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Investigation into Oxygen-Enriched Bottom-Blown Stibnite and Direct

Reduction

Article  in  Metallurgical and Materials Transactions B · March 2014

DOI: 10.1007/s11663-014-0055-6

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Investigation into Oxygen-Enriched Bottom-Blown Stibnite
and Direct Reduction
WEI LIU, HONGLIN LUO, WENQING QING, YONGXING ZHENG, KANG YANG,
and JUNWEI HAN

The direct oxidation of stibnite (Sb2S3) using a gas mixture of nitrogen-oxygen was investigated
in a pilot plant. Steady-state pilot operation of 5 and 10 t/d was normally observed during the
pilot test of 100 days, and a cleaning experiment of high-antimony molten slag from oxygen-
enriched bottom-blown was tested by direct reduction in a laboratory-scale electric furnace.
Autogenous smelting was achieved without adding any other fuel, which guaranteed the fea-
sibility and advantage of oxygen-enriched bottom-blown stibnite. Through analysis and cal-
culation, the sulfur dioxide concentration in offgas was more than 8 pct, which meets the
requirement for the preparation of sulfuric acid. In the reduction experiment, the effects of
added CaO, the ratio of coal (x = actual weight of coal/theoretical weight of coal), and the slag
type on the reduction procedure were considered. The residual slag obtained after reduction
averaged less than 1 g/ton Au and less than 1 wt pct Sb. The metal phase contained iron less
than 3 wt pct, and the recoveries of Au in the metal phase were more than 98 pct. This process
shows significant environmental and economic benefits compared with previous processes.

DOI: 10.1007/s11663-014-0055-6
Ó The Minerals, Metals & Materials Society and ASM International 2014

I. INTRODUCTION metals (e.g., lead, arsenic and cadmium), together with a

ANTIMONY is a silvery and brittle metal with poor
electrical and heat conductivity,[1] and it is mainly used
as an alloying element to enhance the mechanical
strength of other metals (e.g., lead in wet-cell
batteries).[2–5]
Antimony is seldom found as a natural metal because
of its strong affinity to sulfur and other metals such as
copper, lead, silver, and gold.[6] More than 100 minerals
of antimony have been found in nature, and the most
important and abundant one is stibnite, an antimony
sulfide (Sb2S3), exploited for the recovery of antimony
and precious metals (e.g., gold and silver). The world’s
largest natural resource of antimony is in China, and it
primarily contains stibnite (Sb2S3) associated with
pyrite, arsenopyrite, jamesonite, and various oxides if
the deposits are oxidized.[1,6]
The major methods for extractive metallurgy of
antimony from stibnite are pyrometallurgical pro-
cesses.[1,7–9] Traditionally, the commercial route involves
roasting of concentrate, volatilization of antimony
trioxide in a blast furnace, and carbon-based reduction
of the trioxide to metallic antimony in a reverberatory
furnace. In these processes, however, antimony smelting
at a high temperature will cause (1) serious environ-
mental pollution during roasting and smelting because
abundant antimony sulfide and some relevant volatile
WEI LIU, YONGXING ZHENG, and KANG YANG, Doctors,
and HONGLIN LUO and JUNWEI HAN, Masters, WENQING
QING, Professor, are with the School of Minerals Processing and
Bioengineering, Central South University, Changsha 410083, P.R.
China. Contact e-mail: ase.6520@163.com
Manuscript submitted January 6, 2014.
Article published online April 1, 2014.
certain amount of SO2, are emitted through volatiliza-
tion, and (2) large energy consumption, so a lot of
high-quality coal is consumed to sustain the required
temperature [1373 K to 1673 K (1100 °C to 1500 °C)].
Currently, more than three tons of high-quality coal is
required to produce one ton of antimony in China.
Hydrometallurgical methods can also be employed
for processing simple antimony materials or complex
ones containing several metals.[1–4,10–12] Normal hydro-
metallurgical practices call for two steps: leaching and
electrodeposition. In reality, two solvent systems are
used in antimony hydrometallurgy: an alkaline sulfide
system (dominant) and an acidic chloride system. The
alkaline sulfide system has been employed industrially in
the former Soviet Union, China, Australia, and the
United States, but both scientific research and industrial
practice show the limitations in processing high-grade
stibnite using this method. Furthermore, when the ores
contain precious metals and copper, the hydrometallur-
gical methods fail to achieve satisfactory recoveries of
these metals.[5,10,13,14]
There are some improved methods, such as direct
reducing-matte smelting of stibnite concentrate in pyro-
metallurgy, and electrowinning of antimony in hydro-
metallurgy.[7,9,11,14–17] However, no method for recovery
of antimony and other metals ensures adequate envi-
ronmental and economical management. Currently, the
smelting of nearly all nonferrous metals has overcome
the problem of low SO2 emission by adopting enhanced
oxygen-rich smelting technologies, such as copper pyro-
metallurgical practice and the Shuikoushan (SKS) lead
smelting method. In industrial practice, the process has
showed technological advancements in technological
process, mass transfer, unit bed capacity, and specific

