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Paper -1

Paper presented at the seminar on


Quality Control of Copper
“Testing & Quality Control of
Cathodes: An overview Copper & Copper Alloy Products”
by Balachandran.P.Kamath, B. Latchhayya, held at Mumbai on 8-9 December, 1999.
Kiran Prasad Shetty *

Introduction: conditions and the quality is affected. The


primary reasons are as under:
Copper Electro refining has been established
as an industry since 1871 at Nevark, in United a) Co-deposition with copper
States. The basic operating process has
remained the same, but there has been b) Entrapment of electrolyte
tremendous improvement in its application. All
operations have become automated. The c) Entrapment of slimes.
permanent cathode technology has been one
of the largest single factors responsible for Co deposition of impurities:
improvement of quality.
It is well known that each element has an
The main driving force for improvement of electrode potential for deposition. The Electro
cathode quality has been the market demand deposition potential for copper is much higher
for better quality of rods. Till the first half of the than the impurities with the exception of Silver.
century, a copper with a purity of 99.95 % was Co deposition of impurities along with copper
considered good. Today, the copper quality is takes place under the following set of
not decided by the purity level, but by the type conditions:
and level of individual impurities
• Very low copper content in electrolyte
This paper discusses some basic aspects,
which are important to a Refinery operator. It • Presence of silver in electrolyte in
also dwells into certain critical facets of dissolved form
electrorefining, which although well known are
not felt important by the production personnel. • High voltage conditions due to passivation
It may be emphasized that in refinery the etc.
problems get out of hand over a period of time
and it takes equally long time to bring back the Lowering copper concentration of electrolyte to
operations to normalcy. The initial indications of less than 20 gms/ Litre causes deposition of
problems are innocuous but suddenly they take impurities. This may take place in De
a turn in the form of poor efficiency, poor quality, copperising or Liberator cells but not in Electro
high scrap percentages or higher power refining cells.
consumption.
Mechanisms affecting Cathode Silver dissolves to a small extent in Electrolyte
and gets electro deposited since it’s electrode
Quality: potential is higher than Copper. This however
Theoretically, the cathodes produced should be is limited to below 10 ppm normally. Chlorine
absolutely pure under ideal conditions. This is ion causes the Silver to precipitate as Silver
because the impurities which are more reactive Chloride which is highly insoluble in aqueous
than copper dissolve but do not deposit. electrolyte.
Impurities which are less reactive than copper
do not dissolve at all and settle at the bottom of Entrapment of electrolyte:
the cell as slimes. In real practice, however, the
ideal conditions do not prevail under industrial Entrapment of electrolyte is another parameter
causing deterioration in Cathode quality.
*THE AUTHORS ARE WITH STERLITE INDUSTRIES (I) LTD.,COPPER DIVISION,SILVASSA.
1
Nickel, Arsenic and Iron are some of the entrapments are also visible. Figure – 1 gives
impurities, which get entrapped along with the the microscopic structure of fine grain copper
electrolyte. Entrapment is enhanced due to deposit.
rough and spongy cathode deposit. To prevent
this occurrence, one should keep the level of
these impurities below certain limits. Also, the
deposition condition in cells should be such that
spongy and nodular deposits are not formed.

Entrapment of slimes.

Presence of suspended particles in electrolyte


causes the cathode to deteriorate. Besides,
slime causes nodulation in cathodes, which
causes entrapment of more slimes and
electrolyte. The entrapment of slimes also
causes more nodules to form unless the
reagent addition is satisfactory.

Measurement of Cathode Quality


Parameters: Fig – 1: Microscopic structure of
fine grain copper deposit.
1. Visual Inspection :

The first and simplest method is to carry out 3. Analysis :


regular visual inspection of cathodes during
production. In case of ISA process, observing Several methods of analysis are used for
the operation of the Cathode Washing and cathodes. However, the segregation of
stripping machine would give the best indication impurities in cathodes has made it very difficult
to the process operator. to get a representative sample of the cathode
lot. The distribution of impurities is not uniform,
It is well known that use of certain addition
tending to concentrate at top, bottom and
agents give striations on cathode surface. Flow
edges. Different impurities show bias at
pattern has a big bearing on the deposit, which
can be to some extent seen by looking at the different locations. Many methods have been
striations. Daily inspection of cathodes while suggested but none of them have been
stripping can give clear indications of flow accepted universally. The problem is in getting
patterns in cells, problems of deposition if any a representative sample and not of analysis.
and even some indications about the Hence the method of sampling cathode will
consistency of addition agent presence in cells. influence the level of impurities found.
It is absolutely essential that all persons
connected with electrorefining inspect the The instrument for analysis which are adopted
are:
stripping on a day to day basis and correct
various operating parameters regularly, albeit 1. DC Arc spectrometer
making very small changes.
2. Spark Spectrometer.
2. Metallographic Examination
3. ICP
To have a better control over the cathode 4. Atomic Absorption Spectrophotometer
growth, the crystal structure of the cathode can
be viewed using microscope. A sample is taken The two most commonly used sources for
at right angles to the direction of growth,
detection of impurities in copper cathodes are
polished and etched to reveal the grain
low voltage DC arc spectrometer and high
structure. The structure will indicate whether the
voltage AC spark spectrometer
reagents are added at correct level and if the
reagent delivery system is functioning correctly.
Power interruption lines, slime and electrolyte

