Overview Copper
The Purification of Copper Refinery
Electrolyte
James E. Hoffmann
The phrase “purification of copper
refinery electrolyte” is misleading since
typically, impurities are controlled
by withdrawing a bleedstream of the
circulating electrolyte. However, solvent
extraction and ion exchange have also
found some application in impurity
control. This article describes conven-
tional practice, including treatment of
the bleedstream, and other attempts
at electrolyte purification. Impurities
to be discussed include Sb, Bi, As,
Ni, Ca, ammonia, and organic frag-
ments generated from hydrolysis of
conventional cathode growth-modifying
addition agents.
INTRODUCTION
In the production of copper, copper-
bearing sulfide concentrates are first
smelted to copper matte. The molten
matte is oxidized to blister copper by
Peirce-Smith converting and the blister
copper is fire refined and cast to copper
anodes. The copper in these anodes is
purified to high-purity copper cathodes
by electrolysis in a solution of copper
sulfate and sulfuric acid whose nominal
composition is 40–45 g/L copper and
180–200 g/L sulfuric acid.
Although smelting, converting,
and fire refining greatly reduce the
concentration of impurities in copper
concentrates, a small quantity of impuri-
ties remains in the copper anodes. The
quantity of impurities varies depending
upon the concentrate composition and
the smelting, converting, and refining
process. Typical values are shown in
Table I. See the sidebar for descriptions
of impurities in anode copper.
CONTROL OF COPPER
CONCENTRATION
In order to produce a cast anode
that is dimensionally consistent and
30
smooth-surfaced, some oxygen must
be present in the molten anode copper.
Typically, about 0.1–0.3% oxygen is
present, for the most part as cuprous
oxide (Cu2O). During the electrorefining
process, contact of the Cu 2O with
sulfuric acid in the electrolyte results in
its partial dissolution:
Cu2O + H2SO4 = CuSO4 + H2O + Cu
Because dissolution is chemical rather
than electrochemical, this dissolved
copper builds up in the electrolyte. In
order to maintain a constant copper
concentration in the electrolyte, a
continuous electrolyte bleed is electro-
lyzed with insoluble anodes (i.e., an
electrowinning process) to balance
the quantity of copper dissolved chemi-
cally. In many copper refineries, the
bleedstream is only partially decop-
perized then returned to the refinery.
The bleedstream removed for impurity
control is also decopperized. A portion
of the copper recovered from the
impurity bleedstream is quality cathodes;
however, much is not. Although other
techniques for decopperizing, including
solvent extraction, sulfide precipitation,
and hydrolysis are available, most
refineries use electrolytic decopperizing,
sometimes referred to as liberation.
Although the anode oxide concentra-
tion may fix the quantity of copper that
must be removed from the electrolyte, an
additional consideration is the impurities
in the anode. These define the volume
of electrolyte that must be removed for
impurity control. Usually, the elements
that control this bleed volume are
either arsenic or nickel. Less frequently,
bismuth, antimony, calcium, or even
organics may define the impurity bleed-
stream volume. In any case, the quantity
of the controlling impurity entering the
electrolyte daily is determined empiri-
cally. The bleed volume is based on this
value and the impurity concentration
tolerable in the electrolyte.
ELECTROLYTE
PURIFICATION
During the electrolytic refining of
copper, both freely soluble and slightly
soluble compounds are generated from
the impurity elements shown in Table I.
These impurities gradually concentrate
in the electrolyte until they reach
a concentration detrimental to the
electrolytic production of high-purity
copper. At this concentration, continuous
withdrawal and treatment of the refinery
electrolyte is required to maintain the
requisite electrolyte purity.
Bleedstream Removal and
Treatment
The electrolyte bleedstream for
impurities after partial decopperizing is
advanced to a set of electrowinning cells
devoted exclusively to the treatment of
partially decopperized electrolyte. The
electrolyte bleedstream is recirculated
through these cells to electrodeposit
and recover their copper content. As
the copper concentration decreases, the
deposition potential gradually increases
until first bismuth and then antimony
are electrolytically reduced to elemental
form at the cathode. The bismuth and
antimony deposit as a black sludge
containing elemental antimony, bismuth,
and some copper. Most of the copper
remaining in the electrolyte is stripped
electrolytically during the antimony
and bismuth removal.
