Russian Journal of Applied Chemistry, Vol. 76, No. 2, 2003, pp. 191!194.

Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 2, 2003,

pp. 201!204.
Original Russian Text Copyright + 2003 by Zarubitskii.

INORGANIC SYNTHESIS
ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ
AND INDUSTRIAL INORGANIC CHEMISTRY

Refining of Lead To Give Bismuth-Enriched Drosses

O. G. Zarubitskii

Vernadskii Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine

Received June 3, 2002

-
Abstract The results obtained in testing an improved technique for reagent refining of crude lead, which
yields bismuth-enriched drosses in the form of a powder, are presented. The advantages of the method put
into industrial practice are described.

The pyrometallurgical method proposed by Kroll
and Betterton [1, 2] is mainly used at lead works to
remove bismuth admixtures from refined crude lead
(lead bullion). This, the most complicated procedure
is carried out after silver removal. It involves dissolu-
tion of blocks of circulating bismuth drosses at 400oC
and subsequent introduction of magnesium and cal-
cium into melted crude lead at 360 3370oC. These
metals react with bismuth to form intermetallic com-
pounds: Ca3Bi2, Mg3Bi2, Mg2CaBi2, which are poorly
soluble in lead and are deposited on the bath surface.
They are extracted as the so-called [enriched] bismuth
drosses with bismuth content of 335%. Then the bath
is cooled to 340 3350oC and [lean] circulating drosses
containing 0.5 32% Bi are extracted. Repeated circu-
lation of drosses can increase the bismuth content up
to 5 311%, to give a lead3bismuth alloy containing
8 315% Bi [1]. The increase in the bismuth content
from 5 311 to 8 315% results from removal of mag-
nesium and calcium from the drosses with molten
NaOH. A 5 3 6% fraction of Bi passes into the result-
ing alkaline melts.
The existing technology for Pb 3Bi alloy production
does not ensure isolation of bismuth-enriched (to more
than 8 315%) products and is characterized by repeat-
ed dross circulation, which leads to loss of the target
metal and involves additional consumption of reagents
(magnesium, calcium, and sodium hydroxide).
Various methods for dross enrichment with bis-
muth have been proposed. For example, centrifugal
refining can enrich drosses to Bi content of 18 321%
at its initial concentration of 5.7% [3]. Air bubbl-
ing through liquid metal (cupellation) at 900 3 950oC
can raise the bismuth content of a Pb 3Bi alloy being
treated from 14 to 40 3 60%, with simultaneous re-
1070-4272/03/7602-0191 $25.00 C 2003 MAIK
moval of antimony, tin, arsenic, and tellurium [4].
This method has been implemented in industry.
Of special interest are the publications [5 37] de-
scribing the possibility of using organic compounds
in pyrometallurgical processing of lead3bismuth al-
loys. For example, in purifying bismuth to remove
lead and copper by adding sulfur to a metallic melt,
friable yields can be obtained if carbon or masut is
introduced into the metal being refined [5]. It is re-
commended [6] that coal-tar pitch should be added
to a melt to enrich dross with bismuth, which yields
an alloy containing 40% Bi and 60% Pb. Dry drosses
are obtained by adding sawdust to crude lead (modi-
fied Kroll and Betterton method [6, 7]). However,
the authors of [5, 7] did not consider the mechanism
by which the above-mentioned organic compounds
affect the metallurgical processes under consideration.
EXPERIMENTAL
Our experiments and pilot tests made it possible to
develop and put into industrial practice an improved
method for lead refining, which provides lead alloys
with high bismuth content. The technological process
consists in the following. First, magnesium and cal-
cium are introduced into crude lead at 3753 400oC
(rather than the commonly used circulating dross),
and then the temperature of the refining bath is raised
to 475 3 490oC and circulating drosses are loaded.
After settling for 25 335 min, dead oil (0.133 0.18 kg
per 1 ton of lead to be refined) is introduced in por-
tions with continuos agitation at 400 3 470oC. After
liquation, solid powdered drosses (30 3 40% Bi, 50 3
60 Pb, 5310 Zn, 0.0153 0.02 Ag) are extracted, cooled
to room temperature, and classified by sieving with
0.10 3 0.15 mm mesh. Drosses remaining on the sieve
[Nauka/Interperiodica]
192 ZARUBITSKII
are loaded in the lead bath for recirculation, whereas
sifted drosses (3 0.10 3 0.15-mm class) are remelted to
obtain a lead3bismuth alloy. After the removal of dry
drosses, the temperature is lowered to 330oC, and cir-
culating bismuth drosses are taken off. The refining
process is finished according to the standard scheme.
Powder drosses of the +0.10 3 0.15-mm class, con-
taining (%) 12317 Bi, 50 355 Pb, 25 3 40 Zn, and
0.06 3 0.07 Ag, are purified to remove silver, which
diminishes the expenditure of metallic zinc by ap-
proximately 50%, and loss of silver and bismuth, by
approximately 30%. Thus, in contrast to the common
technologies, this method does not involve a labor-