2
DC arc spectrometer continuous to be an 3. The detector and reader.
important spectroscopic technique for solid
samples, while other techniques such as ICP The Sampling device and the source depend
and Atomic absorption work well for liquid on the type of the sample and the analytical
samples. The digestion necessary to put the data desired. As the emission spectrum
solid sample in to a liquid will in many cases emerges from the source it is focussed on to
dilute the sample beyond the detection limits the spectrometer’s entrance slit, where it is
obtainable with these techniques. In addition, dispersed in to its component wavelengths. The
some sample resists digestion even in strong optical elements permit site selection within the
acids. source discharge and thus eliminate the need
to move the entire source assembly. The use of
a) DC Arc Spectrometer mirrors, properly placed also eliminates the
chromatic & spherical aberrations encountered
with lens optics. At the exit slits of spectrometer,
Principle:
the radiation is sensed by a photodetector.
The essential parts of a spectrograph are a slit,
an optical system and a camera for recording
No single source is best for all applications.
the spectrum. The light from the source of
Factors that influence the selection of an
radiation passes through the slit, which is a
excitation source are the concentration of the
narrow vertical aperture, then through the
elements being determined, the vapor
optical system, which includes a prism or
pressures or volatility’s of these elements, the
grating. An image of the slit is produced by
excitation potentials of the atomic lines used in
means of lenses at the point where the light is
the analysis and the physical condition of the
recorded. One such image is produced for each
sample. For solid samples, arc excitation is
radiation having a specific wavelength, and the
more sensitive, while spark excitation are more
result is a series of vertical line images, which
stable. Plasma sources are choices for
constitute the spectrum of the element being
solutions and gaseous samples.
investigated. The optical system may be either
of glass or quartz; the latter transmits in the
ultraviolet region, where many useful lines Factors governing the cathode
occur, as well as in the visible region
quality.
The holders for arc and spark excitation are 1. Anode composition and behavior
housed in a metal box fitted with a safety shield.
of impurities during electrolysis:
b) Atomic Emission Spectrometer
Copper anodes of different origins will have
different chemical compositions, thereby
Principle: different behavior during electrolysis. Major
In atomic emission spectroscopy, a minute part impurities in copper anodes are Ag, As, Au, Bi,
of the sample is vaporized and thermally Fe, Ni, Pb, S, Sb, Se, and Te apart from
excited to the point of atomic emission. An oxygen. The accumulation of these impurities
electric arc or spark supplies the energy can lead o serious complications in
required for these processes, or more recently electrorefining. Typical anode composition is
by a laser or plasma composed of inert gas. given below( Table-1).
The atomic spectrum emitted by the sample is
used to determine its elemental composition. Table-1 : Typical Anode composition
The wavelength at which the intensity
measurement is made identifies the element, Element Concentration
whereas the intensity of the emitted radiation
quantifies its concentration. Cu 99.3 % - 99.7 %
Oxygen 1200–1500 ppm
The instrument may be divided into three major Sulphur < 20 ppm
components.
Iron < 20 ppm

1. The sampling device and source As, Ag, Bi, Sb, Pb, Ni Should be as consistent as
possible from cast to cast.
Ag/Se Molar ratio >1
2. The spectrometer.

3
As (Bi+Sb) molar >2 washing of electrolyte from the cathodes. Fig–
ratio 2 gives the microscopic structure of cathode
Anode composition plays a vital role in cathode deposit entrapped with electrolyte.
quality. The approximate distribution of the
principal elements contained in anode between
cathodes, electrolyte and slime is given below
in %. ( Table-2).

Table – 2 : Distribution of anode impurities in copper


electrorefining .( in %)

Element Cathod Electrolyte Slime


e
Gold 1-1.5 - 98.5-99
Silver 2-3 - 97-98
Copper 98 1.9 0.1
Se & Te 1-2 - 98-99
Lead 1-5 - 95-99
Nickel 15 75 10
Sb 20-30 20 5-60 Fig – 2: Microscopic structure of Cathode
Sn 20-30 20 50-60 deposit entrapped with electrolyte.
S 3-5 - 95-97
Fe 10-20 80 10-20 When the electrolyte contains large amount of
Zn 2 94 4 nickel, iron and zinc sulphates, the solubility of
Al 3 77 20 copper sulphate decreases, and the solution
becomes supersaturated with copper sulphate;
Bi - 22 79
as a result its crystal may separate.
AS 10 70 20 Consequently the concentration of copper ions
in the layer of electrolyte adjacent to the
cathode may become too low and hydrogen will
Impurities can be divided into following groups be released at the cathode together with the
according to their behavior in the electrolysis copper. The current efficiency will consequently
process. decrease and the quality of cathode deposit will
deteriorate.
Ni, Zn, Co, Fe :
It is necessary to ensure that the electrolyte
These are the metals that are more contains little of the these metals
electronegative than the copper and pass
almost completely in to the solution, thereby
gradually accumulating in the electrolyte. Ag, Se, Te, Au:
During the electrolytic refining of copper, nickel
accumulates in the electrolyte faster than the
other impurities, since its content in the anodes These metals are more electropositive than
is always greater than the content of any copper and almost completely pass on to the
elements of this group. Nickel, iron and zinc slime. Metals which do not dissolve in sulphuric
contained in the electrolyte in comparatively acid solution (Pb, Sn) and also relatively week
large quantities do not affect the composition of electrochemically active compounds of Cu2Te,
the cathodes but may give rise to unfavorable Cu2Se and Cu2S also belongs to this group. .
effects in the electrolysis of copper. Sometimes Analysis of slime indicates predominately silver
small amount of iron and nickel do nevertheless bearing compounds Ag2Se, (AgCu)2Se and
appear in the cathode copper. This is explained their analogous tellurides. To prevent physical
by the fact that iron and nickel sulphates remain inclusion of these compounds in copper
in the cathode either with the electrolyte in the cathode, it is required to maintain the atomic
form of inclusions in the pores and inter ratio Ag / (Te+Se) at more than 2.
crystalline cavities or on account of the poor

