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Anode Slimes
Anode Slimes
Anode Slimes
There are numerous viable approaches to nium is volatilized as se02 and passes tent. As an initial step, the direct leach-
the treatment of anode slimes from electro- into the scrubbers where it is converted ing of slimes in concentrated sulfuric
lytic copper refining. Of particular interest to selenious acid. An advantage of this acid serves to solubilize refractory cop-
in the treatment of slimes are the behavior process is the fact that the sulfur dioxide per and nickel compounds.27
and recovery ofselenium. The understanding produced in the roast reduces the sele- Morrison28 has shown that following
of the process chemistry involved in the nious acid in the scrubber solution to sulfuric acid leaching under oxygen
treatment of anode slimes should be aided elemental selenium and the sulfuric acid pressure, more than 85% of the tellu-
considerably by recent work on the formation consumed in the roast is regenerated. 22 rium is solubilized and can be recovered
and characterization of slimes. Most prom- Outokumpu!8 has developed a sig- from solution by the precipitation of tel-
ising is a direct furnace treatment of decop- nificant variation of the sulfatizing roast, lurium as Cu2Te using copper shot.
perized and detellurized slimes, in which which permits the efficient removal and Nippon Mining29 has developed a
selenium is volatilized as the dioxide, im- recovery of selenium. This process in- sulfuric acid leaching process in which
purities such as lead are slagged off, and a volves the roasting of decopperized anode slimes are suspended in 15%
high-quality dore metal is obtained. slimes in the form of a wet filter cake in H 2S04 and reacted with 02 in the pres-
a circulating gas atmosphere furnace at ence of sodium nitrite. Copper and se-
INTRODUCTION
600°C. Sulfur dioxide gas together with lenium extractions of 99% and 95%, re-
Anode slimes from copper electro-re- oxygen is introduced into the roaster spectively, were obtained. However, no
fining are normally processed to recover and the roast gases are absorbed into a mention is made of the behavior of tel-
silver, gold, selenium and tellurium. Circulating solution. The amount of S02 lurium or the solubilization of silver.
Small quantities of palladium and pla- required depends on the quantity of se- To accommodate slimes high in NiO,
tinum can be recovered as well. lenium reduced in the circulating solu- Inco 12 designed a sulfation reactor in
Because copper producers are in- tion. The process is not well suited to which the slimes are contacted with con-
terested in the behavior of impurities in operations where large quantities of centrated sulfuric acid. Copper and
copper electrorefining and in the man- high-selenium slimes are treated. nickel are solubilized (98% and 95%,
ner in which different impurities can respectively), as is a small quantity of
Sulfuric Acid Leaching in the
affect the quality of copper cathodes, the selenium and tellurium. After a water
Presence of Oxygen
numerous processes related to the treat- leach of the residue, selenium and tellu-
ment of anode slimes have been reviewed Aeration in dilute sulfuric acid to re- rium are separated from the solution by
and assessed,! complementing the re- move copper from anode slimes15,23-25 cementation. The remaining selenium is
cent work of Hoffmann2and Zarate and consists of suspending the slimes in hot removed in a later volatilization-scrub-
Gonzalez. 3 This article summarizes the dilute sulfuric acid and blowing with air bing step or in the dore furnace treat-
principal findings of this review. Of par- or oxygen. 26 De Decker et al,16 report ment. 13.!4
ticular importance to slimes treatment is aeration in dilute sulfuric acid to be a
a knowledge of slimes composition. In satisfactory technique for copper re- Oxidizing Roast
this regard, the recent work of Chen and moval with most slimes, except those The oxidation roasting of anode slimes!
