Separation of Cu & As from

acidic electrolytes by
electrodialysis
J.P. Ibáñez, C. Gutiérrez, L. Cifuentes
San Diego, CA., March 4 of 2003
 OUTLINE
➢ Introduction
➢ Electrodialysis and Applications
➢ Objectives
➢ Experimentation
➢ Results and Discussions
➢ Electrodialysis for As Abatement
➢ Conclusions
 INTRODUCTION
Metallic Impurities such as As in Electrolytes

➣ Reduce the quality of cathode Cu

➣ Deleterious effect on Cu deposit
➣ Slimes formation
➣ Lowering the overpotential
➣ Increase of the current density
To minimize the negative effect of As
BLEEDS
➣ Losing of copper
➣ Losing of reagents
➣ Losing of water

TREATMENTS
➣ Solvent Extraction
➣ Ion Exchange
➣ Activated Carbon (Sb)
 Para minimizar los efectos Purgar
è
negativos de estas impurezas
Electrólito

PURGAS

Etapas sucesivas Eliminación è D=1/4

Métodos
de descobrización 1 m3 purga è pérdidas
Alternativos
vía EW y planta de 40 kg de Cu
tratamiento de sulfato 0.2 m3 de H2SO4
3 m3 de H2O
 ELECTRODIALYSIS
Transport of ions through ion exchange
membranes under an electrical field.
Anion Memb. Cation Memb.
Working
X- Solution M+
Anion rich - M+ Cation rich
Solution X MX
X-
MX M+ Solution
X- X- M+
M+
X- M+

Electrical Field
 APPLICATIONS
IN METALLURGY
➢ Purifying molybdenum trioxide
➢ Separation of molybdenum and uranium
➢ Concentrating rhenium acid
➢ Recovering & concentrating sulfuric acid
➢ Reducing sulfate in liquid waste
➢ Recovering of water
 OBJECTIVES

➣ To study the potential use of electrodialysis

for obtaining an As-free copper electrolyte.

➣ To evaluate the effect of current density and

pH on the separation process.
 EXPERIMENTAL
Anode Cathode
Cation memb

A W C
A C
C S C

Chambers
Anion memb

Cation Flux

Anion Flux
 Cell Characteristics
➢ Cation memb.: MC-3470
Membranes
➢ Anion memb.: MA-7500

Electrodes ➢ Anode: Pb anodized w/Co

➢ Cathode: Stainless Steel
➢ Chambers: Acrylic
➢ Chamber’s volume: 46.8 mL
➢ Membrane area: 36 cm2
➢ Electrode area: 36 cm2
Working solution
Cu: 10 g/L
As: 1 g/L
H2SO4: 50 g/L

Other solutions
H2SO4: 50 g/L
K2SO4: 50 g/L

pH of WS 0.6 & 2.8

Current densities 225 & 150 A/m2

Experimental time 3 hours

 RESULTS & DISCUSSIONS
pH i time AC, mmol WS, mmol CC, mmol
A/m2 h Cu As Cu As Cu As

0.6 0 7.53 0.60

150 3 0.08 0.03 3.81 0.57 3.71 0.005

225 3 0.03 0.05 2.33 0.56 5.14 0.004

% ~68 ~7

Cation membrane
As-free
permits only the
transport of copper
Cu electrolyte
 Transport of Cu
8

6
150 A/m2
mmol

4
225 A/m2

0
0 1 2 3
hours

High i Faster the Cu Transport

150 A/m2 ® 0.50 mol/h/m2
225 A/m2 ® 0.75 mol/h/m2
 Transport of As
0,6

0,4 150 A/m2

mmol

225 A/m2
0,2

0
0 1 2 3
hours

Transport of As < 7 % with ~ 0.002 mol/h/m2

➣ Failure of the membrane

Due to
➣ High content of uncharged species
 Speciation of As
1,0

0,8 ~75 %
Feaction of As H3AsO4
0,6
H2AsO4-
0,4
HAsO42-
0,2
~3%
0,0
0 1 2 3 4 5 6 7 8 9 10
pH

Low fraction of transportable ion As stays in WS

Increasing WS pH Increase membrane performance

 Results at pH 2.8
i time AC, mmol WS, mmol CC, mmol
A/m2 h Cu As Cu As Cu As

0 7.81 0.54
150 3 0.16 0.21 3.43 0.34 4.13 nd
% ~ 67 ~ 37
225 2.8 0.07 0.33 0.15 0.19 6.63 nd
% ~ 98 ~ 65

♦ Increase transport of As
Increase of pH ♦ Increase transport of Cu
♦ Maintain the As-free
Cu electrolyte
 ABATEMENT OF As
Cation
(+) memb. (-)
i t % Abatement
A/m2 h w/o Air 0.1 L/min

W 250 12 18 32
H2SO4 500 7 36 39
S

Cu, CuO, Cu2O

PbSO4, Iotite (Pb(S,Ge)(O,OH)4)
 CONCLUSIONS

★ Electrodialysis efficiently separates Cu

and As from acidic electrolytes
★ A Cu electrolyte 100% free of As can
be obtained by using Electrodialysis

★ The abatement of As can be achieved by

anodic oxidation during Electrodialysis