MINERAL PROCESSING AND EXTRACTIVE METALLURGY, 2018

https://doi.org/10.1080/03719553.2017.1421421

Thermodynamic model of metallothermic smelting of ferromolybdenum

D. R. Swinbournea and S. Arnout b

a
School of Engineering, RMIT University, Melbourne, Australia; bInsPyro N. V., Heverlee, Belgium

ABSTRACT ARTICLE HISTORY

Ferromolybdenum, used in alloy steel production, is made by the batch reduction of Received 21 August 2017
molybdenum oxide by silicon and aluminium at high temperatures. In this work, the Accepted 20 December 2017
technology of the process has been reviewed and representative charge mixes compared. A
KEYWORDS
computational thermodynamics model was developed and used to investigate the Ferromolybdenum;
relationships between charge composition and ferroalloy grade and quality, indicated by its aluminothermic smelting;
silicon content. The model predicted satisfactorily the composition of the ferromolybdenum silicothermic smelting;
and waste slag from a typical charge mixture. The silicon content depended on the ratio of thermodynamics; modelling
silicon to molybdenum oxide in the charge and was not sensitive to the assumed smelting
temperature or activity coefficient of silicon in the alloy. Losses of molybdenum to slag as
dissolved oxide were predicted to be much lower than published industrial data, suggesting
that losses in practice are mostly due to the inclusion of unsettled ferromolybdenum droplets.
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Introduction
Molybdenum is a relatively rare element with an aver-
age crustal abundance of only 0.00011 wt-% (Rudnick
and Gao 2003), which is similar to that of tantalum,
tungsten and the rare earth elements. It is found mostly
as ‘molydenite’ MoS2 in granite porphyry or quartz
monazite porphyry orebodies, typically containing
from 0.1 to 0.45 wt-% MoS2 in association with copper
minerals (Rowe 2005). China dominates world pro-
duction of molybdenum ores, having produced
90,000 t of contained molybdenum in 2016, followed
by Chile with 52,000 t and the U.S.A. with 31,600 t
(Shaw 2017). Molybdenite is recovered from ground
ore by flotation to yield a concentrate containing
from 40 to 60 wt-% Mo and up to 38 wt-% S. Typical
molybdenite concentrate compositions are given in
Table 1.
There are many options, both hydrometallurgical
and pyrometallurgical, for the treatment of molybden-
ite concentrates and these have been reviewed by Lash-
een et al. (2015). The great majority of these
concentrates are processed pyrometallurgically and
the first step is invariably oxidative roasting. The con-
centrate is roasted in a multi-hearth roaster at the rela-
tively low temperatures of 680–750°C to minimise
losses of molybdenum as volatile MoO3. The oxidation
reaction is very exothermic so temperature control
requires careful regulation of the oxygen supply to
each hearth of the roaster. The product is known as
‘technical grade molybdic oxide’ and representative
compositions are given in Table 2. About 90% of the
molybdenum is in the form of MoO3, the remaining
10% being MoO2 (Gasik 2013). When examining the
optimisation of parameters involved in ferromolybde-
num smelting, Güven (2010) found by X-ray diffrac-
tion that the technical molybdic oxide available to
him comprised 18.6 wt-% MoO2, the balance being
mostly MoO3 and Mo4O11.
Approximately 70% of all molybdenum produced is
used as an alloy addition in various grades of steel. In
stainless steels, molybdenum improves corrosion
resistance, with typically 3 up to 6 wt-% Mo in the aus-
tenitic grades. In other alloy steels, molybdenum
improves hardenability, increases high-temperature
strength and improves weldability. Nickel-based super-
alloys also have significant contents of molybdenum,
ranging up to 30 wt-% (Shields 2013).
Molybdenum is added to molten steel as either tech-
nical grade molybdic oxide or as ferromolybdenum.
The oxide is readily reduced by carbon in molten
steel, however, there are significant disadvantages
associated with this form of addition. Some MoO3 dis-
solves into the slag and is not reduced, so losses of mol-
ybdenum are significant. When added, a great deal of
‘smoke’ i.e. volatilised molybdenum, forms and the
result can be violent due to the very high vapour
pressure of MoO3, which sublimes at 700°C (Chychko
et al. 2010). This violence causes further molybdenum
loss to the fume, as well as environmental concerns
(Gao et al. 2012). During EAF steelmaking at Udde-
holms AB in Sweden, approximately 7% of the added
molybdenum is reported to be lost as fume (Chychko
2010). Ferromolybdenum as a steel additive is more
expensive than technical molybdic oxide due to the
costs associated with its production, but has several
advantages. It has a high density and a liquidus

