Process Optimization in Copper Experimental: Investigations were conducted as pilotscale
COMMUNICATIONS
Electrorefining
By Michael Stelter* and Hartmut Bombach
With an annual worldwide consumption of 14 Mt, copper
is one of the major metallic materials together with steel and
aluminum. At present, approx. 11 Mt of copper are produced
all over the world by electrorefining in sulfuric acid electro-
lytes. In this process, pyrometallurgically produced anode
copper of 98±99 % Cu is refined to so-called grade A copper
of > 99.994 % Cu. From laboratory research in 1800±1870 the
refining effect of the electric current on copper was known;
this method allowed to remove disturbing accompanying ele-
ments such as lead, nickel, arsenic, antimony and silver. The
first industrial-scale copper electrorefining plant was put into
operation on July 1st, 1876, at Norddeutsche Affinerie in
Hamburg. Since that time the process was developed further
with a lot of more or less significant details. In general all
tankhouses in the world for copper electrorefining are work-
ing with the same process until today. In the fifties the techni-
cal electrolysis for copper refining was processed with a cur-
rent density of 150±200 A/m2. In the last years the current
density could be increased to 320±340 A/m2 by simultaneous
improvement of the cathode quality, although the parameters
ªelectrolyteº and ªanode qualityº did not change essentially.
This was possible substantially by modifying the cell design,
the starter sheets and the optimization of inhibitors and flow
control at the electrodes.[1]
Optimization of copper electrorefining: To further optimize
copper electrorefining the Institut für NE-Metallurgie und
Reinststoffe of the TU Bergakademie Freiberg cooperates
with the copper industry in the following fields:
± Current density increase up to 700 ± 1000 A/m2
± Improvement of the chemical purity of copper cathodes
± Anode processes; passivation of anodes; mechanisms of an-
ode slime formation
± Solubility and redox equilibria in electrolytes
± Optimization of the amounts of the classical additives glue,
thiourea and chloride
± Development of analytical methods for the determination
of the effective concentrations of the additives in the elec-
trolyte
± Development of alternative additives for copper electrore-
fining
± Cathode quality: Improved inhibitor dosing in recent years
[*] Prof. M. Stelter, Dr. H. Bombach
TU Bergakademie Freiberg
Institut für NE-Metallurgie und Reinststoffe
Leipziger Str. 34, D-09599 Freiberg, Germany
E-mail: stelter@inemet.tu-freiberg.de
558  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adem.200400403
tests in 35-l cells with 1 anode and 1 or 2 cathodes under sim-
ulated industrial conditions (Fig. 1). The cathode was made
of stainless steel, the effective area was 800 ” 100 mm. The
used anodes were industrial anodes with different chemical
compositions. The electrode gap was 25 mm. Tests were
usually conducted for one anode life consisting of three cath-
ode periods of equal length. The duration of the anode life,
and thus also of the cathode periods, depended on current
density. The calculated standard duration was 21 days for a
current density of 300 A/m2. Each electrolytic cell had an
own electrolyte cycle. The electrolyte circulation rate was
50 l/h. The standard amounts of additives were 100 g glue
and 60 g thiourea per ton of deposited copper. The inhibitors
were continuously dosed as a solution each prepared for a
period of 24 h. At the start, the synthetic electrolyte contained
40 g/l Cu, 160 g/l H2SO4, 50 mg/l chloride and no additives.
The standard electrolyte temperature was 65 C. Current
density, cell voltage, cathodic and anodic polarization and
electrolyte temperature were measured once a minute and re-
corded by a data acquisition device.
Results
Copper electrorefining at high current densities: To assess the
maximum possible current density under normal industrial
electrolysis conditions, the current density was increased in
steps of 150 A/m2 starting from 400 A/m2.[2] At 400 A/m2,
