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TECHNICAL PAPER 167

Electrolyte impurity control at Chinchpada


Refinery of Sterlite Industries (India) Limited
BALACHANDRAN P. KAMATH, A.K. MITRA, S. RADHAKRISHNAN AND
KIRAN P SHETTY
Sterlite Industries (India) Limited, 1/1/2, Chinchpada, Silvassa – 396 230,
Copper - 2003 - Cobre - 2003 at Santiago, Chile
Union Territory of Dadra & Nagar Haveli, India
kamath_b@sterlite.com

ABSTRACT INTRODUCTION

Sterlite Industries operates copper refinery To meet the stringent demand of customers,
at Silvassa, India using ISA PROCESS with the copper producers are giving prime
a capacity of 1,80,000 TPA. The anodes are importance to produce high quality copper
received from its custom Smelter at cathodes superior than ASTM standards.
Tuticorin, Southern India. The impurities in The major challenge for refinery is to
anode vary substantially especially bismuth, improve cathode quality and appearance
which has varied from 10 ppm to 150 ppm despite fluctuating anode impurity levels.
over the last few years. The backbone in achieving good quality
This paper discusses the various cathode includes the control of electrolyte
operating practices and technologies adopted impurity.
at Sterlite copper refinery for electrolyte Sterlite Copper is an ISA process
impurity management. The main emphasis is licensed copper refinery located in
given for controlling bismuth, antimony, Chinchpada, Silvassa near Mumbai, India.
nickel and iron in the electrolyte. The paper The refinery was commissioned in 1997
discusses the control of bismuth and with the installed capacity of 60000 MTA of
antimony in electrolyte by progressively copper cathodes. The process adopted for
increasing arsenic level in electrolyte. It was refining is the ISA permanent cathode
observed that at a critical arsenic level in the technology. Over the past Six years the
electrolyte, bismuth and antimony reports to company has undergone aggressive
anode slime. expansions along with the de-bottlenecking
Considerable importance is given in to reach the present capacity of 180000
controlling nickel and iron content in MTA. The greatest challenge for Sterlite is
electrolyte by adopting latest low cost acid produce cathode quality at efficiency at par
purification system. This novel method with the international producers irrespective
coupled with an effluent treatment plant of the rapid expansion. The continuous
ensures recovery of sulfuric acid, removal of quality improvement plan has helped the
nickel and iron from electrolyte, production plant to produce copper cathode as per
of disposable nickel sludge besides ensuring ASTM standards and establish itself in the
zero discharge to environment. With a more international market.
suitable impurity management system, The copper refinery receives anode by
Sterlite is able to achieve and sustain the trucks from the smelter situated in southern
cathode quality superior to ASTM standard. India, which is 2000 kms away from the

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refinery. The smelter is a custom smelter Anode Composition


processing concentrates having wide Being a custom feed smelter, the Sterlite
variation in impurity levels. The impurity receives concentrates both from its own
levels have varied in wide range in last six mine situated in Australia and also
years of operation. With the progressive purchased concentrates. The variation in
expansion and due to wide variation in concentrate composition, to some extent is
anode impurities, the impurity levels in nullified by blending the concentrates thus
electrolyte have increased over the years. enabling to have a uniform composition feed
The refinery operates at relatively to the smelter. However sometimes this is
higher current density of 320 Amps/m2. At limited by wide variation of impurity levels
this high current density operation, the in concentrates. This variation in impurity
control of electrolyte impurity is a prime levels in purchased concentrates has a
factor in determining the cathode quality. significant affect on the overall impurity
Sterlite has given utmost attention in balance.
controlling the impurity levels within the The Fig - 1 & Fig- 2 shows the monthly
specified limits. The paper discusses average levels of impurities in anodes for
strategies adopted with the purpose of the last three years.
revamping and modernizing the electrolyte
impurity management system.

Behaviors of Impurities

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Various elements are present in the anode in electrolyte and is oxidized by


different forms/complexes and each of them atmospheric oxygen from a trivalent to
behaves differently during electrorefining. pentavalent state. Only a part of
Primarily during copper electrorefining, antimony and bismuth dissolves in
anode impurities behave in following ways. electrolyte and the rest goes to the slime.