Because of the sparing solubility of
antimony and bismuth in tankhouse
electrolyte, the quantity of electrical
energy associated with their electrolytic
reduction is comparatively small.
However, arsenic may be present in
JOM • July 2004
concentrations up to 20–25 g/L, and a
considerably higher deposition potential
is required to reduce arsenic. Because
arsenic deposits at or near hydrogen
potential, in addition to the high electrical
energy requirements, the formation of
highly toxic hydrogen arsenide (AsH3),
commonly known as arsine, may occur.
To reduce the energy requirements as
well as reduce the likelihood of AsH3
generation, tankhouse electrolyte is
added into the cells dedicated to arsenic
reduction in sufficient quantity to
provide a copper concentration of 3–5
g/L. This promotes the electrolytic
production of copper arsenide (Cu3As).
The quantity of copper required for
the formation of Cu3As is substantial,
approximately 2.5 g per g of arsenic.
The recovery of the copper content
of the Cu3As sludge usually requires
sending the material back to the smelter
for processing.
Other processes are sometimes used
to remove arsenic from the partially
treated electrolyte. These include
solvent extraction and arsenic sulfide
precipitation.
Arsenic can be quantitatively pre-
cipitated from strong sulfuric acid
solutions with hydrogen sulfide. The
use of special precipitate recycling and
aging techniques make possible the
generation of a dense readily filterable
arsenious sulfide precipitate. The use
of potentiometric monitoring of the
hydrogen sulfide addition can ensure
that very little hydrogen sulfide escapes
the precipitation reaction
Arsenic can also be extracted from the
partially treated electrolyte by solvent
extraction. The preferred solvent is
tributyl phosphate (TBP). In order to
improve the distribution coefficient of
arsenic acid between TBP and tankhouse
electrolyte, sufficient additional sulfuric
acid is added to the partially treated
electrolyte to increase its sulfuric acid
concentration to about 600 g/L. The
arsenic acid is recovered from the
loaded TBP by stripping with water. A
washing stage may be required for
the loaded solvent to recover sulfuric
acid. Complete extraction of the arsenic
is rarely accomplished. The aqueous
arsenic-bearing solution can be a
starting material for the production
of arsenic chemicals. The use of TBP
for removing arsenic from copper
2004 July • JOM
refinery bleedstreams was initiated as Table I. Soluble Elemental Impurities in
commercial practice in the 1970s. Anode Copper*
After arsenic removal, the nickel
Arsenic Antimony Bismuth Iron Nickel
sulfate-sulfuric acid solution passes
to nickel recovery and acid treatment. 890 150 65 22 1,260
Nickel is conventionally recovered 182 12 33 112 1,800
660 220 75 — 1,800
by evaporation of the electrolyte to 550 50 45 150 3,750
concentrate and crystallize the nickel 1,720 183 11 7 58
sulfate. The product is very impure and 1,082 — — 10 68
40 10 125 30 1,500
frequently contains calcium, iron, and 1 1 10 50 2,500
copper salts. Nickel sulfate can also 500 400 370 40 1,160
be crystallized by concentrating and * In ppm
cooling the nickel sulfate-sulfuric acid
solution. The nickel sulfate product
requires extensive purification to
produce a saleable crystalline nickel
sulfate product.
The acid remaining after nickel
sulfate crystallization is referred to exchange resin that preferentially
as black acid because charring of the adsorbs sulfuric acid and rejects salts.
organic residues present in it due to the By alternately passing decopperized
strong sulfuric concentration discolors electrolyte and water through the ion-
the acid. It frequently contains some exchange bed, it is possible to separate
arsenic. Options for disposal of the the salts from the acid. Although a
black acid include recycling to the complete separation of the sulfuric acid
copper refinery to reduce the amount is not accomplished, 80–90% can be
of new acid required for makeup, and recovered.
