Copper Refinery Operation

in PT. Smelting

Electrorefining
Application of electrical
potential between
copper anode and metal
cathode in CuSO4H2SO4-H2O electrolyte.
Refining process:
Anode (99% Cu) Cathode (99.99% Cu)

Power supply
Fresh
Anode (+)

SS-blank
Cathode (-)

Cu++ + 2e- = Cuo

Cuo = Cu++ + 2e-

CuSO4 + H2SO4 + H2O

Electrorefining Process
Electrochemically dissolving copper from
impure copper anode to electrolyte
Cuoanode Cu++ + 2eEo = +0.34V
Selectively electroplating pure copper
without anode impurities from electrolyte
onto cathodes
Cu++ + 2e- Cuocathode Eo = -0.34V

Standard Electrochemical
(Reduction) Potentials
3+

Au
+
Ag
2+
Cu
+
BiO

+ 2H
+
HAsO2 + 3H
+
+
SbO
+ 2H
+
2H
2+
Pb
2+
Ni
2+
Co
2+
Fe

+
+
+
+
+
+

3e- ---> Au
o
e- ---> Ag
o
2e- ---> Cu
o
3e- ---> Bi
o
3e- ---> As
o
3e- ---> Sb

+
+
+
+
+

2e2e2e2e2e-

--->
--->
--->
--->
--->

H2
o
Pb
o
Ni
o
Co
o
Fe

1.50 volts
0.80 volts
0.34 volts
+ H2O 0.32 volts
+ H2O 0.25 volts
+ H2O 0.21 volts
0 (pH=0; pH2=1atm)
-0.13 volts
-0.26 volts
-0.28 volts
-0.45 volts

Refining Target
Production of pure copper, free from
impurities (<65ppm)
Separation of valuable impurities - precious
metals Ag, Au, Pt - as slime (by-product)

PT Smelting
Refinery Plant

LME A-GRADE
Copper Cathode
Element
group
1

Element

Symbol Max content

(ppm)

Max content
group (ppm)

Internal <=
ppm

Selenium
Tellurium
Bismuth

Se
Te
Bi

2
2
2

Chromium
Mangan
Antimony
Cadmium
Arsenic
Phosphour

Cr
Mn
Sb
Cd
As
P

4
5
-

15

Lead

Pb

Sulfur

15*

15*

10

Tin
Nickel
Iron
Silicon
Zinc
Cobalt

Sn
Ni
Fe
Si
Zn
Co

10
-

20

Silver

Ag

25

25

6
Total

* measured from cast sample

Data: British Standards Institute, BS 6017:1981

65

3 (Se, Te)
3 (Se, Te, Bi)

2
2
1

4
5

5
10
10

(exclude oxygen)

25

Typical cathode analysis

DATE
2004-08-25
2004-08-24
2004-08-23
2004-08-22
2004-08-21
2004-08-20
2004-08-19
2004-08-18
2004-08-17

BiSeTe SeTe
<3
<3
0.3
0.2
0.3
0.2
0.3
0.2
0.3
0.2
0.3
0.2
0.3
0.2
0.3
0.2
0.3
0.2
0.4
0.3

Ag
<25
6
7
7
7
7
6
7
7
7

Pb Fe
<5 <10
0.7 1
0.6 1
0.9 1
1.1 1
0.9 1
0.7 1
1.2 1
1.4 1
1.2 1

As
<5
0.3
0.3
0.4
0.3
0.5
0.2
0.3
0.4
0.3

Sb S
<4 <15 Bi <2
0.1 3
0.1
0.1 5
0.1
0.1 5
0.1
0.1 4
0.1
0.1 5
0.1
0.1 5
0.1
0.1 3
0.1
0.1 4
0.1
0.1 4
0.1

Se
<2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2

Te
<2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1

Ni
0.2
0.3
0.3
0.1
0.4
0.2
0.2
0.4
0.2

Impurities
<65
11.7
14.7
15.1
14.0
15.3
13.6
13.2
14.7
14.3

Cu
>99.9935
99.9988
99.9985
99.9985
99.9986
99.9985
99.9986
99.9987
99.9985
99.9986

Typical anode analysis

Lot No.
4214
4215
4216
4217
4218
4219
4220
4221
4222
4223
4224
4225
4226

Au (96 Ag (114
gr/t)
gr/t)
99.4 272.0
95.7 277.0
92.7 268.0
87.4 263.0
95.3 276.0
105.1 277.0
111.2 272.0
120.2 286.0
121.1 287.0
115.5 282.0
104.3 272.0
94.7 271.0
94.8 272.0

Cu
(>99.5
%)
99.140
99.090
99.280
99.470
99.060
99.450
99.380
99.360
99.050
99.560
99.260
99.470
99.030

