ISSN 10678212, Russian Journal of NonFerrous Metals, 2015, Vol. 56, No. 3, pp. 251–260. © Allerton Press, Inc.

, 2015.

METALLURGY
OF NONFERROUS METALS

Analysis of the Sulfur Decoppering from Molten Lead

by Powder Injection1
Victor Hugo Gutierrez P.a, *, Alejandro Cruz R.a, **,
Jose Antonio Romero S.a, ***, and Jorge Enrique Rivera S.b, ****
aDepartamentode Ingeniería Metalúrgica, ESIQIEInstituto Politécnico Nacional,
A. Postal 118431, C.P. 07051, D.F. México
b
Universidad Autónoma de Coahuila, Boulevard V. Carranzay José Cárdenas Valdés,
C.P. 25280, Saltillo Coah. México
email: *metalurgico2@hotmail.com, **alcruzr@ipn.mx,
***romeroipn@hotmail.com, ****jenrique.riverasalinas@gmail.com
Received October 3, 2014

Abstract—A copper removal process was carried out in a PbCu alloy through sulfur powder injection of
three different sizes (79.23, 202.83 and 597.15 μm) by a top submerged lance with nitrogen as carrying gas.
The higher copper removal as CuS2 was obtained for the sulfur powder size of 79.23 μm, while the lowest cop
per removal efficiency was attained for the coarse particle size of 597.15 μm. The copper removal was
explained according with a relationship between the residence and melting time. The sizes of 202.83 and
597.15 μm presented a longer residence time that promotes the sulfur coalescence and it is lost by burning.
An injectioncooling trial was developed and a decoppering fraction of 0.29 with a sulfur efficiency of 72.98%
in average was obtained for the fine size. The injectioncooling process represents an attractive route for sec
ondary lead producers in the copper removal from molten lead.

Keywords: lead refining, decoppering, sulfur injection, particle size

DOI: 10.3103/S1067821215030086

1
INTRODUCTION
Lead is one of the most widely used metals in the
world, but it is highly toxic, posing risks for humans
and for the environment if not utilized or treated ade
quately. Lead is the world’s most commonly recycled
metal on an industrial scale, with about 80% of all the
lead produced worldwide applied in the fabrication of
automotive batteries. More than 95% of the batteries
used in the US and Europe are recycled [1]. Recycled
lead maintains the same physicochemical properties
as primary lead and has become the raw material to
produce this metal. In the recycling of lead acidbat
teries, there are some metals impurities, such as Cu,
Ag, As, Sb, etc. [2, 3]. The spent batteries find them
selves at the recycling facility to undergo pyrometal
lurgical operations, most commonly, to produce
refined metals. The pyrometallurgical refining com
prises three main stages [4]: (a) copper drossing,
(b) softenning and (c) desilvering. The copper dross
ing process consists in the removal of impurity com
pounds (mostly antimonies, arsenides, and stannides)
through a cooling process in a large kettle where impu
rities are separate as either solid or immiscible liquid
phases due to the decreasing solubility of the phases at
1 The article is published in the original.
lower temperatures. The impurities are removed by
skimming during cooling, and the molten lead is
finally cooled to about 340°C. To remove the last
amount of copper between 20–200 ppm, sulfur may be
stirred into the melt, and cooling is continued to very
near the freezing point of the melt (~330°C), and the
process is generally termed “sulfur drossing” or “fine
decoppering”. The phases to be removed float on the
lead surface and are called mattes or speiss, depending
on the impurities they contain. They are skimmed off,
tapped off, or otherwise removed [4–6]. Some pro
cesses in lead refining such as removing copper from
lead by a drop in solubility with decreasing tempera
ture and the oxidation of antimony, tin and arsenic to
form oxide dross are carried out under equilibrium
conditions. Other processes such as decoppering with
pyrite/sulfur and caustic refining steps are governed by
kinetics [5]. The reaction of copper and sulfur
occurred in a single stirred reaction vessel feeding sul
fur into the stream of lead at the upper end of the reac
tion vessel, maintaining a dispersion of sulfur in the
stream without substantial backmixing. Reaction
proceeded for sufficient time to affect reaction
between them. During the process, the sulfur must be
thrown into the vortex, at a regular rate over about ten
minutes, or else some floats on the lead surface and it