CONTACT D. R. Swinbourne drs@rmit.edu.au School of Engineering, RMIT University, 124 Latrobe St, Melbourne, VIC 3000, Australia
© 2018 Institute of Materials, Minerals and Mining and The AusIMM Published by Taylor & Francis on behalf of the Institute and The AusIMM
 2 D. R. SWINBOURNE AND S. ARNOUT

Table 1. Representative molybdenite concentrate

compositions (in wt-%).
Climax Mine, Sarcheshmeh mine,
Shanxi, China Colorado, USA Iran (Moazemi-Goodarzi
wt-% (Li et al. 2016) (Nair et al. 1987) et al. 2014)
Mo 43.55 53 57.5
S – 35.6 37.9
Cu 0.03 0.04 0.5
Fe 1.39 0.34 1.99
Pb 4.2 – –
CaO 3.27 – 0.5
SiO2 4.02 3.7 –
MgO – – 0.39
Al2O3 0.18 – 0.23
WO3 1.66 – –

temperature similar to that of steel and so readily sinks
into the bath and dissolves. As a result, a very high yield
of molybdenum in steel can be achieved, leading to bet-
ter control of the final steel composition (Chychko
2010).
Almost all ferromolybdenum marketed contains
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Figure 1. Phase diagram of the Fe–Mo system (Rajkumar and
Hari Kumar 2014).
important that the underlying basis of this smelting
process, and the relationship between processing vari-
ables and output metrics, be optimised to minimise

from 60 to 65 wt-% Mo and maximum contents of sili-

con of 1.5 wt-%, copper of 0.5 wt-%, sulphur and car-
bon of 0.1 wt-% and phosphorus of 0.05 wt-%. The
limits on all impurities are set to prevent the addition
of the often large amounts of ferromolybdenum during
stainless steelmaking causing the resultant alloys to
exceed their minor element specifications. The Fe–
Mo phase diagram, Figure 1, shows that the liquidus
temperature of this alloy is approximately 1600°C,
and rapidly increases at higher molybdenum contents.
China produced almost 80% of the world total pro-
duction of 109,000 t of ferromolybdenum in 2012, with
the next largest producers being Armenia and Japan at
only approximately 5% each (Barrientos and Soria
2016).
The demand for molybdenum is forecast to grow by
an annual average of 3.6% at least until 2024, the major
driver being the expanding energy sector because mol-
ybdenum is used in significant amounts in oil and gas
pipeline steels, and in the high-performance alloys used
in nuclear power plants (Barrera 2016). The most
important technology for ferromolybdenum pro-
duction is the aluminosilicothermic reduction of
molybdic oxide (Jha 2001). For these reasons, it is
molybdenum losses and production costs.
The literature contains only a single reference to a
thermodynamic analysis of the aluminosilicothermic
reduction of molybdic oxide (Derin et al. 2010). How-
ever, that work did not review the technology of the
process or the phase equilibria of the ferroalloy or
slag produced, nor did it take into account the possi-
bility of molybdenum loss to the slag as dissolved
oxide species. The interrelationships between input
and output process parameters were also not
considered.
In this work, the thermodynamics of aluminosili-
cothermic smelting of molybdic oxide, as well as the
technology employed, will be reviewed. Computational
thermodynamics will then be used to examine the
relationships between the mass of reductants used in
the charge mix and the quantity and quality of ferro-
molybdenum produced. An accurate match between
model predictions and practice cannot be expected,
both because reliable industrial data are lacking and
because conditions during smelting are more complex
than can be represented in a relatively simple model.
However, the trends predicted form a strong basis for
understanding the ferromolybdenum smelting process.

Table 2. Representative technical molybdic oxide compositions. Thermodynamic analysis

Langeloth
China Metallurgical Co. Molibdenos y The Ellingham diagram, given as Figure 2, shows that
wt-% Gasik Molybdenum (2013) and Murphy Metales S.A. MoO3 is less stable than FeO and is easily reduced by
(max) (2013) Co. (2007) et al. (1946) (2015)
carbon at high temperatures. However, molybdenum
Mo 50–55 >57 >57 >57
S – 0.1 0.1 0.1 forms the very stable carbides Mo2C and MoC1−x, as
Cu 0.6–1.5 0.24 0.5 0.5 well as several ternary Fe–Mo–C carbides (Pearson
Pb – 0.1 – 0.05
P – 0.03 0.05 0.05 1964), so ferromolybdenum produced by carbon
C – 0.08 – 0.1 reduction would have a significant carbon content.
Sn – 0.03 – –
Sb – 0.03 – – The carbon content of commercial ferromolybdenum
SiO2 5–7 – – – must not exceed 0.1 wt-% so it is evident that carbon
CaO 14–16 – – –
cannot be used as a reductant for MoO3 (Gasik 2013).