consuming procedure of lead bullion purification to
remove zinc introduced into lead to recover silver.
Powder drosses of the 3 0.10 3 0.15-mm class are
remelted under a layer of slam (spent PbCl23ZnCl23
KCl3NaCl electrolyte used at the plant in electro-
chemical reactors for separating lead3bismuth alloys
in ionic melts [8]). In this case, the following reac-
tions occur
Mg3Bi2 + 3PbCl2 = 3MgCl2 + 3Pb + 2Bi,
Ca3Bi2 + 3PbCl2 = 3CaCl2 + 3Pb + 2Bi.
Such a procedure is expedient because lead, which
was previously dumped as a salt in a chloride mixture,
is returned into the production cycle. The resulting
lead3bismuth alloy contains 55 3 65% Bi and the bal-
ance lead.
In pilot tests, we used dead oils of BN-IV and
BN-V brands, which have softening points of 70
and 90oC, respectively. Special bitumens of A and
G brands, and also pitches and other products of
straight-run masut distillation, can be used for this
purpose.
The tests have shown that the initial introduction
of calcium and magnesium into crude lead at 375 3
400oC and subsequent addition of circulating drosses
at higher temperature (475 3 490oC) diminish the loss
of active metals (magnesium and calcium) and thus
make lower the process costs. According to this tech-
nique, the purification to remove bismuth is carried
out at bath saturation with bismuth higher than 2%.
The introduction of calcium and magnesium at 375 3
400oC ensures high dissolution rate at minimum loss
of the active metals, which can be oxidized by at-
mospheric oxygen or moisture. At 475 3 490oC the
dissolution of circulating drosses proceeds faster,
the solubility of all the components added is higher
RUSSIAN JOURNAL OF APPLIED CHEMISTRY
at elevated temperature, and, simultaneously, lead is
deoxidated and cooled. Thus, complete use of the re-
agents is achieved, and drosses very rich in bismuth
are obtained in small amounts. This is also important
for the subsequent introduction of a solid product of
heavy oil residuals, e.g., dead oil, to be carried out
successfully. Under these conditions, fine particles of
bismuth intermetallics do not aggregate, which makes
it possible to obtain bismuth-rich drosses.
In carrying out this operation, dry powder drosses
with high bismuth content (33 337%) are formed as
a phase on the lead surface. The results of X-ray dif-
fraction, mass-spectrometric, microscopic, and chem-
ical analyses suggest that the forming particles of
intermetallic compounds, and especially bismuth in-
termetallide Mg3Bi2, are wetted with bituminous hy-
drocarbons (asphaltenes etc.). This phenomenon elim-
inates wetting of intermetallic particles by liquid lead,
because the adsorption energy of hydrocarbons on
the surface of solid intermetallic particles is higher
than the energy of lead adsorption. Consequently,
bismuth drosses are formed as powders containing
no coarse conglomerates with adsorbed or adhering
lead. This results in that the bismuth drosses are
obtained in powdered (dry) form and contain much
lesser amounts of lead and greater amounts of bis-
muth. According to a mass-spectrometric analysis of
the gas content of samples, the fine powder contains
2.5 and 3 times greater amount of, respectively, hy-
drogen and carbon dioxide than the coarse fraction
does. This may indicate that bitumen is mostly ad-
sorbed on fine-fraction particles of bismuth drosses.
Our physicochemical study has shown that powder
drosses with particle size less than 0.10 3 0.15 mm are
largely composed of bismuth intermetallides (mainly
Mg3Bi2 in amount of 30 335%, according to X-ray
analysis). Drosses with particles larger than 0.10 3
0.15 mm additionally contain intermetallic compounds
of zinc and lead. It was established that the fine frac-
tion of dry powder drosses with particle size less than
0.15 mm contains (%) 43 350 Bi, 35 3 45 Pb, 0.13 0.5
Zn, 0.0023 0.003 Ag, and Ca and Mg the rest. Drosses
of the +0.10 3 0.15-mm class are complex intermetal-
lic compounds of zinc, bismuth, lead, silver, calcium,
and magnesium.
The expenditure for production of bismuth from
an alloy containing 55 3 65% Bi is considerably less
than that for production of the same amount of Bi
from an alloy with bismuth content of 15% (this is the
maximum Bi content ensured by the currently existing
procedures). In this case, the expenditure of electric
power and electrolyte, number of electrolyzers, floor
Vol. 76 No. 2 2003
 REFINING OF LEAD TO GIVE BISMUTH-ENRICHED DROSSES
area, and maintenance staff are diminished. This is
confirmed by the following simple calculation of, e.g.,
the electric power expenditure.
Let us assume that a plant accomplishes electro-
chemical separation of a lead3bismuth alloy contain-
ing, on average, 12% Bi and 88% Pb by the formerly
used technology, i.e., it is necessary to transfer elec-
trochemically 88 tons of Pb from anode to cathode in
order to produce 12 tons of Bi. If, however, a lead3
bismuth alloy enriched with bismuth to 60% by the
