Journal of Alloys and Compounds 636 (2015) 282287

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Separating leadantimony alloy by fractional crystallization using

directional lifting process
Chao Liu, Keqiang Qiu
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, China

a r t i c l e i n f o a b s t r a c t

Article history: The conventional pyrometallurgical method for separating leadantimony alloy produced from jameso-
Received 25 December 2014 nite has a lot of imperfections such as long-term process, tremendous energy cost and harm to the envi-
Received in revised form 7 February 2015 ronment. Therefore, a new method to separate lead and antimony from leadantimony alloy by fractional
Accepted 25 February 2015
crystallization is investigated. The experimental results demonstrate that the lead content decreases with
Available online 3 March 2015
the increase of length to the metal columns bottom. Lead content of the bottom can reach larger than
80% by weight after lifting. In the experimental speed range, the lifting speed has very small impact
Keywords:
on the separation effect. After 4 times lifting, crude lead bullion (larger than 83% by weight) whose lead
Jamesonite
Fractional crystallization
content is close to the eutectic point of leadantimony binary system is gained in the bottom and the
Leadantimony alloy antimony can be used for further rening process without converting into Sb2O3. The separating efcien-
cy of lead in the bottom has reached the theoretical level of fractional crystallization for leadantimony
alloy containing about 40% by weight antimony.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Jamesonite (FePb4Sb6S14) is a complex chalcogenide ore from
Guangxi province, China. The leadantimony components in jame-
sonite exist as solid solution of antimony sulde and lead sulde in
the ore. Since it is of great difculty to separate lead and antimony
from jamesonite by mineral methods, metallurgical methods must
be taken to utilize the ore more effectively [1]. At present, jameso-
nite ore is treated by conventional industrial pyrometallurgy pro-
cess shown in Fig. 1 [2].
In conventional process, desulphurizing roasting in ebullition
furnace is primarily conducted. After the mixtures calcine sinter-
ing and reduction smelting in blast furnace, leadantimony alloy
containing about 40% by weight antimony is obtained as the initial
product. Then the alloy is converted in reverberatory furnace in
order to separate antimony from the alloy by blowing smelting,
in which crude lead bullion containing about 2025% by weight
antimony and antimony oxide powder (antimony white) were got-
ten. In the end, the pure lead and antimony are nally obtained
respectively with the electrolytic rening of crude lead and the
antimony trioxides reduction smelting in reverberatory furnace
[3].
Corresponding author. Tel.: +86 13574858108.
E-mail address: qiuwhs@sohu.com (K. Qiu).
However, it is not hard to see that there are a number of short-
comings in this method. The temperature of reverberatory blowing
and antimony whites reduction smelting is about 950 C and
1100 C respectively, which means high energy consumption. The
low-purity lead bullion contains only 7580% by weight lead, lead-
ing to the poor efciency of electrolytic rening. In this procedure,
antimony is oxidized to Sb2O3 and then reduced to Sb. The direct
recovery ratio of lead and antimony is unsatisfactory due to the
long process by conventional industrial pyrometallurgy process
shown in Fig. 1. In addition, a mass of off-gases and slags, which
do harm to the environment and human health, are produced in
the smelting and blowing process.
Many researchers in China put forward some new methods
such as vacuum distillation, sodium sulde leaching-electrolysis
process, separating lead and antimony in chloride system and the
slurry electrolysis technology to improve this process [35].
However, these methods bring in new difculties such as expen-
sive cost, huge alkali consumption and hard to apply to the indus-
try. Therefore, an innovation without such negative impacts must
be employed to improve this procedure. In this paper presented
here, we aim to put forward a new efcient and economic method
to separate lead and antimony from leadantimony alloy contain-
ing about 40% by weight antimony. Crystallization Separation,
which possesses a lot of superiorities such as low energy cost, sim-
ple technological process, harmlessness to the environment and
economic friendliness, is proposed in our work.