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Figure 2. Ellingham diagram for species relevant to ferromo-
lybdenum smelting.
Both silicon, in the cheaper form of ferrosilicon, and
aluminium can be used as reductants, as seen on
Figure 2. Both reactions are very exothermic;
MoO3 + 1.5Si = Mo + 1.5SiO2 DHo (2000o C)
= −761 kJ mol−1 Mo (1)
MoO3 +2Al = Mo + Al2 O3 DHo (2000o C)
(2)
= −1037 kJ mol−1 Mo
All thermodynamic data are taken from the data-
base of HSC Chemistry for Windows 7.1 (Outotec
2013). The temperature of the products must be
above approximately 2000°C so that the slag is fluid
enough to allow the alloy droplets to effectively separ-
ate. If the amount of heat generated is too large, the
reaction is violent and spatters raw materials out of
the reactor, lowering the yield. The reactor lining can
also seriously erode and lead to a breakout of molten
products. If the amount of heat generated is too
small, the yield will be reduced because the reaction
rate is slow and also alloy droplets will be lost to the
slag. Ferromolybdenum quality may be lowered due
to slag inclusions. If the amount of heat generated is
even smaller, the raw materials may only partially
melt and reaction will be incomplete (Kobayashi 1992).
Whether or not a reaction provides enough heat for
successful smelting can be better assessed by the
‘Zhemchyzhny rule’ – that an energy density (ED) of
2700 kJ kg−1 of products is necessary for a reaction to
proceed without external energy input (Elyutin 1957).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY 3
This rule has been expanded (Yücel et al. 1996), as
follows;
. if ED is greater than 4500 kJ kg−1 then the reaction
is uncontrollably violent,
. between 4500 and 2250 kJ kg−1, the reaction is con-
trollable and requires no external energy input,
. if it is less than 2250 kJ kg−1 then an external energy
supply is necessary.
This simplistic approach has been criticised by
Stoephasius and Friedrich (2004). The work the rule
was based upon was small scale and made no allow-
ance for furnace geometry, heat losses, phase changes
and material losses. Nevertheless, it remains a useful
guide.
Silicon is usually used in the form of ferrosilicon
(75 wt-%Si), which has a composition close to
[Fe.6Si]. Assuming that the additional iron required
is supplied solely as metallic iron, then the equation
for the production of 60 wt-% Mo (equimolar) alloy
can be written as;
MoO3 +1/4[Fe.6Si]+3/3Fe = MoFe + 1.5SiO2
(3)
ED = 3140 kJ kg−1
The ED suggests that silicothermic reduction provides
enough heat for a controllable reaction without
additional heat supply. However, Habashi (1997) has
noted that in practice the use of silicon as a reductant
does not produce enough heat, due to heat losses, to
melt both the slag and the alloy. The ED can be
increased by replacing the added iron with iron ore
Fe2O3;
MoO3 + 1/3Fe2 O3 + 1/3[Fe.6Si]= MoFe + 2SiO2
(4)
ED = 3496kJkg−1
The use of ferrosilicon alone as reductant pro-
duces a slag with a very high silica content which
is viscous and impedes the settling of alloy droplets
(Suri and Gupta 1997). Replacing some of the silicon
with aluminium adds to alumina to the slag and this
significantly lowers the viscosity of the slag, as
shown on Figure 3. In practice, the viscosity is
decreased further by the presence of some unre-
duced FeO, as well as the addition of lime CaO
and fluorspar CaF2. Fluorspar is known to markedly
reduce the viscosity of high-silica slags (Wu et al.
2011). However, the use of aluminium as reductant
involves a high ED;
MoO3 +2Al + Fe = MoFe + Al2 O3
(5)
ED = 4079 kJ kg−1
So its use must be limited to avoid excessively high
temperatures which would lead to high volatilisation
losses of MoO3.
 4 D. R. SWINBOURNE AND S. ARNOUT

in the compositions of the FeSiAl and FeSiCa alloys

Figure 3. Viscosity of SiO2–Al2O3 slag (Nakamoto et al. 2005).
Production technology
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used. The total quantity of reductant used is seen to
be similar in all but two cases (F and G), and the
ratio of aluminium to silicon is also similar for all.
This is somewhat surprising given that the relative
costs of ferrosilicon and aluminium could be expected
to influence the reductant mix, and these costs vary
with location.
Mill scale Fe3O4 was far less common as an oxidic
source of iron than iron ore Fe2O3. The iron contents
of mill scale and iron ore were seldom given, so mill
scale was taken to be 67.5 wt-% Fe (Eissa et al. 2015)
and iron ore 62 wt-% Fe (O’Brien 2009). The fraction
of metallic iron which comprises the total amount of
iron in the charge is very similar in all but two charges
(A and F), where the metallic iron contents are abnor-
mally low.
The ratio of molybdenum to molybdenum plus iron
should be close to 0.6 since the target alloy can be
assumed to be 60 wt-% Mo, although often this target