• Elements less noble than the copper such Build Up of Impurities in Electrolyte
as nickel, iron dissolves in the The initial increase in the impurity level in
electrolyte. electrolyte at Sterlite Copper was
compensated by continuous dilution of the
• Elements like gold, silver, platinum, electrolyte due to addition of more number
selenium, tellurium, which are more of cells as a part of expansion. For initial
noble than the copper remains period there was no need for impurity
undissolved and form an anode slime, control due to continuous dilution. As the
which gradually drops, to the bottom of production capacity increased the impurity
tank. levels had shown an increase in levels in
electrolyte. The Sterlite had intend to keep
• Arsenic, antimony and bismuth present its impurities level well below the specified
as impurities in the anode constitute a limits, which could help in avoiding the
separate group. Most of the arsenic major cathode quality upset due to
present in the anode dissolves in electrolyte composition upset. The Table–I
gives the target electrolyte composition.

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Table –I: Target Electrolyte Composition Electrolyte Impurity Management


Electrolyte impurity management at Sterlite
Concentration Copper basically involves following four
gpl steps.
SL. No. Component 1. Control of bismuth and antimony in
1 Copper 48 – 52 electrolyte by altering the anode and
electrolyte chemistry
2 Sulfuric Acid 160-180 2. Control of arsenic by purification cells
(Electro-winning)
3 Arsenic 12-15
3. Control of nickel, iron and other soluble
4 Antimony < 0.2 impurities by acid purification unit.
4. Control of tellurium by cementation on
5 Bismuth < 0.2 copper.
6 Nickel < 15 Fig - 3 Gives the flowchart for electrolyte
impurity control. Each section is discussed
7 Iron <3 in details.

Bi, Sb PRECIPITATION IN
Liberator cell Outlet
ELECTROLYTE
Electrolyte
Primary Liberator Cells
Normal Cells
Tellurium Free
Leaching Liquor from Leached Electrolyte 3 x 3 De-
slime Plant Copperisation Cells

As rich
Copper Chips cathode
De-Copperised /sludge for
Liquor recycle

DE-TELLURISATION
ARSENIC REMOVAL

Water Heavy Metal Nickel rich


Acid Purification Unit rich Effluent
Precipitation Evaporator
Effluent

Recovered Acid to NiSO4 + Na2SO4


Metal Sulfide/Hydroxide
cellhouse Crystals for sale
NICKEL/IRON REMOVAL

Fig– 3: Schematic Diagram of Electrolyte Purification & Treatment System at Sterlite

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Control of Bismuth and Antimony in • Maintain Minimum As/(Sb+Bi) molar


Electrolyte by Altering the Anode and ratio at more than 2 to prevent formation
Electrolyte Chemistry of floating slime and thereby to prevent
The increase in the antimony and bismuth in top nodulation.
electrolyte observed at the initial stage of
refinery operation. Decopperisation cells • Maintain the minimum absolute arsenic
alone could not take care of the input at more than 350 ppm to prevent anode
through anode. Installation of additional Passivation and reduce nodulation
decopperisation cells did not help in
reducing the bismuth and antimony levels in The arsenic content in the anode plays a
electrolyte. The level of antimony and vital role in the electro-refining of cathode.
bismuth increased above 300 ppm whereas The arsenic has a depassivating effect on the
arsenic was still at 3 gpl level. This also anode. It was observed that whenever the
associated with the lower level of arsenic in absolute arsenic level is less than the 300
anodes. The cellhouse lost its stability due to PPM, heavy nodulation followed by dip in
this in-balance and following symptoms are current efficiency was observed. The scrap
observed. anodes were found to be passivated. Few
layer of unequal passivation observed on the
• Heavy top nodulation on cathode & scrap anodes. The slime on the scrap anode
• Bismuth contamination observed on the found to be very sticky and difficult to wash.
cathode
• Lower current efficiency • Increase arsenic level in electrolyte to
• Passivation of anodes more than 12 gpl and precipitate bismuth
• Higher scrap percentage and antimony in electrolyte.
• Higher power consumption
In order to permanently bring down the
The electrolyte was found to be very bismuth and antimony in electrolyte, after a
much undersaturated resulting in increasing thorough literature survey, it was decided to
bismuth and antimony concentration. This intentionally rise the arsenic level in
together with the lower arsenic in anodes electrolyte and shift the saturation limit of
had augmented the problem resulting in bismuth and antimony. The solubility of
deteriorating the cellhouse operations. After these compounds depends on the
a detailed literature survey various concentration of these in electrolyte and
technologies were studied for selective portion that goes to slime and is influenced
removal of bismuth and antimony from by concentration of other impurities in
electrolyte. However after a thorough anodes. Antimony and bismuth dissolves in
analysis and discussion, it was concluded the electrolyte as trivalent ions. They
that instead of installing a selective removal precipitate from the solution as arsanates
system, the bismuth and antimony levels and so their solubility is determined by the
could be brought down and maintained by concentration of arsenic in electrolyte.
altering the anode and electrolyte chemistry. The arsenic level was increased to more
Three necessary steps were considered to than 12 gpl from the level of 3 gpl
enable the refinery to come back to deliberately and steadily. With the arsenic
normalcy. level reaching 12 gpl, heavy precipitation of
bismuth and antimony observed. The
bismuth and antimony level in the
electrolyte decreased due to precipitation of
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bismuth and antimony arsenates as shown in Fig-4.