http://dx.doi.org/10.1016/j.jallcom.2015.02.190
0925-8388/ 2015 Elsevier B.V. All rights reserved.
 C. Liu, K. Qiu / Journal of Alloys and Compounds 636 (2015) 282287
Fig. 1. Conventional process owsheet for treating jamesonite.
2. Experimental procedures
2.1. Experimental materials and equipments
The leadantimony alloy used in the experiments was crude lead bullion with
about 40% by weight antimony. The impurity content was very little and could be
ignored. A homogenized sample was characterized by XRD (X-ray diffraction), of
which the pattern is given in Fig. 2. The result showed that the main constituents
in the raw material were lead and antimony, with none impurity detected.
In the rst group of experiments, the samples with different lead contents were
self-prepared. Before the separating experiments, the alloy was smelted in melting
furnace, casted to form ingot and pounded into pieces to ensure the convenience for
re-melt. This process was repeated 3 times to guarantee the alloys uniformity. The
experiment apparatus was shown in Fig. 3. The electric resistance furnace with
intelligent temperature controller (provided by Shanghai Guolong Instrument Co.,
Ltd.) employed in the experiments is self-manufactured.
2.2. Experimental methods
The leadantimony alloy was primarily weighed and loaded in a porcelain tube
(20 mm in diameter and 450 mm in length, Fig. 3(a)). The porcelain tube was sup-
ported by a steel tube that was located in the self-manufactured furnace. The steel
tubes top was connected to the speed controller by a steel wire for the lifting of
the tube. The temperature controller set the furnaces temperature which was
higher than the alloys melting point. The temperature was kept constant for an
Fig. 2. XRD pattern of the raw material.
283
hour, meanwhile the molten alloy was stirred by a graphite rod to ensure the
alloys homogeneous mixing. Then the speed controller began to lift the steel tube
up at a certain speed until the whole tube was completely out of the furnace.
During this process, the melt was gradually cooled below the liquidus temperature
and crystallized. The specic gravity of lead was 11.34 g/cm3, which was much
larger than that of antimony, 6.884 g/cm3. The solid crystal oated on the top
and meanwhile the liquid containing more and more lead settled to the bottom.
After the solidication of the whole alloy melt, a long metal column was obtained
as the product.
In our second-part work, the porcelain tube was substituted by graphite
crucible (62 mm in bottom inner diameter, 77 mm in top inner diameter and
250 mm in length, Fig. 3(b)). The graphite crucible had larger capacity so that large
amount of the alloy can be treated. The graphite crucible was supported by a
self-made metal rack whose top was connected to a steel wire. The electric
resistance furnace was re-created to t the graphite crucibles size. During each
experiment, the top of the molten alloy was covered by carbon to prevent the alloy
from oxidizing.
3. Basic principles
Metal separation or rening by fractional crystallization from
the melt is a long standing method. From the twenties of the
19th century to the present, the technique of fractional crystalliza-
tion is long-tested and improved day by day. Fractional crystalliza-
tion from the melt is possible only if the solute concentration in the
solid differs from that in the liquid when the liquid and solid is at
equilibrium [6].
To evaluate the effect of fractional crystallization operations,
the equilibrium distribution coefcient, k, which is an important
parameter, is dened as the ratio (CS/CL) taken from the constitu-
tional diagram. Therefore:
CS
k 1
CL
where for AB binary system, CS is the content of B in the solid and
CL is the content of B in the liquid. The value of k will be greater or
less than unity, depending on whether the solute (B) raises or low-
ers, respectively, the melting point of the solvent (A). For k > 1, the
component B mainly exists in solid; for k < 1, the component B
mainly exists in liquid. Moreover, the larger j1  kj is, the better
separation effect will be got.
The behavior of the metals in the process of metal rening and
separation by fractional crystallization can be predicted from the
phase diagram. With reference to Fig. 4, when melt L containing
B (bL, %B) is cooled to temperature T1, the crystal b1 can be pro-
duced, which is at equilibrium with the B-enriched liquid, b01 . If
the liquid b01 is separated from the crystal b1, a liquid phase, b01 ,
is the rst separated product. When the obtained liquid phase b01
is re-cooled to temperature T2, the liquid b02 , which has a higher
content of B than liquid b01 , is at equilibrium with the crystal b2,
which contains less A than crystal b1. If the process is repeated,
the content of A in the crystal becomes less and less, while the
content of B will accumulate in the liquid phase and, eventually,
reaches or is close to the eutectic point, bE (Fig. 4).
It is apparent that the directional lifting fractional crystalliza-
tion process is macroscopically a continuous version of the
batch-type multi-stage fractional crystallization process described
in Fig. 4.
As shown in the phase diagram (Fig. 5), the melting point of lead
and antimony are 327.5 C and 630.7 C respectively. The metals
show ultimate mutual solubility in liquid and partial miscibility
in solid. At eutectic temperature, the lead is 88.8% by weight while
the antimony is 11.2% by weight [7]. The raw material (about 40%
by weight antimony) used in our experiments is located in the area
of CDE, in which the liquidus is far from the solidus. In other words,
the numerical value of partition ratio k is far from 1, which means
it is theoretically easy to get the antimony solid solution and
lead-rich liquid.
284 C. Liu, K. Qiu / Journal of Alloys and Compounds 636 (2015) 282287