Charge composition
A total of 16 charge compositions are reported in the
literature, with the most comprehensive list being
given by Habashi (1997). Those given in Gasik
(2013) are taken from the earlier work of Durrer
et al. (1972). Unfortunately, the masses and compo-
sitions of ferromolybdenum, slag and dust are not pro-
vided so mass balances cannot be performed. The
reference quantity of molybdenum also varies between
sources, so the charge mixes were recalculated to
100 kg of molybdenum contained in technical molyb-
dic oxide concentrate. Ferrosilicon (75 wt-% Si) is the
most common source of silicon, followed by 50 wt-%
Si alloy. One smelter is reported as having used FeSiAl
alloy alone (Durrer et al. 1972), two used ferrosilicon
plus FeSiAl alloy (Gupta 1992; Kornievskiy et al.
2015) and one used ferrosilicon plus FeSiCa alloy (Dur-
rer et al. 1972).
Seven typical charge compositions using only
ferrosilicon and aluminium as reductants are given in
Table 3. The others were excluded due to uncertainty
was not stated in the references given in Table 3.
This ratio is seen to be a little less than 0.6 in most
charges (except F) due to some of the iron reporting
to the slag as FeO.
The process
Bhardwaj (2014) describes the technology as involving
long sand beds with cylindrical refractory-lined steel
rings to hold the charge. Kornieskiy et al. (2015)
describe steel rings that are 2000 mm diameter and
2000 mm high, lined with 20 mm of chamotte refrac-
tory. Reaction takes place in either ‘top-fired’ mode,
where the rings are filled with reactants then ignited
at the top, or ‘fed reaction’ mode where a small amount
is fired, then raw material is added as the reaction pro-
gresses (Gupta 1992).
A very exothermic ignition mixture, consisting of
aluminium powder and a strong oxidant such as
sodium peroxide Na2O2 (Braithwaite and Haber 1994),
potassium chlorate KClO3 (Suri and Gupta 1997) or

Table 3. Representative charge mixtures.

A B C D E F G
Mo in concentrate/kg 100 100 100 100 100 100 100
Mill scale (Fe3O4)/kg 85.0 – – – – – –
Iron ore (Fe2O3)/kg – 48.0 48.0 41.5 47.6 60.6 45.5
Iron metal/kg – – 36.0 35.9 – – –
FeMo scrap recycle/kg 9.2 – – – – – –
Ferrosilicon (wt-%Si) – kg 63.3 (75) 87.2 (50) 66.7 (75) 59.6 (77) 94.0 (50) 79.5 (75) 75.8 (50)
Aluminium powder/kg 8.3 9.1 6.8 8.1 8.8 9.1 7.6
Lime CaO/kg 4.2 12.5 5.5 – 12.2 15.2 10.6
Fluorspar CaF2/kg 12.5 3.9 3.7 5.7 3.9 12.1 4.5
Dust recycle/kg 15.8 – – – – – –
Silicon in ferrosilicon/kg 47.5 43.6 50.0 45.9 47.0 59.7 37.9
Total reductant (Si + Al) 55.8 52.7 56.9 54.0 55.8 68.7 45.5
Al/Si 0.17 0.21 0.14 0.18 0.19 0.15 0.20
Feo/total Fe 0.25 0.57 0.62 0.65 0.61 0.35 0.57
Mo/(Mo + total iron) 0.59 0.57 0.54 0.57 0.57 0.64 0.60
A: Durrer et al. (1972) B: Murphy et al. (1946) C: Riss and Khodorovsky (1967) D: Vasil’ev (1975) E: Gupta (1992) F: Suri and Gupta (1997) G: Cardarelli (2008).
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 5

Figure 4. Smelting time as a function of target temperature

(Gasik et al. 2009).

barium peroxide Ba2O2 (Habashi 1997), is used to initiate

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the reaction. The smelting period varies from 30 to