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 45B, AUGUST 2014—1281

energy consumption, as well as remarkable environmen-
tal and economic benefits.[18]
The removal of metals from smelting slag can be
conducted via a pyrometallurgical or hydrometallurgical
route. A pyrometallurgical route mainly uses a reduc-
tion of metal oxides contained in the slag, and this
process has been investigated extensively.[19]
Pyrometallurgical treatment of the slag obtained
during smelting of the antimony sulfide ores saves
energy, as the slag can be treated when tapped from the
furnace before it cools down and loses thermal energy to
the ambient air.[20] In this study, the antimony smelting
slag from oxygen-enriched bottom-blown stibnite con-
centrate was directly reduced, thus resulting in
‘‘cleaned’’ slag by the removal of antimony and gold.
Banda et al.[21] separately used CaO, CaF2, and TiO2
as slag modifiers during the carbothermic reduction of
waste smelter slag under vacuum and argon to reduce
the activity of FeO. TiO2 effectively reduced the activity
coefficient of FeO owing to the strong affinity between
the two oxides. Zhai et al.[22] used activated carbon as a
reducing agent with CaO and TiO2 as modifiers to
recover cobalt from a converter slag of Chambishi
Copper Smelter.
Many empirical equations[23–25] have been proposed
to estimate the solubility of nonferrous metals in the slag
as functions of their chemical composition, especially
the contents of SiO2, FeO, and CaO, which will
significantly affect the recovery of valuable metals from
the slag.
The possibility of slag cleaning via the hydrometal-
lurgical route by roasting with sulfuric acid or ferric
sulfate[26] was proposed, and the recovery rates of
copper, cobalt, and zinc were higher than 80 pct.
However, contamination seemed to be a major handicap
as more than 80 pct of Fe was simultaneously extracted
from the slag.
In this study, an oxygen-enriched bottom-blown
stibnite (Figure 1) pilot plant at Central South Univer-
sity, China, was successfully operated for the recovery of
antimony, and the high-antimony molten slag was
directly reduced by coal. The reduction slag was
delivered into the electric heating fore-hearth[27] to the
subside part of antimony metal, and the plant produced
high-antimony slag and residual slag.
II. MATERIALS AND METHODS
A. Materials
Antimony-gold concentrate was supplied by Chenz-
hou Mineral Co. Ltd. (Yuanling, China). Its chemical
composition and species analysis are given in Tables I
and II, respectively. The main components include Fe,
Sb, S, and a relatively high grade of gold. Therefore, the
recovery of gold is important for this stibnite concen-
trate. Table II lists different Sb-containing phases that
are present in the stibnite concentrate and the fractions
of the antimony amount that correspond to each of
these phases. Antimony sulfide (Sb2S3) is the main
antimony species. Ferric oxide, silicon dioxide, and
1282—VOLUME 45B, AUGUST 2014
calcium oxide were of reagent grade and procured from
local suppliers. The natural flux materials consisted of
iron ore, limestone powder, and river sand. The chem-
ical composition of Si, Fe, and Ca in the flux is shown in