4
For silver contamination of cathode there exists arsenates BiAs04, SbAsO4 which separates
the possibility of electrolyte deposition at the from the electrolyte in the form of fine particles,
cathode limited by the solubility of silver in the forming floating slime. This slime adheres to top
electrolyte. When the anode contains a large of the cathode forming top nodules and
amount of silver some of it can pass in to the contaminates them.
solution in the form of AgSO4. In order to
prevent silver from accumulating in the
electrolyte and possibility of codeposition along 0.5
Float slime
with the copper, it is precipitated in slime as 0.4 SbSo4
AgCl by adding Chloride Ion Cl-.

Conc. of Sb, GPL


saturation
0.3
Factor affecting the level of selenium Optimum operating
0.2 range
contamination level in cathode copper is the co
deposition of selenium. Normally the 0.1
concentration of Se is low (<O.2ppm), but care
should be taken to avoid any contamination, 0
particularly by silver refinery leach liquors. 0.1 1 10
Selenium forms complex with thiourea in the Conc. os As, GPL
ratio Se (IV) : CS (NH)2::1:4 particularly when Fig – 3: Solubilities of As and Sb in electrolyte.
there is insufficient silver in anodes to
precipitate silver as Ag2Se. Formation of these
compounds could increase the solubility of The Sb in the anode dissolves in the electrolyte
certain selenides and at the same time is in the trivalent state. . Then in the presence of
absorbed on the cathode surface. High dissolved oxygen in the electrolyte, Sb (III)
concentrations of Te in the electrolyte result in oxidises in to Sb (V) State. Studies reveal that
contaminated copper with poor drawing Sb (V) contributes significantly in floating slime
properties. formation. The floating slime formation could be
controlled, if As/(Sb+Bi) molar ratio is
Gold does not dissolve in the electrolyte and maintained at more than 2. The solubility of
completely goes to the slime. arsenate compounds is strongly influenced by
temperature. One investigation has shown that
As, Bi, Sb: a temperature decrease from 60OC to 50OC
results in 20% decrease in the solubility product
for antimony arsenate.(5).
These metals have potentials very near to the
copper and are most harmful, as they readily Ideally cathode quality will be enhanced by
pass on to the solution and remains in the maintaining low Sb concentration and by
solution and co deposits with the copper under maintaining an electrolyte well under the
conditions of the low copper concentration, high saturation limit of arsenates. Fig - 1 shows the
concentration of these metals in the electrolyte solubilities of Sb and As in electrolyte
and high current density. The presence of these
impurities reduces the electrical conductivity, One method for controlling the floating slime is
ductility and malleability of copper. The the Bolidens process. The Bolidens process for
incorporation of As, Sb and Bi in cathode can eliminating the float slimes is based on
be due to one or more of the following: anode preventing the oxidation of Sb (III) to Sb (V). It
slime occlusion, electrolyte occlusion, direct was found that oxidation of, As (III) to As (V) is
precipitation of impurities from solution apart more rapid than is Sb oxidation. Thus addition
from co deposition(3). of As (III) to electrolyte will minimise the
formation of Sb (V) preventing float slime
Arsenic presents in electrolyte as AsO43-. When formation. The arsenic additions will have a
the concentration of bismuth and animony in similar effect on Bi concentrations. Increasing
electrolyte is low arsenic does not have content of arsenic in anodes also helps.(5)
appreciable effect on the electrolytic process.
But if the electrolyte contains higher Other processes for removing Sb and Bi are
concentration of Bi and Sb , then it forms detailed in Electrolyte purification section.
insoluble compounds Bi2O3.As2O5, and

5
OXYGEN: 3. Electrode Alignment
Oxygen present in the anode as copper oxide
(Cu2O). This chemically dissolves by Electrode alignment has a significant effect on
electrolyte, as opposed to the electrochemical cathode purity as it determines the current
dissolution of metallic copper. density across electrodes. If the electrodes are
not spaced equally, more current passes
Cu2O + H2SO4 CuSO4 + H20 + Cu through the section where the distance
between anode and cathode is less, due
This copper which is accumulated in the comparatively lesser resistance and less
electrolyte must be removed, so that copper current through the section where distance is
concentration remains constant and passivation more. This result in uneven distribution of
of anodes is avoided. This is achieved by using current across cell and localized high current
liberator cells. More on oxygen and passivation density areas are formed resulting in the
is discussed in coming sections. detrimental effects as discussed in previous
section. It is important to keep the anode and
SULPHUR: cathode contacts with the busbar cleaner, as it
is another cause for uneven distribution of
current.
Although anode sulphur content does not have
any direct effect on the cathode sulphur, Also presence of any bent plates can entrap
sulphur content in the anode should be slime deteriorating cathode purity.
prevented for any spewing at the desired
oxygen level.