Dutrizac on anode slimes character- with a high selenium and/ or nickel con- converts copper, nickel and tellurium
ization and formation is especially sig-
nificant. [Drs. Chen and Dutrizac review
their recent work in an article beginning on Dewatered
page 42 of this issue-ed.1 Anode Slimes
PROCESSING APPROACHES
The processes discussed in this paper
•
Sulfatizing Roast
(Also Pelletizing
•
Oxidizing
•
Aeration Leach
•
H2S04 Leach
•
Caustic Pressure
were selected on the basis of their in- Sulfation)
Roast H2SO4 O2 (pressure) Leach
dustrial interest and application. Dif-
ferent approaches to treating anode
slimes are shown in Figure 1. Figure 2 is 1 1 I
••
r:==LJ 1
• i 1
a generalized flowsheet for anode slimes Se 4+ Reduction Oxidizing Se4+ Reduction
treatment using a sulfuric acid leach fol- H2 S04 Leach Soda Roast
S02 Roast S02
lowed by an oxidizing roast. Tables I
and II give information on slimes com-
Sulfatizing
position and treatment at different re- Sulfation Leach
Roast in
fineries.! H2SO4
S02 + O2
l
Sulfatizing Roast
In the sulfatizing roast,!2.!9-2! sulfuric
acid in the presence of air is used as an Dore Furnace J TBRC
oxidant, sulfatizing the base metals and
oxidizing selenium and tellurium. Sele- Figure 1. A flowsheet showing different approaches to the treatment of anode slimes.
Figure 2. A generalized flowsheet for anode slimes treatment using H2SO.leaching and oxidizing
Ag2Se + 3Cl2 ~ 2AgCI.!. + SeCl4
roasting. SeCl4 + 3HzO ~ H 2Se03 + 4HCl
Table I. Survey of Anode Slimes Composition in Different Refineries (All Values Are in wt.%)l
Refinery Cu Ag Au Pt Pd Se Te As Bi Sb Sn Pb Fe Ni
- -
CCR (Noranda) 18.7 19.5 0.18 10.0 1.2 1.14 0.77 1.68 8.0 0.67
Chuquicamata 27 12.0 0.07 4 5 4
Cu Refineries Pty. 27 9.0 0.07 0.7 0.03 5.8 0.25 0.45 7.5 0.15 0.40
ER&S, Australia 13 9.0 0.10 0.09 5.8 0.2 1.2 0.3 3.0 5.0 31.0 2.0
El Salvador, Chile 5 24.0 1.4 21 0.7 3
Hibi Kyodo Co. Ltd.
Tamano Smelter 21.5 9.6 0.50 22.7
IMI Refiners, U.K. 14 5.5 0.07 0.004 0.008 2 0.6 3.5 0.5 3.5 5 22 9
Inco 21.0 6.37 0.12 8.4 1.8 0.50 0.14 0.09 1.7 17.0
Kidd Creek 26.0 12.7 0.15 19.5 0.05 0.45 0.28 0.09 22.0 0.03
Metallurgie Hoboken
Overpelt 17.4 17.2 5.1 0,95 6.8 0.74 6.8 0.35 23.2
Mhangura Copper,
Zimbabwe* 2 62 1.0 0.05 0.1 10 1.0 0.16 0.13 0.07 0.15 1.8 0.1 0.3
Minero Peru 41.0 20.0 0.04 11 1.1
Outokumpu* 8.5 16.8 0.3 46 8,0 5.7
Palabora 53.4 7.8 0.33 0.05 0.07 3,6 2.2 0.15 0.01 4.5
Phelps Dodge, El Paso 27.1 12.2 0.12 0.0007 0.006 8.8 3.1 1.7 0.66 4.65 0.08 0.64
Rabak,Turkey 24.7 4.8 0.11 0.0005 0.002 7.9 3.0 2.3 0.5 0.05
Sarkuysan, Turkey 26.7 4.73 0.10 7.6 2.5 3.6 1.3 1.7 0.82
Southwire, Georgia 10.0 4.1 0.02 0.08 0.35 0.6 1.4 0.5 9.4 5.3 13.1 8.4
It Composition of decopperized anode slimes.
.
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