very smooth cathode deposits were produced in all three
cathode periods (Fig. 2). At 550 A/m2, nodule formation and
overgrowth increased strongly, and this trend continued at
700 A/m2; however, the nodules rounded almost completely
so that no shorts did occur. At 850 A/m2, larger dendrites
formed in the upper part of the cathodes at the end of the
cathode period. From 850 A/m2, the hazard of shorts in-
creased strongly due to strongly nodulated cathode deposits
and the formation of individual dendrites, especially at the
end of the cathode periods. The tests at 1000 and 1150 A/m2
had to be broken off after a few hours due to anode passiva-
tion. In all tests without short circuiting, the cathodic current
efficiency was approx. 100 %. Bath voltage and specific ener-
gy consumption increased almost linearly with the current
density in the investigated range. Thus, the double current
density does not only increase the space-time efficiency by
factor 2 but also doubles the bath voltage and specific energy
consumption. If, as an oversimplification, we assume that the
entire bath voltage in the electrolysis cell is converted into
Ohmic heat, the heat input to the cell would even be in-
creased by the factor 4. The high energy input into the cells at
current densities over 700 A/m2 requires a continuous cool-
ing of the electrolyte under technical conditions.
has allowed to substantially improve the purity of cathode
copper. For instance, the valid ASTM standard B 115±91 for
quality grade 1 cathode copper allows a maximum concentra-
tion of impurities of 65 l g/g copper. The cathode copper
presently produced in modern electrorefining plants under
ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7
Stelter, Bombach/Process Optimization in Copper Electrorefining
(a) (b)
optimum conditions usually has much lower concentrations
for the individual impurities than the maximum impurity
concentrations prescribed by the above standard (Tab. 1).
Normally Ag and S are the highest impurities in the cath-
odes. Therefore our investigations focused on the behaviour
of Ag[3] and S. Higher electrolyte temperatures lead to in-
creased concentrations of silver in the cathodes. Both the cur-
rent density (in the range 300 to 700 A/m2) and the Ag con-
tent of the anode had only a marginal influence on the Ag
content of the cathode. Strong forced convection of the elec-
trolyte resulted in a strong increase of the Ag content in the
cathodes. It can be assumed that Ag ends up in the cathodes
through dissolution of anode slime and subsequent electro-
chemical codeposition with copper. However, higher con-
(a)
Fig. 2. Shape of cathodic depositions at different current densities. (a) 400 A/m2, (b) 550 A/m2, (c) 700 A/m2, (d) 850 A/m2.
ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7
COMMUNICATIONS
Fig. 1. (a) 35-l Electrolysis cell with equipment. 1 ± Cell, 2 ± Anode, 3 ±
Cathode, 4 ± Reference electrodes with Luggin Capillary, 5 ± Data sta-
tion, 6 ± Computer; (b) Photograph of the 35-l Electrolysis cell with
equipment.
tents of Se and As in the anodes lead to a reduction of the Ag
content in the cathodes. Apparently, elemental Ag in the
slime is dissolved more readily than the silver selenium com-
pounds. The incorporation of particles from the anode slime
has only a small influence on the Ag content of the cathodes.
Nowadays the S content in the cathodes is in the range 3 to
6 lg/g for trouble-free operation, as shown in tab. 1. Sources
of S in the cathodes are incorporation of electrolyte, incor-
poration of S containing anode slime particles, and addition-
ally through thiourea. Our investigations show clearly a de-
pendency of the S content in the cathodes from the amount of
thiourea added to the system. An amount of 60 g thiourea
(per ton of copper deposited) leads to a S content in the cath-
odes of 2 to 3 lg/g. Thiourea is therefore a major source of S
(b) (c) (d)
http://www.aem-journal.de  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 559
 Stelter, Bombach/Process Optimization in Copper Electrorefining