2. Current Density 4. Electrolyte composition

Current density (CD) is an important parameter Copper refining electrolyte normally has
in copper electrorefining as operating at higher following composition
current densities lead to decrease in purity of
copper deposit. CD should be optimized to get Table – 3 : Electrolyte Composition
higher production rate and at the same time
higher copper cathode purity. The affect of CD Concentrations
on electrorefining can be explained as below(2). Copper 40-50 gpl
Sulphuric acid 160-180
• At higher CD, copper deposition at cathode gpl
Total Sulphates < 300 gpl
increases, but at the same time it could lead to
dendritic growth at cathode surface. This Nickel <15 gpl
causes slime and electrolyte to get entrapped Arsenic < 15 gpl
on the cathode and lowers cathode purity. Iron < 3 gpl

• Also at higher CD , chances of anode Sb < 500 ppm


passivation are more. The anodes produce Bi <300 ppm
Cu++ ions at faster rate then they convect away
leading to a higher concentration of Cu++ ions at Chloride 25-50 ppm
anode surface resulting in a layer of copper
sulphate. The passivation of anodes having
higher oxygen and low As/(Sb+Bi) ratio can be
And various other impurities dissolved from
partially overcome by operating at lower current
anodes. Apart from this they also contain
densities.
additives added for facilitating smooth
deposition of copper. The temperature is
• At higher CD, chances of impurities such as As,
maintained AT 62-66OC and continuously
Bi and Sb , co depositing with the copper is
circulated at required rate. It is essential that
more.
electrolyte composition be maintained at
optimum level and impurities at as low as

6
possible to avoid any harm to the electrorefining content in the electrolyte. This rapid change
and thereby cathode contamination. suggests that, in an electrolyte already
saturated with Bi, a drop in acid
• The copper concentration in electrolyte during concentration will induce precipitation of Bi.
copper refining is primarily depends on the
anode oxygen content. Copper ions in solution
must be maintained to ensure copper is always
available for deposition at cathode surface, at 0.7

Bi in electrolyte , GPL
level far in excess of impurities. Using liberator 0.6
cells controls copper concentration in 0.5
electrolyte. 0.4
0.3
If copper concentration is lowered, the
0.2
impurities start depositing along with the copper
and contaminate the cathode. Too high 0.1
concentration of copper ions results in 0
crystallization of copper sulfate and chances of 0 100 120 140 160 180 200 220
anode passivation also increases. This also Acid concentration , GPL
increases power consumption.
Fig – 4: Solubility of Bi in electrolyte.
 Acid concentration is maintained in the
electrolyte as the electrical resistance of
cell depends to a considerable degree on The average impurity levels in the cathodes at
the concentration of sulphuric acid in the various acid concentrations in the electrolyte
electrolyte. If the acidity of electrolyte is too are given in Fig –5 & 6 for Se, Sb, Bi, Pb & Ni.
high then following unfavorable processes
occurs 16
Conc. in cathode , ppm

Pb
 The dissolution of anode increases and 12
consequently copper ion concentration in Ni
electrolyte increases. This leads to an
8
increase in number of cells with insoluble
anodes, which is undesirable since in these
cells the cathode purity is low and power 4
consumption increases. The chemical
dissolution at the top of cathode also 0
increases and this leads to broken cathode 0 100 125 150 175 200

 The passage of silver in to the solution 2


increases and some of it may be deposited 1.8
Conc. in cathode , ppm

Se Sb
on the cathodes. 1.6
1.4 Bi
 The concentration of As3+ in solution 1.2
increases. 1
0.8
 Studies(5) reveal that the solubility of Bi in 0.6
the electrolyte is strongly dependent on the 0.4
sulphuric acid concentration. . The variation 0.2
in the concentration of bismuth in the 0
electrolyte as function of acid concentration 0 100 125 150 175 200
is given in Fig - 4 . Acid conc. in electrolyte,gpl

Fig–5 & 6 : Variations of cathode impurities at


different electrolyte acid concentrations.
An increase in the acidity of electrolyte by
only 20gpl (from 150 gpl to 170 gpl) may The figure indicates that for most of the cases
result in the sharp increase of the Bi the impurity levels in the cathode pass through