251
252 GUTIERREZ et al.
is lost by burning. The sulfur must be of a suitable size;
if to fine, it burns before hitting the lead surface. If it is
too coarse, it does not dissolve completely before
emerging again on to the lead surface, where the liquid
sulfur burns [7]. The lead temperature must be main
tained close to the freezing point. The stirring must be
continued for a few minutes following sulfur addition,
before the dross is skimmed. A resolution of copper
into lead will occur when the stirring is prolonged or
with an increase of the temperature. Davey [6] studied
the physical chemistry of lead refining under equilib
rium conditions included copper drossing. They
showed that kinetic consideration governed the opera
tion of decoppering by incorporation sulfur into lead
at low temperature or by stirring the melt with sulfur
and pyrites at higher temperature. Rabah et al [8]
determined the effect of the addition of caustic soda
on decoppering of hard lead using pyrite. Their results
revealed that pyrite 2 stoichiometric ratio and 0.5%
caustic soda at 450°C decreases copper content in the
hard lead alloy from about 0.56% to 0.03% in 30 min.
However with a further increase in the decoppering
time, the residual copper content in the lead alloy re
increase passing through a broad maximum after
40 minutes. Etsuji and Hiromi [9] studied copper
removal from lead by a dry method. An Al–Mg–Zn
master alloy was added to molten lead containing
≥0.5 ppm of copper. The melt was mixed with alkali
metal hydroxide and air blow to form dross for
removal. The dross skimmed in the industrial process
contains essentially PbS and Cu2S, and sometimes
some CuS, as well entangled metallic lead, which is
partly oxidized to PbO [7]. The decoppering process
involves more than one possible reaction, some fast
and some slow, intermediate products or metastable
phases may be formed when reactions proceed away
from thermodynamically equilibrium. In spite of
numerous studies the Cu–S binary system presents
uncertainty regarding phase equilibria, because of a
strong tendency for forming several metastable phases
in this system. The phases formed often possess Xray
diffraction and optical properties similar to those of
equilibrium phases, making phase identification diffi
cult [10]. A number of metastable phases occur in the
Cu–S system. One of these is the CuS2 phase, which is
formed under high temperature and pressure. The
phase is stable at 25°C above 8 Kbar, but can exist
metastably for long periods of time [10]. Pure CuS2
shows metallic conductivity and Pauliparamagnetism
[11]. Even, there is confusion regarding the formal
oxidation state for covellite (CuS). The latter view is
based on the representation of CuS as Cu2S or CuS2,
which reflects the two different S environments in the
crystal structure [12, 13]. The procedure of adding sul
fur powder to remove copper onto the molten lead sur
face and further stirring is an inefficient step in the
lead refining [13, 14]. A technique used to increase the
efficiency of lead refining is the submerged injection of
solid reagents into the melts. Powder injection has
RUSSIAN JOURNAL OF NONFERROUS METALS
become in recent years an important tool in metallur
gical operations focused primarily to steelmaking pro
cesses. The injection efficiency depends mainly on the
interaction (solid particle and conveying gas) with the
liquid metal. Important factors to consider are the real
contacting interfacial area and the residence time
between the liquid metal and solid particle [15]. Pow
der injection process considers two possible reaction
zones [16]. These are, the transitory reaction zone
(reaction between the particle injected and liquid
metal) and the permanent reaction zone (reaction
between the metalslag interfaces). The residence time
of the particle is determined by their velocity relative
to the melt and by the bulk flow velocity of the melt.
Ohguchi et al. [17] studied the desulfurization process
in torpedo cars. They establish a kinetic model in
terms of the mixing time to study the kinetics of pow
der injection and the metalslag reaction considering a
fixed volume of slag. Plascencia et al. [13] carried out
experiments to remove copper from lead bath by con
ventional top addition and injection of sulfur powder.
In addition, they used thermodynamic and kinetic
models to simulate the lead refining. This works deals
with the copper removal in a Pb–Cu alloy through the
sulfur powder injection with nitrogen as conveying gas.
The effect of the sulfur powder size (79.23, 202.83 and
597.15 μm) was evaluated to determine the sulfur effi
ciency in copper removal by the injection process at
400°C. In order to increase the copper removal, an
additional trial was carried out with the best sulfur par
ticle size and a cooling process to reach a temperature
nearly of the freezing point. The slag was analyzed by
Xray powder diffraction and scanning electron
microscope with energy dispersive spectra techniques.
The residence and melting time were determined in
order to explain the experimental behavior.
EXPERIMENTAL
Pb–Cu Alloy Production
Copper contents are reaching levels higher than
0.07 wt % in the secondary lead refining [10]. In this
work a Pb–Cu master alloy with 0.0740% Cu was
manufactured by conventional melting in an electric
furnace to 700°C from pure metals. 11 kg of alloy was
melted in a SiC crucible and poured into an iron mold
to obtain ingots of approximately 900 g each one.
Sulfur Powder Production
Three sulfur powder sizes were used as raw materi
als for the injection trials. J.T. Baker commercial
reagents of sulfur were used in granular and powder
presentation with 99.9 and 99.8% of purity, respec
tively. The medium size was obtained by manual mill
ing of granular sulfur in an agate mortar. The samples
were classified with an optical microscope Carl Zeiss
Axiovert 40MAT. The three sizes of sulfur powder
were named as fine, middle and coarse particles.
Vol. 56 No. 3 2015