60 min and, due to the high temperature and high vola-
tility of MoO3, up to 1% of the molybdenum in the
charge reports as dust (Habashi 1997). A relationship
was found between reaction temperature and smelting
time by Gasik et al. (2009) by varying the amount of alu-
minium in batch sizes of 1–3 t at the Tchelyabinsk Elec-
trometallurgy Plant, as shown on Figure 4. This data,
however, must be regarded as tentative due to the diffi-
culty of measuring such high temperatures and accessing
the reacting charge to take a measurement. Figure 5. Reaction stages for metallothermic reduction of
The cooling period varies from 4 to 16 h and a typi- metal oxides (De Fúccio et al. 1992).
cal alloy block is from 2.5 to 3 t per smelt cycle (Gupta
1992). The alloy and slag have very different coeffi- . all aluminium is oxidised to Al2O3, since the alu-
cients of expansion and so separate readily during cool- minium content of the alloy is less than 0.1 wt-%
ing (Braithwaite and Haber 1994). The reaction cycle is (Braithwaite and Haber 1994),
illustrated in Figure 5. . the FeO content is 10 wt-%, based on data in Table 3,
and
. the CaF2 content is small enough to be neglected.
Slag composition
The few compositions of slag available in the literature
The resulting compositions are plotted on the SiO2–
are given in Table 4. The data for Elyutin et al. (1957)
Al2O3–CaO-10 wt-%FeO phase diagram on Figure 6
are not from practice but were calculated by Habashi
to allow their liquidus temperatures to be estimated.
(1997) from the published charge mix composition.
Also plotted are the published slag compositions
Magnesia MgO presumably originates from slag attack
from Table 4, where SiO2+Al2O3+CaO was normalised
on the refractory lining. The molybdenum contents are
to 90 wt-%. The phase diagram was produced using the
low and very variable, which suggests that it is most
FactSage 7.1 software package (Bale et al. 2009). Slag
likely comprised of molybdenum in entrained ferro-
molybdenum prills. This is further supported by Iva-
nov et al. (1984) who conducted a phase and Table 4. Published ferromolybdenum slag compositions.
structural study on ferromolybdenum slags. Kornieskiy Gavrilovski Elyutin
wt-% et al. (2015) et al. (2014) et al. (1957) Gasik (2013)
The expected slag compositions for all charge mixes
SiO2 62–68 66.5 64.5 60–70
given in Table 3 can be calculated by assuming that; Al2O3 9–13 12.5 9.9 9–13
FeO 7–11 11.5 (by difference) 12.5 7–11
CaO 6–8 6.5 7.4 6–9
. the silicon content of the ferromolybdenum con- CaF2 – 2.4 – –
taining 60 wt-% Mo is 1.5 wt-%, and all remaining MgO 1–3 – – –
Mo 0.06–0.15 0.43 0.23 –
silicon is oxidised to SiO2,
 6 D. R. SWINBOURNE AND S. ARNOUT
Figure 6. Calculated slag compositions from Table 3 on the
SiO2–Al2O3–CaO phase diagram at 10 wt-% FeO. Published
data are from Table 4 where 1 = Kornieskiy et al. (2015) and
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Gasik (2013), 2 = Gavrilovski et al. (2014), 3 = Elyutin et al.
(1957). Liquidus temperature is in oC.
basicities, defined as CaO/SiO2 (wt-%), fall into two
groups i.e. the majority close to 0.05 and the remainder
near 0.12. Slag liquidus temperatures are between 1400
and 1600°C.
Methodology
HSC simulation
Derin et al. (2010) used the software package FactSage
6.0 to model ferromolybdenum smelting where the
reductant was ferrosilicon 50 wt-%Si. Changes in the
quantities of gas, slag and alloy species were given as
the quantity of ferrosilicon increased but very little
was deduced from those changes. The adiabatic temp-
erature as a function of the quantity of ferrosilicon used
was also calculated and shown to reach a maximum
value of 2470°C.
HSC Chemistry for Windows 7.1 software package
(Outotec 2013) is an alternative and user-friendly
way to determine the equilibrium state of a multicom-
ponent multiphase system. It has been successfully
used to examine many metallurgical processes, includ-
ing stainless steel converting (Swinbourne et al. 2010),
copper flash converting (Swinbourne and Kho 2012),
nickel laterite smelting (Swinbourne 2014) and ferrova-
nadium smelting (Swinbourne et al. 2016). All likely
phases in the system are specified as inputs, together
with the species which are in, or likely to be created
in, each phase. The activity coefficients of all species
in each phase, the masses of all input species and the
temperature and pressure of the system are required.
The need to determine activity coefficients from a lit-
erature search is an educational advantage because it
requires the user to understand how the data were
acquired and its limitations. A Gibbs free energy mini-
misation routine calculates the output quantities of all
species in all phases at equilibrium and they can be pre-
sented graphically in many formats.
Input amounts of species
The reaction mixture of Gupta (1992) identified as ‘E’
in Table 3 was taken as input data because it was typical
of the majority of charge mixtures and uses a signifi-
cant amount of CaO as a flux. It also did not contain
any added scrap iron, which simplifies analysis. The
ferrosilicon used contained 50 wt-% Si so the step
sizes for both Fe and Si were equal and set at 1 kg.
The aluminium/silicon mass ratio was 0.19 so the
step size for Al was 0.19 kg. The amount of MoO3 con-
taining 100 kg Mo is 150 kg.
Temperature
Derin et al. (2010) calculated that the adiabatic temp-
erature reached by a typical charge mix was about
2450°C. Heat losses will reduce this, but the reaction
time is short and this limits the temperature decrease.
Gasik (2013) states that the reaction temperature is
typically 2100°C for reactions which are complete in
10 min to 1760°C for those which take 50 min to com-
plete. Cardarelli (2008) states that the temperature
during reaction is 1800°C. In this work, the tempera-
ture was taken to be 2000°C.
Activity coefficient values
The gas phase can be considered to be ideal at such
high temperatures so the activity coefficients of all
gas species were taken to be unity.
Elliott et al. (1963) give the activity coefficients of
iron and molybdenum in binary alloys, but only at a
temperature of 1600°C. They show that the activity
coefficients for a 60 wt-%Mo alloy are approximately
1.3 and 0.8 for molybdenum and iron, respectively.
They can be expected to trend towards unity at higher
temperatures. In the absence of appropriate exper-
imental data, activity coefficients at 2000°C were esti-
mated using the dilute solution model described by
Sigworth and Elliott (1974) and using the tabulation
of Lupis (1983) for the interaction coefficients;

