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DOI 10.

1007/s11015-015-0080-y
Metallurgist, Vol. 59, Nos. 1–2, May, 2015 (Russian Original Nos. 1–2, January–February, 2015)

AUTOCLAVE LEACHING OF ARSENIC FROM


COPPER CONCENTRATE AND MATTE

V. I. Neustroev, K. A. Karimov, UDC 669.333.47:66.046.8


S. S. Naboichenko, and A. A. Kovyazin

Results are given for autoclave leaching of concentrates and mattes from polymetal semiproduct melts
containing arsenic alongside copper. The possibility is demonstrated of selective copper and arsenic
leaching into solution. It is confirmed that with autoclave leaching arsenides are broken down better than
for natural arsenic-containing minerals.
Keywords: leaching, matte, concentrate, copper, arsenic.

The main arsenic-containing minerals in copper ores [1] and concentrates are arsenopyrite (FeAsS) and enargite
(3Cu2S·As2S5 or Cu3AsS4). The proportions of enargite and arsenopyrite in copper concentrates differ in relation to the
deposit [2]. With increased contents (>2.0%) of arsenic within copper concentrates, their pyrometallurgical processing is
connected with contamination of the environment by arsenic compounds and worsening of final copper cathode quality.
Non-traditional pyrometallurgical methods should be used for processing arsenic-containing concentrates, for example,
autoclave leaching.
Tests were performed in a titanium autoclave with a capacity of 1 dm3. An ore copper-arsenic concentrate of the fol-
lowing composition was used, wt.%: 16.8 Cu, 32.2 Fe, 31.4 S, 0.9 Sn, 9.7 As. Its main phases were: chalcopyrite, arsenopy-
rite, enargite, pyrite; approximately 12% copper was represented by secondary sulfides (covellite, bornite). Concentrate size:
83% of fraction 44 μm.
In the first stage, concentrate was treated with acidified copper sulfate solution (180°C; original concentration
10 g/dm3 H2SO4; 16% solid fraction of concentrate in pulp; duration 1.5 h). With an increase in copper sulfate consumption
from 20 to 43 g/dm3 (molar ratio Cu:As = 1.2–2.7), the transfer of iron into the solution increased from 22 to 40%, arsenic
from 4.4 to 26.3%; and with Cu:As > 2.0, the role of copper sulfate consumption appeared to be insignificant. With an
increase in temperature from 140 to 160°C (Cu:As = 1.2; 10 g/dm3 H2SO4; duration 1,5 h), the transfer of arsenic into the
solution increased from 20.6 to 31.5% and iron from 27 to 26%; at 180–200°C, the transfer of iron into solution, and espe-
cially arsenic, decreased to 22.0 and 5–7%, respectively; the copper content in the final solution was markedly reduced. Phase
analysis data for cakes showed that there was a marked increase in the content of chalcosine and iron arsenate. Apparently
with an increase in temperature chalcopyrite becomes an active precipitating agent for copper and strengthens hydrolysis of
arsenic-containing anions and iron (III) sulfate with the formation of insoluble iron arsenate. Favorable results were not given
by an increase in original solution acidity from 5.0.to 53 g/dm3 H2SO4 (180°C, Cu:As = 2.5, duration 1.5 h), the transfer of
iron and arsenic into the solution increased by 7–10%, and the degree of copper deposition decreased by 30%.
In balanced tests (160–180°C, Cu:As = 2.7), not more than 40–42% As and 52–56% Fe passed into the solution, and
up to 62–70% Cu was precipitated; cake composition, %: 37–40 Cu, 16–18 Fe, 27–29 S, 0.6–0.7 Sn. Thus, during hydrothermal
treatment of original concentrate with acidified copper sulfate solution it was impossible to achieve good arsenic extraction

Ural Federal University, Ekaterinburg, Russia; e-mail: neustroev1948@mail.ru, kirill_karimov07@mail.ru. Translated from Metallurg, No. 2,
pp. 72–74, February, 2015. Original article submitted October 8, 2013.