7
a minimum at an acid concentration in the by passivation will have scrap with uneven
vicinity of 160 gpl. This trend appears to apply surface.
both to the elements which contaminate the
cathode mainly by slime occlusion such as Se Passivation can be controlled only by reducing
and Pb, and for which the contamination occurs sulphates, either by dilution or removal. A slight
to a greater extent by electrolyte entrapment. increase in temperature also increases
solubility of copper sulphte, thereby reducing
The contamination of the cathodes at low passivation. One more solution for this problem
acidities (100-125 gpl) appears to have been is the periodical reversal of refining current.
caused by the poor morphology of deposits.
The tendency for increasing contamination of • Apart from this electrolyte contains major
cathode at higher acidity values of 175 –200 gpl impurities such as nickel, arsenic and iron.
can be attributed to increased viscosity and Higher the concentration of these impurities
density of the electrolyte, causing a decrease in higher is the chances of their inclusion in
the limiting current density and in the rate of copper deposit. Electrolyte also contains
slime settlement. Acid level is maintained by other impurities such as Bi, Sb. In order to
adding concentrated sulphuric acid to the keep the level of these impurities it is
system. important to go for electrolyte purification.

• Chloride concentration is maintained in the 5. Electrolyte temperature:


electrolyte due to following reasons.
Electrolyte temperature is one important
 It prevents the passing of silver to the parameter to be controlled in electrorefining.
solution by precipitating it as silver chloride. Higher the temperature, higher is the mobility of
ions in the electrolyte and, consequently the
 Chloride ions work in combination with the conductivity increases. Apart from this
thiourea to reduce the grain size of copper temperature control is necessary for the
deposit via a copper-chloride-thiourea following reasons (1)
complex.
 At higher temperatures the cathode deposit
 It also precipitate out antimony and arsenic crystal structure becomes much coarser,
as antimony oxychloride and arsenic and the density of cathode decreases.
chloride and pass these impurities in to
slime  Too high temperature results in increased
solubility of silver in electrolyte and silver co
Low chloride levels causes soft cathodes due to deposits in cathode along with the copper
grain refinement. High chloride levels causes contaminating the copper and silver loss.
large columnar based crystals and pile of
relatively long, needle like crystals resulting in  High temperature decomposes glue at
increase in shorts. Chloride level in electrolyte faster rate and could lead to glue shortage
is monitored daily and are maintained by at cathode surface resulting in rough
adding hydrochloric acid. growth.

• The another important parameter to be  Low temperature lowers solubility of


monitored is the total sulphates (total copper, thereby increasing chances of
concentration of sulphates associated with anode passivation.
the dissolved metals in electrolyte.). If the
total sulphate levels go above 300 gpl,  Low temperature also increases electrolyte
there is a strong chance for passivation. density, so anode slimes have a tendency
to float increasing chances of slime
Passivation occurs when copper is prevented inclusion in cathode deposit.
from coming off the anode because of copper
sulfate barrier at anode surface. This is most  Lower the temperature, higher is the
undesirable as Passivation causes severe short electrolyte viscosity, so electrolyte moves
growth apart from higher power consumption. unevenly in cells and anode slime gets
This leads to areas of high current density and entrained in the electrolyte.
therefore poor cathode quality. Anode affected

8
 Low surface temperature of the electrolyte  Higher flow rates disturb the slime layer at
resulting due to uncovering of cells may cell bottom and chances of slime inclusion
result in protruding horizontal growth at in the cathode increases. Attempts are
solution line. therefore made to maintain a circulation
rate where the electrolyte is well mixed but
Considering the above facts it is desirable to the slime is not disturbed.
maintain the temperature in the range of 62-
66OC.It is worthy to note here that a section is Hence, given the importance of flow rate,
be cut in, only when the electrolyte temperature following points be followed to ensure target
is at minimum 550C to avoid any precipitation of flow rates are achieved and maintained
impurities at cathode mother blank surface.
8

Amount of slime , mg/sq.cm.hr


6. Electrolyte circulation and flow 7
Adhering slim e
6
Electrolyte circulation plays a vital role in Floating slim e
5
electrorefining of copper. Any major variation in
this could lead to cathode deposit 4
contamination. The continuation circulation of 3
electrolyte at desired rate is necessary to: 2
1
 Maintain optimum electrolyte temperature
0
0 5 10 15 20 25
 Low flow rates provide insufficient reagents Flow Rate ,LPM
and mixing, thereby contributing to rough
growth at cathode surface. Also circulation Fig – 8 : Change of amount of slime in
electrolyte with flow rate
of electrolyte helps in replenishing addition
reagents which have been consumed /
degraded.
 It is important for operating personnel to
have a constant watch on electrolyte
circulation and flow rate and always be
250
maintained at optimum rate of 25 LPM. A
V-notch provision at cell outlet will enable to
200 Grainy deposition
have a proper control over flow rate.
Current Density , A/M2

150  A look at the cathode deposit and the


Semi grainy deposition
direction of striations gives complete
100 picture of flow pattern in the cells.

50 Flat deposition
 Apart from this as the electrolyte is fed to
cells from a common head tank, it is
0 necessary to have all the cells be aligned
0 5 10 15 20 25 and kept at same level, so that each cell
Flow rate , LPM
could experience similar electrolysis
Fig – 7 : Effect of flow rate on deposit at various conditions.
current densities.
 It is advisable to cut off the current,
whenever circulation is stopped or variation
 During electrorefining of copper, the in flow rate is observed. Analysis of
solution near the anode is constantly being cathodes taken from the cell where flow is
enriched with copper ions, while that near stopped indicates higher contamination
the cathode is being depleted. Eventually due to Bi, Sb, and As. especially at cathode
the time arises when the amount of copper top with dark spots
ions becomes insufficient for normal
electrolysis; the deposition of antimony and
arsenic may begin resulting in cathode
contamination.