j
ln gi = ln g0i + 1i X j (6)
j
where gi is the Raoultian activity coefficient, g0i is the
j
Raoultian activity coefficient at infinite dilution, 1i is
the binary first order interaction coefficient between
species i and j, and Xj is the mole fraction of species
j. The temperature variation of the activity coefficient
at infinite dilution can be calculated from the Gibbs
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 7

free energy conversion from the pure substance to the

wt-% standard states by the following equation:
 
0.5585 g0i
D Grwt = RTln (7)
Mi

where Mi is the atomic weight of species ‘i’ in g mol−1.

The Gibbs free energies for converting from the pure
substance to the wt-% standard states were taken
from Rao (1985). Molybdenum is not dilute in ferro-
molybdenum, but it was assumed that the model
would be applicable i.e. that molybdenum can be
taken as equivalent to iron. In equimolar FeMo the
activity coefficients of Fe and Mo were confirmed to
be unity at 2000°C, while the limiting activity coeffi-
cient of silicon was 0.006. As confirmation, activity
coefficients were also calculated utilising the FactSage
7.1 FSstel database (Bale et al. 2009). The activity coef-
ficients of Fe and Mo were calculated to be 0.9 at 2000°
C, while the limiting activity coefficients of silicon and
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aluminium were 0.007 and 0.20, respectively. The

agreement with the Sigworth–Elliott method is
excellent.
The activity coefficients of species in the slag phase
were estimated using the Regular Solution Model of
Ban-Ya (1993), in which the activity coefficients are
given by the following equation;




RTln gi = aij X 2j + ( aij

+ aik − ajk ) X j X k +D Gconv (8)

where γi is the activity coefficient of species ‘i’, αi,j is the
interaction coefficient between species ‘i’ and ‘j’, Xi is
the cation fraction of species ‘i’, and ΔGconv is the
Gibbs free energy for conversion from the hypothetical
regular solution standard state to the pure solid or pure
liquid standard states. The required interaction coeffi-
cients and Gibbs free energy values for conversion from
the hypothetical regular solution standard state to the
pure solid or pure liquid standard states were also
taken from Ban-Ya (1993). The calculated activity coef-
ficients for SiO2, FeO and AlO1.5 at 2000°C are shown
in Figure 7. The activity coefficient for CaO was taken
as unity because, in the modelling, calcium was not
considered to partition to any other phase. Representa-
tive values for the activity coefficients of SiO2, FeO and
AlO1.5 were taken as 2, 0.8 and 0.015, respectively.
O’Neill and Eggins (2002) determined the speciation
of molybdenum in several slags, some of which were
similar in composition to ferromolybdenum slags,
however, the temperature in their work was only
1400°C. They showed that molybdenum was present
as both Mo4+ and Mo6+ in approximately equal pro-
portions in a melt which was in equilibrium with
iron. They calculated activity coefficients for MoO2
and MoO3 and found that γMoO3 had a value close to
0.8 while γMoO2 was about two orders of magnitude
Figure 7. Calculated activity coefficients of SiO2, FeO and
AlO1.5 at 2000°C.
greater. Their work suggests that at temperatures
much higher than 1400°C it would be reasonable to
take γMoO3 as unity and γMoO2 as 100. Gao et al.
(2012) concluded from their results that MoO3 does
not interact with SiO2 i.e. that MoO3 behaves as an
acidic oxide, which supports the assumption that the
activity coefficient of MoO3 is silicate slags is close to
unity.
A summary of all data for the HSC input file is given
as Table 5.
Results and discussion
The masses of species in ferromolybdenum, together
with the composition of the alloy, are given in Figure 8
as a function of the mass of silicon added. Aluminium
is also added in proportion to the amount of silicon,
but cannot be shown. As expected from an examin-
ation of the Ellingham diagram, MoO3 is preferentially
reduced to molybdenum, followed by iron oxide to
iron. The silicon mass rises at large silicon additions
because the reducible oxides have been reduced so
the added silicon simply dissolves in the alloy. The
 8 D. R. SWINBOURNE AND S. ARNOUT