Table III, and the total Si, Fe, and Ca amounts
translated to the presence of SiO2, FeO, and CaO to
help calculate the slag style. The industrial liquid oxygen
and nitrogen were 99 pct pure. Gas flows were moni-
tored by gas flow meters. The chemical composition of
the slag used in the reduction experiment is presented in
Table IV. The slag is antimony rich; it contained
Sb2O3and Sb2O4 through a chemical analysis.
B. Equipment
1. Gas supply system
The gas supply system consisted of a nitrogen storage
tank (14 m3), an oxygen storage tank (5 m3), an oxygen
vaporizer, a nitrogen vaporizer, and two gas-pressure-
regulating valves. Liquid oxygen and nitrogen were
gasified by the vaporizers, and then sent through the gas
pressure regulating valves to control the air pressure
within 0.1 to 0.8 MPa. The gas was mixed with oxygen
(30 to 90 pct) and nitrogen in the oxygen lance that
delivered to bottom-blown furnace.
2. Bottom-blown oxidation furnace
A bottom-blown oxidation furnace (Figures 2 and 3)
with a horizontal cylindrical shape was used. The
furnace’s outermost shell is made of steel plate and
refractory lining. There is a siphon antimony tap, a slag
tap, and an outlet flue at either end, as well as feed hole
on the top of the furnace. The furnace (inner diameter
1120 mm, outside diameter 1644 mm, and length
2000 mm) possesses an actuating device, which can
rotate the barrel a full 90 deg during production and
turn the oxygen lance horizontal or can be replaced after
the blowing end.
3. Oxygen lance
The lance was a uniform cross-section double-pipe
casing (Figure 4). Oxygen was blown through the inner
stainless-steel pipe, and nitrogen was blown through the
annular space between the inner stainless-steel pipe and
the outer heat-resistant steel pipes to protect the oxygen
lance from burning.
4. Dust collection and purification system
A ceramic dust collector and a flue gas desulfurization
tower were used. After water cooling, the offgas from
the bottom-blown furnace outlet flue passed through the
ceramic dust collector to collect antimony trioxide,
volatile Sb2S3, and dust, and then it entered the flue gas
desulfurization tower to remove sulfur dioxide.
5. Pilot flowsheet and operating conditions
Figure 5 shows a flowsheet of the pilot plant describ-
ing the major processing steps used to smelt stibnite
concentrate. The charge consisting of antimony concen-
trate, limestone, river sand, and iron ore was delivered
into the bottom-blown furnace, and then enriched
oxygen was blown to smelt the stibnite. The particle
METALLURGICAL AND MATERIALS TRANSACTIONS B
 Flux Stibnite

Pelletizing
Oxygen+Nitrogen

Oxygen-enriched Bottom-blown oxidation furnace

The molten high antimony slag Flux+coal Smelter offgas Antimony alloy

Oxygen+coal

Oxygen-enriched Bottom-blown reduction furnace Waste heat recovery

Dust
Slag Crude antimony Smelter offgas

Electric heating for-hearth Dust collection High sulfur offgas Fume

Acid-making system Sulfuric acid

Smelter offgas
Fume
High antimony slag Residue slag
Air
Alkali absorption

Air

Fig. 1—The schematic flowsheet of direct recovery of antimony from stibnite concentrate.