9
7. Colloids addition and control is possible to optimize the glue addition rate,
and to have knowledge about flow conditions
The grain refining and leveling agents (Colloids) and glue supply in the cell
are added to the electrolyte as they assist in
smooth, dense deposition of copper deposit. Thiourea {C (H2N)2S} :
These colloids act as grain refining and leveling
agents, without which cathode deposits would It is a white crystalline material and dissolves
be dendrite and soft, entrapping electrolyte and readily in water and helps in smooth deposition
anode slimes. of copper by reducing the grain size, increasing
hardness, brightness and cathode density. It
They most often act as inhibitors. They adsorb gets adsorbed to the cathode surface and
on the cathode surface, where they take part in controls the size and shape of crystals. Studies
the electrochemical deposition of copper. Some also reveal that thiourea acts in conjunction with
of these additives restrict the growth of existing the chlorine ions forming a complex and thus
crystals and thus force the deposition to take facilitating smooth cathode surface. Thiourea is
place via the formation of new nuclei. The also capable of prohibiting the polarising effect
amount of colloids added depends on various of gelatine on the deposition mechanism of
parameters such as composition of electrolyte, copper. It is likely that thiourea acts as a solvent
the current density and others. As said earlier for gelatine.
regular look at the physical appearance and
quality of copper deposit gives good indication Striations on the cathode surface are the best
of colloids addition. indication for the thiourea addition rate.
Striations are the series of small ridges on the
Addition rates may vary at different refineries cathode and follow the same direction as
according to the cathode deposit morphology. If electrolyte flow. Excess thioure addition causes
the continual delivery of reagents stops, coarse deep striations and can entrap slime or
crystal growth occurs after about 4 hrs. If the electrolyte, thus reducing the cathode purity.
stoppage is remedied within that time, fine Thiourea does not decompose, but it is
equipped growth resumes, with no discernible apparently consumed in connection with the
loss of cathode quality(4). deposition of copper.

Glue {Gelatin}: Since thiourea is a sulphur bearing compound,


higher addition rate could lead to sulphur
Glue consists of large protein molecules and contamination of cathode. Cathode flexing
possesses a strong positive charge and gets sound and its strippability gives a good
adsorbed in to the areas in cathode surface, indication for thiourea addition. Thiourea in
where there is a strong negative charge or high electrolyte can be monitored by reatrol system
spots. These spots occur where there is a high
current flow and copper deposition rate is more. Avitone:
Being a poor conductor of electricity it acts as a
inhibitor, preventing any further deposition on It is a sulphonate surfactant and enhances the
these high spots thus enabling cathode to a action of gelatin by allowing the protein to
smoother surface and less shorts. This uniformly spread out and adsorb over greater
eliminates entrapment of slime or electrolyte in area.
these areas. Glue is also consumed by
hydrolysis in the presence of acid and at high 8. Suspended solids and electrolyte
temperature especially during the first half hr of filtration
addition. . It is necessary to have a continuous
dosing of glue. Inefficient glue supply results in The solid particles contaminating the cathodes
pyramidal copper deposits. However
are either anode slimes containing elements or
oversupply of glue makes it less effective in
compounds which are not dissolved during the
cathode surface leveling apart from increasing
electrolytic process or are formed in the bulk of
power consumption.
electrolyte through the increasing concentration
An instrument called COLLAMAT (practiced in of insoluble compounds. The extent of cathode
Norddeutsche Affinerie) could monitor glue contamination due to the occlusion of anode
content in the electrolyte. Using COLLAMAT it slimes may depend on various electrorefining

10
parameters such as anode composition, the Increasing temperature decreases solution
morphology of the cathode deposit, anode density and viscosity, thereby enabling slime to
passivation and the characteristics of the slime settle at the bottom.
i.e. its specific gravity and particle size.
Continuous filtration of the electrolyte helps in
Insoluble solids formed in the bulk of reducing the total suspended solids content in
electrolyte are generally rich in As, Bi and Sb. the electrolyte. It is desirable to filter 100 % of
Depending on their respective concentration in the electrolyte entering the electrolytic cells to
electrolyte; these elements can for from wide maintain the suspended solids well within the
limit of less than 2 ppm. It is important for the
range of insoluble compounds such as
production personnel to monitor the efficiency
antimony and bismuth arsenate (floating
of polishing filter, the filter cloth conditions etc.
slimes). These compounds may have a on regular basis and to take the corrective
detrimental effect on the quality of copper actions immediately as any negligence on this
deposit. part could lead to increase in suspended solids
in the system thereby reducing the cathode
Floating slime can also be formed by purity due to slime entrapment. The efficiency
contamination of electrolyte with oil, lubricants of the filter is monitored by measuring the
or any other petroleum products. suspended solids at inlet and out let of polishing
filter.
Apart from floating slime there exist suspended
particles. The particulate can be classified in to One more possible method for decreasing the
two groups as follows. suspended solids content in the electrolyte is
the addition of flocculating agents. Flocculating
Nodule producers: Cu, C, Sb, Se, Ag agents consists of large organic molecules,
which have anionic, cationic or non-ionic
Non producers of nodules : characteristics. In some refineries flocculent
PbSO4, PbO2, such as Prercol-351 (Colloids Canada Inc),
Superfloc-210 (Cyanamid Canada Inc.) are
Cu2Se, CaSO4. used to settle down the suspended solids to
bottom slime layer. For flocculating agents to be
Electrically conducting and semi conducting successful, it is essential that its addition does
particulates causes nodules on copper not have any affect on cathode morphology.
cathodes whereas non-conducting particulates
do not. Surface characteristics of deposits The suspended solid content in electrolyte need
grown at various temperatures and with various to be analysed daily to have a better control
paticulates present at standard conditions is over their content in the electrolyte. Fig-9
given below in Table – 4. shows the microstructure of copper deposit with
slime entrapment.
Table – 4: Effect of various particulates on Cathode deposit.

