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Overview Copper

The Purification of Copper Refinery


Electrolyte
James E. Hoffmann

The phrase purification of copper smooth-surfaced, some oxygen must cally. The bleed volume is based on this
refinery electrolyte is misleading since be present in the molten anode copper. value and the impurity concentration
typically, impurities are controlled Typically, about 0.10.3% oxygen is tolerable in the electrolyte.
by withdrawing a bleedstream of the present, for the most part as cuprous
ELECTROLYTE
circulating electrolyte. However, solvent oxide (Cu2O). During the electrorefining
PURIFICATION
extraction and ion exchange have also process, contact of the Cu 2O with
found some application in impurity sulfuric acid in the electrolyte results in During the electrolytic refining of
control. This article describes conven- its partial dissolution: copper, both freely soluble and slightly
tional practice, including treatment of soluble compounds are generated from
Cu2O + H2SO4 = CuSO4 + H2O + Cu
the bleedstream, and other attempts the impurity elements shown in Table I.
at electrolyte purification. Impurities Because dissolution is chemical rather These impurities gradually concentrate
to be discussed include Sb, Bi, As, than electrochemical, this dissolved in the electrolyte until they reach
Ni, Ca, ammonia, and organic frag- copper builds up in the electrolyte. In a concentration detrimental to the
ments generated from hydrolysis of order to maintain a constant copper electrolytic production of high-purity
conventional cathode growth-modifying concentration in the electrolyte, a copper. At this concentration, continuous
addition agents. continuous electrolyte bleed is electro- withdrawal and treatment of the refinery
lyzed with insoluble anodes (i.e., an electrolyte is required to maintain the
INTRODUCTION
electrowinning process) to balance requisite electrolyte purity.
In the production of copper, copper- the quantity of copper dissolved chemi-
Bleedstream Removal and
bearing sulfide concentrates are first cally. In many copper refineries, the
Treatment
smelted to copper matte. The molten bleedstream is only partially decop-
matte is oxidized to blister copper by perized then returned to the refinery. The electrolyte bleedstream for
Peirce-Smith converting and the blister The bleedstream removed for impurity impurities after partial decopperizing is
copper is fire refined and cast to copper control is also decopperized. A portion advanced to a set of electrowinning cells
anodes. The copper in these anodes is of the copper recovered from the devoted exclusively to the treatment of
purified to high-purity copper cathodes impurity bleedstream is quality cathodes; partially decopperized electrolyte. The
by electrolysis in a solution of copper however, much is not. Although other electrolyte bleedstream is recirculated
sulfate and sulfuric acid whose nominal techniques for decopperizing, including through these cells to electrodeposit
composition is 4045 g/L copper and solvent extraction, sulfide precipitation, and recover their copper content. As
180200 g/L sulfuric acid. and hydrolysis are available, most the copper concentration decreases, the
Although smelting, converting, refineries use electrolytic decopperizing, deposition potential gradually increases
and fire refining greatly reduce the sometimes referred to as liberation. until first bismuth and then antimony
concentration of impurities in copper Although the anode oxide concentra- are electrolytically reduced to elemental
concentrates, a small quantity of impuri- tion may fix the quantity of copper that form at the cathode. The bismuth and
ties remains in the copper anodes. The must be removed from the electrolyte, an antimony deposit as a black sludge
quantity of impurities varies depending additional consideration is the impurities containing elemental antimony, bismuth,
upon the concentrate composition and in the anode. These define the volume and some copper. Most of the copper
the smelting, converting, and refining of electrolyte that must be removed for remaining in the electrolyte is stripped
process. Typical values are shown in impurity control. Usually, the elements electrolytically during the antimony
Table I. See the sidebar for descriptions that control this bleed volume are and bismuth removal.
of impurities in anode copper. either arsenic or nickel. Less frequently, Because of the sparing solubility of
bismuth, antimony, calcium, or even antimony and bismuth in tankhouse
CONTROL OF COPPER
organics may define the impurity bleed- electrolyte, the quantity of electrical
CONCENTRATION
stream volume. In any case, the quantity energy associated with their electrolytic
In order to produce a cast anode of the controlling impurity entering the reduction is comparatively small.
that is dimensionally consistent and electrolyte daily is determined empiri- However, arsenic may be present in