Table 1. Chemical purity of cathode copper now attainable in industrial electrorefining electrorefining.[4] In this case, Cu+ must additionally be
COMMUNICATIONS

vs. ASTM standard requirements.

Element Required by ASTM Attainable concentrations
[lg/g] [lg/g]
Se 2 < 0.2
Te 2 < 0.3
Bi 1 0.03 ± 0.3
Sb 4 0.5 ± 1.0
Pb 5 0.1 ± 0.3
As 5 0.2 ± 0.7
Fe 10 0.5 ± 1.0
Ni 10 < 0.3 ± 0.5
Sn 5 < 0.2
S 15 3.0 ± 6.0
Ag 25 4.0 ± 15
total 65 10 ± 20
in the cathodes. To achieve an even better purity of the cath-
odes it is thus necessary to replace the thiourea by a sulfur-
free additive.
The S content of the cathodes caused by electrolyte inclu-
sions depends strongly on the roughness of the cathode sur-
face. For extremely smooth cathodes the content is < 1 lg/g
and for heavily nodulated cathodes it is > 50 lg/g.
Equilibrium in the electrolyte: Essential criteria for the selec-
tion of the chemical composition of the electrolyte are an elec-
trical conductivity as high as possible as well as favourable
conditions for cathodic copper deposition. The basic composi-
tion of the electrolytes is 40 to 45 g/l Cu and 160 to 190 g/l
free sulfuric acid in most cases. The electrolyte temperature is
generally between 63 and 68 C. Our investigations focused
on the Cu+/Cu2+ equilibrium in the electrolyte and the beha-
viour of As, Sb and Bi during copper electrorefining.
In addition to the dominant Cu2+ ions, Cu+ ions are always
contained in a sulfuric acid copper sulfate solution if metallic
copper is present. In the near-anode layer the highly reactive
Cu+ ions can influence the anode slime formation via various
redox reactions. In the absence of oxygen a highly tempera-
ture-dependent equilibrium establishes in the electrolyte:
Cu2+ + Cu0 $ 2 Cu+
An electrolyte with 45 g/l Cu2+ contains around 320 mg/l
Cu+ at 65 C under equilibrium conditions. If aerial oxygen is
transported into the electrolyte, the Cu+ ions will react with it
while simultaneously the oxidation of other electrolyte com-
ponents will be induced as well (e.g. As(III), Sb(III), organic
additives). By the reaction with oxygen, the establishment of
the equilibrium is disturbed, so that the electrolytes contain
only 50 to 150 mg/l Cu+ under the conditions of industrial
formed both at the anode and the cathode, which increases
the anodic current efficiency but reduces the cathodic current
efficiency. In addition, trivalent As and Sb are faster oxidized
to the pentavalent form. These two elements are primarily
solved in the trivalent form in the electrolysis. In dependence
on the anode composition, different solubility equilibria oc-
cur; occasionally the electrolyte can become supersaturated
with respect to Sb. Especially if the electrolyte is supersatu-
rated and contains a high concentration of pentavalent Sb,
colloidal As, Sb and Bi compounds of changing chemical
composition are formed.[5] If these so-called ªfloating slimesº
are incorporated into the cathodes, their quality will be con-
siderably impaired.
Effects of glue and thiourea
Additional inhibitors are necessary to obtain a smooth and
compact cathode deposit. Next to all copper electrorefining
plants use bone glue, thiourea and chloride ions as inhibitors
up to this day. An average of 100 g glue and 60 g thiourea are
needed to produce one ton of copper. The chloride concentra-
tion in the electrolyte is set to a constant value of 25 to
60 mg/l. Too many or not enough inhibitors produce a con-
siderable deterioration of cathodic deposition, and thus of the
chemical purity of the copper. This is why various mostly
electrochemical methods for online inhibitor concentration
measurement in the electrolyte have been developed, which
are now used in the industry.[6,7]
Current density potential curves show, that an addition of
0.25 to 0.75 mg/l of glue to the copper electrolyte produces a
marked increase in cathodic polarization.[8] A further increase
of the glue concentration to 1 mg/l and higher, however,
does not lead to a further marked increase in polarization.
The slope steepness of the curves clearly shows that the inhi-
bitor effect of glue is reduced at higher current densities. If
defined quantities of thiourea were added to the electrolyte a
depolarizing (catalyst) effect was found. At higher current
densities, the cathodic polarization was reduced by 20 to
30 mV in comparison with the thiourea-free electrolyte. In in-
dustrial copper electrorefining, glue and thiourea are fre-
quently added in a weight ratio of 100 to 60. For low inhibitor
concentrations, the current density-potential curves recorded
for this ratio showed 5 to 15 mV lower potentials compared
to the curves with only glue addition. It was especially inter-
esting that no stable cathode potentials were set up at current
densities higher than approx. 600 A/m2 and higher inhibitor
(1) concentrations; instead, the potentials oscillated by 50 mV
and more.
Further investigations on the effectiveness of glue, thiour-
ea and chloride in the current density range between 300 and
1000 A/m2 were conducted under quasi-industrial conditions
in the 35-l cells. The cathodic polarization rose from 50 mV at
400 A/m2 to 140 mV at 700 A/m2. Above 700 A/m2 the cur-
rent density had only a weak effect on the value of the ca-
thodic polarization. High current densities influence not only
the absolute value but also the time curve of the cathodic po-

560  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.aem-journal.de ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7
Stelter, Bombach/Process Optimization in Copper Electrorefining

Table 2. Some alternative additives for copper electrorefining.