PB
(0.080
%)
0.265
0.268
0.249
0.247
0.167
0.126
0.170
0.146
0.187
0.187
0.222
0.222
0.286

S
(0.004
%)
0.005
0.002
0.003
0.003
0.004
0.001
0.007
0.003
0.001
0.004
0.001
0.001
0.003

SB
(0.001
%)
0.003
0.003
0.003
0.003
0.002
0.002
0.002
0.001
0.002
0.002
0.003
0.003
0.003

AS
(0.047
%)
0.106
0.110
0.109
0.097
0.066
0.061
0.048
0.051
0.081
0.083
0.113
0.099
0.095

BI
(0.011
%)
0.026
0.030
0.030
0.025
0.022
0.012
0.011
0.012
0.015
0.016
0.019
0.022
0.027

O
(0.150
%)
0.070
0.070
0.370
0.120
0.080
0.050
0.070
0.070
0.070
0.170
0.140
0.080
0.070

SE
(0.056
%)
0.067
0.076
0.072
0.107
0.077
0.067
0.069
0.066
0.061
0.068
0.061
0.078
0.090

TE
(0.021
%)
0.005
0.007
0.008
0.009
0.008
0.008
0.007
0.007
0.007
0.007
0.007
0.007
0.008

ZN %
0.002
0.001
0.001
0.002
0.001
0.001
0.002
0.001
0.001
0.001
0.001
0.001
0.002

FE %
0.002
0.001
0.002
0.002
0.002
0.003
0.004
0.002
0.004
0.003
0.004
0.004
0.001

AL %
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001

NI
(0.052
%)
0.012
0.011
0.010
0.009
0.008
0.008
0.009
0.007
0.007
0.008
0.008
0.009
0.010

SN %
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001

CD %
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001

Operation Control
Electrodes flatness and alignment.
Anode composition (Lead, Arsenic).
Electrolyte parameter (Cu, FA, Cl-,
Impurities, reagent, temperature, flow rate,
and clarity).
Cell monitoring (shorts inspection and
breaking).

Anode life
SS-blank
Cathode

Start
0 day

Fresh
Anode

Anode Scrap
50kgCathode

7th day

100kgCathode

Finish
20th day

Crop Schedule

New anode + new SS blank insertion in cell

ER 7 days: Cathode stripping 50 kg/plate
Blank inserted again
ER 13 days: Cathode stropping 100 kg/plate
Anode scrap discharging
Electrolyte draining
Slime draining
New anode + blank insertion ...

Tankhouse

Plant Layout
Before Exp. Present
654
762
220,000 252,000

Cell Number (cells)

Production (T/Y)

Original
Slime
Treatment Plant

Tellurium
Recovery Plant

Control Room

Diff
108
32,000
Expanded

Electrolyte Circulation Equipment

11

15

19

12

16

20

13

17

21

14

18

22

10

Liberator
Rectifiers

Commercial
Rectifiers
Liberator
Cells

Machine
Area

Anode
Cathode
AnodeScrap
Commercial Cells

Outside View

SIMPLIFIED PROCESS IN REFINERY

Rectifier

2 x 18 kA, 295 V
Thyristor
Power at maximum capacity = 10 MW
Current density 180~314 A/m2

Anode
Cu : 99.2~99.5%
Continuous casting:
Hazelett Contilanod
380 kg/plate, 45 mm thick
970 x 938 mm area
20 Days anode life

Anode Preparation Machine

Spacing 103.5 mm
Lug brushing
Anode verticality
measurement, 5 mm
59 Anodes per cell

Cathode Mother Plate

ISA Process Permanent
Cathode
SUS 316L
Surface 2B
1 x 1 m deposit face
Bottom wax
ABS edge strip
58 Cathodes per cell

Overhead Cranes
2 x 27T capacity
Semi-automatic
electrode bale
Simultaneously 58
anodes and 58
cathodes lifting
Manual positioning

Commercial Cells

762 cells
Polymer concrete
V-notch weir
Cell voltage 0.3 V/cell

Electrode Alignment
Gap between anode
and cathode must be
uniform.
One side lays on
busbar and another
side lays on
insulator.
Touching = short

Inside Tankhouse

Electrolyte

Cu : 48-50 g/l
H2SO4 : 170-180 g/l
Cl- : 50-60 mg/l
Temp : 58-62oC
Flowrate : 35-40 l/m
Steam-heated by
plate heat exchanger

ELECTROLYTE FLOW
head
tank
steam

overflow
CELL

HX
condensate

CIRCULATION
TANK

ELECTROLYTE FLOW DURING 2nd-CROP

CELL
Slime to
leaching
area

Decant Tank

To electrolyte
circulation tank

Leaf filter

Electrolyte
Storage Tank

Heat Exchanger
Plate type HX
Less space than
shell & tube type
Higher heating
efficiency

Reagents
Glue: leveling agent
Thiourea: grain refiner
HCl: grain refiner

Some ER tankhouse add

AVITON

Cropping activity

Cathode Washing & Stripping Machine

Washing by hot water
86oC to melt wax
Flexing to open
Chiseling to peel-off
Apply bottom waxing
Spacing 103.5 mm

Product Cathode
1st-crop = 50
kg/sheet
2nd-crop = 100
kg/sheet
Size 1 x 1 m
LME Grade-A
Capa. 235,000 t/y

Current Efficiency
Ratio between actual cathode deposited and
theoretical deposition by Faradays law
Simplified formula for theoretical deposit:
W (kg) = 1.185 x set kA x hour x cell
Target CE = 96.0 %