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concentrations up to 2025 g/L, and a refinery bleedstreams was initiated as Table I. Soluble Elemental Impurities in
considerably higher deposition potential commercial practice in the 1970s. Anode Copper*
is required to reduce arsenic. Because After arsenic removal, the nickel
Arsenic Antimony Bismuth Iron Nickel
arsenic deposits at or near hydrogen sulfate-sulfuric acid solution passes
potential, in addition to the high electrical to nickel recovery and acid treatment. 890 150 65 22 1,260
energy requirements, the formation of Nickel is conventionally recovered 182 12 33 112 1,800
660 220 75 1,800
highly toxic hydrogen arsenide (AsH3), by evaporation of the electrolyte to 550 50 45 150 3,750
commonly known as arsine, may occur. concentrate and crystallize the nickel 1,720 183 11 7 58
To reduce the energy requirements as sulfate. The product is very impure and 1,082 10 68
40 10 125 30 1,500
well as reduce the likelihood of AsH3 frequently contains calcium, iron, and 1 1 10 50 2,500
generation, tankhouse electrolyte is copper salts. Nickel sulfate can also 500 400 370 40 1,160
added into the cells dedicated to arsenic be crystallized by concentrating and * In ppm
reduction in sufficient quantity to cooling the nickel sulfate-sulfuric acid
provide a copper concentration of 35 solution. The nickel sulfate product
g/L. This promotes the electrolytic requires extensive purification to
production of copper arsenide (Cu3As). produce a saleable crystalline nickel
The quantity of copper required for sulfate product.
the formation of Cu3As is substantial, The acid remaining after nickel
approximately 2.5 g per g of arsenic. sulfate crystallization is referred to exchange resin that preferentially
The recovery of the copper content as black acid because charring of the adsorbs sulfuric acid and rejects salts.
of the Cu3As sludge usually requires organic residues present in it due to the By alternately passing decopperized
sending the material back to the smelter strong sulfuric concentration discolors electrolyte and water through the ion-
for processing. the acid. It frequently contains some exchange bed, it is possible to separate
Other processes are sometimes used arsenic. Options for disposal of the the salts from the acid. Although a
to remove arsenic from the partially black acid include recycling to the complete separation of the sulfuric acid
treated electrolyte. These include copper refinery to reduce the amount is not accomplished, 8090% can be
solvent extraction and arsenic sulfide of new acid required for makeup, and recovered.
precipitation. bleaching with hydrogen peroxide prior Identifying the optimum process
Arsenic can be quantitatively pre- to return to the copper refinery to avoid for recovering sulfuric acid from the
cipitated from strong sulfuric acid potential problems associated with the electrolyte bleedstream requires the
solutions with hydrogen sulfide. The effect of the organic constituents on the consideration of many different factors
use of special precipitate recycling and growth habit of the electrodeposit. associated with the operation of the
aging techniques make possible the Another option is to use the acid copper refinery. These include the cost of
generation of a dense readily filterable somewhere else within the refinery disposal, the cost of concentration, and
arsenious sulfide precipitate. The use complex. Black acid is sometimes recycling. If the electrolyte bleedstream
of potentiometric monitoring of the used in the pressure decopperizing of has a high nickel concentration, the
hydrogen sulfide addition can ensure slimes. This both consumes the acid and value of the nickel salts must also be
that very little hydrogen sulfide escapes destroys most of the organic compounds taken into consideration.
the precipitation reaction present in it because of the very strong
In-Situ Impurity Control
Arsenic can also be extracted from the oxidizing conditions associated with
partially treated electrolyte by solvent the high temperatures and high oxygen The slightly soluble impurities,
extraction. The preferred solvent is pressures used in slimes decopper- antimony and bismuth, are of the
tributyl phosphate (TBP). In order to izing. most concern in the copper refinery.
improve the distribution coefficient of The acid can also be neutralized Their precipitation from the bulk of
arsenic acid between TBP and tankhouse with limestone or lime. This incurs the electrolyte is the cause of copper-
electrolyte, sufficient additional sulfuric substantial reagent costs, requires cathode contamination. Once the
acid is added to the partially treated additional equipment, and generates a precipitate forms it either mechanically
electrolyte to increase its sulfuric acid gypsum cake requiring disposal. If the or cataphoretically reports to the copper
concentration to about 600 g/L. The refinery is located on the same site as cathode, where it is included into the
arsenic acid is recovered from the the smelter, the gypsum cake can be electrodeposit. Thus, changing the
loaded TBP by stripping with water. A recycled back to the smelter where it chemical composition of the electrolyte
washing stage may be required for will report in smelter slags and in the and anodes to ensure that substantially
the loaded solvent to recover sulfuric sulfuric acid plant product. all the bismuth and antimony precipitate
acid. Complete extraction of the arsenic A final method of processing the in the slimes layer that blankets the
is rarely accomplished. The aqueous sulfuric acid is the acid retardation anodes greatly reduces contamination
arsenic-bearing solution can be a process. In this process, the electrolyte of the copper cathodes. This can be
starting material for the production bleedstream, preferably after decop- done by increasing the concentration of
of arsenic chemicals. The use of TBP perizing, is passed through a short pentavalent arsenic in the electrolyte.
for removing arsenic from copper ion-exchange bed containing an anion- Both trivalent antimony and trivalent