Fig-4: Behavior of bismuth and antimony at various concentration of arsenic in electrolyte

The behavior of impurities in electrolyte is Summarizing, the bismuth and


discussed in 3 zones as shown in Fig-4. antimony levels were undersaturated in
zone-1 and concentration was increasing in
Zone -1: The Bismuth and antimony were at electrolyte. In Zone-2 they reached their
the range of 200-350 ppm and arsenic at 4 – saturation limit and maximum bismuth and
6 gpl. The antimony and bismuth were antimony in the electrolyte started
controlled by electrowinning (purification precipitating out as their arsenates at higher
cells). However bismuth and antimony level of arsenic in electrolyte.
levels could not be brought down below 200 In Zone-3, the entire system reached a
ppm. Arsenic doping started in anode new equilibrium state with bismuth and
furnace from Oct-00 to increase the arsenic antimony levels still undersaturated in
content in anode and ultimately in electrolyte, but at lower level of
electrolyte. bismuth/antimony and higher level of
Zone-2: Arsenic started increasing from arsenic. Initially due to heavy precipitation
Oct-02 steadily and when arsenic level of arsentaes, increased body nodulation
reached 10-12 gpl, the bismuth and observed resulting in dip in current
antimony level started decreasing drastically efficiency. However with the bismuth and
as shown in Fig–5. The bismuth and antimony levels reaching steady state of less
antimony arsenates started precipitating than 100 ppm, the body nodulation
heavily and top nodulation and body decreased. The cathode contamination by
nodulation were quite on higher side. Dip in bismuth also reduced. It was very much
current efficiency is also observed. evident with decreased bismuth levels in
Zone–3: With Arsenic level consistently cathode as shown in Fig-7.
above 12 gpl, the bismuth and antimony
levels stabilized at below 100 ppm.

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Control of arsenic in electrolyte Three purification circuits, each having


As discussed earlier, Sterlite had 3 cells in series are utilized. One purification
intentionally increased arsenic level in the system exclusively serve for treating slime
electrolyte over 12 gpl to facilitate the leached liquor. The part of primary liberator
precipitation of bismuth and antimony and cell outlet is taken as feed to other two
thereby to control concentration of antimony purification circuits. A current density of
and bismuth in electrolyte. The arsenic level 220-250 is maintained in the cells. The slime
is maintained between 12-16 gpl and totally leached liquor is first filtered to remove any
controlled in Decopperisation/Purification suspended solids and then passed through
(electrowinning cells). the purification cells.
A study done in the purification system
The input to the purification cells is showed that maximum arsenic removal is
1. Leached liquor from Slime plant after between 1-3 gpl and the operation is being
detellurisation done at same range. The Fig –5 shows the %
2. Normal electrolyte after primary liberator of arsenic and bismuth removed in
cells in main cellhouse. purification cells.