shown is the silicon concentration for 1800°C, where

it is seen that it decreases. The activity coefficient of
silicon in the alloy is similarly uncertain, so also
shown is the silicon concentration for an activity coef-
ficient of silicon of 0.003. Even for this smaller value,
the specification limit for silicon is not exceeded.
The masses of species in the slag, and its compo-
sition, as a function of the amount of silicon in the
charge (together with accompanying aluminium) are
given in Figure 10. The predicted FeO content of the
slag is the best indicator of the reliability of the
model because, unlike silicon and aluminium, iron
distributes appreciably between slag and alloy, and
the FeO content of the slag is a strong function of the
amount of silicon and aluminium reductant in the
charge mix. It is seen that the FeO content is predicted
to be 10.5 wt-% at 47 kg of silicon, which matches very
well with the published data in Table 4. The drop in
silica content of the slag seen at high silicon additions
is not caused by dilution of the slag by alumina but by
Downloaded by [213.224.58.178] at 00:33 11 January 2018

an actual decrease in the mass of silica in the slag. This

can only be a result of reduction of silica from the slag
by the added aluminium reductant. This was verified
by a model in which aluminium was not included in
Figure 8. Mass of species in, and composition of, ferromolyb- the input species. In that case, no decrease in the
denum as a function of the mass of silicon in the charge mix. mass of silica in slag at high silicon inputs was
observed.
mass of silicon reductant required to achieve a ferro- The composition of the slag with respect to the mol-
molybdenum grade of 60 wt-% Mo is predicted to be ybdenum species is shown on Figure 11. Both MoO2
47 kg i.e. 94 kg of ferrosilicon (50 wt-%Si), identical and MoO3 are present at 47 kg of silicon in the charge
to that reported by Gupta in Table 3. The accompany-
ing mass of aluminium added is 8.8 kg of aluminium.
The concentration of silicon in ferromolybdenum is
of particular interest because it is limited by specifica-
tions to a maximum of 1.5 wt-%. The silicon concen-
tration is shown on Figure 9 and is predicted to be,
for the base case where the activity coefficient of silicon
is 0.006, approximately 0.7 wt-% at 47 kg of silicon in
the charge mix. The temperature is uncertain so also

Figure 9. Silicon content of ferromolybdenum as a function of

temperature, the limiting activity coefficient of silicon in ferro- Figure 10. Mass of species in, and composition of, slag as a
molybdenum and the mass of silicon in the charge mix. function of the mass of silicon in the charge mix.
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY 9

wrote that ferromolybdenum slag at the proposed

Mt. Hope plant in the U.S. would be treated to recover
‘occluded metal shot and prills’. The recovery of mol-
ybdenum to the alloy must be sensitive to slag viscosity,
mixing conditions during reaction and the length of the
slag/alloy separation period.
The interrelationships between ferromolybdenum
grade with respect to both molybdenum and silicon,
and the loss of molybdenum to the slag as dissolved
oxides are shown on Figure 12. Aiming for a higher
molybdenum grade of alloy will result in a rapidly
increasing loss of molybdenum oxides to the slag, add-
ing to that resulting from droplet entrainment. Aiming
for a lower molybdenum grade risks exceeding the sili-
con specification, which would be exceeded if the mol-
ybdenum grade of the alloy was below approximately
55 wt-%.
Figure 11. Molybdenum species in slag as a function of the The masses of species in the gas phase, and their
mass of silicon in the charge mix.
partial pressures, are shown on Figure 13. The oxygen
partial pressure is seen to be approximately 10−9 atm at
Downloaded by [213.224.58.178] at 00:33 11 January 2018

mix, with MoO2 dominating. This result conforms 47 kg of silicon addition. The predominant molyb-
with the findings of O’Neill and Eggins (2002). The denum species in the gas is Mo3O9, followed by
assumed value of the activity coefficient of MoO2 at MoO3 and then MoO2. However, the mass of molyb-
100 is uncertain, so it was changed to 50, and then to denum oxides reporting to the gas is only significant
150, to determine the sensitivity of the MoO2 content below about 10 kg of silicon in the charge mix when
to the value of γMoO2. Even at a value of 50 the concen- molybdenum is present as unreduced oxides in the
tration of MoO2 in the slag remains very small. The charge. At 47 kg of silicon, the predominant gas species
equilibrium molybdenum content of the slag is much is SiO, but its mass is very small. The figure shows that
lower than the molybdenum content of industrial at equilibrium in a closed system the loss of molyb-
slags given in Table 4. Almost all of the molybdenum denum to the gas phase is predicted to be trivial, yet
in industrial slags must be present as entrained alloy industrial observations are that molybdenum losses
droplets, a conclusion supported by Cook (2011) who as dust and fume are significant (Habashi 1997;
Gasik, 2013). Volatilisation of molybdenum will be
greater in an open system as applies in practice, but
Table 5. Input data for the HSC file used to simulate it might also be a result of heating of as-yet unreduced
ferromolybdenum smelting at 2000°C. charge mix by reacting charge. In this case, molyb-
Species Amount (kg) Activity coefficient denum losses as dust and fume could be expected to
Gas be less when smelting in the ‘fed-reaction’ mode
N2(g) 0.00001 1
O2(g) 1 (Gupta 1992), where small parcels of mix are added
MoO2(g) 1
MoO3(g) 1
Mo2O6(g) 1
Mo3O9(g) 1
SiO(g) 1
FeO(g) 1