Particulate 500C 700C


Cu Moderately Very few nodules
smooth nodules
C Very rough Round and
nodules moderately rough
nodules
Sb Moderately rough Quite smooth and
nodules rounded nodules
Se Round and Round and
smooth nodules smooth nodules Fig – 9: Microscopic structure of cathode
Ag No nodules No nodules deposit with slime entrapment

The extent of entrapment of particulate


depends much more on the deposit quality than
on the availability of contaminating particulate.

11
9. Other factors. Electrolyte Purification
Power disturbances: - Cathode quality may Many impurities pass on to the electrolyte when
deteriorate if there occurs frequent power anode dissolves and over a period of time they
interruption, resulting in formation of electrolyte accumulate in the electrolyte and when the
layer on the cathode surface and further concentration of these impurities exceeds the
deposition taking place over the this layer. It is limiting concentration, they deteriorate the
advisable to increase the current in increments electrorefining process leading to poor cathode
to avoid any drastic changes taking place. Also quality. Following methods are used in
temperature of the electrolyte to be maintained controlling the impurities.
to avoid precipitation of impurities at the
cathode surface whenever the current is 1. Electrolyte Bleeding
switched off. Fig - 10 shows the power out lines
in cathode deposit microstructure. Bleeding of electrolyte, low in copper helps in
removing major soluble impurities of copper
(derived from soluble Cu2O), arsenic, nickel,
iron, antimony and bismuth. This can be
achieved by:

Copper – Electrodeposited in liberator cells


using insoluble lead anodes (Electrowinning) in
three stages.

Arsenic - Co deposited with the copper during


second and third stages of Electrowinning. A
major proportion of it could be removed by
solvent extraction. The arsenic is recovered in
solution, which is then combined with copper
sulphate to produce copper arsenate byproduct
for sale.

Antimony/Bismuth – Co deposited with the


Fig – 10 : Microscopic structure of cathode copper during second and third stages of
deposit with “power out” lines. Electrowinning. A significant portion of this also
precipitates out on cell walls and pipes, from
where it could be removed. Also some selective
Electrolyte volume shrinkage and drastic removal processes are available for removing
changes in electrolyte parameters could also Sb and Bi, which are discussed in coming
result in poor quality of cathode. Volume section.
shrinkage will result in increase in concentration
of impurities thus harming the electrorefining Nickel/iron - Crystallised in the form of crude
process. hydrated nickel sulphate by evaporating the
decopperised electrolyte in evaporating pans.
Cathode washing is important, as it is The concentrated black acid is sent back the
necessary to remove the adherent electrolyte electrolyte circuit to maintain the acid balance. A
salts on the cathode surface. Also sometimes small of this is discard to prevent a gradual
dilute suplphuric acid is added to the wash build up of Ca, K, Mg and Na ions.
water to maintain the level at 2 gpl as it helps in
removing the oxide layer. Also cathode mother Surface electrolyte bleeding process.(6)
blanks should have minimum temperature of
65oC before placing in electrolyte, as there is At the top 10 mm layer below the surface of
chances of electrolyte impurities precipitating electrolyte inside the cell, the copper
out at surface, when cold plates are put in to concentration diminishes very suddenly to
the electrolyte. about 35 gpl. The difference between this
portion and the bottom portion is nearly 10 gpl.
However impurity concentration is same at all
layers. This enables us to take the surface