Almost 70 % of the arsenic is being Though these systems are used in most of
removed using electro-winning cells. The the plants, they have their own
purification section is equipped with the all disadvantages in term of higher capital cost
the latest safety requirements to take care of and operating cost.
any operational mishaps. At Sterlite the necessity of bleeding the
electrolyte had come little later due to
Control of Nickel, Iron and other soluble progressive and continuous expansion
impurities carried out in the cellhouse. The nickel and
Over the years copper refiners have adopted iron were controlled below the specified
various technologies for the control of nickel limits by continuous dilution of electrolyte
and iron in electrolyte. Most common and as a part of electrolyte make up for
conventional systems used are precipitation additional cells.
method or nickel sulfate evaporator system.
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The electrolyte Nickel/iron control apart. The make up sulfuric acid needed for
system adopted in Sterlite is a unique one. It the cellhouse is purchased from outside. A
is coupled with the acid recovery system. thought was given to recover the sulfuric
Sterlite had carried out an extensive study of acid in the bleed electrolyte before bleeding
all the systems available for removal of it off. The best processes available for this
nickel and iron and zeroed in on purpose were
combination of various technologies. The
electrolyte purification method implemented 1. Ion exchange process
in Sterlite Copper is the latest one and is 2. Membrane/Electro-dialysis
environmental friendly. The system has
many advantages over other available After studying the pros and cons of
technology. Apart from purifying the these two processes Sterlite adopted Ion-
electrolyte, the system recovers sulfuric acid Exchange process due to its easy
from the electrolyte and is more cost- adaptability and comparatively higher acid
effective in terms of capital cost and recovery, when compared to electro-dialysis.
operating cost Thus an acid purification unit was
Following steps are adopted for incorporated in the treatment system to
purification and treatment of bleed recover the sulfuric acid in bleed electrolyte
electrolyte. rather than neutralizing the acids. The
system in known as “Acid purification Unit
• Acid Purification (Recovery) System (APU)” and works on “RECOFLO”
• Precipitation by Sulphidation and technology and is supplied by M/s. Eco-Tec,
Neutralization & Evaporation Canada. The decopperised electrolyte is
taken to APU for treatment.
Each step is briefly discussed. APU is an ion-exchange column. This
process works on the principle that the
Step-1: Acid Purification Unit (APU) certain ion exchange resins have the
Sterlite Copper has disadvantage of having capability to sorb strong acids from the
copper refinery and smelter at 2000 Kms solution, while excluding metallic salts of
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those acids. The process is reversible, in water through a bed of this resin, to separate
that acid can be readily desorbed from the the free acid from the metal. Fig-7 gives the
resin with water. It is thus possible, by operational sequence of APU.
alternatively passing contaminated acid and

Decopperised Sulfuric acid rich


Electrolyte Liquor back to Water
from system
Purification F
I
Cells
L
T Acid Purification Deacidified
E Unit Liquor rich in
R heavy metals
for further
treatment
Fig – 7: acid recovery unit operation

At Sterlite, the bleed electrolyte after passed through the resin, which elutes acid
decopperising in purification cells is passed from the resin and the resulting product
through this resin bed. There are basically containing recovered sulfuric acid is sent
two basic steps in the APU process. I.e. In back to the electrolyte system or used in
the first step the resin adsorbs the sulfuric slime leaching section depending on
acid in the electrolyte, whereas the major requirement. The Table –II gives the
part of impurities such as Nickel, iron, separation efficiencies of APU. The Table-
bismuth, antimony goes in as effluent for III gives the typical composition of APU
further treatment. In the next step, water is feed, product and byproduct streams.

Table – II: Separation Efficiency for APU

SL. No Acid % going to % going to


/Impurities Product waste liquor
(Recycled to
system)
1 Sulfuric Acid 85-90 % 10 –15 %
2 Copper 25 % 75 %
3 Nickel 25 % 75 %
4 Iron 34 % 66 %
5 Arsenic 80-85 % 15-20 %
6 Antimony 50 % 50 %
7 Bismuth 50 % 50 %

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The Table – III gives the typical Composition of Various Streams