Table I. Chemical Composition of the Antimony-Gold Concentrate

Element Sb S Au (g/t) SiO2 FeO CaO MgO Al2O3 As Pb

Content (pct) 45.80 29.81 57.70 9.59 13.53 0.20 0.18 2.52 0.51 0.17

Table II. Fractions of the Antimony in the Stibnite Concentrate that Correspond to Each Sb-Containing Phase

Species Sb-Oxide Sb-Sulfide Sb-Silicate Total

Content of antimony (pct) 4.91 38.71 2.18 45.80

Table III. Chemical Composition of the Flux (Mass Pct)

SiO2 FeO CaO

Iron ore 29.75 49.75 6.64
Limestone powder — — 85
River sand 89.10 2.25 0.25

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 45B, AUGUST 2014—1283

 Table IV. Chemical Composition of the High-Antimony Slag from Oxygen-Enriched Bottom-Blown Stibnite Concentrate
Element Sb SiO2 FeO
Content(pct) 32 23 20
Fig. 2—The schematic diagram of bottom-blown furnace.
Fig. 3—The photo of furnace in the pilot plant.
sizes of limestone, river sand, and iron ore were less than
1 mm. In the smelting process, the antimony sulfide
reacted quickly with the enriched oxygen in the furnace.
The molten products in the furnace were separated by
specific gravity, so that the molten antimony was in the
lowest part and the slag in the upper part. After water
cooling, the offgas from the outlet flue passed through
the ceramic dust collector to collect antimony trioxide,
volatile Sb2S3, and dust, then it entered the flue gas
desulfurization tower to remove sulfur dioxide. Finally,
it was mixed with the air. All smelting products
were sampled for chemical analysis. The offgas was
1284—VOLUME 45B, AUGUST 2014
CaO Pb As S Au (g/ton)
6 0.3 0.63 2 58
monitored for detection of SO2 concentration by the
Environmental Protection Department of Hunan Prov-
ince, China.
C. The Direct Reduction Operation
Carbon-based direct reduction of the antimony
smelting slag in laboratory scale experiment was con-
ducted in an electric furnace. Powdered solid slag (1 kg),
coal, and slag modifier (CaO) at certain weights were
premixed (the particle sizes of all smelting materials
were less than 1 mm), loaded into a graphite crucible,
and then put in the 1473 K (1200 °C) electric furnace.
The carbon used in the reduction process was the
metallurgical coal, 85 wt pct of carbon in the coal. The
weight of metallurgical coal was calculated considering
the antimony in the slag as Sb2O3. After 100 min
smelting, the crucible was taken out and naturally
cooled to room temperature in air. The residual slag and
antimony alloy in the crucible were manually separated,
weighed, ground in a vibrating mill, and sampled. The
contents of antimony, iron, and gold in the residual slag
and antimony alloy were determined by a chemical
analysis.
D. Thermodynamic Analysis of the Process
The Gibbs free energy (DGh) of antimony compounds
reacting at varying temperature was calculated and
given in Figure 6. Obviously, these reactions can occur
spontaneously when temperature is maintained above
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 4—The schematic diagram of oxygen lance. 1—Bottom-blown furnace, 2—hopper, 3—dust collector, 4—flue gas desulfurization tower,
5—nitrogen storage tank, 6—oxygen storage tank, 7—oxygen vaporizer, 8—nitrogen vaporizer, 9 and 10—gas-pressure-regulating valves,
11—fan, and 12—circulating pump.

1. Bottom-blown Furnace 2. Hopper 3. Dust collector 4. Flue gas desulfurization tower 5. Nitrogen storage tank 6. Oxygen storage tank
7. Oxygen vaporizer 8. Nitrogen vaporizer 9,10. Gas pressure regulating valves 11.Fan 12. Circulating pump

Fig. 5—The schematic diagram of the pilot flowsheet of oxygen enriched bottom blown stibnite.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 45B, AUGUST 2014—1285