0026-0894/15/0102-0177 ©2015 Springer Science+Business Media New York 177


into solution, which was due to the tenacity of arsenic-containing minerals. The marked transfer of tin into solution up to
67–72% was unexpected.
A version of autoclave oxidation leaching of concentrate was tested in an oxygen atmosphere with the aim of leach-
ing copper selectively from arsenic and iron. Taking account of data in [2], the following leaching conditions were adopted:
170°C, oxygen pressure pO2 = 0.4 MPa, 5.1 g/dm3 H2SO4; 17% solid fraction in pulp, duration 2 h. The leaching residue (its
yield was 65% of concentrate weight) included: dark-blue sulfide (yield 47%) and hydrated phase of brown color. The com-
position of the sulfide phase (16.7% Cu, 32.4% Fe, 8.9% As) differed little from that of the original concentrate. The hydrate
phase contained, %: 0.96 Cu, 36.6 Fe, 14.7 As. Not more than 1.0% As was transferred into solution. The maximum copper
extraction reached 53%. The results obtained point to the incomplete level of the process, caused by insufficient temperature
and duration, and in addition they confirm the possibility of minimum arsenic transfer into solution.
During performance of autoclave alkali leaching of concentrate (110 g/dm3 NaOH, 3 h) with an increase in pO2 from
0.8 to 1.6 MPa arsenic extraction into solution increased from 70 to 96–99%; the residue obtained (85–87% of the original)
contained 19–20% Cu and 1.3–1.5% As. The problem appeared to be separation of the pulp obtained and treatment of arsenic-
containing solutions. These tests confirmed the tenacity of natural arsenic-containing minerals. Attention is drawn to the high
temperature version (170–190°C) of autoclave oxidation leaching, but additional systematic research is necessary for its use
in production.
It is well known that in copper pyrometallurgy 70–90% of arsenic, and also a significant amount of lead and zinc
pass into the fine dust formed [1]. An increase in fine dust in a melt leads to black copper contamination. It has been pro-
posed [3] that fine dust and similar recycled semiproducts are subjected to reduction melting with preparation of polymetal
matte of the following composition, %: 30–40 Cu, 15 S, 11–25 Pb, 7–24 Fe, 5 As, 2–4 Zn. According to x-ray phase analy-
sis data, PbS, CuS, FeS, PbS·As2S3, FeAs2, Cu3As, ZnS, As2S3, Cu2S are detected within matte.
Data are known for sulfuric acid autoclave leaching of speiss containing %: 32 Cu, 18 Pb, 15 As, 7 Fe [4]. Leaching
at 80°C, pO2 = 1.0 MPa, acidity 650 g/dm3 for 2 h made it possible to extract 82% Cu and 72% As into solution.
We have also studied autoclave leaching of copper mattes obtained. Tests were performed under the following condi-
tions: pulp density L:S = 6:1; pO2 = 0.4 MPa; temperature 140–180°C. Acid content was varied within limits from 10 to 130 g/dm3,
and leaching duration from 0.5 to 2.0 h. Acid consumption appeared to have a considerable effect on leaching results; with a
molar ratio H2SO4/Cu(III) = 0.83 and temperature 180°C, more than 94% was extracted; matte sulfide sulfur was oxidized to
sulfate, and iron extraction reached 30%. A considerable part of arsenic passed into cake in the form of iron (III) arsenate.
x-Ray phase analysis showed that all of the lead within cake was in the form of PbSO4; copper was in the form of Cu3(AsO4)2,
anhydrous CuSO4 and CuSO4·0.67H2O. No sulfide or elemental sulfur were detected within the deposit, which points to total
sulfide oxidation in the course of autoclave leaching and transfer of sulfide into sulfate form. Cake composition %: 6,56 As,
39.20 Pb, 8.26 Fe; the solution contained, g/dm3: 73 Cu, 4 Fe, and 1 As. The cake obtained was given autoclave leaching in
order to evaluate the possibility of arsenic and iron extraction. Tests were carried out at 140–180°C, pulp density L:T =
= (15–30):1, pO2 = 0–0.4 MPa, original sulfuric acid concentration [H2SO4]0 = 20–30 g/dm3. Iron extraction reached 42%,
but with an increase in oxygen pressure it decreased. After 4 h leaching, 32.95% arsenic was transferred into the solution.
Apparently, arsenic and iron are within cake in the form of compounds that are difficult to break down. Copper remained
entirely within the cake after leaching, which points to the stability of copper arsenate under the leaching conditions used.
For selective arsenic extraction, matte was treated with acidified copper sulfate solutions. This was performed at
140–180°C, pulp density L:S = 12:1, 5–10 g/dm3 H2SO4, copper concentration 20–20 g/dm3. As a result of 90 min of leach-
ing, arsenic was extracted into solution by 93%, and iron and zinc by 90%. The residual copper concentration in solution was
6–14 g/dm3, and lead entirely remained within the cake after leaching. According to x-ray phase analysis, all lead is present
in the form of PbSO4, and the remaining arsenic is in the form of an amorphous compound and Cu3(AsO4)2.
Conclusions
1. The best indices for autoclave leaching of copper concentrate containing enargite and arsenopyrite were obtained
with alkaline breakdown, which made it possible to extract into solution up to 99% arsenic and concentrate copper within
cake. However, subsequent solution treatment is difficult.

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2. Autoclave leaching of arsenic-containing matte made it possible to separate arsenic and copper with extraction of
copper (by 94.2%) into solution, containing a small impurity concentration and suitable for subsequent processing by tradi-
tional methods (electro-extraction, evaporation). Lead was concentrated within cake that may be processed by lead producers.
3. With treatment of matte with copper sulfate solution, it was possible extract selectively up to 93% of arsenic into
solution.
4. It was confirmed that with autoclave leaching of arsenic-containing materials arsenides appear to be more readily
broken down compared with natural arsenic-containing minerals.

REFERENCES

1. I. E. Makhov, S. V. Mikhailov, L. D. Shishkina, et al., Behavior of Arsenic and Antimony During Pyrometallurgical
Copper Production, TsNIIEItsvetmet, Moscow (1991).
2. R. Padilla, G. Rodriguez, and M. C. Ruiz, “Copper and arsenic dissolution from chalcopyrite-enargite concentrate
by sulfidation and pressure leaching in H2SO4–O2,” Hydrometallurgy, 100, 152–156 (2010).
3. G. V. Skopov and A. V. Matveev, “Combined processing of polymetal semiproducts of metallurgical production,”
Metallurg, No. 8, 73–76 (2011).
4. K. D. Gerlakh and F. E. Pavlek, “Autoclave leaching of speiss,” in: Gidrometallurgiya [Russian translation], Moscow
(1971), pp. 99–114.

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