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Entrapment of slimes.
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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.
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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).
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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-.
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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.
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
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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
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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
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
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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.
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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.
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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.
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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.
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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.
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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:
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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.)
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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.
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