Fig. 3. The schematic illustration of experimental apparatus: 1, 2 intelligent temperature controller; 3 asbestos paper for electric and thermal insulation; 4 porcelain tube; 5
steel tube; 6 thermocouple; 7 speed controller; 8 resistance wire; 9 metal rack; 10 graphite crucible; (a) resistance furnace with porcelain tube; (b) resistance furnace with
graphite crucible.

4. Results and discussion

The inuences of different raw materials with various lead con-

tents, lifting speeds and lifting times, were investigated in our
work. During each experiment, the actual temperature of different
part of the furnace was measured in advance to make sure that it
was higher than the alloys melting point and the alloy can be
melted and mixed homogeneously. Samples for testing were taken
according to the columns length in order to measure the lead con-
tent of different part. Then the samples were determined by che-
mical analysis to test the lead content: the leadantimony alloy
could be dissolved by sulfuric acidpotassium sulfate mixed solu-
tion. Sodium citrate was used as a masking agent, and sedimenta-
tion of lead sulfate could be quantitatively analyzed by EDTA
Fig. 4. Schematic diagram of metal rening and separation by fractional complex formation titration at pH 5.5.
crystallization.

Fig. 5. The phase diagram of lead and antimony.

 C. Liu, K. Qiu / Journal of Alloys and Compounds 636 (2015) 282287
4.1. Effect of lead content
The effect of lead content on the separation effect was studied
by a series of samples contained 55.1928.20% by weight lead
(Fig. 6). After heat preservation period, the speed controller started
lifting up the steel tube at the speed of about 0.6 mm/min.
The results show that the lead content decreases with the
increase of length to the metal columns bottom as expected. As
observed in Fig. 6ac, the content of lead in the bottom is about
88 wt%, which exactly conformed to the phase diagrams rule. In
Fig. 6d, the lead content of the bottom is 77.11% by weight, which
is also a big improvement compared to the raw materials 28.20%.
Thus the fractional crystallization method is feasible to all the raw
materials with different lead contents. Antimony contents of the
top of the columns all increase about 10wt% compared to the
raw materials. That is because some liquid may become entrapped
by the growing antimony dendrite crystals, once this part is out of
the furnace, a portion of the liquid of this part also solidies on the
top instead of settling [8,9]. On the other hand, the liquid enriched
with lead settles to the bottom.
4.2. Effect of lifting speed
This group of experiments was conducted by resistance furnace
with graphite crucible. After each experiment, a metal column
which is 62 mm in bottom diameter, 70 mm in top diameter and
130 mm in length was gained. The raw materials which contained
about 60% by weight lead were lifted at speed 4.31, 2.50 and
0.69 mm/min till they were totally out of the furnace. When lifting
the graphite crucible, the speed controller used in the experiments
can change lifting speeds ranged from 0.69 mm/min to
Fig. 6. Lead weight percent versus length to the bottom of the metal column with raw materials of various lead contents (by weight): (a) 55.19%. (b) 44.67%. (c) 32.37%.
(d) 28.20%.
285
4.31 mm/min. Fig. 7 shows that the antimony contents of the top
all increase about 20 wt%, which can eliminate the inuence of
lifting speed to the antimony content of the top. On the other hand,
the lead contents of the bottom also vary little with the speed
variation, and they all maintain larger than 80% by weight. We
can draw to the conclusion that in the experimental speed range,
