (%)

Volume (%)

HD MD

80 60 40 20 HD MD

0.3 - 0.45

0.85 - 1.0

0.45 - 0.55

0.55 - 0.65

0.65 - 0.85

1.0 - 1.15

0 0 0,5 1 1,5

particle size (mm)

particle size (m m )

heterodispersed (HD) beads

monodispersed beads (uniform particle sized)

Dr. Guido Fries 20. Juni 2011

1) Stability Tests: heterodispersed vs. monodispersed

Example : Lewatit TP 207 Resin H-Form NaOH HCl Resin Na-Form
(35% swelling)

100
CH2COOH N CH2COOH

80 60 40 20 0 TP 207 HD TP 207 MD
Stability 40 cycles Stability 200 cycles Roll test

Lewatit TP 207 (H-form)

Dr. Guido Fries 20. Juni 2011

1) Operating capacity: heterodispersed vs. monodispersed

60
NaCl: 300 g/l 5 ppm 10 60 C Ca + Mg: pH

50

40 Ca (ppb)

Temperature:

Specific flow rate: 20 BV / h

TP 260 HD

30

20

+ 20%

10

TP 260 MD
0 1000 1400 1800 Bed volume 2200 2600 3000

Dr. Guido Fries 20. Juni 2011

1) Production of Ion Exchange Resins

The worlds most modern production Unit for monodispersed IX resins is operated in Bitterfeld, Germany,

Dr. Guido Fries 20. Juni 2011

2) Selective Ion Exchange Resins

Mechanism of the Ion exchange process with chelating resins
Ion-pair exchange combined with complex formation

CH2-CO-ONa CH2 - N CH2-CO-ONa Ni2+ CH2-CO-O CH2 - N CH2-CO-O + 2 Na+ Ni

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 Only heavy metals and earth alkali metals

additional stability is gained by the chelating effect ( entropy) other important factors: - charge density of the metal - electron configuration coordination geometry

Chelating ligands have a higher selectivity compared to SAC

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2) Selective Ion Exchange Resins

Influence of pH on Affinity of Metals to Lewatit TP207 pH 7 6 5 Ba2+ 4 3 2 1 0
Dr. Guido Fries 20. Juni 2011

Mn2+

Zn2+ Ni2+ Cu2+ RH + M+ RM + H+ Fe3+

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2) Selective Ion Exchange Resins

Effect of Selectivity on Break-Through
Breakthrough experiment from multi-component adsorption on Lewatit TP 207

(Concentration mg/L)

Selectivity Series: Cu >> Zn > Pb > Ni > Cd >>> Ca

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2) Selective Ion Exchange Resins

By adjusting the pH selective removal of metals is feasible!!

CH2-CO-OH CH2 - N CH2-CO-OH

Fe3+>Cu2+> H+> Hg2+ >Pb2+>Ni2+>Zn2+>Cd2+>Co2+>Fe2+>Mn2+>>Ca2+>Mg2+>Sr2+>Ba2+>>> Alkalis

pH 1.2

CH2-CO-OH CH2 - N CH2-CO-ONa

pH 4.0

Fe3+>Cu2+> H+> Hg2+ >Pb2+>Ni2+>Zn2+>Cd2+>Co2+>Fe2+>Mn2+>>Ca2+>Mg2+>Sr2+>Ba2+>>> Alkalis

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Ion Exchange a versatile tool for problem solutions

Applications

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)

Ion Exchange Resins are versatile tools for the mining industry

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Dr. Guido Fries 20. Juni 2011

Ion Exchange Resins for Copper, Nickel & Cobalt Mining

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Dr. Guido Fries 20. Juni 2011

A principle flowsheet for a hydrometallurgical process

Ore

Mineral Processing

Crush / Grind

Concentration

Gangue

Leach

Leach

Residue

Hydrometallurgy

Concentration / Purification

By-products

Ion exchange Reduction

Pure Metal or Compound

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Metal recovery from dilute solutions using Ion Exchange Resins

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Dr. Guido Fries 20. Juni 2011

3) The resin-in-pulp process

Metal bearing pulp

Barren pulp
ent m e v mo t n urre resin c r nte f the o Cou

Stripping column

Pregnant metal solution

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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

Selectivity series
Fe3+> Cu2+> H+> Hg2+> Pb2+> Ni2+> Zn2+> Cd2+> Co2+> Fe2+> Mn2+>> Ca2+> Mg2+>>> Alkalis

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3) Effect of pH on loading of TP 207 by Ni at 45 C

40 Resin loading g/L (wet settled resin)

30

20

10 pH 4.5 0 0 50 100 150 200 250 300 350 400 450 Aqueous concentration mg/L pH 4.0 pH 3.5

(source UBC for IWC Oct.2006)

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3) Copper loaded Lewatit MonoPlus TP 207 XL

Copper loaded Lewatit MonoPlus TP 207 XL from a RIP circuit

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Selective removal of impurities from metal solution using Ion Exchange Resins