12
electrolyte from the rest of the solution, which b) Activated carbon solvent adsorption
has already been decopperised by 15 –20 %. If
this surface electrolyte, low in copper is sent to Activated carbon is known and is widely used
the purification section, the quantity of as adsorbent, but this is rarely utilized in strong
electrolyte purified would be increased by acid solution such as copper electrolyte.
around 20 % and the impurity removal quantity Sumitomo Copper refinery developed a
will also be higher. technique for separation of antimony from
electrolyte using activated carbon under
Acid recovery and neutralization process specific conditions. The presence of As plays a
major role in this adsorption as antimony gets
Electrolyte is bled for electowinning cells at less adsorbed in the form of Sb AsO4.
than 2 gpl copper and around 250 gpl acid
concentration. The electrolyte is passed c) Solvent extraction
through sorption chamber containing ion
exchange resins, where acid is adsorbed in Zeneca Inc. has developed a reagent called
resins and resultant electrolyte is sent to SBX-50, which is suitable for selective removal
neutralisation section. The acid could be of bismuth and antimony through solvent
recovered from the resins by desorption. extraction method. Sbx-50 is a long chain alkyl
ester of phosphoric acid. BHP copper uses this
The electrolyte from sorption chamber is then method for Sb and Bi removal.
neutralised in a mixing tank using caustic or
Soda ash. The pH is maintained at 10-11. d) Norddeutsche Process(5)
During neutralisation most of the impurities are
converted to their respective hydroxides or It is based on the selective adsorption of As, Sb
carbonates and precipitates out from solution. and Bi from electrolyte with stannic acid. The
The tank content is filtered in a filter press. The process not only helps in eliminating float slime
impurity sludge collected from filter press is formation by reducing the Sb concentration but
bagged. The clear liquid is then subjected to the SbAsO4 and Bi AsO4 equilibrium are
evaporation, to recover sodium sulphate broken. The resultant electrolyte becomes
sludge. undersaturated and arsenate precipitation is
eliminated.
2. Selective removal Processes.
e) Barium Carbonate Treatment(7).
.(6)
a) Chelating Resin Adsorption Process
This process to remove bismuth in electrolyte
Since antimony & bismuth are the main was developed in Outokumpu’s Pori Copper
component of the scales present in the pipes refinery. The process is based on the co-
and of floating slimes, it can be called as the precipitation of bismuth from the electrolyte by
most troublesome impurity in electrorefining. means of poorly soluble barium sulphate.
Unitica Co. developed a chelating resin (UR-
3300) which removes Sb and Bi effectively by The feed electrolyte is fed to a mixing tank; in to
adsorption (proposed by Tamano refinery of which barium carbonate is added. Barium
Hibi Kyodo Smelting Company). As the sulphate precipitates, when barium carbonate
electrolyte passes through the packed column decomposes under the effect of the acid
of chelating resin, Sb and Bi are selectively content in the electrolyte. The forming
removed. They are then desorbed by means of sulphates co precipitates bismuth and part of
hydrochloric acid, and then recovered in the antimony . The precipitate is separated by
form of a highly concentrated antimony chloride filtration and the filtered electrolyte is sent back
solution by means of evaporation. Purified to the circulation tank.
electrolyte is then sent back to the circulation
section. The disadvantage of this method is the disposal
of barium sulphate, which contains Bi and
This process doubles the capacity for removing unreacted barium carbonate. (Salts of heavy
antimony from electrolyte.. metals Pb, Sr can also be used instead of Ba
salt.)

13
f) Detellurisation Acknowledgement:
High concentrations of Te in the electrolyte The authors wish to express their deep sense
result in contaminated copper, which has poor of gratitude to the management of Sterlite
drawing properties. If the refinery operates with Industries (I) limited, for giving total support to
the near zero discharge bleeds, the Te which is us with our endeavor to improve quality of our
dissolved in the decopperising operation of cathode and wire rods to international
slimes (leaching) could return to the refinery. standards. We also grateful to them for granting
The tellurium is removed by cementation on Cu the permission to attend this seminar and
at 950C in up flow fixed bed reactor. present the papers.

Apart from above other processes used for


selective removal of impurities whenever References:
impurity level in electrolyte exceeds specified
limit are 1. A.K.Biswas and W.G.Davenport,
“Extractive metallurgy of copper”,
 Combined solvent extraction of As, Sb and Pergamon Press, 1976.
Bi using hydroxamic acid and stripping
using H2S. 2. C.L.Mantell.”Electrochemical Engineering”

 Removal of Bi from electrolyte using 3. T.B.Braun, J.R.Rawling, and K.J.Richards,


Superlig materials ( Superlig 83)involving “Factors affecting the quality of
macrocyclic affixed to silica supports, electrorefined cathode copper.

 Addition of SO2 to reduce pentavalent Sb 4. 0.Forsen, L.Zhu and A.E.Antila.,”


to trivalent state and the addition of Electrochemical Characterization of
chelating agents for Sb and Bi removal gelatine , thiourea and chloride ions in the
(Hitachi process). electrorefining of copper”.

5. V.Baltazar and P.L.Claessens, “Factors


Conclusion affecting the cathode purity during copper
From the above discussions, it can be electrorefining” (AIME, Las Vegas, 1976).
concluded that the high cathode quality can be
obtained if following parameters are 6. T.Shibata, M.Haschiuchi, and T.Kato,
maintained. ”Tamano refinery’s new processes for
removing impurities from electrolyte”.
 Cu++ irons constant availability at cathode
7. Olli V.J.Hyarinen, “Process for selective
surface
removal of bismuth and antimony from an
electrolyte especially in electrolytic refining
 Optimum current density and electrode
of copper”.
alignment

 Availability of appropriate quantity of


additives over cathode surface constantly

 Low concentration of impurities in


electrolyte.

 Uniform electrolyte temperature and flow in


electrolytic cells

 Absence of slime particles in electrolyte.

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