Fig. 6—Relationships between DGh and temperature in antimony
compound reactions.
1473 K (1200 °C) because their DGh < 0. Sb2S3 can be
oxidized to Sb by oxygen. However, antimony metal
phase difficultly existed in the oxidation stage, because
antimony can react with oxygen to form antimony
oxide. Otherwise, Sb2S3 could react with Sb2O3 at
temperatures above 1573 K (1300 °C).
HSC[28] (Outotec, Espoo, Finland) for Windows
software was used to draw predominance diagrams in
the Sb-S-O system. The areas of predominance in
Figure 7 represent the condensed phases in equilibrium
with the vapor phase at 1173 K (900 °C) (solid line),
1373 K (1100 °C) (dashed line), and 1573 K (1300 °C)
(dot-dashed line) as a function of the partial pressures of
S2 and O2 (marked as pS2 and pO2 ; respectively). This
predominance diagram indicates that Sb2S3 in the
presence of oxygen is first oxidized to Sb2O3 as an
intermediate. Then under higher pO2 and low pS2 , it will
be further oxidized to SbO2. Generally in traditional
antimony smelting, stibnite concentrate is first oxidized
to the volatile trioxide in the ‘‘oxidation’’ area of
Figure 7, and then the antimony trioxide is reduced to
metal by a reducing agent such as charcoal or coal in the
‘‘reduction’’ area. If the equilibrium can be attained at
low pS2 , then antimony sulfate would be the final stable
antimony phase in the ‘‘direct oxidation’’ area, which is
the theoretical foundation for direct production of
antimony from stibnite. In addition, in the same pS2
and pO2 , Sb2S3 and Sb2O3 could be more easily
translated to Sb as the temperature increases. This
analysis shows a fact that temperature could affect the
reactions’ condition, or a high temperature help anti-
mony metal easily existed. However, the pS2 and pO2 are
too small and too difficult achieve.
HSC was used to calculate the amounts of products
under equilibrium. The equilibrium amount of Sb2S3 at
the molar ratio of Sb2S3 to O2 of 1:3 is a function of
temperature (Figure 8). To explore how the products of
1286—VOLUME 45B, AUGUST 2014
Fig. 7—Stability diagram for the Sb-S-O system at 1173 K (900 °C)
(solid line), 1373 K (1100 °C) (dashed line), and 1573 K (1300 °C)
(dot-dashed line).
Sb2S3 react with oxygen, the volatility of Sb2S3 was
ignored. At lower than 1173 K (900 °C), Sb2S3 is
oxidized to antimony oxides such as SbO (the major
one), Sb2O3, SbO2, and SO2. Above 1173 K (900 °C),
Sb2S3 is decomposed as Sb and S.
Figure 9 shows the equilibrium conditions of con-
densed phases as a function of pO2 and temperature,
under constant pS2 of 0.1 Pa (blue line), 10 Pa (black
line), and 100 Pa (red line) in the gas phase. It is quite
obvious that if pS2 is decreased, then Sb2S3 will
eventually be converted to antimony. When pO2 is
increased, the antimony metal will be oxidized to oxides.