2004 July JOM 31


bismuth arsenate are slightly soluble IMPURITIES IN COPPER REFINERY ELECTROLYTE
in typical copper electrolyte. Because
of solubility product considerations, 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
increasing the concentration of pentava- copper refinery to copper refinery. The impurities found in copper refinery electrolyte are
lent arsenic depresses the solubility of As, Sb, Bi, Ni, Ca, ammonia, and organic fragments.
trivalent antimony and bismuth. As the
Arsenic
pentavalent As concentration increases
to about 6 g/L, the solubility of Sb and Arsenic is freely soluble in copper refinery electrolyte. It enters the electrolyte as a
Bi decreases from their typical levels 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,
of about 0.30.4 g/L Bi and 0.40.6 including the mean residence time of the arsenic in the electrolyte; the presence of
g/L Sb. As the arsenic concentration other species that may oxidize trivalent arsenic, including atmospheric oxygen; and the
continues to increase in the electrolyte, amount of pentavalent arsenic that is precipitated as insoluble compounds of antimony
the solubility of antimony and bismuth and bismuth. The deposition potential of arsenic is sufficiently greater than that of copper
continues to decrease. As the pentavalent 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
arsenic concentration in the electrolyte tolerable. Arsenic in copper causes a decrease in electrical conductivity. It is most likely to
increases, antimony and bismuth may enter the copper as an inclusion of electrolyte. Thus, as the arsenic concentration increases
precipitate in the bulk of the electrolyte in the electrolyte, its potential for contaminating cathode copper increases.
and create severe contamination prob- Antimony
lems. However, when the pentavalent
arsenic concentration attains a value 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
of 1520 g/L, antimony and bismuth insoluble compound, antimonous arsenate, SbAsO5, with pentavalent arsenic. The actual
concentration will be depressed to less concentration of trivalent antimony is defined by the solubility product of antimonous
than 100 ppm in the electrolyte and no arsenate, which, in turn, is dependent on the concentration of pentavalent arsenic in the
longer contaminate the copper cathodes. electrolyte. The deposition potential of antimony is too high to electrodeposit with
The use of high arsenate concentra- 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
tions in copper refinery electrolyte has causes problems with the mechanical properties of copper, particularly during rolling
the additional advantage of causing or wire drawing of copper.
most of the bismuth and antimony to
Bismuth
report in the slimes, where it can be
removed from the circuit and recovered Bismuth forms oxysulfates and slightly soluble sulfates. In the presence of a sufficiently
as saleable salts. high concentration of pentavalent arsenic ion, the solubility product of bismuth arsenate
defines the bismuth concentration in the electrolyte. Bismuth does not electrolytically
Arsenic recovered as Cu3As in the co-deposit with copper under normal copper electrorefining conditions. Bismuth behaves
liberator circuit can be recycled to the in a similar fashion to antimony. Wire-drawing operations are particularly sensitive to
anode furnace if there is not sufficient occlusions of bismuth compounds.
arsenic entering in the blister copper.
The use of arsenate precipitation
chemistry is finding more and more the electrolyte. This provides the
Ion Exchange of Bismuth and
application in copper refining. A useful opportunity for recovering saleable
Antimony
current description was presented at bismuth and antimony compounds and
Copper 2003 in Chile. Two methods have been described eliminating the substantial process costs
for controlling the concentration of associated with their removal from
PURIFICATION BY SOLVENT
antimony and bismuth: electrolyte the copper refinery slimes. Although a
EXTRACTION AND ION
bleed and precipitation as arsenates. bleedstream may still be necessary for
EXCHANGE
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
Solvent Extraction of Arsenic
of antimony and bismuth from the the Sb and Bi content of the anodes.
The extraction of arsenic using TBP tankhouse circulation system, while Since ion exchange will cause the
was described earlier. It should be arsenate treatment causes these elements preponderance of Sb and Bi to report
stressed that solvent extraction of arsenic to report in the refinery slimes. in the electrolyte, the size of the ion
is both for purification of the electrolyte Purification by ion exchange involves exchange operation will be defined
and arsenic disposal. Those refineries processing sufficient recirculating more by the Sb and Bi content of the
that use solvent extraction for removing electrolyte through an ion exchange anodes than by their concentration in
arsenic from electrolyte claim process operation to decrease the concentration the refinery electrolyte.
superiority over electrowinning because of antimony and bismuth to well below Chelating ion-exchange resins are
of lower energy costs, less handling their solubility limits in the electrolyte. employed for antimony and bismuth
of toxic substance, the elimination of It is important to note that when this recovery from refinery electrolyte. Elu-
possible arsine generation, and the is done the antimony and bismuth tion of the elements is done either with
possibility of recovering a saleable that would ordinarily report in the strong hydrochloric acid or concentrated
arsenic product. refinery slimes is now recovered from brines. Care must be exercised that

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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 collagensgluesto 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