Streams H2SO4 Cu Ni Fe As Bi Sb

APU Feed 225-275 2.0 10 3.0 4.0 0.05 0.05

APU Product 200-240 1.0 2.5 1.0 3.0 0.025 0.025

APU ByProduct 25-35 1.0 7.5 2.0 1.0 0.025 0.025


* All Values in gms/Ltr

Step – 2 : Precipitation & Evaporation the filtrate is sent to evaporator. A


The effluent (rich in metal impurities and crystalliser follows the evaporator in order
with lower acid concentration) is then taken to get mixer of nickel sulfate and sodium
to effluent treatment plant. The effluent is sulfate crystals.
first partially neutralized with caustic/soda This electrolyte purification method
ash up to a ph of 3-3.5. This partial implemented in Sterlite Copper is the latest
neutralization is carried out in order to one and is environmental friendly. The
control the generation of hydrogen sulfide in system has many advantages over other
next step by reducing the sulfuric acid available technology. Apart from purifying
content in the effluent. The partial the electrolyte, the system recovers sulfuric
neutralized liquor is filtered and filtrate is acid from the electrolyte and is more cost-
subjected to sulphidation using sodium effective in terms of capital cost and
sulphide. The residual copper, arsenic, operating cost.
bismuth & antimony precipitates as their A comparison of three processes in
sulfides due to hydrogen sulfide generated technology and environmental aspects is
during the process. The slurry is filtered and given in Table-IV.

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Table-IV: Comparison of various electrolyte treatment processes

Parameter Direct Neutralization Evaporation Sterlite Method


Acid No Only 60 % of the black Yes . 90 % of the sulfuric
recovery acid is recovered acid could be recovered.
Quality of ---- Black acid has Recovered acid with very
acid restricted usage due to less impurities.
recovered higher % of impurities.
Impurity Removes most of the Removes only Nickel Apart from Nickel and iron,
removal impurities. and iron. (Precipitates removes certain % of Bi and
them as their sulfates) Sb in APU. Other impurities
are removed by
precipitation.
Caustic/Lime Very high as all acid Periodic neutralization Very low, as only 10 % of
consumption has to be neutralized of black acid requires the acid has to be
considerable amount of neutralized.
chemicals.
Sludge Very high amount of NiSO4 will be Only 10 % of the sludge
Generation neutralized sludge generated will be generated, when
compared to direct
neutralization.
Capital Cost Less but cumbersome Very high due to Less.
process evaporator
Operating Very High due to Very High due to Lower cost due to lesser
Cost neutralization power/steam cost. consumption of
chemicals cost In addition cost of neutralization chemicals.
neutralization Cost of steam.
chemicals for black
acid.
Others Very labor oriented. Due to high Replacement of resin once
Gypsum storage and temperature operation, in every 5 Years.
disposal is also a the corrosion due to APU operation is fully
problem. high chloride is very Automatic with no Manual
prominent. intervention.
Occupies space. Very Compact.

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Testing and Quality Control electrolyte chemistry. The arsenic level in


It may be emphasized that in refinery, the electrolyte is maintained by operating the
problems gets out of the hand over a period de-copperisation section (Electro-winning)
of time and it takes equally long time to brig efficiently. Adaptation of latest electrolyte
back the operations to normalcy. The initial purification system, which includes ‘Acid
indications of problems are innocuous, but Purification System (APU), controls nickel
suddenly they take a turn in the form of poor and iron in the electrolyte. This system does
efficiency, poor quality and high power a twin job of purifying the electrolyte as
consumption. To have a better control over well as recovering the sulfuric acid for reuse
process, it is necessary to have strong testing in the cellhouse. The effluent treatment
and quality control methods. system ensures production of nickel rich
Various methods are available for byproduct. The system also ensures zero
testing cathode purity and other process discharge to the environment. All solid
parameters such as anode quality, electrolyte waste produced at the refinery are either
composition. The database of all the major recycled or disposed off in an
parameters is maintained and statistical environmentally safe manner. The prime
process and quality control methods are used importance is given for protecting the
to determine the variation in process. Any environment by ensuring zero discharge.
abnormality identified is immediately traced
back to find out the exact reason and the References
necessary remedial actions are taken. 1. A.K. Biswas and W.G. Davenport
Extractive Metallurgy of Copper. 3rd edition,
CONCLUSIONS Pergamon Press, Oxford, England, 1994.
2. B.E. Langer and P. Stantke : EPD
The various methods of electrolyte impurity Congress, The Minerals, Metals & Materials
management methods have helped M/s. Society. 1995, pp. 559-569.
Sterlite to improve the cathode quality to 3. Michael Sheedy : JOM, Vol.50, No.10,
international standards and to make a mark October 1998, pp 66-69
in copper markets. The electrolyte impurity
levels especially bismuth and antimony is
controlled by altering the anode and

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