This diagram indicates that Sb is a stable phase at a high
temperature and low pO2 : When pS2 changes, the
temperature and pO2 change correspondingly. For
example
pS2 = 0.1 Pa, t = 983 K (710 °C), log pO2 < 16
pS2 = 10 Pa, t = 1163 K (890 °C) log, pO2 < 12.5
pS2 = 100 Pa, t = 1453 K (1180 °C), log, pO2 < 9
From all of the above thermodynamic analyses, if the
equilibrium can be attained in the certain amount of
oxygen and smelting temperature, then stable antimony
metal phase could exist in the oxidation stage in theory.
However, antimony metal will oxidize to oxides under a
high amount of oxygen, especially if the temperature
was not up to 1573 K (1300 °C), and Sb2S3 has a high
volatility.
III. RESULTS AND DISCUSSION
A. Oxygen-Enriched Bottom-Blown Stibnite
1. Sb concentration profile during the pilot test
The high-antimony slag and antimony trioxide sam-
ples were taken at a regular time interval about 12 and
24 hours, respectively. The Sb concentrations in the
high-antimony slag and the antimony trioxide are
shown in Figures 10(a) and (b), respectively, and the
sampling number is on the X-axis. Obviously, the
antimony concentration in the high-antimony slag and
antimony trioxide tended to be balanced, which can
METALLURGICAL AND MATERIALS TRANSACTIONS B
 prove that the pilot plant was a steady state. The
averaged basic components during the pilot test are as
follows: Sb 32.20 pct, Au 48.25 g/t, As 0.63 pct, SiO2
23.51 pct, FeO 18.21 pct, CaO 9.40 pct, Pb 0.37 pct, S
0.63 pct (high-antimony slag), and Sb 68.10 pct, Au
16.39 g/t, As 2.64 pct, S 1.12 pct (antimony trioxide).
The maximum and minimum Sb concentrations were
37.8 and 28.3 pct in the high-antimony slag, respec-
tively, and 77.8 and 55.5 pct in the antimony trioxide,
respectively.
Sb2S3 can be oxidized to Sb by oxygen in terms of
theory, and antimony also can react with oxygen to form
antimony oxide, which resulted in that no antimony alloy
was produced at the oxidation smelting stage in the pilot
test. In conclusion, the theories (Section II–D) and pilot
test were provided that antimony metal phase difficultly
existed under 1473 K (1200 °C). The proportions of
Fig. 8—Equilibrium amounts of reduced products as functions of
antimony distributed between antimony trioxide and slag
temperature (Sb2S3:1 kmol, O2:3 kmol). were 55 and 45 pct, respectively. About 61.32 kg of slag
was produced by per 194.75 kg of feeding materials, and
the ratio of slag was 31.49 pct.
0
2. The effect of the ratio of oxygen and total mass of
pS2(g) = 0.1 Pa charge (O/M) on blowing
pS2(g) = 10 Pa
-5 The ratio of the amount of oxygen (Nm3/h) to the
pS2(g) = 100 Pa weight of total mass of charge (t/h) (O/M) is the key
Sb2O3
-10
SbO2 control parameter in the blowing, especially because
Sb2(SO4)3
antimony can easily react with oxygen. When in a high
log pO2(g)