bleaching with hydrogen peroxide prior Identifying the optimum process
to return to the copper refinery to avoid for recovering sulfuric acid from the
potential problems associated with the electrolyte bleedstream requires the
effect of the organic constituents on the consideration of many different factors
growth habit of the electrodeposit. associated with the operation of the
Another option is to use the acid copper refinery. These include the cost of
somewhere else within the refinery disposal, the cost of concentration, and
complex. Black acid is sometimes recycling. If the electrolyte bleedstream
used in the pressure decopperizing of has a high nickel concentration, the
slimes. This both consumes the acid and value of the nickel salts must also be
destroys most of the organic compounds taken into consideration.
present in it because of the very strong
In-Situ Impurity Control
oxidizing conditions associated with
the high temperatures and high oxygen The slightly soluble impurities,
pressures used in slimes decopper- antimony and bismuth, are of the
izing. most concern in the copper refinery.
The acid can also be neutralized Their precipitation from the bulk of
with limestone or lime. This incurs the electrolyte is the cause of copper-
substantial reagent costs, requires cathode contamination. Once the
additional equipment, and generates a precipitate forms it either mechanically
gypsum cake requiring disposal. If the or cataphoretically reports to the copper
refinery is located on the same site as cathode, where it is included into the
the smelter, the gypsum cake can be electrodeposit. Thus, changing the
recycled back to the smelter where it chemical composition of the electrolyte
will report in smelter slags and in the and anodes to ensure that substantially
sulfuric acid plant product. all the bismuth and antimony precipitate
A final method of processing the in the slimes layer that blankets the
sulfuric acid is the acid retardation anodes greatly reduces contamination
process. In this process, the electrolyte of the copper cathodes. This can be
bleedstream, preferably after decop- done by increasing the concentration of
perizing, is passed through a short pentavalent arsenic in the electrolyte.
ion-exchange bed containing an anion- Both trivalent antimony and trivalent
31
bismuth arsenate are slightly soluble
in typical copper electrolyte. Because
of solubility product considerations,
increasing the concentration of pentava-
lent arsenic depresses the solubility of
trivalent antimony and bismuth. As the
pentavalent As concentration increases
to about 6 g/L, the solubility of Sb and
Bi decreases from their typical levels
of about 0.3–0.4 g/L Bi and 0.4–0.6
g/L Sb. As the arsenic concentration
continues to increase in the electrolyte,
the solubility of antimony and bismuth
continues to decrease. As the pentavalent
arsenic concentration in the electrolyte
increases, antimony and bismuth may
precipitate in the bulk of the electrolyte
and create severe contamination prob-
lems. However, when the pentavalent
arsenic concentration attains a value
of 15–20 g/L, antimony and bismuth
concentration will be depressed to less
than 100 ppm in the electrolyte and no
longer contaminate the copper cathodes.
The use of high arsenate concentra-
tions in copper refinery electrolyte has
the additional advantage of causing
most of the bismuth and antimony to
report in the slimes, where it can be
removed from the circuit and recovered
as saleable salts.
Arsenic recovered as Cu3As in the
liberator circuit can be recycled to the
anode furnace if there is not sufficient
arsenic entering in the blister copper.
The use of arsenate precipitation
chemistry is finding more and more
application in copper refining. A useful
current description was presented at
Copper 2003 in Chile.
PURIFICATION BY SOLVENT
EXTRACTION AND ION
EXCHANGE
Solvent Extraction of Arsenic
The extraction of arsenic using TBP
was described earlier. It should be
stressed that solvent extraction of arsenic
is both for purification of the electrolyte
and arsenic disposal. Those refineries
that use solvent extraction for removing
arsenic from electrolyte claim process
superiority over electrowinning because
of lower energy costs, less handling
of toxic substance, the elimination of
possible arsine generation, and the
possibility of recovering a saleable
arsenic product.
32
IMPURITIES IN COPPER REFINERY ELECTROLYTE
Examination of the data shown in Table I shows a wide variation in the composition of
the anodes from various smelters. As a result, electrolyte purification processes vary from
copper refinery to copper refinery. The impurities found in copper refinery electrolyte are
As, Sb, Bi, Ni, Ca, ammonia, and organic fragments.
Arsenic
Arsenic is freely soluble in copper refinery electrolyte. It enters the electrolyte as a
trivalent species, H3AsO3, and is gradually converted to the pentavalent species, H3AsO5.