A B C

A B C

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4) Purification of a Nickel/Cobalt solution; The flowsheet for Goro Nickel; New Caledonia
Limonite Saprolite

Feed Preparation Pressure Acid Leach Counter-current Decantation

Solution Purification Copper Removal Lewatit TP 207 Primary SX Ni/Co Recovery Zinc Removal Lewatit MP 64 Secondary SX Ni/Co Separation Nickel Pyrohydrolysis Nickel Oxide Cobalt Carbonate Precipitation Final Neutralization Tailing dam

Cobalt Carbonate

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Dr. Guido Fries 20. Juni 2011

4) Purification: Lewatit TP 207 for Cu removal before 1st SX

Copper removal from a Nickel sulfate solution before 1st solvent extraction

Merry-go-round

to solvent extraction [Cu2+] < 50 ppb

H2SO4 2 BV, 15%

TP 207

TP 207

TP 207

TP 207

pH adjustment pH 2 - 2.5 Ni2+, Co2+, Cu2+, Zn2+

[Cu2+] 30 35 g/l Electrowinning Acid reuse for regeneration

Primary position Polishing position WORKING FILTERS (WS-System)

Regeneration re. Stand-by

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4) Primary SX: Stripping and its chemistry

Emulsion overflow

Settling chamber
Solvent extractant

Mixer chamber

Aqueous layer

Stripping agent (HCl)

Metal-loaded SX

Chemistry of stripping: Ni2+ Co2+ Zn2+ HCl Ni2+ [CoCl4]2[ZnCl4]2-

to be removed

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Dr. Guido Fries 20. Juni 2011

4) Purification: Lewatit MP64 for Zn removal before 2nd SX

Zink removal from a Nickel/Cobalt chloride solution before 2nd solvent extraction
1. HCl (100g/L)

Merry-go-round

to solvent extraction
[Zn] < 50 ppb 2. water

TP 207

MP 64

MP 64

MP 64

MP 64

Feed with high [HCl] Ni2+, [CoCl4]2-, [ZnCl4]2-

[CoCl4]2Zn2+ + 4 Cl-

1st position

2nd position Polishing position

WORKING FILTERS

Regeneration re. Stand-by

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Dr. Guido Fries 20. Juni 2011

Selective removal of impurities from mining waste water using Ion Exchange Resins

A B C

A B C

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Dr. Guido Fries 20. Juni 2011

4) Precipitation metals in an alkaline environment

pH Pb2+ < 0,5 mg/L Cd2+ < 0,2 mg/L Ni2+ < 0,5 mg/L Zn2+ < 2,0 mg/L Fe2+ < 3,0 mg/L Cu2+ < 0,5 mg/L Cr3+ < 0,5 mg/L Al3+ < 3,0 mg/L NaOH Na2CO3 CaCO3 3 4 5 6 7 8 9 10 11 12 3 4 5 6 7 8 9 10 11 12

Sn2+ < 2,0 mg/L Fe3+ < 3,0 mg/L pH

Precipitation is only economically if the metal concentration is high Ion Exchange provides benefits at low metal concentrations

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Dr. Guido Fries 20. Juni 2011

4) Lewatit TP 207 for selective removal of metals

Lewatit TP207 can be used to remove different metals from mining water selectively
rest concentrations of < 0,1 ppm are achievable

Be
Be2+ 3,5

Mg
Mg2+ 4,6

The Decomplexation-pH-value is the hydrogen concentration, at wich adsorption and desorption are at equilibrium Sc Y La Ti Zr Hf V Nb Ta Cr Mo W Mn
Mn2+ 4,0

B Al
Al3+ 2,2

C Si Ge Sn
Sn2+ <2,0

N P As Sb Bi

Ca Sr
Sr2+ 4,7

Fe Ru Os

Co Rh Ir

Ni Pd Pt

Cu Ag Au

Zn Cd Hg

Ga In Tl
Tl+ 3,7

Ca2+ 4,4 Sc3+ 2,0 TiO2+ 1,2 VO2+ 1,6

Co2+ 2,6 Ni2+ 2,2 Cu2+ 1,0 Zn2+ 2,5

Tc Re

Ba

Pb
Pb2+ 1,8

Ba2+ 4,8 La3+ 2,1

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

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Dr. Guido Fries 20. Juni 2011

4) Example: Ion Exchange for mining waste water polishing

regenerant, rinse Lime or NaOH Thickener Mining waste water
heavy metals

IX

IX

precipitation

heavy metal sludge

landfill

eluate back to precipitation

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Dr. Guido Fries 20. Juni 2011

4) Example: Ion Exchange for mining waste water

regenerant, rinse

heavy metals
IX IX

Mining waste water from tailings ponds

eluate waste water plant

Precipitation is only economically if the metal concentration is high Ion Exchange provides benefits at low metal concentrations

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Dr. Guido Fries 20. Juni 2011

Thank you very much for your attention.

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Dr. Guido Fries 20. Juni 2011

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

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Dr. Guido Fries 20. Juni 2011