O/M, antimony can be oxidized and enter the slag or

-15 flue and FeO is oxidized to Fe2O3. The slag’s liquidus
Sb(l) temperature will increase also. A low O/M resulted from
underreaction, not enough heat, and low fluidity for the
-20
Sb2S3 slag. Figure 11 shows the antimony concentration in the
slag at varied O/M. With the increase of O/M, the
-25 smelting temperature increased and the antimony con-
573 773 973 1173 1373 1573
Temperature/ K
centration in the slag decreased. These results corre-
spond to Figure 9; as the smelting temperature
Fig. 9—Stability diagram for the Sb-S-O system as a function of increased, the area of antimony metal phase grew larger.
temperature at a constant pS2 of 0.1 Pa (blue), 10 Pa (black), and The range of fluctuation of pO2 and pS2 in order to
100 Pa (red) (Color figure online). convert into antimony metal are more wide, thus

60 80

50

40 60
Sb(%)

Sb(%)

30

20 40

10

0 20
0 20 40 60 80 100 0 10 20 30 40
The number of sample The number of sample
(a) (b)
Fig. 10—(a) Sb concentration in the high-antimony slag and (b) in the antimony trioxide during the pilot test.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 45B, AUGUST 2014—1287

increasing temperature more easily existed. The smelting
temperature and the antimony concentration in the slag
can be controlled by O/M in the oxygen-enriched
blowing, and the temperature was stable in the 1473 K
(1200 °C) without adding any other fuel.
To increase the temperature and fluidity of the slag, a
high O/M was chosen, especially in the small size
bottom-blown furnace and small batch test, to control
the slag temperature. The slag’s temperature and fluidity
were increased while the antimony oxidized and entered
the slag or flue if the temperature was not up to 1573 K
(1300 °C). The result was that no antimony alloy was
produced, but high-antimony slag and antimony triox-
ide at the oxidation smelting stage was produced. High-
antimony slag and antimony trioxide need further
reduction to antimony metal.
B. High-Antimony Slag Direct Reduction
1. CaO added to the slag
The slag belongs to the FeO-CaO-SiO2 slag system,
and the contents of iron oxide and silica in the slag are
20 pct FeO and 23 pct SiO2. To save energy and fully
use the slag’s thermal energy in industry and at the same
smelting temperature as the molten slag, the same slag
system as the oxygen-enriched bottom blown was
chosen. However, the slag viscosity is higher at high
silica contents. In addition, a high rate of corrosion of
the MgO-based refractory may also result from the
1483
1453
K
1433
1413
1393
1373
Fig. 11—The temperature of molten and Sb concentrations of slag
with varying O/M.
Table V. Chemical Compositions in the Slag and Metal Phase After Direct Reduction of CaO Added to the Slag Experiments
Slag
Sample No. Au (g/t) Sb (Pct)
1 1.30 0.90
2 3.00 1.90
3 0.90 0.60
4 1.00 1.30
5 0.75 1.15
6 0.60 0.70
Average 1.26 1.09
1288—VOLUME 45B, AUGUST 2014
increased acidity of the slag. For these reasons, any
possibility of decreasing the SiO2 content during the
reduction process should be considered. FeO can be
added for that purpose as it helps to lower the slag’s
surface tension and viscosity by breaking the polymer-
ized chains. However, the FeO content in the starting
slag was already at a high level and cannot be increased
further during the cleaning process to avoid iron oxide
reducing into the metal phase. Another option is to
introduce lime into the slag. Lime is a strong base that
can reduce the solubility of weak bases in the slag. The
ratio was chosen with CaO/SiO2 = 0.4.
The high-antimony slag from oxygen-enriched bot-
tom-blown coal and CaO were mixed and homogenized
before charging into the furnace. The heating of the
loaded furnace up to 1473 K (1200 °C) took 100 min.
Assuming antimony species as Sb2O3, the corresponding
weight of coal was a ratio of 1.4 of theoretically
calculated value. This consideration yields a ratio
x = actual weight of coal / theoretical weight of coal.
The same experiment was conducted six times.
The corresponding gold and antimony chemical
compositions of the residual slag after reduction and
the metal phases are shown in Table V. Each sample
refers to a single experiment. The averaged slag con-
tained 1.26 g/ton Au and 1.17 wt pct Sb. The slag
contained 0.60 to 3.00 g/ton Au, and 0.60 and 1.90 wt
pct Sb. The average recovery of Au in the metal phase
was 98.69 pct. These results show a high recovery the
gold and antimony from the slag. However, the iron
contamination of antimony alloy became unacceptably
high in this case as the metal phases contained up to 10
wt pct iron.
2. The effect of coal amount
To reduce iron contamination in the antimony alloy,
x = 1.2, 1.4, and 1.6 and a smelting time of 80 minutes
were considered to elucidate the effect of coal values on
metal recovery and iron contamination. Each experi-
ment was conducted twice, and the chemical composi-
tions are the average of two same experiments.
The corresponding contents of gold and antimony in
the residual slag and metal phases are shown in
Table VI. Clearly, the metal phase contained less Fe
than previous experiments (Section III–B–1), 1.23 wt
pct Fe in the case of x = 1.2, at t = 80 min. It shows a
rule that the larger amount of coal resulted in higher
iron content in the metal phase. However, the antimony
Metal Phase
Au (g/t) Sb (Pct) Fe (Pct)
173.67 81.20 14.45
174.00 83.00 12.44
162.00 79.00 15.98
191.00 85.30 10.50
179.00 82.10 13.86
165.53 77.80 17.43
174.37 81.40 14.11
METALLURGICAL AND MATERIALS TRANSACTIONS B
 Table VI. Chemical Composition in the Slag and Metal Phase After Direct Reduction of the Effect of Coal Amount Experiment