Why CE drops?
Mainly by short circuit
between anode-cathode
Checked by infra-red
camera, or gaussmeter
Short must be broken to
avoid current loss

SHORT

Shorts/cell vs CE-1
CE1-DK185
100%
99%
98%
97%
96%
95%
94%
93%
92%
91%
90%

CE1-DK312
y = -0.0045x + 0.9721
2

R = 0.5746

y = -0.0112x + 0.9917
2

R = 0.8582

Anode Scrap Washing Machine

Washing anode
scrap by hot water
Anode scrap ratio
11~14%

Electrolyte Purification
Dissolved Cu in electrolyte: 14 kg per ton
Cathode.
Soluble anode impurities build-up: Bi, Co,
Fe, and Ni.
Partially dissolved As and Sb.
Dissolved Se and Te from slime leaching
process.

Liberator Cells
Electrowinning cell
Anode: H2O 2H+ + 1/2O2 + 2e Cathode: Cu++ + 2e- Cu

Using lead anode

Cell voltage = 2.4 volt
Total 32 cells (Primary, Secondary, Tertiary)
Used for stabilizing Cu in electrolyte as anode
dissolve is ~1.4% and reducing some impurities.

LIBERATOR ELECTROLYTE FLOW

Comm. Cell Head Tank

P r im a r y
L ib e r a t o r

Comm. Cell

S e c o n d a ry
L ib e r a t o r

T e r t ia r y
L ib e r a t o r

DDecopperized
e c o p p e r iz a t io n
Solution
T ank

W W TP
3 m3/d

L ib e r a t o r S lu d g e
T re a tm e n t A re a
L ib e r a t o r S lu d g e
S m e lt e r

Primary Liberator
ISA blank cathode
Pb-Sn-Ca anode,
cold rolled
Reducing Cu from
50 40 g/l in the
electrolyte
Saleable liberator
cathode product

Secondary Liberator
Anode scrap as
cathode
Reducing Cu from
40 20 g/l in
electrolyte
Deposited cathode
recycled in smelter

Tertiary Liberator
Anode scrap as
cathode
Reducing Cu from
20 1 g/l , then
deposited As, Sb
and Bi.
Sludge to be
recycled to smelter

Anode Slime
Insoluble elements in
anode is accumulated at
cell bottom (slime).
Au, Pt, As, and Sb
Ag2Se, Ag2Te, Cu2Se,
Cu2S, PbSO4,
Sn(OH)2SO4.
Cu in slime must be
controlled lower than 1%

SLIME DECOPPERIZING PROCESSING

Comm. Cell

S li m e S e t t le r
D ecant
S li m e D e c a n t T a n k
Comm.
Cell

S te a m
S li m e s

O xyge n

D ecant

A u t o c la v e s

Leaching par:
115 deg.C
4.5 kg/cm2
3 hours
15-20% solid dens.

H o ld i n g T a n k
S li m e S lu r r y T a n k
F i lt r a t e

Decopp.
Solution

F i lt e r P r e s s
S u lf u r i c A c i d

C e n tr if u g e
H . W a te r
R e p u lp T a n k

A u t o c la v e F e e d T a n k

F i lt r a t e

C e n tr if u g e
D e c o p p e r i z e d S li m e s

TeRecovery

Slime Leaching

Using autoclave
High temperature
High pressure
Oxygen blowing

Cu + H2SO4 + 1/2 O2 CuSO4 + H2O

Cu2O + 2H2SO4 + 1/2 O2 2CuSO4 + 2H2O
Decopperized slime : tankhouse by-product

Centrifugal Separator
Used for dehydrating
leached slime.
Centrifugal force will
separate fluid as filtrate
Solid material remain
on the screen

Slime analysis
Sample-1

Ave. Aug-04

Typical (21-Jul-04)

% (dry)

57.0
54.0
51.0
48.0
45.0
42.0
39.0
36.0
33.0
30.0
27.0
24.0
21.0
18.0
15.0
12.0
9.0
6.0
3.0
0.0
Pt

Pd

Sn

Ni

Fe

Sb

Te

Cu

Au

As

Bi

Ag

Se

Pb

Elements

Tellurium Recovery
Te Settler

to Commercial

R8 R7

Filter Press

R6 R5

From Te Feed Tank

R4 R3

Cu2Te
Byproduct

Filtrate Tank

Some Te in slime is leached and concentrated in solution

Te-recovery reactor is set at 94 deg.G
Reactor: 4 tanks with 6 cages each :
1 cage = 50 kg x 29 plates = 1.45 ton copper scrap
Treated solution is Te<50 ppm (design)
Cu2Te cropping: 1 tank/week

R2

R1

1000~5000 ppm

Tellurium Reactor

from Slime area

to Commercial <50 ppm

Tellurium Reactors
Filtrate from slime
area: high Te
Te must be
recovered before
returned
Use copper scrap
for cementation of
Cu2Te

Filter Press
Used for Cu2Te
dehydration
Pneumatic air
pressure will
separate solid from
liquid