Metal
Mo 1
Fe 1, step 1 1
Si 1, step 1 0.006
Al 0.19, step 0.19 0.2

Slag
SiO2(CR) 2
AlO1.5 0.015
FeO 0.8
CaO 12 1
CaF2 4 1
MoO3 1
MoO2 100

Pure Figure 12. Grade of ferromolybdenum and loss of molyb-

MoO3 150 1 denum as dissolved oxides in slag to the mass of silicon in
Fe2O3 47 1
the charge mix.
 10 D. R. SWINBOURNE AND S. ARNOUT
Downloaded by [213.224.58.178] at 00:33 11 January 2018
Figure 13. Mass of gas species, and composition, as a function
of the mass of silicon in the charge mix.
periodically to the reacting mixture, than in the ‘top-
fired’ mode. Nothing could be found in the literature
to verify this postulate.
The enthalpy change of the reacting system as a
function of the mass of silicon in the charge mix is
shown as Figure 14. At small amounts of silicon
addition the major changes taking place are the volatil-
isation of molybdenum oxides, all of which are
endothermic;
MoO3 = MoO2 (g)+1/2O2 (g) DHo (2000o C) = +598.3kJ
MoO3 = MoO3 (g) DHo (2000o C) = +260.8kJ
3MoO3 = Mo3 O9 (g) DHo (2000o C) = +60.4kJ
At 47 kg of silicon in the charge mix, the reacting
system is close to producing the maximum enthalpy
change, and therefore the highest temperature of the
ferromolybdenum and slag.
Figure 14. Reaction enthalpy at 2000°C as a function of the
mass of silicon in the charge mix.
In summary, the modelling has shown that for a
typical charge mix in which all additional iron is pro-
vided by Fe2O3, 47 kg of silicon (94 kg of 50 wt-% Si
FeSi) and 9 kg of aluminium per 100 kg of contained
molybdenum provide a very good compromise
between competing factors. It yields the required mol-
ybdenum grade with a silicon content below specifica-
tion, minimises the loss of molybdenum to the slag as
dissolved oxides and results in a high iron recovery i.e.
the FeO content of the slag is low. The resulting slag
has a low liquidus temperature and viscosity, when
CaO and CaF2 fluxes are also added, and yields the
maximum heat of reaction so slag superheat is high.
These slag properties are conducive to the settling of
suspended alloy droplets. However, the modelling
does not consider economic factors which may dictate
a change in the ratio of aluminium to silicon in the
charge mix, based on the relative local costs of alu-
minium and ferrosilicon.
Conclusions
Ferromolybdenum is an important commodity used in
the production of many alloy steels. It is made by the
silicoaluminothermic batch reduction of technical mol-
ybdenum oxide at very high temperatures. In this work,
a computational thermodynamics model using HSC
Chemistry for Windows 7.1 software was created and
its input parameters discussed and justified. The
model predicted satisfactorily the composition of
both the ferromolybdenum and waste slag from a typi-
cal charge mixture. It was found that the silicon con-
tent of the ferromolybdenum produced was not very
(9) sensitive to either the assumed smelting temperature
or the activity coefficient of silicon in the alloy. Losses
(10) of molybdenum to the slag as dissolved oxides occurred
as both MoO2 and MoO3, but the total molybdenum
(11)
losses of dissolved oxides were predicted to be much
lower than the published molybdenum contents of
industrial slags. This suggests that molybdenum losses
to slag in practice are almost entirely due to the
inclusion of unsettled ferromolybdenum droplets.
Losses of molybdenum by oxide volatilisation were
also predicted to be trivial under equilibrium con-
ditions, and it was suggested that the observed losses
may be a result of the heating of as-yet unreacted
charge mix.
Acknowledgements
The authors wish to thank David Langberg for assistance
with the thermodynamic modelling of the ferromolybdenum
and slag phases, and Prof. Michael Gasik of Aalto University,
Finland, for many helpful discussions.
Disclosure statement
No potential conflict of interest was reported by the authors.

ORCID
S. Arnout http://orcid.org/0000-0002-6231-2320
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