IX for Mining Application

Selective Ion Exchange Resins

and

Their Applications for Mining

Dr. Guido Fries

Global Mining Manager, Ion Exchange Applications

[email protected]

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



monomere

+

styrene DVB

starter

crosslinking agent crosslinked

polystyrene

functionalisation

Base for most IX-Materials: Crosslinked Polystyrene



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


Column

reactor

additiveswater

styrene, DVB starterpore generating agent

B) Monodispersed Resins

Product

filtration; (porogene stripping); drying

functionalisation

rinsing

After-treatment



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


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)


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


The world‘s most modern production Unit for monodispersed IX resins is operated

in Bitterfeld, Germany,



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



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+



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



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!!



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


Ion Exchange Resins

for Copper, Nickel & Cobalt

Mining


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


Metal recovery from dilute solutions

using

Ion Exchange Resins


3) The resin-in-pulp process

Metal bearing pulp

Barren pulp

Strippingcolumn

Pregnant metal solution

Counter-current movement

of the resin


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


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


3) Copper loaded Lewatit® MonoPlus TP 207 XL

Copper loaded Lewatit® MonoPlus TP 207 XL from a RIP circuit


A

B

C

A

B

C

Selective removal of impurities from metal solution

using

Ion Exchange Resins


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


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


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


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


A

B

C

A

B

C

Selective removal of impurities from mining waste water

using

Ion Exchange Resins


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


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


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


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.



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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IX for Mining Application