The percentage of trivalent and pentavalent species is a function of a variety of factors,
including the mean residence time of the arsenic in the electrolyte; the presence of
other species that may oxidize trivalent arsenic, including atmospheric oxygen; and the
amount of pentavalent arsenic that is precipitated as insoluble compounds of antimony
and bismuth. The deposition potential of arsenic is sufficiently greater than that of copper
that arsenic is not electrolytically co-deposited with copper. Thus, the presence of high
concentrations of arsenic in copper refinery electrolyte, approximately 20 g/L, is usually
tolerable. Arsenic in copper causes a decrease in electrical conductivity. It is most likely to
enter the copper as an inclusion of electrolyte. Thus, as the arsenic concentration increases
in the electrolyte, its potential for contaminating cathode copper increases.
Antimony
Antimony is only slightly soluble, usually less that 1 g/L, in copper refinery electrolyte.
It may be present as trivalent or pentavalent species. As the trivalent species, it forms an
insoluble compound, antimonous arsenate, SbAsO5, with pentavalent arsenic. The actual
concentration of trivalent antimony is defined by the solubility product of antimonous
arsenate, which, in turn, is dependent on the concentration of pentavalent arsenic in the
electrolyte. The deposition potential of antimony is too high to electrodeposit with
copper. Antimony usually enters the cathode deposit as a particulate oxide or arsenate
by adhering to the cathode surface where it is incorporated into the electrodeposit. It
causes problems with the mechanical properties of copper, particularly during rolling
or wire drawing of copper.
Bismuth
Bismuth forms oxysulfates and slightly soluble sulfates. In the presence of a sufficiently
high concentration of pentavalent arsenic ion, the solubility product of bismuth arsenate
defines the bismuth concentration in the electrolyte. Bismuth does not electrolytically
co-deposit with copper under normal copper electrorefining conditions. Bismuth behaves
in a similar fashion to antimony. Wire-drawing operations are particularly sensitive to
occlusions of bismuth compounds.
the electrolyte. This provides the
Ion Exchange of Bismuth and
opportunity for recovering saleable
Antimony
bismuth and antimony compounds and
Two methods have been described eliminating the substantial process costs
for controlling the concentration of associated with their removal from
antimony and bismuth: electrolyte the copper refinery slimes. Although a
bleed and precipitation as arsenates. bleedstream may still be necessary for
Electrolyte bleed controls the concentra- control of Ni or As, the volume of the
tion by withdrawing the required amount bleedstream will be independent of
of antimony and bismuth from the the Sb and Bi content of the anodes.
tankhouse circulation system, while Since ion exchange will cause the
arsenate treatment causes these elements preponderance of Sb and Bi to report
to report in the refinery slimes. in the electrolyte, the size of the ion
Purification by ion exchange involves exchange operation will be defined
processing sufficient recirculating more by the Sb and Bi content of the
electrolyte through an ion exchange anodes than by their concentration in
operation to decrease the concentration the refinery electrolyte.
of antimony and bismuth to well below Chelating ion-exchange resins are
their solubility limits in the electrolyte. employed for antimony and bismuth
It is important to note that when this recovery from refinery electrolyte. Elu-
is done the antimony and bismuth tion of the elements is done either with
that would ordinarily report in the strong hydrochloric acid or concentrated
refinery slimes is now recovered from brines. Care must be exercised that
JOM • July 2004
 Nickel and arsenic concentrations will
not reduce the cost of arsenic
Nickel present in elemental form in the anode dissolves freely as nickel sulfate. Nickel
oxide is insoluble. High concentrations (i.e., 25g/L) can be present in copper refinery removal, it will decrease the energy
electrolyte without significant contamination of the copper cathode. However, high cost associated with nickel sulfate
concentrations of nickel in the electrolyte can depress the solubility of copper at the recovery and the amount of black
anode-electrolyte interface and result in anode passivation and the cessation of the acid generated.