COMMUNICATIONS
700
cell voltage
polarization / cell voltage [mV]

600

500
Additive Effect

400 Polyethylene glycol (PEG) Substitute of glue

300 Polyethylen glycol ether

cathodic polarization

200 Polyacrylic acids Grain refiner

100 Cationic Polyacrylamides Moderate inhibition

anodic polarization
0 Amines Weak inhibition
0 10 20 30 40 50 60
Triamines
time [min.]
Amino acids Strong inhibition
Fig. 3. Periodical oscillation of cathodic polarization and cell voltage at 700 A/m2(glue
100 g/t, thiourea 60 g/t, chlorid 50 mg/l). Amino (carboxylic) acids Weak inhibition

Perfluoralcylbetaines Inhibiting or activating agent

Sulfonic acids Often depolarizer

larization, and thus of the bath voltage. Up to 550 A/m2, both
the cathodic polarization and the bath voltage remained ap- Sodium butyl sulfonate weak inhibition

proximately constant during one cathode period. At higher Derivatives of thiourea Depolarizer
current densities, periodic oscillations of cathodic polariza- Dimethyl thiourea Strong depolarizer
tion and bath voltage were observed that were reduced to
zero within 8 to 24 h. The oscillations of the cathodic polar-
ization and the bath voltage proceeded synchronously with
identical amplitude height (Fig. 3), which means that they ble alternative to glue. The polarizing effect of PEG on the ca-
were caused by simultaneous periodic changes on the entire thodic copper deposition as a function of the molecular
cathode surface. weight (from 200 to 20000) and the concentration in the cur-
On the basis of the curve shape and further experiments, rent density range between 0 and 1000 A/m2 was investi-
we assume that increased adsorption of the inhibitors takes gated.[9] As an example, Fig. 4 shows the cathodic polariza-
place on the entire cathode surface at high current densities, tions for a current density of 500 A/m2 and an electrolyte
which leads to an increase in cathodic polarization. At a cer- temperature of 75 C, which were taken from the current den-
tain potential, the inhibitor molecules are rapidly desorbed, sity-potential curves. While PEG with a molecular weight up
and the process starts anew. to 600 will lead to no or only a slight increase in cathodic po-
Alternative additives in copper electrorefining: The glue used larization, PEG with a molecular weight of 1000 and more
in copper electrorefining is a natural product and thus differ- will cause a clearly higher increase in cathodic polarization
ent batches will not have the same composition. The use of compared with glue. Increase in the molecular weight to
different types of glue in copper electrorefining resulted in more than 6000 will then lead to no further increase in
different electrochemical efficiencies and different decompo- cathodic polarization. As compared with glue, PEG show an
sition rates. This can lead to problems in the copper electrore- effect even at clearly lower concentrations (Fig. 4).
fining process. As mentioned above, the major source of S in On addition of PEG cathodic polarization increases very
the cathodes is thiourea. Investigations on the optimization of rapidly in the concentration range from 0 to 0.1 mg/l PEG.
the glue, thiourea and chloride additions at high current den- Cathodic polarization reaches its maximum at a PEG concen-
sities have shown that these cease to be sufficiently effective
at current densities higher than approx. 700 A/m2. This find-
ing underscores the necessity of a systematic search of new 200
8
Cathodic polarization [mV]

inhibitor systems for copper electrorefining. 180 7

6
160
From literature a number of investigations are known 140
5
4
about alternative inhibitors which are added without any 120 3
other substance or in combination with glue, thiourea and 100 9
other compounds in copper electrorefining (Tab. 2). How- 80
60 2
ever, in many cases the investigations were made under con-
40
ditions which were quite different from those of industrial 20 1

copper electrorefining. The compounds suggested in litera- 0

ture can be classified into substitutes for glue and substitutes 0 0.2 0.4 0.6 0.8 1
for thiourea. Additive concentration [mg/l]

It is known from literature that polyethylene glycols (PEG) Fig. 4. Cathodic polarization as a function of the molecular weight and concentration
of polyethylene glycols (500 A/m2, 75 C). 1 ± without additives, 2 ± PEG 600, 3 ±
and similar compounds have a clearly inhibitory effect on PEG 1000, 4 ± PEG 1500, 5 ± PEG 2000, 6 ± PEG 3000, 7 ± PEG 6000, 8 ± PEG
copper deposition and, therefore, they might provide a possi- 20000, 9 ± glue.

ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7 http://www.aem-journal.de  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 561
 tration between 0.1 and 0.2 mg/l, but at a glue concentration
COMMUNICATIONS
of about 0.8 mg/l. Further advantages of PEG compared with
glue are the clearly slower chemical decomposition rate, the
possibility of setting a definite cathodic potential by variation
of the molecular weight and the constant chemical composi-
tion. However, our systematic investigations have shown that
there will be no improvement in the deposition type of the
cathode deposits when PEG is only added compared with the
classical inhibitor system of glue and thiourea until now. It is
known in copper electrorefining and electroplating that a
high quality of cathodic deposition can usually only be
achieved through a combination of inhibitors and activators.
The major target of our further investigations is to find addi-
tives that show a depolarizing effect in combination with
PEG. In addition to that criterion these additives should be
sulfurfree to reduce the level of sulfur in the cathodes in com-
parison to the traditional used thiourea.
Received: March 24, 2004
± lowed by thin wall thickness design of functional components
[1] M. Stelter, H. Bombach, Erzmetall 2001, 54, 432.
[2] M. Stelter, H. Bombach, in Copper 2003 ± Cobre 2003,
Volume 5, The Canadian Institute of Mining, Metal-
lurgy an Petroleum, Monteral, Canada, 2003, p. 555±
567.
[3] D. Schab, H. Bombach, K. Hein, Erzmetall 1997, 50, 614.
[4] H. Bombach, K. Hein, D. Schab, Erzmetall 1995, 40, 703.
[5] H. Bombach, K. Hein, R. Vermeersch, BHM 1999, 144,
18.
[6] B. Langer, P. Stantke, EPD Congress (Ed.: G. W. War-
ren), The Minerals, Metals & Materials Society, 1995,
p. 559±569.
[7] M. Goffman, WO-Patent 84/03307.
[8] N. Nesterov, H. Bombach, M. Stelter, in Proc. EMC Con-
gress 2001, Vol. 1, Friedrichshafen, p. 121±130.
[9] M. Stelter, H. Bombach, N. Nesterov, JOM 2002, 54 (4),
32.
______________________
562  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adem.200400417
Material and Process
Development of Advanced
Refractories for Innovative Metal
Processing**
By C. G. Aneziris,* F. Homola and D. Borzov
As the new generation of secondary metallurgy and ad-
vanced continuous casting technologies have been developed
in the last decade, refractory materials have met the greatest
challenge in order to secure the high metal quality under eco-
nomical and ecological aspects. During service refractories
must not only tolerate high temperature but also withstand
stresses (thermal and/or mechanical) as well as resist com-
bined attacks by liquids such as molten metals, slags and
fluxes. Especially in near net shape casting technologies en-
hanced corrosion and erosion performance is required fol-
such as submerged entry nozzles or casting channels.[1,2] In
addition the processing of these advanced refractories has to
fulfil all the requirements for a large geometry component
manufacturing whereby the task of low shrinkage during fir-
ing dominates.
In recent years the Institute of Ceramic, Glass and Con-
struction Materials of the Technische Universität Bergakade-
mie Freiberg has been involved in research studies of process
and material development of MgO carbon bonded materials
(MgO-C) as high-performance refractory ceramics because of
their superior properties according to corrosion and thermal
shock resistance as well as the unique benefits out of a low
shrinkage pyrolisis firing process. MgO-C refractories are es-
tablished construction materials of converters, electric-arc
furnaces, transfer and treatment ladles.[3] The carbon in-
creases the corrosion resistance of magnesia carbon bricks
caused by all types of liquids (molten slag and metals) and
improves their thermomechanical properties, particularly
their thermal shock resistance. In addition carbon offers ex-
cellent electrical properties in order to use these advanced re-
fractories also as smart, functional refractories and especially
as smart refractory casting components.
±
[*] Prof. C. G. Aneziris, Dr. F. Homola, Dr. D. Borzov
TU Bergakademie Freiberg
Institute of Ceramic, Glass and Construction Materials
D-09599 Freiberg, Germany
E-mail: aneziris@ikgb.tu-freiberg.de
[**] The authors would like to thank Bakelite AG and Rütgers AG
for the supplying of the binder system. The financial support
from the Deutsche Forschungsgemeinschaft (DFG) is also
gratefully acknowledged.
ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7