new technology is subjected to electrolysis, it is nec-
essary to dissolve at the anode and precipitate at the
cathode only 8 tons of Pb in order to obtain the same
amount of Bi (12 tons). Consequently, the amount
of lead to be electrolyzed in the second variant is 11
times less than that in the case of the standard tech-
nology. The expenditure of electric power, number of
electrolyzers, etc. will be equally diminished.
The results obtained in industrial tests of the lead
refining technique under consideration, which yields
a bismuth-enriched Pb 3Bi alloy, are presented below.
The experiments were carried out in cauldrons
with capacity of 125 3130 tons of crude lead (lead
bullion). The sequence of operations was described
above. The size classification of powder drosses
yielded 5.3 3 6.0 tons of a fine fraction containing
43.7350.6% Bi and 2.8 33.8 tons of grit with Bi con-
tent of 12.6 317.2%. After remelting of the fine frac-
tion under a fluxing agent (PbCl23ZnCl23KCl3NaCl),
4.23 4.5 tons of alloy with Bi content of 55.1359.9%
were obtained. The process was implemented indus-
trially and ensured a significant technological and
economic effect. The environmental safety was im-
proved, because we used a lesser number of electro-
chemical reactors producing lead by high-temperature
electrolysis of a lead chloride melt.
A somewhat different technique for lead3bismuth
alloy enrichment was also developed and applied in in-
dustry. At one of lead-manufacturing plants, a Bi3Pb
alloy is separated by electrolysis in hexafluorosili-
con electrolyte, following the Betts procedure [1, 9].
A semi-finished product with Bi content of 8 315%
is used as the starting alloy. It is desirable to raise
the content of this metal, but to no more than 30%. If
the bismuth content in Pb 3Bi anode plates is greater,
the anodic process is significantly complicated. As
lead is dissolved, the solid alloy lattice is disrupted
and narrow channels are formed, in which lead hexa-
fluorosilicate is crystallized. At the same time, a large
amount of bismuth is dissolved and deposited at the
cathode. Small pieces of the anode are crumbled and
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76
193
entrained by slam. The surface layer of the pieces
consists of virtually pure bismuth, and the inner layer,
of electrochemically unreacted lead. Industrial tests
have shown that the Betts method for processing of
Pb 3Bi alloys containing more than 30% Bi is inex-
pedient.
Taking into account the aforesaid, we proposed,
developed, and implemented industrially a somewhat
different method for enrichment of bismuth drosses.
The method, which is simpler and less expensive,
consists in the following. To refine lead containing
0.5 + 0.1% Bi, a mixture of bitumen (45 375 wt %)
and sawdust (25 355 wt %) is added, and the process
is performed at lower temperature (370 3390oC). As
a result, powder drosses containing 23 327% Bi are
obtained and delivered to hydroelectrolytic processing
by the Betts method. This procedure involves separa-
tion of drosses and thus eliminates the additional stage
of bath heating to a temperature of 400 3 470oC, at
which drosses are separated in the method described
above. The addition of sawdust (which is less expen-
sive than bitumen) prevents the possible inflamma-
tion of bitumen particles floating-up to the surface
of a lead bath. Sawdust contains moisture, which
evaporates to cool the upper layers of molten lead. It
should be noted that sawdust is introduced into the
liquid metal being refined not simultaneously with
dead oil, but later, when obtaining [dry] powder
drosses. In addition, sawdust plays the same part in
the separation of intermetallic compounds of bismuth
as dead oil.
This method makes lower the cost of bismuth re-
moval from lead because of the use, in addition to
bitumen, of such a less expensive material as sawdust.
Labor conditions are improved owing to the elimina-
tion of the possibility of bitumen inflammation. The
energy expenditure, labor intensity, and reagent con-
sumption are much lowered owing to a significant
decrease in the amount of lead3bismuth alloy to be
processed by an electrolyzer in a hexafluorosilicon
acid solution.
CONCLUSIONS
(1) A modified Kroll and Betterton method for
lead purification to remove bismuth has been pro-
posed and subjected to pilot tests. The improvement
consists in that dead oil or its mixture with sawdust
is introduced into metal melt in a certain stage of re-
fining to yield rich bismuth drosses in the form of
a powder. The separation of the product is also a spe-
cific feature of the process.
No. 2 2003
194 ZARUBITSKII
(2) The method for lead and bismuth separation,
which was developed and implemented industrially,
makes it possible to produce a bismuth3lead alloy
containing up to 55 3 65% Bi.
ACKNOWLEDGMENTS
The author is grateful to I.P. Brovin and V.A. Shle-
enkov (DVGMK, Far-Eastern Mining and Swelting
Combine) for help in the study.
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