electrolytic refining process. Nickel will not electrolytically co-deposit with copper from
• The use of hydrogen sulfide for
copper-refinery electrolytes. Nickel present in the electrodeposit is due to electrolyte
inclusion in the copper electrodeposit. precipitating arsenic from decop-
perized electrolyte should always
Calcium
be among the options considered
Calcium enters the copper refinery in a variety of ways, including leaching from concrete for the removal of arsenic from the
to which the electrolyte is occasionally exposed, and as a minor constituent of the mold electrolyte bleedstream.
wash adhering to the anode after casting and cooling. If process water rather than steam
• Every effort should be made to
condensate is used, it can also be a source of calcium ion. Calcium is slightly soluble in
copper refinery electrolyte as calcium sulfate, and when it precipitates from solution it is recycle black acid to the copper
usually in the form of gypsum, CaSO4.2H2O. Occasionally, it precipitates as a complex refinery. Assertions that black acid
antimony salt. When present at saturation concentration in refinery electrolyte, calcium is detrimental to the quality of
sulfate tends to deposit on the cathode at the interface with the electrolyte. Bismuth cathode produced should require
sulfate in solution tends to enter the calcium sulfate lattice during crystallization.
proof. If black acid cannot be
Thus, the presence of gypsum deposits on the cathode incurs the hazard of bismuth
contamination. recycled to the electrolyte circula-
tion system, it should be considered
Ammonia
for use in pressure decopperizing
Because glue is a protein composed of amino acids, ammonium ion may begin to of refinery slimes or other applica-
accumulate in the electrolyte. It rarely makes its presence known because it has no volatility tions.
in the acid electrolyte. However, because it is a powerful complexing agent for copper, it
• When considering the use of ion
may ultimately create problems in effluent treatment circuits.
exchange for control of antimony
Organic Fragments and bismuth concentration in
Virtually all copper refineries use protein-based collagens—glues—to improve the refinery electrolyte, recognize that
growth habit of the copper electrodeposit. Some of this glue reports in the copper deposit; this practice will also affect the
however, the larger part of it is hydrolyzed by the acidic copper refinery electrolyte. This composition of the refinery slimes
results in a variety of organic fragments in the electrolyte. If, as is the case in many copper
as well as the attendant cost of
refineries, the electrolyte is ultimately evaporated down to strong sulfuric acid, these
fragments are charred by the strong sulfuric acid, creating what is called black acid. Some processing them. This is particu-
refineries are reluctant to recycle black acid to their electrolyte circulation system. Others larly true when the slimes are to be
believe it has a beneficial effect on cathode morphology. processed pyrometallurgically.
• Nickel is the last element to be
recovered from the electrolyte
bleedstream. However, if the
chlorides present in the eluate do not done to control the copper con- concentration of nickel after
pass into the tankhouse electrolyte centration in the copper refinery removal of all other impurities
circulation system, where they would electrolyte and that performed in is less than 20 g/L, provided the
wreak havoc with the quality of the conjunction with treatment of the water balance can tolerate it, some
copper cathodes. impurity bleedstream. That done consideration should be given to
for copper concentration control recycling the nickel-bearing acid
CONCLUSIONS
should be performed in such a back to the refinery to increase the
The chemistry of each copper refinery fashion as to ensure the production ultimate nickel to 20 g/L prior to
is unique and dependent on factors such of high-purity cathode. recovery by evaporation.
as anode composition, environmental • Frequently, the stipulated maxi-
constraints, current density, slimes mum concentration of nickel and
characteristics, labor intensity, energy arsenic allowed in the copper
cost, operating philosophy, and byprod- refinery electrolyte is determined
James E. Hoffmann is a consultant and president
uct markets. Notwithstanding these by anecdotal history. There should of James E. Hoffmann & Associates Co. in
differences, some comments regarding be a constant effort to increase Houston, Texas.
purification of refinery electrolyte are these concentrations consistent
For more information, contact J.E. Hoffmann, James
warranted. with the continued production of
E. Hoffmann & Associates Co., P.O. Box 420545,
• A distinction should be made high-purity cathode at high current Houston, TX 77242-0545; (281) 493-9441; fax (713)
between copper electrowinning efficiencies. Although higher nickel 780-0761; e-mail jehentp@aol.com.

2004 July • JOM 33