Slag Metal Phase

Sample No. The Ratios of Coal (x) Au (g/t) Sb (Pct) Au (g/t) Sb (Pct) Fe (Pct)
1 1.2 0.20 4.70 222.20 94.10 1.34
2 1.2 0.40 6.30 232.40 94.70 1.12
Average 0.30 5.50 227.30 94.40 1.23
3 1.4 0.20 3.00 214.13 93.20 2.61
4 1.4 0.35 2.20 206.93 92.20 3.65
Average 0.28 2.60 210.53 92.70 3.13
5 1.6 0.40 1.40 190.53 87.90 7.90
6 1.6 0.35 1.10 179.60 85.20 10.20
Average 0.38 1.25 185.07 86.55 9.05

Table VII. Chemical Compositions in the Slag and Metal Phase After Direct Reduction of the Effect of Slag Type

Slag Metal phase

Sample No. Au (g/t) Sb (Pct) Recovery of Au Recovery of Sb Au (g/t) Sb (Pct) Fe (Pct) Recovery of Au
1 0.25 0.70 0.28 1.49 220.90 93.00 2.72 97.94
2 0.35 0.70 0.40 1.52 218.45 92.60 2.88 98.94
3 0.40 0.60 0.46 1.32 219.40 93.50 2.45 98.47
4 0.45 0.65 0.47 1.29 213.95 92.60 2.16 98.37
5 0.30 0.70 0.32 1.43 214.40 93.00 2.80 96.81
6 0.60 0.55 0.63 1.10 217.50 92.80 2.92 97.62
Average 0.39 0.65 0.43 1.36 217.43 92.92 2.66 98.03

content in the slag is high with the decreased amount of
coal. Considering the contents of Au and Sb in slag and
impurity of iron in the metal phase, the smelting
condition: x = 1.4 (the weight of coal is the theoretical
calculation value 1.4 times), smelting tempera-
ture = 1473 K (1200 °C), and smelting time = 80 min.
3. The slag type
In this experiment, SiO2, CaO, and coal (x = 1.4)
were added to reduce contents of antimony and gold in
the residual slag and to reduce iron content in the metal
phase. The slag system SiO2:FeO:CaO = 45:27:18 and
80 min smelting time were considered.
Table VII shows chemical compositions in the slag
and metal phase after direct reduction in the slag-type
experiments. The slag averaged contained 0.39 g/ton Au
and 0.65 wt pct Sb, and the averaged recovery of Au
and Sb are 0.39 and 0.65 pct, respectively. The averaged
recovery of Au in the metal phase was 98.03 pct, and the
averaged recovery of Fe in the metal phase was 2.66 pct.
IV. CONCLUSIONS
An oxygen-enriched bottom-blown oxidized stibnite
concentrate was successfully operated in a pilot plant for
the recovery of antimony from stibnite concentrate. In
this process, the oxygen-enriched oxidized stibnite
concentrate and the molten high-antimony slag were
directly reduced by coal. Oxygen autogenous smelting
was realized, which was proven to have high feasibility,
energy savings, and process simplification. Through
analysis and calculation, the concentrate sulfur dioxide
in the offgas was more than 8 pct, which is efficiently
captured as sulfuric acid in the acid-making system.
The high-antimony slag, coal, and slag modifier, in
the slag system SiO2:FeO:CaO = 45:27:18 and ratio of
coal x = 1.4, were mixed and homogenized, and then
put into the 1473 K (1200 °C) furnace for 80 min. The
residual slag averaged contents of less than 1 g/ton Au
and less than 1 wt pct Sb. The metal phase contained
less than 3 wt pct Fe, and the recoveries of Au in the
metal phase were more than 98 pct after reduction. The
recovery of Sb and Au through direct reduction the slag
from oxygen-enriched bottom-blown stibnite concen-
trate is feasible.
ACKNOWLEDGMENTS
The authors would like to acknowledge the National
Natural Science Foundation of China (No. 51204210),
the National High Technology Research and Develop-
ment Program of China (No. 2011AA061001), and the
National ‘‘Twelfth Five-Year’’ Plan for Science &
Technology (No. 2012BAC12B04) for financial sup-
port.
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