lifting speed has very little inuence on the separation effect,
which is different from zone rening for high-purity metals. Thus
high speed is feasible to increase rening efciency.
4.3. Effect of lifting times
As observed in the previous experiments, fractional crystalliza-
tion method used in our experiments can separate lead and
antimony in some extent. Using zone melting as a reference, how-
ever, this process has to be repeated several times to accumulate
the separation effect [10]. Four times repeating lifting processes
using sample which contained 58.35% by weight lead at
4.3 mm/min lifting speed were conducted. The lead content varia-
tions during 4 times lifting processes are illustrated in Fig. 8. As we
can see, the lead content of the bottom maintain larger than 84%
and the lead content of 3 cm from the bottom increases as the lift-
ing time increases. At last, the lead content of this part can reach
almost as high as the bottom. During 4 times lifting, the lead con-
tent of the top decreases, which means the antimony content
increases. The lead content of 10 cm and 12.5 cm of the column
have the same tendency. After 4 times enrichment, the antimony
content of the top can reach 85% by weight.
The bottom part of the column can be used for lead electrolysis
to produce pure lead in higher electrorening efciency, and the
top can be used for antimony electrolysis. The antimony is not
286 C. Liu, K. Qiu / Journal of Alloys and Compounds 636 (2015) 282287

Fig. 7. Lead weight percent versus length to the bottom of the metal column at different lifting speed: (a) 4.31 mm/min. (b) 2.50 mm/min. (c) 0.69 mm/min.

Fig. 8. The lead content variation of bottom (a) and top (b) during 4 times lifting process.

converted into Sb2O3, furthermore, the complex reduction process
and the appended products are avoided. The middle part can be
rened by repeating the previous work.
In the current widely used pyrometallurgy method, the lead
antimony alloy is converted to crude lead bullion and antimony
oxide powder after blowing smelting in the reverberatory furnace.
Our work simplied this procedure by using fractional crystalliza-
tion method to treat leadantimony alloy. Some clear comparisons
are shown in Table 1. Besides, the blowing smelting and reduction
smelting can produce a lot of off-gases and slags which are
hazardous to the environment and human health. Fractional crys-
tallization shows apparent advantages in less material wastage,
simple operation process, improvement in energy consumption
and harmlessness to the environment.
In recent years, some researchers have put forward some
bran-new ideas to treat the jamesonite ore [5]. And these new
methods, the majority of which focus on hydrometallurgy process
to treat the ore, have their own drawbacks. Massive alkali and
power consumption, formidable cost of production and indispens-
able efuent treatment are all problems that are difcult to solve.
Consequently these methods are not widely used. Another method
to separate lead and antimony is vacuum distillation, but it is
mainly used to deal with alloys whose lead weight percentage is
only about 10% [4]. The fractional crystallization process achieves
 C. Liu, K. Qiu / Journal of Alloys and Compounds 636 (2015) 282287 287

Table 1 is larger than 83% by weight) than the industrial production was
Comparision between properties of fractional crystallization and current widely used gained. The antimony was not converted into Sb2O3. The fractional
pyrometallurgy process.
crystallization method showed great advantages for treating lead
Method Products Purity Temperature antimony alloy.
Fractional Crude lead in 8385% by 500600 C
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